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WO2019059019A1 - Composition de résine absorbant l'eau et son procédé de fabrication - Google Patents

Composition de résine absorbant l'eau et son procédé de fabrication Download PDF

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Publication number
WO2019059019A1
WO2019059019A1 PCT/JP2018/033395 JP2018033395W WO2019059019A1 WO 2019059019 A1 WO2019059019 A1 WO 2019059019A1 JP 2018033395 W JP2018033395 W JP 2018033395W WO 2019059019 A1 WO2019059019 A1 WO 2019059019A1
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Prior art keywords
water
resin composition
absorbent resin
weight
crosslinked polymer
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PCT/JP2018/033395
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English (en)
Japanese (ja)
Inventor
宮島　徹
佑介 松原
艶ブン 王
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SDP Global Co Ltd
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SDP Global Co Ltd
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Priority to CN201880060747.2A priority Critical patent/CN111094441B/zh
Priority to JP2019543557A priority patent/JPWO2019059019A1/ja
Publication of WO2019059019A1 publication Critical patent/WO2019059019A1/fr
Anticipated expiration legal-status Critical
Priority to JP2022205177A priority patent/JP2023029421A/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
    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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

Definitions

  • the present invention relates to a water absorbent resin composition and a method for producing the same.
  • a water absorbent resin mainly composed of hydrophilic fibers such as pulp and acrylic acid (salt) is widely used as an absorbent. From the viewpoint of improving Quality of Life (QOL) in recent years, the demand for these sanitary materials has shifted to lighter and thinner ones, and along with this, it has become desirable to reduce the amount of hydrophilic fibers used. .
  • the crosslink density of the water absorbing resin surface is increased by crosslinking the surface of the water absorbing resin, deformation of the swelling gel surface is suppressed, and gel gaps are efficiently formed.
  • a method is already known (see, for example, Patent Document 1).
  • the surface cross-linking alone was not sufficient to make the liquid permeability between the swollen gels sufficient.
  • An object of the present invention is to provide a water-absorbent resin which is excellent in blocking resistance at the time of initial swelling, and excellent in liquid permeability between swollen gels and water absorption performance under load.
  • the present invention relates to a water-soluble vinyl monomer (a1) and / or a cross-linked polymer (A) comprising a vinyl monomer (a2) which becomes a water-soluble vinyl monomer (a1) by hydrolysis and a cross-linking agent (b)
  • a water-absorbent resin composition comprising a water-insoluble alumina-containing fine particle (c) and a water-soluble aluminum salt (d), and having a surface aluminum coverage of 60 to 100% of the crosslinked polymer (A);
  • An aqueous solution containing 0.05 to 5% by weight based on the weight of the crosslinked polymer (A) is added, and then the crosslinked polymer (A) is surface-crosslinked.
  • Surface aluminum coverage Is a
  • the water-absorbent resin composition of the present invention and the water-absorbent resin composition obtained by the production method of the present invention have an initial stage by covering at least a part of the surface with water-insoluble alumina-containing fine particles and a water-soluble aluminum salt. Blocking resistance at the time of swelling is high, and liquid permeability between the swollen gels is very excellent. Therefore, stable absorption performance (for example, liquid diffusivity, absorption rate, absorption amount, etc.) is exhibited stably in various usage conditions.
  • the water-absorbent resin composition of the present invention comprises a water-soluble vinyl monomer (a1) and / or a vinyl monomer (a2) which becomes a water-soluble vinyl monomer (a1) by hydrolysis and a crosslinking agent (b) as essential constitutional units. It contains a crosslinked polymer (A), water-insoluble alumina-containing fine particles (c) and a water-soluble aluminum salt (d).
  • water-soluble vinyl monomer (a1) in the present invention there is no particular limitation on the water-soluble vinyl monomer (a1) in the present invention, and known monomers, for example, at least one water-soluble substituent disclosed in paragraphs 0007 to 0023 of Patent No. 3648553 and ethylenic non Vinyl monomers having a saturated group (for example, anionic vinyl monomers, nonionic vinyl monomers and cationic vinyl monomers), anionic vinyl monomers disclosed in paragraphs 0009 to 0024 of JP-A No.
  • nonionic Vinyl monomer and cationic vinyl monomer selected from the group consisting of carboxy group, sulfo group, phosphono group, hydroxyl group, carbamoyl group, amino group and ammonio group disclosed in paragraphs 0041 to 0051 of JP-A-2005-75982 At least one Vinyl monomer having can be used.
  • a vinyl monomer (a2) [hereinafter, also referred to as a hydrolyzable vinyl monomer (a2), which becomes a water-soluble vinyl monomer (a1) by hydrolysis].
  • a vinyl monomer having at least one hydrolysable substituent which becomes a water-soluble substituent by hydrolysis disclosed in paragraphs 0024 to 0025 of Japanese Patent No. 3648553, JP-A
  • At least one hydrolyzable substituent [1,3-oxo-2-oxapropylene (-CO-O-CO-) group, an acyl group and a cyano group disclosed in paragraphs 0052 to 0055 of the publication No. 2005-75982.
  • the water-soluble vinyl monomer means a vinyl monomer which dissolves at least 100 g in 100 g of water at 25 ° C.
  • the hydrolysability in a hydrolysable vinyl monomer (a2) means the property which is hydrolyzed by the effect
  • the hydrolysis of the hydrolyzable vinyl monomer (a2) may be performed during polymerization, after polymerization, or both of them, but after polymerization is preferable from the viewpoint of the absorption performance of the resulting water-absorbent resin composition.
  • water-soluble vinyl monomers (a1) are preferable from the viewpoint of absorption performance and the like, and anionic vinyl monomers, carboxy (salt) groups, sulfo (salt) groups, amino groups, carbamoyl groups and ammonio groups are more preferable.
  • vinyl monomers having a mono-, di- or tri-alkylammonio group more preferably vinyl monomers having a carboxy (salt) group or carbamoyl group, particularly preferably (meth) acrylic acid (salt) and (meth) ) Acrylamide, in particular (meth) acrylic acid (salt), most preferred acrylic acid (salt).
  • (meth) acrylic acid (salt) means acrylic acid, acrylic acid salt, methacrylic acid or methacrylic acid salt
  • (meth) acrylamide means acrylamide or methacrylamide.
  • alkali metal (lithium, sodium and potassium etc.) salt, alkaline earth metal (magnesium and calcium etc.) salt, ammonium (NH 4 ) salt etc. are mentioned.
  • 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.
  • a water-soluble vinyl monomer (a1) or a hydrolyzable vinyl monomer (a2) When either a water-soluble vinyl monomer (a1) or a hydrolyzable vinyl monomer (a2) is used as a structural unit, one type may be used alone as a structural unit, and two or more types may also be used as a structural unit as necessary. good. The same applies to the case where the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) are used as structural units.
  • their content molar ratio [(a1) / (a2)] is preferably 75/25 to 99/1. And more preferably 85/15 to 95/5, particularly preferably 90/10 to 93/7, and most preferably 91/9 to 92/8. Within this range, the absorption performance is further improved.
  • water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2) as the structural unit of the crosslinked polymer (A), other vinyl monomers (a3) copolymerizable with these as the structural unit Can.
  • the other vinyl monomers (a3) may be used alone or in combination of two or more.
  • Aliphatic ethylenic monomers having 2 to 20 carbon atoms Alkenes (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.); and alkadienes (butadiene, isoprene etc.), etc.
  • the content (mol%) of the other vinyl monomer (a3) units is based on the total number of moles of the water-soluble vinyl monomer (a1) unit and the hydrolyzable vinyl monomer (a2) unit from the viewpoint of absorption performance etc. It is preferably 0 to 5, more preferably 0 to 3, particularly preferably 0 to 2, particularly preferably 0 to 1.5, and the content of the other vinyl monomer (a3) unit is preferably from the viewpoint of absorption performance and the like. Most preferably, it is 0 mol%.
  • the crosslinking agent (b) is not particularly limited and is known (for example, it reacts with a crosslinking agent having two or more ethylenic unsaturated groups disclosed in paragraphs 0031 to 0034 of Japanese Patent No. 3648553, a water-soluble substituent).
  • JP-A 2003-165883 having at least one functional group and at least one crosslinking agent having at least one ethylenically unsaturated group, and at least two functional groups capable of reacting with a water-soluble substituent
  • Crosslinking agents such as disclosed crosslinkable vinyl monomer) can be used to.
  • a crosslinking agent having two or more ethylenically unsaturated groups is preferable, and poly (meth) allyl ether of polyhydric alcohol having 2 to 40 carbon atoms, more preferably carbon number is more preferable.
  • the crosslinking agent (b) may be used alone or in combination of two or more.
  • the content (mol%) of the crosslinker (b) unit is (a1) to (a1) when the other vinyl monomer (a3) of the water-soluble vinyl monomer (a1) unit and the hydrolyzable vinyl monomer (a2) unit is used It is preferably 0.001 to 5, more preferably 0.005 to 3, particularly preferably 0.01 to 1, based on the total number of moles of (a3). Within this range, the absorption performance is further improved.
  • crosslinked polymer (A) As a method of producing the crosslinked polymer (A), known solution polymerization (diathermal polymerization, thin film polymerization, spray polymerization method, etc .; JP-A-55-133413, etc.), known suspension polymerization method, reverse phase polymerization, etc.
  • a water-containing gel polymer (consisting of a cross-linked polymer and water) obtained by turbid polymerization (JP-B 54-30710, JP-A 56-26909, JP-A 1-5 808, etc.) may be used if necessary. It can be obtained by heat drying and crushing.
  • the crosslinked polymer (A) may be used alone or in combination of two or more.
  • the solution polymerization method is preferable, and the aqueous solution polymerization method is particularly preferable since it is not necessary to use an organic solvent etc. and advantageous in terms of production cost, and the water retention amount is large and water soluble.
  • the aqueous solution adiabatic polymerization method is most preferable because a water-absorbent resin with a small amount of components is obtained, and temperature control at the time of polymerization is unnecessary.
  • aqueous solution polymerization When aqueous solution polymerization is performed, a mixed solvent containing water and an organic solvent can be used, and as the organic solvent, methanol, ethanol, acetone, methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide and two or more of them can be used.
  • 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 catalyst When a catalyst is used for the polymerization, conventionally known catalysts for radical polymerization can be used.
  • azo compounds azobisisobutyronitrile, azobiscyanovaleric acid and 2,2'-azobis (2-amidinopropane) hydrochloride are used.
  • inorganic peroxides eg hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate
  • organic peroxides benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, succinic acid peroxide Oxides and di (2-ethoxyethyl) peroxydicarbonate etc
  • redox catalysts sulfites or bisulfites of alkali metals, ammonium sulfite, ammonium bisulfite and ascorbic acid etc, reducing agents and persulfates of alkali metals, Oxidation of ammonium persulfate, hydrogen peroxide and organic peroxides And the like, and the like.
  • the amount (% by weight) of the radical polymerization catalyst used is the water soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), and the other vinyl monomers (a3) of (a1) to (a3) Based on the total weight, 0.0005 to 5 is preferable, and more preferably 0.001 to 2.
  • 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, thiocarbonyl compound Etc. These polymerization control agents may be used alone, or two or more of these may be used in combination.
  • the use amount (% by weight) of the polymerization control agent is the water soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), and the other vinyl monomers (a3) of (a1) to (a3) Based on the total weight, 0.0005 to 5 is preferable, and more preferably 0.001 to 2.
  • the polymerization may be carried out in the presence of a conventionally known dispersant or surfactant, if necessary.
  • a hydrocarbon solvent such as xylene, normal hexane and normal heptane which are conventionally known.
  • the polymerization initiation temperature can be appropriately adjusted depending on the type of catalyst used, but it is preferably 0 to 100 ° C., more preferably 2 to 80 ° C.
  • the solvent is preferably distilled off after the polymerization.
  • 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 composition is further improved.
  • the water content after 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 water-containing gel-like product (hereinafter abbreviated as water-containing gel) in which the crosslinked polymer (A) contains water can be obtained by the polymerization method described above, and the crosslinked polymer (A) can be obtained by further drying the water-containing gel. You can get it.
  • an acid group-containing monomer such as acrylic acid or methacrylic acid
  • the water-containing gel may be neutralized with a base.
  • the neutralization degree of the acid group is preferably 50 to 80 mol%. When the degree of neutralization is less than 50 mol%, the tackiness of the resulting water-containing gel polymer may be high, and the workability at the time of production and use may be deteriorated.
  • the water retention amount of the water-absorbent resin composition obtained may be reduced.
  • the degree of neutralization exceeds 80%, the pH of the obtained resin may be high, which may cause the safety of the skin of the human body.
  • the neutralization may be carried out at any stage after the polymerization of the crosslinked polymer (A) in the production of the water-absorbent resin composition, and for example, a method such as a method of neutralizing in the state of a water-containing gel is preferred. It is illustrated as As a base to be neutralized, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate, sodium hydrogencarbonate and potassium carbonate can usually be used.
  • the water-containing gel obtained by polymerization can be shredded if necessary.
  • the size (longest diameter) of the shredded gel 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 step is further improved.
  • the shredding can be performed by a known method, and shredding can be performed using a shredding apparatus (for example, a beck mill, a rubber chopper, a farm mill, a mincing machine, an impact crusher and a roll crusher) or the like.
  • a shredding apparatus for example, a beck mill, a rubber chopper, a farm mill, a mincing machine, an impact crusher and a roll crusher
  • the content of organic solvent and the moisture, infrared moisture measuring instrument is obtained from the weight loss of the measurement sample when heated.
  • a method of distilling off the solvent (including water) in the water-containing gel As a method of distilling off the solvent (including water) in the water-containing gel, a method of distilling (drying) with hot air at a temperature of 80 to 230 ° C., a thin film drying method by a drum dryer heated to 100 to 230 ° C. (Heating) reduced-pressure drying method, lyophilization method, infrared ray drying method, decantation and filtration can be applied.
  • a crosslinked polymer (A) After drying the water-containing gel to obtain a crosslinked polymer (A), it can be further pulverized.
  • a grinding method for example, a hammer type crusher, an impact type crusher, a roll crusher, a shet type crusher, etc.
  • the particle size of the pulverized crosslinked polymer can be adjusted by sieving, if necessary.
  • the weight-average particle size ( ⁇ m) of the cross-linked polymer (A) optionally sieved 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 is determined using the low tap test sieve shaker and standard sieves (JIS Z8801-1: 2006) according to Perry's Chemical Engineers Handbook 6th Edition (McGrow Hill Book, Inc. 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 from the top, and a pan. About 50 g of the measurement particles are placed in the uppermost sieve and shaken for 5 minutes with a low tap test sieve shaker.
  • the weight of the measurement particles on each sieve and receiver is weighed, and the weight fraction of the particles on each sieve is determined by taking the total as 100% by weight. After plotting the weight fraction on the vertical axis), a line connecting points is drawn to obtain a particle size corresponding to 50% by weight of the weight fraction, which is defined as a weight average particle size.
  • the ratio (% by weight) is preferably 3 or less, more preferably 1 or less.
  • the content of the fine particles can be determined using a graph created when determining the above-described weight average particle diameter.
  • the shape of the crosslinked polymer (A) is not particularly limited, and examples thereof include irregularly crushed, scaly, pearly and rice grains. Among these, from the viewpoint of good interlocking with the fibrous material in paper diaper applications and the like and no concern of detachment from the fibrous material, the irregularly crushed material is preferable.
  • the crosslinked polymer (A) may contain some other components such as a residual solvent and a residual crosslinking component as long as the performance is not impaired.
  • the water-absorbent resin composition of the present invention preferably has a structure in which the surface of the crosslinked polymer (A) is crosslinked by the organic surface crosslinking agent (e).
  • the organic surface crosslinking agent (e) include known polyvalent glycidyl compounds, polyvalent amines, polyvalent aziridine compounds and polyvalent isocyanate compounds described in JP-A-59-189103, JP-A-58-180233, etc.
  • polyhydric alcohols described in JP-A-61-16903 silane coupling agents described in JP-A-61-211305 and JP-A-61-252212, described in JP-A-5-508425.
  • organic surface cross-linking agents of polyvalent oxazoline compounds described in JP-A No. 11-240959, etc. can be used.
  • these surface crosslinking agents polyvalent glycidyl compounds, polyhydric alcohols and polyhydric amines are preferable from the viewpoint of economy and absorption characteristics, and polyvalent glycidyl compounds and polyhydric alcohols are more preferable, and polyvalent glycidyl compounds are more preferable.
  • Glycidyl compounds most preferably ethylene glycol diglycidyl ether.
  • 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 crosslinking agent (e) used is not particularly limited because it can be variously changed depending on the type of the surface crosslinking agent, the conditions for crosslinking, and the target performance. From the viewpoint of absorption characteristics, etc., 0.001 to 3 is preferable based on the weight of the water absorbent resin composition, more preferably 0.005 to 2, and particularly preferably 0.01 to 1.5.
  • the 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, screw mixer, screw extruder, turbulizer, Nauta mixer, double-arm kneader, Cross-linked polymer (A) and organic using mixing equipment such as flow type mixer, V type mixer, minced mixer, ribbon type mixer, air flow type mixer, rotary disk type mixer, conical blender and roll mixer
  • the method of mixing uniformly with the surface crosslinking agent (e) is mentioned.
  • the organic surface crosslinking agent (e) may be used after being diluted with water and / or any solvent.
  • the temperature at the time of mixing the crosslinked polymer (A) and the organic surface crosslinking agent (e) is not particularly limited, it is preferably 10 to 150 ° C., more preferably 20 to 100 ° C., particularly preferably 25 to 80 ° C. is there.
  • the heating temperature is preferably 100 to 180 ° C., more preferably 110 to 175 ° C., particularly preferably 120 to 170 ° C. from the viewpoint of the breakage resistance of the resin particles.
  • the heating time can be appropriately set according to the heating temperature, but is preferably 5 to 60 minutes, more preferably 10 to 40 minutes, from the viewpoint of absorption performance. It is also possible to further crosslink the surface of the water-absorbent resin obtained by surface cross-linking, using an organic surface cross-linking agent of the same or different type as the organic surface cross-linking agent used first.
  • the particle size is adjusted by sieving as required.
  • the average particle size of the obtained particles is preferably 100 to 600 ⁇ m, more preferably 200 to 500 ⁇ m.
  • the content of the 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 composition of the present invention contains water-insoluble alumina-containing fine particles (c).
  • the water-insoluble alumina-containing particles (c) include alumina (aluminum oxide) particles, alumina-modified silica particles, boehmite particles, aluminum hydroxide particles, aluminum phosphate particles, and aluminosilicate particles such as zeolite and montmorillonite.
  • Alumina fine particles and alumina-modified silica fine particles are preferable, and alumina-modified silica fine particles are more preferable, from the viewpoints of easy availability, easy handling, and absorption performance.
  • one type may be used alone, or two or more types may be used in combination.
  • alumina-modified silica generally refers to fine particles having a structure in which at least a portion of the surface of the fine silica particles is coated with alumina.
  • the water-insoluble alumina-containing fine particles (c) in the present invention are preferably spherical or amorphous particles having an average primary particle size of 1 to 100 nm. When the particles are spherical or amorphous, the powder flowability of the water-absorbent resin composition becomes good.
  • the average primary particle diameter of the water-insoluble alumina-containing fine particles (c) is preferably 2 to 80 nm, more preferably 3 to 60 nm, particularly preferably 5 to 50 nm, and most preferably 5 to 20 nm. If the average primary particle size is smaller than 1 nm, the absorption characteristics of the water-absorbent resin composition under load may be deteriorated.
  • the measurement of the average primary particle size of the water-insoluble alumina-containing fine particles (c) may be performed by a conventionally known method, for example, individual particles of 100 or more particles from an image of 50,000 times with a transmission electron microscope Method of measuring the particle diameter from the average of the longest diameter and the shortest diameter of the particle to obtain the average value, a method using a scattering type particle size distribution measuring apparatus using dynamic light scattering or laser diffraction method, or spherical particles The method etc. which are calculated from the specific surface area by BET method are mentioned. When using a commercial item, its catalog value can be substituted.
  • the water-absorbent resin composition of the present invention can be obtained by mixing the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c).
  • a mixing method a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, a Nauta mixer, a double arm kneader, a fluid mixer, a V mixer, a mince mixer, a ribbon type
  • the method include uniform mixing using known mixing devices such as mixers, air-flow mixers, rotary disk mixers, conical blenders and roll mixers.
  • the water-insoluble alumina-containing fine particles (c) may be added simultaneously with the water and / or the solvent.
  • a dispersion in which water-insoluble alumina-containing 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, it is preferable to add by spraying or dripping.
  • the content of water-insoluble alumina-containing microparticles (c) 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 alumina-containing fine particles (c) may be a dispersion obtained by directly granulating the raw material in water and / or a solvent according to a method known in the prior art, and A dispersion obtained by mechanical dispersion in a solvent may be used. From the viewpoint of the stability of the dispersion, it is preferable to use a dispersion obtained by directly granulating the raw material in water and / or a solvent and granulating it.
  • a dispersion of the water-insoluble alumina-containing fine particles (c) can be obtained as a commercial colloidal liquid (sol).
  • the dispersion may contain, if necessary, additives such as any stabilizer.
  • the stabilizer examples include commercially available surfactants and dispersants, commercially available acid compounds [phosphoric acid (salt), boric acid (salt), alkali metal (salt) and alkaline earth metal (salt), hydroxy carbon Acids (salts), fatty acids (salts), etc.] can be mentioned.
  • the temperature when mixing the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c) is preferably 10 to 150 ° C., more preferably 20 to 100 ° C., 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., particularly preferably 35 to 170 ° C. from the viewpoint of the breakage resistance of the resin particles.
  • heating at 180 ° C. or lower indirect heating using steam is possible, which is advantageous in equipment.
  • the water and the solvent to be used in combination may be excessively left in the water absorbent resin, and the absorption performance may be deteriorated.
  • 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 a heating loss method in accordance with JIS K 0067-1992 (Method for testing weight loss and residue of chemical products).
  • the heating time can be appropriately set by 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 composition of the present invention may be sieved to adjust the particle size after mixing the crosslinked polymer (A) and the water-insoluble alumina-containing fine particles (c).
  • 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 the 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 alumina-containing fine particles (c) can be adjusted according to the application of the water-absorbent resin composition, but based on the weight of the crosslinked polymer (A).
  • 0.01 to 1% by weight is preferable, more preferably 0.02 to 0.8% by weight, and particularly preferably 0.05 to 0.5% by weight.
  • the liquid permeability of the water-absorbent resin composition becomes good, which is further preferable.
  • the water absorbent resin composition of the present invention contains a water soluble aluminum salt (d).
  • water-soluble aluminum salts (d) include aluminates (sodium aluminate, potassium aluminate, and hydrates thereof, etc.), sulfates of aluminum and double salts thereof (aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate) And their hydrates], chlorides of aluminum [aluminium chloride, polyaluminium chloride, and hydrates thereof], and organic acid salts of aluminum [aluminium lactate, aluminum acetate, and hydrates thereof] Etc.
  • One kind of (d) may be used alone, or two or more kinds may be used in combination.
  • the water-soluble aluminum salt (d) in the present invention is preferably a crystalline salt having a water solubility of 10 g / 100 g H 2 O or more at 20 ° C.
  • the water solubility of the water-soluble aluminum salt (d) is more preferably 20 g / 100 g H 2 O or more, still more preferably 25 g / 100 g H 2 O or more.
  • the water solubility is smaller than 10 g / 100 g H 2 O, uniform mixing with the crosslinked polymer (A) is difficult, and the liquid permeability of the water-absorbent resin composition is deteriorated.
  • (d) is non-crystalline, elution of the aluminum water-soluble salt easily occurs at the time of swelling of the water-absorbent resin, and the absorption performance is deteriorated. Therefore, (d) is preferably crystalline. If (d) is a highly water-soluble crystalline salt, the surface of the water-absorbent resin is likely to be coated with microcrystalline aluminum water-soluble salt, and the liquid permeability is particularly excellent.
  • water-soluble aluminum salts (d) aluminum sulfates and double salts thereof are preferred from the viewpoint of high crystallinity and high water solubility and easy availability, aluminum sulfate 14-18 hydrate and aluminum sodium sulfate More preferred is dodecahydrate.
  • the water-absorbent resin composition of the present invention can be obtained by mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d).
  • a mixing method a cylindrical mixer, a screw mixer, a screw extruder, a turbulizer, a Nauta mixer, a double arm kneader, a fluid mixer, a V mixer, a mince mixer, a ribbon type
  • the method include uniform mixing using known mixing devices such as mixers, air-flow mixers, rotary disk mixers, conical blenders and roll mixers.
  • the water-soluble aluminum salt (d) In mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d), it is preferable to add the water-soluble aluminum salt (d) while stirring the crosslinked polymer (A).
  • the water-soluble aluminum salt (d) to be added may be added simultaneously with the water and / or the solvent.
  • a solution of water-soluble aluminum salt (d) dissolved in water and / or solvent is added from the viewpoint of workability and liquid permeability. It is further preferred to add an aqueous solution dissolved in a solvent containing water.
  • the content of the water-soluble aluminum salt (d) contained in the solution is preferably 5 to 70% by weight based on the total weight of the solution, more preferably 10 to It is 60% by weight.
  • the temperature at which the cross-linked polymer (A) and the water-soluble aluminum salt (d) are mixed is not particularly limited, but is preferably 10 to 150 ° C., more preferably 20 to 100 ° C., particularly preferably 25 to 80 ° C. .
  • the heating temperature is preferably 25 to 180 ° C., more preferably 30 to 175 ° C., particularly preferably 35 to 170 ° C. from the viewpoint of the breakage resistance of the resin particles.
  • the heating temperature is preferably 25 to 180 ° C., more preferably 30 to 175 ° C., particularly preferably 35 to 170 ° C. from the viewpoint of the breakage resistance of the resin particles.
  • indirect heating using steam is possible, which is advantageous in equipment.
  • the water and the solvent to be used in combination may be excessively left in the water absorbent resin, and the absorption performance may be deteriorated.
  • 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 a heating loss method in accordance with JIS K 0067-1992 (Method for testing weight loss and residue of chemical products).
  • the heating time can be appropriately set according to the heating temperature, but from the viewpoint of absorption performance, preferably 5 to 60 minutes, further Preferably, it is 10 to 40 minutes.
  • a water-absorbent resin obtained by mixing a crosslinked polymer (A) and a water-soluble aluminum salt (d) is further surface-treated with a water-soluble aluminum salt of the same or different type as the water-soluble aluminum salt used first. It is also possible.
  • the water-absorbent resin composition of the present invention may be sieved to adjust the particle size after mixing the crosslinked polymer (A) and the water-soluble aluminum salt (d).
  • 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 the 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-soluble aluminum salt (d) can be adjusted according to the application of the water-absorbent resin composition, but based on the weight of the crosslinked polymer (A). 0.05 to 5% by weight, more preferably 0.1 to 4% by weight, and particularly preferably 0.2 to 3% by weight. Within this range, the liquid permeability of the water-absorbent resin composition becomes good, which is further preferable.
  • water-soluble aluminum salt (d) is a hydrate, it is based on the mass except hydration water.
  • the water-absorbent resin composition of the present invention can be obtained by mixing the crosslinked polymer (A) with the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d). (C) and the water-soluble aluminum salt (d) may be added simultaneously or separately to the crosslinked polymer (A). It is preferable to simultaneously add from the viewpoint of coating uniformity and liquid permeability.
  • the simultaneous addition means that they are added at one time or separately in each step such as the above-mentioned drying, grinding, surface crosslinking and the like.
  • the surface of the crosslinked polymer (A) has a structure crosslinked by the organic surface crosslinking agent (e), the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d)
  • the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) are preferably added simultaneously with or before the addition of the organic surface crosslinking agent (e), and at least one of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) is organically crosslinked
  • the surface aluminum coverage of the crosslinked polymer (A) is 60 to 100%.
  • the surface aluminum coverage is preferably 65 to 100%, more preferably 70 to 100%, and particularly preferably 75 to 100%, from the viewpoints of blocking resistance and liquid permeability and gel strength in initial swelling.
  • the addition amount of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) can be adjusted to the above-mentioned range.
  • the surface aluminum coverage is an index showing the coating state by the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) and can be measured by aluminum element mapping using energy dispersive X-ray analysis described later. .
  • the water-absorbent resin composition 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. Among these, propylene glycol and glycerin are preferable in terms of safety and availability, and propylene glycol is more preferable.
  • one type may be used alone, or two or more types may be used in combination.
  • the 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 crosslinked polymer (A) from the viewpoint of absorption performance and liquid permeability. It is preferably 0.1 to 3, particularly preferably 0.2 to 2.
  • the polyhydric alcohol (f) having 4 or less carbon atoms When the polyhydric alcohol (f) having 4 or less carbon atoms is contained, it may be added in any step, but from the viewpoint of liquid permeability, addition simultaneously with the water-soluble aluminum salt (d) is more preferable, and water insoluble It is particularly preferable to simultaneously add the alumina-containing fine particles (c), the water-soluble aluminum salt (d) and the organic surface crosslinking agent (e).
  • the deposition rate of the water-soluble aluminum salt (d) on the surface of the water-absorbent resin can be controlled, and the coverage and liquid permeability are improved.
  • the water absorbent resin composition of the present invention may further contain a hydrophobic substance (g).
  • the hydrophobic substance (g) includes a hydrophobic substance containing a hydrocarbon group (g1), a hydrophobic substance containing a hydrocarbon group having a fluorine atom (g2), and a hydrophobic substance having a polysiloxane structure (g3) Etc. are included.
  • hydrophobic substance (g1) containing a hydrocarbon group polyolefin resin, polyolefin resin derivative, polystyrene resin, polystyrene resin derivative, wax, long chain fatty acid ester, long chain fatty acid and salts thereof, long chain aliphatic alcohol, long And chain aliphatic amides and mixtures of two or more thereof.
  • the weight of the polyolefin resin is an olefin having 2 to 4 carbon atoms ⁇ ethylene, propylene, isobutylene, isoprene, etc. ⁇ as an essential constituent monomer (the content of the olefin is at least 50% by weight based on the weight of the polyolefin resin)
  • Polymers having an average molecular weight of 1,000 to 1,000,000 eg, polyethylene, polypropylene, polyisobutylene, poly (ethylene-isobutylene) and isoprene etc.
  • a polyolefin resin derivative a polymer having a weight average molecular weight of 1000 to 1,000,000 obtained by introducing a carboxy group (-COOH), 1,3-oxo-2-oxapropylene (-COCOO-) or the like into a polyolefin resin ⁇ eg polyethylene heat Degradation body, polypropylene thermal degradation body, maleic acid modified polyethylene, chlorinated polyethylene, maleic acid modified polypropylene, ethylene-acrylic acid copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, maleated And polybutadiene, ethylene-vinyl acetate copolymer, and maleated ethylene-vinyl acetate copolymer, etc. ⁇ .
  • 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 1000 to 1,000,000 and a polymer having a weight average molecular weight of 1000 to 1,000,000, in which styrene is an essential constituent monomer (the content of styrene is at least 50% by weight based on the weight of the polystyrene derivative) And maleic anhydride copolymer, styrene-butadiene copolymer, and styrene-isobutylene copolymer.
  • Waxes include waxes having a melting point of 50 to 200 ° C. (eg, paraffin wax, beeswax, carbana wax, tallow, etc.).
  • esters of fatty acids having 8 to 30 carbon atoms and alcohols having 1 to 12 carbon atoms ⁇ eg methyl laurate, ethyl laurate, methyl stearate, ethyl stearate, methyl oleate, oleic acid Ethyl, glycerine laurate monoester, glycerine stearate monoester, glycerine oleate monoester, pentaerythritol dilaurate monoester, pentaerythritol stearate monoester, pentaerythritol oleate monoester, sorbit laurate monoester, Sorbit stearic acid monoester, Sorbit oleic acid monoester, Sucrose palmitic acid monoester, Sucrose palmitic acid diester, Sucrose palmitic acid triester, Sucrose stearic acid moester
  • long chain fatty acids and salts thereof include fatty acids having 8 to 30 carbon atoms (eg, lauric acid, palmitic acid, stearic acid, oleic acid, dimer acid and behenic acid etc.), and salts thereof include zinc, calcium, Salts with magnesium or aluminum (hereinafter abbreviated as Zn, Ca, Mg and Al, respectively) ⁇ eg, Ca palmitate, Al palmitate, Ca stearate, Mg stearate, Al stearate etc. ⁇ can be mentioned.
  • fatty acids having 8 to 30 carbon atoms eg, lauric acid, palmitic acid, stearic acid, oleic acid, dimer acid and behenic acid etc.
  • salts thereof include zinc, calcium, Salts with magnesium or aluminum (hereinafter abbreviated as Zn, Ca, Mg and Al, respectively) ⁇ eg, Ca palmitate, Al palmitate, Ca stearate, Mg stearate, Al stearate etc. ⁇ can be
  • the long chain aliphatic alcohol includes aliphatic alcohols having 8 to 30 carbon atoms (eg, lauryl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol etc.). From the viewpoint of moisture resistance of the absorbent article, palmityl alcohol, stearyl alcohol and oleyl alcohol are preferable, and stearyl alcohol is more preferable.
  • an amidated compound 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 Amidated with a long chain fatty acid having 8 to 30 carbon atoms, an amidated 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,
  • An amidated product of a secondary amine having two aliphatic hydrocarbon groups having 1 to 7 carbon atoms and a long chain fatty acid having 8 to 30 carbon atoms can be mentioned.
  • amidated compound 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 one obtained by reacting a primary amine and a carboxylic acid at a ratio of 1 to 1 : It is divided into the thing which reacted by 2.
  • a product reacted at 1: 1 acetic acid N-octylamide, acetic acid N-hexacosylamide, heptacosanoic acid N-octylamide, heptacosanoic acid N-hexacosylamide and the like can be mentioned.
  • Examples of the reaction at 1: 2 include diacetic acid N-octylamide, diacetic acid N-hexacosylamide, diheptacosanic acid N-octylamide, and diheptacosanic acid N-hexacosylamide.
  • the primary amine and the carboxylic acid are reacted at 1: 2, the carboxylic acids used may be the same or different.
  • the amidated product of ammonia or a primary amine having 1 to 7 carbon atoms and a long chain fatty acid having 8 to 30 carbon atoms the product obtained by reacting ammonia or a primary amine with carboxylic acid in a ratio of 1: 1 can be used. It is divided into the reaction products.
  • a product reacted at 1: 1 nonanoic acid amide, nonanoic acid methylamide, nonanoic acid N-heptylamide, heptacosanoic acid amide, heptacosanoic acid N-methylamide, heptacosanoic acid N-heptylamide and heptacosanoic acid N-hexacosylamide Etc.
  • Examples of the amidated compound 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 acetic acid N-methyloctylamide and acetic acid N-methylhexaco Luamide, acetic acid N-octylhexacosylamide, acetic acid N-dihexacosylamide, heptacosanoic acid N-methyloctylamide, heptacosanoic acid N-methylhexacosylamide, heptacosanoic acid N-octylhexacosylamide and heptacosane Acid N-dihexacosylamide and the like.
  • 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 perfluoroalkanes, perfluoroalkenes, perfluoroaryls, perfluoroalkylethers, perfluoroalkylcarboxylic acids, perfluoroalkylalcohols and two of them Mixtures of species or more are 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, and particularly preferably 3 to 7. Within this range, the blocking resistance at the time of initial swelling is further improved.
  • the HLB value means the hydrophilic-hydrophobic balance (HLB) value, and can be determined by the Oda method (new surfactant introduction, page 197, published by Takehiko Fujimoto, Sanyo Chemical Industries, Ltd., published in 1981). .
  • hydrophobic substances (g1) containing a hydrocarbon group are preferable, and long chain fatty acid esters, long chain fatty acids and salts thereof, Long-chain aliphatic alcohols and long-chain aliphatic amides, more preferably Sorbit stearic acid ester, sucrose stearic acid ester, stearic acid, stearic acid Mg, stearic acid Ca, stearic acid Zn and stearic acid Al, particularly preferably Sucrose stearate and Mg stearate, most preferably sucrose stearate.
  • the amount (% by weight) of the hydrophobic substance (g) is preferably 0.001 to 1 based on the weight of the crosslinked polymer (A) from the viewpoint of absorption performance and blocking resistance at the time of initial swelling, more preferably Is from 0.005 to 0.5, particularly preferably from 0.01 to 0.3.
  • the hydrophobic substance (g) When the hydrophobic substance (g) is contained, it may be added in any step, but is added prior to the addition of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) from the viewpoint of absorption performance.
  • the hydrophobic substance (g) is preferably the surface crosslinked by the organic surface crosslinking agent (e). More preferably it is added before.
  • the water-absorbent resin composition of the present invention may contain, if necessary, additives (for example, known preservatives (described in JP-A 2003-225565 and JP-A 2006-131767) and the like, fungicides, antibacterial agents, Antioxidants, UV absorbers, colorants, fragrances, deodorants, liquid flow improvers, organic fibrous materials and the like can also be included.
  • additives for example, known preservatives (described in JP-A 2003-225565 and JP-A 2006-131767) and the like, fungicides, antibacterial agents, Antioxidants, UV absorbers, colorants, fragrances, deodorants, liquid flow improvers, organic fibrous materials and the like can also be included.
  • the content (% by weight) of the additive is preferably 0.001 to 10, more preferably 0.01 to 5, particularly preferably 0.01 to 5 based on the weight of the crosslinked polymer (A).
  • it is 0.05 to 1, most preferably 0.1 to 0.5.
  • the crosslinked polymer (A) is surface-treated using an aqueous colloidal solution of water-insoluble alumina-containing fine particles (c) and an aqueous solution of a water-soluble aluminum salt (d), and then surface cross-linked.
  • aqueous colloidal solution of the water-insoluble alumina-containing fine particles (c) and the water-soluble aluminum salt (d) are as described above.
  • an aqueous colloid solution of water-insoluble alumina-containing fine particles (c), a water-soluble aluminum salt (d) It is further preferable to carry out heat treatment after simultaneously adding the aqueous solution of (a), the organic surface crosslinking agent (e) and the polyhydric alcohol having 4 or less carbon atoms.
  • the water retention amount (g / g) of the water-absorbent resin composition of the present invention and the water-absorbent resin composition obtained by the production method of the present invention (hereinafter referred to as the water-absorbent resin composition of the present invention without distinction) It can be measured by the method described later and is preferably 28 or more, more preferably 33 or more, and still more preferably 35 or more from the viewpoint of the amount of absorption of diapers.
  • the upper limit is preferably 60 or less, more preferably 55 or less, and still more preferably 50 or less from the viewpoint of the amount of absorption under load.
  • the water retention amount can be appropriately adjusted by the amount (% by weight) of the crosslinking agent (b) and the organic surface crosslinking agent (e).
  • the gel flow rate (ml / min) of the water-absorbent resin composition of the present invention can be measured by the method described later, and is preferably 5 to 300 from the viewpoint of diaper absorption rate, and 10 to 280 is more preferable. Preferred and particularly preferred is 15 to 250. It is empirically known that the gel flow rate is contrary to the water retention amount, and there are cases where a high water retention amount is required or a high gel flow rate is required depending on the configuration of the diaper.
  • the apparent density (g / ml) of the water-absorbent resin composition of the present invention is preferably 0.50 to 0.80, more preferably 0.52 to 0.75, particularly preferably 0.54 to 0.70. is there. When it is in this range, the anti-crash resistance of the absorbent article is further improved.
  • the apparent density of the water absorbing resin composition is measured at 25 ° C. in accordance with JIS K7365: 1999.
  • the blocking ratio at the initial swelling of the water-absorbent resin composition of the present invention is preferably 0 to 50%, more preferably 0 to 40%, and particularly preferably 0 to 30%. Within this range, the liquid diffusivity is sufficiently ensured in the absorber, and the absorption performance is stabilized.
  • the gel strength (kN / m 2 ) of the water-absorbent resin composition of the present invention is preferably 2.5 or more, more preferably 2.7 or more. Within this range, the liquid permeability under load is sufficiently ensured, and the absorption performance is stabilized.
  • An absorbent can be obtained using the water-absorbent resin composition of the present invention.
  • a water-absorbent resin composition may be used alone, or may be used as an absorber together with other materials.
  • Other materials include fibrous materials and the like.
  • the structure, manufacturing method and the like of the absorber when used together with the fibrous material are the same as those of known ones (Japanese Patent Application Laid-Open Nos. 2003-225565, 2006-131767 and 2005-097569, 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 include natural fibers such as fluff pulp, and cellulosic chemical fibers such as viscose rayon, acetate and cupra.
  • natural fibers such as fluff pulp
  • cellulosic chemical fibers such as viscose rayon, acetate and cupra.
  • organic synthetic fibers include polypropylene fibers, polyethylene fibers, polyamide fibers, polyacrylonitrile fibers, polyester fibers, polyvinyl alcohol fibers, polyurethane fibers and heat fusible composite fibers (the above-mentioned fibers having different melting points) Fibers in which at least two of them are combined with a sheath-core type, eccentric type, parallel type, etc., fibers obtained by blending at least two of the above fibers, and fibers 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-sealable composite fibers and mixed fibers thereof, and more preferred are fibers obtained It is a fluff pulp, a heat-fusible composite fiber, and a mixed fiber thereof in that it is excellent in the shape-retaining property after water absorption of the water-absorbing agent.
  • the length and thickness of the fibrous material are not particularly limited, and can be suitably used if the length is in the range of 1 to 200 mm and the thickness is in the range of 0.1 to 100 denier.
  • the shape is also not particularly limited as long as it is fibrous, and thin cylindrical, split yarn, staple, filament, web and the like are exemplified.
  • the weight ratio of the water-absorbent resin composition to the fibers is preferably 40/60 to 90/10. More preferably, it is 70/30 to 80/20.
  • An absorbent article can be obtained using the water absorbent resin of the present invention. Specifically, the above-mentioned absorber is used.
  • the absorbent articles are applicable not only to sanitary goods such as disposable diapers and sanitary napkins, but also to various uses such as absorption of various aqueous liquids to be described later, use as a holding agent, use as a gelling agent, and the like.
  • the method for producing the absorbent article and the like are the same as known ones (described in JP-A-2003-225565, JP-A-2006-131767 and JP-A-2005-097569).
  • ⁇ Method of measuring absorption under load> In a cylindrical plastic tube (inner diameter: 25 mm, height: 34 mm) having a nylon mesh of 63 ⁇ m (JIS Z8801-1: 2006) attached to the bottom, 250 to 500 ⁇ m using a 30 mesh sieve and a 60 mesh sieve After weighing 0.16 g of the measurement sample sifted into a range and arranging the cylindrical plastic tube vertically so that the measurement sample has a substantially uniform thickness on a nylon mesh, a weight (weight: 210.6 g, outer diameter: 24.5 mm,).
  • a pressure shaft 9 (weight) in which a circular wire mesh 8 (150 ⁇ m mesh, 25 mm diameter) is vertically bonded to the surface of the swollen gel particles 2 22 g, 47 cm in length, was placed so that the wire mesh and the swollen gel particles were in contact with each other, and further, a weight 10 (88.5 g) was placed on the pressure shaft 9 and allowed to stand for 1 minute.
  • the cock 7 is opened, and the time (T1; seconds) required for the liquid level in the filtration cylinder to change from 60 ml division line 4 to 40 ml division line 5 is measured, and gel flow rate (ml / min) I asked for.
  • ⁇ Method of measuring surface aluminum coverage Fix 10 samples or more of the measurement sample sieved in the range of 250 to 500 ⁇ m using a 30 mesh sieve and a 60 mesh sieve on a sample stand with a carbon tape so that the particles do not overlap with each other. It was set in a JEOL field emission scanning electron microscope “JSM-7000” attached with a line analysis (EDS analysis) apparatus. The magnification was increased by 150 times, one particle was displayed on the screen, and EDS analysis was performed in the elemental mapping mode.
  • the detection area of aluminum which is the target element is S1
  • the detection area of the feature element of the water-absorbent resin composition sodium when the main component of the water-absorbent resin composition is polyacrylic acid sodium salt
  • the detection area is S0.
  • Example 1 Acrylic acid (a1-1) ⁇ Mitsubishi Chemical Co., Ltd., purity 100% ⁇ 131 parts, Crosslinking agent (b-1) ⁇ pentaerythritol triallyl ether, 0.40 parts of Diso-Ltd. ⁇ , deionized water 362 The part was kept at 3 ° C. with stirring and mixing. After nitrogen is introduced into this mixture to make the amount of dissolved oxygen 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 One part of aqueous dihydrochloride solution was added and mixed to initiate polymerization. After the temperature of the mixture reached 80 ° C., a hydrogel was obtained by polymerizing at 80 ⁇ 2 ° C. for about 5 hours.
  • the water-absorbent resin composition (P-1) was obtained.
  • Example 2 While stirring 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 at a high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), fine particles containing water-insoluble alumina (c) Al-L7 (made by Taki Chemical Co., Ltd.) 4.0 parts as ethylene, 0.1 part of ethylene glycol diglycidyl ether as organic surface crosslinking agent (e), as polyhydric alcohol having 4 or less carbon atoms (f) A mixed solution of 0.5 parts of propylene glycol and 1.1 parts of water, and 0.6 parts of sodium aluminum sulfate dodecahydrate as a water-soluble aluminum salt (d), and a polyhydric alcohol having 4 or less carbon atoms A mixed solution of 0.5 parts of propylene glycol as (f) and 1.4 parts of water is simultaneously added, uniformly mixed, and then heated at 130 ° C.
  • Example 3 While stirring 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 at a high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), fine particles containing water-insoluble alumina (c) Al-C20 (manufactured by Taki Chemical Co., Ltd.) as 1.5 parts, ethylene part diglycidyl ether as an organic surface crosslinking agent (e) 0.1 parts, as a polyhydric alcohol having 4 or less carbon atoms (f) Mixed liquid of 0.8 parts of propylene glycol and 1.3 parts of water, and 0.6 parts of sodium aluminum sulfate dodecahydrate as water-soluble aluminum salt (d), polyhydric alcohol having 4 or less carbon atoms A mixed solution of 0.5 parts of propylene glycol as (f) and 1.4 parts of water is simultaneously added, mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain To give a water absorbent resin composition (P-3). ⁇ Proper
  • Example 4 While stirring 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 at a high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), fine particles containing water-insoluble alumina (c) 3.0 parts of Vyral AS-L10 (manufactured by Taki Chemical Co., Ltd.), 0.1 parts of ethylene glycol diglycidyl ether as an organic surface crosslinking agent (e), and a polyhydric alcohol having 4 or less carbon atoms (f) A mixed solution of 0.5 parts of propylene glycol and 1.1 parts of water, and 0.6 parts of sodium aluminum sulfate dodecahydrate as a water-soluble aluminum salt (d), and a polyhydric alcohol having 4 or less carbon atoms A mixed solution of 0.5 parts of propylene glycol as (f) and 1.4 parts of water is simultaneously added, mixed uniformly, and then heated at 130 ° C. for 30 minutes to obtain To give a water absorbent
  • Example 5 While stirring 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 at a high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), fine particles containing water-insoluble alumina (c) 1.0 part of LUDOX CL (manufactured by Sigma Aldrich Japan Co., Ltd.) as a component, 0.1 part of ethylene glycol diglycidyl ether as an organic surface crosslinking agent (e), propylene as a polyhydric alcohol having 4 or less carbon atoms (f) A mixed solution of 1.0 part of glycol and 1.6 parts of water is added, mixed uniformly, heated at 130 ° C.
  • high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm fine particles containing water-insoluble alumina
  • c 1.0 part of LUDOX CL (manufactured by Sigma Aldrich Japan Co., Ltd.) as a component
  • e
  • Example 6 While stirring 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 at a high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), fine particles containing water-insoluble alumina (c) 0.75 parts of LUDOX CL-P (Grace Corporation) as a component, 0.1 parts of ethylene glycol diglycidyl ether as an organic surface crosslinking agent (e), propylene glycol as a polyhydric alcohol having 4 or less carbon atoms (f) A mixed solution of 1.0 part and 1.6 parts of water, 0.6 part of sodium aluminum sulfate dodecahydrate as water-soluble aluminum salt (d), polyhydric alcohol having 4 or less carbon atoms (f) The mixed solution of 0.5 parts of propylene glycol as a mixture and 1.4 parts of water is simultaneously added, mixed uniformly, and then heated at 130 ° C.
  • Comparative Example 1 A water-soluble aluminum salt (d) was added to 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 while stirring at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm). 1.2 parts of sodium aluminum sulfate dodecahydrate, 0.1 parts of ethylene glycol diglycidyl ether as organic surface crosslinking agent (e), propylene glycol as a polyhydric alcohol having 4 or less carbon atoms (f). A mixed solution of 5 parts and 1.1 parts of water was added and uniformly mixed, followed by heating at 130 ° C. for 30 minutes to obtain a water-absorbent resin composition (R-1) for comparison.
  • R-1 water-absorbent resin composition
  • Comparative Example 2 While stirring 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 at a high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), fine particles containing water-insoluble alumina (c 1.0 part of LUDOX CL (manufactured by Sigma Aldrich Japan Co., Ltd.), 0.1 part of ethylene glycol diglycidyl ether as organic surface crosslinking agent (e), and polyhydric alcohol having 4 or less carbon atoms (f) A mixed solution of 1.0 part of propylene glycol and 1.6 parts of water is added and uniformly mixed, and then heated at 130 ° C. for 30 minutes to obtain a water-absorbent resin composition (R-2) for comparison Obtained.
  • R-2 water-absorbent resin composition
  • Example 3 Except that, in Example 1, 1.0 part of LUDOX CL (manufactured by Sigma Aldrich Japan Co., Ltd.) as water-insoluble alumina-containing fine particles (c) is changed to 1.0 part of LUDOX HS-30 (manufactured by Sigma Aldrich Japan Co., Ltd.) In the same manner as in Example 1, a water-absorbent resin composition (R-3) for comparison was obtained.
  • the water-absorbent resin composition of the present invention is high in blocking resistance, liquid permeability and gel strength in initial swelling, and therefore, when applied to various absorbers, it has a large amount of absorption and is excellent in reversion and surface dry feeling.
  • Paper diapers such as children's paper diapers and adult paper diapers
  • napkins such as sanitary napkins
  • paper towels such as incontinent pads and surgical under pads
  • pet sheets It is suitably used for sanitary products such as (pet urine absorbing sheet) and is particularly suitable for disposable diapers.
  • the water-absorbent resin composition of the present invention is not only used for sanitary products but also for pet urine absorbents, urine gelling agents for portable toilets, freshness maintenance agents such as fruits and vegetables, drip absorbers for meats and fishes and shellfishes, disposables It is useful also for various uses, such as thermal insulation, a gelling agent for batteries, a water retention agent such as plants and soils, an anti-condensing agent, a water blocking material and a packing material, 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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

L'invention concerne une résine absorbant l'eau qui, au stade initial de gonflement, présente une excellente résistance au blocage et qui est excellente du point de vue de l'aptitude au passage d'un liquide à travers les particules de gel gonflées et de l'efficacité d'absorption de l'eau à charge. La présente invention porte sur une composition de résine absorbant l'eau qui comporte : un polymère réticulé (A) comportant un monomère vinylique soluble dans l'eau (a1) et/ou un monomère vinylique (a2), qui devient le monomère vinylique soluble dans l'eau (a1) après hydrolyse, et un agent de réticulation (b), en tant que motifs constituants essentiels ; des particules fines (c) contenant de l'alumine, insolubles dans l'eau ; un sel d'aluminium soluble dans l'eau (d). Le polymère réticulé (A) possède un degré de couverture superficielle par l'aluminium de 60 à 100 %.
PCT/JP2018/033395 2017-09-22 2018-09-10 Composition de résine absorbant l'eau et son procédé de fabrication Ceased WO2019059019A1 (fr)

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JPH04120176A (ja) * 1990-09-11 1992-04-21 Nippon Kayaku Co Ltd 吸水剤及びその製造方法
JP2001137704A (ja) * 1999-11-18 2001-05-22 Toagosei Co Ltd 改質された高吸水性樹脂の製造方法
JP2009510177A (ja) * 2005-09-30 2009-03-12 株式会社日本触媒 吸水剤組成物およびその製造方法
JP2011517703A (ja) * 2007-12-19 2011-06-16 ビーエーエスエフ ソシエタス・ヨーロピア 表面架橋超吸収性物質の製造方法
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