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WO2019188669A1 - Particules de résine absorbant l'eau et procédé de production s'y rapportant - Google Patents

Particules de résine absorbant l'eau et procédé de production s'y rapportant Download PDF

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Publication number
WO2019188669A1
WO2019188669A1 PCT/JP2019/011728 JP2019011728W WO2019188669A1 WO 2019188669 A1 WO2019188669 A1 WO 2019188669A1 JP 2019011728 W JP2019011728 W JP 2019011728W WO 2019188669 A1 WO2019188669 A1 WO 2019188669A1
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WIPO (PCT)
Prior art keywords
water
absorbent resin
resin particles
silicon compound
fine particles
Prior art date
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Ceased
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PCT/JP2019/011728
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English (en)
Japanese (ja)
Inventor
佑介 松原
宮島　徹
泰知 松山
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SDP Global Co Ltd
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SDP Global Co Ltd
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Publication date
Application filed by SDP Global Co Ltd filed Critical SDP Global Co Ltd
Priority to JP2020510787A priority Critical patent/JP7257090B2/ja
Priority to CN201980018735.8A priority patent/CN111868145B/zh
Priority to CN202310838820.7A priority patent/CN116769269A/zh
Publication of WO2019188669A1 publication Critical patent/WO2019188669A1/fr
Anticipated expiration legal-status Critical
Priority to JP2023033551A priority patent/JP2023060178A/ja
Ceased legal-status Critical Current

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    • 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
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

Definitions

  • the present invention relates to a water absorbent resin particle and a method for producing the same.
  • water-absorbing resins mainly composed of hydrophilic fibers such as pulp and acrylic acid (salt) are widely used as absorbents. From the viewpoint of improving QOL (Quality Of Life) in recent years, demand for these sanitary materials has been shifting to lighter and thinner ones, and accordingly, the use of hydrophilic fibers has been desired to be reduced. . For this reason, the water-absorbing resin itself is required to have the role of liquid diffusibility and initial absorption in the absorbent body, which has been carried out by hydrophilic fibers so far. A water-absorbing resin having high liquid permeability has been required.
  • Patent Document 1 a method using a lubricant
  • Patent Document 2 a method of setting a specific aspect ratio and particle diameter
  • Patent Document 2 does not mention or recognize any supply amount fluctuation in the feeder, and the method does not satisfy the performance related to the supply amount fluctuation.
  • JP 2014-237133 A Japanese Unexamined Patent Publication No. 2016-055193
  • An object of the present invention is to provide a water-absorbent resin with little fluctuation in the supply amount in the feeder in the production process.
  • the present invention is a water-absorbent resin particle comprising the crosslinked polymer (A) having the water-soluble vinyl monomer (a1) and the crosslinking agent (b) as essential structural units and the water-insoluble silicon compound fine particles (c).
  • the arithmetic average of the Si atom number concentration (atomic%) measured by scanning electron microscope-energy dispersive X-ray analysis at 20 analysis points is 0.5 to 5.0, and the Si atom number concentration A water-absorbent resin particle having a coefficient of variation of 0 to 40%;
  • the water-absorbent resin particles of the present invention and the water-absorbent resin particles obtained by the production method of the present invention have a low coefficient of variation in the number of Si atoms and a low coefficient of variation in the feed amount of the water-insoluble silicon compound fine particles on the surface. Reduce fluctuations in feeder supply.
  • the water-absorbent resin particles of the present invention include a crosslinked polymer (A) having water-soluble vinyl monomer (a1) and a crosslinking agent (b) as essential structural units, and water-insoluble silicon compound fine particles (c).
  • the water-soluble vinyl monomer (a1) in the present invention is not particularly limited, and known monomers, for example, at least one water-soluble substituent and an ethylenic group disclosed in paragraphs 0007 to 0023 of Japanese Patent No. 3648553 are disclosed.
  • Vinyl monomers having a saturated group for example, anionic vinyl monomers, nonionic vinyl monomers and cationic vinyl monomers
  • anionic vinyl monomers disclosed in JP-A-2003-16583, paragraphs 0009 to 0024 nonionic Selected from the group consisting of a carboxylic group, a sulfo group, a phosphono group, a hydroxyl group, a carbamoyl group, an amino group and an ammonio group disclosed in paragraphs 0041 to 0051 of JP-A-2005-75982
  • At least one Vinyl monomer having can be used.
  • anionic vinyl monomers carboxy (salt) groups, sulfo (salt) groups, amino groups, carbamoyl groups, ammonio groups or mono-, di- or tri-alkyl ammonio groups are preferred from the standpoint of absorption performance and the like.
  • Vinyl monomers having a group more preferred are vinyl monomers having a carboxy (salt) group or a carbamoyl group, particularly preferred are (meth) acrylic acid (salt) and (meth) acrylamide, and particularly preferred is (meth) acrylic acid. (Salt), and most preferred is acrylic acid (salt).
  • the “carboxy (salt) group” means “carboxy group” or “carboxylate group”, and the “sulfo (salt) group” means “sulfo group” or “sulfonate group”.
  • (meth) acrylic acid (salt) means acrylic acid, acrylate, methacrylic acid or methacrylate
  • (meth) acrylamide means acrylamide or methacrylamide.
  • the salt include alkali metal (such as lithium, sodium and potassium) salts, alkaline earth metal (such as magnesium and calcium) salts and ammonium (NH 4 ) salt.
  • alkali metal salts and ammonium salts are preferable from the viewpoint of absorption performance and the like, more preferable are alkali metal salts, and particularly preferable are sodium salts.
  • the structural unit of the crosslinked polymer (A) in addition to the water-soluble vinyl monomer (a1), other vinyl monomers (a2) copolymerizable with these can be used as the structural unit.
  • Other vinyl monomers (a2) may be used alone or in combination of two or more.
  • vinyl monomers (a2) that can be copolymerized are not particularly limited, and are known (for example, hydrophobic vinyl monomers disclosed in paragraphs 0028 to 0029 of Japanese Patent No. 3648553, Japanese Patent Application Laid-Open No. 2003-165883). 0025 paragraph and vinyl monomer disclosed in JP-A-2005-75982, paragraph 0058, etc.) can be used. Specifically, for example, the following vinyl monomers (i) to (iii) Can be used.
  • Styrene such as styrene, ⁇ -methylstyrene, vinyltoluene and hydroxystyrene, and halogen substituted products of styrene such as vinylnaphthalene and dichlorostyrene.
  • C2-C20 aliphatic ethylenic monomer Alkenes (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.); and alkadienes (butadiene, isopren
  • monoethylenically unsaturated monomer such as pinene, limonene and indene
  • polyethylene vinyl monomer such as cyclopentadiene, bicyclopentadiene and ethylidene norbornene.
  • the content (mol%) of the other vinyl monomer (a2) unit is preferably 0 to 5, more preferably 0 to 5, based on the number of moles of the water-soluble vinyl monomer (a1) unit from the viewpoint of absorption performance and the like. 3, particularly preferably 0 to 2, particularly preferably 0 to 1.5. From the viewpoint of absorption performance and the like, the content of the other vinyl monomer (a2) units is most preferably 0 mol%.
  • the cross-linking agent (b) is not particularly limited and is known (for example, a cross-linking agent having two or more ethylenically unsaturated groups disclosed in Japanese Patent No. 3648553, paragraphs 0031 to 0034, and a water-soluble substituent.
  • a crosslinking agent having at least one functional group and having at least one ethylenically unsaturated group, and a crosslinking agent having at least two functional groups capable of reacting with a water-soluble substituent Japanese Patent Application Laid-Open No.
  • Crosslinking agents such as disclosed crosslinkable vinyl monomer can be used to.
  • a cross-linking agent having two or more ethylenically unsaturated groups is preferable, and more preferable is poly (meth) allyl ether of a polyhydric alcohol having 2 to 40 carbon atoms, carbon number (Meth) acrylates of 2 to 40 polyhydric alcohols, (meth) acrylamides of polyhydric alcohols having 2 to 40 carbon atoms, particularly preferred are polyallyl ethers of polyhydric alcohols having 2 to 40 carbon atoms, most preferred Pentaerythritol triallyl ether.
  • a crosslinking agent (b) may be used individually by 1 type, or may use 2 or more types together.
  • the content (mol%) of the crosslinking agent (b) unit is based on the total number of moles of the water-soluble vinyl monomer (a1) unit and (a1) to (a2) when the other vinyl monomer (a2) is used. 0.001 to 5 is preferable, 0.005 to 3 is more preferable, and 0.01 to 1 is particularly preferable. Within this range, the absorption performance is further improved.
  • Examples of the method for producing the crosslinked polymer (A) include known solution polymerization (adiabatic polymerization, thin film polymerization, spray polymerization method, etc .; JP-A-55-133413, etc.), known suspension polymerization method and reverse phase suspension. If necessary, a hydrogel polymer (consisting of a crosslinked polymer and water) obtained by suspension polymerization (Japanese Patent Publication No. Sho 54-30710, Japanese Patent Publication No. 56-26909, Japanese Patent Publication No. 1-5808, etc.) is required. It can be obtained by heat drying and grinding.
  • the cross-linked polymer (A) may be a single type or a mixture of two or more types.
  • the solution polymerization method is preferable, and it is advantageous in terms of production cost because it is not necessary to use an organic solvent. Therefore, the aqueous solution polymerization method is particularly preferable, and the water retention amount is large and water-soluble.
  • An aqueous solution adiabatic polymerization method is most preferred because a water-absorbing resin with a small amount of components can be obtained and temperature control during polymerization is unnecessary.
  • a mixed solvent containing water and an organic solvent can be used.
  • the organic solvent include methanol, ethanol, acetone, methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide, and two or more of these.
  • the amount (% by weight) of the organic solvent used is preferably 40 or less, more preferably 30 or less, based on the weight of water.
  • a conventionally known radical polymerization catalyst can be used, for example, an azo compound [azobisisobutyronitrile, azobiscyanovaleric acid and 2,2′-azobis (2-amidinopropane) hydrochloride.
  • Etc. inorganic peroxides (hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.), organic peroxides [benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, succinic acid peroxide, etc.
  • Oxides and di (2-ethoxyethyl) peroxydicarbonate, etc.] and redox catalysts alkali metal sulfites or bisulfites, ammonium sulfites, ammonium bisulfites, ascorbic acids and the like, and alkali metal persulfates, Oxidation of ammonium persulfate, hydrogen peroxide and organic peroxides And the like).
  • These catalysts may be used alone or in combination of two or more thereof.
  • the amount (% by weight) of the radical polymerization catalyst used is 0.0005 based on the total weight of the water-soluble vinyl monomer (a1) and (a1) to (a2) when the other vinyl monomer (a2) is used. To 5 is preferable, and 0.001 to 2 is more preferable.
  • a polymerization control agent such as a chain transfer agent may be used in combination, and specific examples thereof include sodium hypophosphite, sodium phosphite, alkyl mercaptan, alkyl halide, and thiocarbonyl compound. Etc. These polymerization control agents may be used alone or in combination of two or more thereof.
  • the amount (% by weight) of the polymerization control agent used is 0.0005 based on the total weight of the water-soluble vinyl monomer (a1) and (a1) to (a2) when the other vinyl monomer (a2) is used. To 5 is preferable, and 0.001 to 2 is more preferable.
  • the polymerization may be performed in the presence of a conventionally known dispersant or surfactant, if necessary.
  • a conventionally known dispersant or surfactant if necessary.
  • polymerization can be carried out using a conventionally known hydrocarbon solvent such as xylene, normal hexane and normal heptane.
  • the polymerization start temperature can be appropriately adjusted depending on the type of catalyst used, but is preferably 0 to 100 ° C., more preferably 2 to 80 ° C.
  • the content (% by weight) of the organic solvent after distillation is preferably 0 to 10, more preferably 0 to 5, particularly preferably based on the weight of the crosslinked polymer (A). Is 0-3, most preferably 0-1. Within this range, the absorption performance of the water-absorbent resin particles is further improved.
  • the water content (% by weight) after the distillation is preferably 0 to 20, more preferably 1 to 10, particularly preferably 2 to 9, based on the weight of the crosslinked polymer (A). Most preferably, it is 3-8. Within this range, the absorption performance is further improved.
  • the crosslinked polymer (A) can obtain a water-containing gel-like product containing water (hereinafter abbreviated as a water-containing gel), and the water-containing gel is further dried to obtain the crosslinked polymer (A).
  • a water-containing gel a water-containing gel-like product containing water
  • the water-containing gel is further dried to obtain the crosslinked polymer (A).
  • an acid group-containing monomer such as acrylic acid or methacrylic acid
  • the hydrogel may be neutralized with a base.
  • the neutralization degree of the acid group is preferably 50 to 80 mol%.
  • the degree of neutralization is less than 50 mol%, the resulting water-containing gel polymer has high tackiness, and the workability during production and use may deteriorate. Furthermore, the water retention amount of the water-absorbing resin particles obtained may decrease.
  • the neutralization may be performed at any stage after the polymerization of the crosslinked polymer (A) in the production of the water-absorbent resin particles.
  • a method such as neutralization in the state of a hydrogel is preferable.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate can be usually used.
  • the hydrogel obtained by polymerization can be shredded as necessary.
  • the size (longest diameter) of the gel after chopping is preferably 50 ⁇ m to 10 cm, more preferably 100 ⁇ m to 2 cm, and particularly preferably 1 mm to 1 cm. Within this range, the drying property in the drying process is further improved.
  • Shredding can be performed by a known method, and can be performed using a shredding device (for example, a bex mill, rubber chopper, pharma mill, mincing machine, impact pulverizer, and roll pulverizer).
  • a shredding device for example, a bex mill, rubber chopper, pharma mill, mincing machine, impact pulverizer, and roll pulverizer.
  • the content and water content of the organic solvent were measured using an infrared moisture meter [for example, JE400 manufactured by KETT Co., Ltd .: 120 ⁇ 5 ° C., 30 minutes, atmospheric humidity before heating 50 ⁇ 10% RH, lamp specification 100V , 40 W], from the weight loss of the measurement sample when heated.
  • an infrared moisture meter for example, JE400 manufactured by KETT Co., Ltd .: 120 ⁇ 5 ° C., 30 minutes, atmospheric humidity before heating 50 ⁇ 10% RH, lamp specification 100V , 40 W
  • a method of distilling off the solvent (including water) in the hydrogel As a method of distilling off the solvent (including water) in the hydrogel, a method of distilling (drying) with hot air at a temperature of 80 to 230 ° C., a thin film drying method using a drum dryer or the like heated to 100 to 230 ° C. (Heating) reduced pressure drying method, freeze drying method, infrared drying method, decantation, filtration and the like can be applied.
  • the pulverization method is not particularly limited, and a pulverizer (for example, a hammer pulverizer, an impact pulverizer, a roll pulverizer, and a shet airflow pulverizer) can be used.
  • the pulverized crosslinked polymer can be adjusted in particle size by sieving or the like, if necessary.
  • the weight average particle diameter ( ⁇ m) of the crosslinked polymer (A) screened as necessary is preferably 100 to 800, more preferably 200 to 700, next preferably 250 to 600, particularly preferably 300 to 500, most preferably Preferably it is 350-450. Within this range, the absorption performance is further improved.
  • the weight average particle size was measured using a low-tap test sieve shaker and a standard sieve (JIS Z8801-1: 2006), Perry's Chemical Engineers Handbook, 6th edition (Mac Glow Hill Book, 1984). , Page 21). That is, JIS standard sieves are combined in the order of 1000 ⁇ m, 850 ⁇ m, 710 ⁇ m, 500 ⁇ m, 425 ⁇ m, 355 ⁇ m, 250 ⁇ m, 150 ⁇ m, 125 ⁇ m, 75 ⁇ m and 45 ⁇ m, and a tray from the top. About 50 g of the measured particles are put in the uppermost screen and shaken for 5 minutes with a low-tap test sieve shaker.
  • the rate (% by weight) is preferably 3 or less, and more preferably 1 or less.
  • the content of the fine particles can be determined using a graph created when determining the above-mentioned weight average particle diameter.
  • the shape of the crosslinked polymer (A) is not particularly limited, and examples thereof include an irregular crushed shape, a flake shape, a pearl shape, and a rice grain shape. Among these, from the viewpoint of good entanglement with the fibrous material in the use of paper diapers and the like and no fear of dropping off from the fibrous material, an irregular crushed shape is preferable.
  • the cross-linked polymer (A) may contain some other components such as a residual solvent and a residual cross-linking component as long as the performance is not impaired.
  • the water-absorbent resin particles of the present invention preferably have a structure in which the surface of the crosslinked polymer (A) is crosslinked with an organic surface crosslinking agent (e).
  • an organic surface crosslinking agent (e) By crosslinking the surface of the crosslinked polymer (A), the gel strength of the water-absorbent resin particles can be improved, and the desired water retention amount and the amount of absorption under load of the water-absorbent resin particles can be further satisfied.
  • the organic surface crosslinking agent (e) include known polyvalent glycidyl compounds, polyvalent amines, polyvalent aziridine compounds and polyvalent isocyanate compounds described in JP 59-189103 A, JP 58-180233 A.
  • polyhydric alcohols disclosed in JP-A-61-16903 silane coupling agents described in JP-A-61-211305 and JP-A-61-252212, and JP-A-5-508425.
  • organic surface crosslinking agents such as polyvalent oxazoline compounds described in JP-A No. 11-240959.
  • polyvalent glycidyl compounds, polyhydric alcohols and polyhydric amines are preferred, polyvalent glycidyl compounds and polyhydric alcohols are more preferred, and many are particularly preferred.
  • Valent glycidyl compounds most preferred are ethylene glycol diglycidyl ethers.
  • the organic surface crosslinking agent (e) may be used alone or in combination of two or more.
  • the amount (% by weight) of the organic surface cross-linking agent (e) is not particularly limited because it can be variously changed depending on the type of surface cross-linking agent, the conditions for cross-linking, the target performance, and the like. From the viewpoint of absorption characteristics, etc., it is preferably 0.001 to 3, more preferably 0.005 to 2, particularly preferably 0.01 to 1.5, based on the weight of the water absorbent resin particles.
  • Surface crosslinking of the crosslinked polymer (A) can be carried out by mixing the crosslinked polymer (A) and the organic surface crosslinking agent (e) and heating.
  • a mixing method of the crosslinked polymer (A) and the organic surface crosslinking agent (e) a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer (registered trademark), a flexographic type vertical mixing Mixing machine, Nauter type mixer, double arm type kneader, fluid type mixer, V type mixer, minced mixer, ribbon type mixer, airflow type mixer, rotating disk type mixer, conical blender, roll mixer, etc. Examples thereof include a method of uniformly mixing the crosslinked polymer (A) and the organic surface crosslinking agent (e) using an apparatus. At this time, the organic surface cross-linking agent (e) may be diluted with water and / or an arbitrary solvent and used.
  • the temperature at which the cross-linked polymer (A) and the organic surface cross-linking agent (e) are mixed is not particularly limited, but is preferably 10 to 150 ° C, more preferably 20 to 100 ° C, and particularly preferably 25 to 80 ° C. is there.
  • the heating temperature is preferably 100 to 180 ° C., more preferably 110 to 175 ° C., and particularly preferably 120 to 170 ° C. from the viewpoint of breakage resistance of the resin particles. Heating at 180 ° C. or lower is advantageous in terms of equipment because indirect heating using steam is possible, and absorption performance may deteriorate at heating temperatures below 100 ° C.
  • the heating time can be appropriately set depending on the heating temperature, but is preferably 5 to 60 minutes, more preferably 10 to 40 minutes from the viewpoint of absorption performance.
  • the water-absorbing resin obtained by surface cross-linking can be further surface cross-linked using the same or different organic surface cross-linking agent as the organic surface cross-linking agent used first.
  • the particle size is adjusted by sieving as necessary.
  • the average particle size of the obtained particles is preferably 100 to 600 ⁇ m, more preferably 200 to 500 ⁇ m.
  • the content of fine particles is preferably small, the content of particles of 100 ⁇ m or less is preferably 3% by weight or less, and the content of particles of 150 ⁇ m or less is more preferably 3% by weight or less.
  • the water-absorbent resin particles of the present invention include water-insoluble silicon compound fine particles (c).
  • the water-insoluble silicon compound fine particles (c) include silicon dioxide such as fumed silica, wet silica, colloidal silica, and modified silica, and silicate fine particles such as talc, kaolin, zeolite, and montmorillonite. Fumed silica and colloidal silica are preferable from the viewpoints of properties, ease of handling, and absorption performance.
  • (C) may be used individually by 1 type, and may use 2 or more types together.
  • the water-insoluble silicon compound fine particles (c) in the present invention are preferably spherical or irregular particles having an average primary particle diameter of 1 to 100 nm. When the particles are spherical or amorphous, the powder flowability of the water-absorbent resin particles is improved.
  • the average primary particle diameter of the water-insoluble silicon compound fine particles (c) is preferably 2 to 80 nm, more preferably 3 to 60 nm, and particularly preferably 5 to 50 nm. If the average primary particle diameter is less than 1 nm, the absorption characteristics under load of the water-absorbent resin particles may be deteriorated. Moreover, when larger than 100 nm, the liquid permeability of a water-absorbent resin particle may deteriorate.
  • the average primary particle diameter of the water-insoluble silicon compound fine particles (c) may be measured by a conventionally known method. For example, individual particles of 100 or more particles from a 50,000-fold image with a transmission electron microscope are used. A method of measuring the particle diameter from the average of the longest diameter and the shortest diameter of the particle, obtaining an arithmetic average value thereof, a method using a scattering type particle size distribution measuring apparatus using dynamic light scattering or laser diffraction, and a spherical particle. In some cases, a method of calculating from the specific surface area by the BET method may be used. When using a commercial product, the catalog value can be used instead. In addition, when there is a significant difference depending on the measurement method when obtaining by measurement, the method using the transmission electron microscope described above is used.
  • the water absorbent resin particles of the present invention can be obtained by mixing the crosslinked polymer (A) and the water-insoluble silicon compound fine particles (c).
  • the mixing method includes a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer (registered trademark), a flexo-mix vertical mixer, a nauter mixer, a double-arm kneader, and a fluid mixer. , V-type mixers, minced mixers, ribbon-type mixers, air-flow-type mixers, rotary disk-type mixers, conical blenders, roll mixers, and other known mixing devices.
  • a vertical mixer having a cylindrical mixing layer and rotating around a central axis is preferable.
  • the vertical type means that the rotation axis is in the vertical direction (vertical direction)
  • the horizontal type means that the rotation axis is in the horizontal direction.
  • a flexo-mix type vertical type mixer for example, a trade name
  • Flexomix FX, Flexomix FXD both manufactured by Hosokawa Micron Corporation
  • Turbulizer registered trademark
  • water-absorbing resin particles tend to accumulate in the lower part of the mixing tank, and mixing tends to be uneven. It is considered that the water-insoluble silicon compound fine particles (c) are difficult to spread on the surface of the crosslinked polymer (A) and can be uniformly mixed on the surface by mixing at high speed and turbulent flow.
  • Rotational speed at the time of mixing in the flexo-mix type vertical mixer is preferably 1000 to 4000 rpm, more preferably 2000 to 3000 rpm. If it is lower than 1000 rpm, uniform mixing cannot be performed, and if it is higher than 4000 rpm, the water-absorbent resin particles may be broken by impact and fine powder may be generated.
  • the feed amount of the water-absorbent resin particles to the flexographic type vertical mixer is preferably in a range not exceeding the processing capacity according to the model.
  • flexographic mix FXD100 is 50 to 100 kg / h. If it is lower than 50 kg / h, the amount of processing per unit time is small and inefficient, and if it exceeds 100 kg, troubles such as blockage occur.
  • the water-insoluble silicon compound fine particles (c) For mixing the crosslinked polymer (A) and the water-insoluble silicon compound fine particles (c), it is preferable to add the water-insoluble silicon compound fine particles (c) while stirring the crosslinked polymer (A).
  • the added water-insoluble silicon compound fine particles (c) may be added simultaneously with water and / or a solvent.
  • a dispersion in which the water-insoluble silicon compound fine particles (c) are dispersed in water and / or a solvent can be added. From the viewpoint, it is preferable to add a dispersion, and it is more preferable to add an aqueous dispersion. When adding a dispersion liquid, it is preferable to add by spraying or dripping.
  • the content of the water-insoluble silicon compound fine particles (c) contained in the dispersion is preferably 5 to 70% by weight based on the total weight of the dispersion. More preferably, it is 10 to 60% by weight.
  • the dispersion of the water-insoluble silicon compound fine particles (c) may be a dispersion obtained by directly granulating a raw material by reacting with water and / or a solvent by a conventionally known method.
  • a dispersion obtained by mechanical dispersion in a solvent may also be used. From the viewpoint of the stability of the dispersion, it is preferable to use a dispersion obtained by directly granulating raw materials in water and / or a solvent.
  • the dispersion of water-insoluble silicon compound fine particles (c) can be obtained as a commercial product as an aqueous colloidal solution (sol).
  • additives such as arbitrary stabilizers, may be contained in the dispersion liquid as needed.
  • stabilizers include commercially available surfactants and dispersants, commercially available acid compounds [phosphoric acid (salt), boric acid (salt), alkali metal (salt) and alkaline earth metal (salt), hydroxycarboxylic Acid (salt), fatty acid (salt), etc.].
  • the temperature at which the crosslinked polymer (A) and the water-insoluble silicon compound fine particles (c) are mixed is preferably 10 to 150 ° C., more preferably 20 to 100 ° C., and particularly preferably 25 to 80 from the viewpoint of absorption performance. ° C.
  • the heating temperature is preferably 25 to 180 ° C., more preferably 30 to 175 ° C., and particularly preferably 35 to 170 ° C. from the viewpoint of breakage resistance of the resin particles. Heating at 180 ° C. or lower is advantageous in terms of equipment because indirect heating using steam is possible. Moreover, when not heating, the water and solvent used together will remain excessively in the water-absorbent resin, and the absorption performance may deteriorate.
  • the amount of water and solvent remaining in the water absorbent resin is preferably 1 to 10 parts by weight per 100 parts by weight of the water absorbent resin.
  • the amount of water and solvent remaining in the water-absorbent resin can be obtained by the heat loss method in accordance with JIS K0067-1992 (chemical product weight loss and residue test method).
  • the heating time can be appropriately set depending on the heating temperature, but from the viewpoint of absorption performance, preferably 5 to 60 minutes, More preferably, it is 10 to 40 minutes.
  • the water-absorbent resin obtained by mixing the crosslinked polymer (A) and the water-insoluble silicon compound fine particles (c) is the same or different from the water-insoluble silicon compound fine particles used initially, Further surface treatment is possible.
  • the water-absorbent resin particles of the present invention may be used after mixing the crosslinked polymer (A) and the water-insoluble silicon compound fine particles (c), and sieving to adjust the particle size.
  • the average particle size of the particles obtained by adjusting the particle size is preferably 100 to 600 ⁇ m, more preferably 200 to 500 ⁇ m.
  • the content of fine particles is preferably small, the content of particles of 100 ⁇ m or less is preferably 3% by weight or less, and the content of particles of 150 ⁇ m or less is more preferably 3% by weight or less.
  • the content of the water-insoluble silicon compound fine particles (c) can be adjusted according to the use of the water absorbent resin particles, but based on the weight of the crosslinked polymer (A),
  • the content is preferably 0.01 to 1% by weight, more preferably 0.02 to 0.8% by weight, and particularly preferably 0.05 to 0.5% by weight. If it is more than this range, dust will be peeled off from the surface of the water-absorbent resin, and if it is less than this range, moisture absorption blocking tends to occur.
  • the arithmetic average of the Si atom number concentration (atomic%) can be adjusted by the content of the water-insoluble silicon compound fine particles (c) and the addition method.
  • the Si atom number concentration on the surface of the water-absorbent resin particles measured by scanning electron microscope-energy dispersive X-ray analysis is determined by measuring 20 random water-absorbent resin particles.
  • the surface of the water-absorbent resin particles is a surface observed by a scanning electron microscope-energy dispersive X-ray analysis, and the portion from the portion where the water-absorbent resin particles are exposed to the outside air to the inside of about 1 ⁇ m. Show.
  • the electron beam is squeezed under the conditions of an acceleration voltage of 15 eV and a magnification of 100 times, and the intensity of characteristic X-rays observed for each element is detected.
  • the composition of the measured electron beam irradiation region (the surface of the water-absorbent resin particles) can be determined. Since the Si atom number concentration on the surface of the water-absorbent resin particles may vary depending on individual water-absorbent resin particles, it is preferable to measure 20 random water-absorbent resin particles and obtain the arithmetic average value.
  • the arithmetic average of the Si atom number concentration (atomic%) measured by scanning electron microscope-energy dispersive X-ray analysis at an analysis point of 20 of the present invention is 0.5 to 5.0, and is a water-insoluble silicon compound It can adjust with content and addition method of microparticles
  • the amount is more than 5.0, dust is peeled off from the surface of the water-absorbent resin, and when the amount is less than 0.5, moisture absorption is easily blocked.
  • the water-insoluble silicon compound fine particles (c) adhere to the water-absorbent resin particles with a force acting on the powder such as van der Waals force, it is difficult to control the amount of adhesion after adhesion, and turbulent mixing From the viewpoint of adjusting the average Si atom number concentration, it is preferable to mix uniformly.
  • the variation coefficient of the Si atom number concentration measured by scanning electron microscope-energy dispersive X-ray analysis at an analysis point of 20 depends on the method of adding the water-insoluble silicon compound fine particles (c). Although controlled, it is 0 to 40%. From the viewpoint of feed amount control and production efficiency, it is preferably 1 to 30%, more preferably 1 to 25%, and particularly preferably 10 to 25%.
  • the variation coefficient of the Si atom number concentration is an index of the uniformity of Si atoms on the surface of the water-absorbent resin particles, and the lower the value, the more uniformly Si atoms, that is, the water-insoluble silicon compound fine particles (c) are added. If the coefficient of variation exceeds 40%, the feed amount varies, and the performance of the absorbent article varies, which is not preferable.
  • the water-absorbent resin particles of the present invention can be obtained by mixing the crosslinked polymer (A) and the water-insoluble silicon compound fine particles (c).
  • the surface of the crosslinked polymer (A) is an organic surface crosslinking agent (
  • the water-insoluble silicon compound fine particles (c) may be added at any stage before or after the surface crosslinking with the organic surface crosslinking agent (e).
  • the water-insoluble silicon compound fine particles (c) are preferably added simultaneously with or before the addition of the organic surface cross-linking agent (e), and the water-insoluble silicon compound fine particles (c) are added to the organic surface cross-linking agent ( More preferably, it is added simultaneously with the addition of e).
  • the water absorbent resin particles of the present invention may further contain a polyhydric alcohol (f) having 4 or less carbon atoms.
  • a polyhydric alcohol (f) having 4 or less carbon atoms include ethylene glycol, propylene glycol, 1,3-propanediol, glycerin, 1,4-butanediol and the like. Of these, propylene glycol and glycerin are preferable from the viewpoint of safety and availability, and propylene glycol is more preferable.
  • (F) may be used individually by 1 type, and may use 2 or more types together.
  • the use amount (% by weight) of the polyhydric alcohol (f) having 4 or less carbon atoms is preferably 0.05 to 5 based on the weight of the cross-linked polymer (A) from the viewpoint of absorption performance and liquid permeability. Preferably it is 0.1 to 3, particularly preferably 0.2 to 2.
  • the water-insoluble silicon compound fine particles (c) and the organic surface crosslinking agent (e) are preferably added simultaneously.
  • the wettability and permeability of the additive liquid with respect to the crosslinked polymer (A) can be improved, and Si atoms can be made uniform.
  • the water absorbent resin particles of the present invention may further contain a hydrophobic substance (g).
  • a hydrophobic substance (g1) containing a hydrocarbon group a hydrophobic substance (g2) containing a hydrocarbon group having a fluorine atom, and a hydrophobic substance (g3) having a polysiloxane structure Etc. are included.
  • Hydrophobic substances (g1) containing hydrocarbon groups include polyolefin resins, polyolefin resin derivatives, polystyrene resins, polystyrene resin derivatives, waxes, long chain fatty acid esters, long chain fatty acids and salts thereof, long chain aliphatic alcohols, long Chain aliphatic amides and mixtures of two or more thereof are included.
  • the polyolefin resin has a C2-4 olefin ⁇ ethylene, propylene, isobutylene, isoprene, etc. ⁇ as an essential constituent monomer (the olefin content is at least 50% by weight based on the weight of the polyolefin resin).
  • examples thereof include polymers having an average molecular weight of 1,000 to 1,000,000 ⁇ eg, polyethylene, polypropylene, polyisobutylene, poly (ethylene-isobutylene), isoprene, etc. ⁇ .
  • polystyrene resin derivative examples include polymers having a weight average molecular weight of 1,000 to 1,000,000 introduced by introducing a carboxyl group (—COOH), 1,3-oxo-2-oxapropylene (—COOCO—), etc.
  • a polyolefin resin for example, polyethylene heat Degradation, polypropylene thermal degradation, maleic acid modified polyethylene, chlorinated polyethylene, maleic acid modified polypropylene, ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, maleation Polybutadiene, ethylene-vinyl acetate copolymer, and maleated product of ethylene-vinyl acetate copolymer ⁇ .
  • a polyolefin resin for example, polyethylene heat Degradation, polypropylene thermal degradation, maleic acid modified polyethylene, chlorinated polyethylene, maleic acid modified polypropylene, ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, maleation Polybutadiene, ethylene-vinyl acetate copolymer, and maleated product of ethylene-vinyl acetate
  • polystyrene resin a polymer having a weight average molecular weight of 1,000 to 1,000,000 can be used. *
  • polystyrene resin derivative a polymer having a weight average molecular weight of 1,000 to 1,000,000 (for example, styrene-containing styrene as an essential constituent monomer (the content of styrene is at least 50% by weight based on the weight of the polystyrene derivative)).
  • waxes having a melting point of 50 to 200 ° C. for example, paraffin wax, beeswax, carnauba wax, beef tallow, etc.
  • Long chain fatty acid esters include esters of fatty acids having 8 to 30 carbon atoms and alcohols having 1 to 12 carbon atoms (for example, methyl laurate, ethyl laurate, methyl stearate, ethyl stearate, methyl oleate, oleic acid) Ethyl, glycerin lauric acid monoester, glycerin stearic acid monoester, glycerin oleic acid monoester, pentaerythritol lauric acid monoester, pentaerythritol stearate monoester, pentaerythritol oleic acid monoester, sorbit lauric acid monoester, Sorbit stearic acid monoester, sorbit oleic acid monoester, sucrose palmitic acid monoester, sucrose palmitic acid diester, sucrose palmitic acid triester, sucrose stearic acid monoester
  • long-chain fatty acids and salts thereof include fatty acids having 8 to 30 carbon atoms (for example, lauric acid, palmitic acid, stearic acid, oleic acid, dimer acid, and behenic acid), and salts thereof include zinc, calcium, Examples thereof include salts with magnesium or aluminum (hereinafter abbreviated as Zn, Ca, Mg, Al, respectively) ⁇ for example, palmitic acid Ca, palmitic acid Al, stearic acid Ca, stearic acid Mg, stearic acid Al, etc. ⁇ .
  • Zn, Ca, Mg, Al magnesium or aluminum
  • Examples of the long-chain aliphatic alcohol include aliphatic alcohols having 8 to 30 carbon atoms (for example, lauryl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, etc.). From the viewpoint of the moisture resistance of the absorbent article, palmityl alcohol, stearyl alcohol, and oleyl alcohol are preferable, and stearyl alcohol is more preferable.
  • Examples of the long-chain aliphatic amide include an amidated product of a long-chain aliphatic primary amine having 8 to 30 carbon atoms and a carboxylic acid having a hydrocarbon group having 1 to 30 carbon atoms, ammonia, or a primary amine having 1 to 7 carbon atoms. And amidated product of a long chain fatty acid having 8 to 30 carbon atoms, a long chain aliphatic secondary amine having at least one aliphatic chain having 8 to 30 carbon atoms and a carboxylic acid having 1 to 30 carbon atoms, and Examples thereof include amidated products of secondary amines having two aliphatic hydrocarbon groups having 1 to 7 carbon atoms and long chain fatty acids having 8 to 30 carbon atoms.
  • a compound obtained by reacting a primary amine and a carboxylic acid 1: 1 is used. : Divided into those reacted in 2. Examples of the product reacted at 1: 1 include acetic acid N-octylamide, acetic acid N-hexacosylamide, heptacosanoic acid N-octylamide, heptacosanoic acid N-hexacosylamide and the like.
  • Examples of those reacted at 1: 2 include diacetate N-octylamide, diacetate N-hexacosylamide, diheptacosanoic acid N-octylamide, and diheptacosanoic acid N-hexacosylamide.
  • the primary amine and the carboxylic acid are reacted at 1: 2, the carboxylic acid used may be the same or different.
  • amidated products of ammonia or primary amines having 1 to 7 carbon atoms and long chain fatty acids having 8 to 30 carbon atoms include those obtained by reacting ammonia or primary amines with carboxylic acids in a 1: 1 ratio. Divided into reacted products.
  • the ones reacted in 1: 2 include dinonanoic acid amide, dinonanoic acid N-methylamide, dinonanoic acid N-heptylamide, dioctadecanoic acid amide, dioctadecanoic acid N-ethylamide, dioctadecanoic acid N-heptylamide, diheptacosanoic acid amide And diheptacosanoic acid N-methylamide, diheptacosanoic acid N-heptylamide, and diheptacosanoic acid N-hexacosylamide.
  • the carboxylic acid to be used may be the same or different.
  • amidated products of a long-chain aliphatic secondary amine having at least one aliphatic chain having 8 to 30 carbon atoms and a carboxylic acid having 1 to 30 carbon atoms include N-methyloctylamide acetate, N-methylhexacosyl acetate Amide, acetic acid N-octylhexacosylamide, acetic acid N-dihexacosylamide, heptacosanoic acid N-methyloctylamide, heptacosanoic acid N-methylhexacosylamide, heptacosanoic acid N-octylhexacosylamide and heptacosane Examples include acid N-dihexacosylamide.
  • amidated products of secondary amines having two aliphatic hydrocarbon groups having 1 to 7 carbon atoms and long chain fatty acids having 8 to 30 carbon atoms include nonanoic acid N-dimethylamide, nonanoic acid N-methylheptylamide, Nonanoic acid N-diheptylamide, heptacosanoic acid N-dimethylamide, heptacosanoic acid N-methylheptylamide, heptacosanoic acid N-diheptylamide and the like can be mentioned.
  • hydrophobic substance (g2) containing a hydrocarbon group having a fluorine atom examples include perfluoroalkane, perfluoroalkene, perfluoroaryl, perfluoroalkyl ether, perfluoroalkyl carboxylic acid, perfluoroalkyl alcohol, and those 2 A mixture of seeds or more is included.
  • hydrophobic substance (g3) having a polysiloxane structure examples include polydimethylsiloxane, polyether-modified polysiloxane ⁇ polyoxyethylene-modified polysiloxane and poly (oxyethylene / oxypropylene) -modified polysiloxane, etc. ⁇ , carboxy-modified polysiloxane, Epoxy-modified polysiloxane, amino-modified polysiloxane, alkoxy-modified polysiloxane and the like, and mixtures thereof are included.
  • the HLB value of the hydrophobic substance (g) is preferably 1 to 10, more preferably 2 to 8, particularly preferably 3 to 7. Within this range, the blocking resistance during initial swelling is further improved.
  • the HLB value means a hydrophilic-hydrophobic balance (HLB) value, and is determined by the Oda method (new introduction to surfactants, page 197, Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd., published in 1981). .
  • hydrophobic substance (g1) containing a hydrocarbon group is preferred, more preferably a long-chain fatty acid ester, a long-chain fatty acid and a salt thereof, Long chain aliphatic alcohols and long chain aliphatic amides, more preferably sorbite stearate, sucrose stearate, stearic acid, Mg stearate, Ca stearate, Zn stearate and Al stearate, particularly preferably Sucrose stearate and Mg stearate, most preferably sucrose stearate.
  • the amount of use (% by weight) of the hydrophobic substance (g) is preferably 0.001 to 1, more preferably, based on the weight of the crosslinked polymer (A) from the viewpoints of absorption performance and blocking resistance during initial swelling. Is 0.005 to 0.5, particularly preferably 0.01 to 0.3.
  • the hydrophobic substance (g) When the hydrophobic substance (g) is contained, it may be added in any step, but it is preferably added before the addition of the water-insoluble silicon compound fine particles (c) from the viewpoint of absorption performance.
  • the hydrophobic substance (g) In the case where the surface of A) has a structure crosslinked with the organic surface crosslinking agent (e), the hydrophobic substance (g) is further added before the surface crosslinking with the organic surface crosslinking agent (e). preferable.
  • the water-absorbent resin particles of the present invention may contain, as necessary, additives (for example, known preservatives, fungicides, antibacterial agents, oxidation agents (described in JP-A No. 2003-225565 and JP-A No. 2006-131767, etc.)) An inhibitor, an ultraviolet absorber, a chelating agent, a colorant, a fragrance, a deodorant, a liquid permeability improver, and an organic fibrous material).
  • the content (% by weight) of the additive is preferably 0.001 to 10, more preferably 0.01 to 5, particularly preferably based on the weight of the crosslinked polymer (A).
  • it is 0.05 to 1, most preferably 0.1 to 0.5.
  • the production method of the present invention is a method for producing the water-absorbent resin particles of the present invention, wherein the crosslinked polymer (A) having water-soluble vinyl monomer (a1) and crosslinking agent (b) as essential structural units and water-insoluble.
  • the crosslinked polymer (A) is preferably the water-insoluble silicon compound fine particles (c) or The aqueous colloidal solution of the water-insoluble silicon compound fine particles (c) and the surface cross-linking agent are added simultaneously.
  • Specific examples of the water-insoluble silicon compound fine particles (c) or the aqueous colloidal liquid of the water-insoluble silicon compound fine particles (c) are as described above.
  • the addition amount and addition method thereof are also as described above.
  • an aqueous colloidal solution of water-insoluble silicon compound fine particles (c), an organic surface crosslinking agent (e) is simultaneously added by spraying while being mixed by a flexographic type vertical mixer, and then heat-treated.
  • the water retention amount (g / g) of the water-absorbent resin particles of the present invention and the water-absorbent resin particles obtained by the production method of the present invention (hereinafter referred to as the water-absorbent resin particles of the present invention without distinguishing them) will be described later. 25 to 55 is preferable, 30 to 50 is more preferable, and 35 to 45 is particularly preferable. If the water retention amount is lower than this range, the diaper absorption amount is low, and if it is higher than this range, the absorption amount under load is low. The amount of water retention can be appropriately adjusted by the amount (% by weight) used of the crosslinking agent (b) and the organic surface crosslinking agent (e).
  • the gel flow rate (ml / min) of the water-absorbent resin particles of the present invention can be measured by the method disclosed in WO2016 / 143737, etc., and is preferably 5 to 300 from the viewpoint of the diaper absorption rate, 10 to 280 is more preferable, and 15 to 250 is particularly preferable. It is empirically known that the gel flow rate conflicts with the water retention amount, and there are cases where a high water retention amount is required and a high gel flow rate is required depending on the configuration of the diaper.
  • the apparent density (g / ml) of the water-absorbent resin particles of the present invention is preferably 0.50 to 0.80, more preferably 0.52 to 0.75, and particularly preferably 0.54 to 0.70. . Within this range, the anti-fogging property of the absorbent article is further improved.
  • the apparent density of the water absorbent resin particles is measured at 25 ° C. according to JIS K7365: 1999.
  • the moisture absorption blocking rate of the water-absorbent resin particles of the present invention can be measured by the method described later, and is preferably 0 to 50%, more preferably 0 to 30%, and particularly preferably 0 to 20%. Within this range, blocking problems are unlikely to occur regardless of the work environment.
  • An absorbent body can be obtained using the water-absorbent resin particles of the present invention.
  • water-absorbing resin particles may be used alone or may be used together with other materials as an absorber.
  • other materials include fibrous materials.
  • the structure and production method of the absorbent when used together with the fibrous material are the same as those known (JP 2003-225565 A, JP 2006-131767 A, JP 2005-097569 A, etc.). is there.
  • Preferred as the fibrous material are cellulose fibers, organic synthetic fibers, and a mixture of cellulose fibers and organic synthetic fibers.
  • cellulosic fibers examples include natural fibers such as fluff pulp, and cellulosic chemical fibers such as viscose rayon, acetate, and cupra.
  • raw materials conifers, hardwoods, etc.
  • production methods chemical pulp, semi-chemical pulp, mechanical pulp, CTMP, etc.
  • bleaching methods etc. of this cellulose-based natural fiber.
  • organic synthetic fibers examples include polypropylene fibers, polyethylene fibers, polyamide fibers, polyacrylonitrile fibers, polyester fibers, polyvinyl alcohol fibers, polyurethane fibers, and heat-fusible composite fibers (the above fibers having different melting points). And a fiber obtained by compounding at least two of the above into a sheath core type, an eccentric type, a parallel type, and the like, a fiber obtained by blending at least two kinds of the above fibers, and a fiber obtained by modifying the surface layer of the above fibers).
  • fibrous materials preferred are cellulose-based natural fibers, polypropylene-based fibers, polyethylene-based fibers, polyester-based fibers, heat-fusible conjugate fibers, and mixed fibers thereof, and more preferable are obtained.
  • the fluff pulp, the heat-fusible conjugate fiber, and the mixed fiber thereof are preferable in that the water-absorbing agent has excellent shape retention after water absorption.
  • the length and thickness of the fibrous material are not particularly limited and can be suitably used as long as the length is 1 to 200 mm and the thickness is in the range of 0.1 to 100 denier.
  • the shape is not particularly limited as long as it is fibrous, and examples thereof include a thin cylindrical shape, a split yarn shape, a staple shape, a filament shape, and a web shape.
  • the weight ratio of the water-absorbent resin particles to the fibers is preferably 40/60 to 90/10, more preferably Is 70/30 to 80/20.
  • An absorbent article can be obtained using the water absorbent resin of the present invention. Specifically, the absorber is used.
  • the absorbent article is applicable not only to sanitary articles such as paper diapers and sanitary napkins, but also to various uses such as absorption of various aqueous liquids described below, use as a retention agent, and use as a gelling agent.
  • the manufacturing method and the like of the absorbent article are the same as known ones (described in JP 2003-225565 A, JP 2006-131767 A, JP 2005-097569 A, etc.).
  • ⁇ Measurement method of water retention amount> 1.00 g of a measurement sample is placed in a tea bag (20 cm long, 10 cm wide) made of a nylon net having a mesh size of 63 ⁇ m (JIS Z8801-1: 2006), and 1,000 ml of physiological saline (saline concentration 0.9%). The sample was immersed for 1 hour without stirring and then pulled up, suspended for 15 minutes and drained. Thereafter, each tea bag was placed in a centrifuge, centrifuged at 150 G for 90 seconds to remove excess physiological saline, and the weight (h1) including the tea bag was measured to obtain the water retention amount from the following formula. In addition, the temperature of the used physiological saline and measurement atmosphere was 25 degreeC +/- 2 degreeC. Water retention amount (g / g) (h1) ⁇ (h2) In addition, (h2) is the weight of the tea bag measured by the same operation as described above when there is no measurement sample.
  • ⁇ Measurement method of moisture absorption blocking rate> 10 g of the measurement sample passed through a 850 ⁇ m wire mesh (JIS Z8801-1: 2001) is uniformly placed in a 5 cm diameter aluminum cylindrical dish and placed in a constant temperature and humidity chamber of 40 ⁇ 1 ° C. and relative humidity of 80 ⁇ 5%. And left for 3 hours. After measuring the total weight (a) of the measurement sample after standing for 3 hours, the sample was tapped five times with a wire mesh (JIS Z8801-1: 2001) having an opening of 1400 ⁇ m, blocked by moisture absorption and having an opening of 1400 ⁇ m. The weight (b) of the resin particles remaining on the wire mesh was measured, and the moisture absorption blocking rate was determined from the following formula. Moisture absorption blocking rate (%) (b / a) ⁇ 100
  • Example 1 Acrylic acid (a1-1) ⁇ Mitsubishi Chemical Corporation, purity 100% ⁇ 131 parts, Cross-linking agent (b-1) ⁇ Pentaerythritol triallyl ether, Osaka Soda Co., Ltd. ⁇ 0.44 parts and deionized water 362 The part was kept at 3 ° C. with stirring and mixing. After flowing nitrogen into this mixture to reduce the dissolved oxygen amount to 1 ppm or less, 0.5 part of 1% aqueous hydrogen peroxide solution, 1 part of 2% aqueous ascorbic acid solution and 2% 2,2′-azobisamidinopropane Polymerization was initiated by adding and mixing 1 part of an aqueous dihydrochloride solution. After the temperature of the mixture reached 80 ° C., a water-containing gel was obtained by polymerization at 80 ⁇ 2 ° C. for about 5 hours.
  • this water-containing gel was shredded with a mincing machine (12VR-400K manufactured by ROYAL), and mixed and neutralized by adding 108 parts of a 48.5% aqueous sodium hydroxide solution to neutralize the gel (degree of neutralization: 72%). Further, the neutralized hydrogel was dried with a ventilation dryer ⁇ 200 ° C., wind speed 2 m / sec ⁇ to obtain a dried product. The dried product was pulverized with a juicer mixer (Osterizer BLENDER manufactured by Oster), and then sieved to adjust the particle size to a particle size range of 710 to 150 ⁇ m to obtain a crosslinked polymer (A-1).
  • a mincing machine (12VR-400K manufactured by ROYAL
  • the neutralized hydrogel was dried with a ventilation dryer ⁇ 200 ° C., wind speed 2 m / sec ⁇ to obtain a dried product.
  • the dried product was pulverized with a juicer mixer (Osterizer BLENDER manufactured by Oster), and then sieved to adjust
  • Klebosol 30cal25 (Merck colloidal silica, solid content 30%, average primary particle size 25 nm) 1.0 part, ethylene glycol diglycidyl ether 0.1 part as organic surface crosslinking agent (e), carbon number 4 or less
  • a liquid obtained by mixing 1.0 part of propylene glycol as a monohydric alcohol (f) and 1.6 parts of water is spray-added from a spray nozzle and mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain the water absorption Resin particles (P-1) were obtained.
  • the apparent density of (P-1) was 0.58 g / ml.
  • Example 2 While 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (Flexomix FXD100 manufactured by Hosokawa Micron Corporation: rotation speed 3000 rpm, feed rate 50 kg / h) From a spray nozzle, a solution obtained by mixing 0.1 part of ethylene glycol diglycidyl ether as the agent (e), 1.0 part of propylene glycol as the polyhydric alcohol (f) having 4 or less carbon atoms, and 1.6 parts of water After spray addition, uniform mixing, heating at 130 ° C.
  • FXD100 manufactured by Hosokawa Micron Corporation: rotation speed 3000 rpm, feed rate 50 kg / h
  • Example 3 While 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (Flexomix FXD100 manufactured by Hosokawa Micron Corporation: rotation speed 3000 rpm, feed rate 50 kg / h) From a spray nozzle, a solution obtained by mixing 0.1 part of ethylene glycol diglycidyl ether as the agent (e), 1.0 part of propylene glycol as the polyhydric alcohol (f) having 4 or less carbon atoms, and 1.6 parts of water After spray addition, uniform mixing, heating at 130 ° C.
  • Flexomix FXD100 manufactured by Hosokawa Micron Corporation: rotation speed 3000 rpm, feed rate 50 kg / h
  • Example 4 From Example 1, 0.1 part of ethylene glycol diglycidyl ether as the organic surface crosslinking agent (e) is 0.03 part, and 1.0 part of propylene glycol as the polyhydric alcohol (f) having 4 or less carbon atoms is 0.
  • the water-absorbent resin particles (P-4) of the present invention were obtained in the same manner except that 1.6 parts of water was changed to 0.80 parts at 60 parts.
  • the apparent density of (P-4) was 0.58 g / ml.
  • Example 5 From Example 1, 1.0 part of Klebosol 30cal25 (colloidal silica manufactured by Merck Co., Ltd., solid content 30%, average primary particle size 25 nm) as water-insoluble silicon compound fine particles (c) was changed to 0.17 part, and an organic surface crosslinking agent (e ) 0.1 part of ethylene glycol diglycidyl ether as 0.01), 1.0 part of propylene glycol as polyhydric alcohol (f) having 4 or less carbon atoms, 0.30 part, 1.6 parts of water
  • the water-absorbent resin particles (P-5) of the present invention were obtained in the same manner except that was changed to 0.30 part.
  • the apparent density of (P-5) was 0.59 g / ml.
  • Example 6 The same procedure as in Example 1 except that 1.0 part of Klebosol 30cal25 (Merck colloidal silica, solid content 30%, average primary particle size 25 nm) as water-insoluble silicon compound fine particles (c) was changed to 1.5 parts. Inventive water-absorbing resin particles (P-6) were obtained. The apparent density of (P-6) was 0.58 g / ml.
  • Example 7 (P-1) Put 100 parts by weight in a plastic bag and add 0.1 part Aerosil 200 (fumed silica manufactured by Nippon Aerosil Co., Ltd., average primary particle size 12 nm) as water-insoluble silicon compound fine particles (c). Then, the water-absorbent resin particles (P-7) of the present invention were obtained. The apparent density of (P-7) was 0.57 g / ml.
  • Example 8 Acrylic acid (a1-1) ⁇ manufactured by Mitsubishi Chemical Corporation, purity 100% ⁇ 155 parts, crosslinking agent (b-1) ⁇ pentaerythritol triallyl ether, Osaka Soda Co., Ltd. ⁇ 0.54 parts and deionized water 335 The part was kept at 3 ° C. with stirring and mixing. After flowing nitrogen into this mixture to reduce the dissolved oxygen amount to 1 ppm or less, 0.6 part of 1% aqueous hydrogen peroxide solution, 1.2 parts of 2% aqueous ascorbic acid solution and 2% 2,2′-azobis Polymerization was initiated by adding and mixing 8 parts of an amidinopropane dihydrochloride aqueous solution. After the temperature of the mixture reached 90 ° C., a water-containing gel was obtained by polymerization at 90 ⁇ 2 ° C. for about 5 hours.
  • this water-containing gel is shredded with a mincing machine (12 VR-400K manufactured by ROYAL), and then mixed and neutralized by adding 128 parts of 48.5% aqueous sodium hydroxide solution to neutralize the gel (degree of neutralization: 72%). Further, the neutralized hydrogel was dried with a ventilation dryer ⁇ 150 ° C., wind speed 2 m / sec ⁇ to obtain a dried product. The dried product was pulverized with a juicer mixer (OSTERIZER BLENDER manufactured by Oster) and then sieved to adjust the particle size to a particle size range of 710 to 150 ⁇ m to obtain a crosslinked polymer (A-2).
  • Comparative water-absorbing resin particles (R-6) were obtained in the same manner as in Example 1, except that Klebosol 30cal25 as the water-insoluble silicon compound fine particles (c) was not used.
  • the apparent density of (R 6) was 0.60 g / ml.
  • water-absorbent resin particles of the present invention have little fluctuation in the amount of feed in a supply device (feeder) in the production process, when applied to the production of various absorbers, production is stable.
  • Suitable for hygiene items such as adult paper diapers, napkins (sanitary napkins, etc.), paper towels, pads (pads for incontinence, surgical underpads, etc.) and pet sheets (pet urine absorbing sheets). Ideal for disposable diapers.
  • the water-absorbent resin particles of the present invention are not only sanitary products, but also pet urine absorbents, urine gelling agents for portable toilets, freshness preservation agents such as fruits and vegetables, meat and seafood drip absorbents, cold insulation agents, disposable warmers It is also useful for various uses such as battery gelling agents, water retention agents for plants and soil, anti-condensation agents, water-stopping materials and packing materials, and artificial snow.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

La présente invention concerne une résine absorbant l'eau qui peut être introduite à partir d'un dispositif d'alimentation en une quantité ayant moins de variabilité dans un procédé de production. Plus précisément, la présente invention concerne des particules de résine absorbant l'eau contenant un polymère réticulé (A) contenant un monomère vinylique hydrosoluble (a1) et un agent de réticulation (b) en tant que motifs constitutifs essentiels et de fines particules de composé du silicium insoluble dans l'eau (c), la moyenne arithmétique des concentrations atomiques de Si (% atomique), telles que mesurées par spectroscopie à rayons X à dispersion d'énergie-microscope électronique à balayage à 20 points d'analyse étant de 0,5 à 5,0 et le coefficient de variation des concentrations atomiques de Si étant de 0 à 40 %.
PCT/JP2019/011728 2018-03-29 2019-03-20 Particules de résine absorbant l'eau et procédé de production s'y rapportant Ceased WO2019188669A1 (fr)

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CN202310838820.7A CN116769269A (zh) 2018-03-29 2019-03-20 吸水性树脂颗粒
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JP2019130148A (ja) * 2018-01-31 2019-08-08 株式会社三洋物産 遊技機
JP2019130141A (ja) * 2018-01-31 2019-08-08 株式会社三洋物産 遊技機
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