WO2012081355A1 - 吸水性樹脂の製造方法 - Google Patents
吸水性樹脂の製造方法 Download PDFInfo
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- WO2012081355A1 WO2012081355A1 PCT/JP2011/076555 JP2011076555W WO2012081355A1 WO 2012081355 A1 WO2012081355 A1 WO 2012081355A1 JP 2011076555 W JP2011076555 W JP 2011076555W WO 2012081355 A1 WO2012081355 A1 WO 2012081355A1
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- absorbent resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3028—Granulating, agglomerating or aggregating
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- 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
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
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- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/14—Organic medium
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- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
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- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- 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
- C08F2/32—Polymerisation in water-in-oil emulsions
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
Definitions
- the present invention relates to a method for producing a water absorbent resin. More specifically, the present invention relates to a method for producing a water-absorbent resin with little coloration due to high-temperature treatment, less fine powder and coarse powder, and a narrow particle size distribution.
- Water-absorbing resins are widely used in various fields such as sanitary materials such as paper diapers and sanitary products, horticultural materials such as water retention agents and soil conditioners, and water-proofing materials and industrial materials such as anti-condensation agents.
- water-absorbing resin examples include starch-acrylonitrile graft copolymer hydrolyzate, starch-acrylic acid graft copolymer neutralized product, vinyl acetate-acrylic ester copolymer saponified product, acrylic resin, and the like.
- Cross-linked products of acid partial neutralized polymers are known.
- water-absorbent resin used in absorbent articles such as sanitary materials
- the water-absorbent resin when the water-absorbent resin is compounded with white pulverized pulp in the absorbent body, it gives a clean feeling and does not give a feeling of foreign matter due to coloring.
- the water-absorbing resin is required to be white.
- the liquid diffusibility generally tends to decrease as the proportion of fine powder in the water absorbent resin increases. That is, when the fine powder in the water-absorbent resin swells by absorbing bodily fluids or the like, it tends to block the passage for the bodily fluids to diffuse, and so-called “gel blocking” is likely to occur. Since the absorbent that has caused gel blocking has poor liquid diffusibility, the performance of the original absorbent is not fully exhibited, and the amount of liquid reversion increases.
- the thinned absorber has a small content of hydrophilic fibers and a large proportion of the water-absorbent resin, so when using a water-absorbent resin with a large proportion of coarse powder, the absorber is very rugged. Thus, the flexibility is greatly impaired.
- the water-absorbent resin used in the thinned absorbent body excellent in absorption performance and tactile sensation is preferably a water-absorbent resin having a small amount of fine powder and coarse powder and a narrow particle size distribution.
- a production method by aqueous solution polymerization, reverse phase suspension polymerization or the like is known.
- a method for obtaining a water absorbent resin see Patent Document 1
- a method for obtaining a functional resin has been proposed.
- the water-absorbent resin of Patent Document 1 is treated at a high temperature in the drying step or the post-crosslinking step, the entire water-absorbent resin is colored with a surfactant necessary for reverse phase suspension polymerization, and a clean feeling is required. Problems have arisen when used as absorbent articles such as sanitary materials. Further, in Patent Document 2, the amount of fine powder or coarse powder is relatively large, the particle size distribution is wide, and it is not satisfactory as a water-absorbing resin used for a thinned absorbent body excellent in absorption performance and touch. .
- the main object of the present invention is to provide a method for producing a water-absorbing resin with little coloration due to high-temperature treatment, less fine powder and coarse powder, and a narrow particle size distribution.
- the present inventor has performed reverse-phase suspension polymerization using a sucrose fatty acid ester having a specific ester distribution as a surfactant, thereby allowing coloring due to high-temperature treatment. It has been found that a water-absorbent resin with a small amount of fine powder and coarse powder and a narrow particle size distribution can be obtained.
- the present invention has been completed based on such findings, and widely includes the following aspects.
- Item 1 A method for producing a water absorbent resin, (1) Step 1 for producing a slurry in which primary particles are dispersed by reverse-phase suspension polymerization of a water-soluble ethylenically unsaturated monomer in a petroleum hydrocarbon dispersion medium in which a surfactant is dissolved, and (2) ) After cooling the slurry obtained in step 1 to precipitate a part of the surfactant, the water-soluble ethylenically unsaturated monomer is polymerized in the slurry to aggregate the primary particles.
- a sucrose fatty acid comprising the step 2 of making the water-absorbent resin, wherein the surfactant contains a monoester body of 25% by mass or less, a tetraester body of 10% by mass or more, and a tetra or more ester body of 30% by mass or less.
- the petroleum hydrocarbon dispersion medium is selected from the group consisting of maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer, oxidized polyethylene, and ethylene / acrylic acid copolymer.
- Item 2 The method for producing a water-absorbent resin according to Item 1, further comprising at least one polymer dispersant.
- Item 3 The method for producing a water-absorbent resin according to Item 1 or 2, wherein the water-soluble ethylenically unsaturated monomer is at least one selected from the group consisting of (meth) acrylic acid and salts thereof.
- Item 4 A water-absorbent resin obtained by the production method according to any one of Items 1 to 3, wherein the yellowness of heat-resistant coloring is 20 or less.
- Item 5 The production method according to any one of Items 1 to 3, wherein in the particle size distribution, the water-absorbing resin exceeding 850 ⁇ m is 5% by mass or less and the water-absorbing resin having a particle size of 180 ⁇ m or less is 10% by mass or less. Water-absorbing resin obtained.
- a water-absorbent resin with less coloration due to high-temperature treatment, less fine powder and coarse powder, and a narrow particle size distribution is provided.
- the method for producing a water absorbent resin according to the present invention is a method including the following steps 1 and 2.
- Step 2 After cooling the slurry obtained in step 1 to precipitate a part of the surfactant, the water-soluble ethylenically unsaturated monomer is polymerized in the slurry to obtain the primary particles.
- Step 1 is a method in which a water-soluble ethylenically unsaturated monomer is subjected to reverse phase suspension polymerization in a petroleum hydrocarbon dispersion medium in which a surfactant is dissolved, and primary particles are dispersed. This is a step of producing a slurry to be performed.
- the surfactant used in Step 1 is a sucrose fatty acid ester containing a monoester body of 25 mass% or less, a tetraester body of 10 mass% or more, and a tetra or higher ester body of 30 mass% or less.
- the surfactant used in step 1 is a sucrose fatty acid ester obtained by ester-linking sucrose and a fatty acid, and the sucrose fatty acid ester is a monoester, diester, triester, tetraester, or pentaester. Body, hexaester body, heptaester body, and octaester body.
- the content ratio of the mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, and octa-esters in the sucrose fatty acid ester can be calculated using general gel permeation chromatography or the like.
- tetra or higher means tetra, penta, hexa, hepta, and octa
- tetra or higher ester is 30% by mass means that it is included in the sucrose fatty acid ester used as a surfactant.
- the ratio of the total amount of tetra, penta, hexa, hepta, and octaester bodies in the sucrose fatty acid ester is expressed in mass%.
- sucrose fatty acid ester used in the present invention is a mixture of compounds in which any of mono-, di-, tri-, tetra-, penta-, hexa-, and octa-ester fatty acids is ester-bonded to sucrose.
- the monoester body has the highest hydrophilicity, so it is presumed that it tends to exist on the surface of the water absorbent resin obtained by the production method according to the present invention.
- the method for producing a water-absorbent resin according to the present invention includes a treatment under a high temperature condition such as a post-crosslinking step and a drying step as necessary, as will be described later.
- a high temperature condition such as a post-crosslinking step and a drying step as necessary, as will be described later.
- the main subject of the present invention is to provide a production method for obtaining a water-absorbing resin with little coloring. Therefore, it is necessary that the monoester body of sucrose fatty acid ester does not exist as much as possible on the surface of the water absorbent resin.
- the surfactant used in step 1 is a sucrose fatty acid ester containing a monoester in an amount of 25% by mass or less, a water-absorbing resin with little coloring caused by the high-temperature treatment as described above can be obtained. Since it is presumed that the monoester body is most likely to be present on the surface of the water-absorbent resin, it is preferable to use a sucrose fatty acid ester containing no monoester body in the present invention. Contains not less than a monoester, and usually contains 0.1% by mass or more of a monoester.
- sucrose fatty acid ester containing 10% by mass or more of a tetraester body and 30% by mass or less of an ester body of tetra or more as a surfactant, there is little fine powder and coarse powder, and the water absorption is narrow. A resin is obtained.
- the sucrose fatty acid ester used as the surfactant in step 1 is a mixture of compounds in which fatty acids are ester-bonded to hydroxyl groups of sucrose as described above.
- the fatty acid is not particularly limited, and examples thereof include fatty acids having 12 to 22 carbon atoms.
- fatty acids include palmitic acid, stearic acid, oleic acid and the like.
- sucrose fatty acid ester of the present invention the same fatty acid may be ester-bonded to the hydroxyl group in the sucrose molecule, or different fatty acids may be ester-bonded.
- the amount of the sucrose fatty acid ester used as the surfactant is not particularly limited, but may be usually 0.05 to 5 parts by mass with respect to 100 parts by mass of the water-soluble ethylenically unsaturated monomer, for example.
- the amount is preferably 0.1 to 3 parts by mass.
- a petroleum hydrocarbon dispersion medium is used as a dispersion medium in the reverse phase suspension polymerization.
- a petroleum hydrocarbon dispersion medium is not particularly limited.
- aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, and ligroin; cyclopentane, methylcyclopentane, cyclohexane, Examples thereof include alicyclic hydrocarbons such as methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene.
- These petroleum hydrocarbon dispersion media may be used alone or in combination of two or more.
- n-hexane, n-heptane, cyclohexane and the like are preferably used as the petroleum hydrocarbon dispersion medium from the viewpoint of industrial availability, stable quality, and low cost.
- commercially available Exol heptane (ExxonMobil Corp .: containing 75 to 85% of heptane and isomer hydrocarbons) is preferably used as an example of the mixture of the above petroleum hydrocarbon dispersion medium. .
- the amount of the petroleum hydrocarbon dispersion medium used is not particularly limited, but from the viewpoint of easily removing the heat of polymerization and controlling the reaction temperature of the reverse phase suspension polymerization, the water-soluble ethylenically unsaturated monomer is added in an amount of 100 parts by mass. On the other hand, the amount is usually 50 to 600 parts by mass, and more preferably 100 to 550 parts by mass.
- water in an amount of 10 to 200 parts by mass may be used with respect to 100 parts by mass of the petroleum hydrocarbon dispersion medium.
- the amount of water used is good for industrial production and is preferably 10 parts by mass or more from an economically preferable viewpoint, making the dispersion state of the water-soluble unsaturated monomer good, and having a small proportion of coarse powder. From the viewpoint of obtaining a resin, 200 parts by mass or less is preferable.
- the water-soluble ethylenically unsaturated monomer used in step 1 is not particularly limited.
- (meth) acrylic acid in this specification, “acrylic” and “methacrylic” are combined to form “(meta ) Acrylic ”), its salt; 2- (meth) acrylamide-2-methylpropanesulfonic acid, its salt; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2-hydroxyethyl (meth) )
- Nonionic monomers such as acrylate, N-methylol (meth) acrylamide, polyethylene glycol mono (meth) acrylate; N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, diethylamino Amino group-containing unsaturated monomers such as propyl (meth) acrylamide, Grade product, and the like.
- acrylic acid, acrylate, methacrylic acid, methacrylate, acrylamide, methacrylamide, N, N-dimethylacrylamide, etc. are water-soluble ethylenically unsaturated monomers from the viewpoint of industrial availability. It is preferable to use it. More preferred are acrylic acid, acrylate, methacrylic acid, methacrylate and the like.
- the water-soluble ethylenically unsaturated monomer described above may be used as an aqueous solution from the viewpoint of increasing the dispersion efficiency in the petroleum hydrocarbon dispersion medium during reverse phase suspension polymerization.
- concentration of the monomer in such an aqueous solution is not particularly limited, but is usually 20% by mass or more and a saturated concentration or less, and preferably 25 to 70% by mass. More preferably, it is 30 to 55% by mass.
- the acid group is preliminarily alkaline if necessary. You may use what was neutralized with the summing agent.
- an alkaline neutralizing agent is not particularly limited, and examples thereof include alkali metal salt ammonia such as sodium hydroxide and potassium hydroxide.
- these alkaline neutralizers may be used in the form of an aqueous solution from the viewpoint of simplifying the neutralization operation.
- the above alkaline neutralizing agents may be used alone or in combination of two or more.
- the degree of neutralization of all acid groups of the water-soluble ethylenically unsaturated monomer by the alkaline neutralizing agent is not particularly limited, but the absorption capacity is increased by increasing the osmotic pressure of the resulting water-absorbent resin, and surplus From the viewpoint of preventing problems in safety and the like due to the presence of the alkaline neutralizing agent, it is usually in the range of 10 to 100 mol%, more preferably in the range of 30 to 80 mol%.
- a polymer chain in the primary particles formed by polymerization of the monomer using a crosslinking agent as necessary is performed. It may be cross-linked.
- a crosslinking agent hereinafter referred to as an internal crosslinking agent
- an internal crosslinking agent is not particularly limited, but a compound having two or more polymerizable unsaturated groups is used.
- (poly) ethylene glycol in this specification, for example, “polyethylene glycol” and “ethylene glycol” are collectively referred to as “(poly) ethylene glycol”), (poly) propylene glycol, Di- or tri (meth) acrylic acid esters of polyols such as methylolpropane, glycerin polyoxyethylene glycol, polyoxypropylene glycol, (poly) glycerin; and the aforementioned polyols and unsaturated acids such as maleic acid and fumaric acid Unsaturated polyesters obtained by reaction; bisacrylamides such as N, N′-methylenebis (meth) acrylamide; di- or tri (meth) acrylates obtained by reacting polyepoxide with (meth) acrylic acid ; Tolylene diisocyanate, f Di (meth) acrylic acid carbamyl esters obtained by reacting polyisocyanate such as samethylene diisocyanate with hydroxyethyl (meth)
- a compound having two or more other reactive functional groups can be used.
- glycidyl group-containing compounds such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether; (poly) ethylene glycol, (poly) propylene glycol, (poly) glycerin , Pentaerythritol, ethylenediamine, polyethyleneimine, glycidyl (meth) acrylate and the like.
- These internal crosslinking agents may be used alone or in combination of two or more.
- Etc. are preferably used as the internal crosslinking agent.
- the internal cross-linking agent may be used by adding it to the dispersion medium, but it is preferable to use it by adding it to the above-mentioned monomer from the viewpoint of more effectively exerting the effect of the internal cross-linking agent.
- the use amount of the internal cross-linking agent is preferably 0 to 1 mol% with respect to the total amount of monomers used in Step 1 from the viewpoint of sufficiently enhancing the absorption performance of the water-absorbing resin obtained, It is more preferable to set it to ⁇ 0.5 mol%.
- a polymeric dispersant may be used together with the sucrose fatty acid ester described above.
- a polymeric dispersant is not particularly limited, and for example, 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, ethylene / maleic anhydride copolymer, ethylene / propylene / maleic anhydride copolymer, butadiene / maleic anhydride copolymer, oxidized polyethylene, ethylene / Examples include acrylic acid copolymer, ethyl cellulose, and ethyl hydroxyethyl cellulose. These polymer dispersants may be used alone or in combination of two or more.
- maleic anhydride-modified polyethylene maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene / propylene copolymer are used. It is preferable to use a polymer, oxidized polyethylene, an ethylene / acrylic acid copolymer or the like as the polymer dispersant.
- the amount of the polymer dispersant used is a process from the viewpoint of maintaining a good dispersion state of the water-soluble ethylenically unsaturated monomer in the above-mentioned petroleum hydrocarbon dispersion medium and obtaining a dispersion effect commensurate with the amount used.
- the amount of the monomer used in 1 is usually 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer.
- the amount is preferably 0.2 to 3 parts by mass.
- radical polymerization initiators are not particularly limited, but persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t- Peroxides such as butyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, hydrogen peroxide; 2,2′- Azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (N-phenylamidino) propane] dihydrochloride, 2,2′-azobis [2- (N-allylamino) propane] 2 Hydroch
- the amount of radical polymerization initiator used is usually 0.005 to 1 mol% based on the total amount of monomers used in Step 1. From the viewpoint of preventing the polymerization reaction from taking a long time, 0.005 mol% or more is preferable, and from the viewpoint of preventing a rapid polymerization reaction, 1 mol% or less is preferable.
- the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, L-ascorbic acid or the like.
- a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, L-ascorbic acid or the like.
- a chain transfer agent may be used from the viewpoint of controlling the absorption performance of the water absorbent resin obtained by the production method according to the present invention.
- chain transfer agents include hypophosphites, thiols, thiolic acids, secondary alcohols, amines and the like.
- the polymerization reaction temperature in the reverse-phase suspension polymerization method in Step 1 varies depending on the radical polymerization initiator used, but is usually 20 to 110 ° C., preferably 40 to 90 ° C. From the viewpoint of preventing the polymerization rate from being slow and increasing the polymerization time, 20 ° C. or higher is preferable, and from the viewpoint of removing polymerization heat and performing a smooth polymerization reaction, 110 ° C. or lower is preferable.
- the completion of the polymerization reaction can be confirmed based on the phenomenon that the polymerization reaction temperature reaches the highest point and starts to decrease.
- the reaction time may be 0.1 to 4 hours.
- Step 2 according to the production method of the present invention comprises cooling the slurry obtained in Step 1 to precipitate a part of the surfactant, and then water-soluble ethylenically unsaturated monomer in the slurry. Polymerizing the body to agglomerate the primary particles into a water absorbent resin.
- step 2 the water-soluble ethylenically unsaturated monomer added to the slurry obtained in step 1 is absorbed by the primary particles dispersed in the slurry, and the primary is dispersed along with the polymerization of the monomer.
- the particles aggregate to form a water absorbent resin.
- this step includes a step of precipitating a part of the surfactant dissolved in the slurry by cooling the slurry obtained in step 1.
- the method for precipitating a part of the surfactant in the reaction system in the above step 2 is not particularly limited.
- a method of cooling the slurry in which the primary particles obtained in Step 1 are dispersed to precipitate a part of the surfactant before adding the water-soluble ethylenically unsaturated monomer, A method of cooling the slurry in which the primary particles obtained in Step 1 are dispersed to precipitate a part of the surfactant;
- a water-soluble ethylenically unsaturated monomer cooled in advance is added to the slurry in which the primary particles obtained in Step 1 are dispersed, and a part of the surfactant is cooled while cooling the reaction system in Step 2.
- a water-absorbing resin may be produced by performing a polymerization reaction and aggregating the primary particles.
- the degree of precipitation of the surfactant by the above method is not particularly limited, and can be confirmed by turbidity, visual observation or the like.
- the step 2 according to the production method of the present invention includes: (Step 2-A) After cooling the slurry obtained in Step 1 to precipitate a part of the surfactant, a water-soluble ethylenically unsaturated monomer is added to the slurry, and then the slurry In the process, the water-soluble ethylenically unsaturated monomer is polymerized, and the primary particles are aggregated to form a water-absorbent resin.
- the step 2 according to the production method of the present invention includes (Step 2-B) A pre-cooled water-soluble ethylenically unsaturated monomer is added to the slurry obtained in Step 1 to precipitate a part of the surfactant, and then the water-soluble component is added to the slurry. This is a step of polymerizing an ethylenic monomer to agglomerate the primary particles to form a water absorbent resin.
- the step 2 according to the production method of the present invention includes: (Step 2-C) After adding the water-soluble ethylenically unsaturated monomer to Step 1, it is cooled to precipitate a part of the surfactant, and then the water-soluble ethylenic monomer is added to the slurry. This is a step of polymerizing and agglomerating the primary particles to form a water-absorbent resin.
- the temperature at which a part of the surfactant is precipitated is preferably 5 to 40 ° C., more preferably 10 to 30 ° C.
- a temperature of 5 ° C. or higher is preferable.
- 40 degreeC or less is preferable from a viewpoint which prevents that an ethylenically unsaturated monomer diffuses excessively in the said slurry, and obtains a water-absorbing resin with few fine powders.
- step 2 the water-soluble ethylenically unsaturated monomer added to the cooled slurry is a specific monomer type, a neutralization treatment applied as necessary, or a monomer used as an aqueous solution.
- the same concentration as that described in detail in step 1 may be used.
- the amount of the water-soluble ethylenically unsaturated monomer used in Step 2 is 100 parts by mass of the water-soluble ethylenically unsaturated monomer used in Step 1 from the viewpoint of obtaining a moderately aggregated water absorbent resin.
- the amount may be 50 to 300 parts by mass.
- the amount is preferably 100 to 200 parts by mass, and more preferably 120 to 160 parts by mass.
- step 2 the polymerization reaction in step 2 is usually performed using a radical polymerization initiator, and the specific radical polymerization initiator is appropriately selected from those exemplified in step 1 described above, and the above step 1 It may be used according to the amount of the monomer used in step 2 in the same manner as described above.
- step 2 an internal cross-linking agent, a chain transfer agent, a reducing agent and the like may be used as necessary.
- the step is appropriately selected from those exemplified in step 1 above, and in step 2 as in step 1 It may be used according to the amount of monomer used.
- the reaction temperature of the polymerization reaction in step 2 is usually 20 to 110 ° C., although it varies depending on the radical polymerization initiator used.
- the temperature is preferably 40 to 90 ° C.
- the completion of the polymerization reaction in step 2 can also be confirmed based on the phenomenon that the polymerization reaction temperature reaches the highest point and starts to decrease.
- the reaction time may be 0.1 to 4 hours.
- Aggregates of primary particles that are the water-absorbent resin obtained by the above step 2 are also obtained in a slurry state. Therefore, for the purpose of improving the productivity, a water-soluble ethylenically unsaturated monomer is further added to the slurry obtained in Step 2, and the third stage as in the reverse phase suspension polymerization shown in Step 2 above. It is good also as what is obtained by performing multistage reverse phase suspension polymerization which repeats the polymerization reaction after the 1st, and is a water absorbing resin.
- the aggregate of primary particles to be the water-absorbent resin of the present invention is in a gel state containing water, and is obtained in the state of a slurry dispersed in a petroleum hydrocarbon dispersion medium.
- water and petroleum-based hydrocarbon dispersion medium may be removed from the slurry. Specifically, heating the slurry or evaporating and removing the dispersion medium in a reduced pressure environment, removing the dispersion medium using decantation, removing the dispersion medium using a filter, etc. And a method of removing the dispersion medium by distillation and the like. Among them, it is preferable to distill a slurry containing an aggregate of primary particles to be a water absorbent resin to remove water and a petroleum hydrocarbon dispersion medium to obtain the water absorbent resin of the present invention.
- a post-crosslinking step using a post-crosslinking agent may be performed on the water absorbent resin.
- Examples of the post-crosslinking agent used in the post-crosslinking step include compounds having two or more reactive functional groups. Examples thereof include compounds containing diglycidyl groups such as (poly) ethylene glycol diglycidyl ether, (poly) glycerol (poly) glycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether; (poly) Polyols such as ethylene glycol, (poly) propylene glycol, (poly) glycerin, oxetane compounds such as 3-methyl-3-oxetanemethanol, 3-methyl-3-oxetaneethanol, 3-ethyl-3-oxetaneethanol; penta Erythritol; ethylenediamine; polyethyleneimine and the like. These post-crosslinking agents may be used alone or in combination of two or more.
- (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, and the like are suitably used as the post-crosslinking agent.
- the amount of the post-crosslinking agent used is the monomer used in step 1 and step 2 from the viewpoint of enhancing various performances without increasing the absorption capacity of the resulting water-absorbent resin and increasing the cross-linking density near the surface.
- the content may be in the range of 0.005 to 1 mol%, and preferably in the range of 0.01 to 0.5 mol%.
- the post-crosslinking step using the post-crosslinking agent may be performed after completion of the polymerization reaction in step 2, and is not particularly limited.
- the amount of water in the aggregate of primary particles obtained as the water absorbent resin obtained in step 2 may be added, preferably 5 to 200 parts by mass. . More preferably, it is 10 to 100 parts by mass.
- the post-crosslinking step using the post-crosslinking agent is performed according to the amount of water contained in the aggregates of the primary particles to be the water-absorbent resin, so that the surface of the water-absorbent resin is more suitably cross-linked.
- a water-absorbing resin having excellent absorption performance can be obtained.
- the method for adjusting the amount of water contained in the aggregate of primary particles used as the water absorbent resin is not particularly limited.
- the aggregate of primary particles that becomes the water absorbent resin obtained in step 2 is used.
- the post-crosslinking agent used in the post-crosslinking step may be added as it is or as an aqueous solution, but may be added after being dissolved in a hydrophilic organic solvent as necessary.
- a hydrophilic organic solvent is not particularly limited, and examples thereof include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; diethyl ether , Dioxane, and ethers such as tetrahydrofuran; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide.
- These hydrophilic organic solvents may be used alone or in combination of two or more. Alternatively, it may be used as a mixed solvent with water.
- the reaction temperature in the post-crosslinking step is usually 60 ° C. or higher, preferably 70 to 200 ° C. More preferably, it is 80 to 150 ° C.
- the reaction temperature is usually 60 ° C. or higher, preferably 70 to 200 ° C. More preferably, it is 80 to 150 ° C.
- the post-crosslinking reaction time varies depending on the reaction temperature, the type of post-crosslinking agent and the amount of the cross-linker used, and cannot be determined unconditionally. However, it is usually 1 to 300 minutes, preferably 5 to 200. is minutes.
- the water-absorbing resin may be isolated by removing the water and petroleum hydrocarbon dispersion medium described above and then subjected to a drying step.
- the method in a drying process is not specifically limited, For example, heat drying, reduced pressure drying, etc. may be adopted.
- the reaction temperature in the post-crosslinking step described above may be adopted as the temperature in heat drying.
- the time required for drying is not particularly limited, and is usually 1 to 300 minutes. Preferably it is 5 to 200 minutes.
- the water-absorbent resin produced using the above-mentioned method is treated at a high temperature by a post-crosslinking step, a drying step, and attachment to a production apparatus such as a dryer included in the water-absorbent resin production process. May be colored. In the present invention, this degree of coloring is defined as “heat-resistant coloring yellowness”. The yellowness of the heat resistant colorability can be measured by the method shown in the following examples.
- the heat-resistant coloration yellowness exceeds 20, it is recognized that it is clearly colored visually, and it is evaluated that the heat-resistant colorability is poor.
- the aesthetics are greatly impaired and the value as a product is significantly reduced. Since the water-resistant resin obtained by the production method according to the present invention has a heat resistant coloration yellowness of 20 or less, preferably 15 or less, it can be suitably used as an absorbent material for sanitary materials and the like.
- the particle size distribution of the water-absorbent resin obtained by the production method according to the present invention is 5% by mass or less for the water-absorbent resin exceeding 850 ⁇ m and 10% by mass or less for the water-absorbent resin of 180 ⁇ m or less. Moreover, it is preferable that the water absorbing resin of more than 250 ⁇ m and 500 ⁇ m or less is 60% by mass or more.
- the particle size distribution of such a water absorbent resin can be measured by the method shown in the following examples.
- the median particle diameter of the water-absorbent resin suitable for the absorbent body and the absorbent article using it is preferably 200 to 500 ⁇ m, more preferably 250 to 450 ⁇ m.
- the water-absorbent resin obtained by the production method according to the present invention satisfies the above numerical range and is suitably used for water-absorbent articles.
- the median particle diameter of such a water absorbent resin can be measured by the method shown in the following examples.
- the water-absorbent resin obtained by the production method using sucrose fatty acid ester as the surfactant is in a state where the sucrose fatty acid ester is attached to the surface.
- sucrose fatty acid ester tends to be colored and the entire water-absorbent resin tends to be colored.
- the sucrose fatty acid ester used as the surfactant in the step 1 according to the production method of the present invention is obtained by esterifying a fatty acid such as stearic acid to the eight hydroxyl groups of sucrose as described above.
- a fatty acid such as stearic acid
- the influence of the monoester is large, and the influence is reduced as the degree of ester substitution with di, tri, tetra, penta is increased.
- the ester distribution of the monoester body exceeds 25% by mass, the water-absorbent resin is likely to be colored by high-temperature treatment, and the heat-resistant coloring yellowness tends to exceed 20.
- Step 2 when the surfactant is precipitated in the slurry in which the primary particles obtained in Step 1 are dispersed, there is almost no surface active action by the surfactant. Therefore, the particle diameter of the primary particles is increased.
- the surfactant when the surfactant is dissolved without precipitating, the water-soluble ethylenically unsaturated monomer used in Step 2 is uniformly dispersed in the slurry. Absorbed evenly.
- the sucrose fatty acid ester which is a surfactant, varies in hydrophilicity and lipophilicity depending on the number of fatty acid ester substitutions.
- the temperature of the slurry in which the primary particles obtained in step 1 are dispersed is lowered in step 2 to thereby provide a surfactant.
- ester bodies such as mono-, di-, etc. having low lipophilicity are deposited.
- highly lipophilic esters such as penta and hexa are unlikely to precipitate, but on the other hand, they are less affected as surfactants due to their low hydrophilicity.
- the presence of a tetraester body having a balance between lipophilicity and hydrophilicity is important.
- the ester distribution of the tetraester is less than 10% by mass, the distribution of mono-, di-, etc. esters is increased, and the dispersion effect is reduced due to the precipitation of many surfactants in the slurry in step 2.
- the particle diameter of the primary particles is increased.
- the water-soluble ethylenically unsaturated monomer used in step 2 is absorbed unevenly by the primary particles, and the resulting water-absorbent resin tends to contain a large amount of coarse powder.
- the highly lipophilic ester such as penta and hexa has a small influence on dispersion stability compared to mono and di esters, but at least acts as a surfactant.
- the tetra- or higher ester is present in an amount exceeding 30% by mass, the water-soluble ethylenically unsaturated monomer used in Step 2 is excessive in the slurry in which the primary particles obtained in Step 1 are dispersed. Suspended. And the ester body more than tetra has high lipophilicity, and since it becomes difficult to be absorbed by the primary particle obtained at the process 1, it is estimated that the resulting water-absorbent resin tends to contain much fine powder.
- the heat-resistant coloring yellowness, median particle size, and particle size distribution of the water-absorbent resins obtained in each Example and Comparative Example were evaluated by the following methods.
- the particle size of the water-absorbent resin was defined as the median particle size and measured as follows.
- a lubricant 0.25 g of amorphous silica (Degussa Japan Co., Ltd., Sipernat 200) was mixed with 50 g of the water absorbent resin.
- JIS standard sieves were combined in the order of 850 ⁇ m sieve, 500 ⁇ m sieve, 400 ⁇ m sieve, 300 ⁇ m sieve, 250 ⁇ m sieve, 180 ⁇ m sieve, and pan.
- the above water-absorbing resin was put into the combined uppermost sieve and classified by shaking for 20 minutes using a low-tap shaker.
- the mass of the water-absorbent resin remaining on each sieve was calculated as a mass percentage with respect to the total amount, and the particle size distribution was determined from the value. Further, by integrating in order from the larger particle diameter, the relationship between the sieve opening and the integrated value of the mass percentage of the water absorbent resin remaining on the sieve was plotted on a logarithmic probability paper. By connecting the plots on the probability paper with a straight line, the particle diameter corresponding to an integrated mass percentage of 50 mass% was defined as the median particle diameter.
- the pressure was returned to normal pressure, 2.0 g (0.014 mol) of potassium carbonate was added, and the system was again depressurized to 70 mmHg and dehydrated for 10 minutes.
- Table 1 shows the ester distribution of sucrose fatty acid esters used in Examples and Comparative Examples.
- the ester distribution of each sucrose fatty acid ester was analyzed using gel permeation chromatography under the following analysis conditions.
- Example 1 A 2 L round bottom cylindrical separable flask equipped with a stirrer, a two-stage paddle blade, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was prepared. To this flask, 340 g of n-heptane was taken, and 0.92 g of sucrose stearate A (synthesis example) and 0.92 g of maleic anhydride-modified ethylene / propylene copolymer (Mitsui Chemicals, High Wax 1105A) were added. The mixture was heated to 80 ° C. with stirring to dissolve the surfactant, and then cooled to 50 ° C.
- Step 1 The whole amount of the monomer aqueous solution used in Step 1 above is added to the separable flask, and the inside of the system is sufficiently replaced with nitrogen, and then the flask is immersed in a 70 ° C. water bath and heated. Polymerization of No. 1 was performed for 30 minutes to obtain a slurry of Step 1.
- Step 1 The slurry of Step 1 is cooled to 22 ° C., the aqueous monomer solution used in Step 2 at the same temperature is added to the system, and the mixture is absorbed for 30 minutes.
- the flask was immersed in a 70 ° C. water bath to raise the temperature, and the polymerization in Step 2 was performed for 30 minutes.
- Step 2 After the polymerization in Step 2, the temperature of the polymerization reaction solution is raised in an oil bath at 120 ° C., and water and n-heptane are removed by distillation, followed by drying for 30 minutes, whereby the water absorbent resin 229 in a form in which spherical particles are aggregated. 0.2 g was obtained. Table 2 shows the measurement results of each performance.
- Example 2 A 2 L round bottom cylindrical separable flask equipped with a stirrer, a two-stage paddle blade, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was prepared. 340 g of n-heptane was taken into this flask, and sucrose stearate ester B (mixed sucrose fatty acid ester A and Hangzhou Zuiho Chemical Co., Ltd., SE-370 at a mass ratio of 50:50). 92 g, 0.92 g of maleic anhydride-modified ethylene / propylene copolymer (Mitsui Chemicals, High Wax 1105A) was added, the temperature was raised to 80 ° C. with stirring, and the surfactant was dissolved. Until cooled.
- Step 1 The whole amount of the monomer aqueous solution used in Step 1 above is added to the separable flask, and the inside of the system is sufficiently replaced with nitrogen, and then the flask is immersed in a 70 ° C. water bath and heated. Polymerization of No. 1 was performed for 30 minutes to obtain a slurry of Step 1.
- the monomer aqueous solution used in Step 2 is added to the system so that the temperature of the slurry does not become 40 ° C. or less.
- the inside of the reaction system was cooled to 24 ° C., and a part of the surfactant was precipitated. In this state, stirring was performed for 30 minutes, and at the same time, the inside of the system was sufficiently replaced with nitrogen. Then, the temperature was raised and polymerization in Step 2 was performed for 30 minutes.
- Step 2 After polymerization in Step 2, the temperature of the polymerization reaction solution is raised in an oil bath at 120 ° C., water and n-heptane are removed by distillation, and then dried for 30 minutes, whereby the water absorbent resin 232 in the form of aggregated spherical particles is obtained. .3 g was obtained. Table 2 shows the measurement results of each performance.
- Example 3 A 2 L round bottom cylindrical separable flask equipped with a stirrer, a two-stage paddle blade, a reflux condenser, a dropping funnel and a nitrogen gas introduction tube was prepared. Into this flask, 340 g of n-heptane was taken, and sucrose stearate C (Mitsubishi Chemical Foods, Ryoto Sugar Ester S-270, Zhejiang Huawei Chemical Co., Ltd., S-30, mass ratio 50: 0.92 g), 0.92 g of maleic anhydride-modified ethylene / propylene copolymer (Mitsui Chemicals, High Wax 1105A) was added, and the mixture was heated to 80 ° C. with stirring and surface active. After dissolving the agent, it was cooled to 50 ° C.
- sucrose stearate C Mitsubishi Chemical Foods, Ryoto Sugar Ester S-270, Zhejiang Huawei Chemical Co., Ltd., S-30, mass ratio 50: 0.92 g
- Step 1 After adding the entire amount of the monomer aqueous solution used in Step 1 to the separable flask and sufficiently replacing the system with nitrogen, the flask is immersed in a 70 ° C. water bath and heated. Polymerization of No. 1 was performed for 30 minutes to obtain a slurry of Step 1.
- Step 1 The slurry in Step 1 is cooled to 35 ° C., and the cooled monomer aqueous solution used in Step 2 is added to the system, and the reaction system is finally adjusted to 18 ° C. A part of the activator was precipitated, and the mixture was stirred for 30 minutes, and at the same time, the system was sufficiently replaced with nitrogen. Then, the flask was again immersed in a 70 ° C. water bath and the temperature was raised. For 30 minutes.
- Step 2 After polymerization in Step 2, the temperature of the polymerization reaction solution was raised in an oil bath at 120 ° C., and 220 g of water was withdrawn out of the system while refluxing n-heptane by azeotropic distillation of n-heptane and water. 8.17 g (0.94 mmol) of a 2% by weight aqueous solution of glycol diglycidyl ether was added, and a post-crosslinking reaction was performed at 80 ° C. for 2 hours. Thereafter, the temperature of the polymerization reaction solution was raised in a 120 ° C. oil bath to evaporate n-heptane, followed by drying for 30 minutes to obtain 228.7 g of a water-absorbing resin in the form of aggregated spherical particles. Table 2 shows the measurement results of each performance.
- Example 4 In Example 3, the sucrose fatty acid ester C to be used was mixed with sucrose fatty acid ester D (sucrose fatty acid ester A in the synthesis example and S-30, manufactured by Zhejiang Hao Chemical Co., Ltd.) at a mass ratio of 50:50. Except that the temperature in the reaction system for precipitating the surfactant was adjusted to 25 ° C., and the same operation as in Example 3 was performed to obtain a water absorbent resin 231.8 in the form of aggregated spherical particles. Obtained. Table 2 shows the measurement results of each performance.
- sucrose fatty acid ester A used was sucrose fatty acid ester E (sucrose fatty acid ester A in the synthesis example and DK ester F-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in a mass ratio of 50:50. Except that the slurry in Step 1 was cooled to 23 ° C., and the same operation as in Example 1 was performed to obtain 229.6 g of water absorbent resin in the form of aggregated spherical particles. Table 2 shows the measurement results of each performance.
- sucrose fatty acid ester B to be used was mixed with sucrose fatty acid ester F (sucrose fatty acid ester A of synthesis example and SE-370 manufactured by Hangzhou Zuiho Chemical Co., Ltd. at a mass ratio of 20:80. Except that the temperature in the reaction system for precipitating the surfactant was adjusted to 27 ° C., and the same operation as in Example 2 was performed to obtain 227.1 g of the water-absorbing resin in the form of aggregated spherical particles. Obtained. Table 2 shows the measurement results of each performance.
- Example 3 the sucrose fatty acid ester C used was sucrose fatty acid ester G (SE-370 manufactured by Hangzhou Zuiho Chemical Co., Ltd.), Ryoto Sugar Ester S-270 manufactured by Mitsubishi Chemical Foods Co., Ltd. The mixture was mixed at a ratio of 70:30) and the temperature in the reaction system for depositing the surfactant was adjusted to 25 ° C. 219.7 g of a water absorbent resin was obtained. Table 2 shows the measurement results of each performance.
- sucrose fatty acid ester C used was sucrose fatty acid ester H (sucrose fatty acid ester A in the synthesis example and Ryoto Sugar ester S-270, manufactured by Mitsubishi Chemical Foods Co., Ltd.) in a mass ratio of 50: 50) and the temperature in the reaction system for precipitating the surfactant was adjusted to 16 ° C., and the same operation as in Example 3 was performed, and the water-absorbent resin in the form of aggregated spherical particles 230.9 g was obtained.
- Table 2 shows the measurement results of each performance.
- Example 5 the sucrose fatty acid ester C used was sucrose fatty acid ester I (Daiichi Kogyo Seiyaku Co., Ltd., DK Ester F-50, Procter & Gamble Co., Ltd., SEFOSE-1618H). The mixture was changed to a mass ratio of 70:30 and the temperature in the reaction system for precipitating the surfactant was adjusted to 14 ° C., and the same operation as in Example 3 was performed, and the spherical particles were aggregated. 229.5 g of a water absorbent resin was obtained. Table 2 shows the measurement results of each performance.
- the water-absorbing resins of Examples 1 to 4 are water-absorbing resins with little coloration due to high-temperature treatment, less fine powder and coarse powder, and a narrow particle size distribution.
- the water-absorbent resin obtained by the production method according to the present invention is less colored by high-temperature treatment, has less fine powder and coarse powder, and has a narrow particle size distribution, so it is particularly suitable for sanitary materials such as sanitary products and paper diapers that have been made thinner. It can be preferably used.
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Abstract
Description
(1)界面活性剤が溶解した石油系炭化水素分散媒において、水溶性エチレン性不飽和単量体を逆相懸濁重合させ、1次粒子が分散するスラリーを作製する工程1、及び
(2)工程1にて得られるスラリーを冷却して前記界面活性剤の一部を析出させた後、該スラリー中において水溶性エチレン性不飽和単量体を重合させて、前記1次粒子を凝集させて吸水性樹脂とする工程2を含み、前記界面活性剤が、モノエステル体を25質量%以下、テトラエステル体を10質量%以上、及びテトラ以上のエステル体を30質量%以下含むショ糖脂肪酸エステルである吸水性樹脂の製造方法。
(1)界面活性剤が溶解した石油系炭化水素分散媒において、水溶性エチレン性不飽和単量体を逆相懸濁重合させ、1次粒子が分散するスラリーを作製する工程1。
(2)工程1にて得られるスラリーを冷却して前記界面活性剤の一部を析出させた後、該スラリー中において水溶性エチレン性不飽和単量体を重合させて、前記1次粒子を凝集させて吸水性樹脂とする工程2。
本発明の製造方法にかかる工程1は、界面活性剤が溶解した石油系炭化水素分散媒において、水溶性エチレン性不飽和単量体を逆相懸濁重合させ、1次粒子が分散するスラリーを作製する工程である。
本発明の製造方法にかかる工程2は、工程1にて得られるスラリーを冷却して前記界面活性剤の一部を析出させた後、該スラリー中において水溶性エチレン性不飽和単量体を重合させて、前記1次粒子を凝集させて吸水性樹脂とする工程である。
(i)水溶性エチレン性不飽和単量体を添加する前に、前記工程1において得られる1次粒子が分散したスラリーを冷却して界面活性剤の一部を析出させる方法、
(ii)予め冷却した水溶性エチレン性不飽和単量体を、前記工程1において得られる1次粒子が分散したスラリーに添加し、工程2における反応系内を冷却しながら界面活性剤の一部を析出させる方法、又は
(iii)工程1にて得られる界面活性剤が溶解するスラリーに、水溶性エチレン性不飽和単量体を添加した後、反応系内を冷却して界面活性剤の一部を析出させる方法、
等が挙げられる。
(工程2-A)工程1にて得られるスラリーを冷却して前記界面活性剤の一部を析出させた後に、該スラリーに水溶性エチレン性不飽和単量体を添加し、その後、該スラリー中において該水溶性エチレン性不飽和単量体を重合させ、前記1次粒子を凝集させて吸水性樹脂とする工程となる。
(工程2-B)工程1にて得られるスラリーに予め冷却した水溶性エチレン性不飽和単量体を添加して前記界面活性剤の一部を析出させた後に、該スラリー中において該水溶性エチレン性単量体を重合させ前記1次粒子を凝集させて吸水性樹脂とする工程となる。
(工程2-C)工程1に水溶性エチレン性不飽和単量体を添加した後に、冷却して前記界面活性剤の一部を析出させ、その後スラリー中において該水溶性エチレン性単量体を重合させ、前記1次粒子を凝集させて吸水性樹脂とする工程となる。
吸水性樹脂5gを、内径5cm、深さ1.4cmのガラスシャーレに均一の厚みになるように入れ、内温を140℃に設定した熱風乾燥機(ADVANTEC社製)中で4時間加熱した。サンプルをデシケータ中で放冷した後、内径3.1cm深さ1.3cmのガラス製測定容器に入れ、測色色差計ZE-2000(日本電色工業株式会社製)を用いて、三刺激値X、Y、Zを測定し、以下の式から、黄色度を算出した。
別に規定のない限り、吸水性樹脂の粒子径を中位粒子径として規定し、次のようにして測定した。吸水性樹脂50gに、滑剤として、0.25gの非晶質シリカ(デグサジャパン(株)、Sipernat200)を混合した。
攪拌機、温度計、減圧装置及び還流装置を備えた2Lフラスコに、ジメチルスルホキシド(以下、DMSOと表記)500mLを仕込み、90℃まで攪拌しながら加熱した。その中にショ糖154.0g(0.45モル)を添加して溶解させ、系内を70mmHgまで減圧にし、30分間脱水した。
装置:HLC-8120GPC(東ソー(株)製)
カラム:TSKgel SuperH2500(6.0mmID×15cm)×4本(東ソー(株)製)
検出器:RI検出器
溶離液:テトロヒドロフラン
流速:0.6ml/min
カラム温度:40℃
試料濃度:5mg/min
試料注入量:10μL
攪拌機、2段パドル翼、還流冷却器、滴下ロート及び窒素ガス導入管を備えた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n-ヘプタン340gをとり、ショ糖ステアリン酸エステルA(合成例)0.92g、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)、ハイワックス1105A)0.92gを添加し、撹拌しつつ80℃まで昇温して界面活性剤を溶解した後、50℃まで冷却した。
攪拌機、2段パドル翼、還流冷却器、滴下ロート及び窒素ガス導入管を備えた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n-ヘプタン340gをとり、ショ糖ステアリン酸エステルB(合成例のショ糖脂肪酸エステルAと杭州瑞霖化工有限公司製、SE-370を質量比率50:50で混合したもの)0.92g、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)、ハイワックス1105A)0.92gを添加し、撹拌しつつ80℃まで昇温して界面活性剤を溶解した後、50℃まで冷却した。
攪拌機、2段パドル翼、還流冷却器、滴下ロート及び窒素ガス導入管を備えた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n-ヘプタン340gをとり、ショ糖ステアリン酸エステルC(三菱化学フーズ(株)製、リョートーシュガーエステルS-270と、浙江迪耳化工有限公司製、S-30を質量比率50:50で混合したもの)0.92g、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)、ハイワックス1105A)0.92gを添加し、撹拌しつつ80℃まで昇温して界面活性剤を溶解した後、50℃まで冷却した。
実施例3において、使用するショ糖脂肪酸エステルCを、ショ糖脂肪酸エステルD(合成例のショ糖脂肪酸エステルAと、浙江迪耳化工有限公司製、S-30を質量比率50:50で混合したもの)に変更し、界面活性剤を析出させる反応系内の温度を25℃に調節した以外は、実施例3と同様の操作を行い、球状粒子が凝集した形態の吸水性樹脂231.8を得た。各性能の測定結果を表2に示す。
実施例1において、使用するショ糖脂肪酸エステルAを、ショ糖脂肪酸エステルE(合成例のショ糖脂肪酸エステルAと、第一工業製薬(株)製、DKエステルF-50を質量比率50:50で混合したもの)に変更し、工程1のスラリーを23℃に冷却した以外は、実施例1と同様の操作を行い、球状粒子が凝集した形態の吸水性樹脂229.6gを得た。各性能の測定結果を表2に示す。
実施例2において、使用するショ糖脂肪酸エステルBを、ショ糖脂肪酸エステルF(合成例のショ糖脂肪酸エステルAと、杭州瑞霖化工有限公司製、SE-370を質量比率20:80で混合したもの)に変更し、界面活性剤を析出させる反応系内の温度を27℃に調節した以外は、実施例2と同様の操作を行い、球状粒子が凝集した形態の吸水性樹脂227.1gを得た。各性能の測定結果を表2に示す。
実施例3において、使用するショ糖脂肪酸エステルCを、ショ糖脂肪酸エステルG(杭州瑞霖化工有限公司製、SE-370と、三菱化学フーズ(株)製、リョートーシュガーエステルS-270を質量比率70:30で混合したもの)に変更し、界面活性剤を析出させる反応系内の温度を25℃に調節した以外は、実施例3と同様の操作を行い、球状粒子が凝集した形態の吸水性樹脂219.7gを得た。各性能の測定結果を表2に示す。
実施例3において、使用するショ糖脂肪酸エステルCを、ショ糖脂肪酸エステルH(合成例のショ糖脂肪酸エステルAと、三菱化学フーズ(株)製、リョートーシュガーエステルS-270を質量比率50:50で混合したもの)に変更し、界面活性剤を析出させる反応系内の温度を16℃に調節した以外は、実施例3と同様の操作を行い、球状粒子が凝集した形態の吸水性樹脂230.9gを得た。各性能の測定結果を表2に示す。
実施例3において、使用するショ糖脂肪酸エステルCを、ショ糖脂肪酸エステルI(第一工業製薬(株)製、DKエステルF-50と、プロクター・アンド・ギャンブル(株)製、SEFOSE-1618Hを質量比率70:30で混合したもの)に変更し、界面活性剤を析出させる反応系内の温度を14℃に調節した以外は、実施例3と同様の操作を行い、球状粒子が凝集した形態の吸水性樹脂229.5gを得た。各性能の測定結果を表2に示す。
Claims (5)
- 吸水性樹脂の製造方法であって、
(1)界面活性剤が溶解した石油系炭化水素分散媒において、水溶性エチレン性不飽和単量体を逆相懸濁重合させ、1次粒子が分散するスラリーを作製する工程1、及び
(2)工程1にて得られるスラリーを冷却して前記界面活性剤の一部を析出させた後、該スラリー中において水溶性エチレン性不飽和単量体を重合させて、前記1次粒子を凝集させて吸水性樹脂とする工程2を含み、
前記界面活性剤が、モノエステル体を25質量%以下、テトラエステル体を10質量%以上、及びテトラ以上のエステル体を30質量%以下含むショ糖脂肪酸エステルである吸水性樹脂の製造方法。 - 石油系炭化水素分散媒に、無水マレイン酸変性ポリエチレン、無水マレイン酸変性ポリプロピレン、無水マレイン酸変性エチレン・プロピレン共重合体、酸化型ポリエチレン、及びエチレン・アクリル酸共重合体からなる群より選ばれた少なくとも1種の高分子系分散剤をさらに含む、請求項1に記載の吸水性樹脂の製造方法。
- 水溶性エチレン性不飽和単量体が、(メタ)アクリル酸、及びその塩からなる群より選ばれた少なくとも1種である、請求項1又は2に記載の吸水性樹脂の製造方法。
- 耐熱着色性の黄色度が20以下である請求項1~3のいずれか1項に記載の製造方法により得られる吸水性樹脂。
- 粒度分布において、850μmを超える吸水性樹脂が5質量%以下であり、かつ180μm以下の吸水性樹脂が10質量%以下である請求項1~3のいずれか1項に記載の製造方法により得られる吸水性樹脂。
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SG2013038682A SG190709A1 (en) | 2010-12-16 | 2011-11-17 | Method for producing water-absorbent resin |
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WO2013128978A1 (ja) * | 2012-02-29 | 2013-09-06 | 住友精化株式会社 | 吸水性樹脂粒子の製造方法 |
JP5719079B1 (ja) * | 2014-07-11 | 2015-05-13 | 住友精化株式会社 | 吸水性樹脂及び吸収性物品 |
WO2018149750A1 (en) | 2017-02-16 | 2018-08-23 | Basf Se | Water-swellable polymer particles |
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CN114787244A (zh) * | 2019-12-13 | 2022-07-22 | 住友精化株式会社 | 吸水性树脂粒子的制造方法及吸水性树脂粒子 |
CN111908578A (zh) * | 2020-07-20 | 2020-11-10 | 重庆工商大学 | 一种用于处理重金属废水的天然改性絮凝剂的制备方法 |
CN113145086B (zh) * | 2021-05-19 | 2022-04-22 | 万华化学集团股份有限公司 | 一种脂肪酸改性吸附树脂、制备方法和利用其处理阴离子表面活性剂废水的方法 |
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SA111330059B1 (ar) | 2014-08-04 |
EP2653483A1 (en) | 2013-10-23 |
KR20130129229A (ko) | 2013-11-27 |
SG190709A1 (en) | 2013-07-31 |
EP2653483A4 (en) | 2014-04-30 |
BR112013014656A2 (pt) | 2016-09-27 |
TWI534157B (zh) | 2016-05-21 |
CN103261235B (zh) | 2015-01-28 |
CN103261235A (zh) | 2013-08-21 |
US20130273351A1 (en) | 2013-10-17 |
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JPWO2012081355A1 (ja) | 2014-05-22 |
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