WO2009093708A1 - Matière absorbant l'eau et son procédé de fabrication - Google Patents

Matière absorbant l'eau et son procédé de fabrication Download PDF

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Publication number
WO2009093708A1
WO2009093708A1 PCT/JP2009/051115 JP2009051115W WO2009093708A1 WO 2009093708 A1 WO2009093708 A1 WO 2009093708A1 JP 2009051115 W JP2009051115 W JP 2009051115W WO 2009093708 A1 WO2009093708 A1 WO 2009093708A1
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water
absorbing agent
group
polysiloxane
mass
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PCT/JP2009/051115
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English (en)
Japanese (ja)
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Kazushi Torii
Taishi Kobayashi
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Nippon Shokubai Co., Ltd.
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Publication of WO2009093708A1 publication Critical patent/WO2009093708A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • C08F20/00—Homopolymers 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/68—Superabsorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • the present invention relates to a water-absorbing agent containing a water-absorbing resin and a water-soluble polysiloxane having a dissociating group, and a method for producing the same.
  • water-absorbent resins have been widely used as main constituent materials in hygiene materials (absorbent articles) such as disposable diapers, sanitary napkins, incontinence pads, etc. for the purpose of absorbing body fluids (urine and blood).
  • hygiene materials such as disposable diapers, sanitary napkins, incontinence pads, etc.
  • water-absorbing resin include a crosslinked polyacrylic acid partial neutralized product, a hydrolyzate of starch-acrylonitrile graft polymer, a neutralized product of starch-acrylic acid graft polymer, and a vinyl acetate-acrylic acid ester copolymer.
  • Saponified product of polymer, crosslinked carboxymethyl cellulose, hydrolyzate of acrylonitrile copolymer or acrylamide copolymer or cross-linked product thereof, crosslinked product of cationic monomer, crosslinked isobutylene-maleic acid copolymer, 2-acrylamide-2 -A cross-linked product of methylpropanesulfonic acid and acrylic acid is known.
  • water absorption characteristics desired for these water-absorbing agents include high absorption capacity when in contact with aqueous liquids such as body fluids, especially high water absorption capacity under load, excellent absorption rate, liquid permeability, gel strength of swollen gel
  • a suction amount for sucking water from a base material containing an aqueous liquid is a demand for a suction amount for sucking water from a base material containing an aqueous liquid.
  • Patent Documents 1 to 4 disclose a water absorbent resin composition containing a modifier having a hydrocarbon group having a fluorine atom.
  • Patent Document 6 discloses a polyaminoalkylsiloxane complex as a water-containing gel
  • Non-Patent Document 1 discloses a water-containing gel using a cylindrical polysiloxane as a raw material.
  • International Publication No. 2005/077500 pamphlet released on August 18, 2005
  • Japanese Patent Gazette “Special Publication 2006-526691 Publication Date: November 24, 2006”
  • Japanese Patent Gazette “Special Publication No. 8-509522 Publication Date: October 8, 1996)
  • Japanese Patent Gazette “Special Table 2004-512165 Publication Date: April 22, 2004
  • Japanese Patent Publication “Japanese Patent Laid-Open No. 2003-082250 Publication Date: March 19, 2003
  • Japanese Patent Publication “JP 2005-120333 A Publication Date: May 12, 2005)” J. Mater. Chem., 2006, 16, 1746-1750
  • polysiloxane is used as a cross-linking agent, polysiloxane is generally hardly soluble in water and has a water-insoluble property, so it hardly dissolves in a polymerization reaction solution using water as a medium and is uniform. There is a disadvantage that polymerization cannot be performed in the state. For this reason, a simple manufacturing method has not been established.
  • the polymer may be exposed to high temperatures in the drying process and the surface cross-linking process, and the polymer may deteriorate. Accordingly, there is a demand for a water-absorbing agent having heat resistance, which does not cause a decrease in performance of the water-absorbing agent obtained by deterioration of the raw material polymer.
  • the present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to provide an unprecedented water-absorbing agent using a compound having a polysiloxane structure. Furthermore, it is providing the water absorbing agent which has heat resistance.
  • the water-absorbing agent of the present invention is characterized by containing a water-absorbing resin having a structural unit derived from an acid group-containing unsaturated monomer and a water-soluble polysiloxane having a dissociating group in order to solve the above-mentioned problems. .
  • a novel water-absorbing agent containing the water-soluble polysiloxane can be provided. That is, in the water-absorbing agent, the water-soluble polysiloxane is water-soluble, and an organic-inorganic composite in which the water-absorbing resin and the organic-inorganic structure are uniformly crosslinked can be provided. Further, by newly providing a water-absorbing agent having a water-soluble polysiloxane, the possibility of a new design of the water-absorbing agent can be expanded. Moreover, the water-absorbing agent obtained is excellent in saline flow conductivity. Furthermore, since the water-absorbing agent contains an inorganic structure derived from polysiloxane in its structure, it also has heat resistance.
  • the dissociating group is preferably an amino group.
  • the water-absorbing resin having a structural unit derived from an acid group-containing unsaturated monomer and the amino group are chemically bonded to each other and / or the surface of the water-absorbing resin. Can be easily provided.
  • the water-absorbent resin is internally cross-linked by the water-soluble polysiloxane.
  • Such a configuration can provide a new water-absorbing agent that is internally cross-linked with a water-soluble polysiloxane.
  • the surface of the water-absorbent resin is surface-crosslinked with the water-soluble polysiloxane.
  • Such a configuration can provide a water-absorbing agent whose surface is cross-linked with a water-soluble polysiloxane.
  • the water-absorbing resin is preferably formed by polymerizing an unsaturated monomer containing a carboxyl group.
  • the water-soluble resin having a carboxylic acid has a dissociation group of the water-soluble polysiloxane and a carboxyl group of the water-absorption resin.
  • the water-soluble polysiloxane has the following chemical formulas (1) to (4): [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [C j H 2j + 1 OSiO 1.5 ] 1-P Chemical formula (1) [Q (H x ⁇ Z) ⁇ (R 1) 2 N (CH 2) n SiO 1.5 ] p [CH 3 (CH 2) m SiO 1.5 ] 1-P ⁇ ⁇ ⁇ formula (2) [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [R 2 SiO 1.5 ] 1-P ...
  • Chemical formula (3) [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [R 3 NH (CH 2 ) n SiO 1.5 ] 1-P ( 1 )
  • Chemical formula (4) (In the above chemical formulas (1) to (4), n is independently an integer of 1 or more and 6 or less, j is an integer of 0 or more and 4 or less, and m is Any integer of 0 or more and 4 or less, p is independently a value in the range of more than 0 and 1 or less, and R 1 is independently a hydrogen atom, an alkyl group, or a substituted alkyl group.
  • R 2 is a hydrogen atom, a vinyl group or an allyl group
  • Z is a monovalent or divalent anion
  • q is a value multiplied by the neutralization rate
  • R 1 contains an amino group
  • 0.1 or more is a number in the range of 2 or less, if R 1 does not include an amino group, of 0.1 or more and 1 or less
  • x is 1 when Z is a monovalent anion, preferably has at least one of the molecular structure represented by Z is 2 when divalent anion.).
  • the water-soluble polysiloxane has at least one of the molecular structures represented by the chemical formulas (1) to (4), it is easy to synthesize the water-soluble polysiloxane, and the water-absorbing agent is more easily produced. can do.
  • p in the chemical formulas (1) to (4) is preferably 0.3 or more and 1 or less.
  • the water solubility of the monomer used as the raw material for the water-soluble polysiloxane is improved.
  • more uniform mixing with these solvents can be achieved.
  • R 1 is preferably a hydrogen atom and n is preferably 3. That is, in each chemical formula of the water-soluble polysiloxane, the structure [H 2 N (CH 2 ) 3 SiO 1.5 ] p is provided, whereby a water-absorbing agent having excellent water absorption characteristics can be provided. .
  • one R 1 is a hydrogen atom
  • the other R 1 is a 2-aminoethyl group
  • q is It is a number in the range of 0.1 to 2 and x is preferably 1.
  • the solid content with respect to 100 parts by mass of the water-absorbing agent is preferably 70 parts by mass or more.
  • the solid content is less than the above range, not only the fluidity is deteriorated and the production may be hindered, but the water absorbent resin may not be pulverized and may not be controlled to a specific particle size distribution. .
  • the absorbent article according to the present invention is obtained by using 0.001 part by mass or more and 10 parts by mass or less of the water-soluble polysiloxane with respect to 100 parts by mass of the acid group-containing unsaturated monomer. preferable.
  • the absorbent article according to the present invention contains the above water-absorbing agent.
  • the water-absorbing agent is a novel water-absorbing agent containing the water-soluble polysiloxane, a new absorbent article can be provided.
  • the method for producing a water-absorbing agent according to the present invention comprises a hydrogel crosslinked polymer obtained by crosslinking polymerization of an acid group-containing unsaturated monomer in the presence of an internal crosslinking agent.
  • a water-soluble polysiloxane having an amino group is used as the internal crosslinking agent.
  • the inside of the water-absorbent resin is cross-linked with the water-soluble polysiloxane, and thus a novel water-absorbing agent containing the water-soluble polysiloxane is produced. can do.
  • the method for producing a water-absorbing agent according to the present invention comprises a hydrogel crosslinked polymer obtained by crosslinking polymerization of an acid group-containing unsaturated monomer in the presence of an internal crosslinking agent.
  • the method for producing a water-absorbing agent drying to obtain a water-absorbing agent, the water-containing gel-like crosslinked polymer is dried, and the obtained water-containing gel-like crosslinked polymer dried product is used with a water-soluble polysiloxane having an amino group. It is characterized by surface-treating a dried hydrogel crosslinked polymer.
  • the dried hydrogel crosslinked polymer after the surface treatment can be crosslinked with the water-soluble polysiloxane via a covalent bond and / or an ionic bond.
  • a novel water-absorbing agent containing improved water-soluble polysiloxane can be produced.
  • the method for producing a water-absorbing agent according to the present invention comprises a hydrogel crosslinked polymer obtained by crosslinking polymerization of an acid group-containing unsaturated monomer in the presence of an internal crosslinking agent.
  • drying to obtain a water-absorbing agent after drying the water-containing gel-like crosslinked polymer and subjecting the obtained water-containing gel-like crosslinked polymer dried product to surface crosslinking treatment, It is characterized by adding a water-soluble polysiloxane having a water-soluble gel-like crosslinked polymer dried product subjected to a surface crosslinking treatment.
  • the surface of the dried hydrogel crosslinked polymer can be crosslinked with the water-soluble polysiloxane by the action of the water-soluble polysiloxane as the surface treatment agent, and a novel water-absorbing agent containing the water-soluble polysiloxane is produced. can do.
  • the water-soluble polysiloxane has the following chemical formulas (1) to (4): [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [C j H 2j + 1 OSiO 1.5 ] 1-P Chemical formula (1) [Q (H x ⁇ Z) ⁇ (R 1) 2 N (CH 2) n SiO 1.5 ] p [CH 3 (CH 2) m SiO 1.5 ] 1-P ⁇ ⁇ ⁇ formula (2) [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [R 2 SiO 1.5 ] 1-P ...
  • Chemical formula (3) [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [R 3 NH (CH 2 ) n SiO 1.5 ] 1-P ( 1 )
  • Chemical formula (4) (In the above chemical formulas (1) to (4), n is independently an integer of 1 or more and 6 or less, j is an integer of 0 or more and 4 or less, and m is Any integer of 0 or more and 4 or less, p is independently a value in the range of more than 0 and 1 or less, and R 1 is independently a hydrogen atom, an alkyl group, or a substituted alkyl group.
  • R 2 is a hydrogen atom, a vinyl group or an allyl group
  • R 3 is an acryloyl group or a methacryloyl group
  • Z is a monovalent or divalent anion
  • q is neutralized
  • R 1 includes an amino group
  • the number is in the range of 0.1 to 2
  • R 1 does not include an amino group
  • the value is in the range of 0.1 to 1
  • X is 1 when Z is a monovalent anion and Z is a divalent anion In the case of emissions is 2.
  • It preferably has at least one molecular structure represented by
  • the water-soluble polysiloxane has at least one of the molecular structures represented by the chemical formulas (1) to (4), it is easy to synthesize the water-soluble polysiloxane, and the water-absorbing agent is more easily produced. can do.
  • the water-absorbing agent according to the present invention contains a water-absorbing resin having a structural unit derived from an acid group-containing unsaturated monomer and a water-soluble polysiloxane having a dissociating group.
  • the water absorbent resin is crosslinked with polysiloxane. It is sufficient that at least one of the surface or the inside of the water absorbent resin is crosslinked.
  • each compound and water absorbing agent used for obtaining the water absorbing agent according to the present invention will be described.
  • the water-soluble polysiloxane according to the present invention may be simply referred to as polysiloxane.
  • weight is treated as a synonym for “mass”
  • weight% is treated as a synonym for “mass%”.
  • Water-absorbing resin in the present invention, a water-absorbing resin obtained by crosslinking and polymerizing an acid group-containing unsaturated monomer and a water-soluble polysiloxane described later are essential.
  • the water-absorbing resin may be a water-absorbing resin having a cross-linked polymerization structure, and after the acid group and / or its salt-containing unsaturated monomer is polymerized, it undergoes a cross-linking reaction by self-crosslinking during polymerization or polymerization.
  • the obtained water-absorbent resin may be used.
  • the water-absorbent resin has a structural unit derived from an acid group-containing unsaturated monomer, and preferably has the structural unit as a main component. “Having as a main component” means containing 90% or more of the total mass of the water-absorbent resin.
  • structural unit derived from an acid group-containing unsaturated monomer means, for example, an acid in which a double bond part involved in polymerization of an acid group-containing unsaturated monomer is converted to a single bond by a polymerization reaction. The structure of the group-containing unsaturated monomer will be shown.
  • the water-absorbent resin according to the present invention is a water-swellable and water-insoluble crosslinked polymer capable of forming a hydrogel.
  • the water-swellable water-absorbing resin refers to one that absorbs a large amount of water in ion-exchanged water essentially 5 times or more of its own weight, preferably 50 to 1000 times.
  • the water-insoluble water-absorbent resin is preferably an uncrosslinked water-soluble component (water-soluble polymer) in the water-absorbent resin, preferably 50% by mass or less (lower limit 0%), more preferably 25% by mass or less. It is preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less.
  • crosslinked polymer is a polymer having a crosslinked structure (hereinafter referred to as “internal crosslinked structure”) inside a polymer obtained by polymerizing an unsaturated monomer in order to obtain good absorption characteristics. Refers to coalescence.
  • the water-absorbent resin has a structural unit derived from an acid group-containing unsaturated monomer.
  • the water-soluble polysiloxane has a dissociating group.
  • the dissociating group includes both a proton accepting group and a proton donating group. Specific examples include an amino group, a carboxyl group, a sulfonic acid group, a sulfate ester group, and a phosphoric acid group, and an amino group is preferable.
  • the water-soluble polysiloxane according to the present invention preferably has an amino group as a dissociating group.
  • the amino group of the said water-soluble polysiloxane and the carboxyl group of a water absorbing resin will carry out a chemical bond (covalent bond, ionic bond), and inside a water absorbing resin and / Or the surface can be cross-linked.
  • the water-absorbent resin may be subjected to a surface cross-linking treatment that forms a cross-linked structure on the surface of the water-absorbent resin, or may not be subjected to the surface cross-linking treatment.
  • a surface crosslinking treatment is performed.
  • water-absorbing resin comprising the above-mentioned crosslinked polymer
  • examples of the water-absorbing resin comprising the above-mentioned crosslinked polymer include polyacrylic acid partially neutralized polymer, starch-acrylonitrile graft polymer hydrolyzate, starch-acrylic acid graft polymer or neutralized product thereof, carboxy Cross-linked methylcellulose, saponified product of vinyl acetate-acrylic ester copolymer, hydrolyzate of acrylonitrile copolymer or acrylamide copolymer or cross-linked product thereof, carboxyl group-containing cross-linked polyvinyl alcohol modified product, cross-linked cationic monomer 1 type or 2 types or more, such as a crosslinked product of 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid, and a crosslinked isobutylene- (maleic anhydride) copolymer.
  • the water-absorbing resin composed of the above-mentioned crosslinked polymer is obtained by polymerizing and crosslinking an unsaturated monomer, and is subjected to surface crosslinking treatment as necessary.
  • the water-soluble polysiloxane, unsaturated monomer, crosslinkable monomer (internal crosslinker), polymerization initiator, surface crosslinker and the like used for the production of the water absorbent resin will be described.
  • the water-soluble polysiloxane is a water-soluble polysiloxane having a dissociation group.
  • a dissociation group preferably an amino group
  • water-solubility is exhibited, and a water-absorbing agent can be provided by reaction with a water-absorbing resin.
  • the water-absorbing agent can include a polysiloxane structure, a new water-absorbing agent can be designed.
  • the polysiloxane has a dissociation group, preferably an amino group, which the general polysiloxane does not have in the molecular structure. Therefore, the polysiloxane according to the present invention can exhibit water solubility, and can be used by dissolving in an aqueous solution or a highly polar solvent.
  • Water solubility means that a solution of 0.1 g or more, preferably 1 g or more, is dissolved in 100 g of pure water to give a transparent and uniform solution. Furthermore, it can couple
  • the surface treatment agent As the surface treatment agent, the surface of the water-absorbent resin can be cross-linked through covalent bonds and / or ionic bonds by allowing polysiloxane to act on the surface of the surface-crosslinked water-absorbent resin.
  • a water-absorbing agent having an unprecedented structure can be obtained.
  • the water-soluble polysiloxane is not particularly limited, but has a dissociation group, preferably an amino group, and is essential to be water-soluble.
  • a dissociation group preferably an amino group
  • the water-soluble polysiloxane will be described in more detail.
  • the water-soluble polysiloxane will be described mainly with respect to a molecular structure having an amino group.
  • the polysiloxane of the present invention only needs to have a dissociating group, and the amino group portion is replaced with the dissociating group described above. Can be configured.
  • the water-soluble polysiloxane according to the present invention has the following chemical formula (1) to chemical formula (4) as its molecular structure.
  • Chemical formula (1) [Q (H x ⁇ Z) ⁇ (R 1) 2 N (CH 2) n SiO 1.5 ] p [CH 3 (CH 2) m SiO 1.5 ] 1-P ⁇ ⁇ ⁇ formula (2) [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [R 2 SiO 1.5 ] 1-P ...
  • Chemical formula (3) [Q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [R 3 NH (CH 2 ) n SiO 1.5 ] 1-P ( 1 )
  • Chemical formula (4) (In the above chemical formulas (1) to (4), n is independently an integer of 1 or more and 6 or less, j is an integer of 0 or more and 4 or less, and m is Any integer of 0 or more and 4 or less, p is independently a value in the range of more than 0 and 1 or less, and R 1 is independently a hydrogen atom, an alkyl group, or a substituted alkyl group.
  • R 2 is a hydrogen atom, a vinyl group or an allyl group
  • R 3 is an acryloyl group or a methacryloyl group
  • Z is a monovalent or divalent anion
  • q is neutralized
  • R 1 includes an amino group
  • the number is in the range of 0.1 to 2
  • R 1 does not include an amino group
  • the value is in the range of 0.1 to 1
  • X is 1 when Z is a monovalent anion and Z is a divalent anion For emission is 2.
  • the water-soluble polysiloxane having the molecular structure as described above can be synthesized relatively easily. For this reason, it becomes possible to manufacture the water absorbing agent containing the said water-soluble polysiloxane more simply.
  • n, j, and m are in the above-mentioned range, that is, the structure has a structure in which the hydrophobicity of the polysiloxane is difficult to improve.
  • P representing the proportion of each repeating unit in the above chemical formulas (1) to (4) is preferably 0.3 or more and 1 or less, more preferably 0.5 or more and 1 or less. It is particularly preferably 9 or more and 1 or less.
  • the water-solubility of the polysiloxane improves, so that it is particularly easy to dissolve in water or a hydrophilic solvent, so that more uniform mixing with these solvents can be achieved.
  • polysiloxane when polysiloxane is used as a raw material for the water-absorbing agent, it can be efficiently used in the reaction in a solution state, and the water-absorbing agent can be easily obtained.
  • each R 1 is independently a hydrogen atom, an alkyl group, or an allyl group.
  • the alkyl group may be unsubstituted, or a substituent containing any of an amino group, an epoxy group or an unsaturated group may be introduced.
  • An alkyl group into which a substituent is introduced is referred to as a substituted alkyl group.
  • an unsaturated group shows the molecular structure containing a double bond or a triple bond.
  • alkyl group examples include a linear alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. Group, dodecyl group and the like.
  • the allyl group is not particularly limited as long as it contains a 2-propenyl group.
  • the alkyl group and allyl group may be substituted with a substituent containing any of an amino group, an epoxy group, or an unsaturated group, but the substitution position is not particularly limited.
  • the structure in which an alkyl group is substituted with an amino group includes an aminomethyl group, an aminomethyl group, an aminopropyl group, an aminobutyl group, an aminopentyl group, an aminohexyl group, an aminoheptyl group, an aminooctyl group, an aminononyl group, Examples include aminodecyl group, aminoundecyl group, aminododecyl group, and isomers thereof.
  • a 3-aminopropyl group in which R 1 is all hydrogen atoms and n is 3 is more preferable because the raw materials are easily available.
  • R 2 in the chemical formula (3) is a hydrogen atom, a vinyl group or an allyl group.
  • the allyl group is the same allyl group as the allyl group in R 1 described above.
  • Z is a monovalent or divalent anion
  • q is a value obtained by multiplying the neutralization rate
  • R 1 contains an amino group
  • 0.1 The number is in the range of 2 or less and when R 1 does not contain an amino group, the number is in the range of 0.1 or more and 1 or less.
  • R 1 when R 1 includes an amino group, the number of Z coordinated on nitrogen can be doubled compared to when R 1 does not include an amino group.
  • each nitrogen contains one atom, so the neutralization rate is a number in the range of 0.1 to 1 Yes, q is also a number in the range of 0.1 to 1.
  • Z when R 1 contains an amino group, Z can be coordinated to 1 or 2 atoms in the nitrogen contained in R 1 , and neutralization is a number in the range of 0.1 to 1 Multiply the rate by a factor of 2, and the maximum value of q is 2 or less. That is, q is a number in the range from 0.1 to 2.
  • a molecular structure of an amine structure that is not an ammonium salt is included at a ratio of q-1.
  • the monovalent or divalent anion is not particularly limited as long as the properties of the water-absorbing agent obtained when the water-soluble polysiloxane is allowed to act on the water-absorbing resin are not impaired.
  • Specific examples include chloride ions, nitrate ions, sulfate ions, carboxylate anions, and phosphonate anions.
  • the structure of the hydrocarbon bonded to the anion moiety is a hydrocarbon having 1 to 12 carbon atoms, and even a straight chain structure has a side chain structure. You may do it.
  • the polysiloxane structure in the chemical formulas (1) to (4) may be an amine structure.
  • the water absorbent resin and the polysiloxane can be bonded via a covalent bond and / or an ionic bond.
  • the structures of the chemical formulas (1) to (4) are respectively [(R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [C j H 2j + 1 OSiO 1.5 ] 1-P— Chemical formula (1 ′) [(R 1 ) 2 N (CH 2 ) n SiO 1.5 ] p [CH 3 (CH 2 ) m SiO 1.5 ] 1-P ...
  • the mass average molecular weight of the polysiloxane is not particularly limited, but in the case of an ammonium salt structure, it is preferably 5000 or more and 1000000 or less. When the mass average molecular weight is less than 5000, and when it exceeds 1000000, there is a possibility that sufficient absorption characteristics of the resulting water-absorbing agent may not be obtained.
  • the method for producing polysiloxane is not limited to the following method, and may be a method described in Japanese Patent Publication “JP-A-2005-120333” or Japanese Patent Publication “JP-A-2006-45392”. .
  • the polysiloxane used in the present invention includes at least one of the structures represented by the chemical formulas (1) to (4). These chemical formulas (1) to (4) each contain a structure of [q (H x ⁇ Z) ⁇ (R 1 ) 2 N (CH 2 ) n SiO 1.5 ].
  • this structure is referred to as a basic structure for convenience of explanation.
  • [C j H 2j + 1 OSiO 1.5 ], [CH 3 (CH 2 ) m SiO 1.5 ], [R 2 SiO, which are structural parts other than the basic structures of chemical formulas (1) to (4). 1.5 ] and [R 3 NH (CH 2 ) n SiO 1.5 ] are referred to as substructure (1), substructure (2), substructure (3) and substructure (4), respectively.
  • the compound that is a monomer that is a raw material of the basic structure, the substructure (1), the substructure (2), the substructure (3), and the substructure (4) will be described.
  • n in chemical formula (5) is an integer of 1 or more and 6 or less, and R 1 has the same chemical structure as R 1 described above in ⁇ Water-soluble polysiloxane>.
  • R 4 is not particularly limited as long as it is an alkyl group. Specific examples of R 4 include a methyl group, an ethyl group, and a propyl group.
  • R 1 is hydrogen, aminomethylmethoxysilane, aminomethylethoxysilane, aminomethylpropoxysilane, 2-aminoethylmethoxysilane, 2-aminoethylethoxysilane, Examples include 2-aminoethylpropoxysilane, 3-aminopropylmethoxysilane, 3-aminopropylethoxysilane, 3-aminopropylpropoxysilane, and the like. Among these, 3-aminopropylmethoxysilane, 3-aminopropylethoxysilane, and 3-aminopropylpropoxysilane can be preferably used because they are easily available.
  • R 1 may be an alkyl group or an allyl group exemplified above other than a hydrogen atom.
  • Examples of compounds in which one R 1 is a hydrogen atom and the other R 1 has a 2-aminoethyl group include 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) Mention may be made of propyltriethoxysilane and 3- (2-aminoethylamino) propyltripropoxysilane.
  • the allyl group can be further introduced by using a compound having an unsaturated carbonyl group such as acrylic chloride.
  • R 5 is the same structure as the alkyl group exemplified as R 4 in the compound represented by the above chemical formula (5). However, R 4 and R 5 do not have to be the same, and may have different structures. This is because when polysiloxane is produced, the structure containing R 4 is removed from the final product by an elimination reaction.
  • specific compounds include, but are not limited to, tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.
  • Representative examples of specific compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane, and propyltriethoxy.
  • Examples include silane, propyltripropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, and pentyltripropoxysilane.
  • R 2 Si (OR 7 ) 3 Chemical formula (8)
  • the allyl trialkoxysilane shown by these can be used.
  • R 2 is a hydrogen atom, a vinyl group or an allyl group
  • the allyl group is the same as the allyl group which R 1 in the chemical formulas (1) to (4) may have.
  • the structure of R 7 is the same structure as the alkyl group exemplified as R 4 in the compound represented by the above chemical formula (5). However, R 4 and R 7 do not have to be the same, and may have different structures.
  • Representative examples of specific compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, (2-propenyl) methyltrimethoxysilane, (2-propenyl) methyltriethoxysilane, (2- (Propenyl) methyltripropoxysilane, (2-propenyl) ethyltrimethoxysilane, (2-propenyl) ethyltriethoxysilane, (2-propenyl) ethyltripropoxysilane, (2-propenyl) propyltrimethoxysilane, (2- Propenyl) propyltriethoxysilane, (2-propenyl) propyltripropoxysilane, and the like, but are not limited thereto.
  • the compound used as a raw material for the substructure (4) is not particularly limited as long as it can generate the substructure (4).
  • Substructure (4) is generated by reacting amines such as silane and 3-aminopropylpropoxysilane, and acrylic group-introducing compounds such as acryloid chloride or methacrylic group-introducing compounds such as methacryloyl chloride. be able to.
  • p in the chemical formulas (1) to (4) is independently 0.
  • a polysiloxane having a value exceeding 1 and not more than 1 can be obtained.
  • the ratio of the raw materials of the basic structure, substructure (1), substructure (2), substructure (3) and substructure (4) (hereinafter referred to as “polysiloxane raw material”) is particularly limited. However, as the ratio of the raw material of the polysiloxane to the raw material of the basic structure increases, the value of p in the chemical formulas (1) to (4) of the resulting polysiloxane decreases, and the hydrophilicity of the polysiloxane decreases. In order to reduce, it is preferable that the ratio of the raw material of a basic structure is larger than the total amount of the raw material of polysiloxane.
  • the ratio of each raw material is set so that the value of p is preferably 0.3 or more and 1 or less, more preferably 0.5 or more and 1 or less, and particularly preferably 0.9 or more and 1 or less. It is preferable to adjust.
  • the above raw materials are dropped into an acid in an aqueous solution in which an acid is present as a catalyst.
  • an acid hydrochloric acid, nitric acid and the like can be used.
  • the molar ratio of the total amount of the polysiloxane raw material and the acid can be in the range of 1: 1 to 1: 4.
  • the reaction temperature when the polysiloxane raw material is dropped into an aqueous solution containing an acid as a catalyst may be room temperature.
  • the time for polymerizing the polysiloxane raw material varies depending on the type of the polysiloxane raw material to be used, but the polymerization reaction may be generally carried out for 1 to 3 hours.
  • reaction mixture is placed in an open system at a temperature of about 50 ° C. to 80 ° C. to evaporate water from the reaction mixture.
  • This step can be performed using a conventionally known dryer or the like.
  • the polysiloxane contained in the mixture after evaporation of water may be used as a raw material for the water-absorbing agent after being purified, but if there is no problem in the process of producing the water-absorbing agent, it is used without being purified. Also good.
  • Examples of a method for purifying polysiloxane include a method in which the above mixture is dissolved in distilled water and an organic solvent is added to make use of the difference in solubility. As the organic solvent is added, the polysiloxane precipitates. The polysiloxane can be purified by filtering this precipitate.
  • the method for producing the water-absorbing agent according to the present invention can be broadly classified as follows: a step of polymerizing monomers, a polymer obtained by polymerizing the obtained monomers, that is, water content It is divided into a step of drying the gel-like crosslinked polymer and a step of surface cross-linking.
  • the water-absorbing resin containing the water-soluble polysiloxane can be produced by including the water-soluble polysiloxane described above in the water-absorbing resin.
  • step of polymerizing the monomer the step of adding a water-soluble polysiloxane as an internal cross-linking agent to the aqueous solution when polymerizing the monomer (ii)
  • step of surface cross-linking treatment step of adding water-soluble polysiloxane as a surface cross-linking agent (iv)
  • the water-absorbing resin cross-linked with the water-soluble polysiloxane Step of adding siloxane A polymerization step, a drying step, and a surface treatment step included in the method for producing a water absorbing agent will be described below.
  • the acid group-containing unsaturated monomer used to obtain the water-absorbing resin contained in the water-absorbing agent of the present invention is a compound that can obtain a desired crosslinked polymer.
  • a saturated monomer may be used.
  • the unsaturated monomer is water-soluble, a solution reaction with a water-soluble polysiloxane described later can be smoothly performed by aqueous solution polymerization.
  • an unsaturated monomer having an acid form and / or a salt molecular structure thereof can be used.
  • the acid group include a carboxyl group, a sulfo group, an amide group, and an ester group.
  • the acid group-containing unsaturated monomer examples include vinyl sulfonic acid, ⁇ -acryloyloxypropionic acid, methacrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, vinyl sulfonic acid,
  • Examples include acid group-containing simple substances such as 2- (meth) acrylamido-2-methylpropanesulfonic acid and (meth) acryloxyalkanesulfonic acid, and alkali metal salts, ammonium salts and alkylamine salts thereof.
  • the water-absorbent resin is a polymer of partially neutralized acrylic acid
  • acrylic acid and / or a salt thereof neutralized product
  • other unsaturated monomers other than acrylic acid and / or salt thereof may be included as a copolymerization component.
  • other properties such as antibacterial properties and deodorization can be imparted to the finally obtained water absorbent resin, and the water absorbent resin can be obtained at a lower cost.
  • Examples of the other unsaturated monomers include N-vinyl-2-pyrrolidone, N-vinylacetamide, (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2-hydroxy
  • Examples thereof include water-soluble or water-insoluble unsaturated monomers such as ethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, isobutylene, and lauryl (meth) acrylate. These monomers may use only 1 type and may mix and use 2 or more types suitably.
  • Examples of the acid group-containing unsaturated monomer of the present invention include those having the other unsaturated monomer as a copolymerization component.
  • alkali metal salts Alkali metal salts, alkaline earth metal salts, ammonium salts, preferably alkali metal salts may be used.
  • sodium salt or potassium salt should be used at least essential from the viewpoint of the performance of the water-absorbing resin obtained, the industrial availability of the salt of the acid group-containing unsaturated monomer, safety, etc. preferable.
  • the number of moles of acrylic acid and its salt as the main component is preferably 70 to 100 mole% with respect to the total number of moles of all unsaturated monomers used to obtain the water-absorbent resin. More preferably, it is 90 to 100 mol%, and further preferably 95 to 100 mol%.
  • the acid group-containing unsaturated monomer such as acrylic acid is preferably about neutral from the viewpoint of physical properties and pH, and the acid group is preferably neutralized.
  • the neutralization rate of acid groups (mol% of neutralized acid groups in all acid groups) is usually 20 to 100 mol%, preferably 30 to 95 mol%, more preferably 40 to 80 mol%.
  • the neutralization of the acid group may be performed with a monomer, a polymer, or a combination thereof.
  • the water-absorbent resin of the present invention is a cross-linked polymer having an internal cross-linked structure.
  • the internal cross-linking structure of the water-absorbent resin may be obtained by self-crosslinking of an unsaturated monomer without using a cross-linking monomer that is an internal cross-linking agent.
  • those obtained by copolymerizing or reacting the unsaturated monomer and the crosslinking monomer are preferable.
  • the cross-linking monomer as an internal cross-linking agent has two or more polymerizable unsaturated groups or two or more reactive groups in one molecule.
  • the above-described polysiloxane can be used as an internal cross-linking agent.
  • the unsaturated monomer and the polysiloxane can be reacted by the dissociation group portion contained in the polysiloxane, and the polysiloxane structure is formed inside the resulting water-absorbent resin. It is possible to provide a water-absorbing agent having
  • the polysiloxane contains an unsaturated group
  • addition polymerization can occur with the monomer, so that variations in the crosslinking method can be increased, and the crosslinking structure can be increased. Different water-absorbing agents can be obtained.
  • Other internal crosslinking agents include, for example, N, N′-methylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, glycerin tri (meth) acrylate, glycerin acrylate methacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine , Poly (meth) allyloxyalkane, (poly) ethylene glycol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol, polyethylene Glycol, propylene glycol, glycerol, pentaerythritol,
  • the above internal cross-linking agents may be used alone or in combination of two or more. Moreover, the said internal crosslinking agent may be added to a reaction system all at once, and may be divided and added.
  • a cross-linkable monomer having two or more polymerizable unsaturated groups is used in consideration of the absorption characteristics of the finally obtained water-absorbing agent. It is preferably used at the time of polymerization.
  • the amount used when the polysiloxane is used as an internal crosslinking agent is 0.001 mass relative to 100 parts by mass of the acid group-containing unsaturated monomer (excluding the crosslinking agent) used to obtain the water-absorbent resin. It is preferably no less than 10.0 parts by mass, more preferably no less than 0.01 parts by mass and no greater than 5 parts by mass, and particularly preferably no less than 0.1 parts by mass and no greater than 1 part by mass. .
  • the amount of the internal crosslinking agent used is less than 0.001 part by mass, and when it exceeds 10 parts by mass, it is not preferable because sufficient absorption characteristics of the water absorbing agent may not be obtained.
  • the amount of the internal crosslinking agent other than the polysiloxane used is the total number of moles of unsaturated monomers used to obtain the water absorbent resin (crosslinking agent is from the viewpoint of obtaining good physical properties of the water absorbent resin. Is preferably 0.001 to 2 mol%, more preferably 0.005 to 0.5 mol%, still more preferably 0.01 to 0.2 mol%, and particularly preferably 0.03 to 0 mol%. Within the range of 15 mol%. When the amount of the internal cross-linking agent used is less than 0.001 mol% and exceeds 2 mol%, it is not preferable because sufficient absorption characteristics of the water absorbing agent may not be obtained.
  • the internal crosslinking agent is added to the reaction system before, during or after the polymerization of the unsaturated monomer, or after neutralization. What is necessary is just to add.
  • the polysiloxane may be added to the reaction system after polymerization.
  • a water-containing gel-like crosslinked polymer is heated, a water-containing gel-like crosslinked polymer can be dried and internal crosslinking can be caused.
  • the unsaturated monomer is an aqueous solution containing an internal cross-linking agent as necessary.
  • concentration of the unsaturated monomer component in the aqueous monomer solution is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, still more preferably 30 to 65% by mass, particularly preferably from the viewpoint of physical properties. Is 30 to 60% by mass, most preferably 35 to 55% by mass.
  • a solvent other than water may be used in combination as necessary, and the type of solvent used in combination is not particularly limited.
  • the mixing method is not particularly limited, but is preferably added to the monomer or aqueous monomer solution and mixed to be unsaturated. It is adjusted to a monomer aqueous solution.
  • the water-soluble polysiloxane when used as a crosslinkable monomer, from the viewpoint that the water-soluble polysiloxane can be uniformly mixed in the polymerization reaction solution and the polymerization can be easily controlled. It is preferable to perform aqueous solution polymerization or reverse phase suspension polymerization by making the body into an aqueous solution.
  • the reverse phase suspension polymerization is a polymerization method in which an aqueous monomer solution is suspended in a hydrophobic organic solvent in the form of particles.
  • a hydrophobic organic solvent in the form of particles.
  • aqueous solution polymerization is a method of polymerizing an aqueous monomer solution without using a dispersion solvent.
  • US Pat. Nos. 4,462,001, 4,873,299, 4,286,082, 4,973,632, 4,985,518, and 5,124,416 are used.
  • No. 5,250,640, No. 5,264,495, No. 5,145,906 and No. 5,380,808, and European patents such as European Patent Nos. 081636, 09555086, and 0922717.
  • Monomers and polymerization initiators exemplified in these US patents and European patents can also be applied to the present invention.
  • the concentration of the monomer in the aqueous solution depends on the temperature of the aqueous solution and the monomer and is particularly limited. is not. However, it is usually in the range of 10 to 80% by mass, preferably in the range of 10 to 70% by mass, and more preferably in the range of 20 to 60% by mass. Moreover, when performing the said aqueous solution polymerization, you may use together solvents other than water as needed, and the kind of solvent used together is not specifically limited.
  • the above polymerization initiator can be used.
  • active energy rays such as ultraviolet rays, electron beams, and ⁇ rays may be used alone or in combination with the polymerization initiator.
  • the reaction temperature in the above polymerization reaction depends on the type of polymerization initiator used, but is preferably in the range of 15 to 130 ° C., more preferably in the range of 20 to 120 ° C., as the lower limit to the upper limit temperature during the polymerization. If the reaction temperature is out of the above range, the water absorption performance of the water absorbent resin may be deteriorated due to an increase in residual monomers of the obtained water absorbent resin or excessive self-crosslinking reaction, which is not preferable.
  • a water-soluble polysiloxane is adjusted to the above amount and mixed with an aqueous monomer solution during polymerization.
  • the monomer aqueous solution at the time of polymerization is not limited to the monomer aqueous solution before polymerization, and is a concept including a monomer aqueous solution in the middle of polymerization and a gel-like substance containing the water solubility. It may be added one or more times at a stage where the rate is 0 to 99 mol%, further 0 to 70 mol%, particularly 0 to 50 mol%.
  • water-soluble polysiloxane when added to the monomer aqueous solution in the polymerization step, it can be mixed at any timing before and after the introduction of the polymerization initiator, and the timing and method of mixing are particularly limited. However, it is preferably added to the monomer aqueous solution (polymerization rate 0%) before polymerization.
  • hydrogel The hydrogel crosslinked polymer obtained in the polymerization process (hereinafter, hydrogel) may be dried as it is in the case of aqueous solution polymerization, but if necessary, a gel grinder or the like may be used.
  • the gel is pulverized into particles.
  • the temperature of the water-containing gel at the time of gel pulverization is preferably kept at 40 to 95 ° C., more preferably 50 to 80 ° C. from the viewpoint of physical properties.
  • the resin solid content of the hydrated gel is not particularly limited, but is preferably 10 to 70% by mass, more preferably 15 to 65% by mass, and further preferably 30 to 55% by mass from the viewpoint of physical properties.
  • the gel pulverization is performed at the time of polymerization or after polymerization, and can be preferably pulverized by extrusion from a continuous kneader or a porous structure having a pore diameter of 0.3 to 30 mm, more preferably 5 to 30 mm, and even more preferably 5 to 20 mm. .
  • the shape of the hole is not particularly limited, such as a quadrangle such as a circle, a square, and a rectangle, a triangle, and a hexagon. However, the hole is preferably extruded from a circular hole.
  • the said hole diameter can be prescribed
  • the gel may become a string or the gel may not be extruded.
  • the pore diameter of the porous structure is larger than 30 mm, the water-containing gel is not sufficiently dried, so that the effects of the present invention may not be exhibited.
  • the extrusion pulverization apparatus for example, a screw type, a rotary roll type, or the like that can pressure-feed the hydrogel polymer from its supply port to the perforated plate is used.
  • the screw-type extruder may be uniaxial or multi-axial, and may normally be used for extrusion molding of meat, rubber and plastic, or may be used as a pulverizer.
  • meat chopper and dome gran are mentioned.
  • water or a polyhydric alcohol described in the example of the internal cross-linking agent a mixed solution of water and polyhydric alcohol, a solution in which the polyvalent metal described in the example of the internal cross-linking agent is dissolved in water, or a vapor thereof is added. May be.
  • a water-soluble polysiloxane is mixed at the time of sizing (subdividing) the water-containing gel.
  • the polymer obtained by polymerizing the monomer by the above polymerization method is usually a hydrogel crosslinked polymer, and is subjected to drying treatment or pulverization as necessary.
  • the grinding is usually performed before and / or after the drying process.
  • a dried hydrogel crosslinked polymer can be obtained.
  • the drying method includes heat drying, hot air drying, vacuum drying, infrared drying, microwave drying, dehydration by azeotropy with a hydrophobic organic solvent, and high moisture drying using high-temperature steam.
  • Various methods can be adopted so as to be, and there is no particular limitation.
  • the drying treatment is performed by hot air drying, it is usually performed in a temperature range (hot air temperature) of 60 ° C. to 250 ° C., preferably 100 ° C. to 220 ° C., more preferably 120 ° C. to 200 ° C.
  • the drying time depends on the surface area of the polymer, the moisture content, and the type of dryer, and is selected to achieve the desired moisture content. For example, the drying time may be appropriately selected within the range of 1 minute to 5 hours.
  • Water content of the water-absorbent resin that can be used in the present invention (specified by the amount of water contained in the water-absorbent resin or water-absorbing agent / measured for 3 hours of loss on drying at 180 ° C.
  • the ratio expressed by the ratio to the resin is not particularly limited. However, in order to obtain good physical properties of the water-absorbing agent of the present invention containing the water-absorbing resin as a main component, it is preferable that the water content is controllable so that particles (powder) exhibiting fluidity at room temperature.
  • the water-absorbing agent is preferably in a powder state with a water content of 0 to 30% by mass, more preferably in a powder state of 0.2 to 30% by mass, more preferably in a powder state of 0.2 to 20% by mass,
  • the powder state is preferably 0.3 to 15% by mass, and particularly preferably 0.5 to 10% by mass.
  • What is necessary is just to dry-process a water-containing gel-like crosslinked polymer, and to obtain a water absorbing resin so that the water absorbing agent which has the water content in said range may be obtained. If the water content becomes high, the fluidity is deteriorated and the production is hindered, and the water-absorbent resin cannot be pulverized and may not be controlled to a specific particle size distribution.
  • the hydrogel crosslinked polymer obtained after the completion of the polymerization reaction is usually dispersed in a hydrocarbon organic solvent such as hexane. After azeotropic dehydration, the water content of the polymer is adjusted to 40% by mass or less (lower limit 0% by mass, preferably 5% by mass), preferably 30% by mass or less, and then separated from the organic solvent by decantation or evaporation. Depending on the case, it can be dried.
  • the water-absorbent resin of the present invention may be added and mixed with a surface cross-linking agent, a liquid permeability improver, a slipperiness improver, etc., which will be described later, during or after polymerization.
  • a surface cross-linking agent e.g., a liquid permeability improver, a slipperiness improver, etc., which will be described later, during or after polymerization.
  • the addition and mixing can be performed before drying, after drying or after pulverization.
  • the particle size may be adjusted after drying after the step of drying the water-containing gel-like crosslinked polymer described above, but it is preferably specified for improving the physical properties in surface crosslinking described later.
  • the particle size can be appropriately adjusted by polymerization (particularly reversed phase suspension polymerization), pulverization, classification, granulation, fine powder recovery and the like.
  • the mass average particle diameter (D50) before surface crosslinking is adjusted to 200 to 600 ⁇ m, preferably 200 to 550 ⁇ m, more preferably 250 to 500 ⁇ m, and particularly preferably 350 to 450 ⁇ m. Further, the smaller the particle size is less than 150 ⁇ m, the better, and it is usually adjusted to 0 to 5% by mass, preferably 0 to 3% by mass, particularly preferably 0 to 1% by mass. Further, the smaller the number of particles of 850 ⁇ m or more, the better. Usually, it is adjusted to 0 to 5% by mass, preferably 0 to 3% by mass, particularly preferably 0 to 1% by mass.
  • the logarithmic standard deviation ( ⁇ ) of the particle size distribution is preferably 0.20 to 0.40, preferably 0.27 to 0.37, and preferably 0.25 to 0.35.
  • the surface cross-linking of the water-absorbent resin is to provide a uniform cross-linked structure inside the polymer with a portion having a higher cross-linking density in the surface layer of the water-absorbent resin (near the surface: usually several tens of microns or less) That is, a highly crosslinked layer may be formed by radical crosslinking or surface polymerization on the surface, or surface crosslinking may be performed by a crosslinking reaction with a surface crosslinking agent.
  • the surface cross-linking by the surface cross-linking agent performed as necessary in the present invention will be further described.
  • the surface cross-linking agent used in the present invention includes various organic or inorganic cross-linking agents. From the viewpoint of physical properties, cross-linking agents capable of reacting with carboxyl groups, particularly organic surface cross-linking agents, generally polyhydric alcohols. Compounds, epoxy compounds, polyvalent amine compounds or their condensates with haloepoxy compounds, oxazoline compounds, mono-, di- or polyoxazolidinone compounds, polyvalent metal salts, alkylene carbonate compounds, and the like are used.
  • the polysiloxane has a dissociation group, preferably an amino group, it can react with a functional group of the water-absorbent resin and can crosslink the surface of the water-absorbent resin. Thereby, a water-absorbing agent containing polysiloxane can be obtained, and a new water-absorbing agent surface-crosslinked with polysiloxane can be provided.
  • the surface cross-linking agent other than the polysiloxane a compound having two or more functional groups capable of reacting with the functional group of the water-absorbent resin can be used as the surface cross-linking agent.
  • a compound having two or more functional groups capable of reacting with the functional group of the water-absorbent resin can be used as the surface cross-linking agent.
  • polyhydric alcohol compounds, epoxy compounds, polyepoxy compounds, polyvalent amine compounds or their condensates with haloepoxy compounds, oxazoline compounds, mono-, di- or polyoxazolidinone compounds, polyvalent metal salts, alkylene A carbonate compound or the like can be used.
  • surface cross-linking agent used in the present invention are exemplified in US Pat. Nos. 6,228,930, 6071976, and 6254990.
  • mono, di, tri, tetra or polyethylene glycol monopropylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4-trimethyl-1,3-pentanediol, polypropylene glycol, glycerin, polyglycerin , 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, etc.
  • Alcohol compounds epoxy compounds such as ethylene glycol diglycidyl ether and glycidol, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, polyamide polyamine, etc.
  • Haloepoxy compounds such as epichlorohydrin, epibromohydrin, ⁇ -methylepichlorohydrin; condensates of the above polyvalent amine compounds with the above haloepoxy compounds, xazolidinone compounds such as 2-oxazolidinone, ethylene carbonate Examples thereof include, but are not limited to, alkylene carbonate compounds.
  • the amount of the surface cross-linking agent used depends on the compounds used, combinations thereof, and the like, but is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the resin solids, 0.01 mass More preferably within the range of 5 parts by mass to 5 parts by mass.
  • water is preferably used for surface crosslinking.
  • the amount of water used depends on the water content of the water-absorbing resin to be used, it is usually preferably 0.5 to 20 parts by weight, more preferably 0.8 parts per 100 parts by weight of the water-absorbing resin. It is in the range of 5 to 10 parts by mass.
  • the amount of the surface cross-linking agent used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass (parts by mass) of the water-absorbing resin, although it depends on the compounds to be used and combinations thereof. A range of 0.01 parts by mass to 5 parts by mass is more preferable.
  • the amount of water used depends on the water content of the water absorbent resin to be used, but is preferably 0.5 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the water absorbent resin. Within the range of parts by mass.
  • a hydrophilic organic solvent may be used instead of water, or a mixed solvent of water and a hydrophilic organic solvent may be used.
  • the amount of the hydrophilic organic solvent or mixed solvent used in this case is in the range of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, more preferably 0 to 3 parts by weight with respect to 100 parts by weight of the water absorbent resin. It is.
  • the addition of the surface cross-linking agent can be performed by various methods. However, a method in which the surface cross-linking agent is preliminarily mixed with water and / or a hydrophilic organic solvent, if necessary, and then sprayed or dropped into the water-absorbent resin is preferable, and a method of spraying is more preferable.
  • the size of droplets to be sprayed is preferably in the range of 0.1 to 300 ⁇ m, more preferably in the range of 0.1 to 200 ⁇ m, in terms of average particle diameter.
  • the mixing device used when mixing the water-absorbing resin, the surface cross-linking agent, and water or a hydrophilic organic solvent has a large mixing force in order to mix these substances uniformly and reliably. It is preferable.
  • the mixing apparatus include a cylindrical mixer, a double wall conical mixer, a high-speed stirring mixer, a V-shaped mixer, a ribbon mixer, a screw mixer, a double-arm kneader, and a pulverizing kneader. Rotating mixers, airflow mixers, turbulators, batch-type Redige mixers, continuous-type Redige mixers, and the like are suitable.
  • the surface cross-linking agent When mixing the surface cross-linking agent, it may be mixed with a polymer additive having a hydrocarbon group having 7 or more carbon atoms in the side chain before the surface cross-linking or coexisting with the surface cross-linking agent.
  • the water-absorbing agent of the invention can be obtained.
  • water-insoluble fine particle powder when mixing the surface cross-linking agent, water-insoluble fine particle powder may be allowed to coexist within a range that does not hinder the effects of the present invention.
  • the water-absorbing resin after mixing the surface cross-linking agent is preferably heat-treated.
  • the heating temperature water absorbent resin temperature or heat medium temperature
  • the heating time is preferably in the range of 1 minute to 2 hours.
  • Preferable examples of the combination of the heating temperature and the heating time are 180 ° C. for 0.1 to 1.5 hours and 200 ° C. for 0.1 to 1 hour.
  • the surface cross-linking treatment in the present invention there is a method of performing surface cross-linking treatment by irradiating active energy after adding a treatment liquid containing a radical polymerizable compound to the water absorbent resin. It is described in a national published patent publication “Japanese Patent Laid-Open No. 2003-303306”. Moreover, a surface active agent can also be added to the said process liquid, and an active energy can be irradiated and surface crosslinking can also be performed.
  • the water-soluble gel-like crosslinked polymer obtained by subjecting the water-containing gel-like polymer to surface cross-linking treatment is allowed to act on the water-soluble polysiloxane according to the present invention
  • the surface of the dried hydrogel crosslinked polymer can be surface-crosslinked by covalent bonding and / or ionic bonding. Also by this, the water absorbing agent containing polysiloxane can be obtained.
  • the timing which makes water-soluble polysiloxane act on a hydrogel crosslinked polymer dried material is not specifically limited.
  • a method for allowing polysiloxane to act on the surface-crosslinked water-absorbing resin is not particularly limited.
  • polysiloxane may be dissolved in water or a hydrophilic organic solvent and mixed with the water-absorbing resin.
  • a mixing apparatus for example, a cylindrical mixer, a double wall cone mixer, a high-speed stirring mixer, a V-shaped mixer, a ribbon mixer, a screw mixer, a double-arm kneader, a pulverizing kneader, A rotary mixer, an airflow mixer, a turbulizer, a batch-type Redige mixer, a continuous-type Redige mixer, and the like are suitable.
  • the amount of water-soluble polysiloxane used is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, with respect to 100 parts by mass of the water-absorbing resin.
  • the water-soluble polysiloxane is made into a solution for uniform addition, further an aqueous solution or an aqueous solution, and added as a solution to the surface-crosslinked water-absorbing resin.
  • concentration of the solution may be 1 to 50% by mass.
  • a hydrophilic organic solvent may be used.
  • ⁇ Other components contained in water-absorbing agent> a surfactant, a deodorant, an antibacterial agent, a fragrance, a foaming agent, a pigment, a dye, a hydrophilic short fiber, a plasticizer, an adhesive, a fertilizer, an oxidizing agent, Reducing agent, water, salt, chelating agent, bactericidal agent, anti-coloring agent, hydrophilic polymer such as polyethylene glycol and polyerylenimine, hydrophobic polymer such as paraffin, thermoplastic resin such as polyethylene and polypropylene, polyester resin And a step of adding various functions such as addition of a thermosetting resin such as urea resin.
  • the amount of these additives to be used is usually 0 to 30 parts by weight, preferably 0 to 10 parts by weight, more preferably 0 to 1 part by weight with respect to 100 parts by weight of the water absorbent resin.
  • the mixing method of the water-absorbing agent and these additives is not particularly limited.
  • a dry blend method in which powders are mixed with each other, a wet blend method (addition is performed by dispersing or dissolving the additive in a solvent), etc. are adopted. it can.
  • the water-absorbing agent according to the present invention is obtained.
  • the present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and the present invention can be obtained by appropriately combining technical means disclosed in different embodiments. Such embodiments are also included in the technical scope of the present invention.
  • the water-absorbing agent according to the present invention contains a water-absorbing resin having a structural unit derived from an acid group-containing unsaturated monomer and a water-soluble polysiloxane having a dissociating group, preferably an amino group. . More preferably, the water-soluble polysiloxane has at least one molecular structure represented by the chemical formulas (1) to (4).
  • the water-soluble polysiloxane having the amine structure is formed by, for example, a covalent bond between the water-soluble polysiloxane and the water-absorbent resin in the production process, and the elimination of hydrogen atoms and negative ions Z in the water-soluble polysiloxane. Arise.
  • the shape of the water-absorbing agent according to the present invention includes, for example, a sheet shape and a fiber shape, and particularly preferably a particle shape or a spherical shape.
  • the water absorbing agent may be a granulated product.
  • the water-absorbing agent of the present invention is used for absorption of water, various aqueous solutions, aqueous solutions such as urine and blood, and the pure component of the water-absorbing resin is used as the main component in all the components contained in the water-absorbing agent.
  • the content is usually 70% by mass (% by mass) or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and still more preferably 90% by mass or more and 100% by mass or less with respect to 100 parts by mass.
  • the fluidity may deteriorate and the production may be hindered, or the water absorbent resin may not be pulverized or controlled to a specific particle size distribution. There is.
  • the lower limit of the value in 30 minutes of the absorption capacity under non-pressurization (CRC / Centrifuge Retention Capacity) of the water-absorbing agent of the present invention with respect to a 0.90 mass% sodium chloride aqueous solution is preferably 10 g / g, more preferably 15 g / g, More preferably, it is 20 g / g.
  • capacitance (CRC) under no pressure of the water absorbing agent of this invention becomes like this.
  • the absorption capacity without load (CRC) of the water-absorbent resin before the surface crosslinking treatment is preferably controlled in the range of 10 to 60 g / g, more preferably 25 to 40 g / g.
  • the absorption capacity is reduced by the surface cross-linking.
  • it is necessary to suppress the decrease preferably at 95 to 50%, more preferably 90 to 60% of the absorption ratio before surface crosslinking.
  • the reduction in the absorption capacity may be appropriately adjusted depending on the type and amount of the crosslinking agent, reaction temperature, time, and the like.
  • the physiological saline flow inductivity is a value indicating the liquid permeability when the water-absorbing agent swells, and indicates that the larger the value, the higher the liquid permeability.
  • the water-absorbing agent obtained in the present invention is preferably 10 (10 ⁇ 7 ⁇ cm 3 ⁇ s ⁇ g ⁇ 1 ) or more, more preferably 30 (10 ⁇ 7 ⁇ cm 3 ⁇ s ⁇ g ⁇ 1 ) or more, further preferably Is more than 50 (10 ⁇ 7 ⁇ cm 3 ⁇ s ⁇ g ⁇ 1 ), particularly preferably 80 (10 ⁇ 7 ⁇ cm 3 ⁇ s ⁇ g ⁇ 1 ) or more, saline flow conductivity (SFC / Saline Flow Conductivity)
  • SFC / Saline Flow Conductivity saline flow conductivity
  • the value of the saline flow conductivity is not particularly limited, but the upper limit may be about 3000 (10 ⁇ 7 ⁇ cm 3 ⁇ s ⁇ g ⁇ 1 ).
  • AAP Absorption capacity under pressure
  • AAP (Absorbency against Pure) of the water-absorbing agent of the present invention is 8 (g / g) or more, preferably 16 (g / g) or more, more preferably 20 (g / g) or more. Yes, more preferably 22 (g / g) or more, and most preferably 24 (g / g) or more.
  • the water-soluble content of the water-absorbing agent of the present invention is preferably 0 to 35% by mass or less, more preferably 25% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less.
  • the gel strength is weak and the liquid permeability may be inferior.
  • the absorption capacity (CRC, AAP, etc.) may decrease over time.
  • the solid content with respect to 100 parts by mass of the water-absorbing agent is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and particularly preferably 90 parts by mass or more.
  • the water-absorbing agent of the present invention preferably contains 90% by weight or more (upper limit of 100%) of particles having a particle size of 150 ⁇ m or more and less than 850 ⁇ m, more preferably 150 ⁇ m or more and less than 850 ⁇ m, based on the mass of the water-absorbing agent. Is contained in an amount of 95% by weight or more, and more preferably 98% by weight or more of particles of 150 ⁇ m or more and less than 850 ⁇ m.
  • the water-absorbing agent of the present invention is a water-absorbing agent mainly composed of a water-absorbing resin having a crosslinked structure obtained by polymerizing an unsaturated monomer, and the water-absorbing agent has a particle size of less than 850 ⁇ m and 150 ⁇ m or more. Is 90% by weight or more of the whole (the upper limit is 100% by weight).
  • the weight percent of the polysiloxane and the water-absorbing resin according to the present invention is preferably 80% by weight or more (upper limit is 100% by weight or less), more preferably 90% by weight or more, and still more preferably 95% by weight or more in the water-absorbing agent. Particularly preferred is 98% by weight or more.
  • the particle size of the water-absorbing agent is preferably 70% by weight or more (upper limit 100% by weight) of particles having a size of 250 ⁇ m or more.
  • the water-absorbing resin in the present invention and the water-absorbing agent obtained in the present invention are adjusted to a specific particle size in order to achieve the present invention, and preferably particles having a particle size of less than 850 ⁇ m and 150 ⁇ m or more (specified by sieve classification: JIS Z8801-1: 2000) is 90% by weight or more of the whole, more preferably, particles less than 850 ⁇ m and 150 ⁇ m or more are 95% by weight or more, more preferably less than 850 ⁇ m and particles of 150 ⁇ m or more are 98% by weight or more. It is. Moreover, it is preferable that the particle
  • the whole here means the whole water-absorbing resin or water-absorbing agent.
  • the particle size of 250 ⁇ m or more is preferably 70% by weight or more (upper limit 100% by weight), more preferably 75% by weight or more.
  • the weight average particle diameter (D50) of the water absorbent resin or water absorbent is preferably 200 to 600 ⁇ m, more preferably 300 to 600 ⁇ m, still more preferably 300 to 500 ⁇ m, particularly preferably 350 to 450 ⁇ m. If necessary, the particle diameter of the water-absorbing resin or water-absorbing agent may be adjusted by granulation.
  • the particle shape of the water-absorbing resin and water-absorbing agent thus obtained is not particularly limited, such as spherical, crushed, and irregular shapes, but is preferably an irregularly crushed one obtained through the pulverization step. Can be used.
  • the bulk specific gravity (specified in JIS K-3362: 1998) is preferably 0.40 to 0.80 g / ml, more preferably 0.50 to 0.75 g, in terms of the balance between liquid permeability and liquid uptake characteristics. / Ml, more preferably in the range of 0.60 to 0.73 g / ml.
  • the logarithmic standard deviation value ⁇ representing the particle size distribution is preferably in the range of 0.1 to 0.6, more preferably 0.2 to 0.5, still more preferably 0.25 to 0.40, and particularly preferably. It is in the range of 0.25 to 0.38.
  • the water-absorbing agent of the present invention that improves the fluidity of the powder
  • segregation becomes prominent in the hopper or bag, so that diapers, etc. It becomes easy to cause a variation in quality when it is incorporated into the product.
  • the particle size of 850 ⁇ m or more exceeds 10% by weight, the water absorption rate of the water-absorbing agent is slow, and when used in an absorbent article, the absorbent body feels bad, and a foreign body sensation appears, causing discomfort to the user. Is not preferable. Therefore, by adjusting the mass average particle diameter within the preferable range of the present invention, it is possible to obtain a water absorbing agent that is excellent in fluidity and bulk density, does not deteriorate water absorbing performance, and has no problems such as segregation.
  • the mass average particle diameter of the water-absorbing agent may be adjusted by adding and mixing insoluble fine particles or a hydrophilic solvent, preferably water, depending on the purpose and necessity, and further granulating.
  • the adjustment of the mass average particle diameter may be adjusted by dispersion polymerization and dispersion drying in the form of particles as in reverse phase suspension polymerization, but in the case of aqueous solution polymerization, etc., it is usually necessary to be ground and classified after drying.
  • the fine powder is recycled by granulation or the like to adjust to a specific mass average particle size.
  • the heat resistance of the water absorbing agent according to the present invention includes a polysiloxane structure and is excellent in heat resistance.
  • the heat resistance of the water-absorbing agent is evaluated visually based on whether or not the resulting water-absorbing agent is colored.
  • the water-absorbing agent has heat resistance, usually white, which is the color of the polymer, is observed. In this case, it can be determined that the water absorbing agent has not deteriorated in the manufacturing process.
  • the water-absorbing agent does not have heat resistance and the polymer is highly likely to be deteriorated.
  • the temperature in the manufacturing process of the water-absorbing agent is not particularly limited, and the heat-resistance depends on whether the water-absorbing agent is colored at the temperature related to the manufacturing process of the individual water-absorbing agent. Sex is observed.
  • the water-absorbing agent of the present invention is used for applications intended to absorb water and is widely used as an absorber or absorbent article.
  • body fluids such as urine and blood are used. It is suitably used as a sanitary material for absorption.
  • the absorbent body and absorbent article of the present invention comprise the water-absorbing agent of the present invention.
  • the absorber is an absorbent material molded mainly with a water-absorbing agent and hydrophilic fibers.
  • the said absorber is shape
  • the water absorbent content (core concentration) with respect to the total mass of the water absorbent and the hydrophilic fibers is preferably 20 to 100% by weight, more preferably 30 to 100% by weight, and still more preferably 40 to 100%. It is in the range of wt%.
  • core concentration of the water-absorbing agent is higher, the effect of lowering the absorption characteristics of the water-absorbing agent at the time of producing the absorbent body, a paper diaper or the like becomes more prominent.
  • the said absorbent article is an absorbent article provided with the said absorber, the surface sheet which has liquid permeability, and the back sheet
  • the manufacturing method of the said absorbent article first produces an absorber (absorption core) by blending or sandwiching a fiber material and a water absorbing agent, for example. Next, the absorbent body is sandwiched between a liquid-permeable top sheet and a liquid-impermeable back sheet, and if necessary, equipped with an elastic member, a diffusion layer, an adhesive tape, etc.
  • Absorbent articles especially adult paper diapers and sanitary napkins.
  • the absorbent body is used by being compression-molded in a range of density 0.06 to 0.50 g / cc and basis weight 0.01 to 0.20 g / cm 2 .
  • the fiber material used include hydrophilic fibers such as pulverized wood pulp, cotton linters and crosslinked cellulose fibers, rayon, cotton, wool, acetate, and vinylon. Preferably, they are airlaid.
  • the water-absorbent article of the present invention exhibits excellent absorption characteristics.
  • Specific examples of such absorbent articles include diapers for children, sanitary napkins, sanitary materials such as so-called incontinence pads, as well as adult paper diapers that have been growing rapidly in recent years. However, it is not limited to them.
  • the water-absorbent article according to the present invention has a small amount of return due to the excellent absorption characteristics of the water-absorbing agent present in the absorbent article, has a remarkably dry feeling, and greatly reduces the burden on the wearer and the caregiver. be able to.
  • parts by mass may be simply referred to as “parts” and “liters” may be simply referred to as “L”.
  • mass% may be described as “wt%”.
  • CRC centrifuge retention capacity
  • 0.200 g of the water-absorbing agent was uniformly put into a bag (85 mm ⁇ 60 mm) made of a nonwoven fabric (Nangoku Pulp Industries Co., Ltd., trade name: Heaton paper, model: GSP-22) and heat-sealed. It was immersed in an excess (usually about 500 ml) of 0.90% by mass saline (aqueous sodium chloride solution). After 30 minutes, the bag was pulled up and drained for 3 minutes with a centrifugal force (250 G) described in edana ABSORBENCY II 441.1-99 using a centrifuge (manufactured by Kokusan Co., Ltd., centrifuge: model H-122).
  • FIG. 1 is a schematic diagram showing an SFC measurement apparatus 20.
  • a glass tube 22 is inserted into the tank 21, and the lower end of the glass tube 22 is 5 cm above the bottom of the gel 34 in the cell 31 with 0.69 mass% saline solution 23. It is arranged so that it can be maintained at a height. Further, the 0.69 mass% saline solution 23 in the tank 21 is configured to be supplied to the cell 31 through the L-shaped tube 24 with a cock.
  • a collection container 38 that collects the permeated liquid is disposed below the cell 31, and the collection container 38 is installed on an upper pan balance 39. The inner diameter of the cell 31 is 6 cm.
  • a 400 stainless steel wire mesh (aperture 38 ⁇ m) 32 was installed.
  • Artificial urine (1) is calcium chloride dihydrate 0.25 g, potassium chloride 2.0 g, magnesium chloride hexahydrate 0.50 g, sodium sulfate 2.0 g, ammonium dihydrogen phosphate 0.85 g, What added 0.15 g of hydrogen ammonium diphosphate and 994.25 g of pure waters was used.
  • the water absorbing agent (0.900 g) uniformly placed in the container 30 is swollen for 60 minutes in an artificial urine (1) under a pressure of 2.07 kPa (0.3 psi) for 60 minutes. It was. Thereafter, the height of the gel layer of the gel 34 is recorded, and then a 0.69 mass% saline solution 23 is swollen from the tank 21 at a constant hydrostatic pressure under a pressure of 2.07 kPa (0.3 psi). The layers were passed through. This SFC test was performed at room temperature (20 ° C. or more and 25 ° C. or less).
  • the flow rate Fs (T) permeating the swollen gel 34 was determined in units of g / s by dividing the increased mass (g) by the increased time (s). Let Ts be the time at which a constant hydrostatic pressure and a stable flow rate were obtained, use only the data obtained between Ts and 10 minutes for the flow rate calculation, and use the flow rate obtained between Ts and 10 minutes.
  • the value of Fs (T 0), ie the initial flow rate through the gel layer, was calculated.
  • Fs (t 0): flow rate expressed in g / s
  • ⁇ density of NaCl solution (1.003 g / cm 3 )
  • A in cell 31
  • ⁇ P hydrostatic pressure applied to the gel layer (4920 dyne / cm 2 )
  • SFC value is (10 ⁇ 7 ⁇ cm 3 ⁇ s ⁇ g ⁇ 1 ).
  • a stainless steel 400 mesh wire mesh 101 (mesh size 38 ⁇ m) is fused to the bottom of a plastic support cylinder 100 having an inner diameter of 60 mm, and 0.900 g of water absorption is placed on the mesh. It was adjusted so that a load of 1.9 kPa (0.3 psi) or 4.8 kPa (0.7 psi) could be uniformly applied to the water-absorbent resin 102.
  • the piston 103 and the load 104 which have an outer diameter slightly smaller than 60 mm and do not cause a gap with the support cylinder and do not hinder vertical movement, are placed in this order, and a mass W3 (g) of this measuring device set is set. It was measured.
  • a glass filter 106 having a diameter of 90 mm (manufactured by Mutual Riken Glass Co., Ltd., pore diameter: 100 to 120 ⁇ m) is placed inside a petri dish 105 having a diameter of 150 mm, and physiological saline 108 (20 ° C. to 25 ° C.) is placed in the glass filter. It was added so as to be the same level as the top surface.
  • a sheet of filter paper 107 having a diameter of 90 mm (ADVANTEC Toyo Co., Ltd., product name: (JIS P 3801, No. 2), thickness 0.26 mm, retention particle diameter 5 ⁇ m) was placed so that the entire surface was wetted. Excess liquid was removed.
  • the above measuring device set was placed on the wet filter paper, and the liquid was absorbed under load. After 1 hour, the measuring device set was lifted and its mass W4 (g) was measured. And the absorption capacity
  • AAP (W4-W3) /0.9 ⁇ Amount of water-soluble component (water-soluble component)> Weigh out 184.3 g of 0.90 mass% saline in a plastic container with a capacity of 250 ml, add 1.00 g of water-absorbing agent to the aqueous solution, and rotate and stir the stirrer for 16 hours to dissolve the soluble content in the resin. Extracted. Filtration of this extract using 1 sheet of filter paper (ADVANTEC Toyo Co., Ltd., product name: (JISP 3801, No. 2), thickness 0.26 mm, retained particle diameter 5 ⁇ m) gave 50. 0 g was measured and used as a measurement solution.
  • a titration ([NaOH] ml, [HCl] ml) was determined by performing the same titration operation on the measurement solution.
  • the soluble content can be calculated by the following formula.
  • the average molecular weight of the monomer is calculated using the neutralization rate obtained by titration.
  • Soluble content (mass%) 0.1 ⁇ (average molecular weight) ⁇ 184.3 ⁇ 100 ⁇ ([HCl] ⁇ [bHCl]) / 1000 / 1.0 / 50.0
  • Neutralization rate (mol%) (1 ⁇ ([NaOH] ⁇ [bNaOH]) / ([HCl] ⁇ [bHCl])) ⁇ 100 ⁇ Granularity>
  • a water-absorbing resin or water-absorbing agent
  • JIS Z8801-1 (2000) JIS standard sieve of 850 ⁇ m, 710 ⁇ m, 600 ⁇ m, 500 ⁇ m, 425 ⁇ m, 300 ⁇ m, 212 ⁇ m, 150 ⁇ m, 106 ⁇ m, 45 ⁇ m.
  • Solid content (mass%) 100-moisture content (mass%)
  • the measurement method of solid content was performed as follows.
  • Solid content (mass%) ((W2 ⁇ W0) / W1) ⁇ 100 ⁇ Paint shaker test>
  • the paint shaker test (PS) is a paint shaker (Toyo Seisakusho Co., Ltd. Product No. 488) in which a glass container having a diameter of 6 cm and a height of 11 cm is filled with 10 g of glass beads having a diameter of 6 mm and a water-absorbing resin or a water-absorbing agent.
  • the details of the apparatus are disclosed in Japanese Patent Publication “Japanese Patent Laid-Open No. 9-235378”, which is shaken at 800 cycle / min (CPM).
  • the shaker time of 30 minutes is the paint shaker test 1 and the shake time is 10 minutes.
  • the glass beads are removed with a JIS standard sieve having an opening of 2 mm, and a damaged water-absorbing resin or water-absorbing agent is obtained.
  • polysiloxane (B) or (C) instead of the polysiloxane (A) was similarly evaluated for solubility in ion-exchanged water and solubility in a polymerization reaction solution.
  • polysiloxanes (A) to (C) have solubility in ion-exchanged water and polymerization reaction solution.
  • Example 1 In a polypropylene container having an inner diameter of 80 mm and a capacity of 1 liter, acrylic acid 257.6 g, polysiloxane (A) 2.0 mass% aqueous solution 1.58 g, and diethylenetriaminepentaacetic acid-5 sodium aqueous solution 1.0 mass% 1 A solution (A) in which .58 g is mixed, a solution (B) in which 215.2 g of a 48.5% by mass aqueous sodium hydroxide solution and 209.9 g of ion-exchanged water adjusted to 32 ° C. are mixed with a magnetic stirrer. While stirring, the solution (B) was quickly added to the solution (A) in an open system and mixed. A monomer aqueous solution having a liquid temperature increased to about 102 ° C. by heat of neutralization and heat of dissolution was obtained.
  • the stainless bat-shaped container had a bottom surface of 250 mm ⁇ 250 mm, a top surface of 640 mm ⁇ 640 mm, a height of 50 mm, a central cross section of a trapezoid, and an open top surface.
  • Polymerization started soon after the monomer aqueous solution was poured into the vat. Polymerization proceeded while generating water vapor and expanding and foaming up and down, left and right, and then contracted to a size slightly larger than the bottom surface. This expansion and contraction was completed within about 1 minute, and after holding in the polymerization vessel for 4 minutes, the water-containing polymer was taken out.
  • the obtained water-containing polymer was crushed with a meat chopper (ROYAL MEAT CHOPPER VR400K, manufactured by Iizuka Kogyo Co., Ltd.) having a die diameter of 9.5 mm to obtain a finely divided water-containing polymer.
  • the amount of gel charged was about 340 g / min, and pulverization was performed while deionized water was added at 48 g / min in parallel with gel charging.
  • the non-volatile content of the gel after pulverization was 50 to 55% by mass.
  • the finely divided hydrogel crosslinked polymer was spread on a 50 mesh wire net and dried with hot air at 180 ° C. for 35 minutes.
  • the dried product was pulverized with a roll mill, and further classified with a JIS standard sieve having an opening of 710 ⁇ m and an opening of 175 ⁇ m to obtain a water absorbing agent (1).
  • Example 2 The same operation was carried out by changing the amount of the 2.0 mass% aqueous solution of polysiloxane (A) of Example 1 to 157.5 g. Thus, a water absorbing agent (2) was obtained.
  • Example 3 The amount of the 2.0 mass% aqueous solution of the polysiloxane (A) in Example 1 was changed to 1.58 g, and 1.31 g (0.07 mol%) of polyethylene glycol diacrylate (molecular weight 523) was used in the same manner. Was performed. Thus, a water absorbing agent (3) was obtained.
  • Example 4 The amount of the 2.0 mass% aqueous solution of the polysiloxane (A) of Example 1 was changed to 15.75 g, and further using 1.31 g (0.07 mol%) of polyethylene glycol diacrylate (molecular weight 523), the same was performed. In this way, a water absorbing agent (4) was obtained.
  • Example 5 The same operation was performed by changing the polysiloxane (A) of Example 3 to the polysiloxane (B). In this way, a water absorbing agent (5) was obtained.
  • the obtained water-absorbing agent did not repel the liquid during water absorption. And since all the water absorbing agents obtained in the Examples were white without coloring, they were excellent in heat resistance capable of withstanding high temperature conditions during production.
  • Example 6 The same operation was performed by changing the polysiloxane (A) of Example 3 to polysiloxane (C). Thus, a water absorbing agent (6) was obtained.
  • the obtained water-absorbing agent did not repel the liquid during water absorption. And since the water-absorbing agent obtained in the examples was white without coloring, it was excellent in heat resistance capable of withstanding high-temperature conditions during production.
  • Example 1 A 2.0 mass% aqueous solution of the polysiloxane (A) of Example 1 was changed to 0 g, and the same operation was performed using 1.31 g (0.07 mol%) of polyethylene glycol diacrylate (molecular weight 523). . In this way, a comparative water absorbing agent (1) was obtained.
  • the water-absorbing agents (1) to (6) have an uncrosslinked water-soluble component (water-soluble polymer) of 28.7% or less and a centrifuge retention capacity (CRC) of 9
  • the polysiloxanes (A) to (C) act as internal crosslinking agents, and the water absorbing agents (1) to (6) have a crosslinked structure inside the polymer. I understand.
  • the polysiloxanes (A) to (C) act as crosslinking agents. I understand that. That is, it can be understood that a water-absorbing agent containing polysiloxane was obtained.
  • This finely divided hydrogel cross-linked polymer is spread on a 50-mesh wire mesh, dried with hot air at 180 ° C. for 45 minutes, the dried product is pulverized with a roll mill, and further classified by a JIS standard sieve having a mesh opening of 710 ⁇ m. The particles that have passed through are further classified with a JIS standard sieve having a mesh opening of 175 ⁇ m, and the fine particles that have passed through are removed, so that the mass average particle diameter (D50) is 343 ⁇ m and the logarithmic standard deviation ( ⁇ ) of 0.32 is not satisfied. A regularly crushed water-absorbing resin (A) was obtained.
  • Centrifuge retention capacity (CRC) of water-absorbent resin (A) is 33.4 (g / g), water-soluble content is 6.1% by mass, and the ratio of particles having a size that can pass through a sieve having an opening of 150 ⁇ m was 1.0 mass%.
  • a surface cross-linking agent composed of a mixed solution of 0.3 parts by mass of 1,4-butanediol, 0.5 parts by mass of propylene glycol and 2.7 parts by mass of pure water was uniformly mixed with 100 parts by mass of the obtained water absorbent resin.
  • the mixture was then heat treated at 212 ° C. for 35 minutes. Thereafter, the obtained particles were crushed until they passed through a JIS standard sieve having an opening of 710 ⁇ m. Next, a paint shaker test 1 was performed on the crushed particles. Thus, a water-absorbing resin (A) having a crosslinked surface was obtained.
  • Example 7 10 mass parts of 10.0 mass% aqueous solution of polysiloxane (A) was added to 100 mass parts of water absorbent resin (A). The addition was performed so that the solution was uniformly added while stirring the water absorbent resin (A). This mixture was left to dry at 60 ° C. for 30 minutes under no wind. In this manner, a water absorbing agent (7) was obtained.
  • the obtained water-absorbing agent did not repel the liquid during water absorption. And since the water-absorbing agent obtained in the examples was white without coloring, it was excellent in heat resistance capable of withstanding high-temperature conditions during production.
  • Example 8 To 100 parts by mass of the water-absorbent resin (A), a mixed solution consisting of 5.0 parts by mass of a 10.0 mass% aqueous solution of polysiloxane (A) and 5.0 parts by mass of propylene glycol was added. The addition was performed so that the solution was uniformly added while stirring the water absorbent resin (A). This mixture was left to dry at 60 ° C. for 30 minutes under no wind. In this manner, a water absorbing agent (8) was obtained.
  • the obtained water-absorbing agent did not repel the liquid during water absorption. And since the water-absorbing agent obtained in the examples was white without coloring, it was excellent in heat resistance capable of withstanding high-temperature conditions during production.
  • Example 9 To 100 parts by mass of the water-absorbent resin (A), a mixed solution consisting of 5.0 parts by mass of 10.0 mass% aqueous solution of polysiloxane (A) and 5.0 parts by mass of methanol was added. The addition was performed so that the solution was uniformly added while stirring the water absorbent resin (A). This mixture was left to dry at 60 ° C. for 30 minutes under no wind. In this manner, a water absorbing agent (9) was obtained.
  • Example 10 To 83.66 g of 0.5N hydrochloric acid, 4.50 g of 3-aminopropyltrimethoxysilane and 0.42 g of tetramethoxysilane were added dropwise. The solution was stirred at room temperature for 2 hours. The product was transferred to a dryer at 60 ° C. to evaporate and dry the water, and maintained at 100 ° C. for 10 to 16 hours to obtain a product. This product was designated as polysiloxane (D).
  • D polysiloxane
  • This polysiloxane (D) was made into a 10% by mass aqueous solution. This aqueous solution was a clear homogeneous solution.
  • the obtained water-absorbing agent did not repel the liquid during water absorption.
  • Table 3 shows the measurement results of CRC and SFC of the water-absorbing agents (7) to (10) and the comparative water-absorbing agents (2) to (4).
  • APTOMOS represents 3-aminopropyltrimethoxysilane
  • TMOS represents tetramethoxysilane.
  • the water-absorbing agent obtained from the present invention has high liquid permeability (saline flow inductivity) under pressure. Since the comparative water absorbing agent (2) obtained in Comparative Example 2 was not added with polysiloxane, its performance was not sufficient. Moreover, although the comparative water-absorbing agent (3) obtained in Comparative Example 3 is a water-soluble polysiloxane, its performance is not sufficient because it does not have a dissociating group. Finally, since the comparative water-absorbing agent (4) obtained in Comparative Example 4 is a polysiloxane having low water solubility, the performance is not sufficient and the liquid repels remarkably.
  • the water-absorbing agent of the present invention contains a water-absorbing resin having a structural unit derived from an acid group-containing unsaturated monomer and a water-soluble polysiloxane having a dissociating group.
  • a novel water-absorbing agent containing the above polysiloxane can be provided.
  • a water-absorbing agent having a polysiloxane it is possible to expand the possibility of a new design of the water-absorbing agent.
  • the obtained water absorbing agent has an effect that it is excellent in salt solution flow-inductivity.
  • a heat-absorbing water-absorbing agent can also be provided.
  • the water-absorbing agent of the present invention contains polysiloxane and can be used as a part of a new water-absorbing resin.
  • Absorbent articles made of such a water-absorbing agent can be widely used for hygiene materials such as adult paper diapers, children's diapers, sanitary napkins and so-called incontinence pads, which have been growing rapidly in recent years.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention porte sur une matière absorbant l'eau. Ladite matière renferme une résine pouvant absorber l'eau comprenant une unité constitutive dérivée d'un monomère insaturé qui contient un groupe acide et un polysiloxane soluble dans l'eau muni d'un groupe dissociable. De préférence, la structure moléculaire du polysiloxane soluble dans l'eau est représentée par au moins l'une quelconque des formules chimiques suivantes (1) à (4) : formule chimique (1) [q(HxZ)(R1)2N(CH2)nSiO1,5]p[CjH2j+1OSiO1,5]1-p ; formule chimique (2) [q(HxZ)(R1)2N(CH2)nSiO1,5]p[CH3(CH2)mSiO1,5]1-p ; formule chimique (3) [q(HxZ)(R1)2N(CH2)nSiO1,5]p[R2SiO1,5]1-p ; et formule chimique (4) [q(HxZ)(R1)2N(CH2)nSiO1,5]p[R3NH(CH2)nSiO1,5]1-p. L'utilisation d'un composé à structure polysiloxane permet de proposer une matière absorbant l'eau non conventionnelle.
PCT/JP2009/051115 2008-01-24 2009-01-23 Matière absorbant l'eau et son procédé de fabrication WO2009093708A1 (fr)

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JP2013520531A (ja) * 2010-02-18 2013-06-06 ダウ コーニング コーポレーション シロキサン表面改質ヒドロゲル及びヒドロゲル微粒子組成物
JP2013525592A (ja) * 2010-05-07 2013-06-20 エボニック・ストックハウゼン・リミテッド・ライアビリティ・カンパニー 容量増加を有する粒子状高吸水性ポリマー
WO2014041969A1 (fr) 2012-09-11 2014-03-20 株式会社日本触媒 Procédé de fabrication d'un absorbant à base d'acide polyacrylique (polyacrylate) et absorbant
WO2014041968A1 (fr) 2012-09-11 2014-03-20 株式会社日本触媒 Procédé de fabrication d'agent absorbant l'eau à base d'acide polyacrylique (polyacrylate) et agent absorbant l'eau
WO2014054656A1 (fr) 2012-10-01 2014-04-10 株式会社日本触媒 Agent réduisant la poussière comprenant un composé à plusieurs métaux, absorbant d'eau contenant un composé à plusieurs métaux et leur procédé de fabrication
WO2015093594A1 (fr) 2013-12-20 2015-06-25 株式会社日本触媒 Agent d'absorption d'eau (de sel) de poly(acide acrylique), et son procédé de production
US10307732B2 (en) 2013-04-10 2019-06-04 Evonik Corporation Particulate superabsorbent polymer composition having improved stability and fast absorption

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013520531A (ja) * 2010-02-18 2013-06-06 ダウ コーニング コーポレーション シロキサン表面改質ヒドロゲル及びヒドロゲル微粒子組成物
JP2013525592A (ja) * 2010-05-07 2013-06-20 エボニック・ストックハウゼン・リミテッド・ライアビリティ・カンパニー 容量増加を有する粒子状高吸水性ポリマー
KR20130096152A (ko) * 2010-05-07 2013-08-29 에보닉 스톡하우젠, 엘엘씨 용량이 증가된 미립자형 초흡수성 중합체
TWI487717B (zh) * 2010-05-07 2015-06-11 Evonik Corp 具有容量增加之超吸收性聚合物
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WO2014041969A1 (fr) 2012-09-11 2014-03-20 株式会社日本触媒 Procédé de fabrication d'un absorbant à base d'acide polyacrylique (polyacrylate) et absorbant
WO2014041968A1 (fr) 2012-09-11 2014-03-20 株式会社日本触媒 Procédé de fabrication d'agent absorbant l'eau à base d'acide polyacrylique (polyacrylate) et agent absorbant l'eau
WO2014054656A1 (fr) 2012-10-01 2014-04-10 株式会社日本触媒 Agent réduisant la poussière comprenant un composé à plusieurs métaux, absorbant d'eau contenant un composé à plusieurs métaux et leur procédé de fabrication
US10307732B2 (en) 2013-04-10 2019-06-04 Evonik Corporation Particulate superabsorbent polymer composition having improved stability and fast absorption
WO2015093594A1 (fr) 2013-12-20 2015-06-25 株式会社日本触媒 Agent d'absorption d'eau (de sel) de poly(acide acrylique), et son procédé de production
EP4252728A2 (fr) 2013-12-20 2023-10-04 Nippon Shokubai Co., Ltd. Agent absorbant l'eau à base d'acide polyacrylique et/ou d'un de ses sels

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