WO2007141875A1 - Composition de résine hydro-absorbante et son procédé de production - Google Patents

Composition de résine hydro-absorbante et son procédé de production Download PDF

Info

Publication number
WO2007141875A1
WO2007141875A1 PCT/JP2006/311637 JP2006311637W WO2007141875A1 WO 2007141875 A1 WO2007141875 A1 WO 2007141875A1 JP 2006311637 W JP2006311637 W JP 2006311637W WO 2007141875 A1 WO2007141875 A1 WO 2007141875A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
absorbent resin
resin composition
absorbent
mass
Prior art date
Application number
PCT/JP2006/311637
Other languages
English (en)
Japanese (ja)
Inventor
Hiroko Okochi
Original Assignee
Nippon Shokubai Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co., Ltd. filed Critical Nippon Shokubai Co., Ltd.
Priority to JP2006541744A priority Critical patent/JP5020637B2/ja
Priority to PCT/JP2006/311637 priority patent/WO2007141875A1/fr
Publication of WO2007141875A1 publication Critical patent/WO2007141875A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation

Definitions

  • the present invention relates to a method for producing a water-absorbent resin composition and a water-absorbent resin composition, and more specifically, a method for producing a water-absorbent resin composition used for a water absorbent material of a paper diaper and the like. It is intended for a water-absorbent rosin composition obtained by such a production method.
  • the water-absorbent resin particles used in such applications are required to have a large water absorption capacity and water absorption speed.
  • an important characteristic is liquid diffusibility.
  • Liquid diffusibility means the property that when used in a water absorbent material such as a disposable diaper, liquid such as urine rapidly diffuses on the surface of the water absorbent resin particles and between the particles. ing. The liquid that has diffused over a wide range increases the contact area with the water-absorbing resin particles and is likely to be absorbed. Even if the final water absorption capacity and water absorption speed of the water-absorbent resin particles are the same, if the liquid diffusibility is high, the overall water absorption performance is improved. In the case of water-absorbing products that touch the skin, such as disposable diapers, discomfort occurs when the urine accumulates for a long time, but if the urine spreads over a wide area, such discomfort is reduced.
  • the liquid diffusibility means the property that when used in a water absorbent material such as a disposable diaper, liquid such as urine rapidly diffuses on the surface of the water absorbent resin particles and between the particles. ing. The liquid that has diffused over a wide range increases the contact area with the water-absorbing resin particles and is
  • the liquid diffusibility cannot be sufficiently improved by simply mixing the inorganic particles with the water-absorbent resin particles.
  • Patent Document 2 when the water-absorbing resin particles are irradiated with active energy rays, the water-liquid diffusibility, which may improve the water absorption magnification, is not improved.
  • An object of the present invention is a liquid that is a practically important characteristic that does not impair basic water absorption performance, productivity, etc., as a water absorbent resin material used as a water absorbent material for paper diapers. The diffusivity is greatly improved.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-261797
  • Patent Document 2 JP 59-129232 A
  • the method for producing a water-absorbent resin composition according to the present invention has an inorganic fine particle B irradiated with ultraviolet rays of 0.01 parts by weight per 100 parts by weight of the water-absorbent resin A.
  • ⁇ It includes a step of mixing the water-absorbing resin A and the inorganic fine particles B irradiated with ultraviolet rays so as to be LO parts by weight.
  • the method for producing a water-absorbent resin composition according to the present invention has an organic fine particle B of 0.01 to 10 parts by weight with respect to 100 parts by weight of the water-absorbent resin A.
  • the method includes a step of mixing the water-absorbent resin A and the inorganic fine particles B and a step of irradiating the mixture of the water-absorbent resin A and the inorganic fine particles B with ultraviolet rays.
  • the inorganic fine particles B are not present. It is preferably made of metal oxides.
  • the irradiation with ultraviolet rays is performed using light including an ultraviolet region having a wavelength of 200 to 400 nm, an irradiation dose of 100 to 10,000 mjZcm 2 , and an irradiation intensity of 1.
  • ⁇ It is preferably performed by irradiation with LOOOmWZcm 2 for 1 second to 60 minutes.
  • the water-absorbent resin A is preferably water-absorbent resin particles having a mass average particle diameter of 100 to 1000 ⁇ m.
  • a water-absorbent resin composition according to the present invention is a water-absorbent resin composition containing a water-absorbent resin A and inorganic fine particles B, and a liquid diffusion rate (LDV ) Is 2.0 to 1
  • the inorganic fine particles B are preferably irradiated with ultraviolet rays!
  • the inorganic fine particles B are preferably inorganic metal oxides.
  • the inorganic fine particles B are a mixture of two or more kinds of inorganic metal oxides.
  • the mixture of two or more kinds of inorganic metal oxides is a mixture containing silica and titanium oxide.
  • the water-absorbent resin A and the water-absorbing resin A and the inorganic fine particles B that have been subjected to the ultraviolet irradiation treatment have excellent liquid diffusibility (LDV).
  • LDV liquid diffusibility
  • Inorganic fine particles B themselves have a water-absorbing water-absorbing resin Even if A itself is manufactured using ordinary raw materials and manufacturing techniques, the inorganic fine-particles B irradiated with ultraviolet rays are absorbed into the water-absorbing resin. When combined with A, LDV is significantly improved compared to a mixture of water-absorbent resin A and inorganic fine particles B, or a case where water-absorbent resin A is simply subjected to ultraviolet irradiation treatment. However, even if the LDV is significantly improved, the basic water absorption performance, specifically, the absorption capacity under pressure (CRC), the absorption capacity under pressure (AAP), etc. will not be impaired. Can demonstrate.
  • CRC absorption capacity under pressure
  • AAP absorption capacity under pressure
  • the above water-absorbing resin composition is simple and efficient with a relatively simple apparatus by adding inorganic fine particles or ultraviolet irradiation treatment to the ordinary water-absorbing resin manufacturing technology. Can be manufactured. There is no need to use special raw materials or to apply special production methods for the production of water-absorbent fats and oils. As a result, it is possible to provide a water-absorbent resin composition that is economically productive and excellent in performance quality.
  • weight is treated as a synonym for “mass”
  • wt% is treated as a synonym for “mass%”
  • main component is preferably 50 mass% or more, preferably Is treated as meaning that it contains 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
  • X to Y indicating a range indicates that the range is from X to ⁇ .
  • the method for producing a water-absorbent rosin composition according to the present invention includes any of the following steps (I) and (II).
  • the water-absorbent resin composition according to the present invention is preferably obtained by the above production method as an example, and includes the water-absorbent resin A and inorganic fine particles B, and has a liquid diffusion rate (LDV) of 2.0.
  • LDV liquid diffusion rate
  • the performance of the water-absorbent resin composition can be evaluated by the following characteristics or measured values.
  • the specific measurement of each characteristic is based on the measurement method prescribed
  • water absorption in terms of “water absorption”, “water absorption ratio”, “water absorption performance”, and the like is intended to absorb saline, urine and other liquids that are not intended only for water. It is a concept that includes the case of liquid or absorption.
  • LDV Liquid Distribution Velocity
  • Centrifuge retention capacity (CRC: Centriuge Retention Capacity): Also called absorption capacity without pressure, indicates the amount of liquid that can be absorbed by the absorber, and the basic absorption capacity.
  • Absorbency Against Pressure (AAP): Absorbency against Pressure (AAP): Shows the same absorption capacity as CRC, but differs in the absorption capacity under pressure. Also called absorption capacity under pressure. It represents the absorption capacity in the usage environment as an absorbent product.
  • Saline Flow Conductivity Indicates whether the liquid permeability is good or bad. It is shown by the ease of liquid permeation in the swollen water-absorbent rosin composition. Larger value means liquid permeation
  • a normal water-absorbing resin can be used as it is. It may be a water-absorbent coagulant manufactured by applying known raw materials and manufacturing methods.
  • the water-absorbent resin has various forms such as particles, fibers, sheet 'tapes, gels, and the like.
  • a particulate water-absorbing resin that is, a water-absorbing resin particle will be basically described.
  • the present invention is applicable to forms other than particles as long as there is no technical problem.
  • the water-absorbing resin is a water-swellable, water-insoluble crosslinked polymer capable of forming a hydrogel.
  • Water swellability refers to a substance that absorbs a large amount of water in ion-exchanged water, which is essentially 5 times or more, preferably 50 to 1 000 times its own weight.
  • Water-insoluble means that the water-soluble component (water-soluble polymer) of the unbridged water-absorbing resin is preferably 0-50% by mass, more preferably 25
  • the amount is not more than%, more preferably not more than 20% by weight, still more preferably not more than 15% by weight, particularly preferably not more than 10% by weight.
  • the water-absorbent resin having a crosslinked structure obtained by polymerizing an acid group-containing unsaturated monomer is preferable.
  • the acid group-containing unsaturated monomer the ability to use a monomer that becomes an acid group after polymerization by hydrolysis after polymerization, such as acrylonitrile, preferably an acid group-containing unsaturated group that contains an acid group at the time of polymerization It is a monomer.
  • the water-absorbing resin is composed of a polyacrylic acid partially neutralized polymer, a hydrolyzate of starch-acrylonitrile daraf polymer, a starch-acrylic acid graft polymer, and a vinyl acetate-acrylic acid ester copolymer. , Acrylonitrile copolymer or acrylamide copolymer hydrolyzate, or cross-linked products thereof, carboxyl group-containing cross-linked polyvinyl alcohol modified products, cross-linked isobutylene maleic anhydride copolymer, etc. Can do.
  • the polymer is a partially neutralized polyacrylate polymer having a crosslinked structure obtained by polymerizing and crosslinking a monomer having acrylic acid and Z or a salt thereof (neutralized product) as main components.
  • the monomer is mainly composed of acrylic acid and Z or a salt thereof
  • other monomers may be used in combination.
  • methacrylic acid (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, butyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) talyloxyalkane sulfonic acid and its alkali metals Salts, ammonium salts, N-Bulu-2-pyrrolidone, N-Buracetoamide, (Meth) acrylamide, N-Isopropyl (meth) acrylamide, N, N Dimethyl (meth) acrylamide, 2-Hydroxyethyl Water-soluble or hydrophobic unsaturated monomers such as (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, isobutylene
  • the monomer other than acrylic acid (salt) is based on the total amount of acrylic acid used as the main component and Z or a salt thereof. , rather preferably 0 to 30 mol 0/0, more preferably 0: the percentage of LO mol%.
  • the absorption properties of the finally obtained water-absorbing resin (composition) are further improved, and the water-absorbing resin ( Composition) can be obtained even more inexpensively.
  • the water-absorbing resin must have a crosslinked structure.
  • a self-crosslinking type that does not use a crosslinking agent may be used, but a crosslinking agent having two or more polymerizable unsaturated groups or two or more reactive groups in one molecule (for a water absorbent resin) The one obtained by copolymerizing or reacting with the internal crosslinking agent) is preferred.
  • the internal cross-linking agent examples include N, N'-methylenebis (meth) acrylamide,
  • the internal cross-linking agent may be used alone or as a mixture of two or more thereof.
  • the internal cross-linking agent may be added to the reaction system all at once or in divided portions.
  • two or more polymerizable it is preferable to use a compound having an unsaturated group at the time of polymerization.
  • the amount of the internal cross-linking agent used is less than 0.001 mol% and more than 2 mol%, the water-soluble component is increased or the water absorption capacity is decreased. May not be obtained.
  • the internal cross-linking agent is reacted before or during the polymerization of the monomer, after the polymerization, or after the neutralization. Add it to the system.
  • the above-mentioned monomer is polymerized in order to obtain the water-absorbent resin used in the present invention, it is possible to perform Balta polymerization or precipitation polymerization. However, performance and ease of control of the polymerization are possible. Further, from the viewpoint of absorption properties of the swollen gel, it is preferable to perform aqueous solution polymerization or reverse phase suspension polymerization by using the monomer as an aqueous solution.
  • the concentration of the monomer in the aqueous solution (hereinafter referred to as the monomer aqueous solution) is determined by the temperature of the aqueous solution and the monomer, and is not particularly limited.
  • the force is preferably within the range of 10 to 70% by mass, and more preferably within the range of 20 to 60% by mass.
  • a solvent other than water may be used in combination as necessary, and the type of the solvent used in combination is not particularly limited.
  • the reverse phase suspension polymerization is a polymerization method in which an aqueous monomer solution is suspended in a hydrophobic organic solvent.
  • Aqueous solution polymerization is a method of polymerizing an aqueous monomer solution without using a dispersion solvent. 4625001 specification, 4873299 specification, 4286082 specification, 4973632 specification, 4985518 specification, 5124416 specification, 525 0640 specification, 5264495 specification, 5145906
  • U.S. Patent Nos. 5380808 and European Patents such as European Patent Nos. 0811636, 0955086, and 0922717. Measurers and initiators are also applicable in the present invention.
  • the polymerization After the polymerization, it is usually a water-containing gel-like cross-linked polymer, and is dried as necessary, and usually pulverized before and Z or after drying to form water-absorbent rosin particles.
  • the drying is usually performed in a temperature range of 60 ° C to 250 ° C, preferably 100 ° C to 220 ° C, more preferably 120 ° C to 200 ° C.
  • the drying time depends on the surface area of the polymer, the moisture content, and the type of dryer, and is selected to achieve the desired moisture content.
  • the water absorption performance of the water-absorbent resin particles alone is excellent, the water absorption performance of the finally obtained water-absorbent resin composition is likely to be excellent.
  • the LDV or SFC of the water-absorbent resin composition can be improved while maintaining a high CRC and AAP, and a high LDV value (for example, 3. OmmZs or more) that has not been achieved conventionally can be obtained.
  • a high LDV value for example, 3. OmmZs or more
  • the performance of the water-absorbent resin composition can be improved.
  • the water-absorbent rosin particles themselves are also excellent in L DV and SFC, LDV and SFC can be further improved.
  • the water-absorbent resin particles and further the water-absorbent resin composition described below are adjusted to a specific particle size.
  • particles of 150 ⁇ m or more and less than 850 ⁇ m (specified by sieve classification: JIS 28801-1: 2000) account for 90% by mass or more, more preferably 150 m or more and less than 850 ⁇ m
  • the total particle size is 95% by mass or more, and more preferably, the particle size is 150 m or more and less than 850 m is 98% by mass or more.
  • grains of 300 m or more are 60 mass% or more of the whole.
  • the whole means all the water-absorbent resin particles in the water-absorbent resin composition.
  • the mass average particle diameter (D50) of the water-absorbent resin particles is 100 to 1000 ⁇ m, preferably 200 to 710 ⁇ m, more preferably 200 to 600 ⁇ m, and still more preferably 300 to 600 ⁇ m. m, particularly preferably 300 to 500 ⁇ m, most preferably 350 to 450 ⁇ m.
  • the particle diameter of the water-absorbent resin particles may be adjusted by granulation, if necessary.
  • the logarithmic standard deviation ( ⁇ ⁇ ) of the particle size distribution of the water-absorbent resin particles according to the present invention is preferably 0.1 to 0.45, more preferably 0.25 to 0.45, More preferably, it is 0.30 to 0.40.
  • the logarithmic standard deviation ( ⁇ ⁇ ) of the particle size distribution means that the smaller the value, the narrower the particle size distribution.
  • particles of 300 m or more means particles remaining on a JIS standard sieve having an opening of 300 m measured after classification by a sieve classification method described later. Point to.
  • the term “particles less than 300 m” refers to particles that have passed through a mesh having an opening of 300 m measured after classification by the classification method described later. The same applies to the size of the other openings. Further, when 50% by mass of particles are classified by a mesh having an opening of 300 m, the mass average particle diameter (D50) is 300 m.
  • the particle shape of the water-absorbing resin particles is not limited to a spherical shape, a crushed shape, an indeterminate shape, or the like, but an indeterminate crushed shape obtained through a pulverization step can be preferably used.
  • the particle size of the water-absorbent resin particles is prepared by polymerization, hydrated polymer pulverization (also referred to as water-containing polymer fragmentation), drying, pulverization, classification, granulation, mixing of a plurality of water-absorbent rosin particles, and the like. This can be done as appropriate.
  • Surface-absorbing water-absorbing resin particles can be used as the water-absorbing resin particles.
  • the surface-crosslinked water-absorbing resin particles are further subjected to surface crosslinking (secondary crosslinking) on the water-absorbing resin particles.
  • cross-linking agents for performing surface cross-linking. From the viewpoint of physical properties, polyhydric alcohol compounds, epoxy compounds, polyamine compounds or generally On the other hand, condensates with mouth epoxy compounds, oxazoline compounds, molded compounds, or polyoxazolidinone compounds, polyvalent metal salts, alkylene carbonate compounds and the like are used.
  • the surface cross-linking agents exemplified in US Pat. Nos. 6,228,930, 6071976, 6,254,990 and the like can be used.
  • Divalent amine compounds such as epichlorohydrin, epipibrohydrin, a-methylepoxychlorohydrin; condensates of the polyvalent amine compounds with the haloepoxy compounds; 2-oxazolidinone Oxazolidinone compounds (US6559239); oxetane compounds; cyclic urea compounds; alkylene carbonate compounds such as ethylene carbonate (US5409771) and the like.
  • cross-linking agents it is preferable to use at least one oxetane compound (US2002Z72471), cyclic urea compound, and polyhydric alcohol power, more preferably 2 to C: LO oxetane compound.
  • a polyhydric alcohol having at least one selected from polyhydric alcohol or more preferably 3 to 8 carbon atoms is used.
  • the amount of the surface cross-linking agent used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the water-absorbent resin, although it depends on the compounds used and combinations thereof. A range of 0.01 parts by mass to 5 parts by mass is more preferable.
  • Water is preferably used for surface crosslinking.
  • the amount of water used depends on the water content of the water-absorbent resin used, but is usually preferably 0.5 to 20 parts by mass, more preferably 0 to 100 parts by mass of the water-absorbent resin. 5 ⁇ : The range of LO parts by mass. Further, in the present invention, it is preferably 0 to: L0 parts by mass, more preferably 0 to 5 parts by mass, and still more preferably 100 parts by mass of a water-absorbent resin that may use a hydrophilic organic solvent other than water. The range is 0 to 3 parts by mass.
  • the size of the droplets to be sprayed is more preferably 10-200 ⁇ m, preferably 1 to 300 ⁇ m in average particle size.
  • water-insoluble fine particle powder and surfactant may be allowed to coexist in a range that does not hinder the effect of the present invention.
  • the water-absorbent resin after mixing with the crosslinking agent is preferably heat-treated.
  • the heating temperature (specified by the heat medium temperature) is preferably 100 to 250 ° C, more preferably 150 to 250 ° C, and the heating time is preferably 1 The range is from minutes to 2 hours.
  • Preferable examples of the combination of temperature and time are 0.1 to 1.5 hours at 180 ° C and 0.1 to 1 hour at 200 ° C.
  • water-absorbent rosin particles affect the properties of the finally obtained water-absorbent rosin composition. Accordingly, water-absorbent rosin particles are preferably those excellent in performance required for the water-absorbent rosin composition. For example, those having the following characteristics are desirable.
  • the water-absorbent resin particles are powders that exhibit fluidity even at room temperature, in addition to the physical properties of the resulting water-absorbent resin composition.
  • the water content of the water-absorbing resin particles (specified by the amount of water contained in the water-absorbing resin particles)
  • the Z particles lg were evenly spread in an aluminum cup with a diameter of 5 cm, and the drying loss at 105 ° C was 3 hours.
  • the (measurement) rate is preferably 0.1 to 40% by mass, more preferably 0.2 to 30% by mass, even more preferably 0.3 to 15% by mass, and particularly preferably 0.5 to: LO mass. % Powder state. If the water content of the water-absorbing slag particles is more than 40% by mass, the water absorption ratio decreases, and if the water content is less than 0.1% by mass, the liquid wicking property may decrease.
  • the soluble content is set to 25% by mass or less (lower limit 0% by mass). More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.
  • the CRC value of the water-absorbent resin particles can be set to 20 to 50 gZg, preferably 20 to 45 g, more preferably 20 to 40 gZg, and most preferably 20 to 35 gZg.
  • the AAP value of the water-absorbent resin composition tends to be lower than the AAP value of the water-absorbent resin particles. Therefore, the AAP value of the water-absorbent rosin particles can be set to 10 to 35 gZg, preferably 15 to 35 gZg, more preferably 18 to 30 gZg.
  • the water-absorbent resin composition is usually higher than the water-absorbent resin particles.
  • the higher the SFC value of the water-absorbent resin particles the higher the SFC value of the water-absorbent resin composition. Therefore, the SFC value of the water-absorbent rosin particles can be set to l to 1500 ⁇ 10 _7 ′ cm 3 • s, preferably 10 to 500 ⁇ 10 _7 ′ cm 3 ′ s′g _1 .
  • the water-absorbent resin composition is much more improved than the water-absorbent resin particles. Accordingly, the LDV of the water-absorbing resin particles may be relatively low, but the higher the LDV of the water-absorbing resin particles, the higher the LDV of the water-absorbing resin composition. is there. Therefore, the LDV value of the water-absorbent rosin particles can be set to 0.1 mmZs or more, preferably 0.5 mmZs or more.
  • the inorganic fine particles function to improve the LDV of the water-absorbent rosin composition.
  • the inorganic fine particles basically, inorganic materials used in ordinary chemical products and pharmaceuticals can be used.
  • inorganic materials that are safe in terms of health safety. It is desirable to use an inorganic material that does not easily cause problems such as alteration and deterioration that easily develop the intended function by the production process of the water-absorbent rosin composition, particularly, the ultraviolet irradiation treatment.
  • inorganic materials for photocatalysts including titanium oxide and other general inorganic oxides can be used.
  • An inorganic substance for photocatalyst is a substance that exhibits a chemical or physical photocatalytic function by irradiation with light, mainly irradiation with ultraviolet rays.
  • the desired function of improving LDV, etc. is manifested by changes in the physical or chemical state of the inorganic particles for photocatalysts caused by ultraviolet irradiation.
  • various inorganic oxides that can improve the LDV can be used by changing the chemical bonding of the particle surface by irradiating with large energy rays such as ultraviolet rays.
  • Specific examples include general inorganic oxides such as silica. These inorganic fine particles may be used alone or in combination of two or more.
  • the shape of the inorganic fine particles is not only spherical but also elliptical spherical, polygonal, flake shaped, fibrous, and indefinite. There are shapes, and any shape is acceptable.
  • the average particle size of the inorganic fine particles can be measured directly with a transmission electron microscope or with a particle size distribution measuring device using scattered light.
  • the measurement method can be selected from various methods depending on the size of the particles. Usually, the method generally used for measuring the relevant particle size is used. For example, there are a method of measuring the particle diameter using direct observation with a transmission electron microscope, a dynamic light scattering method, and a method of selecting an appropriate dispersion medium and using a laser diffraction Z-scattering particle size distribution analyzer.
  • the value measured using a laser diffraction Z-scattering particle size distribution analyzer is generally expressed as a volume average particle size.
  • the average particle size of the inorganic fine particles is Inn! ⁇ 100 ⁇ m is preferred. More preferably, it is 1 nm-50 micrometers, More preferably, it is lnm-1 micrometer, Most preferably, it is 1 nm-10 Onm. If the particle size of the inorganic fine particles is too large or too small, the target liquid diffusibility cannot be sufficiently improved.
  • the surface of the inorganic fine particles is physically and chemically changed by the ultraviolet irradiation treatment. As a result, the LDV of the water-absorbent resin composition is improved.
  • Known or commercially available inorganic fine particles can be used as they are if they are effective for improving the LDV of the water-absorbent rosin composition.
  • the water absorbing function of the water absorbent resin composition is basically performed by the water absorbent resin particles, the organic fine particles are not required to absorb water. If there is water absorption, liquid diffusibility may be hindered. It is desirable to be water-insoluble that does not dissolve or change quality due to water absorption.
  • the inorganic fine particles include, for example, mineral products such as talc, kaolin, fullerite, bentonite, activated clay, barite, natural wasphaltam, strontium ore, ilmenite, pearlite; aluminum sulfate 14-18 hydrate (Or anhydride), aluminum compounds such as potassium aluminum sulfate 12 hydrate, sodium aluminum sulfate 12 hydrate, ammonium aluminum sulfate 12 hydrate, aluminum chloride, polyaluminum chloride, aluminum oxide; Other metal salts, metal oxides and metal hydroxides; hydrophilic amorphous silica (eg, dry method: ReolosilQS-20, Tokuyama Co., precipitation method: DEGUSSA Siperna t22S, Sipernat 2200); Magnesium oxide complex (eg, ENGELHARD Attagel # 50), oxide complexes such as a silicon oxide / aluminum oxide complex, and a silicon oxide / magnesium oxide complex; Also, mineral products such as
  • inorganic metal oxides such as silica, titanium oxide, tin oxide, niobium oxide, strontium titanate, zinc oxide, iron oxide and tungsten oxide, silicic acid (salt) such as natural zeolite and synthetic zeolite , Kaolin, talc, clay and bentonite are preferred. These may be used alone or in combination of two or more.
  • Two or more types of inorganic fine particles may be two or more types of inorganic metal oxides. More specifically, two or more types of inorganic metal oxides are different types of inorganic metal oxides (for example, different types of inorganic metal oxides such as silica and titanium oxide).
  • inorganic metals when two or more different inorganic metals are contained in one compound (for example, a compound containing aluminum and silicon atoms, such as alumina silicate), or an acid of the same type of metal And the like (including cases where the valence of the metal is different).
  • a compound containing aluminum and silicon atoms, such as alumina silicate such as aluminum and silicon atoms, such as alumina silicate
  • an acid of the same type of metal And the like including cases where the valence of the metal is different.
  • the inorganic fine particles are two or more kinds of inorganic metal oxides, it is preferable to include silica and acid titanium.
  • an inorganic metal oxide is an oxidant of a metal element, and an oxide of a typical metal element and an oxide of a transition metal element are known. Titanium oxide, silica, etc. are transition metal oxides. Titanium oxide has three crystal systems: anatase, rutile, and brookite. The crystal system of titanium oxide is not particularly limited, but anatase type is more preferable because it exhibits the most photocatalytic action.
  • Silica is generally a generic name for nickel silicate and includes synthetic amorphous silicon dioxide, natural amorphous silicate and crystalline silicate. “Aerosil 200” (manufactured by Nippon Aerosol Jil) is included in synthetic amorphous silica.
  • These inorganic fine particles may be in a dispersed colloidal state of water, a hydrophilic organic solvent, or a mixture of water and a hydrophilic organic solvent.
  • examples of these dispersed colloidal inorganic fine particles include “Aldrich Ludox HS-30” (Du Pont), “Aldrich Ludox CLJ (Du Pont)”, “STS-21” (Ishihara Sangyo) Etc.
  • the inorganic fine particles B are a mixture of two or more kinds of inorganic fine particles, the mixing ratio can be arbitrarily changed.
  • the inorganic fine particle B is a mixture of two types of inorganic fine particles of silica and titanium oxide
  • the optimum addition amount (mixed) is selected according to the mixing property and the required properties of the water-absorbent resin.
  • Mass ratio can be determined.
  • inorganic fine particles when two or more kinds of inorganic fine particles are mixed, a desired property can be obtained by combining the properties (particle shape, particle size, cohesiveness, bulk specific gravity) that each inorganic oxide has specifically. Properties can be expressed.
  • inorganic fine particles have various advantages and disadvantages depending on the type. Therefore, by combining two or more types of inorganic fine particles in an arbitrary ratio in a combination that complements each of the advantages and disadvantages, the properties of the disadvantages can be reduced while maintaining the properties of the advantages. Can be made.
  • water-absorbent resin A and the inorganic fine particles B can also be added to the water-absorbent resin composition within a range that does not impair the purpose of the present invention.
  • Additive components include deodorants, antibacterial agents, fragrances, foaming agents, pigments, dyes, plasticizers, adhesives, surfactants, fertilizers, oxidizing agents, reducing agents, water, salts, chelating agents, bactericides Agents, hydrophilic polymers such as polyethylene glycol, paraffin, hydrophobic polymers, thermoplastic resins such as polyethylene and polypropylene, and thermosetting resins such as polyester resin and urea resin.
  • the inorganic fine particles B subjected to the ultraviolet irradiation treatment can also be added after the ultraviolet irradiation treatment with the same material.
  • the amount of components other than the water-absorbent resin A and inorganic fine particles B is such that the water-absorbent resin A and The amount can be set in the range of 0 to 15% by mass with respect to the total amount of inorganic fine particles B.
  • a general mixing method for particulate materials can be applied as long as uniform mixing is possible.
  • a dry blend method in which particles are mixed as they are, but wet mixing using inorganic fine particles as a slurry or colloid may be employed.
  • Specific mixing apparatuses include ordinary mixers such as a V-type mixer and a ribbon-type mixer, a screw-type mixer, a rotating disk-type mixer, an air-flow-type mixer, and a batch-type mixer. , Continuous-type, paddle type mixer, etc.
  • a water-absorbing resin composition containing water-absorbing resin A and inorganic fine particles B irradiated with ultraviolet rays may be manufactured by applying ordinary water-absorbing resin manufacturing technology.
  • the water-absorbing resin A and the inorganic fine particles B are uniformly mixed.
  • a technique used for normal water absorbent resin production or mixing of granular materials can be applied.
  • A: B 100: 0.0 1 to: L00: 8
  • A: B 100: 0.01 to 100: 5
  • A: B 100: 0.01 to: L00: 3.
  • A: B 100: 0.01 to: L00: 1.
  • the mixing is preferably performed on the surface of the water-absorbent resin, and the surface of the water-absorbent resin composition is coated with inorganic fine particles.
  • the total amount of the water-absorbing resin A and the inorganic fine particles B is 60% by mass or more, preferably 85% by mass or more, more preferably 90% by mass with respect to the entire water-absorbing resin composition. % Or more, more preferably 95% by mass or more.
  • step (I) or (II) is adopted depending on the timing of applying the ultraviolet irradiation treatment to the inorganic fine particles B.
  • the ultraviolet irradiation treatment technology and the ultraviolet irradiation device used in the production technology of various chemical products including the usual water absorbent resin production can be used.
  • the ultraviolet irradiation device include a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, and a halogen lamp.
  • the conditions for the ultraviolet irradiation treatment include other wavelengths that should include light in the ultraviolet region of 200 to 400 nm! /, Or even! /.
  • the ultraviolet irradiation conditions are as follows: irradiation intensity 1 to: L000mWZcm 2 , irradiation dose of 100 to 10000 mjZc m 2 , for 1 second to 60 minutes.
  • the irradiation intensity is more preferably 1 to 500 mWZcm 2 , further preferably 1 to 300 mWZcm 2 , and most preferably 1 to 100 mWZcm 2 .
  • Irradiation dose is more preferably 100 ⁇ 5000MjZcm 2, still more preferably 100 ⁇ 3000miZcm 2, most preferably 100 ⁇ 1000mjZcm 2.
  • the irradiation time is more preferably 0.2 to 30 minutes, further preferably 0.5 to 15 minutes, and most preferably 1 to 10 minutes.
  • the ultraviolet irradiation intensity is defined by the method described in the examples described later.
  • both the inorganic fine particles B and the mixture of the water-absorbent resin A and the inorganic fine particles B are irradiated on the entire ultraviolet irradiated object. It is preferable to uniformly irradiate with ultraviolet rays. It is more preferable to uniformly irradiate ultraviolet rays to the entire ultraviolet irradiated object by stirring the ultraviolet irradiated object.
  • a general stirring device can be used as a device for stirring the ultraviolet irradiation object during ultraviolet irradiation, and examples thereof include a vibratory mixer, a ribbon mixer, and a paddle mixer.
  • the shorter the wavelength of ultraviolet rays the higher the treatment effect on the inorganic fine particles, but the higher the cost, such as the complexity of the treatment apparatus. If the energy intensity is low, the intended effect will not be sufficiently improved. Even if the UV irradiation treatment is too strong or too long, the effect is not improved, and the inorganic fine particles or the water-absorbing resin particles are easily deteriorated or damaged.
  • the temperature inside the treatment apparatus may rise.
  • the maximum temperature may be close to 60 ° C.
  • the LDV improvement effect is not recognized so much. Therefore, the LDV improvement effect by ultraviolet irradiation is not due to the temperature rise.
  • the total amount of the water-absorbent resin composition containing a mixture of the water-absorbent resin A and the inorganic fine particles B (before hydrogenated calorie before irradiation with ultraviolet rays).
  • Water in an amount of 0.1 to 5% by mass with respect to the total amount of the water-absorbent rosin composition) can be added.
  • the amount of water to be added is preferably 0.1 to 1% by mass.
  • inorganic fine particle B which is well-familiar with water, increases the degree of performance improvement by ultraviolet irradiation treatment.
  • LDV can also be improved by adding water to a mixture of inorganic fine particles B and water-absorbing resin A irradiated with ultraviolet rays. In this case, the difference in the degree of LDV improvement due to the type of inorganic fine particles B is not so much observed.
  • Adding water to the inorganic fine particles B and irradiating them with ultraviolet rays is also effective for improving the performance of LDV and the like.
  • a water-absorbent rosin composition is obtained.
  • the water-absorbent resin composition can be produced by combining various production processes employed in the production of a normal water-absorbent resin composition.
  • the constituents of the water-absorbent resin composition include water-absorbent resin A and inorganic fine particles.
  • Another additive may be included as long as the effects of the present invention are not impaired.
  • the shape and dimensions of the water-absorbent resin composition are basically the same as those of the water-absorbent resin composition. Although the basic characteristics have many in common with the water-absorbing resin, there are also characteristics that show significant differences compared to the water-absorbing resin. In addition, it is preferable that a water-absorbent rosin composition is a particulate form.
  • Liquid diffusion rate (LDV) 2.0 ⁇ : LOmmZs (more preferably 2.8 ⁇ : LOmmZs, more preferably 3.0 ⁇ : LOmmZs, particularly preferably 3.5 ⁇ : LOmmZs).
  • Centrifuge retention capacity 20-50 gZg (more preferably 20-45 gZg, more preferably 20-40 gZg, most preferably 20-35 g / g).
  • Absorptive power against pressure (AAP) 10 to 35 gZg (more preferably 15 to 30 gZg, still more preferably 18 to 30 g / g).
  • Saline flow conductivity (SFC) l to 1500 X 10 _7 'cm 3 's'g _1 (more preferably 10 to
  • LDV is a parameter indicating "liquid absorption and raising characteristics".
  • the CRC is mainly related to the amount of absorbent material or the amount of liquid absorbed by the absorbent body.
  • LDV is mainly related to the rate at which liquid diffuses in absorbent articles or absorbents, and in particular to the rate at which initial liquid is absorbed.
  • the liquid diffusion and absorption capacity of the liquid will be inferior when a load such as body weight is applied to the water-absorbent resin composition.
  • the liquid does not diffuse in the absorbent body or absorbent article, causing the liquid to block. For example, problems such as leakage and skin irritation are likely to occur during actual use in disposable diapers.
  • the CRC is 20 gZg or more, and it is excellent in LDV! /, And it is drastically improved so that it is difficult to achieve with conventional water-absorbent resin compositions, resulting in liquid diffusibility. It becomes an excellent water-absorbent resin composition.
  • the water-absorbent resin composition has the following characteristics with respect to water content, soluble content, and particle size in addition to the above-mentioned LDV, SFC, CRC, and AAP.
  • the water content of the water-absorbent resin composition according to the present invention is such that the water content relative to the total amount of the water-absorbent resin composition containing the water-absorbent resin A and the inorganic fine particles B (the water-absorbent resin composition). Stipulated by the amount of moisture contained in stipulated by the loss on drying for 3 hours at Z105 ° C). When water is added to the water-absorbent rosin composition, the water content after the addition is specified.
  • the water content of the water-absorbent resin composition can be appropriately set to 0.1 to 40% by mass by drying or hydrogenation. More preferably, it is 0.2-30 mass%, More preferably, it is 0.3-15 mass%, Most preferably, it is 0.5-10 mass%.
  • the water content force is higher than 0% by mass, the water absorption capacity may be decreased.
  • the water content is lower than 0.1% by mass, the liquid suction property may be deteriorated.
  • the amount of soluble component of the water-absorbent rosin composition is preferably as small as possible.
  • the soluble content is set to 25% by mass or less (lower limit 0% by mass). More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less.
  • the particle size of the water-absorbent resin composition is a mixed particle size of the water-absorbent resin particles described above and the inorganic particles B described above. Depending on the mixing ratio of the inorganic fine particles B, the water-absorbent resin composition can be set to a preferable particle size range. In addition, the water-absorbent resin composition also preferably has a particle size range of the water-absorbent resin particles described above.
  • the water-absorbent resin composition obtained in the present invention can be used for various applications in which ordinary water-absorbent resin compositions are used. Especially suitable for applications that require high liquid diffusibility ing.
  • sanitary materials such as adult paper ommu, which has been growing rapidly in recent years, and children's ommu and medical napkins, so-called incontinence pads. It can also be used for applications where water-absorbent rosin compositions have been used in the past, such as agriculture, horticulture, cable water-stoppers, civil engineering / architecture, and food.
  • part by mass may be referred to as “part by weight” or simply “part”
  • liter may be simply referred to as “L”.
  • mass% may be described as “wt%”.
  • the water-absorbent resin composition absorbs moisture, so that the water-absorbent resin composition is appropriately removed from the final product. After separation and drying under reduced pressure at low temperature (for example, ImmHg or less, 12 hours at 60 ° C).
  • the centrifuge retention capacity shows an absorption capacity of 30 minutes with no pressure applied to 0.90% by mass saline solution.
  • a bag 85mm x 60mm made of non-woven fabric (trade name: Heaton Paper, model: GSP-22) made of non-woven fabric (trade name: Heatron Paper, Co., Ltd.) ) And then heat-sealed and then immersed in 0.90% by weight (usually about 500 ml) of 0.90% by weight saline (aqueous sodium chloride solution) at room temperature. Pull bag up and centrifuge after 30 minutes After draining for 3 minutes using the centrifugal force (250G) described in “edana ABSORBEN CY II 441. 1-99” using a machine (Kokusan Co., Ltd., centrifuge: Model H-122), the quality of the bag The amount Wl (g) was measured.
  • Absorptive power against pressure shows an absorption capacity of 60 minutes at 4.83 kPa against 0.90 mass% saline solution.
  • AAP is sometimes referred to as absorption capacity under pressure at 4.83 kPa.
  • a stainless steel 400 mesh wire mesh (mesh size 38 ⁇ m) was fused to the bottom of a support cylinder made of plastic with an inner diameter of 60 mm, and room temperature (20-25 ° C), humidity 50% RH. Under the condition, 0.900 g of water-absorbent rosin particles or water-absorbent rosin composition was uniformly sprayed on the net. In addition, the outer diameter is slightly less than 60mm, adjusted to allow a uniform load of 4.83kPa (0.7 psi) to the water-absorbent particles or composition. A piston and a weight that do not create a gap with the support cylinder and that do not hinder vertical movement were placed in this order, and the mass Wa (g) of this measuring apparatus was measured.
  • a 90 mm diameter glass filter (manufactured by Mutual Science Chemical Glass Co., Ltd., pore diameter: 100 to 120 m) is placed inside a 150 mm diameter Petri dish, and 0.9% by mass saline solution (20 to 25). ° C) was added to the same level as the top surface of the glass filter.
  • a sheet of filter paper with a diameter of 90 mm (ADVANTEC Toyo Co., Ltd., product name “2”, thickness 0.26 mm, retention particle diameter 5 m) was placed so that the entire surface was wetted and excess liquid was removed. .
  • the above measuring device set was placed on the wet filter paper, and the liquid was absorbed under load. After 1 hour, the measuring apparatus was lifted and its mass Wb (g) was measured. And from Wa and Wb, the absorptivity (AAP) (gZg) with respect to a pressure was computed according to the following formula.
  • the saline flow conductivity is a value indicating the liquid permeability during swelling of the water-absorbent resin particles or the water-absorbent resin composition.
  • SFC Saline Flow Conductivity
  • the water-absorbent coagulant particles or water-absorbent coagulant composition (0.900 g) uniformly placed in a container is swollen in artificial urine (1) for 60 minutes under a pressure of 0.3 psi (2.07 kPa). The height of the gel layer of the gel was recorded. Next, under a pressure of 0.3 psi (2.07 kPa), 0.69 mass% saline was passed through the gel layer in which the tank was swollen with a constant hydrostatic pressure. This SFC test was performed at room temperature (20-25 ° C). Using a computer and a balance, the amount of liquid passing through the gel layer at 20 second intervals as a function of time was recorded for 10 minutes.
  • the flow rate Fs (T) through which the liquid passes through the swollen gel (mainly between the particles) was determined in gZs by dividing the increased mass (g) by the increased time (s). Let Ts be the time at which a constant hydrostatic pressure and a stable flow rate were obtained, use only the data obtained between Ts and 10 minutes for the flow rate calculation, and use the flow rate obtained between Ts and 10 minutes.
  • A Area above the gel layer in cell 41 (28. 27 cm 2 )
  • the unit of the SFC value is (10- 7 ⁇ cm 3 's'g- 1).
  • a glass tube is inserted in the tank, and the lower end of the glass tube is 0.
  • Artificial urine (1) consists of calcium chloride dihydrate 0.25 g, potassium chloride 2.0 g, magnesium chloride hexahydrate 0.50 g, sodium sulfate !; um 2.0 g, A mixture of ammonium dihydrogen phosphate 0.85 g, hydrogen phosphate 2-ammonium phosphate 0.15 g, and pure water 994.25 g was used.
  • Water-absorbent waving particles or water-absorbing waving resin composition with 850 ⁇ m, 710 ⁇ m, 600 ⁇ m, 500 ⁇ m, 425 ⁇ m, 300 m, 212 m, 150 m, 45 m, etc.
  • the classification method for measuring the mass average particle diameter (D50) is as follows: 10.0 g of water-absorbent resin particles or water-absorbent resin composition at room temperature (20 to 25 ° C) and humidity of 50% RH. Under the above conditions, the above sieved JIS standard sieve (THE IIDA TESTING SIEVE: diameter 8cm) was charged and the vibration classifier (IIDA SIEVE SHAKER ⁇ TYPE: ES-65 type, SER. No. 0501) was used for 5 minutes. Classification was performed.
  • the trough sheet was made with SUS304 stainless steel grade 2B finish. [0155] A particulate water-absorbent resin composition in the trough groove of the trough 'sheet installed at an angle of 20 ° 1. OOg
  • ⁇ 0.005 g was spread evenly between 0-20 cm scales. Furthermore, the particulate water-absorbent rosin composition was more evenly dispersed using a spatula.
  • the liquid used for liquid soaking is edible blue No. 1 (Tokyo Kasei Kogyo Co., Ltd.) at a ratio of 0. Olg to 1 L of physiological saline (0.90 mass% salt-sodium aqueous solution). Colored physiological saline was used.
  • Liquid uptake time is measured at the same time that the stainless steel screen mesh comes in contact with the liquid after adjusting the liquid level in the reservoir to the lowest trough force of 0.5 cm. Started. Liquid wicking time (WR) represents the time (sec) that the liquid has been sucked up to 10cm to the scale position.
  • the screen mesh force of the liquid and the stainless steel in the liquid storage tank The lowest position force of the S trough is soaked up to 0.5cm above the liquid surface in the vertical direction 1.35 ⁇ : L 40mmZs It was.
  • liquid diffusion rate (LDV) is calculated by the following equation.
  • the water-absorbing resin in the water-absorbing resin is based on the average molecular weight of the monomer and the titration amount obtained by the above operation.
  • the soluble amount can be calculated by the following formula.
  • Soluble content (mass%) 0. I X (average molecular weight) X 184.3 X 100 X ([HC1] — [bHCl]) / 1000/1. 0/50. 0
  • the average molecular weight of the monomer was calculated using the neutralization rate obtained by titration.
  • hydrogel crosslinked polymer was subdivided to have a diameter of about 5 mm or less.
  • This finely divided hydrogel crosslinked polymer was spread on a 50-mesh wire mesh, dried with hot air at 180 ° C for 50 minutes, and the dried product was pulverized using a roll mill.
  • a JIS standard sieve having a mesh size of 150 m
  • an irregularly crushed water-absorbent resin particle (1) having a mass average particle diameter of 350 m was obtained.
  • the centrifuge retention capacity (CRC) of the water-absorbent resin particles (1) was 33.0 gZg, and the soluble content was 9.0% by mass.
  • the resulting water-absorbent resin particles (1) 100 parts by weight of 1, 4 butanediol 0.32 parts by weight, propylene glycol 0.5 parts by weight, pure water 2.73 parts by weight surface treatment After the agent was mixed uniformly, the mixture was heat-treated at 200 ° C for 30 minutes. Further, the particles were pulverized until passing through a JIS standard sieve having an opening of 600 / z m. In this way, water-absorbent rosin particles (A1) having a crosslinked surface were obtained.
  • the obtained water-absorbent lumps were pulverized using a roll mill and further classified with a JIS standard sieve having an opening of 600 ⁇ m.
  • the particles having passed 600 m in the above operation are classified with a JIS standard sieve having an opening of 150 ⁇ m, thereby removing the water absorbent resin particles having passed the JIS standard sieve having an opening of 150 ⁇ m, Water-absorbent rosin particles (2) were obtained.
  • the soluble content of the water-absorbent rosin particles (2) was 7% by mass.
  • ultraviolet light including a wavelength of 200 to 400 nm, ultraviolet light intensity meter (Ushio) Machine made UIT250, illumination intensity measured by the light receiver UVD- S254) is ultraviolet
  • the distance power of 9cm from a separable flask made of quartz outer wall was also irradiated for 5 minutes.
  • Example 1 a water-absorbent resin composition (E2) was obtained in the same manner as in Example 1 except that water was not mixed.
  • Example 3 In a stainless steel container, 1 part by mass of water was added to the water-absorbent resin composition (E2) obtained in Example 2 and sufficiently mixed with stirring. The obtained mixture was pulverized and passed through a JIS standard sieve having an opening of 600 ⁇ m to obtain a water-absorbent resin composition (E3).
  • Example 1 titanium oxide for photocatalyst (ST-01 from Ishihara Sangyo) was changed to 2.5 parts by weight (solid content 40%) of titanium oxide for photocatalyst (STS-21 from Ishihara Sangyo), and water was mixed. Except for not combining, the same operation as in Example 1 was carried out to obtain a water-absorbent resin composition (E4).
  • Example 1 the same operation as in Example 1 except that the photocatalyst acid titanium oxide (ST-01 manufactured by Ishihara Sangyo Co., Ltd.) was changed to 3 parts by mass of silica (Aerosil 200 manufactured by Nippon Oil & Gas Company). To obtain a water-absorbent resin composition (E5).
  • Example 5 silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was used in the same manner as in Example 5 except that 0.3 part by mass was changed to 1 part by mass. Obtained.
  • Example 6 a water-absorbent resin composition (E7) was obtained in the same manner as in Example 6 except that water was not mixed.
  • Example 7 In a stainless steel container, add 1 part by mass of water to the water-absorbent resin composition (E7) obtained in Example 7. In addition, the mixture was sufficiently stirred and mixed. The obtained mixture was pulverized and passed through a JIS standard sieve having an opening of 600 ⁇ m to obtain a water-absorbent resin composition (E8).
  • Example 9 the same operation as in Example 9 was performed except that titanium oxide for photocatalyst (ST-01 manufactured by Ishihara Sangyo Co., Ltd.) was changed to 0.3 parts by mass of silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) A water-absorbent rosin composition (E10) was obtained.
  • a water-absorbent resin composition (E11) was obtained in the same manner as in Example 10, except that silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was changed to 1 part by mass in Example 10.
  • Example 2 1 part by mass of titanium oxide for photocatalyst (ST-01 manufactured by Ishihara Sangyo Co., Ltd.), 5 parts by mass of titanium oxide for photocatalyst (ST-OD O. 5 manufactured by Ishihara Sangyo Co., Ltd. and Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.)
  • a water absorbent resin composition (E15) was obtained in the same manner as in Example 2, except that the amount was changed to 0.5 parts by mass.
  • a mixture of titanium oxide for photocatalyst (ST-01, manufactured by Ishihara Sangyo Co., Ltd.) and silica (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) at a mass ratio of 1: 1 is placed in a quartz separable flask equipped with stainless steel stirring blades. !
  • UV light including 200 to 400 nm wavelength, UV light with an irradiation intensity of 65 kWZcm 2 measured with a UV integrated light meter (UIT250 manufactured by Usio Electric Co., Ltd., UVD-S254)
  • Irradiation was performed from a distance of 9 cm from the outer wall of the quartz separable flask for 5 minutes to obtain an ultraviolet treatment mixture.
  • 100 parts by mass of the water-absorbent resin particles (A1) obtained in Production Example 1 were mixed with 1 part by mass of the ultraviolet treatment mixture to obtain a water-absorbent resin composition (E16).
  • Example 2 the same procedure as in Example 2 was performed, except that 1 part by mass of titanium oxide for photocatalyst (ST-01, manufactured by Ishihara Sangyo Co., Ltd.) was changed to 0.3 part by mass. (E1
  • Example 2 the same procedure as in Example 2 was performed, except that 1 part by mass of titanium oxide for photocatalyst (ST-01, manufactured by Ishihara Sangyo Co., Ltd.) was changed to 0.1 part by mass. (E1
  • Example 2 titanium oxide for photocatalyst (ST-01, manufactured by Ishihara Sangyo Co., Ltd.) was used in the same manner as in Example 2 except that 1 part by mass was changed to 2 parts by mass. E19) was obtained.
  • Example 20 In Example 7, the same procedure as in Example 7 was performed, except that 1 part by mass of silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was changed to 0.1 part by mass. )
  • Example 7 Except that 1 part by mass of silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was changed to 2 parts by mass, the same operation as in Example 7 was carried out to obtain a water absorbent resin composition (E21). Obtained.
  • water-absorbent resin particles (A1) obtained in Production Example 1 and 1 part by weight of photocatalytic acid titanium oxide (ST-01 from Ishihara Sangyo) were stirred in a stainless steel container, and then water 1 A mass part was added and mixed thoroughly with stirring. Thereafter, it was heat-cured in an oven at 60 ° C. for 1 hour, and the resulting mixture was pulverized and passed through a JIS standard sieve having an opening of 600 ⁇ m to obtain a water-absorbent resin composition (E22).
  • Example 22 the same operation as in Example 22 was performed, except that photocatalyst acid titanium (Ishihara Sangyo ST-01) was changed to silica (Aerosil 200, Nippon Aerosil Co., Ltd.) 0.3 parts by mass. And a water-absorbent rosin composition (E23) was obtained.
  • Example 23 the same procedure as in Example 23 was performed, except that the mass of silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was changed to 1 part by mass. Got.
  • Titanium oxide for photocatalyst (ST-01 manufactured by Ishihara Sangyo Co., Ltd.) 100 parts by mass of the water-absorbent resin particles (A1) obtained in Production Example 1 are mixed with 1 part by mass to obtain an absorbent polymer composition (E25). Obtained.
  • the water-absorbent resin particles (A1) obtained in Production Example 1 are placed in a quartz separable flask equipped with stainless steel stirring blades. While stirring at 400 rpm, ultraviolet rays (including wavelengths of 200 to 400 nm, ultraviolet rays) Measured with integrated light meter (UIT250, receiver UVD—S254) Irradiation intensity of ultraviolet light) is 65kWZcm 2, were irradiated for 5 minutes from the separable flask made of quartz outer wall from a distance of 9c m.
  • the water-absorbent resin particles (A1) obtained in Production Example 1 are placed in a quartz separable flask equipped with stainless steel stirring blades. While stirring at 400 rpm, ultraviolet rays (including wavelengths of 200 to 400 nm, ultraviolet rays) An integrating luminometer (ultraviolet light with an irradiation intensity of 65 kWZcm 2 measured by UIT250 manufactured by Usio Electric Co., Ltd., UVD-S254) was irradiated for 5 minutes from a distance of 9 cm from the outer wall of the quartz separable flask.
  • silica (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) is mixed with 100 parts by mass of the obtained UV-treated water-absorbing resin, and further 1 part by mass of water is added, and the mixture is sufficiently stirred and then crushed.
  • a water-absorbing resin composition (E27) was obtained by passing through a JIS standard sieve having a mesh opening of 600 ⁇ m.
  • the water absorbent resin particles (A1) obtained in Production Example 1 were used as comparative water absorbent resin particles (C1).
  • the water-absorbent resin particles (A1) obtained in Production Example 1 are placed in a quartz separable flask equipped with stainless steel stirring blades. While stirring at 400 rpm, ultraviolet rays (including wavelengths of 200 to 400 nm, ultraviolet rays)
  • An integrating luminometer (ultraviolet light with an irradiation intensity of 65 kWZcm 2 measured by UIT250 manufactured by Usio Electric Co., Ltd., UVD-S254) was irradiated for 5 minutes from a distance of 9 cm from the outer wall of the quartz separable flask. After the irradiation, the composition was crushed and passed through a JIS standard sieve having a mesh size of 600 m to obtain a comparative water-absorbent resin composition (C2).
  • ⁇ Comparative Example 4 100 parts by weight of the water-absorbent resin particles (Al) obtained in Production Example 1 and 2.5 parts by weight of a slurry solution of photocatalytic acid titanium (STS-21) manufactured by Ishihara Sangyo Co., Ltd. The mixture was sufficiently stirred and mixed. Thereafter, it was heat-cured in an oven at 60 ° C for 1 hour, and the resulting mixture was pulverized and passed through a JIS standard sieve having an opening of 600 ⁇ m to obtain a comparative water-absorbent resin composition (C4).
  • STS-21 photocatalytic acid titanium
  • Comparative Example 5 Except that the mass of silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was changed to 1 part by mass, the same operation as in Comparative Example 5 was carried out to obtain a comparative water absorbent resin composition (C6 )
  • the water-absorbent resin particles (A1) obtained in Production Example 1 are placed in a quartz separable flask equipped with stainless steel stirring blades. While stirring at 400 rpm, ultraviolet rays (including wavelengths of 200 to 400 nm, ultraviolet rays) An integrating luminometer (ultraviolet light with an irradiation intensity of 65 kWZcm 2 measured by UIT250 manufactured by Usio Electric Co., Ltd., UVD-S254) was irradiated for 5 minutes from a distance of 9 cm from the outer wall of the quartz separable flask.
  • Comparative Example 7 the same procedure as in Comparative Example 7 was performed, except that titanium oxide for photocatalyst (ST-01 manufactured by Ishihara Sangyo Co., Ltd.) was changed to 1 part by mass of silica (Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.). A greave composition (C8) was obtained.
  • the water absorbent resin particles (A2) obtained in Production Example 2 were used as comparative water absorbent resin particles (C9).
  • Table 1 compares the differences in the manufacturing conditions in each of the examples and comparative examples described above.
  • the term “ultraviolet irradiation” indicates an object irradiated with ultraviolet rays.
  • the item of water addition shows the amount of water added while distinguishing the timing of water addition before, after, and without UV irradiation. Since the inorganic fine particles are coated on the surface of the water-absorbent resin, the soluble content and particle size of the water-absorbent resin composition were almost the same as the soluble content and particle size of the water-absorbent resin.
  • Example 1 Titanium oxide 1.0 mixture Before irradiation 1.0
  • Example 2 Titanium oxide 1.0 mixture-Example 3
  • Example 4 Titanium oxide 1.0 mixture After irradiation 1.0
  • Example 4 Titanium oxide slurry 2.5 mixture-Example 5 (E 5) Silica 0.3 mixture Before irradiation 1.0
  • Example 6 Silica 1.0 mixture Before irradiation 1.0
  • Example 7 Silica 1.0 mixture-Example 8
  • Example 9 (E 9) Titanium oxide 1.0 Inorganic particles ⁇ Example 10 0 (E 10) Silica 0.3 Inorganic particles ⁇
  • Example 1 1 E 1 1) Silica 1.0 Inorganic particles ⁇ Implementation Example 1 2 (E 1 2) Titanium oxide 1.0 Inorganic particle after irradiation 1.0
  • Example 1 3 (E 1 3) Silica 0.3 Inorganic particle after irradiation 1.0
  • Example 1 4 (E 4) Titanium oxide slurry 2.5
  • Example 2 1 (E 2 1) Silica 2 mixture 1
  • Example 22 (E 22) Titanium oxide 1.0-Non-irradiated 1.0
  • Example 23 (E 23) Silica 0.3-Non-irradiated 1.0
  • Example 24 (E 24) Silica 1.0- Non-irradiated 1.0
  • Example 25 (E 25) Titanium oxide 1.0--Example 26 (E 26) Titanium oxide 1.0 Resin particles after irradiation 1.0
  • Example 2 7 (E 27) Silica 1.0 Resin particles after irradiation 1.0 Comparative example 1 (C 1) ⁇ ⁇ Comparative example 2 (C 2) Resin particles ⁇ Comparative example 3 (C 3) ⁇ One Non-irradiated 1.0 Comparative example 4 (C 4) Titanium oxide slurry 2.5 ⁇ ⁇ Comparative example 5 (C 5) Silica 0.3 ⁇ One Comparative Example 6 (C 6) Silica 1.0 ⁇ ⁇ Comparative Example 7 (C 7) Titanium oxide 1.0 Resin particles
  • Examples 1 to 22 and 24 are not so different from CRC and AAP in comparison with Comparative Example 1 in which the water-absorbent particles (Al) remain, but SFC is improved and LDV is markedly It has been improved. This confirms that it is more suitable for water-absorbing materials such as disposable diapers, which require improved SFC and LDV performance than CRC and AAP.
  • the water-absorbent resin A water-absorbent resin particles (A1) subjected to ultraviolet irradiation
  • the inorganic fine particles B not subjected to ultraviolet irradiation may be combined. LDV does not improve much.
  • LDV may be improved by adding water.
  • the water-absorbent rosin composition of the present invention is useful as a water-absorbing material for paper diapers, for example.

Landscapes

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

Abstract

La présente invention concerne une composition de résine hydro-absorbante dans laquelle les propriétés de diffusion dans un liquide (à savoir, les caractéristiques significatives dans la pratique) ont été en grande partie améliorées sans altérer la performance hydro-absorbante fondamentale, la productivité et ainsi de suite en tant que matériau en résine hydro-absorbant utilisé en tant que matériau hydro-absorbant dans les couches-culottes en papier, etc. La présente invention concerne un procédé de production d'une composition de résine hydro-absorbante qui implique l'étape de mélanger une résine hydro-absorbante A à des microparticules inorganiques B ayant été irradiées par des rayons UV de sorte que la quantité de microparticules inorganiques B soit régulées dans une gamme de 0,01 à 10 parties en poids pour 100 parties en poids de la résine hydro-absorbante A. Ainsi, on peut produire une composition de résine hydro-absorbante ayant une vitesse de diffusion dans un liquide (VDL) dans la gamme de 2,0 à 10 mm/s.
PCT/JP2006/311637 2006-06-09 2006-06-09 Composition de résine hydro-absorbante et son procédé de production WO2007141875A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2006541744A JP5020637B2 (ja) 2006-06-09 2006-06-09 吸水性樹脂組成物の製造方法
PCT/JP2006/311637 WO2007141875A1 (fr) 2006-06-09 2006-06-09 Composition de résine hydro-absorbante et son procédé de production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/311637 WO2007141875A1 (fr) 2006-06-09 2006-06-09 Composition de résine hydro-absorbante et son procédé de production

Publications (1)

Publication Number Publication Date
WO2007141875A1 true WO2007141875A1 (fr) 2007-12-13

Family

ID=38801146

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/311637 WO2007141875A1 (fr) 2006-06-09 2006-06-09 Composition de résine hydro-absorbante et son procédé de production

Country Status (2)

Country Link
JP (1) JP5020637B2 (fr)
WO (1) WO2007141875A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2163266A1 (fr) * 2008-09-12 2010-03-17 The Procter & Gamble Article absorbant comprenant un matériau absorbant l'eau

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05209022A (ja) * 1991-07-18 1993-08-20 Mitsui Toatsu Chem Inc 硬化性組成物、水性ゲル及びそれらの用途
JP2000095965A (ja) * 1998-09-24 2000-04-04 Tokai Carbon Co Ltd カーボンブラックの改質方法
JP2001011341A (ja) * 1999-07-02 2001-01-16 Kansai Research Institute 水系分散用顔料及び水性顔料分散液
JP2006008963A (ja) * 2004-06-21 2006-01-12 Inkuriizu:Kk コーティング材及び光触媒分散用液剤

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05209022A (ja) * 1991-07-18 1993-08-20 Mitsui Toatsu Chem Inc 硬化性組成物、水性ゲル及びそれらの用途
JP2000095965A (ja) * 1998-09-24 2000-04-04 Tokai Carbon Co Ltd カーボンブラックの改質方法
JP2001011341A (ja) * 1999-07-02 2001-01-16 Kansai Research Institute 水系分散用顔料及び水性顔料分散液
JP2006008963A (ja) * 2004-06-21 2006-01-12 Inkuriizu:Kk コーティング材及び光触媒分散用液剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2163266A1 (fr) * 2008-09-12 2010-03-17 The Procter & Gamble Article absorbant comprenant un matériau absorbant l'eau
WO2010030717A2 (fr) * 2008-09-12 2010-03-18 The Procter & Gamble Company Article absorbant comprenant un matériau absorbant l'eau
WO2010030717A3 (fr) * 2008-09-12 2010-07-01 The Procter & Gamble Company Article absorbant comprenant un matériau absorbant l'eau
US8404149B2 (en) 2008-09-12 2013-03-26 The Procter & Gamble Company Absorbent article comprising water-absorbing material

Also Published As

Publication number Publication date
JPWO2007141875A1 (ja) 2009-10-15
JP5020637B2 (ja) 2012-09-05

Similar Documents

Publication Publication Date Title
JP4683405B2 (ja) 吸水性樹脂組成物とその製造方法
JP6359600B2 (ja) ポリアクリル酸系吸水性樹脂粉末の製造方法
JP6320968B2 (ja) 粒子状吸水剤及びその製造方法
JP5022226B2 (ja) 吸水性樹脂の表面処理方法
JP5362212B2 (ja) 吸水剤組成物およびその製造方法
JP5706351B2 (ja) 吸水性樹脂を主成分とする粒子状吸水剤
JP5084513B2 (ja) 改質された吸水性樹脂の製造方法
JP5367364B2 (ja) 吸水性樹脂を主成分として含む吸水剤およびその製造方法
JP5591448B2 (ja) 吸水剤およびその製造方法
JP6029800B2 (ja) 吸水性樹脂粒子
JP5879023B2 (ja) 吸水性樹脂を主成分とする粒子状吸水剤
JP5270921B2 (ja) 吸水剤の製造方法
JP4326752B2 (ja) 吸水剤の製造方法
JP2009209373A (ja) 吸水剤およびその製造方法、並びに、衛生材料
JP2006057075A (ja) 不定形破砕状の粒子状吸水剤
TW200427714A (en) Water-absorbing agent
JP2006055833A (ja) 吸水性樹脂を主成分とする粒子状吸水剤
US20070203280A1 (en) Method for manufacturing water-absorbing resin composition and water-absorbing resin composition
KR20160140659A (ko) 입자상 흡수제 및 그의 제조 방법
JP4308382B2 (ja) 吸水剤およびその製造方法
JP2007077366A (ja) 吸水剤の製法
JP2010094656A (ja) 微粒子が固着してなる吸水剤
JP2008018328A (ja) 粒子状吸水剤およびその製造方法
JP2007321008A (ja) 改質された吸水性樹脂の製法
JP5329023B2 (ja) 吸水性樹脂の表面処理方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2006541744

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 06766549

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06766549

Country of ref document: EP

Kind code of ref document: A1