WO2018147317A1 - Particules de résine absorbant l'eau, et absorbeur et article absorbant dans lesquels celles-ci sont utilisées - Google Patents

Particules de résine absorbant l'eau, et absorbeur et article absorbant dans lesquels celles-ci sont utilisées Download PDF

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WO2018147317A1
WO2018147317A1 PCT/JP2018/004185 JP2018004185W WO2018147317A1 WO 2018147317 A1 WO2018147317 A1 WO 2018147317A1 JP 2018004185 W JP2018004185 W JP 2018004185W WO 2018147317 A1 WO2018147317 A1 WO 2018147317A1
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water
absorbent resin
resin particles
linking
surface cross
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PCT/JP2018/004185
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English (en)
Japanese (ja)
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恵 冨岡
祐介 上田
真吾 磯部
智孝 青山
一裕 高橋
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Ｓｄｐグローバル株式会社
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Priority to JP2018567459A priority Critical patent/JPWO2018147317A1/ja
Publication of WO2018147317A1 publication Critical patent/WO2018147317A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Definitions

  • the present invention relates to a water-absorbent resin particle, an absorbent body using the same, and an absorbent article.
  • absorbent polymers mainly absorbent fibers such as pulp and acrylic acid (salt)
  • SAP Super Absorbent Polymer
  • Patent Document 1 a method of adding a solid silicon compound such as silica (Patent Document 1) or a hydrophobic substance (Patent Documents 2 and 3) has been proposed. There has also been proposed a method for improving the absorption rate by a method of adding a foaming agent such as urea before the polymerization (Patent Document 4).
  • An object of the present invention is to provide water-absorbing resin particles capable of achieving both absorption speed under pressure and liquid permeability between swollen gels without reducing water absorption performance, and a method for producing the same.
  • the present invention relates to a crosslinked polymer of a monomer composition
  • a monomer composition comprising a water-soluble vinyl monomer (a1) and / or a vinyl monomer (a2) which becomes a water-soluble vinyl monomer (a1) by hydrolysis and an internal crosslinking agent (b)
  • the physiological saline absorption under 0.3 psi pressure measured by the Demand Wettability test method is 3 g / g or more and less than 9 g / g after 60 seconds, 8 g / g or more and less than 15 g / g after 120 seconds, 180 Water-absorbent resin particles that are 12 g / g or more and less than 30 g / g after 2 s, and 20 g or more but less than 30 g / g after 300 s; an absorber comprising the water-absorbing resin particles, in particular An absorbent comprising the water-absorbent resin particles and a fibrous material; an absorbent article comprising the absorbent.
  • the water-absorbent resin particles of the present invention and the water-absorbent resin particles produced by the production method of the present invention have the above-described characteristics to solve the above-mentioned problems and have the excellent characteristics described in detail below.
  • a thin hygienic material with a high water-absorbing resin ratio because of its high absorption rate under pressure and high water retention performance at the same time despite its excellent liquid permeability between swollen gels.
  • it When applied to an absorbent article, it exhibits stable and excellent absorption performance (for example, liquid diffusibility, absorption speed, and absorption amount) in any state, and is less prone to fog.
  • 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 kind Vinyl monomer having can be used.
  • Vinyl monomer (a2) which becomes water-soluble vinyl monomer (a1) by hydrolysis [hereinafter also referred to as hydrolyzable vinyl monomer (a2). ]
  • vinyl monomers having at least one hydrolyzable substituent which becomes a water-soluble substituent by hydrolysis disclosed in paragraphs 0024 to 0025 of Japanese Patent No. 3648553,
  • At least one hydrolyzable substituent [1,3-oxo-2-oxapropylene (—CO—O—CO—) group, acyl group and cyano group disclosed in paragraphs 0052 to 0055 of JP-A-2005-75982 Vinyl monomer having a group etc.] can be used.
  • the water-soluble vinyl monomer means a vinyl monomer that dissolves at least 100 g in 100 g of water at 25 ° C.
  • the hydrolyzability in the hydrolyzable vinyl monomer (a2) means a property that is hydrolyzed by the action of water and, if necessary, a catalyst (an acid or a base) to become water-soluble. Hydrolysis of the hydrolyzable vinyl monomer (a2) may be performed either during polymerization, after polymerization, or both of them, but from the viewpoint of the absorption performance of the resulting water-absorbent resin particles, it is preferably after polymerization.
  • water-soluble vinyl monomers (a1) are preferable from the viewpoint of absorption performance, and more preferable are anionic vinyl monomers, carboxy (salt) groups, sulfo (salt) groups, amino groups, carbamoyl groups, and ammonio groups.
  • a vinyl monomer having a mono-, di- or tri-alkylammonio group more preferably a vinyl monomer having a carboxy (salt) group or a carbamoyl group, particularly preferably (meth) acrylic acid (salt) and (meta ) Acrylamide, particularly preferred is (meth) acrylic acid (salt), 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.
  • crosslinked polymer (A) in addition to the water-soluble vinyl monomer (a1) and the hydrolyzable vinyl monomer (a2), other vinyl monomers (a3) copolymerizable therewith are used as the structural unit. Can do. Other vinyl monomers (a3) may be used alone or in combination of two or more.
  • the other copolymerizable vinyl monomer (a3) is not particularly limited, and is known (for example, a hydrophobic vinyl monomer disclosed in paragraphs 0028 to 0029 of Japanese Patent No. 3648553, Japanese Patent Laid-Open No. 2003-165883).
  • 0025 paragraph and vinyl monomer disclosed in JP-A-2005-75982, paragraph 0058, etc. can be used.
  • 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 (a3) unit is based on the total number of moles of the water-soluble vinyl monomer (a1) unit and hydrolyzable vinyl monomer (a2) unit from the viewpoint of absorption performance and the like. 0 to 5, more preferably 0 to 3, particularly preferably 0 to 2, particularly preferably 0 to 1.5. From the viewpoint of absorption performance, the content of other vinyl monomer (a3) units is preferably Most preferably, it is 0 mol%.
  • the content of the crosslinked polymer (A) as a constituent unit (expression of the content of the water-soluble vinyl monomer (a1) unit, etc.) and the content as a component of the monomer composition (water-soluble vinyl monomer (a1)) ) Is not particularly distinguished in the present specification.
  • cross-linking agent (b) is not particularly limited and is known (for example, 2 ethylenically unsaturated groups disclosed in paragraphs 0031 to 0034 of Japanese Patent No. 3648553). At least one functional group capable of reacting with a water-soluble substituent, having at least one functional group capable of reacting with a water-soluble substituent, and having at least one functional group capable of reacting with a water-soluble substituent.
  • a crosslinking agent having two or more ethylenically unsaturated groups is preferable, and more preferable is triallyl cyanurate, triallyl isocyanurate, and a poly (poly (2) having 2 to 10 carbon atoms).
  • Meta) allyl ethers particularly preferred are triallyl cyanurate, triallyl isocyanurate, tetraallyloxyethane and pentaerythritol triallyl ether, 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 (% by weight) of the crosslinking agent (b) in the monomer composition is such that when the other vinyl monomer (a3) of the water-soluble vinyl monomer (a1) and hydrolyzable vinyl monomer (a2) is used ( Based on the total weight of the vinyl monomers of a1) to (a3), 0.05 to 0.7 is preferable, more preferably 0.1 to 0.6, and particularly preferably 0.15 to 0.5. . 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 radical polymerization catalyst can be used, for example, an azo compound [azobisisobutyronitrile, azobiscyanovaleric acid, 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 peroxide and di- (2-ethoxyethyl) peroxydicarbonate and the like] and redox catalyst (alkali metal sulfite or bisulfite, ammonium sulfite, ammonium bisulfite, ascorbic acid and the like reducing agent and alkali metal persulfate, ammonium persulfate, Combination with oxidizing agents such as hydrogen peroxid
  • the amount (% by weight) of the radical polymerization catalyst used is that of the water-soluble vinyl monomer (a1) and hydrolyzable vinyl monomer (a2), and when using other vinyl monomers (a3), Based on the total weight, it is preferably 0.0005 to 5, more preferably 0.001 to 2.
  • the polymerization may be performed in the presence of a dispersant or a surfactant as necessary.
  • a dispersant or a surfactant as necessary.
  • polymerization can be carried out using a 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 5 to 80 ° C.
  • the solvent such as an organic solvent and water
  • 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 hydrogel polymer 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). If necessary, the hydrogel polymer obtained as described above can be neutralized by mixing with an alkali.
  • a shredding device for example, a bex mill, rubber chopper, pharma mill, mincing machine, impact pulverizer, and roll pulverizer.
  • Alkalis known in the art ⁇ patent 3205168 etc. ⁇ can be used. Among these, from the viewpoint of water absorption performance, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable, sodium hydroxide and potassium hydroxide are more preferable, and sodium hydroxide is particularly preferable.
  • the neutralization rate is preferably 50 to 100%, more preferably 60 to 80% from the viewpoint of liquid permeability.
  • the content and water content of the organic solvent were measured using an infrared moisture meter [JE400 manufactured by KETT Co., Ltd .: 120 ⁇ 5 ° C., 30 minutes, atmospheric humidity before heating 50 ⁇ 10% RH, lamp specifications 100V, 40W ] Is obtained from the weight loss of the measurement sample when heated.
  • a method of distilling off the solvent including water
  • 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 heated to 100 to 230 ° C., (heating ) Vacuum drying, freeze drying, infrared drying, decantation, filtration, etc. can be applied.
  • the crosslinked polymer (A) can be pulverized after drying.
  • 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 crosslinked polymer (A) when screened may contain some other components such as a residual solvent and a residual crosslinking component.
  • the weight average particle diameter ( ⁇ m) of the crosslinked polymer (A) is preferably 100 to 800, more preferably 200 to 700, next preferably 250 to 600, particularly preferably 300 to 500, and most preferably 350 to 450. It is. 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 for use as a disposable diaper and no fear of dropping off from the fibrous material, an irregularly crushed shape is preferable.
  • the crosslinked polymer (A) preferably contains a hydrophobic substance (g) from the viewpoint of surface modification and liquid permeability.
  • hydrophobic substance (g) As the 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.
  • 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, carbana 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 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 moisture resistance of the absorbent article 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). .
  • a hydrophobic substance (g1) containing a hydrocarbon group is preferable from the viewpoint of the moisture resistance of the absorbent article, 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 monoester.
  • the crosslinked polymer (A) has a structure (that is, a surface crosslinked structure) surface-crosslinked by a surface crosslinking liquid containing at least one surface crosslinking agent (c).
  • the ratio of the surface crosslinking agent (c) unit in the surface-crosslinked polymer (A) is 0.03 to 0.5% by weight based on the total weight of the vinyl monomer units used in the crosslinked polymer (A). It is preferably 0.05 to 0.3% by weight, particularly preferably 0.08 to 0.2% by weight.
  • the surface cross-linking liquid preferably contains a solvent together with at least one surface cross-linking agent (c).
  • the type of the solvent is not particularly limited, but polyhydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, etc.) and water are preferably used, and the solvent can be used alone or in combination of two or more. You may use together.
  • the resin particles surface-crosslinked by the surface crosslinking liquid have a uniform crosslinked structure.
  • Examples of the surface crosslinking agent (c) include known polyvalent glycidyl compounds, polyvalent amines, polyvalent aziridine compounds and polyvalent isocyanate compounds described in JP-A No. 59-189103, JP-A No. 58-180233. And polyhydric alcohols described in JP-A-61-16903, silane coupling agents described in JP-A-61-211305 and JP-A-61-252212, and JP-A-5-508425. Alkylene carbonate, polyvalent oxazoline compounds described in JP-A No. 11-240959, and polyvalent metal salts described in JP-A Nos. 51-136588 and 61-257235) and the like. Can be used. As the surface crosslinking agent (c), one type may be used alone, or two or more types may be used in combination.
  • the surface cross-linking temperature is the boiling point of the surface cross-linking agent in the surface cross-linking liquid (co-boiling point when water is used in combination). It is preferable that the temperature is lower than the lower temperature and the temperature at which the surface crosslinking agent causes a dehydration condensation reaction. If the surface crosslinking temperature is higher than the boiling point of the polyhydric alcohol, it becomes a diluent.
  • the surface crosslinking temperature has a boiling point of 184 ° C. and a boiling point of 104 ° C. in the case of a 50% aqueous solution. Accordingly, when the surface crosslinking temperature is higher than the boiling point of propylene glycol or a 50% aqueous solution thereof, propylene glycol does not contribute to the reaction and becomes a diluent.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, sorbitol and the like.
  • the valence of the polyhydric alcohol is 2 to 8 valence, more preferably 2 to 3 from the viewpoint of absorption performance. And particularly preferably divalent.
  • polyvalent glycidyl compound examples include polyglycidyl ethers of polyhydric alcohols such as ethylene glycol diglycidyl ether, glycerin triglycidyl ether, and sorbitol polyglycidyl ether.
  • the number of glycidyl groups per molecule is preferably 2 to 10 and more preferably 2 to 4 from the viewpoint of absorption performance.
  • a polyvalent glycidyl compound may be used individually by 1 type, and may use 2 or more types together.
  • the polyvalent metal salt examples include salts of at least one metal selected from the group consisting of magnesium, calcium, zirconium, aluminum, and titanium with the above inorganic acid or organic acid.
  • a polyvalent metal salt By containing a polyvalent metal salt, the surface of the water-absorbent resin particles is modified, and the blocking resistance and liquid permeability are improved, which is preferable.
  • inorganic acid salts of aluminum and inorganic acid salts of titanium are preferable, aluminum sulfate, aluminum chloride, potassium aluminum sulfate and sodium aluminum sulfate are more preferable, and aluminum sulfate and aluminum sulfate are particularly preferable.
  • Sodium aluminum sulfate most preferred is sodium aluminum sulfate. These may be used alone or in combination of two or more.
  • the method for producing water-absorbent resin particles of the present invention includes a surface crosslinking step of subjecting the crosslinked polymer (A) to a surface crosslinking treatment with a surface crosslinking liquid containing at least one surface crosslinking agent (c), It is preferable to carry out the process twice or more. It is preferable to perform the treatment twice or more because a thick surface-crosslinked structure (also referred to as a surface cross-linked structure) can be formed, and the initial absorption rate and the ability to pass between swollen gels can be expected.
  • a thick surface-crosslinked structure also referred to as a surface cross-linked structure
  • a surface cross-linking agent containing a polyvalent glycidyl compound and / or a polyvalent metal salt is used in the first surface cross-linking step. It is more preferable to use a polyvalent glycidyl compound and a polyvalent metal salt in combination.
  • the epoxy equivalent of the polyvalent glycidyl compound is preferably 60 to 600, more preferably 100 to 300, and the number of functional groups is preferably 2 to 6, more preferably 2 to 4.
  • the epoxy equivalent means a value obtained by dividing the molecular weight of the polyvalent glycidyl compound by the number of glycidyl groups in one molecule.
  • a polyvalent glycidyl compound In the second surface cross-linking step, it is preferable to use a polyvalent glycidyl compound, an alkylene carbonate, or a polyhydric alcohol from the viewpoint of permeability to water-absorbent resin particles. More preferred are polyvalent glycidyl compounds and alkylene carbonates.
  • the epoxy equivalent of the polyvalent glycidyl compound is preferably 60 to 600, more preferably 100 to 300, and the number of functional groups is preferably 2 to 6, more preferably 2 to 4.
  • the alkylene carbonate ethylene carbonate and propylene carbonate are preferable from the viewpoint of permeability to the water-absorbent resin, and ethylene carbonate is more preferable.
  • the molecular weight of the polyhydric alcohol is preferably 50 to 500, more preferably 70 to 200.
  • the valence is 2 to 8 valence, more preferably 2 to 3 valence, from the viewpoint of absorption performance.
  • the amount (% by weight) of the surface crosslinking agent (c) used is the water-soluble vinyl monomer (a1) or hydrolyzable vinyl monomer used in the crosslinked polymer (A) from the viewpoint of absorption performance.
  • the vinyl monomer (a3) of (a2) and internal crosslinking agent (b) 0.03 to 0 based on the total weight of the monomer composition of (a1) to (a3) 0.5 is preferable, 0.05 to 0.3 is more preferable, and 0.08 to 0.2 is particularly preferable. By setting this range, the absorption rate and the liquid permeability between the swollen gels are improved.
  • the surface cross-linking liquid in the first and second surface cross-linking steps is composed of a polyvalent glycidyl compound, a polyhydric alcohol, and water. From the viewpoint of liquid permeability, it is preferable from the viewpoint of simplifying the production line and reducing the procurement cost of materials.
  • the weighted average of the SP values of the components of the surface cross-linking liquid is preferably 10.5 to 14.5, more preferably 11 to 14, particularly preferably Is 12-13.
  • the density and thickness balance of the surface cross-linked structure and the cross-linking uniformity become good, and the absorption performance under pressure and the liquid permeability between the swollen gels become good. If it is less than 10.5, the surface cross-linked structure may be too thin. If it exceeds 14.5, the surface cross-linking structure may be non-uniform or the surface cross-linking density may be too low.
  • the weighted average is calculated by weighting the weight fraction of each component when all components other than water in the surface cross-linking liquid are defined as 100.
  • the apparatus used for uniformly mixing the cross-linked polymer (A) and the surface cross-linking agent in the surface cross-linking step may be an ordinary mixer, such as a cylindrical mixer, a screw type mixer, a screw type extruder, Turbulizer, Nauter mixer, double-arm kneader, fluid mixer, V mixer, minc mixer, ribbon mixer, fluid mixer, airflow mixer, rotating disk mixer, conical Examples include a blender and a roll mixer.
  • an ordinary mixer such as a cylindrical mixer, a screw type mixer, a screw type extruder, Turbulizer, Nauter mixer, double-arm kneader, fluid mixer, V mixer, minc mixer, ribbon mixer, fluid mixer, airflow mixer, rotating disk mixer, conical Examples include a blender and a roll mixer.
  • the temperature at which the crosslinked polymer (A) and the surface crosslinking agent are uniformly mixed in the surface crosslinking step 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 cross-linked polymer (A) and the surface cross-linking agent are uniformly mixed and then heated to 100 ° C. or higher and lower than 150 ° C.
  • the heating temperature is 110 to 145 ° C. from the viewpoint of absorption characteristics. Is more preferable, and 125 to 140 ° C. is particularly preferable.
  • the heating time in the first surface cross-linking step is preferably 5 to 60 minutes, more preferably 10 to 40 minutes, from the viewpoint of absorption characteristics. If it is out of this range, the absorption performance and moisture absorption blocking property may deteriorate.
  • the resin particles cross-linked in the first surface cross-linking step and the surface cross-linking agent are preferably mixed and then heated to 100 ° C. or higher and lower than 190 ° C. From the viewpoint, 110 to 180 ° C is more preferable, and 125 to 175 ° C is particularly preferable.
  • the heating time in the second surface cross-linking step is preferably 5 to 60 minutes, more preferably 10 to 40 minutes, from the viewpoint of absorption characteristics. If it is out of this range, the absorption performance and moisture absorption blocking property may deteriorate.
  • the heating temperature after the third time is preferably 165 ° C. or more and less than 190 ° C., and the heating time is preferably 5 to 60 minutes.
  • the water-absorbent resin particles of the present invention may further contain water-insoluble inorganic particles (f), and the production method of the present invention may include a step of mixing water-insoluble inorganic particles (f).
  • the surface of the water-absorbent resin particles is surface-treated with the water-insoluble inorganic particles (f), thereby improving the blocking resistance and liquid permeability of the water-absorbent resin particles.
  • water-insoluble inorganic particles (f) examples include colloidal silica, fumed silica, clay and talc. Colloidal silica and silica are preferable and more preferable from the viewpoints of availability, ease of handling, and absorption performance. Is colloidal silica.
  • One type of water-insoluble inorganic particles (f) may be used alone, or two or more types may be used in combination.
  • the amount (% by weight) of the water-insoluble inorganic particles (f) used is preferably from 0.01 to 5, more preferably from 0.05 to 1, particularly preferably from 0. 1 to 0.5.
  • the water-insoluble inorganic particles (f) When the water-insoluble inorganic particles (f) are contained, it is preferable to mix the water-absorbing resin particles and the water-insoluble inorganic particles (f), and the mixing can be performed by the same method as the mixing of the polyvalent metal salt. The conditions are the same.
  • a step of adjusting the particle size of the water-absorbent resin particles may be performed.
  • the particle size adjustment can be performed in the same manner as the particle size adjustment of the above-mentioned crosslinked polymer (A), and the particle size after the particle size adjustment is also the same.
  • 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 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 moisture absorption blocking property of the water-absorbent resin particles of the present invention 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.
  • the moisture absorption blocking property is measured by the following method. ⁇ Hygroscopic blocking rate> 10 g of water-absorbing resin that has passed through a metal mesh (JIS Z8801-1: 2001) with an opening of 850 ⁇ m is uniformly placed in an aluminum cylindrical dish having a diameter of 5 cm, and a constant temperature and humidity chamber of 40 ⁇ 1 ° C. and relative humidity of 80 ⁇ 5%. Leave in for 3 hours.
  • the lower limit is preferably 0.54, more preferably 0.56, and the upper limit is preferably 0.68, more preferably 0.65. Preferably it is 0.62. If it is less than 0.54, the absorption rate increases, but the liquid permeability between the swollen gels tends to be low, which is not preferable from the viewpoint of urine diffusion in the diaper. On the other hand, if it exceeds 0.68, the absorption rate is slow, which may be undesirable from the viewpoint of initial leakage of diapers. Within this range, the anti-fogging property of the absorbent article is further improved.
  • the apparent density is measured at 25 ° C. according to JIS K7365: 1999.
  • the amount of physiological saline absorbed under a 0.3 psi pressure (sometimes abbreviated as DW value) measured by Demand Wettability test method (hereinafter also referred to as DW test) is 3 g / g or more and 9 g after 60 seconds. / G, 8 g / g or more and less than 15 g / g after 120 seconds, 12 g / g or more and less than 20 g / g after 180 seconds, and 20 g or more and less than 30 g / g after 300 seconds.
  • the DW value indicates such a passage of time, it is possible to ensure that the absorption rate under pressure (that is, the absorption amount per unit time) is high.
  • the DW test can be performed by the method described later.
  • the DW value after 30 seconds is preferably 1 g / g or more, and more preferably 2.0 g / g or more from the viewpoint of initial leakage of diapers.
  • the upper limit is preferably less than 3 g / g, more preferably less than 2.8 g / g from the viewpoint of urine diffusion in the diaper. Since the DW value after 30 seconds has a positive correlation with the surface wettability of the water-absorbent resin particles, the addition amount of the surface treatment agent can be appropriately adjusted. Therefore, for example, when it is necessary to increase the surface wettability of the water-absorbent resin particles in order to adjust the DW value after 30 seconds, it can be easily realized by increasing the addition amount of the polyvalent metal salt as the surface treatment agent. Can do.
  • the DW value after 60 seconds is 3 g / g or more, preferably 4 g / g or more, more preferably 5 g / g or more from the viewpoint of initial leakage of diapers.
  • the upper limit is less than 9 g / g from the viewpoint of urine diffusion in the diaper, preferably less than 8 g / g, and more preferably less than 7 g / g. Since the DW value after 60 seconds has a positive correlation with the surface wettability of the water-absorbent resin particles, the addition amount of the surface treatment agent can be appropriately adjusted. Therefore, for example, when it is necessary to increase the surface wettability of the water-absorbent resin particles in order to adjust the DW value after 30 seconds, it can be easily realized by increasing the addition amount of the polyvalent metal salt as the surface treatment agent. Can do.
  • the DW value after 120 seconds is 8 g / g or more, preferably 10 g / g or more, more preferably 11 g / g or more from the viewpoint of dryness of the diaper.
  • the upper limit is less than 15 g / g from the viewpoint of urine diffusion in the diaper, preferably less than 13 g / g, and more preferably less than 12 g / g. Since the DW value after 120 seconds has a positive correlation with the strength of surface cross-linking, it can be appropriately adjusted by the amount of the surface cross-linking agent with respect to the water-absorbent resin particles. Therefore, for example, when it is necessary to increase the strength of surface cross-linking in order to adjust the DW value after 120 seconds, it can be easily realized by increasing the amount of surface cross-linking agent used.
  • the DW value after 180 seconds is 12 g / g or more, preferably 15 g / g or more, more preferably 17 g / g or more from the viewpoint of dryness of the diaper.
  • the upper limit is less than 30 g / g from the viewpoint of urine diffusion in the diaper, preferably less than 20 g / g, and more preferably less than 18 g / g. Since the DW value after 180 seconds has a positive correlation with the strength of surface cross-linking, it can be appropriately adjusted by the amount of the surface cross-linking agent with respect to the water-absorbent resin particles. Therefore, for example, when it is necessary to increase the strength of surface crosslinking in order to adjust the DW value after 180 seconds, it can be easily realized by increasing the amount of the surface crosslinking agent used.
  • the DW value after 300 seconds is 20 g / g or more, preferably 22 g / g or more, more preferably 24 g / g or more from the viewpoint of diaper dryness.
  • the upper limit is less than 30 g / g from the viewpoint of urine diffusion in the diaper, preferably less than 28 g / g, and more preferably less than 26 g / g. Since the DW value after 300 seconds has a positive correlation between internal crosslinking and surface crosslinking, it can be appropriately adjusted by the amount of internal crosslinking agent and the amount of surface crosslinking agent with respect to the water-absorbent resin particles. Therefore, for example, when it is necessary to increase the strength of surface cross-linking in order to adjust the DW value after 300 seconds, it can be easily realized by increasing the amount of surface cross-linking agent used.
  • the water-absorbent resin particles preferably have an amount of water-soluble polymer that is a water-soluble polymer reduced by adjusting the amount of internal crosslinking agent added and the amount of water before surface crosslinking. Is 10% or less. If the water-soluble content exceeds 10%, the soluble content is not eluted at the time of water absorption, gel blocking occurs, and the liquid passing performance and the water absorption capacity are adversely affected. From the viewpoint of liquid permeability, it is preferably 8% or less, more preferably 5% or less. Ideally, it is preferably 0%.
  • the water-soluble component can be measured by the following method.
  • ⁇ Water-soluble content> In a 300 ml plastic container, 100 g of 0.9 wt% saline is weighed, 1.2 g of the water-absorbent resin composition is added to the saline, sealed with a wrap, and stirred for 3 hours by rotating a stirrer at 500 rpm. A water-soluble extract from which the water-soluble component of the water-absorbent resin composition is extracted is prepared. And this water-soluble extract is filtered using the filter paper made from ADVANTEC Toyo Co., Ltd. (product name; JIS P 3801, No. 2, thickness 0.26 mm, reserved particle diameter 5 ⁇ m).
  • a N / 50 KOH aqueous solution is titrated with respect to a blank test solution obtained by adding 30 g of ion-exchanged water to 20 g of 0.9 wt% saline until the pH of the saline becomes 10. Then, a titration amount ([W KOH, b ] ml) of an N / 50 aqueous KOH solution necessary for the pH of the 0.9 wt% saline solution to be 10 is obtained. Thereafter, titration of an N / 10 aqueous HCl solution is performed until the pH of the saline solution is 2.7. Then, a titration amount of N / 10 HCl aqueous solution ([W HCl, b ] ml) necessary for the pH of the 0.9 wt% saline solution to be 2.7 is obtained.
  • the above measurement solution is subjected to the same operation as the above titration operation, and a titration amount of N / 50 KOH aqueous solution necessary for the measurement solution to have a pH of 10 ([W KOH, S ] ml).
  • a titration amount of N / 50 KOH aqueous solution necessary for the measurement solution to have a pH of 10 [W KOH, S ] ml.
  • the centrifugal retention amount of saline (centrifugation retention capacity: hereinafter also referred to as CRC) (g / g) is 27 or more from the viewpoint of water absorption characteristics and other physical properties. Is preferable, 29 or more is more preferable, and 30 or more is more preferable. Further, the upper limit is preferably 40 or less, and more preferably 38 or less. CRC (g / g) can be measured by the method described later.
  • GBP (0 psi swelling pressure) (darcies) is preferably 40 or more, more preferably 50 or more, and still more preferably 60 or more, from the viewpoint of water absorption characteristics and other physical properties. . GBP (darcies) can be measured by the method described later.
  • GBP 0.3 psi swelling pressure
  • Darcies is preferably 1.0 or more, more preferably 1.5 or more, and further preferably 2.5 or more, from the viewpoint of the relationship between water absorption characteristics and other physical properties.
  • GBP can be measured by the method described later.
  • the absorption rate measured by the Vortex test method of the water-absorbent resin particles (hereinafter also referred to as absorption rate (Vortex)) can be measured by the method described later, From the viewpoint of the relationship with other physical properties, it is 50 seconds or less.
  • Centrifugal holding capacity, gel bed permeability at 0 psi swelling pressure, gel bed permeability at 0.3 psi swelling pressure, absorption rate under 0.3 psi pressure measured by Demand Wettability test method and absorption measured by Vortex test method The speed is measured by the following method in a room of 25 ⁇ 2 ° C. and humidity of 50 ⁇ 10%, respectively. The temperature of the physiological saline used is adjusted to 25 ° C. ⁇ 2 ° C. in advance.
  • the GBP test at 0.3 psi swelling pressure is to determine the liquid permeability to the swollen gel under conditions commonly referred to as “under load” conditions, and the under load GBP described in US Pat. No. 5,236,668. It is measured according to the test method (unit: [darcies]). In addition, it means that the higher the GBP at 0.3 psi swelling pressure, the better the liquid permeability under load, and the better the liquid permeability in a state close to actual use.
  • ⁇ Absorption amount under 0.3 psi pressure measured in Demand Wettability test> This is measured by the DW method described in paragraphs 0117 to 0121 of JP-A-2014-005472 using 0.50 g of water-absorbent resin particles and physiological saline.
  • the absorption capacity per gram of water-absorbent resin particles under a 0.3 psi load condition is judged by the amount of absorption (g) on a measuring table connected to a burette and an air introduction pipe. is there. That is, when the water-absorbing resin particles start to absorb water and the first bubble introduced from the air introduction pipe reaches the surface of the physiological saline in the burette, the measurement start time is set as the measurement start time.
  • the amount of physiological saline absorbed by the water-absorbent resin particles is read from the amount of decrease in saline. Then, the amount of absorption (g) per 1 g of water-absorbent resin particles after a predetermined time (30 seconds, 60 seconds, 120 seconds, 180 seconds, and 300 seconds) has elapsed since the start of measurement is obtained.
  • the absorber of the present invention contains 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. Examples of other materials include fibrous materials.
  • 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 base materials preferred are cellulose-based natural fibers, polypropylene-based fibers, polyethylene-based fibers, polyester-based fibers, heat-fusible composite fibers, and mixed fibers thereof, and more preferable are obtained.
  • the fluff pulp, the heat-fusible conjugate fiber, and the mixed fiber thereof are used in that the shape-retaining property of the obtained water-absorbing agent after water absorption is excellent.
  • 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.
  • the absorbent article of the present invention uses the above absorber.
  • 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.).
  • Example 1 Acrylic acid (a1-1) ⁇ manufactured by Mitsubishi Chemical Corporation, purity 100% ⁇ 135 parts, cross-linking agent (b-1) ⁇ pentaerythritol triallyl ether, manufactured by Daiso Corporation ⁇ 0.678 parts and deionized water 315 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 0.3 parts of a 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.
  • ethylene carbonate as the second surface cross-linking agent was further stirred at a high speed (high speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm).
  • a mixed solution (0.05 weight part of the SP value of the components excluding water: 14.7) mixed with 0.05 part and water as a solvent was added and mixed uniformly, and then heated at 170 ° C. for 30 minutes.
  • water-absorbent resin particles (P-2) of the present invention were obtained.
  • Crosslinking agent (b-1) ⁇ Pentaerythritol triallyl ether, manufactured by Daiso Co., Ltd. ⁇ A crosslinked polymer obtained in the same manner as in Example 1 except that 0.678 part was changed to 0.815 part (A- 3) While stirring 100 parts at high speed (high speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), 0.1 part ethylene glycol diglycidyl ether as the first surface cross-linking agent and propylene glycol 1 as the solvent .2 parts and 1.2 parts of water mixed solution (weighted average of SP values of components excluding water: 12.4) was added and mixed uniformly, then heated at 130 ° C.
  • Example 5 Crosslinking agent (b-1) ⁇ Pentaerythritol triallyl ether, manufactured by Daiso Co., Ltd. ⁇ A crosslinked polymer (A-) obtained in the same manner as in Example 1 except that 0.678 part was changed to 0.951 part.
  • Crosslinking agent (b-1) ⁇ Pentaerythritol triallyl ether, manufactured by Daiso Co., Ltd. ⁇ A crosslinked polymer obtained in the same manner as in Example 1 except that 0.678 part was changed to 0.406 part (A- 7) While stirring 100 parts at high speed (high speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), 0.04 part of ethylene glycol diglycidyl ether as the first surface cross-linking agent and sulfuric acid as polyvalent metal salt Add 0.6 parts of sodium aluminum dodecahydrate, 0.78 part of propylene glycol as solvent, and 0.78 part of water (weighted average of SP values of components except water: 12.5) After uniform mixing, the mixture was heated at 140 ° C.
  • Example 8 While 100 parts of the crosslinked polymer (A-2) obtained in the same manner as in Example 2 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), ethylene glycol disulfide as a surface crosslinking agent was added thereto. A mixed solution of 0.08 part of glycidyl ether, 0.3 part of sodium aluminum sulfate 12 hydrate as a polyvalent metal salt, 2 parts of propylene glycol as a solvent and 2 parts of water as a solvent (for components other than water) SP value load average: 12.5) was added and uniformly mixed, then heated at 130 ° C.
  • Example 9 While 100 parts of the crosslinked polymer (A-1) obtained in the same manner as in Example 1 was stirred at high speed (high speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), ethylene glycol disulfide as a surface crosslinking agent was added thereto. Add 0.12 parts of glycidyl ether, 3.2 parts of propylene glycol as a solvent, and 3.2 parts of water as a solvent, and a mixed solution (SP value load average of components excluding water: 12.5). After uniform mixing, the mixture is heated at 140 ° C.
  • Example 10 While 100 parts of the crosslinked polymer (A-4) obtained in the same manner as in Example 4 was stirred at high speed (high speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), ethylene glycol disulfide as a surface crosslinking agent was added thereto. After adding a mixed solution in which 0.1 part of glycidyl ether and 6.7 parts of water as a solvent were mixed (weight average of SP value of components excluding water: 10.2) and mixing uniformly, 25 ° C. at 25 ° C.
  • Example 11 While 100 parts of the crosslinked polymer (A-7) obtained in the same manner as in Example 7 was stirred at high speed (high-speed stirring turbulizer manufactured by Hosokawa Micron: rotation speed 2000 rpm), ethylene glycol disulfide as a surface crosslinking agent was added thereto. Add 0.08 parts of glycidyl ether, 1.47 parts of propylene glycol as a solvent and 1.47 parts of water as a solvent (SP value load average of components excluding water: 12.5) After mixing uniformly, heat at 110 ° C.
  • Cross-linking agent (b-1) ⁇ Pentaerythritol triallyl ether, manufactured by Daiso Corporation ⁇ Except that 0.678 part was changed to 0.027 part, comparative water-absorbent resin particles (P '-7) was obtained.
  • Evaluation performance is CRC (g / g), GBP (darcies) at 0 psi swelling pressure, GBP (darcies) at 0.3 psi swelling pressure, 30 seconds under 0.3 psi pressure, 60 seconds, 120 seconds After, 180 seconds, 300 seconds later each physiological saline absorption (g / g) (DW value) (in the table, pressurization DW30, pressurization DW60, pressurization DW120, pressurization DW180, pressurization DW300, respectively) And water-soluble (%), apparent density (g / ml), and Vortex (sec).
  • the absorption rate under 0.3 psi pressure is excellent.
  • the liquid permeability (GBP) between the swollen gels was very good.
  • the DW value is generally low from the initial (after 30 seconds, 60 seconds) to the middle (after 120 seconds) and under 0.3 psi pressure. The absorption rate was slow and the GBP was low.
  • the surface cross-linking concentration was increased to improve the absorption rate under pressure, the CRC tended to decrease.
  • the Examples can achieve high GBP even at low surface cross-linking concentrations, while the Comparative Example has higher surface cross-linking to achieve high GBP. It is thought that the agent concentration was necessary and a significant decrease in CRC was observed.
  • Comparative Example 4 although the GBP is high, the initial absorption rate is considered to be low because the surface is hydrophobized. Therefore, the example shows that a high GBP can be realized even with a low crosslinking concentration, so that the balance between CRC and GBP is improved. This was particularly noticeable in the examples where the two-stage surface crosslinking was performed.
  • the water-absorbent resin particles of the present invention have excellent absorption rate under pressure, high liquid permeability between swollen gels, and absorbability excellent in initial leakage and dryness when applied to various absorbers.
  • Paper diapers children's disposable diapers, adult disposable diapers, etc.
  • napkins sanitary napkins, etc.
  • paper towels paper towels
  • pads incontinence pads, surgical underpads, etc.
  • pet sheets pet urine
  • the water-absorbent resin particles obtained by the production method of the present invention are not only sanitary products, but also pet urine absorbents, urine gelling agents for portable toilets, freshness retaining agents such as fruits and vegetables, meat and seafood drip absorbents, It is also useful for various applications such as cold insulation agents, disposable warmers, gelling agents for batteries, water retention agents for plants and soil, anti-condensation agents, water-stopping materials and packing materials, and artificial snow.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des particules de résine absorbant l'eau capables de réaliser à la fois une vitesse d'absorption sous pression et une perméabilité aux liquides entre des gels gonflés sans abaisser la performance d'absorption d'eau. La présente invention concerne des particules de résine absorbant l'eau comprenant un polymère réticulé (A) d'une composition de monomères qui comprend des monomères de vinyle solubles dans l'eau (a1) et/ou des monomères de vinyle hydrolysables (a2) et qui comprend également un agent de réticulation interne (b), les particules de résine absorbant l'eau ayant une structure qui est réticulée en surface par une solution de réticulation de surface contenant au moins un agent de réticulation de surface (c), et ayant une fraction soluble dans l'eau de 10 % ou moins, la quantité d'absorption de solution saline physiologique des particules de résine absorbant l'eau sous une pression de 0,3 psi mesurée par un procédé de test de mouillabilité à la demande étant de 3 à 9 g/g après 60 secondes, de 8 à 15 g/g après 120 secondes, de 12 à 30 g/g après 180 secondes, et de 20 à 30 g/g après 300 secondes.
PCT/JP2018/004185 2017-02-10 2018-02-07 Particules de résine absorbant l'eau, et absorbeur et article absorbant dans lesquels celles-ci sont utilisées WO2018147317A1 (fr)

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JP2019141754A (ja) * 2018-02-16 2019-08-29 Ｓｄｐグローバル株式会社 吸水性樹脂粒子、これを用いた吸収体及び吸収性物品、並びに吸水性樹脂粒子の製造方法
JP2020093065A (ja) * 2018-12-12 2020-06-18 住友精化株式会社 吸水性樹脂粒子
WO2020122217A1 (fr) * 2018-12-12 2020-06-18 住友精化株式会社 Particules de résine absorbante, corps absorbant, et article absorbant
WO2020122214A1 (fr) * 2018-12-12 2020-06-18 住友精化株式会社 Particules de résine absorbante, et article absorbant
JP2020121090A (ja) * 2019-01-30 2020-08-13 住友精化株式会社 吸水性樹脂粒子、吸収体及び吸収性物品
JP2020121092A (ja) * 2019-01-30 2020-08-13 住友精化株式会社 吸収性物品
JP2020125472A (ja) * 2019-02-04 2020-08-20 Ｓｄｐグローバル株式会社 吸水性樹脂粒子及びその製造方法
CN112341563A (zh) * 2020-10-28 2021-02-09 万华化学集团股份有限公司 一种改善抗结块性能的吸水树脂制备方法
JP2021510741A (ja) * 2018-11-13 2021-04-30 エルジー・ケム・リミテッド 高吸水性樹脂およびその製造方法
EP3985048A4 (fr) * 2019-09-30 2022-08-24 LG Chem, Ltd. Composition de polymère superabsorbant et son procédé de préparation
EP4083115A4 (fr) * 2020-10-29 2023-08-30 Lg Chem, Ltd. Procédé de préparation d'un polymère superabsorbant
US11931720B2 (en) 2017-12-11 2024-03-19 Lg Chem, Ltd. Superabsorbent polymer composition and method for preparing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11931720B2 (en) 2017-12-11 2024-03-19 Lg Chem, Ltd. Superabsorbent polymer composition and method for preparing the same
JP2019141754A (ja) * 2018-02-16 2019-08-29 Ｓｄｐグローバル株式会社 吸水性樹脂粒子、これを用いた吸収体及び吸収性物品、並びに吸水性樹脂粒子の製造方法
JP7108422B2 (ja) 2018-02-16 2022-07-28 Ｓｄｐグローバル株式会社 吸水性樹脂粒子、これを用いた吸収体及び吸収性物品、並びに吸水性樹脂粒子の製造方法
JP2021510741A (ja) * 2018-11-13 2021-04-30 エルジー・ケム・リミテッド 高吸水性樹脂およびその製造方法
US11466131B2 (en) 2018-11-13 2022-10-11 Lg Chem, Ltd. Superabsorbent polymer and preparation method thereof
WO2020122214A1 (fr) * 2018-12-12 2020-06-18 住友精化株式会社 Particules de résine absorbante, et article absorbant
WO2020122217A1 (fr) * 2018-12-12 2020-06-18 住友精化株式会社 Particules de résine absorbante, corps absorbant, et article absorbant
JP2020093065A (ja) * 2018-12-12 2020-06-18 住友精化株式会社 吸水性樹脂粒子
JP2020121092A (ja) * 2019-01-30 2020-08-13 住友精化株式会社 吸収性物品
JP2020121090A (ja) * 2019-01-30 2020-08-13 住友精化株式会社 吸水性樹脂粒子、吸収体及び吸収性物品
JP2020125472A (ja) * 2019-02-04 2020-08-20 Ｓｄｐグローバル株式会社 吸水性樹脂粒子及びその製造方法
EP3985048A4 (fr) * 2019-09-30 2022-08-24 LG Chem, Ltd. Composition de polymère superabsorbant et son procédé de préparation
CN112341563A (zh) * 2020-10-28 2021-02-09 万华化学集团股份有限公司 一种改善抗结块性能的吸水树脂制备方法
EP4083115A4 (fr) * 2020-10-29 2023-08-30 Lg Chem, Ltd. Procédé de préparation d'un polymère superabsorbant

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