WO2024071258A1 - 吸水性樹脂粒子の製造方法 - Google Patents
吸水性樹脂粒子の製造方法 Download PDFInfo
- Publication number
- WO2024071258A1 WO2024071258A1 PCT/JP2023/035291 JP2023035291W WO2024071258A1 WO 2024071258 A1 WO2024071258 A1 WO 2024071258A1 JP 2023035291 W JP2023035291 W JP 2023035291W WO 2024071258 A1 WO2024071258 A1 WO 2024071258A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- mass
- absorbent resin
- resin particles
- added
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
- A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
- A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
-
- 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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- 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
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Definitions
- the present invention relates to a method for producing water-absorbent resin particles, and more specifically, to a method for producing water-absorbent resin particles that constitute an absorbent material suitable for use in sanitary materials such as disposable diapers, sanitary napkins, and incontinence pads.
- water-absorbent resins have been widely used in the field of sanitary materials such as disposable diapers, sanitary napkins, and incontinence pads.
- cross-linked polymers of partially neutralized acrylic acid salts have excellent water-absorbing properties, and because the raw material, acrylic acid, is easily available industrially, they can be produced at low cost with consistent quality, and are less susceptible to spoilage or deterioration, making them a preferred water-absorbent resin.
- the gel that is produced when absorbent resins absorb bodily fluids such as human urine is affected by various components in the bodily fluids (e.g., vitamin C and iron in urine), and the gel deteriorates. For this reason, various additives (e.g., human urine stabilizers) are being added, and the manufacturing methods of absorbent resins are being improved.
- various additives e.g., human urine stabilizers
- sulfite compounds which are reducing agents, are effective as human urine stabilizers and are expected to increase the gel stability of water-absorbent resins.
- the addition of sulfite compounds to water-absorbent resins can cause problems such as a deterioration in the general water-absorbency performance of the water-absorbent resin (e.g., the amount of saline water absorbed) and yellowing under high temperature and humidity conditions.
- the main objective of the present invention is to provide a method for producing water-absorbent resin particles that have good general water-absorption performance (e.g., physiological saline water absorption capacity) required of water-absorbent resins, and further, that are inhibited from yellowing under high temperature and high humidity conditions and have high gel stability.
- general water-absorption performance e.g., physiological saline water absorption capacity
- the present inventors have conducted intensive research to solve the above problems. As a result, they have found that in a manufacturing method for obtaining water-absorbent resin particles by subjecting water-containing gel particles obtained by polymerizing a water-soluble ethylenically unsaturated monomer to a surface cross-linking treatment, a step of adding a chelating agent, a sulfite compound, and an organic antioxidant to the water-containing gel particles before the surface cross-linking treatment is performed, and further, when the water content of the water-containing gel particles when the sulfite compound is added in this step is within a predetermined range, water-absorbent resin particles having good general water absorption performance required for a water-absorbent resin, suppressed yellow coloring under high temperature and high humidity, and having high gel stability can be suitably manufactured.
- the present invention is an invention that was completed based on such knowledge and through further intensive research.
- the present invention provides the following configuration.
- Item 1 A process 1 for polymerizing a water-soluble ethylenically unsaturated monomer to obtain hydrogel particles;
- the water content of the hydrous gel particles when the sulfite compound is added is 20% by mass or more and 75% by mass or less.
- Item 2. The method for producing water-absorbent resin particles according to Item 1, wherein the step 2 further includes a step of adjusting the water content of the hydrous gel particles.
- Item 4. The method for producing water-absorbent resin particles according to any one of Items 1 to 3, wherein in the step 2, a water content of the hydrous gel particles when the organic antioxidant is added is 20 mass% or more.
- Item 5. The method for producing water-absorbent resin particles according to any one of Items 1 to 4, wherein in the step 2, an amount of the sulfite-based compound added is 0.001 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the water-soluble ethylenically unsaturated monomer.
- Item 6 The method for producing water-absorbent resin particles according to any one of Items 1 to 5, wherein in the step 2, an amount of the chelating agent added is 0.001 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the water-soluble ethylenically unsaturated monomer.
- Item 7. The method for producing water-absorbent resin particles according to any one of Items 1 to 6, wherein in the step 2, an amount of the organic antioxidant added is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the sulfite-based compound.
- Item 8 The physiological saline water absorption is 40 to 70 g/g; The yellowness index after being left for 14 days in an environment of 70° C.
- An absorbent body comprising the water-absorbent resin particles according to item 8.
- An absorbent article comprising the absorbent body according to item 9.
- the present invention can provide a method for producing water-absorbent resin particles that have good general water-absorption performance required of a water-absorbent resin (e.g., physiological saline water absorption capacity), and further have high gel stability with suppressed yellowing under high temperature and high humidity.
- the present invention can also provide water-absorbent resin particles that have good physiological saline water absorption capacity, suppressed yellowing under high temperature and high humidity, and high gel stability, an absorbent body containing the water-absorbent resin particles, and an absorbent article containing the absorbent body.
- FIG. 4 is a schematic diagram of a device for measuring the amount of physiological saline solution absorbed under a load of 4.14 kPa.
- FIG. 2 is a schematic diagram of a measuring device used for measuring gel strength.
- water-soluble refers to a solubility of 5% by mass or more in water at 25°C.
- a numerical value connected with “ ⁇ ” means a numerical range that includes the numerical values before and after " ⁇ " as the lower and upper limits.
- the manufacturing method of water-absorbent resin particles of the present invention comprises step 1 of polymerizing a water-soluble ethylenically unsaturated monomer to obtain hydrous gel particles, step 2 of adding a chelating agent, a sulfite compound and an organic antioxidant to the hydrous gel particles, and step 3 of performing a surface cross-linking treatment on the hydrous gel particles, in this order, and is characterized in that the water content of the hydrous gel particles when adding the sulfite compound in step 2 is 20% by mass or more and 75% by mass or less.
- the water-absorbent resin particles manufactured by the manufacturing method of the present invention having such characteristics have good general water absorption performance required for water-absorbent resins (e.g., physiological saline water absorption amount, etc.), and further have high gel stability by suppressing yellow coloring under high temperature and high humidity.
- the manufacturing method of water-absorbent resin particles of the present invention will be described in detail below.
- Step 1 is a step of polymerizing a water-soluble ethylenically unsaturated monomer to obtain hydrogel particles.
- a method for polymerizing a water-soluble ethylenically unsaturated monomer typical polymerization methods such as aqueous solution polymerization, emulsion polymerization, and reversed-phase suspension polymerization are used.
- aqueous solution polymerization polymerization is carried out by heating an aqueous solution of a water-soluble ethylenically unsaturated monomer while stirring as necessary.
- reversed-phase suspension polymerization polymerization is carried out by heating a water-soluble ethylenically unsaturated monomer in a hydrocarbon dispersion medium while stirring.
- Step 1 may further include a step of pulverizing the hydrous gel obtained by polymerizing the water-soluble ethylenically unsaturated monomer to obtain hydrous gel particles.
- pulverization of the hydrous gel is usually not necessary since the hydrous gel particles are generated by polymerization.
- step 1 for obtaining hydrous gel particles an example of reverse phase suspension polymerization is described below.
- the polymerization is carried out in the presence of a radical polymerization initiator.
- a radical polymerization initiator As described below, an internal crosslinking agent may be added to the water-soluble ethylenically unsaturated monomer as necessary to produce hydrogel particles having an internal crosslinked structure.
- water-soluble ethylenically unsaturated monomers include (meth)acrylic acid (in the present specification, "acrylic” and “methacrylic” are collectively referred to as “(meth)acrylic", the same applies below) and salts thereof; 2-(meth)acrylamido-2-methylpropanesulfonic acid and salts thereof; nonionic monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, N-methylol(meth)acrylamide, and polyethylene glycol mono(meth)acrylate; and amino group-containing unsaturated monomers and quaternized products thereof such as N,N-diethylaminoethyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, and diethylaminopropyl(meth)
- water-soluble ethylenically unsaturated monomers from the viewpoint of industrial ease of availability, etc., (meth)acrylic acid or a salt thereof, (meth)acrylamide, and N,N-dimethylacrylamide are preferred, and (meth)acrylic acid and a salt thereof are more preferred.
- These water-soluble ethylenically unsaturated monomers may be used alone or in combination of two or more kinds.
- acrylic acid and its salts are widely used as raw materials for water-absorbent resins, and these acrylic acid and/or its salts may be copolymerized with the other water-soluble ethylenically unsaturated monomers mentioned above.
- acrylic acid and/or its salts are used as the main water-soluble ethylenically unsaturated monomer in an amount of 70 to 100 mol % based on the total water-soluble ethylenically unsaturated monomers.
- the water-soluble ethylenically unsaturated monomer may be dispersed in a hydrocarbon dispersion medium in the form of an aqueous solution and subjected to reversed-phase suspension polymerization.
- a hydrocarbon dispersion medium in the form of an aqueous solution
- the concentration of the water-soluble ethylenically unsaturated monomer in this aqueous solution is preferably in the range of 20% by mass to the saturated concentration or less.
- the concentration of the water-soluble ethylenically unsaturated monomer is more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less.
- the concentration of the water-soluble ethylenically unsaturated monomer is more preferably 25% by mass or more, even more preferably 28% by mass or more, and even more preferably 30% by mass or more.
- the acid group may be neutralized in advance with an alkaline neutralizing agent, if necessary.
- alkaline neutralizing agents include alkali metal salts such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium carbonate, etc.; ammonia, etc.
- alkaline neutralizing agents may be used in the form of an aqueous solution to simplify the neutralization operation.
- the alkaline neutralizing agents described above may be used alone or in combination of two or more types.
- the degree of neutralization of the water-soluble ethylenically unsaturated monomer by the alkaline neutralizing agent is preferably 10 to 100 mol%, more preferably 30 to 90 mol%, even more preferably 40 to 85 mol%, and even more preferably 50 to 80 mol%, in terms of the degree of neutralization of all acid groups possessed by the water-soluble ethylenically unsaturated monomer.
- radical polymerization initiator examples include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, and hydrogen peroxide, as well as 2,2'-azobis(2-amidinopropane) dihydrochloride and 2,2'-azobis[2-(N-phenylenediamine)-2-methylpropane].
- persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate
- peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone per
- azo compounds examples include 2,2'-azobis[2-(N-allylamidino)propane] dihydrochloride, 2,2'-azobis ⁇ 2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane ⁇ dihydrochloride, 2,2'-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide ⁇ , 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], and 4,4'-azobis(4-cyanovaleric acid).
- radical polymerization initiators potassium persulfate, ammonium persulfate, sodium persulfate, and 2,2'-azobis(2-amidinopropane) dihydrochloride are preferred from the viewpoint of easy availability and ease of handling.
- These radical polymerization initiators may be used alone or in combination of two or more.
- the radical polymerization initiator can also be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, or L-ascorbic acid.
- the amount of radical polymerization initiator used is, for example, 0.00005 to 0.01 mole per mole of water-soluble ethylenically unsaturated monomer. By using such an amount, it is possible to avoid a sudden polymerization reaction and to complete the polymerization reaction within an appropriate time.
- the internal crosslinking agent may be one capable of crosslinking the polymer of the water-soluble ethylenically unsaturated monomer used, such as (poly)ethylene glycol (the term “(poly)” refers to the case where the "poly" prefix is used or not).
- unsaturated polyesters obtained by reacting polyols such as diols and triols, such as (poly)propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and (poly)glycerin, with unsaturated acids, such as (meth)acrylic acid, maleic acid, and fumaric acid; bisacrylamides such as N,N-methylenebisacrylamide; di(meth)acrylic acid esters or tri(meth)acrylic acid esters obtained by reacting polyepoxides with (meth)acrylic acid; di(meth)acrylic acid carbamyl esters obtained by reacting polyisocyanates, such as tolylene diisocyanate and hexamethylene diisocyanate, with hydroxyethyl (meth)acrylate; allylated starch, allylated cellulose, diallyl phthalate, N,N',N''-
- a polyglycidyl compound more preferably a diglycidyl ether compound, and it is preferable to use (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, or (poly)glycerin diglycidyl ether.
- These internal cross-linking agents may be used alone or in combination of two or more kinds.
- the amount of the internal crosslinking agent used is preferably 0.000001 to 0.02 mol, more preferably 0.00001 to 0.01 mol, even more preferably 0.00001 to 0.005 mol, and even more preferably 0.00005 to 0.002 mol per mol of the water-soluble ethylenically unsaturated monomer.
- hydrocarbon dispersion medium examples include aliphatic hydrocarbons having 6 to 8 carbon atoms, such as n-hexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, and n-octane; alicyclic hydrocarbons, such as cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, trans-1,2-dimethylcyclopentane, cis-1,3-dimethylcyclopentane, and trans-1,3-dimethylcyclopentane; and aromatic hydrocarbons, such as benzene, toluene, and xylene.
- aliphatic hydrocarbons having 6 to 8 carbon atoms such as n-hexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylp
- hydrocarbon dispersion media n-hexane, n-heptane, and cyclohexane are particularly preferred because they are easily available industrially, have stable quality, and are inexpensive.
- These hydrocarbon dispersion media may be used alone or in combination of two or more types.
- a commercially available product such as Exxol Heptane (manufactured by Exxon Mobil Corp.: contains 75 to 85% by mass of heptane and its isomers) can also be used to obtain favorable results.
- the amount of the hydrocarbon dispersion medium used is preferably 100 to 1500 parts by mass, and more preferably 200 to 1400 parts by mass, per 100 parts by mass of the water-soluble ethylenically unsaturated monomer in the first stage, from the viewpoint of uniformly dispersing the water-soluble ethylenically unsaturated monomer and facilitating control of the polymerization temperature.
- reversed-phase suspension polymerization is carried out in one stage (single stage) or in multiple stages of two or more stages, and the above-mentioned first stage polymerization refers to the polymerization reaction in a single stage or in a multiple stage polymerization (the same applies below).
- a dispersion stabilizer In the reversed-phase suspension polymerization, a dispersion stabilizer can be used to improve the dispersion stability of the water-soluble ethylenically unsaturated monomer in the hydrocarbon dispersion medium. As the dispersion stabilizer, a surfactant can be used.
- Surfactants that can be used include, for example, sucrose fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkylarylformaldehyde condensed polyoxyethylene ethers, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene polyoxypropyl alkyl ethers, polyethylene glycol fatty acid esters, alkyl glucosides, N-alkyl gluconamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, phosphate esters of polyoxyethylene alkyl ethers, and phosphate esters of poly
- surfactants it is particularly preferable to use sorbitan fatty acid esters, polyglycerin fatty acid esters, and sucrose fatty acid esters from the standpoint of dispersion stability of the monomer. These surfactants may be used alone or in combination of two or more.
- the amount of surfactant used is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 20 parts by mass, per 100 parts by mass of the first stage water-soluble ethylenically unsaturated monomer.
- a polymeric dispersant As the dispersion stabilizer used in the reversed phase suspension polymerization, a polymeric dispersant may be used in combination with the above-mentioned surfactant.
- polymeric dispersants include maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, maleic anhydride modified ethylene-propylene copolymer, maleic anhydride modified EPDM (ethylene-propylene-diene terpolymer), maleic anhydride modified polybutadiene, maleic anhydride-ethylene copolymer, maleic anhydride-propylene copolymer, maleic anhydride-ethylene-propylene copolymer, maleic anhydride-butadiene copolymer, polyethylene, polypropylene, ethylene-propylene copolymer, oxidized polyethylene, oxidized polypropylene, oxidized ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, ethylhydroxyethyl cellulose, etc.
- polymeric dispersants it is particularly preferable to use maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-propylene copolymer, maleic anhydride-ethylene-propylene copolymer, polyethylene, polypropylene, ethylene-propylene copolymer, oxidized polyethylene, oxidized polypropylene, and oxidized ethylene-propylene copolymer, from the viewpoint of dispersion stability of the monomer.
- These polymeric dispersants may be used alone or in combination of two or more kinds.
- the amount of polymeric dispersant used is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 20 parts by mass, per 100 parts by mass of the first stage water-soluble ethylenically unsaturated monomer.
- a thickener can be added to an aqueous solution containing a water-soluble ethylenically unsaturated monomer to carry out reverse suspension polymerization.
- a thickener in this way to adjust the viscosity of the aqueous solution, it is possible to control the median particle size obtained in reverse suspension polymerization.
- thickeners for example, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylic acid, partially neutralized polyacrylic acid, polyethylene glycol, polyacrylamide, polyethyleneimine, dextrin, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, etc. can be used. Note that, if the stirring speed during polymerization is the same, the higher the viscosity of the water-soluble ethylenically unsaturated monomer aqueous solution, the larger the primary particles and/or secondary particles obtained tend to be.
- aqueous monomer solution containing a water-soluble ethylenically unsaturated monomer is dispersed in a hydrocarbon dispersion medium in the presence of a dispersion stabilizer.
- the dispersion stabilizer surfactant or polymeric dispersant
- the dispersion stabilizer may be added either before or after the addition of the aqueous monomer solution, so long as it is before the start of the polymerization reaction.
- Such reverse phase suspension polymerization can be carried out in one stage or in multiple stages (two or more stages). From the viewpoint of increasing productivity, it is preferable to carry out the polymerization in two to three stages.
- the water-soluble ethylenically unsaturated monomer is added to the reaction mixture obtained in the first stage of polymerization reaction and mixed, and the second and subsequent stages of reversed-phase suspension polymerization can be performed in the same manner as the first stage.
- the reaction temperature for the polymerization reaction is preferably 20 to 110°C, and more preferably 40 to 90°C, from the viewpoints of promoting rapid polymerization and shortening the polymerization time, thereby improving economy, and of easily removing the heat of polymerization to allow the reaction to proceed smoothly.
- Step 2 is a step of adding a chelating agent, a sulfite compound, and an organic antioxidant to the hydrogel particles obtained in step 1.
- the water content of the hydrogel particles when the sulfite compound is added in step 2 is 20% by mass or more and 75% by mass or less.
- the water content of the hydrous gel particles when a sulfite compound is added to the hydrous gel particles is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, with preferred ranges being 20 to 75% by mass, 30 to 75% by mass, etc.
- the water content of the hydrous gel particles when the chelating agent is added to the hydrous gel particles in step 2 is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 150% by mass or less, more preferably 100% by mass or less, and even more preferably 75% by mass or less, with preferred ranges being 20-150% by mass, 20-75% by mass, 30-75% by mass, etc.
- the water content of the hydrogel particles when the organic antioxidant is added to the hydrogel particles in step 2 is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 150% by mass or less, more preferably 100% by mass or less, and even more preferably 75% by mass or less, with preferred ranges being 20 to 150% by mass, 20 to 75% by mass, 30 to 75% by mass, etc.
- step 2 further includes a step of adjusting the moisture content of the hydrous gel particles obtained in step 1.
- the moisture content of the hydrous gel particles produced in step 1 is less than 20% by mass, water can be added to the hydrous gel particles, and if the moisture content is more than 75% by mass, the hydrous gel particles can be heated to evaporate the water, thereby adjusting the moisture content to within the range of 20% to 75% by mass.
- the moisture content of the obtained hydrous gel particles usually exceeds 75% by mass (for example, the moisture content is often within the range of 100 to 250% by mass), so it is effective to provide a step of adjusting the moisture content of the hydrous gel particles obtained in step 1.
- the chelating agent, sulfite compound, and organic antioxidant are added to the hydrogel particles.
- they can be added in the order of the chelating agent, sulfite compound, and organic antioxidant, or at least two of them can be added simultaneously.
- the amount of sulfite compound added in step 2 is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.05 parts by mass or more, and is preferably 3.0 parts by mass or less, more preferably 1.0 parts by mass or less, even more preferably 0.50 parts by mass or less, even more preferably 0.25 parts by mass or less, with preferred ranges being 0.001 to 3.0 parts by mass, 0.01 to 1.0 parts by mass, etc., relative to 100 parts by mass of the water-soluble ethylenically unsaturated monomer.
- the amount of the chelating agent added in step 2 is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and even more preferably 0.003 parts by mass or more, relative to 100 parts by mass of the water-soluble ethylenically unsaturated monomer, and is preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less, more preferably 0.50 parts by mass or less, even more preferably 0.10 parts by mass or less, and even more preferably 0.05 parts by mass or less, with preferred ranges being 0.001 to 2.0 parts by mass, 0.002 to 1.0 parts by mass, etc.
- the amount of organic antioxidant added in step 2 is preferably 0.10 parts by mass or more, more preferably 0.30 parts by mass or more, and is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with preferred ranges being 0.10 to 20 parts by mass, 0.30 to 10 parts by mass, etc., per 100 parts by mass of the sulfite compound.
- the chelating agent, sulfite compound, and organic antioxidant are each added to the hydrogel particles in the form of an aqueous solution.
- concentration of each component in the aqueous solution may be adjusted so as to obtain the above-mentioned addition amount.
- the concentration of the aqueous solution of the chelating agent added to the hydrogel particles is preferably 0.1 to 50 mass%, more preferably 0.5 to 40 mass%.
- the concentration of the aqueous solution of the sulfite compound added to the hydrogel particles is preferably 1 to 20 mass%, more preferably 5 to 20 mass%.
- concentration of the aqueous solution of the organic antioxidant added to the hydrogel particles is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%.
- sulfite compounds include sodium sulfite, potassium sulfite, calcium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, sodium pyrosulfite, and potassium pyrosulfite. Only one type of sulfite compound may be used, or two or more types may be used.
- the chelating agent is preferably ethylenediamine-N,N'-disuccinic acid, diethylenetriaminepentaacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, etc.
- the chelating agent may exist in the form of a salt. Examples of the salt include sodium salts and potassium salts. Only one type of chelating agent may be used, or two or more types may be used.
- the organic antioxidants preferably include ascorbic acids, erythorbic acids, gallic acids, protocatechuic acids, benzimidazoles, and alkylhydroxyanisoles. Only one type of organic antioxidant may be used, or two or more types may be used.
- Step 3 is a step of subjecting the hydrogel particles to surface cross-linking to which the chelating agent, the sulfite compound and the organic antioxidant have been added in step 2.
- the surfaces of the hydrogel particles are cross-linked by the surface cross-linking (surface cross-linking reaction).
- Examples of surface cross-linking agents include compounds having two or more reactive functional groups.
- polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin
- polyglycidyl compounds such as (poly)ethylene glycol diglycidyl ether, (poly)glycerin diglycidyl ether, (poly)glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, (poly)propylene glycol polyglycidyl ether, and (poly)glycerol polyglycidyl ether
- haloepoxy compounds such as epichlorohydrin, epibromohydrin, and ⁇ -methylepichlorohydrin
- isocyanate compounds such as 2,4-to
- polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin; (poly)ethylene glycol diglycidyl ether, (poly)glycerin diglycidyl ether, (poly)glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, (poly)propylene glycol polyglycidyl ether, (poly)glycerin di ...
- Polyglycidyl compounds such as roll polyglycidyl ether; ethylene carbonate, propylene carbonate, 4,5-dimethyl-1,3-dioxolane-2-one, 4,4-dimethyl-1,3-dioxolane-2-one, 4-ethyl-1,3-dioxolane-2-one, 4-hydroxymethyl-1,3-dioxolane-2-one, 1,3-dioxan-2-one, 4-methyl-1,3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, 1,3-dioxopan-2-one, and other carbonate compounds (e.g., alkylene carbonates) are preferred.
- These surface crosslinking agents may be used alone or in combination of two or more.
- the amount of the surface cross-linking agent used is preferably 0.00001 to 0.01 mol, more preferably 0.00005 to 0.005 mol, and even more preferably 0.0001 to 0.002 mol, per mol of the total amount of water-soluble ethylenically unsaturated monomers used in the polymerization.
- the surface cross-linking agent may be added as it is or as an aqueous solution, but if necessary, it may be added as a solution using a hydrophilic organic solvent as a solvent.
- hydrophilic organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc.; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, dioxane, tetrahydrofuran, etc.; amides such as N,N-dimethylformamide; sulfoxides such as dimethyl sulfoxide, etc.
- These hydrophilic organic solvents may be used alone, in combination of two or more types, or as a mixed solvent with water.
- the water content of the hydrogel particles is preferably in the range of 1 to 75% by mass, more preferably in the range of 5 to 60% by mass, even more preferably in the range of 10 to 50% by mass, and even more preferably in the range of 15 to 40% by mass.
- the reaction temperature in the surface cross-linking reaction is preferably 50 to 250°C, more preferably 60 to 180°C, even more preferably 60 to 140°C, and even more preferably 70 to 120°C.
- the reaction time in the surface cross-linking reaction is preferably 1 to 300 minutes, and more preferably 5 to 200 minutes.
- the step 3 preferably further includes a drying step of the water-absorbent resin particles obtained by surface-treating the hydrous gel particles.
- a drying step may be included in which water, the hydrocarbon dispersion medium, and the like are removed by distillation by applying energy such as heat from the outside.
- the system in which the hydrous gel particles are dispersed in the hydrocarbon dispersion medium is heated to once distill off the water and the hydrocarbon dispersion medium from the system by azeotropic distillation. At this time, if only the distilled hydrocarbon dispersion medium is returned to the system, continuous azeotropic distillation is possible.
- the temperature in the system during drying is maintained below the azeotropic temperature with the hydrocarbon dispersion medium, which is preferable from the viewpoint of the resin being less likely to deteriorate.
- the water and the hydrocarbon dispersion medium are distilled off to obtain dried water-absorbent resin particles.
- the drying process by distillation may be performed under normal pressure or under reduced pressure. From the viewpoint of increasing the drying efficiency, it may also be performed under a stream of nitrogen or the like.
- the drying temperature is preferably 70 to 250°C, more preferably 80 to 180°C, even more preferably 80 to 140°C, and even more preferably 90 to 130°C.
- the drying temperature is preferably 40 to 160°C, and more preferably 50 to 110°C.
- the loss on drying of the water-absorbent resin particles obtained by the manufacturing method of the present invention is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, with a preferred range being 1 to 10% by mass, etc.
- a surface cross-linking step using a surface cross-linking agent is carried out after polymerization of monomers by reversed-phase suspension polymerization
- the above-mentioned drying step by distillation is carried out after the surface cross-linking step is completed.
- the surface cross-linking step and the drying step may be carried out simultaneously.
- the water-absorbent resin particles of the present invention may contain additives according to the purpose.
- additives include inorganic powders, surfactants, oxidizing agents, radical chain inhibitors, and antibacterial agents.
- the fluidity of the water-absorbent resin particles can be further improved by adding 0.05 to 5 parts by mass of amorphous silica as an inorganic powder to 100 parts by mass of the water-absorbent resin particles.
- the additives are preferably hydrophilic or water-soluble.
- the additives are preferably added to the water-absorbent resin particles obtained after the surface cross-linking step.
- the content of the water-absorbent resin (excluding additives) including moisture (loss on drying) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
- the water-absorbent resin particles obtained by the manufacturing method of the present invention have good water-absorption performance (e.g., physiological saline water absorption capacity) generally required of water-absorbent resins, and furthermore, yellowing under high temperature and high humidity conditions is suppressed, and the particles have high gel stability.
- good water-absorption performance e.g., physiological saline water absorption capacity
- the water-absorbent resin particles of the present invention have, for example, a saline water absorption of 40 to 70 g/g, a yellowness index of less than 40 after being left for 14 days in an environment of 70° C. and 90% relative humidity, and a gel strength of 5500 N/m 2 or more after being left for 14 hours in an environment of 37° C. and 60% relative humidity.
- the water-absorbent resin particles of the present invention are suitably produced by the production method of the present invention, but are not limited to water-absorbent resin particles produced by the production method, and may be any particles that satisfy the above-mentioned saline water absorption, yellowness index after being left for 14 days in an environment of 70° C. and 90% relative humidity, and gel strength after being left for 14 hours in an environment of 37° C. and 60% relative humidity.
- the physiological saline water absorption capacity of the water-absorbent resin particles of the present invention is preferably 40 g/g or more, more preferably 45 g/g or more, and even more preferably 50 g/g or more.
- the upper limit is preferably 70 g/g or less, and the preferred range is 40 to 70 g/g, 45 to 70 g/g, etc.
- the physiological saline water retention capacity of the water-absorbent resin particles of the present invention is preferably 25 g/g or more, more preferably 30 g/g or more, and is preferably 60 g/g or less, more preferably 55 g/g or less, and even more preferably 50 g/g or less, with preferred ranges being 25 to 60 g/g, 30 to 55 g/g, etc.
- the physiological saline water absorption capacity of the water-absorbent resin particles obtained by the manufacturing method of the present invention under a load of 4.14 kPa is preferably 5 mL/g or more, more preferably 10 mL/g or more, and is preferably 40 mL/g or less, more preferably 35 mL/g or less, and even more preferably 30 mL/g or less, with preferred ranges being 5 to 40 mL/g, 10 to 30 mL/g, etc.
- the saline water absorption capacity, saline water retention capacity, and saline water absorption capacity under a load of 4.14 kPa of the water-absorbent resin particles were each measured using the method described in the Examples.
- the water-absorbent resin particles of the present invention have an "initial yellowness value" evaluated by the method described in the Examples, which is preferably less than 20, more preferably less than 15, and even more preferably less than 10.
- the lower limit of the yellowness value is, for example, 0.
- the water-absorbent resin particles of the present invention preferably have a yellowness index after being left for 7 days in an environment of 70°C and 90% relative humidity, as evaluated by the method described in the Examples, of less than 40, more preferably less than 38, and even more preferably less than 30.
- the lower limit of the yellowness index is, for example, 5.
- the water-absorbent resin particles of the present invention preferably have a yellowness index after being left for 14 days in an environment of 70°C and 90% relative humidity, as evaluated by the method described in the Examples, of less than 40, and more preferably less than 38.
- the lower limit of the yellowness index is, for example, 10.
- the water absorbent resin particles of the present invention have an "initial gel strength" of preferably 5500 N/ m2 or more, more preferably 6200 N/ m2 or more, as evaluated by the method described in the Examples.
- the upper limit of the initial gel strength is, for example, 20000 N/ m2 .
- the water absorbent resin particles of the present invention have a "gel strength after standing at 37°C for 14 hours" evaluated by the method described in the Examples of preferably 5500 N/ m2 or more, more preferably 6200 N/ m2 or more.
- the upper limit of the gel strength is, for example, 20000 N/ m2 .
- the water-absorbing resin particles of the present invention constitute an absorbent body used in sanitary materials such as sanitary products and disposable diapers, and are suitably used in absorbent articles containing the absorbent body.
- the absorbent using the water-absorbent resin particles of the present invention contains the water-absorbent resin particles of the present invention.
- the absorbent may further contain hydrophilic fibers.
- the absorbent configuration include a sheet-like structure in which water-absorbent resin particles are fixed on a nonwoven fabric or between multiple nonwoven fabrics, a mixed dispersion obtained by mixing water-absorbent resin particles and hydrophilic fibers to obtain a uniform composition, a sandwich structure in which water-absorbent resin particles are sandwiched between layered hydrophilic fibers, and a structure in which water-absorbent resin particles and hydrophilic fibers are wrapped in tissue.
- the absorbent may contain other components, such as adhesive binders such as heat-fusible synthetic fibers, hot melt adhesives, and adhesive emulsions to improve the shape retention of the absorbent.
- the content of water-absorbent resin particles in the absorbent is preferably 5 to 100% by mass, more preferably 10 to 95% by mass, even more preferably 20 to 90% by mass, and even more preferably 30 to 80% by mass.
- Hydrophilic fibers include cellulose fibers such as cotton-like pulp obtained from wood, mechanical pulp, chemical pulp, and semi-chemical pulp, artificial cellulose fibers such as rayon and acetate, and fibers made of synthetic resins such as polyamide, polyester, and polyolefin that have been hydrophilically treated.
- the average fiber length of hydrophilic fibers is usually 0.1 to 10 mm, or may be 0.5 to 5 mm.
- the absorbent article of the present invention can be made by holding an absorbent body using the water-absorbent resin particles of the present invention between a liquid-permeable sheet (top sheet) through which liquid can pass and a liquid-impermeable sheet (back sheet) through which liquid cannot pass.
- the liquid-permeable sheet is placed on the side that comes into contact with the body, and the liquid-impermeable sheet is placed on the opposite side that comes into contact with the body.
- Liquid-permeable sheets include nonwoven fabrics such as air-through, spunbond, chemical bond, and needle-punch types made of fibers such as polyethylene, polypropylene, and polyester, as well as porous synthetic resin sheets.
- Liquid-impermeable sheets include synthetic resin films made of resins such as polyethylene, polypropylene, and polyvinyl chloride.
- the water-absorbent resin particles obtained in the following manufacturing examples and the water-absorbent resin particles obtained in the examples and comparative examples were evaluated by the following various tests. Unless otherwise specified, the measurements were performed in an environment of a temperature of 25 ⁇ 2°C and a relative humidity of 50 ⁇ 10%.
- Example 1 [Production process of hydrogel particles (step 1)] A round-bottomed cylindrical separable flask with an inner diameter of 11 cm and a volume of 2 L was prepared, which was equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a stirring blade having two stages of four inclined paddle blades with a blade diameter of 5 cm. 293 g of n-heptane was added to this flask as a hydrocarbon dispersion medium, and 0.736 g of maleic anhydride-modified ethylene-propylene copolymer (Mitsui Chemicals, Inc., Hiwax 1105A) was added as a polymeric dispersant.
- step 1 A round-bottomed cylindrical separable flask with an inner diameter of 11 cm and a volume of 2 L was prepared, which was equipped with a reflux condenser, a dropping funnel, a nitrogen gas inlet tube, and a stirring blade having two stages of four inclined paddle blades with a blade diameter
- the aqueous liquid prepared above was added to a separable flask and stirred for 10 minutes.
- a surfactant solution prepared by heating and dissolving 0.736 g of sucrose stearate with an HLB of 3 (Ryoto Sugar Ester S-370, Mitsubishi Chemical Foods Corporation) in 6.62 g of n-heptane as a surfactant in a 20 mL vial was then added.
- the system was thoroughly purged with nitrogen while stirring at a stirrer speed of 500 rpm, and the flask was immersed in a water bath at 70° C. to raise the temperature, and polymerization was carried out for 60 minutes to obtain a first-stage polymerization slurry.
- the contents of the separable flask system were cooled to 27°C while stirring at a stirrer speed of 1000 rpm, and then the entire amount of the second-stage aqueous liquid was added to the first-stage polymerization slurry liquid, and the system was replaced with nitrogen for 30 minutes. After that, the flask was again immersed in a 70°C water bath to raise the temperature, and the polymerization reaction was carried out for 60 minutes to obtain hydrous gel particles.
- Step 2 After obtaining the hydrous gel particles, the flask was immersed in an oil bath set at 125°C, and 175.1 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane (first water content adjustment step). Then, 4.42 g of a 0.5% by mass aqueous solution of trisodium ethylenediamine-N,N'-disuccinic acid was added under stirring. At this time, the water content of the hydrous gel particles when the aqueous solution of trisodium ethylenediamine-N,N'-disuccinic acid was added was 62% by mass.
- step 3 [Surface cross-linking step (step 3)] Then, 84.7 g of water was extracted from the system by azeotropic distillation of n-heptane and water again while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2% by mass aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the mixture was kept at 83° C. for 2 hours. Then, n-heptane was evaporated at 125° C. to dry the mixture, and the mixture was passed through a sieve with an opening of 850 ⁇ m to obtain 225.7 g of water-absorbent resin particles.
- Step of adding additives to water-absorbent resin particles 0.5 parts by mass of amorphous silica (Toxil NP-S, Oriental Silicas Corporation) was mixed with 100 parts by mass of the obtained water absorbent resin particles to obtain 226.8 g of water absorbent resin particles (1).
- the physiological saline water absorption capacity of the water absorbent resin particles (1) was 65 g/g
- the physiological saline water retention capacity was 43 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 14 mL/g.
- Example 1 The same operation as in Example 1 was performed except that 4.42 g of 0.5 mass% ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was not used, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [surface cross-linking step] was changed from 84.7 g to 80.3 g, to obtain 224.0 g of water-absorbent resin particles (2).
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 62 mass%, and the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 63 mass%.
- the physiological saline water absorption amount of the water-absorbent resin particles (2) was 62 g/g, the physiological saline water retention amount was 42 g/g, and the physiological saline water absorption amount under a load of 4.14 kPa was 18 mL/g.
- Example 2 The same operation as in Example 1 was performed except that the 20% by mass aqueous sodium sulfite solution was not used, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [Surface cross-linking step] was changed from 84.7 g to 83.0 g, to obtain 225.5 g of water-absorbent resin particles (3).
- the water content of the hydrous gel particles when the aqueous solution of ethylenediamine-N,N'-disuccinic acid trisodium was added was 62% by mass, and the water content of the hydrous gel particles when the aqueous solution of L(+)-ascorbic acid was added was 64% by mass.
- the physiological saline water absorption amount of the water-absorbent resin particles (3) was 61 g/g, the physiological saline water retention amount was 37 g/g, and the physiological saline water absorption amount under a load of 4.14 kPa was 18 mL/g.
- Example 3 The same operation as in Example 1 was performed except that the 0.1% by mass L(+)-ascorbic acid aqueous solution was not used, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [Surface cross-linking step] was changed from 84.7 g to 82.5 g, to obtain 224.8 g of water-absorbent resin particles (4).
- the water content of the hydrogel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 62% by mass, and the water content of the hydrogel particles when the sodium sulfite aqueous solution was added was 64% by mass.
- the physiological saline water absorption amount of the water-absorbent resin particles (4) was 73 g/g, the physiological saline water retention amount was 42 g/g, and the physiological saline water absorption amount under a load of 4.14 kPa was 16 mL/g.
- Example 2 The same operation as in Example 1 was performed except that the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the first water content adjustment step was changed from 175.1 g to 253.8 g, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [surface cross-linking step] was changed from 84.7 g to 6.1 g, to obtain 221.4 g of water-absorbent resin particles (5).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 26 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 28 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 29 mass%.
- the physiological saline water absorption capacity of the water-absorbent resin particles (5) was 59 g/g
- the physiological saline water retention capacity was 36 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 23 mL/g.
- Example 3 The same operation as in Example 1 was performed except that the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the first water content adjustment step was changed from 175.1 g to 223.2 g, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [surface cross-linking step] was changed from 84.7 g to 36.7 g, to obtain 223.8 g of water-absorbent resin particles (6).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 40 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 42 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 43 mass%.
- the physiological saline water absorption capacity of the water-absorbent resin particles (6) was 66 g/g
- the physiological saline water retention capacity was 43 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 12 mL/g.
- Example 4 The same operation as in Example 1 was performed except that the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the first water content adjustment step was changed from 175.1 g to 157.6 g, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [surface crosslinking step] was changed from 84.7 g to 102.2 g, to obtain 225.1 g of water-absorbent resin particles (7).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 70 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 72 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 73 mass%.
- the physiological saline water absorption capacity of the water-absorbent resin particles (7) was 64 g/g
- the physiological saline water retention capacity was 42 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 12 mL/g.
- Example 4 The same operation as in Example 1 was performed except that the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the first water content adjustment step was changed from 175.1 g to 135.8 g, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [surface cross-linking step] was changed from 84.7 g to 124.1 g, to obtain 223.8 g of water-absorbent resin particles (8).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 80 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 82 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 83 mass%.
- the physiological saline water absorption capacity of the water-absorbent resin particles (8) was 67 g/g
- the physiological saline water retention capacity was 46 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 12 mL/g.
- Step 2 After obtaining the hydrous gel particles, the flask was immersed in an oil bath set at 125°C, and 135.8 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane (first water content adjustment step). Then, 2.21 g of a 20% by mass aqueous sodium sulfite solution was added under stirring. At this time, the water content of the hydrous gel particles when the aqueous sodium sulfite solution was added was 80% by mass.
- step 3 [Surface cross-linking step (step 3)] Then, 34.9 g of water was extracted from the system by azeotropic distillation of n-heptane and water again while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2% by mass aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the mixture was kept at 83° C. for 2 hours. Then, n-heptane was evaporated at 125° C. to dry the mixture, and the mixture was passed through a sieve with an opening of 850 ⁇ m to obtain 221.1 g of water-absorbent resin particles.
- Example 5 [Production process of hydrogel particles (step 1)] The same procedure as in the [Production process of hydrogel particles] of Example 1 was carried out to obtain hydrogel particles.
- Step 2 After obtaining the hydrous gel particles, the flask was immersed in an oil bath set at 125°C, and 135.8 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane (first water content adjustment step). Then, 4.42 g of a 0.5% by mass aqueous solution of trisodium ethylenediamine-N,N'-disuccinic acid was added under stirring. At this time, the water content of the hydrous gel particles when the aqueous solution of trisodium ethylenediamine-N,N'-disuccinic acid was added was 80% by mass.
- step 3 [Surface cross-linking step (step 3)] Then, 32.3 g of water was extracted from the system by azeotropic distillation of n-heptane and water again while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2 mass% aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the mixture was kept at 83 ° C. for 2 hours. Then, n-heptane was evaporated at 125 ° C. to dry the mixture, and the mixture was passed through a sieve with an opening of 850 ⁇ m to obtain 222.7 g of water-absorbent resin particles.
- Example 6 [Production process of hydrogel particles (step 1)] The same procedure as in the [Production process of hydrogel particles] of Example 1 was carried out to obtain hydrogel particles.
- Step 2 After obtaining the hydrous gel particles, the flask was immersed in an oil bath set at 125°C, and 135.8 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane (first water content adjustment step). Then, 2.21 g of a 0.2 mass% L(+)-ascorbic acid aqueous solution was added under stirring. At this time, the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 80 mass%.
- step 3 [Surface cross-linking step (step 3)] Then, 34.5 g of water was extracted from the system by azeotropic distillation of n-heptane and water again while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2 mass% aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the mixture was kept at 83 ° C. for 2 hours. Then, n-heptane was evaporated at 125 ° C. to dry the mixture, and the mixture was passed through a sieve with an opening of 850 ⁇ m to obtain 223.7 g of water-absorbent resin particles.
- step 3 After obtaining the hydrous gel particles, the flask was immersed in an oil bath set at 125°C, and 251.5 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2% by mass aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the mixture was kept at 83°C for 2 hours. Then, n-heptane was evaporated at 125°C to dry, and the mixture was passed through a sieve with an opening of 850 ⁇ m to obtain 217.6 g of water-absorbing resin particles.
- amorphous silica (Toxil NP-S, Oriental Silicas Corporation) was mixed to 100 parts by mass of the obtained mixture to obtain water-absorbent resin particles (12).
- the physiological saline water absorption of the water-absorbent resin particles (12) was 60 g/g, the physiological saline water retention was 42 g/g, and the physiological saline water absorption under a load of 4.14 kPa was 14 mL/g.
- step 3 After obtaining the hydrous gel particles, the flask was immersed in an oil bath set at 125°C, and 251.5 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2% by mass aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the mixture was kept at 83°C for 2 hours. Then, n-heptane was evaporated at 125°C to dry, and the mixture was passed through a sieve with an opening of 850 ⁇ m to obtain 226.8 g of water-absorbent resin particles.
- Step of adding additives to water-absorbent resin particles 20 g of the water-absorbent resin particles obtained in the [Surface cross-linking step] was weighed into a round-bottomed cylindrical separable flask with an inner diameter of 11 cm equipped with an anchor-shaped stirring blade made of fluororesin. Next, while stirring at 300 rpm, 0.2 g of a 1.0 mass% aqueous solution of diethylenetriaminepentaacetic acid.pentasodium (DTPA.5Na) was dropped into the separable flask with a Pasteur pipette, and a mixture was obtained by stirring for 10 minutes.
- DTPA.5Na diethylenetriaminepentaacetic acid.pentasodium
- the physiological saline water absorption capacity of the water-absorbent resin particles was 58 g/g, the physiological saline water retention capacity was 40 g/g, and the physiological saline water absorption capacity under a load of 4.14 kPa was 21 mL/g.
- Comparative Example 8 The same operation as in Comparative Example 7 was carried out except that 0.2 g of a 1.0 mass% aqueous solution of ethylenediamine-N,N'-disuccinic acid.trisodium (EDDS.3Na) was used instead of 0.2 g of a 1.0 mass% aqueous solution of diethylenetriaminepentaacetic acid.pentasodium (DTPA.5Na) in Comparative Example 7, to obtain 218.8 g of water absorbent resin particles (14).
- EDDS.3Na ethylenediamine-N,N'-disuccinic acid.trisodium
- DTPA.5Na diethylenetriaminepentaacetic acid.pentasodium
- the physiological saline water absorption of the water absorbent resin particles (14) was 56 g/g, the physiological saline water retention was 39 g/g, and the physiological saline water absorption under a load of 4.14 kPa was 23 mL/g.
- Example 7 The same operation as in Example 1 was carried out except that 4.42 g of 0.5 mass% diethylenetriaminepentaacetic acid.pentasodium (DTPA.5Na) aqueous solution was used instead of 4.42 g of 0.5 mass% ethylenediamine-N,N'-disuccinic acid.trisodium aqueous solution in Example 1, to obtain 225.6 g of water-absorbent resin particles (15).
- DTPA.5Na diethylenetriaminepentaacetic acid.pentasodium
- the water content of the hydrous gel particles when the diethylenetriaminepentaacetic acid.pentasodium aqueous solution was added was 62 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 64 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 65 mass%.
- the physiological saline water absorption of the water-absorbent resin particles (15) was 58 g/g
- the physiological saline water retention was 39 g/g
- the physiological saline water absorption under a load of 4.14 kPa was 14 mL/g.
- Example 8 The same operation as in Example 1 was carried out except that 4.42 g of 0.5 mass% ethylenediamine-N,N'-disuccinic acid ⁇ trisodium aqueous solution was replaced with 4.42 g of 0.5 mass% ethylenediaminetetramethylenephosphonic acid (EDTMP ⁇ 8H) aqueous solution, and 224.6 g of water-absorbent resin particles (16) were obtained.
- ETMP ⁇ 8H ethylenediaminetetramethylenephosphonic acid
- the water content of the hydrous gel particles when the ethylenediaminetetramethylenephosphonic acid aqueous solution was added was 62 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 64 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 65 mass%.
- the physiological saline water absorption of the water-absorbent resin particles (16) was 61 g/g
- the physiological saline water retention was 37 g/g
- the physiological saline water absorption under a load of 4.14 kPa was 18 mL/g.
- Example 9 [Production process of hydrogel particles (step 1)] The same procedure as in the [Production process of hydrogel particles] of Example 1 was carried out to obtain hydrogel particles.
- Step 2 After obtaining the hydrous gel particles, the flask was immersed in an oil bath set at 125°C, and 175.1 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane (first water content adjustment step). Then, 4.42 g of a 0.5% by mass aqueous solution of trisodium ethylenediamine-N,N'-disuccinic acid was added under stirring. At this time, the water content of the hydrous gel particles when the aqueous solution of trisodium ethylenediamine-N,N'-disuccinic acid was added was 62% by mass.
- step 3 [Surface cross-linking step (step 3)] Then, 56.7 g of water was extracted from the system by azeotropic distillation of n-heptane and water again while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2% by mass aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the mixture was kept at 83° C. for 2 hours. Then, n-heptane was evaporated at 125° C. to dry the mixture, and the mixture was passed through a sieve with an opening of 850 ⁇ m to obtain 219.7 g of water-absorbent resin particles.
- Example 10 In Example 9, 8.83 g of 0.5 mass% ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was used instead of 4.42 g of 0.5 mass% ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the second water content adjustment step was changed from 15.3 g to 19.7 g, and the same operation as in Example 9 was performed to obtain 225.7 g of water-absorbent resin particles (18).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 62 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 57 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 52 mass%.
- the physiological saline water absorption capacity of the water-absorbent resin particles (18) was 64 g/g
- the physiological saline water retention capacity was 40 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 11 mL/g.
- Example 11 In Example 9, 2.21 g of 0.5% by mass ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was used instead of 4.42 g of 0.5% by mass ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the second water content adjustment step was changed from 15.3 g to 13.1 g, and the same operation as in Example 9 was performed to obtain 223.4 g of water-absorbent resin particles (19).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 62% by mass
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 57% by mass
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 52% by mass.
- the physiological saline water absorption capacity of the water-absorbent resin particles (19) was 62 g/g
- the physiological saline water retention capacity was 46 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 10 mL/g.
- Example 12 The same operation as in Example 9 was performed except that 3.31 g of a 20% by mass aqueous sodium sulfite solution was used instead of 2.21 g of a 20% by mass aqueous sodium sulfite solution in Example 9, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the third water content adjustment step was changed from 12.7 g to 13.6 g, to obtain 223.8 g of water-absorbent resin particles (20).
- the water content of the hydrous gel particles when the aqueous ethylenediamine-N,N'-disuccinic acid trisodium solution was added was 62% by mass
- the water content of the hydrous gel particles when the aqueous sodium sulfite solution was added was 57% by mass
- the water content of the hydrous gel particles when the aqueous L(+)-ascorbic acid solution was added was 52% by mass.
- the physiological saline water absorption of the water-absorbent resin particles (20) was 67 g/g
- the physiological saline water retention was 50 g/g
- the physiological saline water absorption under a load of 4.14 kPa was 8 mL/g.
- Example 13 The same operation as in Example 9 was performed except that 1.10 g of a 20% by mass aqueous sodium sulfite solution was used instead of 2.21 g of a 20% by mass aqueous sodium sulfite solution in Example 9, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the third water content adjustment step was changed from 12.7 g to 11.8 g, to obtain 224.6 g of water-absorbent resin particles (21).
- the water content of the hydrous gel particles when the aqueous solution of ethylenediamine-N,N'-disuccinic acid trisodium was added was 62% by mass
- the water content of the hydrous gel particles when the aqueous solution of sodium sulfite was added was 57% by mass
- the water content of the hydrous gel particles when the aqueous solution of L(+)-ascorbic acid was added was 52% by mass.
- the physiological saline water absorption amount of the water-absorbent resin particles (21) was 65 g/g
- the physiological saline water retention amount was 45 g/g
- the physiological saline water absorption amount under a load of 4.14 kPa was 11 mL/g.
- Example 14 The same operation as in Example 9 was performed except that 11.0 g of a 0.2 mass% L(+)-ascorbic acid aqueous solution was used instead of 2.21 g of a 0.2 mass% L(+)-ascorbic acid aqueous solution in Example 9, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [Surface crosslinking step] was changed from 56.7 g to 65.5 g, to obtain 226.8 g of water-absorbent resin particles (22).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 62 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 57 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 52 mass%.
- the saline water absorption capacity of the water-absorbent resin particles (22) was 62 g/g
- the saline water retention capacity was 45 g/g
- the saline water absorption capacity under a load of 4.14 kPa was 22 mL/g.
- Example 15 The same operation as in Example 9 was performed except that 1.10 g of a 0.2 mass% L(+)-ascorbic acid aqueous solution was used instead of 2.21 g of a 0.2 mass% L(+)-ascorbic acid aqueous solution in Example 9, and the amount of water extracted from the system by azeotropic distillation of n-heptane and water in the [Surface crosslinking step] was changed from 56.7 g to 55.6 g, to obtain 224.0 g of water-absorbent resin particles (23).
- the water content of the hydrous gel particles when the ethylenediamine-N,N'-disuccinic acid trisodium aqueous solution was added was 62 mass%
- the water content of the hydrous gel particles when the sodium sulfite aqueous solution was added was 57 mass%
- the water content of the hydrous gel particles when the L(+)-ascorbic acid aqueous solution was added was 52 mass%.
- the physiological saline water absorption capacity of the water-absorbent resin particles (23) was 66 g/g
- the physiological saline water retention capacity was 46 g/g
- the physiological saline water absorption capacity under a load of 4.14 kPa was 10 mL/g.
- the water content of the hydrous gel particles was calculated as follows: It was calculated by the following formula using the amount of water W1 (g) contained in the aqueous liquid used in the production of hydrous gel particles in the [hydrous gel particle production step (step 1)], the amount of water W2 (g) contained in the aqueous additive solution added to the system in the [additive addition step (step 2)], the amount of water W3 (g) extracted from the system by azeotropic distillation of n-heptane and water in the [additive addition step (step 2)], the amount of water W4 (g) extracted from the system by azeotropic distillation of n-heptane and water in the [surface crosslinking step (step 3)], and the amount of water-soluble ethylenically unsaturated monomer M1 (g) contained in the aqueous liquid used in the production of hydrous gel particles in the [hydrous gel particle production step (step 1)].
- the sieve was tilted at an angle of about 30 degrees to the horizontal and left for 30 minutes to filter out excess water.
- ⁇ Saline water retention capacity> A cotton bag (membrane broad 60, 100 mm wide x 200 mm long) containing 2.0 g of water-absorbent resin particles was placed in a 500 mL beaker. 500 g of 0.9% by mass sodium chloride aqueous solution (physiological saline) was poured into the cotton bag containing the water-absorbent resin particles at once so as not to cause any lumps, the top of the cotton bag was tied with a rubber band, and the bag was left to stand for 30 minutes to swell the water-absorbent resin particles.
- the cotton bag was dehydrated for 1 minute using a dehydrator (manufactured by Kokusan Co., Ltd., product number: H-122) set to a centrifugal force of 167 G, and the mass Wd (g) of the cotton bag containing the swollen gel after dehydration was measured.
- the same operation was performed without adding the water-absorbent resin particles, the empty mass We (g) of the cotton bag when wet was measured, and the physiological saline water retention was calculated from the following formula.
- Saline water retention capacity (g/g) [Wd-We]/2.0
- the measuring device includes a burette part 1, a clamp 3, a conduit 5, a stand 11, a measurement table 13, and a measurement part 4 placed on the measurement table 13.
- the burette part 1 has a burette tube 21 with a scale, a rubber stopper 23 that seals the opening at the top of the burette tube 21, a cock 22 connected to the tip of the bottom of the burette tube 21, and an air introduction tube 25 and a cock 24 connected to the bottom of the burette tube 21.
- the burette part 1 is fixed with a clamp 3.
- the flat measurement table 13 has a through hole 13a with a diameter of 2 mm formed in its center, and is supported by a height-variable stand 11.
- the through hole 13a of the measurement table 13 and the cock 22 of the burette part 1 are connected by a conduit 5.
- the inside diameter of the conduit 5 is 6 mm.
- the measuring section 4 has a Plexiglas cylinder 31, a polyamide mesh 32 adhered to one opening of the cylinder 31, and a weight 33 that can move up and down within the cylinder 31.
- the cylinder 31 is placed on the measuring table 13 via the polyamide mesh 32.
- the inner diameter of the cylinder 31 is 20 mm.
- the opening of the polyamide mesh 32 is 75 ⁇ m (200 mesh).
- the weight 33 has a diameter of 19 mm and a mass of 119.6 g, and can apply a load of 4.14 kPa (0.6 psi) to the water-absorbent resin particles 10a that are uniformly arranged on the polyamide mesh 32 as described below.
- the stopcocks 22 and 24 of the burette part 1 were closed, and 0.9% by mass physiological saline adjusted to 25°C was poured into the burette tube 21 through the opening at the top of the burette tube 21.
- the top opening of the burette tube 21 was sealed with a rubber stopper 23, and then the stopcocks 22 and 24 were opened.
- the inside of the conduit 5 was filled with 0.9% by mass saline 50 to prevent air bubbles from entering.
- the height of the measurement table 13 was adjusted so that the height of the water surface of the 0.9% by mass saline solution 50 that reached the through hole 13a was the same as the height of the upper surface of the measurement table 13. After the adjustment, the height of the water surface of the 0.9% by mass saline solution 50 in the burette tube 21 was read on the scale of the burette tube 21, and this position was set as the zero point (the reading at 0 seconds).
- a test for coloring of the water-absorbent resin particles over time was carried out as follows. That is, 2.0 g of water-absorbent resin particles were uniformly placed in a glass petri dish with an inner diameter of 3 cm and a depth of 1 cm, and the container was stored for a specified number of days (7 days or 14 days) in a thermostatic chamber (Espec Corp., LHU-113) set at a temperature of 70 ⁇ 2°C and a relative humidity of 90 ⁇ 2%. Thereafter, the container was removed from the thermostatic chamber and left to cool to room temperature for a while.
- a thermostatic chamber Espec Corp., LHU-113
- the entire amount of water-absorbent resin particles in a glass measuring container with an inner diameter of 3 cm was placed in the container, and the yellowness of the water-absorbent resin particles was measured with a color difference meter (Color Meter ZE6000, Nippon Denshoku Industries Co., Ltd.). The yellowness was calculated from the X, Y, and Z (tristimulus values) of the obtained water-absorbent resin particles using the following formula.
- the gel strength at each temperature and after the rest time was measured using an apparatus having the measurement principle shown in FIG. 2.
- the apparatus shown in FIG. 2 is composed of a support part 50a, a movable base plate 60, a drive part 70 for driving the movable base plate 60, and a measurement part 80.
- a stand 53 is fixed to the upper part of a support 52 erected on a support stand 51.
- the movable base plate 60 is attached to the support 52 so as to move up and down.
- the movable base plate 60 can be loaded with a measurement sample (gel) 61.
- a pulse motor 71 is mounted on the stand 53, and the movable base plate 60 is moved up and down via a wire 73 by rotating a pulley 72.
- a pressure-sensitive shaft 84 with a disk is attached to a load cell 81 for measuring the strain caused by deformation via a precision spring 82 and a connecting shaft 83.
- the pressure-sensitive shaft 84 with a disk has a disk at its tip. The diameter of the disk can be changed depending on the measurement conditions.
- a weight 90 can be mounted on the top of the pressure-sensitive shaft 84 with a disk.
- the operating principle of the device for measuring gel strength is as follows.
- a precision spring 82 is fixed to a load cell 81 (stress detector) above, and the pressure-sensitive shaft 84 with a disk is connected to the bottom and suspended vertically with a predetermined weight 90 placed on it.
- the movable base plate 60 with the measurement sample 61 placed on it rises at a constant speed due to the rotation of the pulse motor 71.
- a constant-speed load is applied to the measurement sample 61 via the precision spring 82, and the strain caused by deformation is measured by the load cell 81, and the hardness is measured and calculated.
- the gel strength value (N/ m2 ) was measured using a Curdmeter-MAX (Asuka Kikai, product number: ME-500) with a disk of 16 mm diameter for the pressure-sensitive shaft 84 with a disk, a load of 400 g, a speed of 7 seconds/inch, and viscous mode settings under the following temperature and standing time conditions: (initial gel strength) and (gel strength after standing at 37°C for 14 hours).
- thermohygrostat Espec Corp., LHU-113 set at a temperature of 37 ⁇ 2°C and a relative humidity of 60 ⁇ 10%, after which the plastic wrap was removed from the beaker containing the swollen gel, and the gel strength was measured by the method described above. The gel strength value at this time was taken as the gel strength (14-hour value).
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Hematology (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
項1. 水溶性エチレン性不飽和単量体を重合し、含水ゲル粒子を得る工程1と、
前記含水ゲル粒子に対して、キレート剤、亜硫酸塩系化合物及び有機酸化防止剤を添加する工程2と、
前記含水ゲル粒子に対して、表面架橋処理を施す工程3と、
をこの順に備え、
前記工程2において、前記亜硫酸塩系化合物を添加する際の前記含水ゲル粒子の含水率が、20質量%以上75質量%以下である、吸水性樹脂粒子の製造方法。
項2. 前記工程2は、前記含水ゲル粒子の含水率を調整する工程をさらに含む、項1に記載の吸水性樹脂粒子の製造方法。
項3. 前記工程2において、前記キレート剤を添加する際の前記含水ゲル粒子の含水率が、20質量%以上である、項1又は2に記載の吸水性樹脂粒子の製造方法。
項4. 前記工程2において、前記有機酸化防止剤を添加する際の前記含水ゲル粒子の含水率が、20質量%以上である、項1~3のいずれか1項に記載の吸水性樹脂粒子の製造方法。
項5. 前記工程2において、前記亜硫酸塩系化合物の添加量が、前記水溶性エチレン性不飽和単量体100質量部に対して、0.001質量部以上3.0質量部以下である、項1~4のいずれか1項に記載の吸水性樹脂粒子の製造方法。
項6. 前記工程2において、前記キレート剤の添加量が、前記水溶性エチレン性不飽和単量体100質量部に対して、0.001質量部以上2.0質量部以下である、項1~5のいずれか1項に記載の吸水性樹脂粒子の製造方法。
項7. 前記工程2において、前記有機酸化防止剤の添加量が、前記亜硫酸塩系化合物100質量部に対して、0.1質量部以上20質量部以下である、項1~6のいずれか1項に記載の吸水性樹脂粒子の製造方法。
項8. 生理食塩水吸水量が40~70g/gであり、
70℃、90%相対湿度の環境下で14日間放置した後の黄色度が40未満であり、
37℃、60%相対湿度の環境下で14時間放置した後のゲル強度が5500N/m2以上である、吸水性樹脂粒子。
項9. 項8に記載の吸水性樹脂粒子を含んでなる、吸収体。
項10. 項9に記載の吸収体を含んでなる、吸収性物品。
本発明の吸水性樹脂粒子の製造方法は、水溶性エチレン性不飽和単量体を重合し、含水ゲル粒子を得る工程1と、前記含水ゲル粒子に対して、キレート剤、亜硫酸塩系化合物及び有機酸化防止剤を添加する工程2と、前記含水ゲル粒子に対して、表面架橋処理を施す工程3とをこの順に備え、前記工程2において、前記亜硫酸塩系化合物を添加する際の前記含水ゲル粒子の含水率が、20質量%以上75質量%以下であることを特徴とする。このような特徴を備える本発明の製造方法によって製造される吸水性樹脂粒子は、吸水性樹脂に求められる一般的な吸水性能(例えば生理食塩水吸水量など)が良好であって、さらに、高温高湿下での黄色着色が抑制され、高いゲル安定性を備えている。以下、本発明の吸水性樹脂粒子の製造方法について詳述する。
工程1は、水溶性エチレン性不飽和単量体を重合し、含水ゲル粒子を得る工程である。水溶性エチレン性不飽和単量体の重合方法としては、代表的な重合法である水溶液重合法、乳化重合法、逆相懸濁重合法等が用いられる。水溶液重合法では、水溶性エチレン性不飽和単量体水溶液を、必要に応じて攪拌しながら、加熱することにより重合が行われる。また、逆相懸濁重合法では、水溶性エチレン性不飽和単量体を、炭化水素分散媒中、攪拌下で加熱することにより重合が行われる。
[水溶性エチレン性不飽和単量体]
水溶性エチレン性不飽和単量体としては、例えば、(メタ)アクリル酸(本明細書においては、「アクリル」及び「メタクリル」を合わせて「(メタ)アクリル」と表記する。以下同様)及びその塩;2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸及びその塩;(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、2-ヒドロキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、ポリエチレングリコールモノ(メタ)アクリレート等の非イオン性単量体;N,N-ジエチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノプロピル(メタ)アクリレート、ジエチルアミノプロピル(メタ)アクリルアミド等のアミノ基含有不飽和単量体及びその4級化物等が挙げられる。これらの水溶性エチレン性不飽和単量体の中でも、工業的に入手が容易であること等の観点から、(メタ)アクリル酸又はその塩、(メタ)アクリルアミド、N,N-ジメチルアクリルアミドが好ましく、(メタ)アクリル酸及びその塩がより好ましい。なお、これらの水溶性エチレン性不飽和単量体は、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
当該重合工程に添加されるラジカル重合開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩類、メチルエチルケトンパーオキシド、メチルイソブチルケトンパーオキシド、ジ-t-ブチルパーオキシド、t-ブチルクミルパーオキシド、t-ブチルパーオキシアセテート、t-ブチルパーオキシイソブチレート、t-ブチルパーオキシピバレート、過酸化水素等の過酸化物類、並びに、2,2’-アゾビス(2-アミジノプロパン)2塩酸塩、2,2’-アゾビス〔2-(N-フェニルアミジノ)プロパン〕2塩酸塩、2,2’-アゾビス〔2-(N-アリルアミジノ)プロパン〕2塩酸塩、2,2’-アゾビス{2-〔1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル〕プロパン}2塩酸塩、2,2’-アゾビス{2-メチル-N-〔1,1-ビス(ヒドロキシメチル)-2-ヒドロキシエチル〕プロピオンアミド}、2,2’-アゾビス〔2-メチル-N-(2-ヒドロキシエチル)-プロピオンアミド〕、4,4’-アゾビス(4-シアノ吉草酸)等のアゾ化合物等を挙げることができる。これらのラジカル重合開始剤の中でも、入手が容易で取り扱いやすいという観点から、好ましくは、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム及び2,2’-アゾビス(2-アミジノプロパン)2塩酸塩が挙げられる。これらラジカル重合開始剤は、単独で用いても、2種以上を組み合わせて用いてもよい。また、前記ラジカル重合開始剤は、亜硫酸ナトリウム、亜硫酸水素ナトリウム、硫酸第一鉄、及びL-アスコルビン酸等の還元剤と併用して、レドックス重合開始剤として用いることもできる。
内部架橋剤としては、使用する水溶性エチレン性不飽和単量体の重合体を架橋できるものが挙げられ、例えば、(ポリ)エチレングリコール〔「(ポリ)」とは「ポリ」の接頭語がある場合とない場合を意味する。以下同様〕、(ポリ)プロピレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、トリメチロールプロパン、(ポリ)グリセリン等のジオール、トリオール等のポリオール類と(メタ)アクリル酸、マレイン酸、フマル酸等の不飽和酸とを反応させて得られる不飽和ポリエステル類;N,N-メチレンビスアクリルアミド等のビスアクリルアミド類;ポリエポキシドと(メタ)アクリル酸とを反応させて得られるジ(メタ)アクリル酸エステル類又はトリ(メタ)アクリル酸エステル類;トリレンジイソシアネート、ヘキサメチレンジイソシアネート等のポリイソシアネートと(メタ)アクリル酸ヒドロキシエチルとを反応させて得られるジ(メタ)アクリル酸カルバミルエステル類;アリル化澱粉、アリル化セルロース、ジアリルフタレート、N,N’,N’’-トリアリルイソシアヌレート、ジビニルベンゼン等の重合性不飽和基を2個以上有する化合物;(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)プロピレングリコールジグリシジルエーテル、(ポリ)グリセリンジグリシジルエーテル等のジグリシジル化合物、トリグリシジル化合物等のポリグリシジル化合物;エピクロルヒドリン、エピブロムヒドリン、α-メチルエピクロルヒドリン等のエピハロヒドリン化合物;2,4-トリレンジイソシアネート、ヘキサメチレンジイソシアネート等のイソシアネート化合物等の反応性官能基を2個以上有する化合物;3-メチル-3-オキセタンメタノール、3-エチル-3-オキセタンメタノール、3-ブチル-3-オキセタンメタノール、3-メチル-3-オキセタンエタノール、3-エチル-3-オキセタンエタノール、3-ブチル-3-オキセタンエタノール等のオキセタン化合物等が挙げられる。これらの内部架橋剤の中でも、ポリグリシジル化合物を用いることが好ましく、ジグリシジルエーテル化合物を用いることがより好ましく、(ポリ)エチレングリコールジグリシジルエーテル、(ポリ)プロピレングリコールジグリシジルエーテル、(ポリ)グリセリンジグリシジルエーテルを用いることが好ましい。これらの内部架橋剤は、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
炭化水素分散媒としては、例えば、n-ヘキサン、n-ヘプタン、2-メチルヘキサン、3-メチルヘキサン、2,3-ジメチルペンタン、3-エチルペンタン、n-オクタン等の炭素数6~8の脂肪族炭化水素;シクロヘキサン、メチルシクロヘキサン、シクロペンタン、メチルシクロペンタン、trans-1,2-ジメチルシクロペンタン、cis-1,3-ジメチルシクロペンタン、trans-1,3-ジメチルシクロペンタン等の脂環族炭化水素;ベンゼン、トルエン、キシレン等の芳香族炭化水素等が挙げられる。これらの炭化水素分散媒の中でも、特に、工業的に入手が容易であり、品質が安定しており且つ安価である点で、n-ヘキサン、n-ヘプタン、シクロヘキサンが好適に用いられる。これらの炭化水素分散媒は、単独で用いてもよく、2種類以上を組み合わせて用いてもよい。なお、炭化水素分散媒の混合物の例としては、エクソールヘプタン(エクソンモービル社製:ヘプタン及びその異性体の炭化水素75~85質量%含有)等の市販品を用いても好適な結果を得ることができる。
(界面活性剤)
逆相懸濁重合では、水溶性エチレン性不飽和単量体の炭化水素分散媒中での分散安定性を向上させるために、分散安定剤を用いることもできる。その分散安定剤としては、界面活性剤を用いることができる。
また、逆相懸濁重合で用いられる分散安定剤としては、上述した界面活性剤と共に、高分子系分散剤を併せて用いてもよい。
所望によりその他の成分を、水溶性エチレン性不飽和単量体を含む水溶液に添加して逆相懸濁重合を行うようにしてもよい。その他の成分としては、増粘剤、連鎖移動剤等の各種の添加剤を添加することができる。
逆相懸濁重合を行うにあたっては、例えば、分散安定剤の存在下に、水溶性エチレン性不飽和単量体を含む単量体水溶液を、炭化水素分散媒に分散させる。このとき、重合反応を開始する前であれば、分散安定剤(界面活性剤や高分子系分散剤)の添加時期は、単量体水溶液添加の前後どちらであってもよい。
工程2は、工程1で得られた含水ゲル粒子に対して、キレート剤、亜硫酸塩系化合物及び有機酸化防止剤を添加する工程である。本発明は、工程2において、亜硫酸塩系化合物を添加する際の含水ゲル粒子の含水率が20質量%以上75質量%以下である。
工程3は、工程2でキレート剤、亜硫酸塩系化合物及び有機酸化防止剤が添加された含水ゲル粒子に対して、表面架橋を施す工程である。表面架橋によって、含水ゲル粒子の表面が架橋される(表面架橋反応)。内部架橋構造を有する含水ゲル粒子に対して表面架橋反応を施すことによって、吸水性樹脂粒子の表面近傍の架橋密度を高めて、荷重下での生理食塩水吸水量等の諸性能を高めた吸水性樹脂粒子を得ることができる。
本発明の吸水性樹脂粒子は、例えば、生理用品、紙オムツ等の衛生材料に用いられる吸収体を構成するものであり、前記吸収体を含む吸収性物品に好適に用いられる。
[含水ゲル粒子の製造工程(工程1)]
還流冷却器、滴下ロート、窒素ガス導入管、並びに、攪拌機として、翼径5cmの4枚傾斜パドル翼を2段で有する攪拌翼を備えた内径11cm、2L容の丸底円筒型セパラブルフラスコを準備した。このフラスコに、炭化水素分散媒としてn-ヘプタン293gをとり、高分子系分散剤として無水マレイン酸変性エチレン・プロピレン共重合体(三井化学株式会社、ハイワックス1105A)0.736gを添加し、攪拌しつつ80℃まで昇温して分散剤を溶解した後、50℃まで冷却した。一方、内容積300mLのビーカーに、水溶性エチレン性不飽和単量体として80.5質量%のアクリル酸水溶液92.0g(1.03モル)をとり、氷水で冷却しつつ、20.9質量%の水酸化ナトリウム水溶液147.7gを滴下して75モル%の中和を行った後、水溶性ラジカル重合剤として過硫酸カリウム0.0736g(0.272ミリモル)、内部架橋剤としてエチレングリコールジグリシジルエーテル0.010g(0.057ミリモル)を加えて溶解し、第1段目の水性液を調製した。そして、上記にて調製した水性液をセパラブルフラスコに添加して、10分間攪拌した後、20mL-バイアル瓶中において、n-ヘプタン6.62gに界面活性剤としてHLB3のショ糖ステアリン酸エステル(三菱化学フーズ株式会社、リョートーシュガーエステルS-370)0.736gを加熱溶解した界面活性剤溶液を、さらに添加して、撹拌機の回転数を500rpmとして攪拌しながら系内を窒素で十分に置換した後、フラスコを70℃の水浴に浸漬して昇温し、重合を60分間行うことにより、第1段目の重合スラリー液を得た。
前記含水ゲル粒子を得た後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら175.1gの水を系外へ抜き出した(第1の含水率調整工程)。その後、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gを撹拌下で添加した。このとき、前記エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であった。続いて、20質量%の亜硫酸ナトリウム水溶液2.21gを撹拌下で添加した。このとき、前記亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は64質量%であった。続いて、0.2質量%のL(+)-アスコルビン酸水溶液2.21gを撹拌下で添加した。このとき、前記L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は65質量%であった。
その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、84.7gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。その後、n-ヘプタンを125℃にて蒸発させて乾燥させ、さらに目開き850μmの篩に通過させることで、吸水性樹脂粒子225.7gを得た。
得られた吸水性樹脂粒子100質量部に対して0.5質量部の非晶質シリカ (オリエンタルシリカズコーポレーション、トクシールNP-S)を混合することによって吸水性樹脂粒子(1)226.8gを得た。吸水性樹脂粒子(1)の生理食塩水吸水量は65g/g、生理食塩水保水量は43g/g、4.14kPa荷重下での生理食塩水吸水量は14mL/gであった。
実施例1において、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gを用いなかったこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、84.7gから80.3gに変更したこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(2)224.0gを得た。なお、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は63質量%であった。吸水性樹脂粒子(2)の生理食塩水吸水量は62g/g、生理食塩水保水量は42g/g、4.14kPa荷重下での生理食塩水吸水量は18mL/gであった。
実施例1において、20質量%の亜硫酸ナトリウム水溶液を用いなかったこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、84.7gから83.0gに変更したこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(3)225.5gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は64質量%であった。吸水性樹脂粒子(3)の生理食塩水吸水量は61g/g、生理食塩水保水量は37g/g、4.14kPa荷重下での生理食塩水吸水量は18mL/gであった。
実施例1において、0.1質量%のL(+)-アスコルビン酸水溶液を用いなかったこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、84.7gから82.5gに変更したこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(4)224.8gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は64質量%であった。吸水性樹脂粒子(4)の生理食塩水吸水量は73g/g、生理食塩水保水量は42g/g、4.14kPa荷重下での生理食塩水吸水量は16mL/gであった。
実施例1において、第1の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、175.1gから253.8gに変更したこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、84.7gから6.1gに変更したこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(5)221.4gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は26質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は28質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は29質量%であった。吸水性樹脂粒子(5)の生理食塩水吸水量は59g/g、生理食塩水保水量は36g/g、4.14kPa荷重下での生理食塩水吸水量は23mL/gであった。
実施例1において、第1の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、175.1gから223.2gに変更したこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、84.7gから36.7gに変更したこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(6)223.8gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は40質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は42質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は43質量%であった。吸水性樹脂粒子(6)の生理食塩水吸水量は66g/g、生理食塩水保水量は43g/g、4.14kPa荷重下での生理食塩水吸水量は12mL/gであった。
実施例1において、第1の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、175.1gから157.6gに変更したこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、84.7gから102.2gに変更したこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(7)225.1gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は70質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は72質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は73質量%であった。吸水性樹脂粒子(7)の生理食塩水吸水量は64g/g、生理食塩水保水量は42g/g、4.14kPa荷重下での生理食塩水吸水量は12mL/gであった。
実施例1において、第1の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、175.1gから135.8gに変更したこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、84.7gから124.1gに変更したこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(8)223.8gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は80質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は82質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は83質量%であった。吸水性樹脂粒子(8)の生理食塩水吸水量は67g/g、生理食塩水保水量は46g/g、4.14kPa荷重下での生理食塩水吸水量は12mL/gであった。
[含水ゲル粒子の製造工程(工程1)]
実施例1の[含水ゲル粒子の製造工程]と同様の操作を行い、含水ゲル粒子を得た。
前記含水ゲル粒子を得た後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら135.8gの水を系外へ抜き出した(第1の含水率調整工程)。その後、20質量%の亜硫酸ナトリウム水溶液2.21gを撹拌下で添加した。このとき、前記亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は80質量%であった。その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、89.2gの水を系外へ抜き出した(第2の含水率調整工程)。その後、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gを撹拌下で添加した。このとき、前記エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は40質量%であった。続いて、0.2質量%のL(+)-アスコルビン酸水溶液2.21gを撹拌下で添加した。このとき、前記L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は42質量%であった。
その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、34.9gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。その後、n-ヘプタンを125℃にて蒸発させて乾燥させ、さらに目開き850μmの篩に通過させることで、吸水性樹脂粒子221.1gを得た。
実施例1の[吸水性樹脂粒子への添加剤添加工程]と同様の操作を行い、吸水性樹脂粒子(9)222.2gを得た。吸水性樹脂粒子(9)の生理食塩水吸水量は65g/g、生理食塩水保水量は43g/g、4.14kPa荷重下での生理食塩水吸水量は14mL/gであった。
[含水ゲル粒子の製造工程(工程1)]
実施例1の[含水ゲル粒子の製造工程]と同様の操作を行い、含水ゲル粒子を得た。
前記含水ゲル粒子を得た後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら135.8gの水を系外へ抜き出した(第1の含水率調整工程)。その後、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gを撹拌下で添加した。このとき、前記エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は80質量%であった。その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、91.8gの水を系外へ抜き出した(第2の含水率調整工程)。その後、20質量%の亜硫酸ナトリウム水溶液2.21gを撹拌下で添加した。このとき、前記亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は40質量%であった。続いて、0.2質量%のL(+)-アスコルビン酸水溶液2.21gを撹拌下で添加した。このとき、前記L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は41質量%であった。
その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、32.3gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。その後、n-ヘプタンを125℃にて蒸発させて乾燥させ、さらに目開き850μmの篩に通過させることで、吸水性樹脂粒子222.7gを得た。
実施例1の[吸水性樹脂粒子への添加剤添加工程]と同様の操作を行い、吸水性樹脂粒子(10)223.8gを得た。吸水性樹脂粒子(10)の生理食塩水吸水量は65g/g、生理食塩水保水量は41g/g、4.14kPa荷重下での生理食塩水吸水量は20mL/gであった。
[含水ゲル粒子の製造工程(工程1)]
実施例1の[含水ゲル粒子の製造工程]と同様の操作を行い、含水ゲル粒子を得た。
前記含水ゲル粒子を得た後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら135.8gの水を系外へ抜き出した(第1の含水率調整工程)。その後、0.2質量%のL(+)-アスコルビン酸水溶液2.21gを撹拌下で添加した。このとき、前記L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は80質量%であった。その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、89.6gの水を系外へ抜き出した(第2の含水率調整工程)。その後、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gを撹拌下で添加した。このとき、前記エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は40質量%であった。続いて、20質量%の亜硫酸ナトリウム水溶液2.21gを撹拌下で添加した。このとき、前記亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は42質量%であった。
その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、34.5gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。その後、n-ヘプタンを125℃にて蒸発させて乾燥させ、さらに目開き850μmの篩に通過させることで、吸水性樹脂粒子223.7gを得た。
実施例1の[吸水性樹脂粒子への添加剤添加工程]と同様の操作を行い、吸水性樹脂粒子(11)224.8gを得た。吸水性樹脂粒子(11)の生理食塩水吸水量は59g/g、生理食塩水保水量は39g/g、4.14kPa荷重下での生理食塩水吸水量は17mL/gであった。
[含水ゲル粒子の製造工程(工程1)]
実施例1の[含水ゲル粒子の製造工程]と同様の操作を行い、含水ゲル粒子を得た。
前記含水ゲル粒子を得た後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら251.5gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。その後、n-ヘプタンを125℃にて蒸発させて乾燥させ、さらに目開き850μmの篩に通過させることで、吸水性樹脂粒子217.6gを得た。
前記[表面架橋工程]で得られた吸水性樹脂粒子100質量部に対して、ジエチレントリアミン5酢酸(DTPA・5H)0.7質量部、亜硫酸ナトリウム2質量部、及び、L(+)-アスコルビン酸0.02質量部を粉体のまま添加し、明和工業株式会社製クロスロータリー混合機を用いて、30分間(条件、公転回転数50rpm、自転回転数50rpm)混合して混合物を得た。さらに、得られた前記混合物100質量部に対して0.5質量部の非晶質シリカ(オリエンタルシリカズコーポレーション、トクシールNP-S)を混合することによって吸水性樹脂粒子(12)を得た。吸水性樹脂粒子(12)の生理食塩水吸水量は60g/g、生理食塩水保水量は42g/g、4.14kPa荷重下での生理食塩水吸水量は14mL/gであった。
[含水ゲル粒子の製造工程(工程1)]
実施例1の[含水ゲル粒子の製造工程]と同様の操作を行い、含水ゲル粒子を得た。
前記含水ゲル粒子を得た後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら251.5gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。その後、n-ヘプタンを125℃にて蒸発させて乾燥させ、さらに目開き850μmの篩に通過させることで、吸水性樹脂粒子226.8gを得た。
フッ素樹脂製の碇型撹拌翼を備えた内径11cmの丸底円筒型セパラブルフラスコに、前記[表面架橋工程]で得られた吸水性樹脂粒子20gを量りとった。次に、300rpmで撹拌しながら、1.0質量%のジエチレントリアミン5酢酸・5ナトリウム(DTPA・5Na)水溶液0.2gをパスツールピペットにてセパラブルフラスコ内に滴下し、10分間攪拌することによって混合物を得た。この混合物を100℃で30分間加熱した後、加熱後の混合物100質量部に対して、亜硫酸ナトリウム0.2質量部、及び、L(+)-アスコルビン酸0.002質量部を粉体のまま添加し、明和工業株式会社製クロスロータリー混合機を用いて、30分間(条件、公転回転数50rpm、自転回転数50rpm)混合して混合物を得た。さらに、得られた前記混合物100質量部に対して0.5質量部の非晶質シリカ(オリエンタルシリカズコーポレーション、トクシールNP-S)を混合することによって吸水性樹脂粒子を得た。吸水性樹脂粒子の生理食塩水吸水量は58g/g、生理食塩水保水量は40g/g、4.14kPa荷重下での生理食塩水吸水量は21mL/gであった。
比較例7において、1.0質量%のジエチレントリアミン5酢酸・5ナトリウム(DTPA・5Na)水溶液0.2gのかわりに、1.0質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム(EDDS・3Na)水溶液0.2gを用いたこと以外は比較例7と同様の操作を行い、吸水性樹脂粒子(14)218.8gを得た。吸水性樹脂粒子(14)の生理食塩水吸水量は56g/g、生理食塩水保水量は39g/g、4.14kPa荷重下での生理食塩水吸水量は23mL/gであった。
実施例1において、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gのかわりに、0.5質量%のジエチレントリアミン5酢酸・5ナトリウム(DTPA・5Na)水溶液4.42gを用いたこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(15)225.6gを得た。なお、ジエチレントリアミン5酢酸・5ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は64質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は65質量%であった。吸水性樹脂粒子(15)の生理食塩水吸水量は58g/g、生理食塩水保水量は39g/g、4.14kPa荷重下での生理食塩水吸水量は14mL/gであった。
実施例1において、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gのかわりに、0.5質量%のエチレンジアミンテトラメチレンホスホン酸(EDTMP・8H)水溶液4.42gを用いたこと以外は実施例1と同様の操作を行い、吸水性樹脂粒子(16)224.6gを得た。なお、エチレンジアミンテトラメチレンホスホン酸水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は64質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は65質量%であった。吸水性樹脂粒子(16)の生理食塩水吸水量は61g/g、生理食塩水保水量は37g/g、4.14kPa荷重下での生理食塩水吸水量は18mL/gであった。
[含水ゲル粒子の製造工程(工程1)]
実施例1の[含水ゲル粒子の製造工程]と同様の操作を行い、含水ゲル粒子を得た。
前記含水ゲル粒子を得た後、125℃に設定した油浴にフラスコを浸漬し、n-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら175.1gの水を系外へ抜き出した(第1の含水率調整工程)。その後、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gを撹拌下で添加した。このとき、前記エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であった。その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、15.3gの水を系外へ抜き出した(第2の含水率調整工程)。その後、20質量%の亜硫酸ナトリウム水溶液2.21gを撹拌下で添加した。このとき、前記亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は57質量%であった。その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、12.7gの水を系外へ抜き出した(第3の含水率調整工程)。続いて、0.2質量%のL(+)-アスコルビン酸水溶液2.21gを撹拌下で添加した。このとき、前記L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は52質量%であった。
その後、再びn-ヘプタンと水との共沸蒸留により、n-ヘプタンを還流しながら、56.7gの水を系外へ抜き出した。その後、フラスコに表面架橋剤として2質量%のエチレングリコールジグリシジルエーテル水溶液4.42g(0.507ミリモル)を添加し、83℃で2時間保持した。その後、n-ヘプタンを125℃にて蒸発させて乾燥させ、さらに目開き850μmの篩に通過させることで、吸水性樹脂粒子219.7gを得た。
実施例1の[吸水性樹脂粒子への添加剤添加工程]と同様の操作を行い、吸水性樹脂粒子(17)220.8gを得た。吸水性樹脂粒子(17)の生理食塩水吸水量は64g/g、生理食塩水保水量は42g/g、4.14kPa荷重下での生理食塩水吸水量は16mL/gであった。
実施例9において、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gのかわりに、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液8.83gを用いたこと、及び、第2の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、15.3gから19.7gに変更したこと以外は実施例9と同様の操作を行い、吸水性樹脂粒子(18)225.7gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は57質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は52質量%であった。吸水性樹脂粒子(18)の生理食塩水吸水量は64g/g、生理食塩水保水量は40g/g、4.14kPa荷重下での生理食塩水吸水量は11mL/gであった。
実施例9において、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液4.42gのかわりに、0.5質量%のエチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液2.21gを用いたこと、及び、第2の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、15.3gから13.1gに変更したこと以外は実施例9と同様の操作を行い、吸水性樹脂粒子(19)223.4gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は57質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は52質量%であった。吸水性樹脂粒子(19)の生理食塩水吸水量は62g/g、生理食塩水保水量は46g/g、4.14kPa荷重下での生理食塩水吸水量は10mL/gであった。
実施例9において、20質量%の亜硫酸ナトリウム水溶液2.21gのかわりに、20質量%の亜硫酸ナトリウム水溶液3.31gを用いたこと、及び、第3の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、12.7gから13.6gに変更したこと以外は実施例9と同様の操作を行い、吸水性樹脂粒子(20)223.8gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は57質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は52質量%であった。吸水性樹脂粒子(20)の生理食塩水吸水量は67g/g、生理食塩水保水量は50g/g、4.14kPa荷重下での生理食塩水吸水量は8mL/gであった。
実施例9において、20質量%の亜硫酸ナトリウム水溶液2.21gのかわりに、20質量%の亜硫酸ナトリウム水溶液1.10gを用いたこと、及び、第3の含水率調整工程においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、12.7gから11.8gに変更したこと以外は実施例9と同様の操作を行い、吸水性樹脂粒子(21)224.6gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は57質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は52質量%であった。吸水性樹脂粒子(21)の生理食塩水吸水量は65g/g、生理食塩水保水量は45g/g、4.14kPa荷重下での生理食塩水吸水量は11mL/gであった。
実施例9において、0.2質量%のL(+)-アスコルビン酸水溶液2.21gのかわりに、0.2質量%のL(+)-アスコルビン酸水溶液11.0gを用いたこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、56.7gから65.5gに変更したこと以外は実施例9と同様の操作を行い、吸水性樹脂粒子(22)226.8gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は57質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は52質量%であった。吸水性樹脂粒子(22)の生理食塩水吸水量は62g/g、生理食塩水保水量は45g/g、4.14kPa荷重下での生理食塩水吸水量は22mL/gであった。
実施例9において、0.2質量%のL(+)-アスコルビン酸水溶液2.21gのかわりに、0.2質量%のL(+)-アスコルビン酸水溶液1.10gを用いたこと、及び、[表面架橋工程]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出す水の量を、56.7gから55.6gに変更したこと以外は実施例9と同様の操作を行い、吸水性樹脂粒子(23)224.0gを得た。なお、エチレンジアミン-N,N’-ジコハク酸・3ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は62質量%であり、亜硫酸ナトリウム水溶液を添加する際の含水ゲル粒子の含水率は57質量%であり、L(+)-アスコルビン酸水溶液を添加する際の含水ゲル粒子の含水率は52質量%であった。吸水性樹脂粒子(23)の生理食塩水吸水量は66g/g、生理食塩水保水量は46g/g、4.14kPa荷重下での生理食塩水吸水量は10mL/gであった。
含水ゲル粒子の含水率は、以下のように算出した。[含水ゲル粒子の製造工程(工程1)]において含水ゲル粒子の製造に用いた水性液に含まれる水量W1(g)、[含水ゲル粒子への添加剤添加工程(工程2)]において系内に加えた添加剤水溶液に含まれる水量W2(g)、[含水ゲル粒子への添加剤添加工程(工程2)]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出した水量W3(g)、[表面架橋工程(工程3)]においてn-ヘプタンと水との共沸蒸留により系外へ抜き出した水量W4(g)、及び、[含水ゲル粒子の製造工程(工程1)]において含水ゲル粒子の製造に用いた水性液に含まれる水溶性エチレン性不飽和単量体量M1(g)を用いて、以下の式により算出した。
含水ゲル粒子の含水率(質量%)=(W1+W2-W3-W4)×100/M1
500mL容のビーカーに、0.9質量%塩化ナトリウム水溶液(生理食塩水)500gを量り取り、3cmのスターラーバー(リング無)で600rpmで撹拌させながら、吸水性樹脂粒子2.0gをママコが発生しないように分散させた。撹拌させた状態で60分間放置し、吸水性樹脂粒子を十分に膨潤させた。その後、あらかじめ目開き75μm標準篩の質量Wa(g)を測定しておき、これを用いて、上記ビーカーの内容物をろ過し、篩を水平に対して約30度の傾斜角となるように傾けた状態で、30分間放置することにより余剰の水分をろ別した。膨潤ゲルの入った篩の質量Wb(g)を測定し、以下の式により、生理食塩水吸水能を算出した。
生理食塩水吸水量(g/g)=[Wb-Wa]/2.0
吸水性樹脂粒子2.0gを量り取った綿袋(メンブロード60番、横100mm×縦200mm)を500mL容のビーカー内に設置した。吸水性樹脂粒子の入った綿袋中に0.9質量%塩化ナトリウム水溶液(生理食塩水)500gをママコができないように一度に注ぎ込み、綿袋の上部を輪ゴムで縛り、30分静置させることで吸水性樹脂粒子を膨潤させた。30分経過後の綿袋を、遠心力が167Gとなるよう設定した脱水機(株式会社コクサン製、品番:H-122)を用いて1分間脱水し、脱水後の膨潤ゲルを含んだ綿袋の質量Wd(g)を測定した。吸水性樹脂粒子を添加せずに同様の操作を行い、綿袋の湿潤時の空質量We(g)を測定し、以下の式から生理食塩水保水量を算出した。
生理食塩水保水量(g/g)=[Wd-We]/2.0
4.14kPa荷重下での生理食塩水吸水量(荷重下吸水量)は、図1に概略を示す測定装置を用いて測定した。測定は、1種の吸水性樹脂粒子について2回行い、平均値を求めた。測定装置は、ビュレット部1、クランプ3、導管5、架台11、測定台13、及び測定台13上に置かれた測定部4を備えている。ビュレット部1は、目盛が記載されたビュレット管21と、ビュレット管21の上部の開口を密栓するゴム栓23と、ビュレット管21の下部の先端に連結されたコック22と、ビュレット管21の下部に連結された空気導入管25及びコック24とを有する。ビュレット部1はクランプ3で固定されている。平板状の測定台13は、その中央部に形成された直径2mmの貫通孔13aを有しており、高さが可変の架台11によって支持されている。測定台13の貫通孔13aとビュレット部1のコック22とが導管5によって連結されている。導管5の内径は6mmである。
4.14kPa荷重下の生理食塩水吸水能(mL/g)=Wc(mL)/吸水性樹脂粒子の質量(g)
吸水性樹脂粒子2.0gを、予め恒量(W1(g))としたアルミホイルケース(8号)に入れ、アルミホイルケースの口を軽く閉じ、この試料入りアルミホイルケースの合計質量W2(g)を精秤した。上述した試料入りアルミホイルケースを、内温を105℃に設定した熱風乾燥機(ADVANTEC社製、型式:FV-320)で2時間乾燥させた。乾燥後の試料入りアルミホイルケースをデシケーター中で室温まで放冷した。放冷後の試料入りアルミホイルケースの合計質量W3(g)を測定した。以下の式から、試料の乾燥減量を算出した。
乾燥減量[質量%]=[{(W2-W1)-(W3-W1)}/(W2-W1)]×100
吸水性樹脂粒子2.0gを、内径3cmのガラス製測定容器に入れ、その吸水性樹脂粒子の黄色度を、標準用白板で測色色差計の三刺激値である、X、Y、Zを補正した色差計(Color Meter ZE6000,日本電色工業株式会社製)で測定し、得られた吸水性樹脂粒子のX,Y,Z(三刺激値)から、下記式により黄色度を算出して初期値とした。
人工尿を用いて、吸水性樹脂粒子が吸水したゲル(膨潤ゲル)の試験を行った。
以下の組成の人工尿を調製した。
尿素:20.0g
塩化ナトリウム:8.0g
塩化カルシウム二水和物:0.3g
硫酸マグネシウム七水和物:0.8g
L(+)-アスコルビン酸:0.2g
イオン交換水:970.9g
内容積100mLのビーカーに、上記人工尿39.0gを量り取り、マグネチックスターラーバー(8mmφ×30mm、リング無し)を投入し、マグネチックスターラー(iuchi社製:HS-30D)の上に配置し、マグネチックスターラーバーを600rpmで回転させた。次に、吸水性樹脂粒子1.00gを攪拌中のビーカー内に投入し、回転渦が消えて液面が水平になるまで攪拌を行い、測定試料となる膨潤ゲルを調製した。膨潤ゲルを調製した直後に、膨潤ゲルの入ったビーカーをラップ(三菱ケミカル株式会社製、ダイアラップ)で覆った。
各温度及び静止時間後におけるゲル強度は、それぞれ、図2に示す測定原理を有する装置を用いて測定した。図2に示す装置は、支持部50a、可動台板60、可動台板60を駆動するための駆動部70、及び測定部80から構成される。支持部50aにおいて、支柱台51に立てられた支柱52の上部に架台53が固定されている。支柱52には、上下に移動するように可動台板60が取り付けられている。可動台板60は、測定試料(ゲル)61を搭載することができる。架台53上にはパルスモーター71が搭載され、プーリー72を回転させることによって、ワイヤー73を介して可動台板60を上下に移動する。測定部80において、変形により生ずる歪みを計測するためのロードセル81に、精密スプリング82及び連継軸83を介してディスク付き感圧軸84が取り付けられている。ディスク付き感圧軸84は、先端にディスクを有する。測定条件により、ディスクの直径は変更することができる。ディスク付き感圧軸84の上部には重り90を搭載することができる。ゲル強度を測定する装置の作動原理は、次のとおりである。精密スプリング82を、上方のロードセル81(応力検出器)に固定し、下方にはディスク付き感圧軸84を連結して所定の重り90を乗せて垂直に懸吊してある。測定試料61を乗せた可動台板60は、パルスモーター71の回転により一定速度で上昇する。精密スプリング82を介して測定試料61に定速荷重を加え、変形により生ずる歪みをロードセル81で計測し、硬さを測定演算するものである。ゲル強度値(N/m2)は、Curdmeter-MAX(飛鳥機器製、品番:ME-500)を用いて、ディスク付き感圧軸84のディスク16mmφ、荷重400g、スピード7秒/インチ、粘稠モード設定で、下記の(ゲル強度の初期値)、及び(37℃で14時間静置後のゲル強度)の温度及び静置時間の条件でそれぞれ測定を行った。
ラップで覆われた膨潤ゲルが入ったビーカーを、温度25±2℃、相対湿度50±10%の環境下で60分間静置した後に、膨潤ゲルが入ったビーカーからラップを外し、上述の方法によりゲル強度を測定した。この時のゲル強度の値をゲル強度(初期値)とした。
ラップで覆われた膨潤ゲルが入ったビーカーを、温度37±2℃、相対湿度60±10%に設定した恒温恒湿機(エスペック株式会社製、LHU-113)内で14時間静置した後に、膨潤ゲルが入ったビーカーからラップを外し、上述の方法によりゲル強度を測定した。この時のゲル強度の値をゲル強度(14時間値)とした。
3 クランプ
4 測定部
5 導管
10a 吸水性樹脂粒子
11 架台
13 測定台
13a 貫通孔
21 ビュレット管
22 コック
23 ゴム栓
24 コック
25 空気導入管
31 円筒
32 ポリアミドメッシュ
33 重り
50 食塩水
50a 支持部
51 支柱台
52 支柱
53 架台
60 可動台板
61 測定試料
70 駆動部
71 パルスモーター
72 プーリー
73 ワイヤー
80 測定部
81 ロードセル
82 精密スプリング
83 連継軸
84 ディスク付き感圧軸
90 重り
Claims (10)
- 水溶性エチレン性不飽和単量体を重合し、含水ゲル粒子を得る工程1と、
前記含水ゲル粒子に対して、キレート剤、亜硫酸塩系化合物及び有機酸化防止剤を添加する工程2と、
前記含水ゲル粒子に対して、表面架橋処理を施す工程3と、
をこの順に備え、
前記工程2において、前記亜硫酸塩系化合物を添加する際の前記含水ゲル粒子の含水率が、20質量%以上75質量%以下である、吸水性樹脂粒子の製造方法。 - 前記工程2は、前記含水ゲル粒子の含水率を調整する工程をさらに含む、請求項1に記載の吸水性樹脂粒子の製造方法。
- 前記工程2において、前記キレート剤を添加する際の前記含水ゲル粒子の含水率が、20質量%以上である、請求項1又は2に記載の吸水性樹脂粒子の製造方法。
- 前記工程2において、前記有機酸化防止剤を添加する際の前記含水ゲル粒子の含水率が、20質量%以上である、請求項1又は2に記載の吸水性樹脂粒子の製造方法。
- 前記工程2において、前記亜硫酸塩系化合物の添加量が、前記水溶性エチレン性不飽和単量体100質量部に対して、0.001質量部以上3.0質量部以下である、請求項1又は2に記載の吸水性樹脂粒子の製造方法。
- 前記工程2において、前記キレート剤の添加量が、前記水溶性エチレン性不飽和単量体100質量部に対して、0.001質量部以上2.0質量部以下である、請求項1又は2に記載の吸水性樹脂粒子の製造方法。
- 前記工程2において、前記有機酸化防止剤の添加量が、前記亜硫酸塩系化合物100質量部に対して、0.1質量部以上20質量部以下である、請求項1又は2に記載の吸水性樹脂粒子の製造方法。
- 生理食塩水吸水量が40~70g/gであり、
70℃、90%相対湿度の環境下で14日間放置した後の黄色度が40未満であり、
37℃、60%相対湿度の環境下で14時間放置した後のゲル強度が5500N/m2以上である、吸水性樹脂粒子。 - 請求項8に記載の吸水性樹脂粒子を含んでなる、吸収体。
- 請求項9に記載の吸収体を含んでなる、吸収性物品。
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020257003392A KR20250078427A (ko) | 2022-09-29 | 2023-09-27 | 흡수성 수지 입자의 제조 방법 |
| CN202380058155.8A CN119677785A (zh) | 2022-09-29 | 2023-09-27 | 吸水性树脂颗粒的制造方法 |
| EP23872480.1A EP4600273A1 (en) | 2022-09-29 | 2023-09-27 | Method for producing water absorbent resin particles |
| JP2024550426A JPWO2024071258A1 (ja) | 2022-09-29 | 2023-09-27 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-156300 | 2022-09-29 | ||
| JP2022156300 | 2022-09-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024071258A1 true WO2024071258A1 (ja) | 2024-04-04 |
Family
ID=90478085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2023/035291 Ceased WO2024071258A1 (ja) | 2022-09-29 | 2023-09-27 | 吸水性樹脂粒子の製造方法 |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP4600273A1 (ja) |
| JP (1) | JPWO2024071258A1 (ja) |
| KR (1) | KR20250078427A (ja) |
| CN (1) | CN119677785A (ja) |
| TW (1) | TW202424065A (ja) |
| WO (1) | WO2024071258A1 (ja) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005029751A (ja) | 2003-07-11 | 2005-02-03 | Sumitomo Seika Chem Co Ltd | 吸水性樹脂組成物 |
| WO2011040530A1 (ja) * | 2009-09-30 | 2011-04-07 | 株式会社日本触媒 | 粒子状吸水剤及びその製造方法 |
| JP2018131558A (ja) * | 2017-02-16 | 2018-08-23 | Sdpグローバル株式会社 | 吸水性樹脂粒子及びその製造方法 |
| WO2021006178A1 (ja) * | 2019-07-05 | 2021-01-14 | 住友精化株式会社 | 粒子状吸水性樹脂組成物 |
-
2023
- 2023-09-27 JP JP2024550426A patent/JPWO2024071258A1/ja active Pending
- 2023-09-27 WO PCT/JP2023/035291 patent/WO2024071258A1/ja not_active Ceased
- 2023-09-27 CN CN202380058155.8A patent/CN119677785A/zh active Pending
- 2023-09-27 KR KR1020257003392A patent/KR20250078427A/ko active Pending
- 2023-09-27 EP EP23872480.1A patent/EP4600273A1/en active Pending
- 2023-09-28 TW TW112137381A patent/TW202424065A/zh unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005029751A (ja) | 2003-07-11 | 2005-02-03 | Sumitomo Seika Chem Co Ltd | 吸水性樹脂組成物 |
| WO2011040530A1 (ja) * | 2009-09-30 | 2011-04-07 | 株式会社日本触媒 | 粒子状吸水剤及びその製造方法 |
| JP2018131558A (ja) * | 2017-02-16 | 2018-08-23 | Sdpグローバル株式会社 | 吸水性樹脂粒子及びその製造方法 |
| WO2021006178A1 (ja) * | 2019-07-05 | 2021-01-14 | 住友精化株式会社 | 粒子状吸水性樹脂組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202424065A (zh) | 2024-06-16 |
| JPWO2024071258A1 (ja) | 2024-04-04 |
| CN119677785A (zh) | 2025-03-21 |
| EP4600273A1 (en) | 2025-08-13 |
| KR20250078427A (ko) | 2025-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3896096B1 (en) | Water absorbent resin particles | |
| WO2012144564A1 (ja) | 吸水性樹脂、吸収体及び吸収性物品 | |
| JPWO2018180864A1 (ja) | 吸水性樹脂 | |
| WO2018159802A1 (ja) | 吸水性樹脂及び吸収性物品 | |
| EP4501447A1 (en) | Water-absorbing resin composition, production method therefor, absorber, and absorbent article | |
| EP3936529A1 (en) | Water absorbent resin particles, absorber and absorbent article | |
| JP2021058771A (ja) | 吸水性樹脂粒子、吸収性物品、吸水性樹脂粒子を製造する方法、及び吸収体の加圧下での吸収量を高める方法 | |
| WO2024214752A1 (ja) | 吸水性樹脂粒子の製造方法、吸水性樹脂粒子、吸収体及び吸収性物品 | |
| WO2024071258A1 (ja) | 吸水性樹脂粒子の製造方法 | |
| KR20240089202A (ko) | 흡수성 수지 조성물, 흡수체, 흡수성 물품, 및 흡수성 물품으로부터의 흡수성 수지 입자의 분리 처리 방법 | |
| JP6752319B2 (ja) | 吸水性樹脂粒子 | |
| WO2025004971A1 (ja) | 吸水性樹脂粒子の製造方法、吸水性樹脂粒子、吸収体及び吸収性物品 | |
| JP7769631B2 (ja) | 吸水性樹脂、吸収体及び吸収性物品 | |
| US20250222433A1 (en) | Method for producing water-absorbing resin composition | |
| EP4480462A1 (en) | Water absorbent resin particles and absorbent article | |
| EP4186930A1 (en) | Water-absorbing resin composition, absorbent, and absorptive article | |
| WO2025164341A1 (ja) | 吸水性樹脂粒子の製造方法、及び吸水性樹脂粒子 | |
| WO2025204970A1 (ja) | 吸水性樹脂粒子の製造方法 | |
| CN121399195A (en) | Method for producing water-absorbent resin particles, absorber, and absorbent article | |
| JP2025117644A (ja) | 吸水性樹脂粒子を製造する方法 | |
| WO2023074862A1 (ja) | 吸水性樹脂組成物、吸収体、及び吸収性物品 | |
| WO2022255300A1 (ja) | 吸水性樹脂の製造方法、吸水性樹脂、吸収体及び吸収性物品 | |
| TW202333636A (zh) | 吸水性樹脂組成物、吸收體及吸收性物品 | |
| WO2024176759A1 (ja) | 吸水性樹脂組成物 | |
| WO2022210678A1 (ja) | 吸水性樹脂、吸収体及び吸収性物品 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23872480 Country of ref document: EP Kind code of ref document: A1 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 202380058155.8 Country of ref document: CN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 202517015000 Country of ref document: IN |
|
| WWP | Wipo information: published in national office |
Ref document number: 202380058155.8 Country of ref document: CN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2024550426 Country of ref document: JP |
|
| WWP | Wipo information: published in national office |
Ref document number: 202517015000 Country of ref document: IN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2023872480 Country of ref document: EP |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2023872480 Country of ref document: EP Effective date: 20250429 |
|
| WWP | Wipo information: published in national office |
Ref document number: 1020257003392 Country of ref document: KR |
|
| WWP | Wipo information: published in national office |
Ref document number: 2023872480 Country of ref document: EP |