WO2022131837A1 - 고흡수성 수지 및 이의 제조 방법 - Google Patents
고흡수성 수지 및 이의 제조 방법 Download PDFInfo
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- WO2022131837A1 WO2022131837A1 PCT/KR2021/019247 KR2021019247W WO2022131837A1 WO 2022131837 A1 WO2022131837 A1 WO 2022131837A1 KR 2021019247 W KR2021019247 W KR 2021019247W WO 2022131837 A1 WO2022131837 A1 WO 2022131837A1
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- WIPO (PCT)
- Prior art keywords
- hydrophobic
- particles
- superabsorbent polymer
- polymer
- hydrophobic particles
- Prior art date
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- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
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- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical compound OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- MDSQKJDNWUMBQQ-UHFFFAOYSA-M sodium myreth sulfate Chemical compound [Na+].CCCCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O MDSQKJDNWUMBQQ-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
- 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
- C08J3/005—Processes for mixing polymers
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
Definitions
- the present invention relates to a super absorbent polymer and a method for preparing the same. More specifically, it relates to a superabsorbent polymer having a plurality of micropores and exhibiting an improved absorption rate and high surface tension, and a method for manufacturing the superabsorbent polymer capable of manufacturing the same.
- Super Absorbent Polymer is a synthetic polymer material that can absorb water 500 to 1,000 times its own weight. Material), etc., are named differently.
- the superabsorbent polymer as described above started to be put to practical use as a sanitary tool, and is now widely used as a soil repair agent for horticulture, water-retaining material for civil engineering and construction, a sheet for seedlings, a freshness maintenance agent in the food distribution field, and a material for poultice. .
- Such superabsorbent polymers are mainly used in the field of sanitary materials such as diapers and sanitary napkins.
- the superabsorbent polymer is generally included in a state spread in the pulp.
- efforts have been made to provide sanitary materials such as diapers having a thinner thickness, and as a part of that, the content of pulp is reduced or, further, so-called pulpless diapers such as diapers in which no pulp is used are used. Development is actively underway.
- the superabsorbent polymer used for sanitary materials such as pulp-free diapers with reduced pulp content or pulp-free diapers not only acts as an absorbent for absorbing liquids such as urine, but also plays a role of pulp. It is required to exhibit not only absorption performance but also a fast absorption rate.
- a method of improving a specific surface area by introducing a pore structure into the superabsorbent polymer is mainly used.
- a foaming agent may be used to generate bubbles or a gas such as carbon dioxide gas, air, or nitrogen gas may be injected.
- a gas such as carbon dioxide gas, air, or nitrogen gas
- the bubbles are unstable in the neutralization solution, if a bubble stabilizer capable of trapping these bubbles is not used, the bubbles come out of the neutralization solution, making it impossible to prepare a super absorbent polymer having a pore structure.
- the foam stabilizer is used in excess, there has been a problem in that general physical properties of the superabsorbent polymer are reduced.
- the present invention relates to a superabsorbent polymer resin having a developed porous structure including a large number of predetermined micropores and exhibiting an improved absorption rate and excellent physical properties such as high surface tension, and a method for manufacturing the same.
- a powder-type base resin comprising an acrylic acid-based monomer having an acidic group and at least a portion of the acidic group neutralized and a crosslinking polymer of an internal crosslinking agent;
- a superabsorbent polymer comprising a surface cross-linking layer formed on the base resin, wherein the cross-linked polymer is additionally cross-linked through a surface cross-linking agent,
- the superabsorbent polymer has an average of 7 or more pores per particle, and the plurality of pores have an average diameter of 100 ⁇ m or less, a maximum diameter of 300 ⁇ m or less, and a diameter greater than or equal to the average diameter and less than or equal to the maximum diameter.
- the particles having pores are 10 to 50% by number of the total superabsorbent polymer particles,
- the superabsorbent polymer has a surface tension of 65 mN/m or more and a vortex time at 24.0° C. of 40 seconds or less.
- step 1 preparing a monomer composition comprising an acrylic acid-based monomer having an acidic group and at least a portion of the acidic group neutralized, a polymerization initiator, an internal crosslinking agent, and an aqueous dispersion of hydrophobic particles (step 1);
- step 2 preparing a hydrogel polymer by cross-linking and polymerizing the monomer composition in the presence of a foaming agent or a bubble generator (step 2);
- step 3 drying and pulverizing the hydrogel polymer to form a powdery base resin
- step 4 In the presence of a surface crosslinking agent, further crosslinking the surface of the base resin to form a surface crosslinking layer (step 4),
- the aqueous dispersion of hydrophobic particles is a colloidal solution in which first and second hydrophobic particles are dispersed, and the ratio of the average particle diameter of the second hydrophobic particles to the average particle diameter of the first hydrophobic particles is 5 to 100,
- a method for preparing a super absorbent polymer is provided.
- the superabsorbent polymer of the present invention may have an average diameter of 100 ⁇ m or less and a large number of micropores having a maximum diameter of 300 ⁇ m or less. As a result, as the specific surface area of the superabsorbent polymer is greatly increased, an improved absorption rate may be exhibited.
- Such a superabsorbent polymer can be prepared by introducing two types of hydrophobic particles having different particle diameters in the form of an aqueous dispersion in the polymerization step. , since the use of a surfactant, which is usually used as a bubble stabilizer, is minimized or unnecessary, thereby reducing physical properties such as surface tension of the superabsorbent polymer can be minimized.
- a superabsorbent polymer which is preferably used for a pulp-free diaper or an ultra-thin diaper, etc., exhibiting excellent absorption rate and excellent other physical properties.
- polymer refers to a polymerized state of an acrylic acid-based monomer, which is a water-soluble ethylenically unsaturated monomer, and may cover all water content ranges or particle diameter ranges.
- a polymer having a water content (moisture content) of about 40% by weight or more in a state before drying after polymerization may be referred to as a hydrogel polymer, and particles in which the hydrogel polymer is pulverized and dried may be referred to as a crosslinked polymer. have.
- super absorbent polymer particle refers to a particulate material comprising an acidic group and a crosslinked polymer in which an acrylic acid-based monomer in which at least a portion of the acidic group is neutralized is polymerized and crosslinked by an internal crosslinking agent.
- crosslinked polymer refers to a polymer having a three-dimensional network structure in which main chains formed by polymerization of the acrylic acid-based monomer are crosslinked by the internal crosslinking agent.
- the term “super absorbent polymer” refers to a crosslinked polymer containing an acidic group and polymerized with an acrylic acid-based monomer in which at least a portion of the acidic group is neutralized, or a powder composed of particles of a superabsorbent polymer obtained by pulverizing the crosslinked polymer, depending on the context. ) in the form of a base resin, or through additional processes such as surface crosslinking, fine powder reassembly, drying, pulverization, classification, etc. for the crosslinked polymer or the base resin, all of which are in a state suitable for commercialization used to do Accordingly, the term “super absorbent polymer” may be interpreted as including a plurality of super absorbent polymer particles.
- average diameter of pores means an average value of the longest diameter value of each of a plurality of pores included in the superabsorbent polymer.
- maximum diameter of the pores means the maximum value among the longest diameter values of each of the plurality of pores included in the superabsorbent polymer.
- the specific surface area in the superabsorbent polymer particles needs to be increased. Accordingly, in order to realize a superabsorbent polymer having a high specific surface area, a method of forming a plurality of pores in the superabsorbent polymer by inducing a foaming process during the manufacturing process or a method of mechanically modifying the superabsorbent polymer has been used. However, in the case of the superabsorbent polymer manufacturing method according to the foaming process, a surfactant-type bubble stabilizer is used in order for the bubbles generated during the process to be trapped inside the polymer without escaping to the outside of the crosslinked polymer.
- the pore size When the pore size is large, the pore size range is wide, and the aspect ratio of the superabsorbent polymer particles is low, it is easily broken by the process environment or the physical properties are deteriorated under pressure due to uneven surface crosslinking efficiency. In addition, in the case of the method for manufacturing the superabsorbent polymer due to mechanical deformation, excessive load on equipment during the process was increased, causing a decrease in productivity.
- the present inventors have found that when two types of hydrophobic particles having different average particle diameters are used in the form of an aqueous dispersion instead of a commonly used bubble stabilizer, a plurality of pores having an average diameter of 100 ⁇ m or less and a maximum diameter of 300 ⁇ m or less are high. It was confirmed that it was possible to implement a superabsorbent polymer having a developed pore structure by forming an average of 7 or more per particle of the absorbent polymer. In addition, in the superabsorbent polymer, 10 to 50% by number of the particles having pores having a diameter greater than or equal to the average diameter and less than or equal to the maximum diameter, that is, particles having one or more relatively large pores. .
- the superabsorbent polymer may have a developed porous structure in which micropores having relatively small diameters are very uniformly distributed.
- the superabsorbent polymer not only exhibits an ultra-high absorption rate but also has a high surface tension. Specifically, when two types of hydrophobic particles having different particle diameters are added in the polymerization step of the monomer in the form of an aqueous dispersion, the input of a separate surfactant-type bubble stabilizer is minimized or without substantial input of the bubble stabilizer, a foaming agent or It was confirmed that it is possible to prepare a superabsorbent polymer having a developed porous structure in which pores of small size and uniform shape are uniformly distributed over the entire area of the cross-linked polymer by effectively trapping and stabilizing the bubbles generated by the bubble generator.
- the two types of hydrophobic particles are not used in the form of a powder, but are each in the form of a "water-soluble particle dispersion", that is, each of the hydrophobic particles is precipitated or It is added to the monomer composition in the form of a colloidal solution stably dispersed without agglomeration.
- a water-soluble particle dispersion that is, each of the hydrophobic particles is precipitated or It is added to the monomer composition in the form of a colloidal solution stably dispersed without agglomeration.
- each hydrophobic particle is stably dispersed without agglomeration between particles by the dispersion stabilizer in the aqueous dispersion.
- the dispersion stabilizer may stabilize the hydrophobic particle by inducing an electrostatic repulsive force between particles by forming an electric double layer on the surface of the hydrophobic particle, or the surface of the hydrophobic particle It is also possible to prevent the particles from aggregating with each other by inducing a steric repulsive force between the particles.
- the hydrophobic particles agglomerate with each other or sink due to gravity, so that dispersion stabilization of the hydrophobic particles cannot be achieved. Accordingly, when an aqueous dispersion of hydrophobic particles that does not contain a dispersion stabilizer is used together with a blowing agent in the polymerization step, it is difficult to improve the absorption rate of the superabsorbent polymer because it is impossible to effectively trap air bubbles and thus pores cannot be formed in the superabsorbent polymer. there is a problem.
- the type of the dispersion stabilizer, etc. will be further described with respect to the manufacturing method to be described later.
- the first hydrophobic particles have an average particle diameter of less than 1 ⁇ m
- the second hydrophobic particles have an average particle diameter of 1 ⁇ m or more. This is to lower the interfacial energy of bubbles in the monomer composition when large particles and small particles exist together, so that small bubbles can be stably maintained even with a small amount. Accordingly, the superabsorbent polymer according to the exemplary embodiment exhibits a more improved absorption rate and high surface tension, and thus can be very preferably applied to various sanitary materials.
- the superabsorbent polymer may include: a powder-type base resin including an acrylic acid-based monomer having an acidic group and at least a portion of the acidic group neutralized and a crosslinking polymer of an internal crosslinking agent; and a surface crosslinking layer formed on the base resin, wherein the crosslinked polymer is further crosslinked via a surface crosslinking agent.
- the superabsorbent polymer is a porous superabsorbent polymer including a plurality of pores, and each of the plurality of pores has an average diameter of 100 ⁇ m or less and a maximum diameter of 300 ⁇ m or less.
- the average diameter of the plurality of pores included in the superabsorbent polymer exceeds 100 ⁇ m or the maximum diameter exceeds 300 ⁇ m, the specific surface area of the superabsorbent polymer cannot be sufficiently secured, so that an improvement in the absorption rate is expected. difficult.
- the surface of the superabsorbent polymer may be easily worn or broken during the process, so that physical properties may decrease and fine powder may increase.
- the superabsorbent polymer according to the exemplary embodiment has a pore structure in which micropores are uniformly distributed, compared to the porous superabsorbent polymer having a plurality of pores having an average diameter of 100 ⁇ m or less but a maximum diameter exceeding 300 ⁇ m. As it has, it is possible to exhibit a high absorption capacity while having a significantly improved absorption rate.
- the plurality of pores included in the superabsorbent polymer may have an average diameter of 1 ⁇ m to 100 ⁇ m and a maximum diameter of 250 ⁇ m to 300 ⁇ m.
- pores satisfying the above-described average and maximum diameters may be included in an average of 7 or more, or 7 to 30 pores per particle of the superabsorbent polymer.
- pores having a diameter greater than or equal to the average diameter and less than or equal to the maximum diameter are 10 to 50%, or 20 to 40% of the total number of superabsorbent polymer particles.
- One or more may be formed only on the corresponding particle. This may mean that on a majority of the superabsorbent polymer particles, a large number of micropores having a diameter close to or slightly smaller than the average diameter are formed in a very uniform and narrow diameter distribution.
- the superabsorbent polymer may have a developed pore structure in which a large number of micropores having very uniform diameters are formed in most particles.
- the above-described super absorbent polymer can exhibit a greatly improved absorption rate.
- a superabsorbent polymer foamed and manufactured using a conventional foaming agent or a bubble generator, etc. does not have a sufficiently developed porous structure because it is difficult to stabilize the bubbles, or a significant amount of bubbles Since the use of a stabilizer is unavoidable, the surface tension and other physical properties of the superabsorbent polymer may be reduced.
- the average diameter and maximum diameter of pores in the above-described superabsorbent polymer, the average number of pores per particle, and the ratio of particles having relatively large pores, etc. are determined using the surface and/or internal images of the superabsorbent polymer particles to be measured. It can be confirmed by observation with an electron microscope. More specifically, it can be obtained by measuring the longest diameter of each of the pores included in the superabsorbent polymer particles, then taking the average value of the longest diameters of the measured pores as the average diameter, and taking the maximum value as the maximum diameter.
- the average number of pores per particle can be measured and calculated, and the number of pores when the longest diameter of the pores has a value greater than or equal to the average diameter;
- a ratio of particles having pores having a diameter greater than or equal to the average diameter and less than or equal to the maximum diameter may be calculated.
- it is preferable to select 300 or more pores for one superabsorbent polymer sample eg, a superabsorbent polymer sample prepared through a single process
- the acrylic acid-based monomer is a compound represented by the following formula (1):
- R 1 is an alkyl group having 2 to 5 carbon atoms including an unsaturated bond
- M 1 is a hydrogen atom, a monovalent or divalent metal, an ammonium group, or an organic amine salt.
- the acrylic acid-based monomer includes at least one selected from the group consisting of acrylic acid, methacrylic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof.
- the acrylic acid-based monomer may have an acidic group and at least a portion of the acidic group is neutralized.
- the monomer may be partially neutralized with an alkali material such as sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like.
- the degree of neutralization of the acrylic acid-based monomer may be 40 to 95 mol%, or 40 to 80 mol%, or 45 to 75 mol%.
- the range of the neutralization degree may be adjusted according to the final physical properties. However, if the degree of neutralization is too high, the neutralized monomer may be precipitated and polymerization may be difficult to proceed smoothly. have.
- the concentration of the acrylic acid-based monomer may be about 20 to about 60 wt%, preferably about 40 to about 50 wt%, based on the monomer composition including the raw material and solvent of the super absorbent polymer, and the polymerization time and It may be an appropriate concentration in consideration of the reaction conditions and the like. However, if the concentration of the monomer is too low, the yield of the superabsorbent polymer may be low and economic feasibility may occur. Conversely, if the concentration is too high, a part of the monomer is precipitated or the grinding efficiency is low when the polymerized hydrogel polymer is pulverized. Process problems may occur, and the physical properties of the superabsorbent polymer may be deteriorated.
- the term 'internal crosslinking agent' used in this specification is a term used to distinguish it from a surface crosslinking agent for crosslinking the surface of the superabsorbent polymer particles to be described later. serves to make The crosslinking in the above step proceeds without a surface or internal division, but when the surface crosslinking process of the superabsorbent polymer particles to be described later proceeds, the surface of the particles of the superabsorbent polymer finally produced has a structure crosslinked by a surface crosslinking agent, The interior has a structure crosslinked by the internal crosslinking agent.
- the internal crosslinking agent any compound may be used as long as it enables the introduction of crosslinking during polymerization of the acrylic acid-based unsaturated monomer.
- the internal crosslinking agent includes a crosslinking agent having at least one functional group capable of reacting with the water-soluble substituent of the acrylic acid-based unsaturated monomer and at least one ethylenically unsaturated group;
- a crosslinking agent having at least two functional groups capable of reacting with a water-soluble substituent of the monomer and/or a water-soluble substituent formed by hydrolysis of the monomer may be used.
- the internal crosslinking agent is N,N'-methylenebisacrylamide, trimethylpropane tri(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate.
- acrylate propylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, butanediol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate, glycerin tri ( acrylate-based compounds such as meth)acrylate and pentaerythol tetraacrylate; Ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly(ethylene
- crosslinking polymerization of the water-soluble ethylenically unsaturated monomer in the presence of such an internal crosslinking agent may be carried out by thermal polymerization, photopolymerization or hybrid polymerization in the presence of a polymerization initiator, optionally a thickener, plasticizer, storage stabilizer, antioxidant, etc. There, the specific details will be described later.
- the superabsorbent polymer further includes a surface cross-linking layer formed by additional cross-linking of a cross-linked polymer included in the base resin through a surface cross-linking agent on at least a portion of the surface of the base resin. This is to increase the surface crosslinking density of the superabsorbent polymer.
- the superabsorbent polymer when the superabsorbent polymer further includes a surface crosslinking layer, it has a structure having a higher crosslinking density on the outside than on the inside.
- the surface crosslinking agent any surface crosslinking agent that has been conventionally used in the manufacture of super absorbent polymers may be used without any particular limitation.
- the surface crosslinking agent is one selected from the group consisting of a polyhydric alcohol-based compound, a polyvalent epoxy-based compound, a polyamine compound, a haloepoxy compound, a condensation product of a haloepoxy compound, an oxazoline-based compound, and an alkylene carbonate-based compound may include more than one.
- the polyhydric alcohol-based compound includes mono-, di-, tri-, tetra- or polyethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4-trimethyl-1, 3-pentanediol, polypropylene glycol, glycerol, polyglycerol, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Alternatively, 1,2-cyclohexanedimethanol may be used.
- polyvalent epoxy compound ethylene glycol diglycidyl ether, glycidol, or the like may be used.
- polyamine compound ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, or polyamide polyamine may be used.
- haloepoxy compound epichlorohydrin, epibromohydrin or ⁇ -methylepichlorohydrin may be used.
- oxazoline-based compound mono-, di-, or polyoxazolidinone may be used.
- alkylene carbonate compound ethylene carbonate, propylene carbonate, or glycerol carbonate may be used.
- one of the surface crosslinking agents described above may be used alone or in combination with each other.
- an alkylene carbonate compound such as ethylene carbonate may be used as the surface crosslinking agent.
- the superabsorbent polymer may include first hydrophobic particles and second hydrophobic particles, wherein the first hydrophobic particles have an average particle diameter of less than 1 ⁇ m, and the second hydrophobic particles have an average particle diameter of 1 ⁇ m or more.
- the hydrophobic particle means a water-insoluble particle having a contact angle of 50° or more with respect to water or not soluble in water. Particles having a contact angle with respect to water of less than 50° and water-soluble particles can be dissolved in the monomer composition in the form of an aqueous solution, making it difficult to trap air bubbles generated in the polymerization process, whereas hydrophobic particles are located inside the neutralizing solution. It is located at the interface between the neutralizing solution and the bubble, such as carbon dioxide, which is hydrophobic in
- each of the first hydrophobic particles and the second hydrophobic particles has a contact angle with respect to water of 50° or more. More specifically, each of the first hydrophobic particles and the second hydrophobic particles may have a contact angle with respect to water of 70° or more, 100° or more, 120° or more, or 150° or more, and 175° or less.
- the contact angles of the first and second hydrophobic particles may be measured in the following manner, respectively.
- a coating solution in which each hydrophobic particle is dispersed in a methylene chloride solvent at a concentration of 5% by weight is prepared.
- this coating solution is dried at room temperature to remove the remaining solvent.
- water is dropped on the coating layer dropwise to measure the contact angle, and this is the contact angle of each hydrophobic particle.
- the first hydrophobic particles have an average particle diameter of less than 1 ⁇ m, specifically 10 nm or more and less than 1 ⁇ m. More specifically, the average particle diameter of the first hydrophobic particles may be 10 nm or more, 50 nm or more, or 100 nm or more, and 800 nm or less, 600 nm or less, 400 nm or less, or 300 nm or less.
- the second hydrophobic particles have an average particle diameter of 1 ⁇ m or more, specifically, 1 ⁇ m to 100 ⁇ m. More specifically, the average particle diameter of the second hydrophobic particles may be 2 ⁇ m or more, or 3 ⁇ m or more, and 50 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less, or 7 ⁇ m or less.
- the average particle diameter of the hydrophobic particles means D50
- the “particle diameter Dn” means the particle diameter at n% of the cumulative distribution of the number of particles according to the particle diameter. That is, D50 is the particle size at 50% of the cumulative distribution of the number of particles according to the particle size, D90 is the particle size at 90% of the cumulative distribution of the number of particles according to the particle size, and D10 is 10% of the cumulative distribution of the number of particles according to the particle size It is the particle diameter at the point.
- the Dn may be measured using a laser diffraction method.
- the powder to be measured in the dispersion medium After dispersing the powder to be measured in the dispersion medium, it is introduced into a commercially available laser diffraction particle size measuring device (eg, Microtrac S3500) to measure the difference in diffraction pattern depending on the particle size when the particles pass through the laser beam to measure the particle size distribution to calculate D10, D50, and D90 can be measured by calculating the particle diameter at the point used as 10%, 50%, and 90% of the particle number cumulative distribution according to the particle diameter in a measuring apparatus.
- a laser diffraction particle size measuring device eg, Microtrac S3500
- a ratio of the average particle diameter of the second hydrophobic particle to the average particle diameter of the first hydrophobic particle may be 5 to 100, more specifically, 10 to 50.
- first hydrophobic particles and the second hydrophobic particles may be included in a weight ratio of 1:5 to 1:50.
- the second hydrophobic particle is included in an excessively small amount compared to the first hydrophobic particle, it may be difficult to trap and maintain gas in the monomer composition, and when the second hydrophobic particle is included in an excessively large amount compared to the first hydrophobic particle
- the size of the pores may be increased.
- the second hydrophobic particles may be used in an amount of 6 times or more, 8 times or more, or 10 times or more compared to the weight of the first hydrophobic particles, and 40 times or less, 30 times or less, or 20 times or less by weight. may be included.
- first hydrophobic particle and the second hydrophobic particle may be each independently selected from the group consisting of hydrophobic silica, a metal salt of a fatty acid having 7 to 24 carbon atoms, and hydrophobic organic particles.
- both the first hydrophobic particle and the second hydrophobic particle are hydrophobic silica; or
- one of the first hydrophobic particles and the second hydrophobic particles is hydrophobic silica, and the other is a metal salt of a fatty acid having 7 to 24 carbon atoms;
- Both the first hydrophobic particle and the second hydrophobic particle may be a metal salt of a fatty acid having 7 to 24 carbon atoms.
- hydrophobic silica refers to silica having a contact angle with respect to water of 50° or more due to a small content of silanol (-SiOH) on the surface, and hydrophobic silica known in the art may be used without limitation.
- the metal salt of a fatty acid having 7 to 24 carbon atoms refers to a compound in which a metal cation is bonded instead of a hydrogen ion of a carboxyl group at the end of an unsaturated or saturated fatty acid having a linear structure and having 7 to 24 carbon atoms in the molecule,
- the metal salt may be a monovalent metal salt or a divalent or higher polyvalent metal salt.
- the hydrophobic particle is a metal salt of a fatty acid having less than 7 carbon atoms, it is not possible to collect the bubbles generated in the form of particles by being ionized in an aqueous solution. Dispersion can be difficult.
- the metal salt of the fatty acid when it is a monovalent metal salt, it has a structure in which one fatty acid carboxylate anion is bonded to an alkali ion, which is a monovalent metal cation.
- the metal salt of the fatty acid when it is a polyvalent metal salt of divalent or higher, it has a structure in which a fatty acid carboxylate anion having a valence number of the metal cation is bonded to the metal cation.
- the hydrophobic particles may be a metal salt of a saturated fatty acid having 12 to 20 carbon atoms.
- the hydrophobic particles include a metal salt of lauric acid containing 12 carbon atoms in the molecule; a metal salt of tridecyl acid containing 13 carbon atoms in the molecule; a metal salt of myristic acid containing 14 carbon atoms in the molecule; a metal salt of pentadecanoic acid containing 15 carbon atoms in the molecule; a metal salt of palmitic acid containing 16 carbon atoms in the molecule; a metal salt of margaric acid containing 17 carbon atoms in the molecule; a metal salt of stearic acid containing 18 carbon atoms in the molecule; a metal salt of nonadecylic acid containing 19 carbon atoms in the molecule; And it may be a metal salt of at least one saturated fatty acid selected from the group consisting of a metal salt of arachidic acid containing 20 carbon
- the metal salt of the fatty acid may be a stearic acid metal salt, for example, at least one stear selected from the group consisting of calcium stearate, magnesium stearate, sodium stearate, zinc stearate and potassium stearate. It may be a metal salt of an acid.
- the hydrophobic organic particles include ethylene polymers, propylene polymers, styrene polymers, butadiene polymers, styrene-butadiene copolymers, alkyl acrylate polymers, alkyl methacrylate polymers, alkyl acrylate-acrylonitrile copolymers, acrylonitrile-butadiene group consisting of copolymers, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-alkyl acrylate-styrene copolymers, alkyl methacrylate-butadiene-styrene copolymers and alkyl acrylate-alkyl methacrylate copolymers It may be one or more hydrophobic polymer particles selected from.
- the superabsorbent polymer may include particles having a particle diameter of about 150 to about 850 ⁇ m in an amount of 90% by weight or more, or 90 to 100% by weight based on the total weight, and the particle diameter of the superabsorbent polymer particles is determined by the European Nonwoven Fabric Industry Association. (European Disposables and Nonwovens Association, EDANA) can be measured according to the standard EDANA WSP 220.3 method. The above-described average diameter of pores, longest diameter, average number of pores per particle, and the ratio of particles having pores of a predetermined diameter, etc. can be measured and calculated for the superabsorbent polymer particles having a particle diameter of 150 to about 850 ⁇ m. .
- the superabsorbent polymer may have a vortex time of 40 seconds or less, 39 seconds or less, or 38 seconds or less at 24.0°C.
- the absorption rate is excellent as the value is smaller, so that the lower limit of the absorption rate is 0 seconds in theory, but may be, for example, 5 seconds or more, or 10 seconds or more, or 20 seconds or more. In this case, a method of measuring the absorption rate of the superabsorbent polymer will be described in more detail in Examples to be described later.
- the superabsorbent polymer may have a surface tension of 65 mN/m or more, 66 mN/m or more, or 68 mN/m or more, and 72 mN/m or less, or 71 mN/m or less.
- the method of measuring the surface tension of the superabsorbent polymer will be described in more detail in Examples to be described later.
- the superabsorbent polymer has a centrifugal retention capacity (CRC) greater than 27 g/g measured according to the method of EDANA method WSP 241.3, and absorbent under pressure (AUP) of 0.7 psi measured according to the method of EDANA method WSP 242.3 This may be greater than 20 g/g. More specifically, the superabsorbent polymer has a centrifugal retention capacity (CRC) of 27.5 g/g or more, or 28 g/g or more, and 34 g/g or less, or 33 g, measured according to the method of EDANA method WSP 241.3. It can be less than /g.
- the superabsorbent polymer has an absorbency under pressure (AUP) of 0.7 psi measured according to the method of WSP 242.3 of the EDANA method of 21 g/g or more, 22 g/g or more, or 23 g/g or more, and 28 g/g or less, or 27 g/g or less.
- AUP absorbency under pressure
- the superabsorbent polymer has an acid group and at least a portion of the acid group is neutralized acrylic acid-based monomer, a polymerization initiator, an internal crosslinking agent, and preparing a monomer composition comprising an aqueous dispersion of hydrophobic particles (step 1); preparing a hydrogel polymer by cross-linking and polymerizing the monomer composition in the presence of a foaming agent or a bubble generator (step 2); drying and pulverizing the hydrogel polymer to form a powdery base resin (step 3); and further crosslinking the surface of the base resin in the presence of a surface crosslinking agent to form a surface crosslinking layer (step 4).
- the aqueous dispersion of hydrophobic particles is a colloidal solution in which first and second hydrophobic particles are dispersed, and a ratio of the average particle diameter of the second hydrophobic particles to the average particle diameter of the first hydrophobic particles is 5 to 100.
- the aqueous dispersion of the hydrophobic particles may be in the form of an aqueous dispersion including the first hydrophobic particles and the second hydrophobic particles, and the first aqueous dispersion of hydrophobic particles and the second hydrophobic in which the first hydrophobic particles are dispersed
- the second aqueous dispersion of hydrophobic particles in which particles are dispersed may be mixed.
- first hydrophobic particles have an average particle diameter of less than 1 ⁇ m
- second hydrophobic particles have an average particle diameter of 1 ⁇ m or more
- description of the first hydrophobic particles and the second hydrophobic particles is as described above see
- This is a step of preparing a monomer composition comprising an acrylic acid-based monomer having an acidic group and at least a portion of the acidic group neutralized, a polymerization initiator, an internal crosslinking agent, and an aqueous dispersion of hydrophobic particles.
- a monomer composition comprising an acrylic acid-based monomer having an acidic group and at least a portion of the acidic group neutralized, a polymerization initiator, an internal crosslinking agent, and an aqueous dispersion of hydrophobic particles.
- the first hydrophobic particles and the second hydrophobic particles may be included in the aqueous dispersion in an amount of 0.01 to 60% by weight based on the total weight of the aqueous dispersion.
- the content of the hydrophobic particles in the hydrophobic aqueous dispersion is too low, the attraction force between the particles is lowered and dispersion stability is improved, but there is a problem that a large amount must be added when preparing the superabsorbent polymer, and the content of the hydrophobic particles in the hydrophobic aqueous dispersion If this is too high, a problem of poor dispersion stability may occur due to agglomeration between particles.
- the content of the hydrophobic particles in the aqueous dispersion is suitable as high as possible within a range in which dispersion stability can be ensured. This is because the higher the content of the hydrophobic particles in the aqueous dispersion, the better the bubble trapping ability, so that the superabsorbent polymer may exhibit a more developed porous structure and an improved absorption rate.
- the first hydrophobic particles and the second hydrophobic particles may be uniformly dispersed in the aqueous dispersion by a dispersion stabilizer surrounding the particle surface such as a surfactant and a polymer, respectively.
- the surfactant mainly forms an electric double layer on the surface of the hydrophobic particle to induce an electrostatic repulsive force between the particles to stabilize the hydrophobic particle, thereby improving the dispersion stability of the hydrophobic particle.
- the polymer is adsorbed to the surface of the hydrophobic particles to induce a steric repulsive force between the particles to prevent the particles from aggregating with each other, thereby improving the dispersion stability of the hydrophobic particles.
- one or more surfactants selected from the group consisting of cationic surfactants, anionic surfactants, amphoteric surfactants and nonionic surfactants may be used as the surfactant.
- two or more surfactants may be used in terms of dispersion stabilization of the hydrophobic particles. More specifically, in consideration of the form of the hydrophobic particles, for example, the form of metal salts of saturated fatty acids, in order to more effectively disperse these hydrophobic particles in water, _ nonionic surfactants and anionic surfactants, for example, A nonionic surfactant to which a long-chain hydrocarbon having 10 or more carbon atoms is bound and a sulfate-based anionic surfactant may be used together.
- examples of the cationic surfactant include dialkyldimethylammonium salts and alkylbenzylmethylammonium salts
- examples of the anionic surfactants include alkylpolyoxyethylene sulfate, monoalkylsulfate, alkylbenzenesulfonate, and monoalkylphosphate. , sodium lauryl sulfate, sodium dodecyl sulfate or sodium laureth sulfate; and the like.
- polyalkylene glycol polyethyleneimide, polyvinyl alcohol, polyacrylamide, or polyvinylpyrrolidone may be used.
- each of the first hydrophobic particles and the second hydrophobic particles may be used in an amount of 0.005 to 1 parts by weight based on 100 parts by weight of the acrylic acid-based monomer.
- the first hydrophobic particle may be used in an amount of 0.005 parts by weight or more, or 0.007 parts by weight or more, and 0.25 parts by weight or less, 0.1 parts by weight or less, or 0.05 parts by weight or less, based on 100 parts by weight of the acrylic acid-based monomer.
- the second hydrophobic particles may be used in an amount of 0.025 or more, or 0.035 parts by weight or more, and 0.75 parts by weight or less, 0.5 parts by weight or less, or 0.25 parts by weight or less, based on 100 parts by weight of the acrylic acid-based monomer.
- the first hydrophobic particles and the second hydrophobic particles may be used in a weight ratio of 1:5 to 1:50 as described above.
- the total weight of the first hydrophobic particle and the second hydrophobic particle may be 0.01 to 2 parts by weight based on 100 parts by weight of the acrylic acid-based monomer. If the total content of the hydrophobic particles is too low, it may not act as a bubble stabilizer, and if the total content of the aqueous dispersion of the hydrophobic particles is too high, the surface tension of the superabsorbent polymer may be lowered and the flowability of the hydrophobic particles may be increased.
- the internal crosslinking agent may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer.
- the internal crosslinking agent is 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight, or 0.2 parts by weight or more, and 5 parts by weight or less, 3 parts by weight or less, or 2 parts by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. part by weight or less, 1 part by weight or less, or 0.7 part by weight or less. If the content of the upper internal crosslinking agent is too low, crosslinking does not occur sufficiently, and it may be difficult to implement strength above an appropriate level.
- the monomer composition may further include a polymerization initiator for initiating a polymerization reaction of the monomer.
- the polymerization initiator is not particularly limited as long as it is generally used in the production of superabsorbent polymers.
- a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation may be used according to a polymerization method.
- a certain amount of heat is generated by irradiation such as ultraviolet irradiation, and a certain amount of heat is generated according to the progress of the polymerization reaction, which is an exothermic reaction, so a thermal polymerization initiator may be additionally included.
- the photopolymerization initiator may be used without limitation in its composition as long as it is a compound capable of forming radicals by light such as ultraviolet rays.
- photopolymerization initiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, benzyl dimethyl ketal Ketal), acyl phosphine (acyl phosphine), and alpha-aminoketone ( ⁇ -aminoketone) may be used at least one selected from the group consisting of.
- acylphosphine commercially available lucirin TPO, that is, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) may be used.
- lucirin TPO that is, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) may be used.
- the photopolymerization initiator may be included in a concentration of about 0.01 to about 1.0 wt% based on the monomer composition. If the concentration of the photopolymerization initiator is too low, the polymerization rate may be slowed, and if the concentration of the photopolymerization initiator is too high, the molecular weight of the superabsorbent polymer may be small and physical properties may be non-uniform.
- thermal polymerization initiator at least one selected from the group consisting of a persulfate-based initiator, an azo-based initiator, hydrogen peroxide, and ascorbic acid may be used.
- a persulfate-based initiator include sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), ammonium persulfate (Ammonium persulfate; (NH 4 ) 2 S 2 O 8 ) and the like
- examples of the azo-based initiator include 2,2-azobis-(2-amidinopropane)dihydrochloride (2,2-azobis(2-amidinopropane) dihydrochloride), 2 , 2-Azobis-(N,N-dimethylene)isobutyramidine dihydrochloride (2,2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride), 2-(carbamoylazo)is
- the thermal polymerization initiator may be included in a concentration of about 0.001 to about 0.5 wt% based on the monomer composition. If the concentration of the thermal polymerization initiator is too low, additional thermal polymerization hardly occurs, and the effect of adding the thermal polymerization initiator may be insignificant. have.
- the polymerization initiator may be used in an amount of 2 parts by weight or less based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. That is, when the concentration of the polymerization initiator is too low, the polymerization rate may be slowed and the residual monomer may be extracted in a large amount in the final product, which is not preferable. Conversely, when the concentration of the polymerization initiator is higher than the above range, the polymer chain constituting the network is shortened, so that the content of the water-soluble component increases, and the physical properties of the resin may be lowered, such as lowering the absorbency under pressure, which is not preferable.
- the monomer composition may further include additives such as a thickener, a plasticizer, a preservation stabilizer, and an antioxidant, if necessary.
- additives such as a thickener, a plasticizer, a preservation stabilizer, and an antioxidant, if necessary.
- the monomer composition including the monomer may be in a solution state dissolved in a solvent such as water, and the solid content in the monomer composition in the solution state, that is, the concentration of the monomer, the internal crosslinking agent, and the polymerization initiator It may be appropriately adjusted in consideration of time and reaction conditions.
- the solids content in the monomer composition may be 10 to 80% by weight, or 15 to 60% by weight, or 30 to 50% by weight.
- the monomer composition has a solid content in the above range, it is not necessary to remove unreacted monomers after polymerization by using the gel effect phenomenon that occurs in the polymerization reaction of a high concentration aqueous solution, and the pulverization efficiency when pulverizing the polymer to be described later is improved. It can be advantageous to control.
- the solvent that can be used at this time can be used without limitation in its composition as long as it can dissolve the above-mentioned components, for example, water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene Glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl At least one selected from ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate and N,N-dimethylacetamide may be used in combination.
- a step of cross-linking the monomer composition to prepare a hydrogel polymer is performed.
- bubbles are generated from the foaming agent or the bubble generator, and the specific surface area of the prepared hydrogel polymer can be increased by effectively trapping the two types of hydrophobic particles dispersed in water.
- a carbonate-based foaming agent may be used as the foaming agent.
- the carbonate-based foaming agent foams during polymerization and forms pores in the hydrogel polymer to increase the surface area, and for example, sodium bicarbonate (sodium hydrogen carbonate), sodium carbonate (sodium carbonate), potassium bicarbonate ( At least one selected from the group consisting of potassium bicarbonate, potassium carbonate, calcium bicarbonate, calcium bicarbonate, magnesium bicarbonate and magnesium carbonate. can be used
- the carbonate-based foaming agent may be used in an amount of 50 ppmw or more and 1 part by weight or less based on 100 parts by weight of the acrylic acid-based monomer.
- the content of the foaming agent is less than 50 ppmw, the role as a foaming agent may be insignificant, and when the content of the foaming agent exceeds 1 part by weight, there are too many pores in the cross-linked polymer, so the gel strength of the superabsorbent polymer produced decreases and the density becomes small. It can cause problems in distribution and storage.
- the carbonate-based foaming agent may be 100 ppmw or more, 0.8 parts by weight or less, or 0.7 parts by weight or less, based on 100 parts by weight of the acrylic acid-based monomer.
- the carbonate-based foaming agent and (total content of the first hydrophobic particles and the second hydrophobic particles) may be used in a weight ratio of 1:0.01 to 1:10.
- the aqueous dispersion of hydrophobic particles is used in an excessively low content compared to the carbonate-based foaming agent, it is difficult to effectively trap the generated bubbles, thereby increasing the pore size, and when used in an excessively high content compared to the foaming agent, the flowability of the final product This may cause problems such as faster speed, lower bulk density, and lower surface tension.
- the sum of the weights of the first hydrophobic particles and the second hydrophobic particles is 0.05 times or more, 0.1 times or more, or 0.5 times or more, and 5 times or less, 3 times or less, or 2 times compared to the weight of the carbonate-linked foaming agent. It may be less than twice the weight.
- a bubble generator may be used in place of the foaming agent.
- any microbubble generator, etc. previously used for foaming the monomer composition during the manufacturing process of the superabsorbent polymer may be used without any particular limitation.
- One example of such a microbubble generator is through a tubular flow path having a plurality of protruding pins mounted therein, for example, passing the monomer composition at a predetermined feed rate, for example, 50 to 1500 (L/min). While doing so, the monomer composition may be foamed by colliding with the protruding pins.
- An example of such a microbubble generator is disclosed in Korean Patent Application Laid-Open No. 2020-0128969, and it is of course also possible to obtain and apply commercial products applied in the examples to be described later.
- Surfactants such as alkyl sulfate-based compounds and polyoxyethylene alkyl ether-based compounds that are commonly used as foam stabilizers in Steps 1 and 2 described above may not be used.
- sodium dodecyl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, or sodium myreth sulfate An alkyl sulfate-based compound that is an anionic surfactant such as myreth sulfate) or an alkyl ether sulfate-based compound that is a non-ionic surfactant such as polyoxyethylene lauryl ether may not be used. Accordingly, the problem that the surface tension of the superabsorbent polymer is lowered due to the use of the surfactant can be prevented.
- the polymerization of the monomer composition in the presence of such an aqueous dispersion of hydrophobic particles is not particularly limited in structure as long as it is a commonly used polymerization method.
- the polymerization method is largely divided into thermal polymerization and photopolymerization according to the polymerization energy source.
- thermal polymerization when thermal polymerization is carried out, it may be carried out in a reactor having a stirring shaft such as a kneader.
- the process may be carried out in a reactor equipped with a conveyor belt, the polymerization method described above is an example, and the present invention is not limited to the polymerization method described above.
- the hydrogel polymer obtained by thermal polymerization by supplying hot air or heating the reactor to a reactor such as a kneader having a stirring shaft is fed to the reactor outlet according to the shape of the stirring shaft provided in the reactor.
- the discharged hydrogel polymer may be in the form of several centimeters to several millimeters.
- the size of the obtained hydrogel polymer may vary depending on the concentration and injection rate of the injected monomer composition, and a hydrogel polymer having a weight average particle diameter of 2 to 50 mm can be obtained.
- the form of the hydrogel polymer obtained may be a hydrogel polymer on a sheet having the width of the belt.
- the thickness of the polymer sheet varies depending on the concentration and injection rate of the monomer composition to be injected, but it is preferable to supply the monomer composition so that a polymer sheet having a thickness of about 0.5 to about 10 cm can be obtained.
- the monomer composition is supplied so that the thickness of the polymer on the sheet is too thin, the production efficiency is low, which is undesirable. it may not happen
- drying and pulverizing the hydrogel polymer to form a powdery base resin is performed. If necessary, in order to increase the efficiency of the drying step, a step of coarsely pulverizing before drying may be further performed.
- the grinder used is not limited in configuration, but specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, cutting Including any one selected from the group of crushing devices consisting of a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, and a disc cutter
- a vertical pulverizer a turbo cutter
- a turbo grinder a turbo grinder
- a rotary cutter mill Including any one selected from the group of crushing devices consisting of a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, and a disc cutter
- cutting Including any one selected from the group of crushing devices consisting of a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, and a disc cutter
- Gel pulverization of the hydrogel polymer may be performed so that the particle diameter of the hydrogel polymer is 0.01 mm to 50 mm, or 0.01 mm to 30 mm. That is, in order to increase drying efficiency, the hydrogel polymer is preferably pulverized into particles of 50 mm or less. However, since aggregation between particles may occur during excessive pulverization, the hydrogel polymer is preferably gel pulverized into particles of 0.01 mm or more.
- the gel pulverization of the hydrogel polymer is performed in a state where the water content is relatively low, a phenomenon in which the hydrogel polymer adheres to the surface of the gel pulverizer may appear.
- steam, water, a surfactant, an anti-agglomeration agent eg, clay, silica, etc.
- a persulfate-based initiator, an azo-based initiator, hydrogen peroxide, a thermal polymerization initiator, an epoxy-based crosslinking agent, a diol-based crosslinking agent, a crosslinking agent containing an acrylate of a polyfunctional group having a bifunctional group or a trifunctional group or more, a monofunctional crosslinking agent containing a hydroxyl group and the like may be added to the hydrogel polymer.
- the hydrogel polymer may be dried.
- the drying may be carried out at a temperature of 120 to 250 °C, preferably 140 to 200 °C, more preferably 150 to 200 °C.
- the drying temperature may be defined as the temperature of the thermal medium supplied for drying or the temperature inside the drying reactor including the thermal medium and the polymer in the drying process. If the drying time is long due to the low drying temperature, the process efficiency is lowered. In order to prevent this, the drying temperature is preferably 120° C. or higher. In addition, when the drying temperature is higher than necessary, the surface of the hydrogel polymer is excessively dried, which may increase the generation of fine powder in the subsequent pulverization step, and the physical properties of the final resin may decrease. In order to prevent this, the drying temperature is It is preferable that it is 250 degrees C or less.
- the drying time may be performed for about 20 to about 90 minutes, but is not limited thereto.
- the drying method of the drying step may be selected and used without limitation in its composition, as long as it is commonly used in the drying process of the hydrogel polymer. Specifically, the drying step may be performed by a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation. After the drying step, the moisture content of the polymer may be about 5 to about 10% by weight.
- the base resin which is a polymer powder obtained after the pulverization step, may have a particle diameter of about 150 to about 850 ⁇ m.
- the grinder used for grinding to such a particle size is specifically, a pin mill, a hammer mill, a screw mill, a roll mill, a disc mill, or a jog. A mill (jog mill) or the like may be used, but the present invention is not limited to the above-described examples.
- the base resin obtained after pulverization is classified according to particle size.
- the polymer having a particle diameter of about 150 to about 850 ⁇ m is classified, and only the base resin having such a particle diameter may be subjected to a surface crosslinking reaction step.
- superabsorbent polymer particles may be formed by surface crosslinking while heat-treating the base resin powder in the presence of a surface crosslinking agent.
- the surface crosslinking induces a crosslinking reaction on the surface of the base resin powder in the presence of a surface crosslinking agent, and a surface modification layer (surface crosslinking layer) may be formed on the surface of the base resin powder through this surface crosslinking.
- the content of the surface crosslinking agent may be appropriately selected depending on the type of the surface crosslinking agent added or reaction conditions, but about 0.001 to about 5 parts by weight may be used based on 100 parts by weight of the base resin. If the content of the surface crosslinking agent is too low, the surface modification may not be properly performed, and the physical properties of the final resin may be deteriorated. Conversely, when an excessive amount of the surface crosslinking agent is used, the basic water absorption performance of the resin may be deteriorated due to excessive surface crosslinking reaction, which is not preferable.
- a method of mixing the surface crosslinking agent with the base resin is not limited in its configuration.
- a method of mixing the surface crosslinking agent and the base resin powder in a reaction tank, spraying the surface crosslinking agent on the base resin powder, or a method of continuously supplying and mixing the base resin and the surface crosslinking agent to a continuously operated mixer can be used.
- the surface crosslinking agent When the surface crosslinking agent is added, water may be mixed together and added in the form of a surface crosslinking solution.
- water When water is added, there is an advantage that the surface crosslinking agent can be uniformly dispersed in the polymer.
- the content of the added water is about 1 to about 1 to 100 parts by weight of the base resin for the purpose of inducing even dispersion of the surface crosslinking agent and preventing agglomeration of the polymer powder and at the same time optimizing the surface penetration depth of the surface crosslinking agent. It is preferably added in a proportion of about 10 parts by weight.
- the above-mentioned surface crosslinking step further uses one or more selected from the group consisting of polyvalent metal salts, for example, aluminum salts, more specifically aluminum sulfate, potassium salt, ammonium salt, sodium salt and hydrochloride salt, in addition to the surface crosslinking agent. can proceed.
- polyvalent metal salts for example, aluminum salts, more specifically aluminum sulfate, potassium salt, ammonium salt, sodium salt and hydrochloride salt.
- the liquid permeability of the superabsorbent polymer prepared by the method of the embodiment can be further improved.
- the polyvalent metal salt may be added to the surface crosslinking solution together with the surface crosslinking agent, and may be used in an amount of 0.01 to 4 parts by weight based on 100 parts by weight of the base resin powder.
- the surface crosslinking process may be performed using a surface crosslinking solution containing water and/or a hydrophilic organic solvent (eg, an alcohol-based polar organic solvent such as methanol) as a liquid medium together with the above-described surface crosslinking agent.
- a hydrophilic organic solvent eg, an alcohol-based polar organic solvent such as methanol
- the content of water and hydrophilic organic solvent is about 100 parts by weight of the base resin powder for the purpose of inducing even dispersion of the surface crosslinking solution and preventing agglomeration of the base resin powder and at the same time optimizing the surface penetration depth of the surface crosslinking agent. It can be applied by adjusting the addition ratio.
- the structure of the method of adding the above-mentioned surface crosslinking solution to the base resin powder there is no particular limitation on the structure of the method of adding the above-mentioned surface crosslinking solution to the base resin powder.
- a method of mixing the surface crosslinking solution and the base resin powder in a reaction tank, spraying the surface crosslinking solution on the base resin powder, continuously supplying the base resin powder and the surface crosslinking solution to a continuously operated mixer and mixing method and the like can be used.
- the base resin powder to which the surface crosslinking solution is added is heated from an initial temperature of 20°C to 130°C to a maximum temperature of 140°C to 200°C over 10 minutes to 30 minutes, and the maximum temperature is Heat treatment may be performed by holding for 5 to 60 minutes. More specifically, the heat treatment may be performed by maintaining the highest temperature of 140°C to 200°C, or 170°C to 195°C for 5 minutes to 60 minutes, or 10 minutes to 50 minutes.
- the super absorbent polymer resin that appropriately satisfies the physical properties of the embodiment can be more effectively prepared.
- a means for increasing the temperature for the surface crosslinking reaction is not particularly limited. It can be heated by supplying a heating medium or by directly supplying a heat source. At this time, as the type of heating medium that can be used, a fluid having an elevated temperature such as steam, hot air, or hot oil may be used, but the present invention is not limited thereto. Considering it, it can be appropriately selected.
- the directly supplied heat source may be a heating method through electricity or a heating method through a gas, but is not limited to the above-described example.
- the inorganic material may be, for example, at least one selected from the group consisting of silica, clay, alumina, silica-alumina composite, and titania, and preferably silica.
- These inorganic substances may be used in an amount of 0.01 parts by weight or more, or 0.05 parts by weight or more, or 0.1 parts by weight or more, and 5 parts by weight or less, or 3 parts by weight or less, or 1 part by weight or less based on 100 parts by weight of the superabsorbent polymer.
- the superabsorbent polymer obtained according to the above-described manufacturing method maintains excellent absorption performance such as water holding capacity and absorbency under pressure, and satisfies improved absorption rate, etc.
- Ash, in particular, an ultra-thin sanitary material with a reduced content of pulp, etc. can be suitably used.
- the aqueous dispersion of hydrophobic particles used in Examples below was prepared as follows.
- each of the hydrophobic silica was gradually added while dispersing so as to be 0.2 wt% and 2 wt% based on the total weight of the final aqueous dispersion.
- the mixture was stirred at a temperature of 45° C. at 8000 rpm for 30 minutes.
- the pH of the aqueous dispersion was 9, and the average particle diameter (D50) of the hydrophobic silica was measured/calculated in the same manner as in Preparation Example 1.
- each of hydrophobic silica having an average particle diameter of 0.3 ⁇ m and a contact angle to water of 130° and hydrophobic silica having an average particle diameter of 3 ⁇ m and a contact angle to water of 130° was 0.2 wt% and 4 based on the total weight of the final aqueous dispersion
- An aqueous hydrophobic silica dispersion was prepared in the same manner as in Preparation Example 3, except that it was added so as to be % by weight.
- a monomer solution was prepared by mixing 0.27 parts by weight of ethylene glycol diglycidyl ether with 100 parts by weight of acrylic acid and 0.1 parts by weight of Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide as a photoinitiator.
- the monomer composition was introduced into a polymerization reactor composed of a moving conveyor belt, and UV polymerization was performed for 3 minutes by irradiating ultraviolet rays through a UV irradiation device to prepare a sheet-shaped hydrogel polymer.
- the hydrogel polymer After cutting the hydrogel polymer to have an average size of about 300 mm or less, it was put into a grinder (with a porous plate including a plurality of holes having a diameter of 10 mm) to cut the hydrogel. Then, the pulverized hydrogel was dried in a dryer capable of transferring air volume up and down. The water-containing gel was uniformly dried by flowing hot air at 180° C. so that the moisture content of the dried powder was about 2% or less. The dried resin was pulverized with a grinder and classified to obtain a base resin having a size of 150 to 850 ⁇ m.
- the base resin powder was gradually heated from the initial temperature of around 80°C, and it was operated to reach the maximum reaction temperature of 190°C after 30 minutes. After reaching the maximum reaction temperature, a sample of the final prepared superabsorbent polymer was taken after further reaction for 15 minutes. After the surface crosslinking process, the superabsorbent polymer of Example 1 having a particle diameter of 150 ⁇ m to 850 ⁇ m was prepared by classifying it with a standard mesh sieve according to ASTM standards.
- the zinc stearate aqueous dispersion prepared in Preparation Example 2 and the calcium stearate aqueous dispersion prepared in Preparation Example 1 were each added in an amount of 0.01 to 100 parts by weight of acrylic acid.
- a super absorbent polymer was prepared in the same manner as in Example 1, except that 0.1 parts by weight and calcium stearate were added in an amount of 0.1 parts by weight based on 100 parts by weight of acrylic acid.
- Example 1 without using both the carbonate-based foaming agent and the aqueous dispersion of hydrophobic particles, the hydrogel was cut to have an average size of about 300 mm or less, followed by a pulverizer (including a plurality of holes having a diameter of 8 mm) A superabsorbent polymer was prepared in the same manner as in Example 1, except that it was put into a perforated plate) and pulverized under each condition.
- Example 1 the superabsorbent polymer resin was used in the same manner as in Example 1, except that 1 part by weight of a 3 wt% sodium dodecyl sulfate (SDS) solution was added instead of the hydrophobic silica aqueous dispersion prepared in Preparation Example 3 was prepared.
- SDS sodium dodecyl sulfate
- Example 1 the same method as in Example 1 was used, except that 7 parts by weight of a 3 wt% hydrophilic silica aqueous dispersion solution (Klebosol 20, Merck Co.) was added instead of the hydrophobic silica aqueous dispersion prepared in Preparation Example 3 Thus, a super absorbent polymer was prepared.
- Example 1 the same method as in Example 1 was used, except that 0.15 parts by weight of hydrophobic fumed silica in powder form (Reolosil ® DM-30S, Tokuyama Corporation) was added instead of the hydrophobic silica aqueous dispersion prepared in Preparation Example 3 Thus, a super absorbent polymer was prepared.
- hydrophobic fumed silica in powder form Reolosil ® DM-30S, Tokuyama Corporation
- Example 1 the same as in Example 1, except that the aqueous dispersion of hydrophobic silica in which only the hydrophobic silica having an average particle diameter of 0.3 ⁇ m prepared in Preparation Example 5 was dispersed was added instead of the aqueous dispersion of the hydrophobic silica prepared in Preparation Example 3 Method was used to prepare a super absorbent polymer. At this time, the hydrophobic silica of Comparative Example 5 was added in the same weight as the total weight of the two types of hydrophobic particles of Example 1.
- a super absorbent polymer was prepared in the same manner as in Example 1, except that only the aqueous calcium stearate dispersion prepared in Preparation Example 1 was added instead of the aqueous hydrophobic silica dispersion prepared in Preparation Example 3 in Example 1. At this time, the calcium stearate of Comparative Example 6 was added in the same weight as the total weight of the two types of hydrophobic particles of Example 1.
- the surface and internal images of the superabsorbent polymer particles were measured using a scanning electron microscope (SEM) device. Thereafter, the number of pores capable of measuring the longest diameter per each superabsorbent polymer was calculated from the measured image, and the average diameter and maximum diameter of pores were calculated based on the longest diameter of each pore for these 300 or more pores. . In addition, the average number of pores per particle was calculated from the number of pores for which the longest diameter was measured.
- SEM scanning electron microscope
- the number of pores having a diameter greater than or equal to the average diameter and the number of particles having the corresponding pores are measured, and from this, the maximum diameter greater than or equal to the average diameter is measured.
- the proportion of particles with pores having a diameter less than or equal to the diameter was calculated.
- the superabsorbent polymer of Example 3 unlike the superabsorbent polymer of Comparative Example 2, has an average diameter of 1 to 100 ⁇ m and a plurality of pores having a maximum diameter of 280 to 300 ⁇ m, evenly formed. It can be confirmed that it has been In addition, in the superabsorbent polymer of Example 3, it was confirmed that an average of 7 or more, for example, 7 to 30 pores were formed per particle, and the ratio of particles having pores having a diameter greater than or equal to the average diameter and less than or equal to the maximum diameter was found to be high. It was confirmed that about 20 to 40% by number of the water absorbent resin particles.
- the superabsorbent polymers prepared in Examples and Comparative Examples were evaluated for physical properties in the following manner, and are shown in Table 1 below. Unless otherwise indicated, all processes were performed in a constant temperature and humidity room (23 ⁇ 0.5° C., relative humidity 45 ⁇ 0.5%) for the evaluation of the following properties, and the average value of three measurements was taken as measurement data to prevent measurement errors.
- physiological saline or saline means 0.9 wt% sodium chloride (NaCl) aqueous solution.
- Centrifugation retention capacity was measured by absorption magnification under no load according to European Disposables and Nonwovens Association (EDANA) standard EDANA WSP 241.3.
- the superabsorbent polymer W 0 (g, about 0.2 g) was uniformly put in a non-woven bag and sealed, and then immersed in a physiological saline solution of 0.9 wt% sodium chloride aqueous solution at room temperature. After 30 minutes, the bag was centrifuged and the bag was drained at 250G for 3 minutes, and the mass W 2 (g) of the bag was measured. In addition, after performing the same operation without using a superabsorbent polymer, the mass W 1 (g) at that time was measured. Using each mass thus obtained, CRC (g/g) was calculated according to Equation 1 below to confirm the water retention capacity.
- absorbency under pressure was measured according to the method of European Disposables and Nonwovens Association standard EDANA WSP 242.3.
- a stainless steel 400 mesh wire mesh was mounted on the bottom of a plastic cylinder having an inner diameter of 60 mm.
- Resin W 0 (g, 0.90 g) obtained in Examples 1 to 6 and Comparative Examples 1 to 4 was uniformly sprayed on the wire mesh under the conditions of 23 ⁇ 2° C. and 45% relative humidity, and 4.83 kPa (0.7 psi), the outer diameter of the piston is slightly smaller than 60 mm, there is no gap with the inner wall of the cylinder, and the vertical movement is not disturbed.
- the weight W 3 (g) of the device was measured.
- a glass filter having a diameter of 125 mm and a thickness of 5 mm was placed inside a petro dish having a diameter of 150 mm, and physiological saline composed of 0.90 wt% sodium chloride was placed at the same level as the upper surface of the glass filter.
- the measuring device was mounted on a glass filter, and the liquid was absorbed under load for 1 hour. After 1 hour, the measuring device was lifted and the weight W 4 (g) was measured.
- AUP (g/g) was calculated according to Equation 2 below to confirm the absorbency under pressure.
- AUP(g/g) [W 4 (g) - W 3 (g)]/ W 0 (g)
- W 0 (g) is the initial weight (g) of the superabsorbent polymer
- W 3 (g) is the sum of the weight of the superabsorbent polymer and the weight of the device capable of applying a load to the superabsorbent polymer
- W 4 (g) is the sum of the weight of the superabsorbent polymer and the weight of a device capable of applying a load to the superabsorbent polymer after saline is absorbed into the superabsorbent polymer for 1 hour under a load (0.7 psi).
- the absorption rate (vortex time) of the superabsorbent polymers of Examples and Comparative Examples was measured in the following manner.
- the surface tension of the superabsorbent polymers of Examples and Comparative Examples was measured as follows.
- Example 1 SBC hydrophobic silica (0.3) hydrophobic silica (3) 100 300 7 27 29.1 25.2 37 68
- Example 3 SBC hydrophobic silica (0.3) Ca-st (5) 77 280 13 32 29.4 25.0 28 67
- Example 4 SBC Zn-st (0.1) Ca-st (5) 82 294 9 47 28.3 24.7 32 67 Comparative Example 1 - - 80
- the average diameter was 100 ⁇ m or less. , it was confirmed that the pores having a maximum diameter of 300 ⁇ m or less had a pore structure in which an average of 7 or more pores per particle were included. In addition, the proportion of particles having pores having a diameter greater than or equal to the average diameter was about 10 to 50%, and it was confirmed that fine pores close to the average diameter were formed very uniformly on the remaining majority particles.
- the superabsorbent polymer of the above example exhibits a surface tension of a certain level or more and a fast absorption rate without a decrease in absorption performance compared to the superabsorbent polymer of the comparative example.
- the superabsorbent polymer of the above example exhibits a significantly improved absorption rate compared to Comparative Example 1 in which the foaming agent and the bubble stabilizer are not used.
- the superabsorbent polymer of the above example has a faster absorption rate compared to Comparative Example 2 using sodium dodecyl sulfate (SDS), which is mainly used as a conventional foam stabilizer, and exhibits high surface tension while at the same time.
- SDS sodium dodecyl sulfate
- the superabsorbent polymer of Example 5 used only the aqueous hydrophobic silica dispersion having an average particle size of less than 1 ⁇ m and the superabsorbent polymer of Comparative Example 6 using only the aqueous hydrophobic silica dispersion having an average particle diameter of more than 1 ⁇ m.
- the superabsorbent polymer of Comparative Example 6 using only the aqueous hydrophobic silica dispersion having an average particle diameter of more than 1 ⁇ m.
- a developed porous structure in which a large number of micropores of uniform diameter is formed is formed, indicating a fast absorption rate.
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Abstract
Description
발포 | 기포 안정제 종류 |
고흡수성 수지 기공 구조 |
고흡수성 수지 물성 |
||||||||
제1 소수성 입자 (평균 입경,㎛) |
제2 소수성 입자 (평균 입경,㎛) |
평균 직경 (㎛) |
최대 직경 (㎛) |
입자당 평균 기공 (개) |
평균 직경 이상 기공 형성된 입자 비율 (개수%) |
CRC (g/g) |
AUP (g/g) |
흡수 속도 (초) |
S/T (mN/m) |
||
실시예 1 | SBC | 소수성 실리카 (0.3) |
소수성 실리카 (3) |
100 | 300 | 7 | 27 | 29.1 | 25.2 | 37 | 68 |
실시예 2 | 기포 발생기 | 소수성 실리카 (0.3) |
소수성 실리카 (3) |
58 | 257 | 26 | 15 | 29.8 | 24.0 | 23 | 69 |
실시예 3 | SBC | 소수성실리카 (0.3) |
Ca-st (5) |
77 | 280 | 13 | 32 | 29.4 | 25.0 | 28 | 67 |
실시예 4 | SBC | Zn-st(0.1) | Ca-st (5) |
82 | 294 | 9 | 47 | 28.3 | 24.7 | 32 | 67 |
비교예 1 | - | - | 80 | 200 | 0 | - | 27.0 | 24.0 | 60 | 70 | |
비교예 2 | SBC | SDS | 314 | 650 | 2 | 100 | 27.5 | 24.8 | 47 | 58 | |
비교예 3 | SBC | 친수성 실리카 | - | - |
0 | - | 26.8 | 24.1 | 78 | 70 | |
비교예 4 | SBC | 소수성 실리카분말 | - |
- |
0 | - | 27.0 | 24.5 | 75 | 69 | |
비교예 5 | SBC | 소수성 실리카 (0.3) | 276 |
587 |
3 | 82 | 28.0 | 24.6 | 52 | 67 | |
비교예 6 | SBC | Ca-st (5) |
184 |
522 |
5 | 75 | 28.2 | 25.0 | 45 | 67 |
Claims (16)
- 산성기를 가지며 상기 산성기의 적어도 일부가 중화된 아크릴산계 단량체 및 내부 가교제의 가교 중합체를 포함하는 분말 형태의 베이스 수지; 및상기 베이스 수지 상에 형성되어 있고, 상기 가교 중합체가 표면 가교제를 매개로 추가 가교된 표면 가교층을 포함하는 고흡수성 수지로서,상기 고흡수성 수지는 입자당 평균 7개 이상의 복수의 기공들을 포함하고, 상기 복수의 기공들은 평균 직경이 100 ㎛ 이하이면서, 최대 직경이 300 ㎛ 이하이며, 상기 평균 직경 이상 최대 직경 이하의 직경을 갖는 기공을 갖는 입자가 전체 고흡수성 수지 입자의 10 내지 50 개수%이고,상기 고흡수성 수지는 표면 장력이 65 mN/m 이상이고 24.0℃에서의 흡수 속도(vortex time)가 40 초 이하인, 고흡수성 수지.
- 제1항에 있어서,상기 고흡수성 수지는 제1 소수성 입자 및 제2 소수성 입자를 포함하고,상기 제1 소수성 입자는 1 ㎛ 미만의 평균 입경을 가지고,상기 제2 소수성 입자는 1 ㎛ 이상의 평균 입경을 갖는.고흡수성 수지.
- 제2항에 있어서,상기 제1 소수성 입자의 평균 입경에 대한 상기 제2 소수성 입자의 평균 입경의 비가 5 내지 100인, 고흡수성 수지.
- 제2항에 있어서,상기 제1 소수성 입자 및 상기 제2 소수성 입자는 1:5 내지 1:50의 중량비로 포함되는, 고흡수성 수지.
- 제2항에 있어서,상기 제1 소수성 입자 및 상기 제2 소수성 입자는 소수성 실리카, 탄소수 7 내지 24의 지방산의 금속염 및 소수성 유기 입자로 구성되는 군으로부터 각각 독립적으로 선택되는, 고흡수성 수지.
- 제5항에 있어서,상기 지방산의 금속염은 칼슘 스테아레이트, 마그네슘 스테아레이트, 소듐 스테아레이트, 아연 스테아레이트 및 포타슘 스테아레이트로 구성되는 군으로부터 선택되는 1종 이상의 스테아르산의 금속염인, 고흡수성 수지.
- 제1항에 있어서, 상기 고흡수성 수지는 입자당 평균 7 내지 30개의 기공들을 포함하는 고흡수성 수지.
- 제1항에 있어서,상기 표면 가교제는 다가 알코올계 화합물, 다가 에폭시계 화합물, 폴리아민 화합물, 할로에폭시 화합물, 할로에폭시 화합물의 축합 산물, 옥사졸린계 화합물 및 알킬렌 카보네이트계 화합물로 구성되는 군으로부터 선택되는 1종 이상을 포함하는, 고흡수성 수지.
- 제1항에 있어서,상기 고흡수성 수지는 EDANA 법 WSP 241.3의 방법에 따라 측정한 원심분리 보수능(CRC)이 27 g/g 초과이고, EDANA 법 WSP 242.3의 방법에 따라 측정한 0.7 psi의 가압 흡수능(AUP)이 20 g/g 초과인, 고흡수성 수지.
- 산성기를 가지며 상기 산성기의 적어도 일부가 중화된 아크릴산계 단량체, 중합 개시제, 내부 가교제 및 소수성 입자 수분산액을 포함하는 단량체 조성물을 준비하는 단계(단계 1);발포제 또는 기포 발생기의 존재 하에, 상기 단량체 조성물을 가교 중합하여 함수겔 중합체를 제조하는 단계(단계 2);상기 함수겔 중합체를 건조 및 분쇄하여 분말 형태의 베이스 수지를 형성하는 단계(단계 3); 및표면 가교제의 존재 하에, 상기 베이스 수지의 표면을 추가 가교하여 표면 가교층을 형성하는 단계(단계 4)를 포함하고,상기 소수성 입자 수분산액은 제1 소수성 입자 및 제2 소수성 입자가 분산되어 있는 콜로이드 용액이고, 상기 제1 소수성 입자의 평균 입경에 대한 상기 제2 소수성 입자의 평균 입경의 비가 5 내지 100인, 고흡수성 수지의 제조 방법.
- 제10항에 있어서,상기 제1 소수성 입자는 1 ㎛ 미만의 평균 입경을 가지고,상기 제2 소수성 입자는 1 ㎛ 이상의 평균 입경을 갖는.고흡수성 수지의 제조 방법.
- 제10항에 있어서,상기 제1 소수성 입자 및 제2 소수성 입자는 각각 상기 아크릴산계 단량체 100 중량부 대비 50ppmw 이상 1 중량부 이하로 사용되는, 고흡수성 수지의 제조 방법.
- 제10항에 있어서,상기 제1 소수성 입자 및 상기 제2 소수성 입자의 총중량은 상기 아크릴산계 단량체 100 중량부 대비 0.01 내지 2 중량부인,고흡수성 수지의 제조 방법.
- 제10항에 있어서, 제1 및 제2 소수성 입자는 적어도 비이온성 계면활성제 및 음이온성 계면활성제의 존재 하에 상기 소수성 입자 수분산액에 분산되어 있는 고흡수성 수지의 제조 방법.
- 제10항에 있어서,상기 표면 가교제는 다가 알코올계 화합물, 다가 에폭시계 화합물, 폴리아민 화합물, 할로에폭시 화합물, 할로에폭시 화합물의 축합 산물, 옥사졸린계 화합물 및 알킬렌 카보네이트계 화합물로 구성되는 군으로부터 선택되는 1종 이상을 포함하는, 고흡수성 수지의 제조 방법.
- 제10항에 있어서,상기 표면 가교는 20℃ 내지 130℃의 초기 온도에서 10 분 내지 30 분에 걸쳐 140℃ 내지 200℃의 최고 온도로 승온하고, 상기 최고 온도를 5 분 내지 60 분 동안 유지하여 열처리함으로써 진행되는, 고흡수성 수지의 제조 방법.
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