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WO2006068067A1 - Procédé servant à produire des particules de résine absorbant l'eau - Google Patents

Procédé servant à produire des particules de résine absorbant l'eau Download PDF

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Publication number
WO2006068067A1
WO2006068067A1 PCT/JP2005/023224 JP2005023224W WO2006068067A1 WO 2006068067 A1 WO2006068067 A1 WO 2006068067A1 JP 2005023224 W JP2005023224 W JP 2005023224W WO 2006068067 A1 WO2006068067 A1 WO 2006068067A1
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WIPO (PCT)
Prior art keywords
water
resin particles
weight
absorbent resin
precursor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2005/023224
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English (en)
Japanese (ja)
Inventor
Kenya Matsuda
Yasuhiro Nawata
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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Priority to JP2006548955A priority Critical patent/JPWO2006068067A1/ja
Publication of WO2006068067A1 publication Critical patent/WO2006068067A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/002—Nozzle-type elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
    • C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide

Definitions

  • the present invention relates to a method for producing water-absorbent resin particles. More specifically, the present invention relates to a method for producing water-absorbent rosin particles having a high water absorption capacity even under a load.
  • Water-absorbent coagulants are widely used in various fields such as sanitary materials such as disposable diapers and sanitary items, agricultural and horticultural materials such as water retention materials and soil improvement materials, water-proofing materials for cables, and anti-condensation materials. Has been.
  • Examples of such a water-absorbing resin include a hydrolyzate of starch-acrylonitrile graft copolymer, a neutralized product of starch-acrylic acid graft copolymer, and a keny of butyl acetate acrylate copolymer.
  • polyacrylic acid partially neutralized products are known. In particular, polyacrylic acid partially neutralized products are excellent in productivity and economy, and thus are suitably used for sanitary materials and the like.
  • water-absorbing articles such as disposable diapers tend to be thinned by reducing the content of hydrophilic fibers that are bulky and having a small amount of water absorption, increasing the proportion of water-absorbing resin having a large amount of water absorption.
  • the water-absorbent resin used in the absorbent containing a high concentration of water-absorbent resin has excellent water absorption rate, gel strength during swelling, and water absorption performance under load. It is required to be.
  • the water absorption capacity when the water absorption capacity is increased, the water absorption capacity generally tends to decrease the water absorption speed, gel strength, and water absorption capacity under load.
  • the body fluid when water-absorbing resin is used for the absorber, the body fluid is not sufficiently absorbed by the water-absorbing resin when the absorbent is heavily loaded. The performance of the liquid is not fully demonstrated, and the amount of return of the liquid increases.
  • the method using a crosslinking agent has a problem in the safety and reactivity of the crosslinking agent used.
  • crosslinkers with high reactivity such as isocyanate groups have skin irritation, so control of unreacted crosslinkers for use in hygiene materials that may come into direct contact with the skin. Need to be strict.
  • polyhydric alcohol since polyhydric alcohol has low reactivity, it requires a high reaction temperature and a long reaction time, so that not only the productivity is low, but also the water-absorbent resin particles after surface crosslinking are colored or deteriorated. Sometimes.
  • Patent Document 1 Japanese Patent Laid-Open No. 59-189103
  • Patent Document 2 JP-A-58-180233
  • An object of the present invention is to provide a method for producing water-absorbent resin particles having a high water absorption capacity under no load and also having a high water absorption capacity under a load.
  • the present invention relates to a precursor (A) of water-absorbent resin particles obtained by polymerizing a water-soluble ethylenically unsaturated monomer, and 100 parts by weight of the water-soluble ethylenically unsaturated monomer.
  • the present invention relates to a method for producing water-absorbent resin particles in which 0.01 to 10 parts by weight of a compound (B) having two or more polymerizable unsaturated groups is mixed and the resulting mixture is reacted.
  • FIG. 1 is a schematic explanatory diagram of an apparatus for measuring water absorption under pressure. Explanation of symbols
  • the precursor of the water-absorbent resin particles is obtained by polymerizing a water-soluble ethylenically unsaturated monomer.
  • Examples of the water-soluble ethylenically unsaturated monomer include (meth) acrylic acid ["(meth) atari” means “atari” or “metatali”. The same shall apply hereinafter), 2- (meth) acrylamide, 2-methylpropanesulfonic acid or alkali metal salts thereof; (meth) acrylamide, N, N-dimethylacrylamide, 2-hydroxyethyl (meth) acrylate, N— Nonionic monomers such as methylol (meth) acrylamide; amino group-containing unsaturated monomers such as jetylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, or quaternized products thereof They may be used alone or in combination of two or more.
  • Examples of the alkali metal in the alkali metal salt include lithium, sodium and potassium.
  • the water-soluble ethylenically unsaturated monomer is preferable because it is easily available industrially. Is at least one selected from the group consisting of (meth) acrylic acid and its alkali metal salts, (meth) acrylamide and N, N-dimethylacrylamide, more preferably (meth) acrylic acid and (meth) At least one selected from the group consisting of sodium acrylate
  • the water-soluble ethylenically unsaturated monomer can usually be used as an aqueous solution. It is preferable that the concentration of the water-soluble ethylenically unsaturated monomer in the aqueous solution of the water-soluble ethylenically unsaturated monomer is 25% by weight to the saturated concentration.
  • the acid group may be neutralized with an alkali metal and used as an alkali metal salt.
  • the degree of neutralization of water-soluble ethylenically unsaturated monomers with alkali metals is problematic in terms of safety, etc. due to the presence of surplus alkali metals with high osmotic pressure and high water absorption speed of the resulting water-absorbent resin particles. From the viewpoint of preventing the occurrence, it is preferably within the range of 10 to LOO mol% of the acid groups of the water-soluble ethylenically unsaturated monomer before neutralization.
  • the alkali metal include lithium, sodium, and potassium. Of these, sodium and potassium are preferred.
  • the polymerization method of the water-soluble ethylenically unsaturated monomer is not particularly limited, and examples thereof include a reverse phase suspension polymerization method and an aqueous solution polymerization method.
  • polymerization is performed by heating a water-soluble ethylenically unsaturated monomer aqueous solution, a water-soluble radical polymerization initiator, and, if necessary, a crosslinking agent while stirring as necessary. Done.
  • a water-soluble ethylenically unsaturated monomer aqueous solution a surfactant and Z or a polymer protective colloid, a water-soluble radical polymerization initiator, and, if necessary, a crosslinking agent as a hydrocarbon.
  • Polymerization is carried out by heating under stirring in a system solvent.
  • sorbitan fatty acid ester for example, sorbitan fatty acid ester, (poly) glycerin fatty acid ester ["(poly)” means both the case with and the prefix of "poly”. The same shall apply hereinafter), non-ionic surfactants such as sucrose fatty acid ester, sorbitol fatty acid ester, polyoxyethylene alkylphenol ether, hexaglyceryl monobelate Agents: Fatty acid salts, alkylbenzene sulfonates, alkylmethyl taurates, polyoxyethylene alkylphenol ether sulfates, and cation surfactants such as polyoxyethylene alkyl ether sulfonates. May be used alone or in combination of two or more. Among them, sorbitan fatty acid ester, polyglycerol fatty acid ester and sucrose fatty acid ester are preferable.
  • polymer protective colloid examples include ethyl cellulose, ethyl hydroxyethyl cellulose, polyethylene oxide, anhydrous maleated polyethylene, anhydrous maleated polybutadiene, and anhydrous maleated EPDM (ethylene Z propylene Z gen Z ter Polymers)), etc., which may be used alone or in combination of two or more.
  • the amount of the surfactant and Z or the polymer protective colloid is determined depending on the water-soluble ethylenic unsaturated from the viewpoint of the control of the particle size of the water-absorbent resin particles and the suspension stability during polymerization. Preferably it is 0.05-5 weight part with respect to 100 weight part of monomer aqueous solution, More preferably, it is 0.1-3 weight part. If the amount of surfactant and Z or polymer protective colloid is less than 0.05 parts by weight, the suspension stability during polymerization tends to be low, and if it is more than 5 parts by weight, the amount is only commensurate with the amount. However, there is a tendency to be economically disadvantageous.
  • water-soluble radical polymerization initiator examples include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; hydrogen peroxide perhydrogen; 2, 2'-azobis (2-amidinopropan ) Azo compounds such as dihydrochloride and azobis (cyananovaleric acid) can be used, and these can be used alone or in combination of two or more.
  • persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate
  • hydrogen peroxide perhydrogen 2, 2'-azobis (2-amidinopropan ) Azo compounds
  • dihydrochloride and azobis (cyananovaleric acid) can be used, and these can be used alone or in combination of two or more.
  • potassium persulfate, ammonium persulfate and sodium persulfate are preferred because they are readily available and have good storage stability.
  • the water-soluble radical polymerization initiator can be used as a redox polymerization initiator when used in combination with a sulfite or the like.
  • the amount of the water-soluble radical polymerization initiator is usually preferably 0.00 per mole of the water-soluble ethylenically unsaturated monomer from the viewpoint of shortening the polymerization reaction time and preventing a rapid polymerization reaction. 001 to 0.02 mol, more preferably 0.0001 to 0.01 mol.
  • hydrocarbon solvent examples include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, and lignin; fats such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane.
  • Cyclic hydrocarbon compounds; aromatic hydrocarbon compounds such as benzene, toluene, xylene, and the like can be mentioned. These may be used alone or in combination of two or more.
  • n-hexane, n-heptane and cyclohexane are preferable because they are easily available industrially, have stable quality, and are inexpensive.
  • the amount of the hydrocarbon-based solvent is usually preferably 50 to 600 with respect to 100 parts by weight of the water-soluble ethylenically unsaturated monomer, from the viewpoint of removing the heat of polymerization and easily controlling the polymerization temperature. Part by weight, more preferably 100 to 550 parts by weight.
  • crosslinking agent for example, (poly) ethylene glycol [“(poly)” means with or without the prefix “poly”. The same shall apply hereinafter), (poly) propylene glycol, 1,4 butanediol, trimethylolpropane, diols such as (poly) glycerin, triols and polyols, and unsaturated acids such as (meth) acrylic acid, maleic acid and fumaric acid.
  • Et al. May be used alone or in combination of two or more.
  • ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycerin diglycidyl ether and N, N, -methylenebisacrylamide are It is preferable because of its excellent reactivity at low temperatures.
  • the amount of the crosslinking agent is 100% by weight of a water-soluble ethylenically unsaturated monomer from the viewpoint of suppressing the water-soluble property of the obtained polymer by appropriate crosslinking and exhibiting sufficient water absorption.
  • the amount is preferably 3 parts by weight or less, more preferably 0.001 to 1 part by weight based on the part.
  • the reaction temperature during the polymerization varies depending on the type of the water-soluble radical polymerization initiator to be used, and thus cannot be determined unconditionally.
  • the reaction temperature is preferably 20 to 110 ° C., more preferably 40 to 90, from the viewpoint of allowing the polymerization to proceed rapidly to shorten the polymerization time and easily removing the heat of polymerization to perform the reaction smoothly.
  • the reaction time is usually from 0.1 to 4 hours.
  • a precursor of water-absorbent resin particles can be obtained by polymerizing a water-soluble ethylenically unsaturated monomer by force.
  • the obtained water-absorbing resin particles precursor is appropriately adjusted in water content, then mixed with a compound having two or more polymerizable unsaturated groups, and subjected to the reaction.
  • a feature of the present invention is that after obtaining a water-absorbent resin particle precursor by polymerizing a water-soluble ethylenically unsaturated monomer, the resulting water-absorbent resin particle precursor and polymerizability are obtained. The point is that a compound having two or more unsaturated groups is mixed and the resulting mixture is reacted.
  • the timing for carrying out the reaction is not particularly limited, and may be immediately after the polymerization of the precursor of the water-absorbent resin particles, during the drying step, or after the drying.
  • Examples of the compound having two or more polymerizable unsaturated groups include diols such as (poly) ethylene glycol, (poly) propylene glycol, 1,4 butanediol, trimethylolpropane, and (poly) glycerin. , Triols and polyols and unsaturated polyesters obtained by reacting (meth) acrylic acid, maleic acid, fumaric acid and other unsaturated acids; bisacrylamides such as N, N'-methylenebisacrylamide; Rilphthalate, N, ⁇ ', ⁇ , ... Examples thereof include compounds having two or more polymerizable unsaturated groups such as triallyl isocyanurate and divinylbenzene.
  • diols such as (poly) ethylene glycol, (poly) propylene glycol, 1,4 butanediol, trimethylolpropane, and (poly) glycerin.
  • Triols and polyols and unsaturated polyesters obtained
  • At least one selected from the group consisting of N, N, monomethylene bisacrylamide and (poly) ethylene glycol diatalate is preferable from the viewpoint of easy mixing with a water-soluble ethylenically unsaturated monomer. .
  • the amount of the compound having two or more polymerizable unsaturated groups is 0. 100 parts by weight of the water-soluble ethylenically unsaturated monomer used in the polymerization of the precursor of the water-absorbent resin particles. 01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, more preferably 0.05 to 3 parts by weight.
  • Quantity of compound having 2 or more polymerizable unsaturated groups Water-soluble ethylenically unsaturated monomer 100 parts by weight If less than 0.01 part by weight, the reaction of the surface layer becomes insufficient and the load There is a tendency that the amount of water absorption below does not increase, and when the amount is more than 10 parts by weight, the reaction becomes excessive, so that the water-absorbent resin particles do not exhibit sufficient water absorption. .
  • the water-soluble ethylenically unsaturated monomer and the radical polymerization initiator used in mixing the precursor of the water-absorbent resin particles and the compound having two or more polymerizable unsaturated groups are a water-absorbent resin. It may be the same as or different from the one used during the polymerization of the particle precursor.
  • Examples of the water-soluble ethylenically unsaturated monomer include (meth) acrylic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid or alkali metal salts thereof; Nonionic monomers such as rilamide, N, N-dimethylacrylamide, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide; jetylaminoethyl (meth) acrylate, jetylaminopropyl ( Examples thereof include amino group-containing unsaturated monomers such as (meth) acrylate and quaternized compounds thereof, and these may be used alone or in combination of two or more.
  • Examples of the alkali metal in the alkali metal salt include lithium, sodium, and potassium.
  • the water-soluble ethylenically unsaturated monomer can usually be used as an aqueous solution. It is preferable that the concentration of the water-soluble ethylenically unsaturated monomer in the aqueous solution of the water-soluble ethylenically unsaturated monomer is 25% by weight to the saturated concentration.
  • the acid group May be neutralized with alkali metal.
  • the degree of neutralization of water-soluble ethylenically unsaturated monomers with alkali metals increases the osmotic pressure of the resulting water-absorbent resin particles, increases the water absorption rate, and there are problems with safety due to the presence of excess alkali metals.
  • the alkali metal include lithium, sodium, and potassium. Of these, sodium and potassium are preferred.
  • the amount of the water-soluble ethylenically unsaturated monomer used in mixing the precursor of the water-absorbent resin particles and the compound having two or more polymerizable unsaturated groups is determined by the amount of the water-absorbent resin particles.
  • the amount is preferably 0.05 to 10 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the water-soluble ethylenically unsaturated monomer used for the polymerization of the precursor.
  • the amount of the water-soluble ethylenically unsaturated monomer used is more than 10 parts by weight, the effect corresponding to the amount cannot be obtained, and it tends to be economically disadvantageous.
  • radical polymerization initiator examples include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; 2,2'-azobis (2-amidinopropane) dihydrochloride, azobis Azoi compounds such as (Cyananovalerate); hydrogen peroxide, etc. may be mentioned, and these may be used alone or in combination of two or more.
  • persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate
  • 2,2'-azobis (2-amidinopropane) dihydrochloride 2,2'-azobis (2-amidinopropane) dihydrochloride
  • azobis Azoi compounds such as (Cyananovalerate)
  • hydrogen peroxide, etc. may be mentioned, and these may be used alone or in combination of two or more.
  • potassium persulfate, ammonium persulfate and sodium persulfate are preferable from the viewpoint of easy availability and
  • the radical polymerization initiator can be used as a redox polymerization initiator when used in combination with a sulfite or the like.
  • the amount of the radical polymerization initiator is preferably from 0.0001 to 0.02 moles per mole of the compound having two or more polymerizable unsaturated groups and Z or water-soluble ethylenically unsaturated monomer. More preferably from 0.0001 to 0.01 mol.
  • a hydrophilic organic solvent may be used as a solvent, if necessary.
  • hydrophilic organic solvent examples include lower alcohols such as methyl alcohol, ethyl alcohol, n- propyl alcohol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, jetyl ether, dioxane and tetrahydrofuran. Ethers, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, and the like. These hydrophilic organic solvents may be used alone or in combination of two or more. Good.
  • the mixing of the precursor of the water-absorbent rosin particles and the compound having two or more polymerizable unsaturated groups can be performed in the presence of water.
  • the amount of water when mixing the precursor of the water-absorbent resin particles and the compound having two or more polymerizable unsaturated groups varies depending on the type, particle size and water content of the water-absorbent resin particles.
  • the amount is preferably 1 to 150 parts by weight per 100 parts by weight of the water-soluble ethylenically unsaturated monomer subjected to the polymerization.
  • the amount of water in this case is as necessary when mixing the water contained in the polymerization reaction, the precursor of the water-absorbent resin particles and the compound having two or more polymerizable unsaturated groups. Means the total amount of water used.
  • the surface layer of the water-absorbent resin particles can be polymerized.
  • a compound having two or more unsaturated groups can be reacted more suitably.
  • the reaction temperature at the time of reacting the mixture of the precursor of the water-absorbent resin particles with the compound having two or more polymerizable unsaturated groups is preferably 20 to 190 ° C, more preferably 40 to 150 °. C.
  • the reaction temperature is less than 20 ° C, the reaction is difficult to proceed and the reaction tends to take an excessive amount of time.
  • the reaction temperature exceeds 190 ° C, the resulting water-absorbent resin particles tend to be decomposed. is there.
  • the reaction time refers to the reaction temperature, the type of compound having two or more polymerizable unsaturated groups, and the type thereof. However, it is preferably 1 to 300 minutes, more preferably 5 to 200 minutes.
  • the average particle diameter of the water-absorbent slag particles obtained by force is usually the point of preventing gel blocking due to fine powder in the absorbent article, and prevents the soft feeling due to coarse particles. From the viewpoint of improving the property, it is desired to be 100 to 600 111, preferably 200 to 500 m.
  • the average particle diameter is a value when measured by the method described in Test Example 1-1 (1) described later.
  • the amount of water absorption of the water-absorbent resin particles under no load can be measured by the method described in Test Example 1 (2).
  • the water absorption amount of the water-absorbent resin particles is preferably 40 g Zg or more under no load from the viewpoint of sufficient liquid absorption performance and reduced liquid return in an absorbent article. .
  • the amount of water absorption under load of the water-absorbent resin particles can be measured by the method described in Test Example 1- (3).
  • the load at the time of measurement is set to 2.07 kPa from the viewpoint of reproducing the state where the load is applied to the absorbent body when an infant uses a water absorbent article.
  • the water-absorbent resin particles have a water absorption amount of 20 mLZg or more under a pressure of 07 kPa from the viewpoint of reducing the amount of liquid returned from the absorber under load.
  • a water-soluble ethylenically unsaturated monomer is polymerized by force to obtain a precursor of water-absorbent resin particles, a compound having two or more polymerizable unsaturated groups and the water-absorbent resin Mixing particle precursors and reacting with water-soluble ethylenically unsaturated monomers and Z or radical polymerization initiators as necessary, water-absorbent resin with high water absorption capacity under load Particles are obtained.
  • the reason why the water-absorbent resin particles having a high water absorption capacity under load is obtained is not clear, but is presumed to be based on the following reasons.
  • additives such as a lubricant, deodorant and antibacterial agent may be further added to the water-absorbent resin particles of the present invention depending on the purpose.
  • reaction solution was cooled to room temperature, and a monomer aqueous solution for the second-stage polymerization was added dropwise thereto, followed by stirring for 30 minutes. Thereafter, the inside of the system was replaced with nitrogen gas, the temperature was raised to 70 ° C., and the second-stage reversed-phase suspension polymerization was performed.
  • the resulting polymerization reaction product was coarsely pulverized with a SUS meat chopper, and then dried with a hot air dryer at 105 ° C for 60 minutes.
  • the coarsely pulverized product was pulverized with a desktop mixer and classified with a JIS standard sieve having an opening of 1 000 ⁇ m to obtain a precursor (A3) of water-absorbent grease particles.
  • All the precursor (A1) of the water-absorbent resin particles obtained in Production Example 1 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an anchor blade, a cooler, and a gas introduction tube.
  • 4 weight 0 / oN, N the over methylenebisacrylamide solution 11. 5 g, 80 weight 0/0 Atari Le acid solution 1.
  • aqueous solution mixed with 84g and 2 wt% aqueous solution of potassium persulfate 92mg prepared Then, the aqueous solution was sprayed with the aqueous solution while stirring the precursor of the water-absorbent resin particles at 200 rpm!
  • the total amount of the precursor (A2) of the water-absorbing resin particles obtained in Production Example 2 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an anchor blade, a cooler, and a gas introduction tube.
  • Example 4 The whole amount of the precursor (A2) of the water-absorbent resin particles obtained in the same manner as in Production Example 2 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an end blade, a cooler and a gas introduction tube.
  • the whole amount of the precursor (A2) of the water-absorbent resin particles obtained in the same manner as in Production Example 2 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an end blade, a cooler and a gas introduction tube.
  • the whole amount of the precursor (A2) of the water-absorbent resin particles obtained in the same manner as in Production Example 2 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an end blade, a cooler and a gas introduction tube.
  • 16 wt% polyethylene glycol Atari rate [Kyoeisha I ⁇ Co., Ltd., trade name: Light Atari rate 14EG- A] solution 23. 0 g, 80 weight 0/0 aqueous solution of acrylic acid 3. 68 g Contact An aqueous solution was prepared by mixing 184 mg of a 2% by weight aqueous potassium persulfate solution, and the aqueous solution was added by spraying while stirring the precursor of the water-absorbent coagulate particles at 200 rpm.
  • the water-absorbing resin particle precursor (A2) having a water content of 3.5% by weight and an average particle diameter of 352 m obtained in the same manner as in Production Example 2 was subjected to measurement of water absorption performance as it was.
  • the whole amount of the precursor (A2) of the water-absorbent resin particles obtained in the same manner as in Production Example 2 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an end blade, a cooler and a gas introduction tube.
  • All the precursor (A2) of the water-absorbing resin particles obtained in the same manner as in Production Example 2 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an end blade, a cooler and a gas introduction tube.
  • an aqueous solution in which 1.84 g of 80 wt% aqueous acrylic acid solution and 92 mg of 2 wt% potassium persulfate aqueous solution were mixed was prepared, and the precursor of the water-absorbent resin particles was stirred at 200 rpm. The aqueous solution was added by spraying.
  • the whole amount of the precursor (A2) of the water-absorbent resin particles obtained in the same manner as in Production Example 2 was placed in a flask having an internal volume of 2 liters equipped with a stirrer, an end blade, a cooler and a gas introduction tube.
  • a 4% by weight 1,4-butanediol aqueous solution 23.Og was prepared, and the aqueous solution was added by spraying while stirring the water-absorbent resin particles at 200 rpm.
  • the average particle diameter, water absorption, and water absorption under pressure of the water-absorbent resin particles obtained in each Example and each Comparative Example were measured by the following methods.
  • Table 1 shows the performance results of the water-absorbent resin particles.
  • the weight of the water-absorbent resin particles remaining on each sieve is calculated as a percentage by weight with respect to the total amount, and is accumulated in the order of decreasing particle diameter, thereby remaining on the sieve openings and sieves.
  • the relationship between the weight percentage and the integrated value was plotted on a logarithmic probability paper. By connecting the plots on the probability paper with a straight line, the particle diameter corresponding to 50% by weight of the cumulative weight percentage was taken as the average particle diameter.
  • the amount of water absorption was determined.
  • the water absorption starting force of the water-absorbing resin particles under a pressure of 2.07 kPa was also measured using a measuring device X whose schematic configuration is shown in FIG.
  • the measuring device X shown in FIG. 1 includes a burette part 1, a conduit 2, a measuring table 3, and a measuring part 4.
  • a cock 12 is provided at the bottom of the bullet 10
  • the intake pipe 11 is connected to the side.
  • a cock 13 is connected to the upper part of the intake pipe 11.
  • a rubber stopper 14 is attached to the top of the bullet 10.
  • a conduit 2 having a diameter of 6 mm is attached to the lower end of the burette 1, and is connected to a hole having a diameter of 2 mm formed in the center of the measuring table 3.
  • the measurement unit 4 is placed on the measurement table 3 and includes a cylinder 40, a nylon mesh 41 and a weight 42 attached to the bottom of the cylinder 40.
  • the inner diameter of the cylinder 40 is 2.
  • Nylon mesh 41 is formed to 200 mesh (aperture 75 ⁇ m). A predetermined amount of the water-absorbent resin particles 5 is uniformly distributed on the nylon mesh 41.
  • the mass of the weight 42 is 59.8 g and its bottom diameter is 1.9 cm. The bottom of the weight 42 is fitted into the cylinder 40 so as to move up and down while in contact with the water-absorbing resin particles 5. With this weight 42, a load of 2.0 07 kPa is applied to the water-absorbing resin particles 5.
  • a method for measuring the physiological saline water-absorbing capacity of the water-absorbent resin particles under a load using the measuring device X will be described below.
  • the measurement table 3 is so positioned that the upper surface of the measurement table 3 and the top of 0.9 mass% physiological saline sprayed from the conduit port (not shown) at the center of the measurement table 3 are at the same height. Adjust the height.
  • 0.1 lg of water-absorbing resin particles 5 are uniformly distributed on the nylon mesh 41 of the cylinder 40, and the weight 42 is fitted into the cylinder 40, and the bottom thereof is evenly placed on the water-absorbing resin particles. Make contact. Thereafter, the measuring unit 4 is placed on the measuring table 3 so that the center part coincides with the conduit port of the central part of the measuring table 3. When the measuring unit 4 is placed on the measuring table 3, the water-absorbent resin particles 5 begin to absorb the physiological saline coming out from the conduit port (not shown) through the nylon mesh 41.
  • the water-absorbent resin particles obtained by the production method of the present invention have a high water absorption amount under no load and under load, and therefore can be suitably used for sanitary materials such as sanitary products and disposable diapers. You can.

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Abstract

Procédé servant à produire des particules de résine absorbant l'eau lequel comprend les étapes consistant à : mélanger un précurseur (A) pour des particules de résine absorbant l'eau avec un composé (B) ayant deux ou plus de deux groupes insaturés polymérisables, le précurseur (A) étant un précurseur obtenu en polymérisant un monomère éthylénique soluble dans l'eau et la quantité du composé (B) étant de 0,01-10 parties en poids pour 100 parties en poids du monomère éthylénique soluble dans l'eau ; et faire réagir le mélange résultant. Les particules de résine absorbant l'eau sont utilisables, par exemple, dans des produits d'hygiène tels que des couches jetables et des serviettes hygiéniques, dans des matières pour l'agriculture et l'horticulture telles que des matières stockant de l'eau et des matières améliorant le sol et des matières industrielles telles qu'une matière arrêtant l'eau pour des câbles et une matière pour empêcher la condensation de rosée.
PCT/JP2005/023224 2004-12-24 2005-12-19 Procédé servant à produire des particules de résine absorbant l'eau Ceased WO2006068067A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010505985A (ja) * 2006-10-05 2010-02-25 ビーエーエスエフ ソシエタス・ヨーロピア 吸水性ポリマー粒子をモノマー溶液の液滴の重合によって製造する方法
WO2014162843A1 (fr) * 2013-04-05 2014-10-09 株式会社日本触媒 Procédé de production d'un matériau absorbant l'eau, et matériau absorbant l'eau

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01126314A (ja) * 1987-11-12 1989-05-18 Nippon Shokubai Kagaku Kogyo Co Ltd 改良された吸水性樹脂の製造法
JPH04130113A (ja) * 1990-09-20 1992-05-01 Mitsubishi Petrochem Co Ltd 巨大ビーズ状吸水性樹脂の製造法
JPH0517509A (ja) * 1991-07-11 1993-01-26 Mitsubishi Petrochem Co Ltd 高吸水性ポリマーの製造法
JPH05320270A (ja) * 1992-05-27 1993-12-03 Nippon Kayaku Co Ltd 吸水性ポリマーの製造法
JPH11130968A (ja) * 1997-10-29 1999-05-18 Mitsubishi Chemical Corp 吸水性樹脂及びその製造方法
JPH11333292A (ja) * 1998-03-26 1999-12-07 Nippon Shokubai Co Ltd 吸水剤およびその製造方法と用途

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01126314A (ja) * 1987-11-12 1989-05-18 Nippon Shokubai Kagaku Kogyo Co Ltd 改良された吸水性樹脂の製造法
JPH04130113A (ja) * 1990-09-20 1992-05-01 Mitsubishi Petrochem Co Ltd 巨大ビーズ状吸水性樹脂の製造法
JPH0517509A (ja) * 1991-07-11 1993-01-26 Mitsubishi Petrochem Co Ltd 高吸水性ポリマーの製造法
JPH05320270A (ja) * 1992-05-27 1993-12-03 Nippon Kayaku Co Ltd 吸水性ポリマーの製造法
JPH11130968A (ja) * 1997-10-29 1999-05-18 Mitsubishi Chemical Corp 吸水性樹脂及びその製造方法
JPH11333292A (ja) * 1998-03-26 1999-12-07 Nippon Shokubai Co Ltd 吸水剤およびその製造方法と用途

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010505985A (ja) * 2006-10-05 2010-02-25 ビーエーエスエフ ソシエタス・ヨーロピア 吸水性ポリマー粒子をモノマー溶液の液滴の重合によって製造する方法
WO2014162843A1 (fr) * 2013-04-05 2014-10-09 株式会社日本触媒 Procédé de production d'un matériau absorbant l'eau, et matériau absorbant l'eau

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