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WO2024176758A1 - Composition de résine absorbant l'eau - Google Patents

Composition de résine absorbant l'eau Download PDF

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Publication number
WO2024176758A1
WO2024176758A1 PCT/JP2024/003048 JP2024003048W WO2024176758A1 WO 2024176758 A1 WO2024176758 A1 WO 2024176758A1 JP 2024003048 W JP2024003048 W JP 2024003048W WO 2024176758 A1 WO2024176758 A1 WO 2024176758A1
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WO
WIPO (PCT)
Prior art keywords
mass
water
deodorant
resin composition
antibacterial metal
Prior art date
Application number
PCT/JP2024/003048
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English (en)
Japanese (ja)
Inventor
渉太 森島
Original Assignee
住友精化株式会社
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Filing date
Publication date
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Publication of WO2024176758A1 publication Critical patent/WO2024176758A1/fr

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Classifications

    • 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
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • 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
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015—Biocides
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels

Definitions

  • the present invention relates to a water-absorbent resin composition, and more specifically to a water-absorbent resin composition that constitutes an absorbent material suitable for use in sanitary materials such as disposable diapers, sanitary napkins, and incontinence pads.
  • water-absorbent resins have been widely used in the field of sanitary materials such as disposable diapers, sanitary napkins, and incontinence pads.
  • cross-linked polymers of partially neutralized acrylic acid salts have excellent water-absorbing properties, and because the raw material, acrylic acid, is easily available industrially, they can be produced at low cost with consistent quality, and are less susceptible to spoilage or deterioration, making them a preferred water-absorbent resin.
  • Absorbent articles such as disposable diapers, sanitary napkins, and incontinence pads are mainly composed of an absorbent body located in the center that absorbs and retains bodily fluids such as urine and menstrual blood excreted from the body, a liquid-permeable surface sheet (top sheet) located on the side that comes into contact with the body, and a liquid-impermeable back sheet (back sheet) located on the opposite side that comes into contact with the body.
  • the absorbent body is usually composed of hydrophilic fibers such as pulp and water-absorbent resin.
  • absorbents When such absorbents are used, for example, as sanitary materials, they may emit unpleasant odors such as ammonia after absorbing bodily fluids, particularly urine, blood, sweat, etc.
  • the inventor attempted to inhibit the decomposition reaction of urea by urease and suppress the generation of ammonia by inactivating urease using a deodorant containing an antibacterial metal such as silver.
  • a deodorant containing an antibacterial metal such as silver.
  • the inventor discovered a problem in that when a large amount of L-cystine (a sulfur-containing amino acid) is present in urine, such as in the urine of a patient with cystinuria, the antibacterial metal binds to L-cystine, weakening the antibacterial metal's ability to inactivate urease, and the deodorant effect is not fully exerted.
  • L-cystine a sulfur-containing amino acid
  • the main objective of the present invention is to provide a water-absorbent resin composition that has an excellent deodorizing effect on urine that contains a large amount of L-cystine.
  • the present inventors have conducted extensive research to solve the above problems. As a result, they have found that, in a water-absorbent resin composition containing water-absorbent polymer particles, by combining an antibacterial metal-containing deodorant and a porous deodorant, and further setting the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant to a predetermined ratio or more, and further setting the sum (x+y) of the content x (% by mass) of the porous deodorant and the content y (% by mass) of the antibacterial metal-containing deodorant in the entire water-absorbent resin composition to a predetermined ratio or more, the water-absorbent resin composition exhibits a high deodorizing function against ammonia and the like even when urine containing a large amount of L-cystine is absorbed.
  • a water-absorbing resin composition comprising an antibacterial metal-containing deodorant, a porous deodorant, and water-absorbing polymer particles, the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 or more;
  • a water absorbent resin composition wherein the sum (x+y) of a content rate x (mass%) of the porous deodorant and a content rate y (mass%) of the antibacterial metal-containing deodorant in the entire water absorbent resin composition is 0.10 mass% or more.
  • the water-absorbing resin composition according to Item 1 wherein the sum (x+y) of the content x (% by mass) and the content y (% by mass) is 0.50% by mass or less.
  • Item 3 The water absorbent resin composition according to Item 1 or 2, wherein the antibacterial metal contained in the antibacterial metal-containing deodorant contains at least one selected from the group consisting of silver, copper, zinc, bismuth, cobalt, aluminum, and nickel.
  • the antibacterial metal-containing deodorant comprises at least one selected from the group consisting of silver powder, silver chloride (I), silver oxide (I), and a substance carrying at least one metal ion selected from the group consisting of silver ions and zinc ions.
  • the porous deodorant comprises at least one selected from the group consisting of activated carbon, silicon dioxide, and silicates.
  • the water absorbent resin composition according to any one of Items 1 to 5, wherein the antibacterial metal-containing deodorant has a median particle diameter of 0.1 ⁇ m to 100 ⁇ m, and the porous deodorant has a median particle diameter of 1 ⁇ m to 100 ⁇ m.
  • An absorbent article comprising an antibacterial metal-containing deodorant, a porous deodorant, and water-absorbing polymer particles, the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 or more;
  • the sum (x+y) of the content x (mass%) of the porous deodorant and the content y (mass%) of the antibacterial metal-containing deodorant based on the total amount of the antibacterial metal-containing deodorant, the porous deodorant, and the water-absorbent polymer particles is 0.10 mass% or more.
  • the present invention provides a water-absorbent resin composition that has an excellent deodorizing effect on urine that contains a large amount of L-cystine.
  • FIG. 4 is a schematic diagram of a device for measuring the amount of physiological saline solution absorbed under a load of 4.14 kPa.
  • water-soluble refers to a solubility of 5% by mass or more in water at 25°C.
  • a numerical value connected with “ ⁇ ” means a numerical range that includes the numerical values before and after " ⁇ " as the lower and upper limits.
  • the water-absorbent resin composition of the present invention is a water-absorbent resin composition containing an antibacterial metal-containing deodorant, a porous deodorant, and water-absorbent polymer particles, characterized in that the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 or more, and the sum (x+y) of the content x (% by mass) of the porous deodorant and the content y (% by mass) of the antibacterial metal-containing deodorant in the entire water-absorbent resin composition is 0.10% by mass or more.
  • the water-absorbent resin composition of the present invention having such characteristics exerts an excellent deodorizing effect on urine containing a large amount of L-cystine.
  • the water-absorbent resin composition of the present invention will be described in detail below.
  • the inventor attempted to inhibit the decomposition reaction of urea by urease and suppress the generation of ammonia by inactivating urease using a deodorant containing an antibacterial metal such as silver.
  • a deodorant containing an antibacterial metal such as silver.
  • the inventor's investigation revealed the problem that when a large amount of L-cystine (a sulfur-containing amino acid) is present in urine, such as in the urine of patients with cystinuria, the antibacterial metal tends to bind to L-cystine, weakening the urease inactivation effect of the antibacterial metal and preventing the deodorant effect from being fully exerted.
  • L-cystine a sulfur-containing amino acid
  • the present inventors have found that, in a water absorbent resin composition containing water absorbent polymer particles, an antibacterial metal-containing deodorant and a porous deodorant are used in combination, the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant is set to 0.8 or more, and further, the sum (x+y) of the content x (% by mass) of the porous deodorant and the content y (% by mass) of the antibacterial metal-containing deodorant in the entire water absorbent resin composition is set to 0.10% by mass or more, whereby the antibacterial metal-containing deodorant and the porous deodorant function synergistically, and the water absorbent resin composition exhibits a high deodorizing function against ammonia even when absorbing urine containing a large amount of L-cystine.
  • the porous deodorant adsorbs L-cystine in urine, preventing L-cystine from inhibiting the urease inactivation action of the antibacterial metal-containing deodorant, allowing the urease inactivation action of the antibacterial metal-containing deodorant to be optimally exerted, allowing the water absorbent resin composition to exert a high deodorizing function against ammonia, etc.
  • At least a portion of the antibacterial metal-containing deodorant e.g., 20% by mass to 100% by mass, 50% by mass to 100% by mass, 80% by mass to 100% by mass, 90% by mass to 100% by mass, 95% by mass to 100% by mass, or 100% by mass
  • the antibacterial metal-containing deodorant may be disposed on the surface of the water absorbent polymer particle, and at least a portion of the antibacterial metal-containing deodorant may permeate the inside of the water absorbent polymer particle.
  • the porous deodorant e.g., 20% by mass to 100% by mass, 50% by mass to 100% by mass, 80% by mass to 100% by mass, 90% by mass to 100% by mass, 95% by mass to 100% by mass, or 100% by mass
  • the entire antibacterial metal-containing deodorant may be disposed on the surface of the water absorbent polymer particle.
  • at least a portion of the antibacterial metal-containing deodorant and at least a portion of the porous deodorant may be disposed on the surface of the water-absorbent polymer particles.
  • the antibacterial metal-containing deodorant is a deodorant containing an antibacterial metal.
  • the antibacterial metal is preferably a metal that exerts an inactivating effect on urease.
  • the "antibacterial metal” is at least one selected from the group consisting of gold, silver, copper, platinum, zinc, bismuth, titanium, tungsten, nickel, iron, tin, mercury, lead, palladium, aluminum, cobalt, molybdenum, chromium, vanadium, and zirconium.
  • the "antibacterial metal-containing deodorant” is a deodorant containing an antibacterial metal to a degree that exerts a substantial antibacterial effect, for example, a deodorant containing 1 mass % or more of antibacterial metal (when two or more kinds of antibacterial metals are contained, the total amount is used as the basis).
  • the antibacterial metal-containing deodorant is, for example, contained in the water absorbent resin composition in the form of particles.
  • the antibacterial metal may include at least one selected from the group consisting of silver, copper, zinc, bismuth, cobalt, aluminum, and nickel, may include at least one selected from the group consisting of silver, copper, and zinc, or may include at least one of silver and zinc.
  • Antibacterial metal-containing deodorants include, for example, at least one selected from the group consisting of silver powder, silver chloride (I), silver oxide (I), and materials carrying at least one of the metal ions silver ions and zinc ions.
  • the material on which the metal ions are carried may be, for example, a porous material.
  • the porous material may include, for example, at least one selected from the group consisting of zeolite, activated carbon, silicon dioxide, silicate, titania, alumina, aluminum hydroxide, and magnesium hydroxide, may include at least one selected from the group consisting of zeolite, activated carbon, and silicon dioxide, or may include zeolite.
  • silver zinc zeolite is suitable as a porous material carrying silver ions and zinc ions.
  • the porous substance when the substance that carries the metal ions is a porous substance, the porous substance may be a substance that can function as a deodorant by itself.
  • the porous substance and the porous deodorant described below may be substances with the same chemical composition or different substances.
  • the median particle diameter (D50 (median diameter), volume basis) of the antibacterial metal-containing deodorant is 0.1 ⁇ m to 100 ⁇ m, 0.1 ⁇ m to 50 ⁇ m, 0.1 ⁇ m to 10 ⁇ m, 0.1 ⁇ m to 5 ⁇ m, 0.1 ⁇ m to 3 ⁇ m, 0.5 ⁇ m to 1 00 ⁇ m, 0.5 ⁇ m to 50 ⁇ m, 0.5 ⁇ m to 10 ⁇ m, 0.5 ⁇ m to 5 ⁇ m, 0.5 ⁇ m to 3 ⁇ m, 0.8 ⁇ m to 100 ⁇ m, 0.8 ⁇ m to 50 ⁇ m, 0.8 ⁇ m to 10 ⁇ m, 0.8 ⁇ m to 5 ⁇ m, 0.8 ⁇ m to 3 ⁇ m, 1 ⁇ m to 100 ⁇ m, 1 ⁇ m to 50 ⁇ m,
  • the BET specific surface area of the antibacterial metal-containing deodorant is large, the frequency of contact between the antibacterial metal and urease increases, while the frequency of contact between the antibacterial metal and L-cystine also increases. Also, if the BET specific surface area of the antibacterial metal-containing deodorant is too large, there is a possibility that the degree of dust generation increases.
  • the BET specific surface area of the porous deodorant is preferably 100 m 2 /g to 2000 m 2 /g, 100 m 2 /g to 1500 m 2 /g, 100 m 2 /g to 1000 m 2 /g, 100 m 2 /g to 800 m 2 /g, 300 m 2 /g to 2000 m 2 /g, 300 m 2 /g to 1500 m 2 /g, 300 m 2 /g to 1000 m 2 /g, 300 m 2 /g to 800 m 2 /g, 500 m 2 /g to 2000 m 2 /g, 500 m 2 /g to 1500 m 2 /g, 500 m 2 /g to 1000 m 2 /g or 500 m 2 /g to 800 m 2 /g.
  • the BET specific surface area of the antibacterial metal-containing deodorant can be measured using a specific surface area measuring device, and specifically, is a value measured by the method described in the Examples.
  • the sum (x+y) of the content x (mass%) of the porous deodorant and the content y (mass%) of the antibacterial metal-containing deodorant is 0.10 mass% or more.
  • the sum (x+y) is 0.10 mass% to 0.80 mass%, 0.10 mass% to 0.60 mass%, 0.10 mass% to 0.50 mass%, 0.10 mass% to 0.40 mass%, 0.10 mass% to 0.35 mass%, 0.10 mass% to 0.30 mass%, 0.13 mass% to 0.80 mass%, 0.13 mass% to 0.60 mass%, 0.
  • the dust generation rate increases, which may reduce the handleability of the water absorbent resin composition.
  • the sum (x+y) is preferably 0.50% by mass or less.
  • the content y (mass%) of the antibacterial metal-containing deodorant in the entire water absorbent resin composition of the present invention is 0.020 mass% to 0.12 mass%, 0.020 mass% to 0.08 mass%, 0.020 mass% to 0.06 mass%, 0.020 mass% to 0.04 mass%, 0.024 mass% to 0.12 mass%, 0.024 mass% to 0.
  • the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 or more.
  • the ratio (X/Y) may be 0.8 to 15.0, 0.8 to 12.0, 0.8 to 10.0, 0.8 to 8.0, 0.8 to 5.0, 1.0 to 15.0, 1.0 to 12.0, 1.0 to 10.0, 1.0 to 8.0, 1.0 to 5.0, 2.0 to 15.0, 2.0 to 12.0, 2.0 to 10.0, 2.0 to 8.0, 2.0 to 5.0, 3.0 to 15.0, 3.0 to 12.0, 3.0 to 10.0, 3.0 to 8.0, or 3.0 to 5.0.
  • the antibacterial metal-containing deodorant may be disposed on the surface of the water-absorbent polymer particles (i.e., the antibacterial metal-containing deodorant is present on the surface of the water-absorbent polymer particles).
  • the antibacterial metal-containing deodorant adheres to the surface of the water-absorbent polymer particles, and the antibacterial metal-containing deodorant can be disposed on the surface of the water-absorbent polymer particles.
  • the porous deodorant is a deodorant that is porous and does not substantially contain the above-mentioned antibacterial metal.
  • the term "deodorant that does not substantially contain antibacterial metal” includes deodorants that contain antibacterial metal to an extent that they do not exhibit substantial antibacterial properties and deodorants that do not contain antibacterial metal at all, for example, a deodorant that contains less than 1 mass % of antibacterial metal.
  • the porous deodorant may contain at least one selected from the group consisting of activated carbon, silicon dioxide, and silicates, or may contain at least one of activated carbon and silicon dioxide.
  • the porous deodorant contains at least activated carbon, and the proportion (mass %) is, for example, 80% to 100% by mass, 90% to 100% by mass, or 95% to 100% by mass.
  • the median particle size of the porous deodorant may be 1 ⁇ m to 100 ⁇ m, 1 ⁇ m to 80 ⁇ m, 1 ⁇ m to 60 ⁇ m, 10 ⁇ m to 100 ⁇ m, 10 ⁇ m to 80 ⁇ m, 10 ⁇ m to 60 ⁇ m, 15 ⁇ m to 100 ⁇ m, 15 ⁇ m to 80 ⁇ m, 15 ⁇ m to 60 ⁇ m, 20 ⁇ m to 100 ⁇ m, 20 ⁇ m to 80 ⁇ m, or 20 ⁇ m to 60 ⁇ m.
  • the median particle size (D50 (median size), volume basis) of the porous deodorant can be measured using a laser diffraction particle size distribution measuring device, and specifically, is a value measured by the method described in the Examples.
  • the shape of the porous deodorant is preferably crushed or cylindrical, and more preferably crushed.
  • the BET specific surface area of the porous deodorant is preferably 100 m 2 /g to 3000 m 2 /g, 100 m 2 /g to 2500 m 2 /g, 100 m 2 /g to 2000 m 2 /g, 100 m 2 /g to 1500 m 2 /g, 500 m 2 /g to 3000 m 2 /g, 500 m 2 /g to 2500 m 2 /g, 500 m 2 /g to 2000 m 2 /g, 500 m 2 /g to 1500 m 2 /g, 1000 m 2 /g to 3000 m 2 /g, 1000 m 2 / g to 2500 m 2 /g, 1000 m 2
  • the BET specific surface area may be from 1000 m 2 /g to 2000 m 2 /g or from 1000 m 2 /g to 1500 m 2 /g.
  • the BET specific surface area of the porous deodorant is large, it can efficiently adsorb L-cystine contained in urine.
  • the BET specific surface area of the porous deodorant is too large, the strength of the porous deodorant decreases due to the individual pores becoming finer, and there is a possibility that the above-mentioned dust generation rate increases, so that the upper limit of the BET specific surface area is preferably 2000 m 2 /g.
  • the BET specific surface area of the porous deodorant can be measured using a specific surface area measuring device, and specifically, is a value measured by the method described in the Examples.
  • the activated carbon used as the porous deodorant is activated carbon having a polar functional group (hydrophilic functional group) on the surface (i.e., hydrophilic activated carbon).
  • polar functional groups include hydroxyl groups, carboxyl groups, and phenol groups.
  • Activated carbon having polar functional groups on the surface is commercially available, for example, as activated carbon for liquid phase and activated carbon for water treatment.
  • Sources of activated carbon include, for example, coconut shells, infusible or carbonized organic materials, and infusible resins such as phenolic resins.
  • organic materials include polyacrylonitrile, pitch, polyvinyl alcohol, and cellulose. Of these, it is preferable that activated carbon is derived from wood (sawdust), coconut shells, and pitch (for example, coal pitch).
  • the content x (mass%) of the porous deodorant in the water absorbent resin composition of the present invention is, for example, 0.05 mass% to 0.40 mass%, 0.05 mass% to 0.35 mass%, 0.05 mass% to 0.30 mass%, 0.08 mass% to 0.40 mass%, 0.08 mass% to 0.35 mass%, 0.08 mass% to 0.30 mass%, 0.10 mass% to 0.4 ...
  • % to 0.35 mass% 0.10 mass% to 0.30 mass%, 0.15 mass% to 0.40 mass%, 0.15 mass% to 0.35 mass%, 0.15 mass% to 0.30 mass%, 0.20 mass% to 0.40 mass%, 0.20 mass% to 0.35 mass%, 0.20 mass% to 0.30 mass%, 0.25 mass% to 0.40 mass% , 0.25% to 0.35% by weight, or 0.25% to 0.30% by weight.
  • the iodine adsorption amount of the porous deodorant may be, for example, 100 mg/g to 3000 mg/g, 100 mg/g to 2000 mg/g, 500 mg/g to 3000 mg/g, or 500 mg/g to 2000 mg/g.
  • the iodine adsorption capacity of activated carbon here is a value measured in accordance with JIS K1474:2014.
  • the drying loss of a porous deodorant When the drying loss of a porous deodorant is low (in other words, the purity of the porous deodorant is high), it is easier to exert a deodorizing effect, but it also tends to generate dust. Taking this into consideration, the drying loss of the porous deodorant may be, for example, 0.1% to 15.0%, 0.1% to 10.0%, 0.1% to 5.0%, 0.5% to 15.0%, 0.5% to 10.0%, 0.5% to 5.0%, 1.0% to 15.0%, 1.0% to 10.0%, or 1.0% to 5.0%.
  • the loss on drying of the porous deodorant here is the value measured in accordance with JIS K1474:2014.
  • the pH of the porous deodorant may be, for example, 3.0 to 12.0, 3.0 to 11.0, 3.0 to 8.0, 3.0 to 5.0, 4.0 to 12.0, 4.0 to 11.0, 4.0 to 8.0, or 4.0 to 5.0.
  • the pH of the porous deodorant here is the value measured in accordance with JIS K1474:2014.
  • the porous deodorant may be disposed on the surface of the water-absorbent polymer particles (i.e., the porous deodorant may be present on the surface of the water-absorbent polymer particles).
  • the porous deodorant may be attached to the surface of the water-absorbent polymer particles, and the porous deodorant can be disposed on the surface of the water-absorbent polymer particles.
  • water-absorbent polymer particles contained in the water-absorbent resin composition of the present invention will be described in detail.
  • the water-absorbent polymer particles contained in the water-absorbent resin composition of the present invention are crosslinked polymers of water-soluble ethylenically unsaturated monomers, i.e., structural units derived from water-soluble ethylenically unsaturated monomers.
  • the polymer is composed of a crosslinked polymer having the following structure:
  • the water-absorbent polymer particles' water-absorption speed by the Vortex method may be, for example, 10 to 80 seconds, 10 to 60 seconds, 10 to 40 seconds, 20 to 80 seconds, 20 to 60 seconds, 20 to 40 seconds, 30 to 80 seconds, 30 to 60 seconds, or 30 to 40 seconds.
  • the water absorption rate of water-absorbent polymer particles using the Vortex method is a value measured using the method described in the Examples.
  • the saline water retention capacity of the water-absorbent polymer particles may be, for example, 20 g/g to 60 g/g, 20 g/g to 55 g/g, 20 g/g to 50 g/g, 25 g/g to 60 g/g, 25 g/g to 55 g/g, 25 g/g to 50 g/g, 30 g/g to 60 g/g, 30 g/g to 55 g/g, or 30 g/g to 50 g/g.
  • the physiological saline water absorption capacity of the water-absorbent polymer particles under a load of 4.14 kPa may be, for example, 10 mL/g to 40 mL/g, 10 mL/g to 35 mL/g, 10 mL/g to 30 mL/g, 13 mL/g to 40 mL/g, 13 mL/g to 35 mL/g, 13 mL/g to 30 mL/g, 15 mL/g to 40 mL/g, 15 mL/g to 35 mL/g, or 15 mL/g to 30 mL/g.
  • the saline water retention capacity of the water-absorbent polymer particles and the saline water absorption capacity under a load of 4.14 kPa were each measured using the method described in the Examples.
  • the median particle size of the water-absorbing polymer particles is, for example, 150 ⁇ m to 850 ⁇ m, 150 ⁇ m to 600 ⁇ m, 150 ⁇ m to 550 ⁇ m, 150 ⁇ m to 500 ⁇ m, 150 ⁇ m to 450 ⁇ m, 150 ⁇ m to 400 ⁇ m, 200 ⁇ m to 850 ⁇ m, 200 ⁇ m to 600 ⁇ m, 200 ⁇ m to 550 ⁇ m, 200 ⁇ m to 500 ⁇ m, 200 ⁇ m to 450 ⁇ m, 200 ⁇ m to 400 ⁇ m, 240 ⁇ m to 850 ⁇ m, 240 ⁇ m to 600 ⁇ m, 240 ⁇ m to 550 ⁇ m, 240 ⁇ m to 500 ⁇ m, 240 ⁇ m to 450 ⁇ m, 240 ⁇ m It may be up to 400 ⁇ m, 260 ⁇ m to 850 ⁇ m, 260 ⁇ m to 600 ⁇ m, 260 ⁇ m to 550 ⁇ m, 260 ⁇ m to 500 ⁇ m, 260 ⁇ m to 450 ⁇ m, 260 ⁇ m to 400 ⁇ m, 280 ⁇
  • the water-absorbing polymer particles may be in a form consisting of a single particle, or in a form consisting of an aggregate of fine particles (primary particles) (secondary particles).
  • primary particles fine particles
  • secondary particles examples of the shape of the primary particles include an approximately spherical shape, an irregularly crushed shape, a plate shape, etc.
  • examples of the shape include an approximately spherical single particle shape having a smooth surface shape such as a perfect sphere or an oval sphere.
  • the median particle size of the water-absorbent polymer particles can be measured using a JIS standard sieve, and specifically, is the value measured by the method described in the examples.
  • the typical polymerization methods used for polymerizing water-soluble ethylenically unsaturated monomers include aqueous solution polymerization, emulsion polymerization, and reversed-phase suspension polymerization.
  • aqueous solution polymerization method polymerization is carried out by heating an aqueous solution of the water-soluble ethylenically unsaturated monomer, with stirring as necessary.
  • reversed-phase suspension polymerization method polymerization is carried out by heating the water-soluble ethylenically unsaturated monomer in a hydrocarbon dispersion medium, with stirring.
  • a specific example of a method for producing water-absorbent polymer particles is a method for producing water-absorbent polymer particles by reverse phase suspension polymerization of a water-soluble ethylenically unsaturated monomer in a hydrocarbon dispersion medium, which includes a step of carrying out polymerization in the presence of a radical polymerization initiator and a step of surface cross-linking the hydrogel-like material obtained by polymerization in the presence of a surface cross-linking agent.
  • an internal cross-linking agent may be added to the water-soluble ethylenically unsaturated monomer as necessary to form a hydrogel-like material having an internal cross-linking structure.
  • water-soluble ethylenically unsaturated monomers include (meth)acrylic acid (in the present specification, "acrylic” and “methacrylic” are collectively referred to as “(meth)acrylic", the same applies below) and salts thereof; 2-(meth)acrylamido-2-methylpropanesulfonic acid and salts thereof; nonionic monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, N-methylol(meth)acrylamide, and polyethylene glycol mono(meth)acrylate; and amino group-containing unsaturated monomers and quaternized products thereof such as N,N-diethylaminoethyl(meth)acrylate, N,N-diethylaminopropyl(meth)acrylate, and diethylaminopropyl(meth)
  • water-soluble ethylenically unsaturated monomers from the viewpoint of industrial ease of availability, etc., (meth)acrylic acid or a salt thereof, (meth)acrylamide, and N,N-dimethylacrylamide are preferred, and (meth)acrylic acid and a salt thereof are more preferred.
  • These water-soluble ethylenically unsaturated monomers may be used alone or in combination of two or more kinds.
  • acrylic acid and its salts are widely used as raw materials for water-absorbent polymer particles, and these acrylic acid and/or its salts may be copolymerized with the other water-soluble ethylenically unsaturated monomers mentioned above.
  • acrylic acid and/or its salts are used as the main water-soluble ethylenically unsaturated monomer in an amount of 70 to 100 mol % based on the total water-soluble ethylenically unsaturated monomers.
  • the water-soluble ethylenically unsaturated monomer may be dispersed in a hydrocarbon dispersion medium in the form of an aqueous solution and subjected to reversed-phase suspension polymerization.
  • a hydrocarbon dispersion medium in the form of an aqueous solution
  • the concentration of the water-soluble ethylenically unsaturated monomer in this aqueous solution is preferably in the range of 20% by mass to the saturated concentration or less.
  • the concentration of the water-soluble ethylenically unsaturated monomer is more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less.
  • the concentration of the water-soluble ethylenically unsaturated monomer is more preferably 25% by mass or more, even more preferably 28% by mass or more, and even more preferably 30% by mass or more.
  • the acid group may be neutralized in advance with an alkaline neutralizing agent, if necessary.
  • alkaline neutralizing agents include alkali metal salts such as sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium carbonate, etc.; ammonia, etc.
  • alkaline neutralizing agents may be used in the form of an aqueous solution to simplify the neutralization operation.
  • the alkaline neutralizing agents described above may be used alone or in combination of two or more types.
  • the degree of neutralization of the water-soluble ethylenically unsaturated monomer by the alkaline neutralizing agent is preferably 10 to 100 mol%, more preferably 30 to 90 mol%, even more preferably 40 to 85 mol%, and even more preferably 50 to 80 mol%, in terms of the degree of neutralization of all acid groups possessed by the water-soluble ethylenically unsaturated monomer.
  • radical polymerization initiator examples include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, and hydrogen peroxide, as well as 2,2'-azobis(2-amidinopropane) dihydrochloride and 2,2'-azobis[2-(N-phenylenediamine)-2-methylpropane].
  • persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate
  • peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone per
  • azo compounds examples include 2,2'-azobis[2-(N-allylamidino)propane] dihydrochloride, 2,2'-azobis ⁇ 2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane ⁇ dihydrochloride, 2,2'-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide ⁇ , 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], and 4,4'-azobis(4-cyanovaleric acid).
  • radical polymerization initiators potassium persulfate, ammonium persulfate, sodium persulfate, and 2,2'-azobis(2-amidinopropane) dihydrochloride are preferred from the viewpoint of easy availability and ease of handling.
  • These radical polymerization initiators may be used alone or in combination of two or more.
  • the radical polymerization initiator can also be used as a redox polymerization initiator in combination with a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, or L-ascorbic acid.
  • the amount of radical polymerization initiator used is, for example, 0.00005 to 0.01 mole per mole of water-soluble ethylenically unsaturated monomer. By using such an amount, it is possible to avoid a sudden polymerization reaction and to complete the polymerization reaction within an appropriate time.
  • the internal crosslinking agent may be one capable of crosslinking the polymer of the water-soluble ethylenically unsaturated monomer used, such as (poly)ethylene glycol (the term “(poly)” refers to the case where the "poly" prefix is used or not).
  • unsaturated polyesters obtained by reacting polyols such as diols and triols, such as (poly)propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and (poly)glycerin, with unsaturated acids, such as (meth)acrylic acid, maleic acid, and fumaric acid; bisacrylamides such as N,N-methylenebisacrylamide; di(meth)acrylic acid esters or tri(meth)acrylic acid esters obtained by reacting polyepoxides with (meth)acrylic acid; di(meth)acrylic acid carbamyl esters obtained by reacting polyisocyanates, such as tolylene diisocyanate and hexamethylene diisocyanate, with hydroxyethyl (meth)acrylate; allylated starch, allylated cellulose, diallyl phthalate, N,N',N''-
  • a polyglycidyl compound more preferably a diglycidyl ether compound, and it is preferable to use (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, or (poly)glycerin diglycidyl ether.
  • These internal cross-linking agents may be used alone or in combination of two or more kinds.
  • the amount of the internal crosslinking agent used is preferably 0.000001 to 0.02 mol, more preferably 0.00001 to 0.01 mol, even more preferably 0.00001 to 0.005 mol, and even more preferably 0.00005 to 0.002 mol per mol of the water-soluble ethylenically unsaturated monomer.
  • hydrocarbon dispersion medium examples include aliphatic hydrocarbons having 6 to 8 carbon atoms, such as n-hexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 3-ethylpentane, and n-octane; alicyclic hydrocarbons, such as cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, trans-1,2-dimethylcyclopentane, cis-1,3-dimethylcyclopentane, and trans-1,3-dimethylcyclopentane; and aromatic hydrocarbons, such as benzene, toluene, and xylene.
  • aliphatic hydrocarbons having 6 to 8 carbon atoms such as n-hexane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylp
  • hydrocarbon dispersion media n-hexane, n-heptane, and cyclohexane are particularly preferred because they are easily available industrially, have stable quality, and are inexpensive.
  • These hydrocarbon dispersion media may be used alone or in combination of two or more types.
  • a commercially available product such as Exxol Heptane (manufactured by Exxon Mobil Corp.: contains 75 to 85% by mass of heptane and its isomers) can also be used to obtain favorable results.
  • the amount of the hydrocarbon dispersion medium used is preferably 100 to 1500 parts by mass, and more preferably 200 to 1400 parts by mass, per 100 parts by mass of the water-soluble ethylenically unsaturated monomer in the first stage, from the viewpoint of uniformly dispersing the water-soluble ethylenically unsaturated monomer and facilitating control of the polymerization temperature.
  • reversed-phase suspension polymerization is carried out in one stage (single stage) or in multiple stages of two or more stages, and the above-mentioned first stage polymerization refers to the polymerization reaction in a single stage or in a multiple stage polymerization (the same applies below).
  • a dispersion stabilizer In the reversed-phase suspension polymerization, a dispersion stabilizer can be used to improve the dispersion stability of the water-soluble ethylenically unsaturated monomer in the hydrocarbon dispersion medium. As the dispersion stabilizer, a surfactant can be used.
  • Surfactants that can be used include, for example, sucrose fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, alkylarylformaldehyde condensed polyoxyethylene ethers, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene polyoxypropyl alkyl ethers, polyethylene glycol fatty acid esters, alkyl glucosides, N-alkyl gluconamides, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, phosphate esters of polyoxyethylene alkyl ethers, and phosphate esters of poly
  • surfactants it is particularly preferable to use sorbitan fatty acid esters, polyglycerin fatty acid esters, and sucrose fatty acid esters from the standpoint of dispersion stability of the monomer. These surfactants may be used alone or in combination of two or more.
  • the amount of surfactant used is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 20 parts by mass, per 100 parts by mass of the first stage water-soluble ethylenically unsaturated monomer.
  • a polymeric dispersant As the dispersion stabilizer used in the reversed phase suspension polymerization, a polymeric dispersant may be used in combination with the above-mentioned surfactant.
  • polymeric dispersants include maleic anhydride modified polyethylene, maleic anhydride modified polypropylene, maleic anhydride modified ethylene-propylene copolymer, maleic anhydride modified EPDM (ethylene-propylene-diene terpolymer), maleic anhydride modified polybutadiene, maleic anhydride-ethylene copolymer, maleic anhydride-propylene copolymer, maleic anhydride-ethylene-propylene copolymer, maleic anhydride-butadiene copolymer, polyethylene, polypropylene, ethylene-propylene copolymer, oxidized polyethylene, oxidized polypropylene, oxidized ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethyl cellulose, ethylhydroxyethyl cellulose, etc.
  • polymeric dispersants it is particularly preferable to use maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-propylene copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-propylene copolymer, maleic anhydride-ethylene-propylene copolymer, polyethylene, polypropylene, ethylene-propylene copolymer, oxidized polyethylene, oxidized polypropylene, and oxidized ethylene-propylene copolymer, from the viewpoint of dispersion stability of the monomer.
  • These polymeric dispersants may be used alone or in combination of two or more kinds.
  • the amount of polymeric dispersant used is preferably 0.1 to 30 parts by mass, and more preferably 0.3 to 20 parts by mass, per 100 parts by mass of the first stage water-soluble ethylenically unsaturated monomer.
  • a thickener can be added to an aqueous solution containing a water-soluble ethylenically unsaturated monomer to carry out reverse suspension polymerization.
  • a thickener in this way to adjust the viscosity of the aqueous solution, it is possible to control the median particle size obtained in reverse suspension polymerization.
  • thickeners for example, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylic acid, partially neutralized polyacrylic acid, polyethylene glycol, polyacrylamide, polyethyleneimine, dextrin, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, etc. can be used. Note that, if the stirring speed during polymerization is the same, the higher the viscosity of the water-soluble ethylenically unsaturated monomer aqueous solution, the larger the primary particles and/or secondary particles obtained tend to be.
  • aqueous monomer solution containing a water-soluble ethylenically unsaturated monomer is dispersed in a hydrocarbon dispersion medium in the presence of a dispersion stabilizer.
  • the dispersion stabilizer surfactant or polymeric dispersant
  • the dispersion stabilizer may be added either before or after the addition of the aqueous monomer solution, so long as it is before the start of the polymerization reaction.
  • Such reverse phase suspension polymerization can be carried out in one stage or in multiple stages (two or more stages). From the viewpoint of increasing productivity, it is preferable to carry out the polymerization in two to three stages.
  • the water-soluble ethylenically unsaturated monomer is added to the reaction mixture obtained in the first stage of polymerization reaction and mixed, and the second and subsequent stages of reversed-phase suspension polymerization can be performed in the same manner as the first stage.
  • the reaction temperature for the polymerization reaction is preferably 20 to 110°C, and more preferably 40 to 90°C, from the viewpoints of promoting rapid polymerization and shortening the polymerization time, thereby improving economy, and of easily removing the heat of polymerization to allow the reaction to proceed smoothly.
  • the water-absorbent polymer particles of the present invention are obtained by adding a surface crosslinking agent to the hydrogel having an internal crosslinked structure obtained by polymerizing a water-soluble ethylenically unsaturated monomer to crosslink (surface crosslinking reaction).
  • This surface crosslinking reaction is preferably carried out in the presence of a surface crosslinking agent after the polymerization of the water-soluble ethylenically unsaturated monomer.
  • the crosslinking density near the surface of the water-absorbent polymer particles can be increased, and water-absorbent polymer particles with improved performance such as water absorption capacity under load can be obtained.
  • Examples of surface cross-linking agents include compounds having two or more reactive functional groups.
  • polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, trimethylolpropane, glycerin, polyoxyethylene glycol, polyoxypropylene glycol, and polyglycerin
  • polyglycidyl compounds such as (poly)ethylene glycol diglycidyl ether, (poly)glycerin diglycidyl ether, (poly)glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, (poly)propylene glycol polyglycidyl ether, and (poly)glycerol polyglycidyl ether
  • haloepoxy compounds such as epichlorohydrin, epibromohydrin, and ⁇ -methylepichlorohydrin
  • isocyanate compounds such as 2,4-to
  • polyglycidyl compounds such as (poly)ethylene glycol diglycidyl ether, (poly)glycerin diglycidyl ether, (poly)glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, (poly)propylene glycol polyglycidyl ether, and (poly)glycerol polyglycidyl ether are preferred.
  • These surface crosslinking agents may be used alone or in combination of two or more.
  • the amount of the surface cross-linking agent used is preferably 0.00001 to 0.01 mol, more preferably 0.00005 to 0.005 mol, and even more preferably 0.0001 to 0.002 mol, per mol of the total amount of water-soluble ethylenically unsaturated monomers used in the polymerization.
  • the surface cross-linking agent may be added as it is or as an aqueous solution, but if necessary, it may be added as a solution using a hydrophilic organic solvent as a solvent.
  • hydrophilic organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc.; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, dioxane, tetrahydrofuran, etc.; amides such as N,N-dimethylformamide; sulfoxides such as dimethyl sulfoxide, etc.
  • These hydrophilic organic solvents may be used alone, in combination of two or more types, or as a mixed solvent with water.
  • the timing of adding the surface cross-linking agent may be after the polymerization reaction of the water-soluble ethylenically unsaturated monomer has been almost completely completed. It is preferable to add the agent in the presence of moisture in the range of 1 to 400 parts by mass, more preferably in the range of 5 to 200 parts by mass, even more preferably in the range of 10 to 100 parts by mass, and even more preferably in the range of 20 to 60 parts by mass, relative to 100 parts by mass of the water-soluble ethylenically unsaturated monomer.
  • the amount of moisture means the total amount of moisture contained in the reaction system and the moisture used as necessary when adding the surface cross-linking agent.
  • the reaction temperature in the surface cross-linking reaction is preferably 50 to 250°C, more preferably 60 to 180°C, even more preferably 60 to 140°C, and even more preferably 70 to 120°C.
  • the reaction time in the surface cross-linking reaction is preferably 1 to 300 minutes, and more preferably 5 to 200 minutes.
  • a drying step may be included in which water, the hydrocarbon dispersion medium, and the like are removed by distillation by adding energy such as heat from the outside.
  • the system in which the hydrogel is dispersed in the hydrocarbon dispersion medium is heated, and the water and the hydrocarbon dispersion medium are once distilled out of the system by azeotropic distillation. At this time, if only the distilled hydrocarbon dispersion medium is returned to the system, continuous azeotropic distillation is possible.
  • the temperature in the system during drying is maintained below the azeotropic temperature with the hydrocarbon dispersion medium, which is preferable from the viewpoint of the resin being less likely to deteriorate.
  • the water and the hydrocarbon dispersion medium are distilled off to obtain water-absorbing polymer particles.
  • the drying process by distillation may be performed under normal pressure or under reduced pressure. From the viewpoint of increasing the drying efficiency, it may also be performed under a stream of nitrogen or the like.
  • the drying temperature is preferably 70 to 250°C, more preferably 80 to 180°C, even more preferably 80 to 140°C, and even more preferably 90 to 130°C.
  • the drying temperature is preferably 40 to 160°C, and more preferably 50 to 110°C.
  • a surface cross-linking step using a surface cross-linking agent is carried out after polymerization of monomers by reversed-phase suspension polymerization
  • the above-mentioned drying step by distillation is carried out after the surface cross-linking step is completed.
  • the surface cross-linking step and the drying step may be carried out simultaneously.
  • the water-absorbent resin composition of the present invention may contain additives according to the purpose.
  • additives include inorganic powders, surfactants, oxidizing agents, reducing agents, metal chelating agents, radical chain inhibitors, antioxidants, antibacterial agents, and the like.
  • the fluidity of the water-absorbent resin composition can be further improved by adding 0.05 to 5 parts by mass of amorphous silica as inorganic powder per 100 parts by mass of water-absorbent polymer particles.
  • the additives are preferably hydrophilic or water-soluble.
  • the content of water-absorbent polymer particles is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
  • the water-absorbent resin composition of the present invention can be produced, for example, by mixing water-absorbent polymer particles, a particulate antibacterial metal-containing deodorant, and a porous deodorant in a solid phase.
  • the water-absorbing resin composition of the present invention is preferably used for absorbent articles such as sanitary napkins and paper diapers.
  • the absorbent article of the present invention is an absorbent article containing an antibacterial metal-containing deodorant, a porous deodorant, and water-absorbing polymer particles, and the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 or more, and the sum (x+y) of the content x (% by mass) of the porous deodorant and the content y (% by mass) of the antibacterial metal-containing deodorant based on the total amount of the antibacterial metal-containing deodorant, the porous deodorant, and the water-absorbing polymer particles is 0.10% by mass or more.
  • the more detailed configuration of the absorbent article of the present invention can be set in the same manner as the above-mentioned water-absorbing resin composition.
  • the absorbent using the water-absorbing resin composition of the present invention includes the particulate water-absorbing resin composition of the present invention.
  • the absorbent may further include hydrophilic fibers.
  • Examples of the absorbent configuration include a sheet-like structure in which water-absorbing polymer particles are fixed on a nonwoven fabric or between multiple nonwoven fabrics, a mixed dispersion obtained by mixing the particulate water-absorbing resin composition and hydrophilic fibers to a uniform composition, a sandwich structure in which the particulate water-absorbing resin composition is sandwiched between layered hydrophilic fibers, and a structure in which the particulate water-absorbing resin composition and hydrophilic fibers are wrapped in tissue.
  • the absorbent may also contain other components, such as adhesive binders such as heat-fusible synthetic fibers, hot melt adhesives, and adhesive emulsions, in order to improve the shape retention of the absorbent.
  • the content of the water-absorbent resin composition in the absorbent is preferably 5 to 100% by mass, more preferably 10 to 95% by mass, even more preferably 20 to 90% by mass, and even more preferably 30 to 80% by mass.
  • Hydrophilic fibers include cellulose fibers such as cotton-like pulp obtained from wood, mechanical pulp, chemical pulp, and semi-chemical pulp, artificial cellulose fibers such as rayon and acetate, and fibers made of synthetic resins such as polyamide, polyester, and polyolefin that have been hydrophilically treated.
  • the average fiber length of hydrophilic fibers is usually 0.1 to 10 mm, or may be 0.5 to 5 mm.
  • the absorbent article of the present invention can be produced by holding an absorbent using the particulate water-absorbent resin composition of the present invention between a liquid-permeable sheet (top sheet) through which liquid can pass and a liquid-impermeable sheet (back sheet) through which liquid cannot pass.
  • the liquid-permeable sheet is placed on the side that comes into contact with the body, and the liquid-impermeable sheet is placed on the opposite side that comes into contact with the body.
  • Liquid-permeable sheets include nonwoven fabrics such as air-through, spunbond, chemical bond, and needle-punch types made of fibers such as polyethylene, polypropylene, and polyester, as well as porous synthetic resin sheets.
  • Liquid-impermeable sheets include synthetic resin films made of resins such as polyethylene, polypropylene, and polyvinyl chloride.
  • a water-absorbent resin composition comprising an antibacterial metal-containing deodorant, a porous deodorant, and water-absorbent polymer particles, wherein a ratio (X/Y) of a content X (parts by mass) of the porous deodorant to a content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 or more, and a sum (x+y) of a content x (% by mass) of the porous deodorant and a content y (% by mass) of the antibacterial metal-containing deodorant in the entire water-absorbent resin composition is 0.10% by mass or more.
  • the sum (x+y) of the content x (mass%) and the content y (mass%) is 0.10 mass% to 0.80 mass%, 0.10 mass% to 0.60 mass%, 0.10 mass% to 0.50 mass%, 0.10 mass% to 0.40 mass%, 0.10 mass% to 0.35 mass%, 0.10 mass% to 0.30 mass%, 0.13 mass% to 0.80 mass% %, 0.13% by mass to 0.60% by mass, 0.13% by mass % to 0.50 mass%, 0.13 mass% to 0.40 mass%, 0.13 mass% to 0.35 mass%, 0.13 mass% to 0.30 mass%, 0.18 mass% to 0.80 mass%, 0.18 mass% to 0.60 mass%, 0.18 mass% to 0.50 mass%, 0.18 mass% to 0.40 mass%, 0.18 mass% to 0.35 mass%, 0.18% by mass to 0.30% by mass, 0.20% by mass to 0.8 0 mass%, 0.20 mass% to 0.60 mass%, 0.20 mass% to 0.50 mass%, 0.20 mass% to 0.
  • the water absorbent resin composition according to (1) above which has a content of 40% by mass.
  • the porous deodorant comprises at least one selected from the group consisting of activated carbon, silicon dioxide, and silicates.
  • the water-absorbing polymer particles have a water-absorbing speed measured by a Vortex method of 10 seconds to 80 seconds, 10 seconds to 60 seconds, 10 seconds to 40 seconds, 20 seconds to 80 seconds, 20 seconds to 60 seconds, 20 seconds to 40 seconds, 30 seconds to 80 seconds, 30 seconds to 60 seconds, or 30 seconds to 40 seconds.
  • the water-absorbing resin composition according to any one of (1) to (7) above.
  • An absorbent article comprising an antibacterial metal-containing deodorant, a porous deodorant, and water-absorbent polymer particles, wherein a ratio (X/Y) of a content X (parts by mass) of the porous deodorant to a content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 or more, and a sum (x+y) of a content x (% by mass) of the porous deodorant and a content y (% by mass) of the antibacterial metal-containing deodorant based on a total amount of the antibacterial metal-containing deodorant, the porous deodorant, and the water-absorbent polymer particles is 0.10% by mass or more.
  • the sum (x+y) of the content x (mass%) and the content y (mass%) is 0.10 mass% to 0.50 mass%, 0.10 mass% to 0.40 mass%, 0.10 mass% to 0.35 mass%, 0.10 mass% to 0.30 mass%, 0.18 mass% to 0.50 mass%, 0.18 mass% to 0.40 mass%, 0.18 mass% to 0.35 mass% %, 0.18% by mass to 0.30% by mass, 0.30% by mass to 0.50% by mass, or 0.30% by mass to 0.40% by mass.
  • the absorbent article according to (9) or (10) above, wherein the ratio (X/Y) of the content X (parts by mass) of the porous deodorant to the content Y (parts by mass) of the antibacterial metal-containing deodorant is 0.8 to 15.0, 0.8 to 12.0, 0.8 to 10.0, 0.8 to 8.0, 0.8 to 5.0, 1.0 to 15.0, 1.0 to 12.0, 1.0 to 10.0, 1.0 to 8.0, 1.0 to 5.0, 2.0 to 15.0, 2.0 to 12.0, 2.0 to 10.0, 2.0 to 8.0, 2.0 to 5.0, 3.0 to 15.0, 3.0 to 12.0, 3.0 to 10.0, 3.0 to 8.0, or 3.0 to 5.0.
  • the porous deodorant comprises at least one selected from the group consisting of activated carbon, silicon dioxide, and silicates.
  • the water absorption speed of the water-absorbent polymer particles by the Vortex method is 10 seconds to 80 seconds, 10 seconds to 60 seconds, 10 seconds to 40 seconds, 20 seconds to 80 seconds, 20 seconds to 60 seconds, 20 seconds to 40 seconds, 30 seconds to 80 seconds, 30 seconds to 60 seconds, or 30 seconds to 40 seconds.
  • the absorbent article according to any one of (9) to (13).
  • water-absorbent polymer particles, activated carbon as a porous deodorant, and water-absorbent resin compositions obtained in the examples and comparative examples were evaluated by the following various tests. Unless otherwise specified, measurements were performed in an environment with a temperature of 25 ⁇ 2°C and a humidity of 50 ⁇ 10%.
  • the aqueous liquid prepared above was added to a separable flask and stirred for 10 minutes.
  • a surfactant solution prepared by heating and dissolving 0.736 g of sucrose stearate with an HLB of 3 (Ryoto Sugar Ester S-370, Mitsubishi Chemical Foods Corporation) in 6.62 g of n-heptane as a surfactant in a 20 mL vial was then added.
  • the system was thoroughly purged with nitrogen while stirring at a stirrer speed of 550 rpm, and the flask was immersed in a water bath at 70° C. to raise the temperature, and polymerization was carried out for 60 minutes to obtain a first-stage polymerization slurry.
  • the contents of the separable flask system were cooled to 25°C while stirring at a stirrer speed of 1000 rpm, and then the entire amount of the second-stage aqueous liquid was added to the first-stage polymerization slurry liquid, and the system was replaced with nitrogen for 30 minutes. After that, the flask was again immersed in a 70°C water bath to raise the temperature, and the polymerization reaction was carried out for 60 minutes to obtain a hydrous gel polymer.
  • the flask was immersed in an oil bath set at 125°C, and 259.9 g of water was extracted from the system by azeotropic distillation of n-heptane and water while refluxing n-heptane. Then, 4.42 g (0.507 mmol) of a 2% by mass aqueous solution of ethylene glycol diglycidyl ether was added to the flask as a surface crosslinking agent, and the flask was kept at 83°C for 2 hours.
  • the n-heptane was evaporated at 125°C to dry the particles, and the particles were passed through a sieve with 850 ⁇ m mesh to obtain 226.1 g of water-absorbent polymer particles.
  • the saline water retention capacity of the water-absorbent polymer particles was 42 g/g
  • the water absorption speed was 39 seconds
  • the median particle size was 360 ⁇ m
  • the saline water absorption capacity under a load of 4.14 kPa was 20 ml/g.
  • the cotton bag was dehydrated for 1 minute using a dehydrator (Kokusan Co., Ltd., product number: H-122) set to a centrifugal force of 167 G, and the mass Wd (g) of the cotton bag containing the swollen gel after dehydration was measured.
  • the same operation was performed without adding the water-absorbent polymer particles, the empty mass We (g) of the cotton bag when wet was measured, and the physiological saline water retention was calculated from the following formula.
  • Saline water retention capacity (g/g) [Wd-We]/2.0
  • the mass of the water-absorbing polymer particles remaining on each sieve was calculated as a mass percentage relative to the total amount to obtain the particle size distribution.
  • the particle size distribution was calculated by accumulating the particles remaining on the sieve in order of particle size from the largest to the smallest, and the relationship between the sieve opening and the accumulated value of the mass percentage of the water-absorbent polymer particles remaining on the sieve was plotted on a logarithmic probability paper.
  • the particle size corresponding to an accumulated mass percentage of 50% by mass was determined as the median particle size by connecting the plots on the probability paper with a straight line.
  • the measuring device includes a burette part 1, a clamp 3, a conduit 5, a stand 11, a measurement table 13, and a measurement part 4 placed on the measurement table 13.
  • the burette part 1 has a burette tube 21 with a scale, a rubber plug 23 that seals the opening at the top of the burette tube 21, a cock 22 connected to the tip of the bottom of the burette tube 21, and an air introduction tube 25 and a cock 24 connected to the bottom of the burette tube 21.
  • the burette part 1 is fixed with a clamp 3.
  • the flat measurement table 13 has a through hole 13a with a diameter of 2 mm formed in its center, and is supported by a height-variable stand 11.
  • the through hole 13a of the measuring table 13 and the cock 22 of the burette part 1 are connected by a conduit 5.
  • the inside diameter of the conduit 5 is 6 mm.
  • the measuring section 4 has a Plexiglas cylinder 31, a polyamide mesh 32 attached to one opening of the cylinder 31, and a weight 33 that can move up and down inside the cylinder 31.
  • the cylinder 31 is placed on the measuring table 13 via the polyamide mesh 32.
  • the inner diameter of the cylinder 31 is 20 mm.
  • the opening of the polyamide mesh 32 is 75 ⁇ m (200 mesh).
  • the weight 33 has a diameter of 19 mm and a mass of 119.6 g, and can apply a load of 4.14 kPa (0.6 psi) to the water-absorbent polymer particles 10a that are uniformly arranged on the polyamide mesh 32 as described below.
  • the stopcocks 22 and 24 of the burette part 1 were closed, and 0.9% by mass physiological saline adjusted to 25°C was poured into the burette tube 21 through the opening at the top of the burette tube 21.
  • the top opening of the burette tube 21 was sealed with a rubber stopper 23, and then the stopcocks 22 and 24 were opened.
  • the inside of the conduit 5 was filled with 0.9% by mass saline 50 to prevent air bubbles from entering.
  • the height of the measurement table 13 was adjusted so that the height of the water surface of the 0.9% by mass saline solution 50 that reached the through hole 13a was the same as the height of the upper surface of the measurement table 13. After the adjustment, the height of the water surface of the 0.9% by mass saline solution 50 in the burette tube 21 was read on the scale of the burette tube 21, and this position was set as the zero point (the reading at 0 seconds).
  • Activated carbon (Carborafine-6, manufactured by Osaka Gas Chemicals Co., Ltd.) having a BET specific surface area of 1345 m 2 /g, a median particle size of 46 ⁇ m, an ignition residue of 0.4%, a loss on drying of 3.2%, a pH of 4.9 and a crushed shape was prepared.
  • Example 1 To 100 parts by mass of the water-absorbent polymer particles obtained in the manufacturing example, 0.03 parts by mass of silver-zinc zeolite (Zeomic HD10N, manufactured by Sinanen Zeomic Co., Ltd., median particle size 2.1 ⁇ m, BET specific surface area 653 m2 /g) was added as an antibacterial metal-containing deodorant, and 0.10 parts by mass of the above-mentioned activated carbon was added as a porous deodorant, and these were mixed by rotating them for 30 minutes under conditions of a rotation speed of 50 rpm and a revolution speed of 50 rpm using a cross rotary mixer manufactured by Meiwa Kogyo Co., Ltd., to obtain a water-absorbent resin composition. The median particle size and BET specific surface area of the antibacterial metal-containing deodorant were measured by the same measuring method as that for the activated carbon described above.
  • Example 2 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of activated carbon added was changed to 0.30 parts by mass.
  • Example 3 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was changed to 0.10 parts by mass.
  • Example 4 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.10 parts by mass and the amount of activated carbon added was 0.30 parts by mass.
  • Example 5 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.06 parts by mass and the amount of activated carbon added was 0.20 parts by mass.
  • Example 1 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.015 parts by mass and the amount of activated carbon added was 0.05 parts by mass.
  • Example 2 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.06 parts by mass and the amount of activated carbon added was 0.03 parts by mass.
  • Example 3 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.015 parts by mass and no activated carbon was added.
  • Example 4 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.03 parts by mass and no activated carbon was added.
  • Example 5 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.06 parts by mass and no activated carbon was added.
  • Example 6 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the amount of silver-zinc zeolite added was 0.10 parts by mass and no activated carbon was added.
  • Example 7 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the silver-zinc zeolite was not added and the amount of activated carbon added was 0.03 parts by mass.
  • Example 8 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the silver-zinc zeolite was not added and the amount of activated carbon added was 0.05 parts by mass.
  • Example 9 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the silver-zinc zeolite was not added and the amount of activated carbon added was 0.10 parts by mass.
  • Example 10 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the silver-zinc zeolite was not added and the amount of activated carbon added was 0.20 parts by mass.
  • Example 11 A water-absorbent resin composition was obtained in the same manner as in Example 1, except that the silver-zinc zeolite was not added and the amount of activated carbon added was 0.30 parts by mass.
  • Deodorization rate (%) [(ammonia concentration in Reference Example 1 - ammonia concentration in Examples or Comparative Examples) / ammonia concentration in Reference Example 1] x 100
  • a glass suction bottle with a capacity of 500 mL was prepared.
  • a SUS hopper (upper inner diameter 88 mm x foot inner diameter 18 mm) was set so that the height from the bottom of the suction bottle to the outlet of the hopper was 180 mm, and the suction port of the suction bottle and a dust generation meter (manufactured by Shibata Scientific Co., Ltd., digital indicator LD-5R type) were connected with a glass tube (inner diameter 7.7 mm x length 300 mm).
  • the deodorizing rate of Comparative Example 9 in which the content x of the porous deodorant in the water absorbent resin composition is 0.10 mass%, is 20%, and the deodorizing rate of Comparative Example 6, in which the content y of the antibacterial metal-containing deodorant in the water absorbent resin composition is 0.10 mass%, is 60%.
  • Example 3 in which the content x of the porous deodorant in the water absorbent resin composition is 0.10 mass% and the content y of the antibacterial metal-containing deodorant is 0.10 mass%, is extremely high at 98%, and it can be seen that a synergistic effect between the antibacterial metal-containing deodorant and the porous deodorant is exerted, which cannot be predicted from the results of Comparative Examples 6 and 9 (the sum of the deodorizing rates of Comparative Examples 6 and 9 is 80%).
  • the synergistic effect of the deodorizing rate of the water-absorbent resin composition shown in Table 2 is the deodorizing rate of the example divided by the sum of the deodorizing rates of the comparative examples in which each deodorant was used alone.
  • the synergistic effect of Example 3 is a value calculated by deodorizing rate of Example 3 (98) / (deodorizing rate of Comparative Example 9 (20) + deodorizing rate of Comparative Example 6 (60)). If the standard value exceeds 1.00, it can be said that a synergistic effect is being exerted.

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Abstract

L'invention concerne une composition de résine absorbant l'eau ayant un excellent effet désodorisant.　La composition de résine absorbant l'eau contient un désodorisant contenant un métal antibactérien, un désodorisant poreux et des particules de polymère absorbant l'eau. Le rapport (X/Y) de la teneur X (parties en masse) du désodorisant poreux à la teneur Y (parties en masse) du désodorisant contenant un métal antibactérien est égal ou supérieur à 0,8, et dans la totalité de la composition de résine absorbant l'eau, la somme (x + y) de la teneur x (% en masse) du désodorisant poreux et la teneur y (% en masse) du désodorisant contenant un métal antibactérien est égale ou supérieure à 0,10 % en masse.
PCT/JP2024/003048 2023-02-22 2024-01-31 Composition de résine absorbant l'eau WO2024176758A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0411948A (ja) * 1990-04-27 1992-01-16 Hagiwara Giken:Kk 抗菌性吸水性成形体
JPH0810616A (ja) * 1994-06-30 1996-01-16 Hokuriku Fine Chem:Kk 吸水性組成物およびその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0411948A (ja) * 1990-04-27 1992-01-16 Hagiwara Giken:Kk 抗菌性吸水性成形体
JPH0810616A (ja) * 1994-06-30 1996-01-16 Hokuriku Fine Chem:Kk 吸水性組成物およびその製造方法

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