WO2007011058A1 - Water absorbing resin composition - Google Patents

Water absorbing resin composition Download PDF

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Publication number
WO2007011058A1
WO2007011058A1 PCT/JP2006/314717 JP2006314717W WO2007011058A1 WO 2007011058 A1 WO2007011058 A1 WO 2007011058A1 JP 2006314717 W JP2006314717 W JP 2006314717W WO 2007011058 A1 WO2007011058 A1 WO 2007011058A1
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WO
WIPO (PCT)
Prior art keywords
absorbing resin
water absorbing
resin composition
cyclodextrin
fragrant material
Prior art date
Application number
PCT/JP2006/314717
Other languages
French (fr)
Inventor
Hirotama Fujimaru
Nobuyuki Harada
Kunihiko Ishizaki
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 JP2007558364A priority Critical patent/JP2009501803A/en
Publication of WO2007011058A1 publication Critical patent/WO2007011058A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/46Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/01Deodorant compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/262Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/216Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/80Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special chemical form
    • A61L2300/802Additives, excipients, e.g. cyclodextrins, fatty acids, surfactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/68Superabsorbents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16Cyclodextrin; Derivatives thereof

Definitions

  • the present invention relates to a water absorbing resin composition. More particularly, the present invention relates to a water absorbing resin composition which comprises : at least one substance selected from the group consisting of cyclodextrin and a cyclodextrin derivative including a fragrant material, unsaturated aliphatic aldehyde having 6 to 10 carbon atoms and unsaturated aliphatic alcohol having 6 to 10 carbon atoms; and a water absorbing resin.
  • the present invention relates to aromatic deodorants and sanitary goods (including absorbing articles such as diapers and the like) that exhibit an enhanced persistent effect of the aroma, are excellent in odor stability and good-looking appearance, and can be readily manufactured industrially, accompanied by excellent smell-reducing property and durability.
  • the present invention relates to a water absorbing resin composition in which cyclodextrin or a cyclodextrin derivative including a fragrant material, unsaturated aliphatic aldehyde having 6 to 10 carbon atoms, or unsaturated aliphatic alcohol having 6 to 10 carbon atoms is included inside of a water absorbing resin, and for example, relates to a water absorbing resin composition which can be suitably used as aromatic gels and sanitary goods .
  • the present invention provides a water absorbing resin composition which is not only excellent in persistence of the aroma and stability of the aroma, but also effective in relieving fatigue and stress when it is used in environmental fragrances and sanitary goods.
  • Known liquid form fragrances usually include an alcohol as a base, while known gel form ones are prepared by gelling with a water insoluble gelatinizing agent such as a water absorbing resin, a water soluble gelatinizing agent such as agar or carrageen, a metal soap, a clay mineral such as montmorillonite, silica or the like. Furthermore,' in the granular form, activated charcoal is utilized, and in the solid form, silica gel or the like is utilized.
  • Known fragrances for use in rooms and cars include those in the form of liquid, gel, granule, or solid.
  • Known liquid form fragrances usually include an alcohol as a base, while known gel form ones are prepared by gelling with a water soluble gelatinizing agent such as agar or carrageen, a metal soap, a clay mineral such as montmorillonite, silica or the like.
  • a water soluble gelatinizing agent such as agar or carrageen, a metal soap, a clay mineral such as montmorillonite, silica or the like.
  • activated charcoal is utilized, and in the solid form, silica gel or the like is utilized.
  • Patent Documents 1 to 6 a composition including a water absorbing resin and a compound such as cyclodextrin or the like
  • Patent Document 7 to impart an antibacterial or sterilizing effect
  • water absorbing resin compositions to which a positive aromatic function was imparted have been proposed.
  • a composition to which an aromatic function was imparted by water absorbing resin powder and powder including a fragrant material in a water soluble resin Patent Document 8
  • a gelatinous composition containing a fragrant material and cyclodextrin Patent Document 9
  • a composition in which a water absorbing resin, a water-thickening (water increase viscosity) polymer, and a fragrance are combined Patent Document 10
  • a composition including a reaction product of maleic anhydride with ammonia a water absorbing resin and a fragrance
  • any one of the conventional products did not exhibit persistence of the aroma that is satisfactory enough because of readily volatilized aroma according to the conventional products. Therefore, even though the aforementioned water absorbing resin is used in an absorbing article such as a diaper, persistence (sustained release) of the aroma cannot be sufficient. Aiming at improvement of the persistence, various attempts to allow the gelatinizing agent such as the aforementioned water absorbing resin to form a complex with a fragrant material have been also carried out.
  • the fragrant materials are generally hydrophobic, and complex formation with a hydrophilic gelatinizing agent cannot be readily carried out.
  • the problem is intended to be solved by using a surfactant or the like in combination, however, satisfactory effect has not be currently achieved in terms of emission of an abnormal smell derived from the surfactant, as well as persistence of the aroma.
  • Patent Document 9 discloses a fragrant material composition containing highly water absorbing polymer fine particles carrying a fragrant material, the composition being characterized in that highly water absorbing polymer fine particles allowed to absorb an aqueous solution and/or an aqueous dispersion of the fragrant material are dispersed in an oily dispersion medium.
  • Patent Document 13 discloses a deodorizing fragrant material composition containing at least one compound selected from the group consisting of isopulegol, 3- (3-isopropylphenyl) butanal, p-ethyl- ⁇ , ⁇ -dimethylhydrocinnamaldehyde, ethyl vanillin, 1-ethoxy- (3, 7-dimethy1-1, ⁇ -octadiene-3-yloxy) -ethane, octahydro-8, 8-dimethyl-2-naphthalene carboxyaldehyde, salicyl aldehyde, dihydrojasmon, 3, 7-dimethyl-l-octanal, cis-jasmon, cinnamic alcohol, cedrenol, 1- (5, 5-dimethyl-l-cyclohexene-l-yl) -4-pentene-l-one, ⁇ —damascone, ⁇ —damascen
  • Patent Document 1 International Patent Publication No. WO98/26808
  • Patent Document 2 International Patent Publication No. WO2001/26808
  • Patent Document 3 Japanese Patent Publication No. 2000-079159
  • Patent Document 4 International Patent Publication No. WO2000/01479
  • Patent Document 5 Japanese Patent Publication No. 2004-346130
  • Patent Document 6 Japanese Patent Publication No. 2004-285202
  • Patent Document 7 Japanese Patent Publication No. 2003-146803
  • Patent Document 8 Japanese Patent Publication No . S62-236860
  • Patent Document 9 Japanese Patent Publication No. H7-241333
  • Patent Document 10 Japanese Patent Publication No. 2000-014760
  • Patent Document 11 Japanese Patent Publication No. 2000-135280
  • Patent Document 12 Japanese Patent Publication No. 2003-064393
  • Patent Document 13 Japanese Patent Publication No. 2003-321697
  • the present invention provides a fragrance or sanitary goods exhibiting a persistent effect of the aroma for a long period of time, having excellent gel stability and good-looking appearance of the composition, with high industrial productivity. Moreover, according to use as a composition that is excellent in a smell-masking property in sanitary goods, absorbing articles that impart a comfortable sense of relief can be provided.
  • an aromatic composition including a fragrant material and cyclodextrin and/or a cyclodextrin derivative inside of a water absorbing resin can markedly improve persistence of the aroma and stability of the fragrant material, and in addition, can drastically decrease adherence of the deposit interior of the vessel or interior of the sanitary goods, which may be beneficial to the appearance. Accordingly, the present invention was accomplished.
  • an aromatic composition containing unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms (particularly, trans-2-hexenal and/or cis-3-hexenol) and a water absorbing resin is not only excellent in persistence of the aroma and stability of the aroma, but also effective in relieving fatigue and stress when the aromatic composition is used in environmental fragrances or sanitary goods.
  • the present invention was accomplished.
  • the water absorbing resin composition of the present 'invention comprises: at least one substance selected from the group consisting of cyclodextrin including a fragrant material, a dextrin derivative including a fragrant material, unsaturated aliphatic aldehyde having 6 to 10 carbon atoms and unsaturated aliphatic alcohol having 6 to 10 carbon atoms; and a polycarboxylic acid type water absorbing resin.
  • cyclodextrin including a fragrant material
  • a dextrin derivative including a fragrant material
  • a polycarboxylic acid type water absorbing resin According to the present invention, fragrances and sanitary goods exhibiting a persistent effect of the aroma for a long period of time, having excellent gel stability and good-looking appearance of the composition, with high industrial productivity can be provided.
  • fragrances and sanitary goods which are excellent in persistence of the aroma and stability of the aroma, and can relieve fatigue and stress can be provided.
  • sanitary goods such as disposable diapers and the like and fragrances exhibiting an excellent deodorization effect or antibacterial effect can be provided.
  • the water absorbing resin of the present invention is a hydrophilic cross-linked polymer which can form a hydro gel upon contact with water and which has a water-swelling property and water insolubility.
  • the water-swelling property refers to a property of essentially absorbing a large quantity of water, i.e., 5 times or more, preferably, from 50 times to 1000 times the own weight in ion exchanged water.
  • the water insolubility means that the content of water extractables in the resin is essentially 0 to 50% by weight, preferably 0 to 25% by weight, more preferably 0 to 15% by weight, and still more preferably 0 to 10% by weight, and that the polymer is substantially insoluble in water.
  • a water absorbing resin examples include at least one polycarboxylic acid (a salt thereof) type water absorbing resin selected from polyacrylic acid-partially neutralized polymers, hydrolysates of a starch-acrylonitrile graft polymer, starch-acrylic acid graft polymers, saponified products of a vinyl acetate-acrylic acid ester copolymer, hydrolysates of an acrylonitrile copolymer or an acrylamide copolymer or cross-linked polymers thereof, carboxyl group-containing cross-linked polyvinyl alcohol denatured products, cross-linked isobutylene-maleic anhydride copolymers, carboxyalkylated cellulose such as carboxy methyl cellulose and polyaspartic acid cross-linked polymers, and polyamino acid type water absorbing resins such as polyglutamic acid.
  • polycarboxylic acid (a salt thereof) type water absorbing resin selected from polyacrylic acid-partially neutralized polymers, hydrolysates of
  • a polyacrylic acid salt type water absorbing resin may be used.
  • the polyacrylic acid (a salt thereof) type water absorbing resin in the present invention refers to one having total % by mole of acrylic acid and/or salts thereof in total monomer used in the polymerization (excluding crosslinking agent) essentially being 50 to 100% by mole, more preferably 70 to 100% by mole, still more preferably 90 to 100% by mole, particularly preferably 95 to 100% by mole, and most preferably substantially 100% by mole.
  • the acrylic acid salt used in the present invention as a principal component may be, in light of the physical property and long-term stability of the gel, preferably a monovalent salt of acrylic acid selected from alkali metal salts, ammonium salts and amine salts, more preferably an alkali metal acrylic acid salt, and still more preferably, an alkali metal acrylic acid salt selected from sodium salts, lithium salts and potassium salts .
  • a polyvalent metal salt such as a calcium salt or an aluminum salt may be used in combination in the range to provide the water-swelling property.
  • Neutralization ratio of the water absorbing resin obtained according to the present invention may be 20 to 99% by mole, preferably 50 to 95% by mole, and more preferably 60 to 90% by mole of the acid group. This neutralization may be carried out on the monomer component before the polymerization, or may be carried out during the polymerization or on the polymer after completing the polymerization. Furthermore, the neutralization of the monomer component and the neutralization of the polymer may be combined. It is preferred that a neutralizing treatment with an alkali, preferably a neutralizing treatment with sodium hydroxide or sodium carbonate, is carried out on acrylic acid as the monomer component .
  • a polyacrylic acid (a salt thereof) cross-linked polymer obtained by polymerization and crosslinking of a monomer including acrylic acid and/or a salt thereof (neutralized product) as a principal component may be used.
  • the water absorbing resin used for allowing the fragrant material and cyclodextrin and/or the cyclodextrin derivative described later to be included inside of the water absorbing resin is preferably subjected to surface crosslinking for allowing the fragrant material and cyclodextrin and/or the cyclodextrin derivative to be uniformly distributed in the water absorbing resin composition.
  • the water absorbing resin used for allowing the unsaturated organic compound described later to be included inside of the water absorbing resin is preferably subjected to surface crosslinking for allowing the unsaturated organic compound to be uniformly distributed in the water absorbing resin composition.
  • the surface crosslinking of the water absorbing resin is to provide the surface layer (on and close to the surface: usually, several 10 ⁇ m or less away from the surface) of the water absorbing resin having a uniform cross-linked structure inside of the polymer further with a part having a higher crosslinking density.
  • crosslinking agent which can react with a carboxyl group, generally, a polyhydric alcohol compound, an epoxy compound, a polyvalent amine compound or a condensate thereof with a haloepoxy compound, an oxazoline compound, a mono-, di-, or polyoxazolidinone compound, a polyvalent metal salt, an alkylene carbonate compound or the like may be used.
  • the form of the water absorbing resin which may be used in the method of the present invention is not particularly limited, but may be in a particulate form such as irregularly crushed form or sphere, or in the form of powder, gel, sheet, rod, fiber, film or the like. In general, taking into consideration of use in sanitary goods or fragrances which are applications of the same, a particulate form or a powdery form is preferred.
  • the mass median particle size thereof is generally 100 to 50000 ⁇ m before the surface crosslinking or after the surface crosslinking.
  • the mass median particle size thereof may be preferably 100 to 20000 ⁇ m, more preferably 200 to 20000 ⁇ m, still more preferably 300 to 20000 ⁇ m, and particularly preferably 500 to 10000 ⁇ m before the surface crosslinking or after the surface crosslinking.
  • ratio of the particles having a particle diameter of less than 150 ⁇ m may be 0 to 5% by weight, more preferably 0 to 3% by weight, and particularly preferably 0 to 1% by weight before the surface crosslinking or after the surface crosslinking.
  • ratio of the particles having a particle diameter of less than 300 ⁇ m in the water absorbing resin may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and still more preferably 0 to 1% by weight in light of the persistence of sustained release of the aromatic ingredient.
  • mass median particle size of the water absorbing resin may be preferably 200 ⁇ m to 850 ⁇ m, and particularly preferably 300 ⁇ m to 600 ⁇ m in light of the absorption properties.
  • ratio of the particles having a particle diameter of less than 150 ⁇ m in the water absorbing resin may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and particularly preferably 0 to 1% by weight in light of the absorption properties.
  • These preferable particle size and ratio of the particles are applicable to not only the water absorbing resin but also the water absorbing resin composition.
  • centrifuge retention capacity CRC
  • AAP Absorbency against pressure
  • absorbency against pressure (absorbency under load) for a physiological saline solution (0.9% by weight aqueous sodium chloride solution) under a pressure of 20 g/cm 2 may be preferably 10 to 60 (g/g) , and more preferably 20 to 40 (g/g)
  • absorbency against pressure (absorbency under load) for a physiological saline solution under a pressure of 50 g/cm 2 may be preferably 15 to 40 (g/g) , and more preferably 15 to 30 (g/g) .
  • the water extractables and particle size distribution of the water absorbing resin are preferably adjusted to fall within the above range .
  • the fragrant material and cyclodextrin and/or the cyclodextrin derivative described later are allowed to be included inside of the water absorbing resin.
  • regulation of crosslinking density of the water absorbing resin i.e., regulation of swelling capacity of the water absorbing resin may be important.
  • the regulation of the crosslinking density can be executed to some extent by controlling the polymerization conditions in synthesis of the water absorbing resin, in particular, amount of the internal crosslinking agent, monomer concentration in the polymerization and the like.
  • the swelling capacity of the water absorbing resin falls within preferably of about 2 times to 400 times when the fragrant material and cyclodextrin and/or the cyclodextrin derivative are allowed to be included inside of the water absorbing resin.
  • the water absorbing resin may be turned into a polymerized gel.
  • Such swelling may also be carried out by adding water to the water absorbing resin either before drying or after drying.
  • the swelling capacity of the water absorbing resin can be determined by dividing the weight of water absorbed in the water absorbing resin by the weight of the water absorbing resin (weight ratio) .
  • Cyclodextrin for use in the present invention may be formed by cyclizing linkage of 6 to 10 molecules of d-glucose via ⁇ -1,4 bonds.
  • Six d-glucose molecules bind to form one referred to as ⁇ -cyclodextrin; seven d-glucose molecules bind to form one referred to as ⁇ -cyclodextrin; eight d-glucose molecules bind to form one referred to as ⁇ -cyclodextrin; nine d-glucose molecules bind to form one referred to as ⁇ -cyclodextrin; and ten d-glucose molecules bind to form one referred to as ⁇ -cyclodextrin.
  • any one of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin can be used.
  • ⁇ -Cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin are most commonly obtainable cyclodextrin.
  • the using amount of cyclodextrin may preferably fall within the range to permit dissolution of cyclodextrin (derivative) in water together with the fragrant material ingredient after the inclusion of the fragrant material inside of cyclodextrin.
  • cyclodextrin can be suitably used in the range of preferably 1 to 10000 parts by mass, more preferably 1 to 1000 parts by mass, and still more preferably 1 to 500 parts by mass per 100 parts by mass of the fragrant material.
  • cyclodextrin and/or various cyclodextrin derivatives can be used in the present invention.
  • cyclodextrin derivative examples include e.g., hydroxymethyl cyclodextrin, hydroxyethyl cyclodextrin, hydroxypropyl cyclodextrin, hydroxybutyl cyclodextrin, dimethyl cyclodextrin, trimethyl cyclodextrin, diethyl cyclodextrin, triethyl cyclodextrin, carboxymethyl cyclodextrin, glucosyl cyclodextrin, maltosyl cyclodextrin, dimaltosyl cyclodextrin, cyclodextrin epichlorohydrin polymers and the like.
  • cyclodextrin derivatives In connection with the using amount of these cyclodextrin derivatives, it can be suitably used in the range of preferably 1 to 10000 parts by mass, more preferably 1 to 1000 parts by mass, and still more preferably 1 to 500 parts by mass of the cyclodextrin derivative per 100 parts by mass of the fragrant material.
  • the unsaturated organic compound described later is allowed to be included inside of the water absorbing resin.
  • regulation of crosslinking density of the water absorbing resin i.e., regulation of swelling capacity of the water absorbing resin may be important.
  • the regulation of the crosslinking density can be executed to some extent by controlling the polymerization conditions in synthesis of the water absorbing resin, in particular, amount of the internal crosslinking agent, monomer concentration in the polymerization and the like.
  • the water absorbing resin composition of the present invention preferably contains unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms (more preferably 6 to 8 carbon atoms) , and still more preferably contains unsaturated aldehyde or unsaturated alcohol selected from hexenal and hexenol.
  • unsaturated aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms (more preferably 6 to 8 carbon atoms)
  • still more preferably contains unsaturated aldehyde or unsaturated alcohol selected from hexenal and hexenol selected from hexenal and hexenol.
  • it is important to allow more preferably, straight-chain unsaturated aldehyde or alcohol, and more preferably, hexenal and/or hexenol to be included inside of the water absorbing resin.
  • hexenol having 6 carbon atoms
  • hexenol having 6 carbon atoms
  • hexenol having 6 carbon atoms
  • straight-chain unsaturated alcohol such as trans-2-hexenol, cis-2-hexenol, trans-3-hexenol, cis-3-hexenol and the like.
  • hexenal which may be used in the present invention include straight-chain unsaturated aldehyde, or branched form thereof such as trans-2-hexenal, cis-2-hexenal, trans-3-hexenal and cis-3-hexenal, and the like.
  • straight-chain unsaturated alcohol or straight-chain unsaturated aldehyde and more preferably cis-3-hexenol and/or trans-2-hexenal may be used.
  • unsaturated aldehyde or alcohol inside of the water absorbing resin, persistence of the aroma is markedly improved. Accordingly, an aromatic composition that is a water absorbing resin composition with stabilized aroma, and further, with excellent good-looking appearance can be provided. Additionally, when the water absorbing resin composition of the present invention is used in sanitary goods such as diapers, a deodorizing action and an antibacterial action may be exerted to give favorable diapers.
  • Cis-3-hexenol which may be used in the present invention is otherwise referred to as leaf alcohol, which is included in leaves, and is an aromatic component which reportedly participates in a green note.
  • trans-2-hexenal is otherwise referred to as leaf aldehyde, which is a compound reportedly being a source of a phytogenic young green note and also exhibiting an antibacterial action.
  • Such cis-3-hexenol and/or trans-2-hexenal may be obtained by synthesis, or may be obtained from a natural source.
  • cis-3-hexenol and/or trans-2-hexenal may be single compound, a compound containing these as naturally occurring products, or a mixed extract .
  • the weight ratio falls in the range of preferably 1/99 to 99/1, and more preferably 20/80 to 80/20.
  • cyclodextrin and/or the cyclodextrin derivative is used, and in place of the unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms, other ingredient, particularly a fragrant material ingredient may be also added.
  • cyclodextrin and/or the cyclodextrin derivative is used, and in combination with the unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms, other ingredient, particularly a fragrant material ingredient may be also added.
  • the fragrant material refers to an additive that is added for imparting or enhancing an aromatic odor, and the preparation thereof.
  • the fragrant material which can be used in the present invention may be any various ones such as naturally occurring fragrant materials, synthetic fragrant materials and compound fragrant materials as long as they are volatile and can emit a fragrant odor at an ordinary temperature.
  • any one of animal fragrant materials and plant fragrant materials can be used.
  • the animal fragrant material include e.g., musk, ambergris, civet, castoreum and the like.
  • the plant fragrant material include e.g. , fragrant materials obtained from flower such as rose, jasmine, orange flower, violet or the like, and fragrant materials obtained from fruit skin, leaf, root, bud, bark or trunk of lemon, rosemary, iris, cinnamon or the like, and the like.
  • the fragrant material for use in the present invention may be, for example, the following compound. (Fragrant Material of Alcohols)
  • Hydrocarbons such as cinnamic alcohol, ⁇ -pinene, camphene, limonene, myrcene and cadinene; alcohols such as anise alcohol, geraniol, citronellol, cinnamyl alcohol, phenylethyl alcohol, petipenol, menthol, benzyl alcohol and linalool.
  • Aldehydes such as 3, 7-dimethyl-l-octanal, 4 (3)- ( 4-hydroxy-4-methylpentyl) -3-cyclohexene-l-carboxyaldehyde , 4-methylphenyl acetaldehyde, 3-methyl-5-phenyl pentanal, methoxydicyclopentadiene carboxyaldehyde, trimethyIcyclohexene carboxyaldehyde, octahydro-8, 8-dimethyl-2-naphthalene carboxyaldehyde, 3- (3-isopropylphenyl) butanal, p-ethyl- ⁇ , ⁇ -dimethylhydrocinnamaldehyde, salicyl aldehyde, anise aldehyde, ⁇ -amyl cinnamaldehyde, oxycitronellal, citral, citronellal, cyclamen aldehyde, pan
  • Ketones such as irone, carvone, cycloheptadecanone, jasmon, cipetone, benzylidene acetone, muscone and ⁇ -ionone.
  • Esters such as ethyl benzoate, ethyl acetate, geranyl acetate, linalyl acetate and methyl salicylate.
  • Phenol ethers such as anisole, anethole, eugenol, safrole, diphenyl oxide and neroline.
  • Lactones such as coumarin, ambrettolide, exaltolide and coumarin; quinones such as p-oxyanisole and hydroquinone dimethyl ether; acids such as anisic acid, cinnamic acid, citronellic acid and phenylacetic acid.
  • cis-3-hexenol and/or trans-2-hexenal can be used each alone, but two or more thereof may be compounded to prepare a desired fragrance. Additionally, as the aforementioned naturally occurring fragrant material and synthetic fragrant material, at least one fragrant 1 material may be further compounded in addition to cis-3-hexenol and/or trans-2-hexenal to produce a desired aroma. Examples of the compounded flavor include floral type, oriental type, sibley type, natural type, citrus type, fusea type and the like.
  • solubility of the fragrant material in water is preferably not less than 0 but not greater than 10, more preferably not less than 0 but not greater than 7, and most preferably not less than 0 but not greater than 5.
  • This solubility means the amount (g) of dissolution per 100 g of ion exchanged water at 20 0 C.
  • the fragrant material for use in the present invention may be preferably liquid at an ordinary temperature (20 to 25°C) .
  • the melting point of the fragrant material may be preferably not higher than 20 0 C, more preferably not higher than 10 0 C, and particularly preferably not higher than 0 0 C .
  • the boiling point of the fragrant material may be preferably not lower than 80 0 C, more preferably not lower than 100 0 C, and still more preferably not lower than 120°C .
  • the fragrant material which is not liquid at an ordinary temperature but, for example, is solid or crystal at an ordinary temperature is not preferred for use in the present invention because it is not uniformly integrated or complexed with the water absorbing resin.
  • unsaturated aldehyde having 6 to 10 carbon atoms or unsaturated alcohol having 6 to 10 carbon atoms is preferred, and hexenal or hexenol is more preferred.
  • a fragrant material and cyclodextrin and/or a cyclodextrin derivative are preferably included inside of the water absorbing resin in light of persistence of the aroma and stability of the fragrant material.
  • the inclusion inside of the water absorbing resin it is not necessary to be present uniformly inside, but it is permissible that they are integrated or complexed with the water absorbing resin.
  • they may be included in a micro domain (sea-island state) in the water absorbing resin or included on the surface, or alternatively, may be clathrated inside thereof.
  • the present inventors found that by allowing the fragrant material and cyclodextrin and/or the cyclodextrin derivative to be included inside of the water absorbing resin, sanitary goods or fragrances with markedly improved persistence of the aroma and with stabilized fragrant material, which are further accompanied by excellent good-looking appearance can be provided.
  • the water absorbing resin generally has a three-dimensional network structure
  • inclusion of the fragrant material and cyclodextrin and/or the cyclodextrin derivative inside of the water absorbing resin was first enabled by controlling the size of the network to be larger than the size of the cyclodextrin and/or the cyclodextrin derivative.
  • the compound described above can be added in the production step of the water absorbing resin, or may be added to the water absorbing resin following the production.
  • the following methods (A) to (F) can be illustrated, but not limited thereto:
  • the resulting water absorbing resin composition is preferably gelatinous (hydro gel form) .
  • the method (A) or (B) is preferred among the aforementioned methods .
  • the water absorbing resin composition of the present invention can be produced with an excellent efficiency without evaporation of the fragrant material during the production.
  • the water absorbing resin composition is preferably in a powder form in light of processibility and water absorption capacity of the diaper.
  • the aforementioned method (D) is preferred.
  • the size and form of the resulting water absorbing resin composition may be determined ad libitum depending on the intended use.
  • Composition Ratio In the water absorbing resin composition of the present invention, compounding ratio of the fragrant material and the water absorbing resin can be selected ad libitum depending on the intended aromatic performance, however, the amount of the water absorbing resin may be usually 1 to 100000 parts by mass, more preferably 1 to 10000 parts by mass, and still more preferably 10 to 10000 parts by mass per 100 parts by mass of the fragrant material.
  • the amount of the water absorbing resin may be preferably 1 to 10000 parts by mass, and more preferably 1 to 1000 parts by mass per 100 parts by mass of total amount of the cyclodextrin including the fragrant material, the cyclodextrin derivative including the fragrant material, the unsaturated aliphatic aldehyde and unsaturated aliphatic alcohol. Furthermore, the amount of the water absorbing resin is preferably 1 to 10000 parts by mass, and more preferably 1 to 1000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic aldehyde and the unsaturated aliphatic alcohol.
  • the water absorbing resin composition of the present invention can be also used in a dry state.
  • the solvent, water is substantially free (moisture content being not higher than 20%) to give a solid state.
  • it is preferably used in a water based gelatinous state in light of the aromatic function thereof.
  • the water based gelatinous state refers to a form in which an aqueous liquid is incorporated into the three-dimensional network of the water absorbing resin, which is an aqueous system having a solid-like appearance.
  • This aqueous liquid may be water alone and/or a mixture of water and a hydrophilic organic solvent such as ethanol, including preferably 50 to 100% by weight of water, more preferably 70 to 100% by weight of water, and particularly preferably 90 to 100% by weight of water.
  • a hydrophilic organic solvent such as ethanol
  • the water absorbing resin composition of the present invention is preferably used in a dry state in light of the absorption capacity, usability and the like.
  • the amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the fragrant material, cyclodextrin and/or the cyclodextrin derivative and the water absorbing resin.
  • the amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the cyclodextrin including the fragrant material, the cyclodextrin derivative including the fragrant material, the unsaturated aliphatic aldehyde, the unsaturated aliphatic alcohol and the water absorbing resin.
  • the amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic aldehyde, the unsaturated aliphatic alcohol and the water absorbing resin.
  • the water absorbing resin or water absorbing resin composition according to the present invention described above may further include other ingredient as needed in an amount of 0 to 20% by weight, and preferably 0 to 5% by weight.
  • the other ingredient include antimicrobials, foaming agents, pigments, dyes, plasticizers, adhesives, surfactants, fertilizers, oxidizing agents, reducing agents, water, salts, chelating agents (preferably, aminocarboxylic acid) , bacteriocides, hydrophilic polymers such as polyethylene glycol and polyethylene imine, hydrophobic polymers such as paraffin, thermoplastic resins such as polyethylene and polypropylene, thermosetting resins such as polyester resins and urea resins, and the like.
  • the method for producing the water absorbing resin or water absorbing resin composition according to the present invention may include a step of imparting a variety of functions such as a step of adding these other ingredients or the like.
  • Method for Producing Water Absorbing Resin Composition In the method for allowing the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde to be included inside of the water absorbing resin, the compound described above can be added in the production step of the water absorbing resin or can be added to the water absorbing resin following the production step, with or without using cyclodextrin and/or the derivative thereof.
  • the case in which the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde is present inside of the water absorbing resin may also involve the case in which cyclodextrin and/or the derivative thereof is present as well as the case in which cyclodextrin and/or the derivative thereof is not present.
  • the case in which the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde is present inside of the water absorbing resin is not limited to the case in which it is uniformly present inside, but also include the case in which it is integrated or complexed with the water absorbing resin.
  • the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde may be included in a micro domain (sea-island state) in the water absorbing resin or included on the surface of the water absorbing resin, or alternatively, may be clathrated inside of the water absorbing resin.
  • the present inventors found that by allowing the unsaturated organic compound (alcohol and aldehyde) to be included inside of the water absorbing resin, sanitary goods or fragrances with markedly improved persistence of the aroma and with stabilized fragrant material, which are further accompanied by excellent good-looking appearance can be provided.
  • the water absorbing resin generally has a three-dimensional network structure
  • inclusion of the unsaturated organic compound inside of the water absorbing resin was first enabled by controlling the size of the network to be larger than the size of the unsaturated organic compound.
  • the method for allowing the unsaturated organic compound (alcohol and aldehyde) to be included inside of the water absorbing resin for example, the following methods (Al) to (Dl) may be illustrated, but not limited thereto:
  • aqueous liquid a method in which an aqueous liquid is prepared from the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde, and the aqueous liquid is allowed to be absorbed to the water absorbing resin.
  • This aqueous liquid may include water and a hydrophilic organic solvent such as, e.g., ethanol;
  • (Dl) a method in which the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde is added in the surface crosslinking step, the agglomerating step or the like of the water absorbing resin.
  • the resultant composition is preferably gelatinous (hydro gel form) in light of stability of the fragrant material and persistence of the odor.
  • the method (Al) or (Bl) is preferred among the aforementioned methods.
  • the water absorbing resin composition of the present invention is used in sanitary goods, it is preferably in a powder form in light of processibility and water absorption capacity of the diaper, and the aforementioned method (Dl) is preferably employed.
  • the size and form of the resulting water absorbing resin composition may be determined ad libitum depending on the intended use. [Composition Ratio]
  • compounding ratio of the unsaturated aliphatic alcohol and unsaturated aliphatic aldehyde, and the water absorbing resin can be selected ad libitum depending on the intended aromatic performance, however, the amount of the water absorbing resin may be 1 to 100000 parts by mass, more preferably 1 to 10000 parts by mass, and still more preferably 10 to 10000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic alcohol and unsaturated aliphatic aldehyde.
  • the water absorbing resin in case of use as a fragrance, is preferably used in a water based gelatinous state in light of the aromatic function thereof.
  • the water based gelatinous state and the aqueous liquid are as described above.
  • the amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde and the water absorbing resin.
  • the water absorbing resin composition of the present invention produced by the aforementioned method for the production referred to by way of example may be either gelatinous (for example, state of the moisture content beyond 20%, particularly 50 to 99.999%), or a dried matter (for example, moisture content being not higher than 20%) .
  • the water absorbing resin composition of the present invention has a particulate form, and for example, has a centrifuge retention capacity (CRC) described later of preferably 20 g/g to 100 g/g and more preferably 25 to 50 g/g, and an absorbency under load (absorbency against pressure: AAP) of preferably 10 to 60 g/g and more preferably 20 to 40 g/g.
  • CRC centrifuge retention capacity
  • AAP absorbency under load
  • absorbency against pressure (absorbency under load) for a physiological saline solution (0.9% by weight aqueous sodium chloride solution) under a pressure of 20 g/cm 2 may be preferably 20 g/g to 40 g/g, while absorbency against pressure (absorbency under load) for a physiological saline solution under a pressure of 50 g/cm 2 may be preferably 15 g/g to 40 g/g, in light of absorption properties desired for sanitary goods.
  • the water extractables and particle size distribution may be adjusted to fall within the above range.
  • the form of the water absorbing resin composition of the present invention is not particularly limited, but may be in a particulate form such as irregularly crushed form or sphere, or in the form of powder, gel, sheet, rod, fiber, film or the like.
  • the water absorbing resin composition described later has a mass median particle size of 100 to 50000 ⁇ m.
  • the water absorbing resin composition described later may be particles or powder having a mass median particle size of preferably 100 to 20000 ⁇ m, more preferably 200 to 20000 ⁇ m, still more preferably 300 to 20000 ⁇ m and particularly preferably 500 to 10000 ⁇ m, or gelling material of the same.
  • ratio of the particles having a particle diameter of less than 150 ⁇ m may 17
  • ratio of the particles having a particle diameter of less than 300 ⁇ m in the water absorbing resin composition may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and still more preferably 0 to 1% by weight in light of the persistence of sustained release of the aromatic ingredient.
  • mass median particle size of the water absorbing resin composition may be preferably 200 ⁇ m to 850 ⁇ m, and particularly preferably 300 ⁇ m to 600 ⁇ m in light of the absorption properties.
  • ratio of the particles having a particle diameter of less than 150 ⁇ m in the water absorbing resin composition may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and particularly preferably 0 to 1% by weight in light of the absorption properties.
  • the water absorbing resin composition of the present invention provides sanitary goods and fragrances exhibiting a persistent effect of the aroma for a long period of time, being excellent in stability of the color, having excellent gel stability and good-looking appearance of the composition, with high industrial productivity. Furthermore, when the water absorbing resin composition of the present invention (particularly, particulate form water absorbing resin composition) is used in sanitary goods such as diapers and feminine protection products, favorable deodorization effect and durability (preventive property of gel deterioration) may be exhibited. Moreover, the water absorbing resin composition of the present invention provides sanitary goods and fragrances that are excellent in persistence of the aroma and stability of the aroma, and effective in relieving fatigue and stress.
  • the water absorbing resin composition of the present invention also has a masking effect and an antibacterial effect resulting from the fragrant material ingredient, it can be also used as a deodorizing antimicrobial agent, which can be utilized, for example, as a fragrance or deodorant for use in rooms and cars as well as sanitary goods.
  • a deodorizing antimicrobial agent which can be utilized, for example, as a fragrance or deodorant for use in rooms and cars as well as sanitary goods.
  • the water absorbing resin composition of the present invention particularly, particulate water absorbing resin composition
  • favorable deodorization effect, antibacterial effect and durability preventive property of gel deterioration
  • characteristics excellent in stability of the color in white powder for a long period of time may be shown.
  • an absorbent core (formed product) can be obtained by forming together with other arbitrary material such as a hydrophilic fiber.
  • Form of the absorbent core is not particularly limited, but may be processed preferably into the sheet-like, cylindrical, film-like or fibrous form, particularly preferably into the sheet-like form (may be also referred to as web form) .
  • the absorbent core can be obtained by thus processing into such a form.
  • the hydrophilic fiber which can be used in the present invention is not particularly limited, but illustrative examples include e.g., ground wood pulp, cotton linters, as well as crosslinked cellulosic fibers, rayon, cotton, wool, acetate, vinylon and the like, which may be preferably airlied.
  • the absorbent core according to the present invention is an absorbent core including the particulate water absorbing agent and the hydrophilic fiber
  • content of the particulate water absorbing agent (hereinafter, may be also referred to as core concentration) based on total weight of the particulate water absorbing agent and the hydrophilic fiber falls within preferably the range of 20 to 100% by weight, more preferably the range of 25 to 90% by weight, and still more preferably the range of 30 to 80% by weight.
  • core concentration content of the particulate water absorbing agent based on total weight of the particulate water absorbing agent and the hydrophilic fiber falls within preferably the range of 20 to 100% by weight, more preferably the range of 25 to 90% by weight, and still more preferably the range of 30 to 80% by weight.
  • Such absorbent core is preferably subjected to formation under compression to give the density in the range of 0.001 to 0.50 g/cc, and the weighing capacity in the range of 0.01 to 0.20 g/cm 2 .
  • the absorbing article in which the water absorbing resin of the present invention is used (final consumer goods) is equipped with the aforementioned absorbent core of the present invention, a surface sheet with liquid permeability and a back sheet with liquid impermeability.
  • the method for the production of the absorbing article according to the present invention is not particularly limited, but for example, any one of production methods can be adopted in which the absorbing article such as a disposable diaper or a sanitary napkin is obtained by sandwiching the absorbent core between a substrate with liquid permeability (the surface sheet) and a substrate with liquid impermeability (the back sheet) , and 'mounting an elastic part, a diffusion layer, a pressure sensitive adhesive tape and the like as needed. 14717
  • a water absorbing resin in an amount of 0.2 g was uniformly put in a bag (60 mm x 60 mm) made of unwoven fabric and sealed.
  • the bag was immersed in 100 g of a 0.9% aqueous sodium chloride solution at 25 ( ⁇ 3) 0 C.
  • the bag was taken out of the solution 24 hours later, subjected to dewatering for 3 minutes at 250 G using a centrifuge, and then measured the weight Wl of the bag made of unwoven fabric.
  • Weight W2 of the bag was measured after conducting similar operation without using any water absorbing resin. Absorption capacity was then calculated from the weight Wl and weight W2 according to the formula 1.
  • the measurement may be performed after arbitrarily crushing to allow for the sampling of 0.2 g.
  • Formula 1: GVs (Wl-W2)/0.2 - 1
  • a 0.90% by weight aqueous sodium chloride solution (physiological saline solution) was weighed to put 184.3 g in a plastic vessel with a lid having a capacity of 250 ml.
  • aqueous sodium chloride solution physiological saline solution
  • Into the aqueous solution was added 1.00 g of the water absorbing resin, and extractables in the resin were extracted by stirring the mixture for 24 hours.
  • the extracted liquid was filtrated with one sheet of filter paper (Advantec Toyo Kaisha, Ltd., trade name: (JIS P 3801, No. 2) , thickness: 0.26 mm, retaining particle size: 5 ⁇ m) , and 50.0 g of thus resulting filtrate was weighed to give a solution for the measurement.
  • filter paper Advanced Toyo Kaisha, Ltd., trade name: (JIS P 3801, No. 2) , thickness: 0.26 mm, retaining particle size: 5 ⁇ m
  • the physiological saline solution alone was titrated with a 0.1 N aqueous NaOH solution to the pH of 10 and thereafter titrated with a 0.1 N aqueous HCl solution to the pH of 2.7 to thereby determine blank titers ( [bNaOH] ml,
  • the water absorbing resin powder or the water absorbing resin composition was subjected to sieve classification using JIS standard sieves having a mesh opening size of 53 mm, 45 mm, 31.5 mm, 22.4 mm, 11.3 mm, 8 mm, 5.6 mm, 4 mm, 2.8 mm, 1.4 mm, 1 mm, 850 ⁇ m, 710 ⁇ m, 600 ⁇ m, 500 ⁇ m, 425 ⁇ m, 300 ⁇ m, 212 ⁇ m, 150 ⁇ m, 106 ⁇ m, 75 ⁇ m and the like (JIS Z8801-1 (2000) or equivalents thereof) , and the residual percentages were plotted on a logarithmic probability paper. Accordingly, the mass median particle size (D50) was read.
  • the sieve classification was carried out by charging 10 g of the water absorbing resin under the conditions at the room temperature (20 to 25°C) and relative humidity of 50 ⁇ 5% RH in the aforementioned JIS standard sieve (The IIDA TESTING SIEVE: internal diameter : 80 mm) and conducting classification using a Ro-Tap sieve shaker (manufactured by Iida-seisakusho Japan Corporation, ES-65 sieve shaker) for 10 minutes.
  • the mass median particle size (D50) is, as described in United States Patent No. 5051259 and the like, the particle diameter of the particles left on the standard sieve corresponding to 50% by weight of the entire particles among the standard sieves having a certain mesh opening size.
  • any standard sieve described in JIS Z8801-1 may be arbitrarily selected for the measurement. [Absorbency against Pressure]
  • aqueous monomer solution containing 340.6 parts of a 37% by weight aqueous sodium acrylate solution, 39.5 parts of acrylic acid, 1 part of a 10% aqueous polyethylene glycol diacrylate solution and 33.8 parts of ion exchanged water were added 1.9 parts of a 1% hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184; manufactured by Ciba Specialty Chemicals) solution in acrylic acid and 1.9 parts of a 3% aqueous sodium persulfate solution in a nitrogen atmosphere. Thereto was irradiated an ultraviolet ray in the state of the aqueous solution temperature being 5°C to execute the polymerization.
  • a 1% hydroxycyclohexyl phenyl ketone trade name: IRGACURE 184; manufactured by Ciba Specialty Chemicals
  • the water absorbing resin (1) had an mass median particle size of 1500 ⁇ m, and a ratio of the particles having a particle diameter of less than
  • aqueous monomer solution containing 340.6 parts of a 37% aqueous sodium acrylate solution, 39.5 parts of acrylic acid, 1 part of a 10% aqueous polyethylene glycol diacrylate solution and 33.8 parts of ion exchanged water were added 1.9 parts of a 1% hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184; manufactured by Ciba Specialty Chemicals) solution in acrylic acid and 1.9 parts of a 3% aqueous sodium persulfate solution in a nitrogen atmosphere. Thereto was irradiated an ultraviolet ray in the state of the aqueous solution temperature being 22°C to execute the polymerization.
  • a 1% hydroxycyclohexyl phenyl ketone trade name: IRGACURE 184; manufactured by Ciba Specialty Chemicals
  • the water absorbing resin (2) had an mass median particle size of 1000 ⁇ m. In the water absorbing resin (2), ratio of the particles having a particle diameter of less than 150 ⁇ m was 0.1% by weight. Additionally, GVs (g/g) and extractables ratio (%) of the water absorbing resin (2) were 37 (g/g) and 9% by weight, respectively.
  • aqueous solution containing 1.5 parts of a fragrant material (1) including 10% cis-3-hexenol, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 47 parts of ion exchanged water was produced.
  • aqueous solution was added 1 part of the water absorbing resin (1) to obtain the water absorbing resin composition (1) of the present invention.
  • the water absorbing resin composition (1) is a gelatinous composition.
  • Example 2 An aqueous solution containing 1 part of the fragrant material (1) including 10% cis-3-hexenol, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, and 180 parts of ion exchanged water was produced. To this aqueous solution was added 4.5 parts of the water absorbing resin (2) to obtain the water absorbing resin composition (2) of the present invention.
  • the water absorbing resin composition (2) is a gelatinous composition.
  • aqueous solution containing 1.5 parts of the fragrant material (1) including 10% cis-3-hexenol, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.0001 parts of Food Yellow No. 4 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 47 parts of ion exchanged water was produced.
  • To this aqueous solution was added 1 part of the water absorbing resin (3) to obtain the water absorbing resin composition (3) of the present invention.
  • the water absorbing resin composition (3) is a gelatinous composition.
  • Example 4 In a similar manner to Example 1 except that cis-3-hexenol was changed into trans-2-hexenal, the water absorbing resin composition (4) of the present invention was obtained.
  • the water absorbing resin composition (4) is a gelatinous composition.
  • Example 2 In a similar manner to Example 1 except that the fragrant material (1) was changed into a fragrant material including 5% cis-3-hexenol, 5% trans-2-hexenal, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, the water absorbing resin composition (5) of the present invention was obtained.
  • the water absorbing resin composition (5) is a gelatinous composition.
  • the comparative water absorbing resin composition (1) is a gelatinous composition.
  • Example 6 Comparative Example 2 In a similar manner to Example 1 except that the water absorbing resin (1) was not used, the comparative composition (2) of the present invention was obtained. (Example 6)
  • a water absorbing resin composition (6) was obtained by adding 1.5 parts of cis-3-hexenol to 100 parts of the water absorbing resin (1) followed by mixing.
  • the water absorbing resin composition (6) is a powdery composition.
  • the water absorbing resin compositions (1) to (5) in an amount of 20 g were each placed in a 500-ml glass beaker, and left to stand at room temperature. One month later, the weight of the aromatic compositions decreased by nearly half. However, they were still in a transparent gelatinous state without deposition onto the vessel, and also the aroma was maintained.
  • Example 7 In a similar manner to Example 7 except that the water absorbing resin was not added, a comparative composition (3) was obtained.
  • Example 8 An aqueous solution containing 1.5 parts of the fragrant material (1) including 10% cis-3-hexenol, 15% triethyl citrate and 75% ethyl alcohol as ingredients, 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.2 parts of ⁇ -cyclodextrin and 47 parts of pure water was produced. To this aqueous solution was added 1 part of the water absorbing resin (1) obtained in Reference Example 1 to obtain the water absorbing resin composition (8) of the present invention.
  • the water absorbing resin composition (8) is a gelatinous composition.
  • the water absorbing resin composition (9) is a gelatinous composition.
  • Example 10 In a similar manner to Example 9 except that polyoxyethylene sorbitan monolaurate was used in place of ⁇ -cyclodextrin, a comparative composition (4) was obtained.
  • the comparative composition (4) was apparently in a white turbid state.
  • the comparative composition (4) is a gelatinous composition. (Example 10)
  • the water absorbing resin composition (10) is a gelatinous composition.
  • the water absorbing resin composition (11) is a gelatinous composition.
  • Absorbency against pressure of the water absorbing resin (4) for a physiological saline solution under a condition of the pressure being 20 g/cm 2 was 7 (g/g) .
  • Absorbency against pressure of the water absorbing resin (4) for a physiological saline solution under a condition of the pressure being 50 g/cm 2 was 5 (g/g) .
  • (Reference Example 5) A surface treatment agent composed of a mixed liquid of 0.4 parts by mass of 1, 4-butanediol, 0.6 parts by mass of propylene glycol and 3.0 parts by mass of pure water was homogenously mixed with 100 parts by mass of the water absorbing resin (4) obtained in Reference Example 4. This mixture was subjected to a heat treatment at 200°C for 30 minutes.
  • a water absorbing resin (5) was obtained by pulverizing the particles thus subjected to the heat treatment into the particles that pass through a JIS standard sieve having a mesh opening size of 850 ⁇ m.
  • the water absorbing resin (5) exhibited GVs (g/g) of 24 (g/g).
  • the extractables ratio (%) of the water absorbing resin (4) was 7% by weight.
  • Absorbency against pressure of the water absorbing resin (5) for a physiological saline solution under a condition of the pressure being 20 g/cm 2 was 25 (g/g) .
  • Absorbency against pressure of the water absorbing resin (5) for' a physiological saline solution under a condition of the pressure being 50 g/cm 2 was 21 (g/g) .
  • Example 12 ⁇ -Cyclodextrin including the fragrant material (1) therein was obtained by mixing 1 part of the fragrant material (1) used in Example 1 and 2 parts of ⁇ -cyclodextrin to allow the fragrant material (1) to be absorbed to ⁇ -cyclodextrin. Next, an aqueous solution was produced by dissolving 3 parts of ⁇ -cyclodextrin including the fragrant material (1) in 180 parts of ion exchanged water. A water absorbing resin composition (12) was obtained by adding 4.5 parts of the water absorbing resin (2) to this aqueous solution. The water absorbing resin composition (12) is a gelatinous composition. (Example 13)
  • Example 12 In a similar manner to Example 12 except that 1.5 parts of the fragrant material (1) and 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) were allowed to be included in ⁇ -cyclodextrin, a water absorbing resin composition (13) was obtained.
  • the water absorbing resin composition (13) is a gelatinous composition.
  • Example 14 In a similar manner to Example 12, ⁇ -cyclodextrin including the fragrant material (1) therein was obtained.
  • An aqueous solution (14) was obtained by dissolving 1 part of this ⁇ -cyclodextrin in 5 parts of ion exchanged water.
  • This aqueous solution (14) was homogenously mixed with 100 parts of the water absorbing resin (5) obtained in Reference Example (5) . After mixing, this mixture was left to stand in a 60 0 C windless oven for 1 hour.
  • a powdery water absorbing resin composition (14) having a mass median particle size of 420 ⁇ m, and including 0.5% by weight of the particle ingredient having a particle diameter of less than 150 ⁇ m was obtained by passing through a JIS standard sieve having a mesh opening size of 850 ⁇ m.
  • the water absorbing resin composition (14) exhibited GVs (g/g) of 23 (g/g) .
  • the extractables ratio (%) of the water absorbing resin composition (14) was 7% by weight .
  • Absorbency against pressure of the water absorbing resin composition (14) for a physiological saline solution under a condition of the pressure being 20 g/cm 2 was 23 (g/g) .
  • Absorbency against pressure of the water absorbing resin composition (14) for a physiological saline solution under a condition of the pressure being 50 g/cm 2 was 20 (g/g) .
  • Example 14 In a similar manner to Example 14 except that the fragrant material (1) was replaced with the fragrant material (2) , a particulate water absorbing resin composition (15) having a mass median particle size of 420 ⁇ m, and including 0.2% by weight of the particle ingredient having a particle diameter of less than 150 ⁇ m was obtained.
  • the ingredients of the fragrant material (2) were 10% by weight trans-2-hexenal, 15% by weight citric acid triethyl ester and 75% by weight ethyl alcohol.
  • the water absorbing resin composition (15) exhibited GVs (g/g) of 23 (g/g) .
  • the extractables ratio (%) of the water absorbing resin composition (15) was 7% by weight .
  • the vessel charged with the swollen gel was covered with a lid, and left to stand in a 37°C dryer for one day. ' After leaving to stand, the state of the gel was visually observed to reveal that any of the water absorbing resin compositions (6), (14), (15) and (16) kept a stable gelatinous state.
  • Each 75 parts of the water absorbing resin compositions (14) to (16), and 25 parts of pulverized wood pulp as a hydrophilic fiber were subjected to dry blending using a mixer.
  • the resultant mixture was subjected to pneumatic molding on a wire screen of 400 mesh (mesh opening size: 38 ⁇ m) with a batch type pneumatic device.
  • a web having a size of 120 mm * 400 mm was formed.
  • this web was pressed for 5 seconds under a pressure of 2 kg/cm 2 , thus obtaining an absorbent core having a basis weight of 0.047 g/cm 2 and a core concentration of 75% by weight.
  • a back sheet, the aforementioned absorbent core and a top sheet were attached to each other in this order with double-stick tapes, and two so-called tape fasteners were then provided to the resultant attached product, thus obtaining absorbent articles (1) to (3) that were disposable diapers.
  • the aforementioned back sheet is constituted from liquid-impermeable polypropylene and has a so-called leg gather.
  • the aforementioned top sheet is constituted from liquid-permeable polypropylene.
  • 50 ml of a physiological saline solution (0.9% by weight aqueous sodium chloride solution) was charged to the absorbing articles (1) to (3) from the side of the top sheet. Further, each 50 ml of the physiological saline solution was additionally charged at intervals of 20 minutes.
  • the physiological saline solution of 250 ml in total was charged. Thereafter, the absorbing articles (1) to (3) charged with the physiological saline solution were left to stand in a windless at 37°C for 16 hours. When 50 ml of the physiological saline solution was charged again to the absorbing articles (1) to (3) after leaving to stand for 16 hours, the entire physiological saline solution was absorbed. (Evaluation 8) Evaluation was conducted in a similar manner to
  • the water absorbing resin composition of the present invention provides sanitary goods and fragrances that are excellent in persistence of the aroma and stability of the aroma, and effective in relieving fatigue and stress. Still further, because the water absorbing resin composition of the present invention also exhibits a masking effect and an antibacterial effect resulting from the fragrant material ingredient, it can be also used as a deodorizing antimicrobial agent, which can be utilized, for example, as fragrances or deodorants for use in rooms and cars as well as sanitary goods. Stability of the fragrant material may be remarkably improved throughout the course of production over the article of trade. In addition, in case of use in sanitary goods such as disposable diapers, favorable deodorization effect, antibacterial effect and durability may be exhibited.

Abstract

The present invention provides fragrances and sanitary goods exhibiting a persistent effect of the aroma for a long period of time, and further exhibiting an excellent deodorization effect. The present invention is directed to a water absorbing resin composition containing at least one substance selected from the group consisting of cyclodextrin including a fragrant material, a dextrin derivative including a fragrant material, unsaturated aliphatic aldehyde and unsaturated aliphatic alcohol having 6 to 10 carbon atoms, and a polycarboxylic acid type water absorbing resin. Preferably, unsaturated aldehyde or unsaturated alcohol selected from hexenal and hexenol may be used.

Description

Description
WATER ABSORBING RESIN COMPOSITION
This application claims priority on Patent Application No. 2005-209655 filed in JAPAN on July 20, 2005 and Patent Application No. 2005-209659 filed in JAPAN on July 20, 2005, the entire contents of which are hereby incorporated by reference .
Technical Field
The present invention relates to a water absorbing resin composition. More particularly, the present invention relates to a water absorbing resin composition which comprises : at least one substance selected from the group consisting of cyclodextrin and a cyclodextrin derivative including a fragrant material, unsaturated aliphatic aldehyde having 6 to 10 carbon atoms and unsaturated aliphatic alcohol having 6 to 10 carbon atoms; and a water absorbing resin. For example, the present invention relates to aromatic deodorants and sanitary goods (including absorbing articles such as diapers and the like) that exhibit an enhanced persistent effect of the aroma, are excellent in odor stability and good-looking appearance, and can be readily manufactured industrially, accompanied by excellent smell-reducing property and durability. The present invention relates to a water absorbing resin composition in which cyclodextrin or a cyclodextrin derivative including a fragrant material, unsaturated aliphatic aldehyde having 6 to 10 carbon atoms, or unsaturated aliphatic alcohol having 6 to 10 carbon atoms is included inside of a water absorbing resin, and for example, relates to a water absorbing resin composition which can be suitably used as aromatic gels and sanitary goods . The present invention provides a water absorbing resin composition which is not only excellent in persistence of the aroma and stability of the aroma, but also effective in relieving fatigue and stress when it is used in environmental fragrances and sanitary goods.
Background Art In recent years, as attentions to hygiene and health grow, sensitivity to odor and aroma at home tends to be elevated. In particular, removal of bad smells as typified by smells of pets such as dogs and cats has been raised as a problem to be solved, and further, needs for pleasant aroma have been increased for relieving fatigue and stress. In regard to sanitary goods such as diaper and the like, a bad smell may be emitted when urine or the like is absorbed. There exist needs for removal of the bad smell and for pleasant aroma, also in connection with the sanitary goods. In order to meet the needs as described above," a number of fragrances for use in rooms and cars have been conventionally proposed. Known fragrances include those in the form of liquid, gel, granule, or solid. Known liquid form fragrances usually include an alcohol as a base, while known gel form ones are prepared by gelling with a water insoluble gelatinizing agent such as a water absorbing resin, a water soluble gelatinizing agent such as agar or carrageen, a metal soap, a clay mineral such as montmorillonite, silica or the like. Furthermore,' in the granular form, activated charcoal is utilized, and in the solid form, silica gel or the like is utilized.
Known fragrances for use in rooms and cars include those in the form of liquid, gel, granule, or solid. Known liquid form fragrances usually include an alcohol as a base, while known gel form ones are prepared by gelling with a water soluble gelatinizing agent such as agar or carrageen, a metal soap, a clay mineral such as montmorillonite, silica or the like. Furthermore, in the granular form, activated charcoal is utilized, and in the solid form, silica gel or the like is utilized.
Moreover, a number of techniques related to compositions in which a water absorbing resin is combined with a deodorant have been conventionally proposed for the purpose of removing a bad smell. For example, in order to reduce the smell, to impart a deodorizing function by a composition including a water absorbing resin and a compound such as cyclodextrin or the like (Patent Documents 1 to 6) , as well as to impart an antibacterial or sterilizing effect (Patent Document 7) was proposed. However, these merely have an smell-reducing function, but do not impart a positive aromatic function for relieving fatigue and stress of human.
In addition to the reduction in the smell, to further meet the needs for aromas, water absorbing resin compositions to which a positive aromatic function was imparted have been proposed. For example, a composition to which an aromatic function was imparted by water absorbing resin powder and powder including a fragrant material in a water soluble resin (Patent Document 8), a gelatinous composition containing a fragrant material and cyclodextrin (Patent Document 9) , a composition in which a water absorbing resin, a water-thickening (water increase viscosity) polymer, and a fragrance are combined (Patent Document 10), a composition including a reaction product of maleic anhydride with ammonia, a water absorbing resin and a fragrance (Patent Document 11) , and the like were proposed.
Although a variety of fragrances have been thus used, any one of the conventional products did not exhibit persistence of the aroma that is satisfactory enough because of readily volatilized aroma according to the conventional products. Therefore, even though the aforementioned water absorbing resin is used in an absorbing article such as a diaper, persistence (sustained release) of the aroma cannot be sufficient. Aiming at improvement of the persistence, various attempts to allow the gelatinizing agent such as the aforementioned water absorbing resin to form a complex with a fragrant material have been also carried out. However, the fragrant materials are generally hydrophobic, and complex formation with a hydrophilic gelatinizing agent cannot be readily carried out. For example, the problem is intended to be solved by using a surfactant or the like in combination, however, satisfactory effect has not be currently achieved in terms of emission of an abnormal smell derived from the surfactant, as well as persistence of the aroma.
Further, the art disclosed in Patent Document 9 is disadvantageous in that persistence of sustained release of the aromatic ingredient is insufficient, and that cyclodextrin, which is deposited as the moisture is evaporated during the use, is adhered interior of the vessel or interior of the sanitary goods leading to problems of impossible practical applications also in respect of the appearance. Moreover, Patent Document 12 discloses a fragrant material composition containing highly water absorbing polymer fine particles carrying a fragrant material, the composition being characterized in that highly water absorbing polymer fine particles allowed to absorb an aqueous solution and/or an aqueous dispersion of the fragrant material are dispersed in an oily dispersion medium. Furthermore, Patent Document 13 discloses a deodorizing fragrant material composition containing at least one compound selected from the group consisting of isopulegol, 3- (3-isopropylphenyl) butanal, p-ethyl-α, α-dimethylhydrocinnamaldehyde, ethyl vanillin, 1-ethoxy- (3, 7-dimethy1-1, β-octadiene-3-yloxy) -ethane, octahydro-8, 8-dimethyl-2-naphthalene carboxyaldehyde, salicyl aldehyde, dihydrojasmon, 3, 7-dimethyl-l-octanal, cis-jasmon, cinnamic alcohol, cedrenol, 1- (5, 5-dimethyl-l-cyclohexene-l-yl) -4-pentene-l-one, α—damascone, β—damascenone, α, 3, 3-trimethylcyclohexanemethyl formate, trimethylcyclohexene carboxyaldehyde, vanillin,
4(3)- (4-hydroxy-4-methylpentyl) -3-cyclohexene-l-carboxyald ehyde, cis-3-hexenol, vetiveryl acetate, 4-methylphenyl acetaldehyde, 3-methyl-5-phenylpentanal, methoxydicyclopentadiene carboxyaldehyde, and linalyl cinnamate, as an active ingredient.
Under such circumstances, various fragrances have been used, however, according to conventional fragrances (for example, Patent Document 12) , the fragrant material is liable to be evaporated, and thus, persistence of the aroma is not satisfactory. Additionally, they are not satisfactory also in terms of relief of the fatigue and stress.
[Patent Document 1] International Patent Publication No. WO98/26808 [Patent Document 2] International Patent Publication No. WO2001/26808
[Patent Document 3] Japanese Patent Publication No. 2000-079159
[Patent Document 4] International Patent Publication No. WO2000/01479
[Patent Document 5] Japanese Patent Publication No. 2004-346130
[Patent Document 6] Japanese Patent Publication No. 2004-285202 [Patent Document 7] Japanese Patent Publication No. 2003-146803
[Patent Document 8] Japanese Patent Publication No . S62-236860 [Patent Document 9] Japanese Patent Publication No. H7-241333 [Patent Document 10] Japanese Patent Publication No. 2000-014760
[Patent Document 11] Japanese Patent Publication No. 2000-135280
[Patent Document 12] Japanese Patent Publication No. 2003-064393 [Patent Document 13] Japanese Patent Publication No. 2003-321697
Disclosure of the Invention
Accordingly, the present invention provides a fragrance or sanitary goods exhibiting a persistent effect of the aroma for a long period of time, having excellent gel stability and good-looking appearance of the composition, with high industrial productivity. Moreover, according to use as a composition that is excellent in a smell-masking property in sanitary goods, absorbing articles that impart a comfortable sense of relief can be provided.
In order to solve the problems described above, the present inventors elaborately investigated, and consequently found that an aromatic composition including a fragrant material and cyclodextrin and/or a cyclodextrin derivative inside of a water absorbing resin can markedly improve persistence of the aroma and stability of the fragrant material, and in addition, can drastically decrease adherence of the deposit interior of the vessel or interior of the sanitary goods, which may be beneficial to the appearance. Accordingly, the present invention was accomplished. Moreover, in view of the foregoing circumstances, the present inventors further investigated elaborately, and consequently found that an aromatic composition containing unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms (particularly, trans-2-hexenal and/or cis-3-hexenol) and a water absorbing resin is not only excellent in persistence of the aroma and stability of the aroma, but also effective in relieving fatigue and stress when the aromatic composition is used in environmental fragrances or sanitary goods. Thus, the present invention was accomplished.
Accordingly, the water absorbing resin composition of the present 'invention comprises: at least one substance selected from the group consisting of cyclodextrin including a fragrant material, a dextrin derivative including a fragrant material, unsaturated aliphatic aldehyde having 6 to 10 carbon atoms and unsaturated aliphatic alcohol having 6 to 10 carbon atoms; and a polycarboxylic acid type water absorbing resin. According to the present invention, fragrances and sanitary goods exhibiting a persistent effect of the aroma for a long period of time, having excellent gel stability and good-looking appearance of the composition, with high industrial productivity can be provided. According to the present invention, fragrances and sanitary goods which are excellent in persistence of the aroma and stability of the aroma, and can relieve fatigue and stress can be provided. According to the present invention, sanitary goods such as disposable diapers and the like and fragrances exhibiting an excellent deodorization effect or antibacterial effect can be provided.
Best Mode for Carrying Out the Invention
Hereinafter, the present invention will be described in more detail.
(1) Water Absorbing Resin
The water absorbing resin of the present invention is a hydrophilic cross-linked polymer which can form a hydro gel upon contact with water and which has a water-swelling property and water insolubility. The water-swelling property refers to a property of essentially absorbing a large quantity of water, i.e., 5 times or more, preferably, from 50 times to 1000 times the own weight in ion exchanged water. Also, the water insolubility means that the content of water extractables in the resin is essentially 0 to 50% by weight, preferably 0 to 25% by weight, more preferably 0 to 15% by weight, and still more preferably 0 to 10% by weight, and that the polymer is substantially insoluble in water. Measurement methods of these will be defined in the Example described later. Examples of such a water absorbing resin include at least one polycarboxylic acid (a salt thereof) type water absorbing resin selected from polyacrylic acid-partially neutralized polymers, hydrolysates of a starch-acrylonitrile graft polymer, starch-acrylic acid graft polymers, saponified products of a vinyl acetate-acrylic acid ester copolymer, hydrolysates of an acrylonitrile copolymer or an acrylamide copolymer or cross-linked polymers thereof, carboxyl group-containing cross-linked polyvinyl alcohol denatured products, cross-linked isobutylene-maleic anhydride copolymers, carboxyalkylated cellulose such as carboxy methyl cellulose and polyaspartic acid cross-linked polymers, and polyamino acid type water absorbing resins such as polyglutamic acid. Particularly, a polyacrylic acid salt type water absorbing resin may be used. Furthermore, the polyacrylic acid (a salt thereof) type water absorbing resin in the present invention refers to one having total % by mole of acrylic acid and/or salts thereof in total monomer used in the polymerization (excluding crosslinking agent) essentially being 50 to 100% by mole, more preferably 70 to 100% by mole, still more preferably 90 to 100% by mole, particularly preferably 95 to 100% by mole, and most preferably substantially 100% by mole. The acrylic acid salt used in the present invention as a principal component may be, in light of the physical property and long-term stability of the gel, preferably a monovalent salt of acrylic acid selected from alkali metal salts, ammonium salts and amine salts, more preferably an alkali metal acrylic acid salt, and still more preferably, an alkali metal acrylic acid salt selected from sodium salts, lithium salts and potassium salts . A polyvalent metal salt such as a calcium salt or an aluminum salt may be used in combination in the range to provide the water-swelling property.
Neutralization ratio of the water absorbing resin obtained according to the present invention may be 20 to 99% by mole, preferably 50 to 95% by mole, and more preferably 60 to 90% by mole of the acid group. This neutralization may be carried out on the monomer component before the polymerization, or may be carried out during the polymerization or on the polymer after completing the polymerization. Furthermore, the neutralization of the monomer component and the neutralization of the polymer may be combined. It is preferred that a neutralizing treatment with an alkali, preferably a neutralizing treatment with sodium hydroxide or sodium carbonate, is carried out on acrylic acid as the monomer component .
Preferably, a polyacrylic acid (a salt thereof) cross-linked polymer obtained by polymerization and crosslinking of a monomer including acrylic acid and/or a salt thereof (neutralized product) as a principal component may be used.
Furthermore, in the present invention, the water absorbing resin used for allowing the fragrant material and cyclodextrin and/or the cyclodextrin derivative described later to be included inside of the water absorbing resin is preferably subjected to surface crosslinking for allowing the fragrant material and cyclodextrin and/or the cyclodextrin derivative to be uniformly distributed in the water absorbing resin composition. Moreover, in the present invention, the water absorbing resin used for allowing the unsaturated organic compound described later to be included inside of the water absorbing resin is preferably subjected to surface crosslinking for allowing the unsaturated organic compound to be uniformly distributed in the water absorbing resin composition. The surface crosslinking of the water absorbing resin is to provide the surface layer (on and close to the surface: usually, several 10 μm or less away from the surface) of the water absorbing resin having a uniform cross-linked structure inside of the polymer further with a part having a higher crosslinking density.
Although there exist various crosslinking agents for carrying out the surface crosslinking, in light of the physical property, a crosslinking agent which can react with a carboxyl group, generally, a polyhydric alcohol compound, an epoxy compound, a polyvalent amine compound or a condensate thereof with a haloepoxy compound, an oxazoline compound, a mono-, di-, or polyoxazolidinone compound, a polyvalent metal salt, an alkylene carbonate compound or the like may be used.
Surface crosslinking methods of them are also described in various European Patents such as European Patent Nos . 0349240, 0605150, 0450923, 0812873, 0450924 and 0668080, various Japanese Patents such as Japanese Patent Publication Nos. H7-242709 and 7-224304, various United States Patents such as United States Patent Nos. 5409771, 5597873, 5385983, 5610220, 5633316, 5674633 and 5462972, and various International Published Patents such as International Patent Publication Nos. WO99/42494, WO99/43720 and WO99/42496, which surface crosslinking methods and the water absorbing resins can be also applied to the present invention. The form of the water absorbing resin which may be used in the method of the present invention is not particularly limited, but may be in a particulate form such as irregularly crushed form or sphere, or in the form of powder, gel, sheet, rod, fiber, film or the like. In general, taking into consideration of use in sanitary goods or fragrances which are applications of the same, a particulate form or a powdery form is preferred. When the water absorbing resin is powder, the mass median particle size thereof (defined by sieve classification) is generally 100 to 50000 μm before the surface crosslinking or after the surface crosslinking. In light of persistent sustained release effect of the aromatic ingredient, the mass median particle size thereof may be preferably 100 to 20000 μm, more preferably 200 to 20000 μm, still more preferably 300 to 20000 μm, and particularly preferably 500 to 10000 μm before the surface crosslinking or after the surface crosslinking. In light of persistent sustained release effect of the aromatic ingredient, ratio of the particles having a particle diameter of less than 150 μm may be 0 to 5% by weight, more preferably 0 to 3% by weight, and particularly preferably 0 to 1% by weight before the surface crosslinking or after the surface crosslinking.
Particularly, in case of use as a fragrance, ratio of the particles having a particle diameter of less than 300 μm in the water absorbing resin may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and still more preferably 0 to 1% by weight in light of the persistence of sustained release of the aromatic ingredient. Additionally, when it is used in sanitary goods such as disposable diapers in particular, mass median particle size of the water absorbing resin may be preferably 200 μm to 850 μm, and particularly preferably 300 μm to 600 μm in light of the absorption properties. Particularly, when it is used in sanitary goods such as disposable diapers, ratio of the particles having a particle diameter of less than 150 μm in the water absorbing resin may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and particularly preferably 0 to 1% by weight in light of the absorption properties. These preferable particle size and ratio of the particles are applicable to not only the water absorbing resin but also the water absorbing resin composition.
Furthermore, as a physical property of the water absorbing resin, centrifuge retention capacity (CRC) described later may be 20 g/g to 100 g/g, and more preferably 25 to 50 g/g. Absorbency against pressure (AAP) of the water absorbing resin may be preferably 10 g/g to 60 g/g, and still more preferably 20 to 40 g/g. More specifically, as a physical property of the water absorbing resin, absorbency against pressure (absorbency under load) for a physiological saline solution (0.9% by weight aqueous sodium chloride solution) under a pressure of 20 g/cm2 may be preferably 10 to 60 (g/g) , and more preferably 20 to 40 (g/g) , while absorbency against pressure (absorbency under load) for a physiological saline solution under a pressure of 50 g/cm2 may be preferably 15 to 40 (g/g) , and more preferably 15 to 30 (g/g) . The water extractables and particle size distribution of the water absorbing resin are preferably adjusted to fall within the above range .
In the present invention, it is preferred that the fragrant material and cyclodextrin and/or the cyclodextrin derivative described later are allowed to be included inside of the water absorbing resin. To this end, regulation of crosslinking density of the water absorbing resin, i.e., regulation of swelling capacity of the water absorbing resin may be important. The regulation of the crosslinking density can be executed to some extent by controlling the polymerization conditions in synthesis of the water absorbing resin, in particular, amount of the internal crosslinking agent, monomer concentration in the polymerization and the like. In the present invention, the swelling capacity of the water absorbing resin falls within preferably of about 2 times to 400 times when the fragrant material and cyclodextrin and/or the cyclodextrin derivative are allowed to be included inside of the water absorbing resin. According to such swelling, the water absorbing resin may be turned into a polymerized gel. Such swelling may also be carried out by adding water to the water absorbing resin either before drying or after drying. When the swelling capacity of the water absorbing resin is beyond 400 times, strength of the resultant water absorbing resin composition may be deteriorated, while when the swelling capacity is below two times, there may be a case in which the fragrant material and cyclodextrin and/or the cyclodextrin derivative are not allowed to be included inside of the water absorbing resin. The swelling capacity of the water absorbing resin can be determined by dividing the weight of water absorbed in the water absorbing resin by the weight of the water absorbing resin (weight ratio) . (2) Cyclodextrin
Cyclodextrin for use in the present invention may be formed by cyclizing linkage of 6 to 10 molecules of d-glucose via α-1,4 bonds. Six d-glucose molecules bind to form one referred to as α-cyclodextrin; seven d-glucose molecules bind to form one referred to as β-cyclodextrin; eight d-glucose molecules bind to form one referred to as γ-cyclodextrin; nine d-glucose molecules bind to form one referred to as δ-cyclodextrin; and ten d-glucose molecules bind to form one referred to as ε-cyclodextrin. In the present invention, any one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin can be used. α-Cyclodextrin, β-cyclodextrin and γ-cyclodextrin are most commonly obtainable cyclodextrin. The using amount of cyclodextrin may preferably fall within the range to permit dissolution of cyclodextrin (derivative) in water together with the fragrant material ingredient after the inclusion of the fragrant material inside of cyclodextrin. In this respect, cyclodextrin can be suitably used in the range of preferably 1 to 10000 parts by mass, more preferably 1 to 1000 parts by mass, and still more preferably 1 to 500 parts by mass per 100 parts by mass of the fragrant material.
Also, cyclodextrin and/or various cyclodextrin derivatives can be used in the present invention.
Illustrative examples of such cyclodextrin derivative include e.g., hydroxymethyl cyclodextrin, hydroxyethyl cyclodextrin, hydroxypropyl cyclodextrin, hydroxybutyl cyclodextrin, dimethyl cyclodextrin, trimethyl cyclodextrin, diethyl cyclodextrin, triethyl cyclodextrin, carboxymethyl cyclodextrin, glucosyl cyclodextrin, maltosyl cyclodextrin, dimaltosyl cyclodextrin, cyclodextrin epichlorohydrin polymers and the like. In connection with the using amount of these cyclodextrin derivatives, it can be suitably used in the range of preferably 1 to 10000 parts by mass, more preferably 1 to 1000 parts by mass, and still more preferably 1 to 500 parts by mass of the cyclodextrin derivative per 100 parts by mass of the fragrant material.
In the present invention, it is preferred that the unsaturated organic compound described later is allowed to be included inside of the water absorbing resin. To this end, regulation of crosslinking density of the water absorbing resin, i.e., regulation of swelling capacity of the water absorbing resin may be important. The regulation of the crosslinking density can be executed to some extent by controlling the polymerization conditions in synthesis of the water absorbing resin, in particular, amount of the internal crosslinking agent, monomer concentration in the polymerization and the like. [Unsaturated Aliphatic Aldehyde or Unsaturated Aliphatic
Alcohol Having 6 to 10 Carbon Atoms (preferably, hexenal or hexenol) ]
The water absorbing resin composition of the present invention preferably contains unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms (more preferably 6 to 8 carbon atoms) , and still more preferably contains unsaturated aldehyde or unsaturated alcohol selected from hexenal and hexenol. According to the present invention, in light of persistence of the aroma and stability of the aroma, it is important to allow more preferably, straight-chain unsaturated aldehyde or alcohol, and more preferably, hexenal and/or hexenol to be included inside of the water absorbing resin.
Illustrative examples of hexenol (having 6 carbon atoms) which may be used in the present invention include straight-chain unsaturated alcohol such as trans-2-hexenol, cis-2-hexenol, trans-3-hexenol, cis-3-hexenol and the like. Illustrative examples of hexenal which may be used in the present invention include straight-chain unsaturated aldehyde, or branched form thereof such as trans-2-hexenal, cis-2-hexenal, trans-3-hexenal and cis-3-hexenal, and the like. Preferably, straight-chain unsaturated alcohol or straight-chain unsaturated aldehyde, and more preferably cis-3-hexenol and/or trans-2-hexenal may be used. By including such unsaturated aldehyde or alcohol inside of the water absorbing resin, persistence of the aroma is markedly improved. Accordingly, an aromatic composition that is a water absorbing resin composition with stabilized aroma, and further, with excellent good-looking appearance can be provided. Additionally, when the water absorbing resin composition of the present invention is used in sanitary goods such as diapers, a deodorizing action and an antibacterial action may be exerted to give favorable diapers.
Cis-3-hexenol which may be used in the present invention is otherwise referred to as leaf alcohol, which is included in leaves, and is an aromatic component which reportedly participates in a green note. Further, trans-2-hexenal is otherwise referred to as leaf aldehyde, which is a compound reportedly being a source of a phytogenic young green note and also exhibiting an antibacterial action. Such cis-3-hexenol and/or trans-2-hexenal may be obtained by synthesis, or may be obtained from a natural source. Additionally, cis-3-hexenol and/or trans-2-hexenal may be single compound, a compound containing these as naturally occurring products, or a mixed extract . When cis-3-hexenol and/or trans-2-hexenal are used as a mixture, the weight ratio falls in the range of preferably 1/99 to 99/1, and more preferably 20/80 to 80/20. [Other Ingredient]
In the water absorbing resin composition of the present invention, cyclodextrin and/or the cyclodextrin derivative is used, and in place of the unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms, other ingredient, particularly a fragrant material ingredient may be also added. Preferably, in the water absorbing resin composition of the present invention, cyclodextrin and/or the cyclodextrin derivative is used, and in combination with the unsaturated aliphatic aldehyde or unsaturated aliphatic alcohol having 6 to 10 carbon atoms, other ingredient, particularly a fragrant material ingredient may be also added. [Fragrant Material]
The fragrant material refers to an additive that is added for imparting or enhancing an aromatic odor, and the preparation thereof.
The fragrant material which can be used in the present invention may be any various ones such as naturally occurring fragrant materials, synthetic fragrant materials and compound fragrant materials as long as they are volatile and can emit a fragrant odor at an ordinary temperature.
As the ^naturally occurring fragrant material, any one of animal fragrant materials and plant fragrant materials can be used. Examples of the animal fragrant material include e.g., musk, ambergris, civet, castoreum and the like. Examples of the plant fragrant material include e.g. , fragrant materials obtained from flower such as rose, jasmine, orange flower, violet or the like, and fragrant materials obtained from fruit skin, leaf, root, bud, bark or trunk of lemon, rosemary, iris, cinnamon or the like, and the like.
The fragrant material for use in the present invention may be, for example, the following compound. (Fragrant Material of Alcohols)
Hydrocarbons such as cinnamic alcohol, α-pinene, camphene, limonene, myrcene and cadinene; alcohols such as anise alcohol, geraniol, citronellol, cinnamyl alcohol, phenylethyl alcohol, petipenol, menthol, benzyl alcohol and linalool.
(Fragrant Material of Aldehydes)
Aldehydes such as 3, 7-dimethyl-l-octanal, 4 (3)- ( 4-hydroxy-4-methylpentyl) -3-cyclohexene-l-carboxyaldehyde , 4-methylphenyl acetaldehyde, 3-methyl-5-phenyl pentanal, methoxydicyclopentadiene carboxyaldehyde, trimethyIcyclohexene carboxyaldehyde, octahydro-8, 8-dimethyl-2-naphthalene carboxyaldehyde, 3- (3-isopropylphenyl) butanal, p-ethyl-α,α-dimethylhydrocinnamaldehyde, salicyl aldehyde, anise aldehyde, α-amyl cinnamaldehyde, oxycitronellal, citral, citronellal, cyclamen aldehyde, paniline, phenyl acetaldehyde and piperonal.
(Fragrant Material of Ketones)
Ketones such as irone, carvone, cycloheptadecanone, jasmon, cipetone, benzylidene acetone, muscone and α-ionone. (Fragrant Material of Esters)
Esters such as ethyl benzoate, ethyl acetate, geranyl acetate, linalyl acetate and methyl salicylate.
(Fragrant Material of Ethers) Phenol ethers such as anisole, anethole, eugenol, safrole, diphenyl oxide and neroline.
(Fragrant Material of Acids)
' Lactones such as coumarin, ambrettolide, exaltolide and coumarin; quinones such as p-oxyanisole and hydroquinone dimethyl ether; acids such as anisic acid, cinnamic acid, citronellic acid and phenylacetic acid.
In addition to the aforementioned fragrant materials, any of the fragrant materials described in, for example, "Perfume and Flavor Chemicals Vol. 1 and Vol. 2; Steffen Arctander Allured Pub. Co., 1994", "Gosei Koryo (Synthetic Fragrant Materials) , Kagaku to Shohin Chishiki (Chemistry and Knowledge on Commercial Products) ; written by Motoichi Indo, Pub. Kagaku Kogyo Nippo, 1996", "Perfume and Flavor Materials of Natural Origin; Steffen Arctander Allured Pub. Co. 1994" and "Kaori-no Hyakka (Various Subjects on Aroma); Japan
Perfumery and Flavoring Assoc. , Asakura Publishing Co. , Ltd. , 1989" and the like can be used.
As the aforementioned naturally occurring fragrant material and synthetic fragrant material, cis-3-hexenol and/or trans-2-hexenal can be used each alone, but two or more thereof may be compounded to prepare a desired fragrance. Additionally, as the aforementioned naturally occurring fragrant material and synthetic fragrant material, at least one fragrant1 material may be further compounded in addition to cis-3-hexenol and/or trans-2-hexenal to produce a desired aroma. Examples of the compounded flavor include floral type, oriental type, sibley type, natural type, citrus type, fusea type and the like.
In light of ease in including cyclodextrin or the cyclodextrin derivative, and in light of sustained releasing property of the aromatic ingredient, an oil soluble fragrant material is preferred among the aforementioned fragrant materials. In this respect, solubility of the fragrant material in water is preferably not less than 0 but not greater than 10, more preferably not less than 0 but not greater than 7, and most preferably not less than 0 but not greater than 5. This solubility means the amount (g) of dissolution per 100 g of ion exchanged water at 200C. When the solubility of the used fragrant material in water is so high and the fragrant material is hydrophilic, interaction with the water absorbing resin is increased. Therefore, sustained release property of the aromatic ingredient may be apt to be reduced. Moreover, the fragrant material for use in the present invention may be preferably liquid at an ordinary temperature (20 to 25°C) . The melting point of the fragrant material may be preferably not higher than 200C, more preferably not higher than 100C, and particularly preferably not higher than 00C . The boiling point of the fragrant material may be preferably not lower than 800C, more preferably not lower than 1000C, and still more preferably not lower than 120°C . The fragrant material which is not liquid at an ordinary temperature but, for example, is solid or crystal at an ordinary temperature is not preferred for use in the present invention because it is not uniformly integrated or complexed with the water absorbing resin. Among the aforementioned oil soluble fragrant materials, unsaturated aldehyde having 6 to 10 carbon atoms or unsaturated alcohol having 6 to 10 carbon atoms is preferred, and hexenal or hexenol is more preferred.
[Water Absorbing Resin Composition and Method for Production Thereof]
In the water absorbing resin composition according to the present invention, a fragrant material and cyclodextrin and/or a cyclodextrin derivative are preferably included inside of the water absorbing resin in light of persistence of the aroma and stability of the fragrant material. In the present invention, as for the inclusion inside of the water absorbing resin, it is not necessary to be present uniformly inside, but it is permissible that they are integrated or complexed with the water absorbing resin. For example, they may be included in a micro domain (sea-island state) in the water absorbing resin or included on the surface, or alternatively, may be clathrated inside thereof.
The present inventors found that by allowing the fragrant material and cyclodextrin and/or the cyclodextrin derivative to be included inside of the water absorbing resin, sanitary goods or fragrances with markedly improved persistence of the aroma and with stabilized fragrant material, which are further accompanied by excellent good-looking appearance can be provided. Although the water absorbing resin generally has a three-dimensional network structure, inclusion of the fragrant material and cyclodextrin and/or the cyclodextrin derivative inside of the water absorbing resin was first enabled by controlling the size of the network to be larger than the size of the cyclodextrin and/or the cyclodextrin derivative. In the method for allowing the fragrant material and cyclodextrin and/or the cyclodextrin derivative to be included inside of the water absorbing resin, the compound described above can be added in the production step of the water absorbing resin, or may be added to the water absorbing resin following the production. For example, the following methods (A) to (F) can be illustrated, but not limited thereto:
(A) a method in which the fragrant material is previously mixed with cyclodextrin and/or the cyclodextrin derivative, and an aqueous solution is prepared from the resulting mixture, which aqueous solution is allowed to be absorbed to the water absorbing resin;
(B) a method in which the fragrant material is previously mixed with cyclodextrin and/or the cyclodextrin derivative, and an aqueous solution is prepared from the resulting mixture, which aqueous solution is allowed to be absorbed to the water absorbing resin, followed by drying;
(C) a method in which the fragrant material is added to cyclodextrin and/or the cyclodextrin derivative dissolved in water and mixed to obtain an aqueous solution, and the resulting aqueous solution is allowed to be absorbed to the water absorbing resin;
(D) a method in which the fragrant material is added to cyclodextrin and/or the cyclodextrin derivative dissolved in water and mixed to obtain an aqueous solution, and the resulting aqueous solution is allowed to be absorbed to the water absorbing resin, followed by drying;
(E) a method in which the fragrant material and cyclodextrin and/or the cyclodextrin derivative are added to a monomer or a polymerized gel in the polymerization step of the water absorbing resin;
(F) a method in which the fragrant material and cyclodextrin and/or the cyclodextrin derivative are added in the surface crosslinking step, agglomerating step or the like of the water absorbing resin.
In light of stability of the fragrant material and persistence of the odor, the resulting water absorbing resin composition is preferably gelatinous (hydro gel form) . In light of ease of manipulation and energy efficiency, the method (A) or (B) is preferred among the aforementioned methods . In case of the method (A) or (B) , the water absorbing resin composition of the present invention can be produced with an excellent efficiency without evaporation of the fragrant material during the production. When the water absorbing resin composition of the present invention is used in sanitary goods, the water absorbing resin composition is preferably in a powder form in light of processibility and water absorption capacity of the diaper. When the water absorbing resin composition of the present invention is used in sanitary goods, the aforementioned method (D) is preferred. Moreover, the size and form of the resulting water absorbing resin composition may be determined ad libitum depending on the intended use. [Composition Ratio] In the water absorbing resin composition of the present invention, compounding ratio of the fragrant material and the water absorbing resin can be selected ad libitum depending on the intended aromatic performance, however, the amount of the water absorbing resin may be usually 1 to 100000 parts by mass, more preferably 1 to 10000 parts by mass, and still more preferably 10 to 10000 parts by mass per 100 parts by mass of the fragrant material. Also, the amount of the water absorbing resin may be preferably 1 to 10000 parts by mass, and more preferably 1 to 1000 parts by mass per 100 parts by mass of total amount of the cyclodextrin including the fragrant material, the cyclodextrin derivative including the fragrant material, the unsaturated aliphatic aldehyde and unsaturated aliphatic alcohol. Furthermore, the amount of the water absorbing resin is preferably 1 to 10000 parts by mass, and more preferably 1 to 1000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic aldehyde and the unsaturated aliphatic alcohol.
The water absorbing resin composition of the present invention can be also used in a dry state. In the dry state, the solvent, water, is substantially free (moisture content being not higher than 20%) to give a solid state. However, in case of use as a fragrance, it is preferably used in a water based gelatinous state in light of the aromatic function thereof. The water based gelatinous state refers to a form in which an aqueous liquid is incorporated into the three-dimensional network of the water absorbing resin, which is an aqueous system having a solid-like appearance. This aqueous liquid may be water alone and/or a mixture of water and a hydrophilic organic solvent such as ethanol, including preferably 50 to 100% by weight of water, more preferably 70 to 100% by weight of water, and particularly preferably 90 to 100% by weight of water. To the contrary, when it is used in sanitary goods including absorbing articles such as diapers, the water absorbing resin composition of the present invention is preferably used in a dry state in light of the absorption capacity, usability and the like.
When the water absorbing resin composition of the present invention is in a water based gelatinous state, the amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the fragrant material, cyclodextrin and/or the cyclodextrin derivative and the water absorbing resin. The amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the cyclodextrin including the fragrant material, the cyclodextrin derivative including the fragrant material, the unsaturated aliphatic aldehyde, the unsaturated aliphatic alcohol and the water absorbing resin. The amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic aldehyde, the unsaturated aliphatic alcohol and the water absorbing resin. When the amount of the aqueous liquid is beyond 50000 parts by mass, the strength of the water absorbing resin composition may be insufficient, and may result in impossibility of retaining the gelatinous state to lead to failure in application to practical use. [Other Ingredient]
The water absorbing resin or water absorbing resin composition according to the present invention described above may further include other ingredient as needed in an amount of 0 to 20% by weight, and preferably 0 to 5% by weight. Examples of the other ingredient include antimicrobials, foaming agents, pigments, dyes, plasticizers, adhesives, surfactants, fertilizers, oxidizing agents, reducing agents, water, salts, chelating agents (preferably, aminocarboxylic acid) , bacteriocides, hydrophilic polymers such as polyethylene glycol and polyethylene imine, hydrophobic polymers such as paraffin, thermoplastic resins such as polyethylene and polypropylene, thermosetting resins such as polyester resins and urea resins, and the like. The method for producing the water absorbing resin or water absorbing resin composition according to the present invention may include a step of imparting a variety of functions such as a step of adding these other ingredients or the like. [Method for Producing Water Absorbing Resin Composition] In the method for allowing the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde to be included inside of the water absorbing resin, the compound described above can be added in the production step of the water absorbing resin or can be added to the water absorbing resin following the production step, with or without using cyclodextrin and/or the derivative thereof. In the present invention, the case in which the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde is present inside of the water absorbing resin may also involve the case in which cyclodextrin and/or the derivative thereof is present as well as the case in which cyclodextrin and/or the derivative thereof is not present. Moreover, in the present invention, the case in which the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde is present inside of the water absorbing resin is not limited to the case in which it is uniformly present inside, but also include the case in which it is integrated or complexed with the water absorbing resin. For example, the unsaturated aliphatic alcohol and/or unsaturated aliphatic aldehyde may be included in a micro domain (sea-island state) in the water absorbing resin or included on the surface of the water absorbing resin, or alternatively, may be clathrated inside of the water absorbing resin.
The present inventors found that by allowing the unsaturated organic compound (alcohol and aldehyde) to be included inside of the water absorbing resin, sanitary goods or fragrances with markedly improved persistence of the aroma and with stabilized fragrant material, which are further accompanied by excellent good-looking appearance can be provided. Although the water absorbing resin generally has a three-dimensional network structure, inclusion of the unsaturated organic compound inside of the water absorbing resin was first enabled by controlling the size of the network to be larger than the size of the unsaturated organic compound. As the method for allowing the unsaturated organic compound (alcohol and aldehyde) to be included inside of the water absorbing resin, for example, the following methods (Al) to (Dl) may be illustrated, but not limited thereto:
(Al) a method in which an aqueous liquid is prepared from the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde, and the aqueous liquid is allowed to be absorbed to the water absorbing resin. This aqueous liquid may include water and a hydrophilic organic solvent such as, e.g., ethanol;
(Bl) a method in which the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde is mixed with a water soluble polymer such as cyclodextrin, and an aqueous liquid is prepared from this mixture, followed by allowing the aqueous liquid to be absorbed to the water absorbing resin.
(Cl) a method in which the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde is added to a monomer or a polymerized gel in the polymerization step of the water absorbing resin;
(Dl) a method in which the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde is added in the surface crosslinking step, the agglomerating step or the like of the water absorbing resin.
When the water absorbing resin composition of the present invention is used as a fragrance, the resultant composition is preferably gelatinous (hydro gel form) in light of stability of the fragrant material and persistence of the odor. In light of ease of manipulation and energy efficiency, the method (Al) or (Bl) is preferred among the aforementioned methods. When the water absorbing resin composition of the present invention is used in sanitary goods, it is preferably in a powder form in light of processibility and water absorption capacity of the diaper, and the aforementioned method (Dl) is preferably employed. Also, the size and form of the resulting water absorbing resin composition may be determined ad libitum depending on the intended use. [Composition Ratio]
In the water absorbing resin composition of the present invention, compounding ratio of the unsaturated aliphatic alcohol and unsaturated aliphatic aldehyde, and the water absorbing resin can be selected ad libitum depending on the intended aromatic performance, however, the amount of the water absorbing resin may be 1 to 100000 parts by mass, more preferably 1 to 10000 parts by mass, and still more preferably 10 to 10000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic alcohol and unsaturated aliphatic aldehyde.
The water absorbing resin, in case of use as a fragrance, is preferably used in a water based gelatinous state in light of the aromatic function thereof. The water based gelatinous state and the aqueous liquid are as described above. When the water absorbing resin composition of the present invention is in a water based gelatinous state, the amount of the aqueous liquid incorporated into the three-dimensional network may be preferably 200 to 50000 parts by mass, and more preferably 500 to 10000 parts by mass per 100 parts by mass of total amount of the unsaturated aliphatic alcohol or unsaturated aliphatic aldehyde and the water absorbing resin. When the amount of the aqueous liquid is beyond 50000 parts by mass, the strength of the water absorbing resin composition may be insufficient, and may result in impossibility of retaining the gelatinous state to lead to failure in application to practical use. [Form and the Like of Water Absorbing Resin Composition]
The water absorbing resin composition of the present invention produced by the aforementioned method for the production referred to by way of example may be either gelatinous (for example, state of the moisture content beyond 20%, particularly 50 to 99.999%), or a dried matter (for example, moisture content being not higher than 20%) . In case of being the dried matter, the water absorbing resin composition of the present invention has a particulate form, and for example, has a centrifuge retention capacity (CRC) described later of preferably 20 g/g to 100 g/g and more preferably 25 to 50 g/g, and an absorbency under load (absorbency against pressure: AAP) of preferably 10 to 60 g/g and more preferably 20 to 40 g/g. In particular, when the water absorbing resin composition of the present invention is used in sanitary goods such as absorbing articles, absorbency against pressure (absorbency under load) for a physiological saline solution (0.9% by weight aqueous sodium chloride solution) under a pressure of 20 g/cm2 may be preferably 20 g/g to 40 g/g, while absorbency against pressure (absorbency under load) for a physiological saline solution under a pressure of 50 g/cm2 may be preferably 15 g/g to 40 g/g, in light of absorption properties desired for sanitary goods. The water extractables and particle size distribution may be adjusted to fall within the above range.
The form of the water absorbing resin composition of the present invention is not particularly limited, but may be in a particulate form such as irregularly crushed form or sphere, or in the form of powder, gel, sheet, rod, fiber, film or the like. The water absorbing resin composition described later has a mass median particle size of 100 to 50000 μm. In light of persistent sustained release effect of the aromatic ingredient, the water absorbing resin composition described later may be particles or powder having a mass median particle size of preferably 100 to 20000 μm, more preferably 200 to 20000 μm, still more preferably 300 to 20000 μm and particularly preferably 500 to 10000 μm, or gelling material of the same. In this water absorbing resin composition, ratio of the particles having a particle diameter of less than 150 μm may 17
32
be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and particularly preferably 0 to 1% by weight.
Particularly, in case of the use as a fragrance, ratio of the particles having a particle diameter of less than 300 μm in the water absorbing resin composition may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and still more preferably 0 to 1% by weight in light of the persistence of sustained release of the aromatic ingredient. Additionally, when it is used in sanitary goods such as disposable diapers in particular, mass median particle size of the water absorbing resin composition may be preferably 200 μm to 850 μm, and particularly preferably 300 μm to 600 μm in light of the absorption properties. Particularly, when it is used in sanitary goods such as disposable diapers, ratio of the particles having a particle diameter of less than 150 μm in the water absorbing resin composition may be preferably 0 to 5% by weight, more preferably 0 to 3% by weight, and particularly preferably 0 to 1% by weight in light of the absorption properties. (8) Application
The water absorbing resin composition of the present invention provides sanitary goods and fragrances exhibiting a persistent effect of the aroma for a long period of time, being excellent in stability of the color, having excellent gel stability and good-looking appearance of the composition, with high industrial productivity. Furthermore, when the water absorbing resin composition of the present invention (particularly, particulate form water absorbing resin composition) is used in sanitary goods such as diapers and feminine protection products, favorable deodorization effect and durability (preventive property of gel deterioration) may be exhibited. Moreover, the water absorbing resin composition of the present invention provides sanitary goods and fragrances that are excellent in persistence of the aroma and stability of the aroma, and effective in relieving fatigue and stress. Still further, because the water absorbing resin composition of the present invention also has a masking effect and an antibacterial effect resulting from the fragrant material ingredient, it can be also used as a deodorizing antimicrobial agent, which can be utilized, for example, as a fragrance or deodorant for use in rooms and cars as well as sanitary goods. In addition, when the water absorbing resin composition of the present invention (particularly, particulate water absorbing resin composition) is used in sanitary goods such as diapers, favorable deodorization effect, antibacterial effect and durability (preventive property of gel deterioration) may be exhibited, and characteristics excellent in stability of the color in white powder for a long period of time may be shown. In particular, when the water absorbing resin composition of the present invention is used in a sanitary goods application, an absorbent core (formed product) can be obtained by forming together with other arbitrary material such as a hydrophilic fiber. Form of the absorbent core is not particularly limited, but may be processed preferably into the sheet-like, cylindrical, film-like or fibrous form, particularly preferably into the sheet-like form (may be also referred to as web form) . The absorbent core can be obtained by thus processing into such a form.
The hydrophilic fiber which can be used in the present invention is not particularly limited, but illustrative examples include e.g., ground wood pulp, cotton linters, as well as crosslinked cellulosic fibers, rayon, cotton, wool, acetate, vinylon and the like, which may be preferably airlied. When the absorbent core according to the present invention is an absorbent core including the particulate water absorbing agent and the hydrophilic fiber, content of the particulate water absorbing agent (hereinafter, may be also referred to as core concentration) based on total weight of the particulate water absorbing agent and the hydrophilic fiber falls within preferably the range of 20 to 100% by weight, more preferably the range of 25 to 90% by weight, and still more preferably the range of 30 to 80% by weight. Such absorbent core is preferably subjected to formation under compression to give the density in the range of 0.001 to 0.50 g/cc, and the weighing capacity in the range of 0.01 to 0.20 g/cm2. Moreover, the absorbing article in which the water absorbing resin of the present invention is used (final consumer goods) is equipped with the aforementioned absorbent core of the present invention, a surface sheet with liquid permeability and a back sheet with liquid impermeability. Although the method for the production of the absorbing article according to the present invention is not particularly limited, but for example, any one of production methods can be adopted in which the absorbing article such as a disposable diaper or a sanitary napkin is obtained by sandwiching the absorbent core between a substrate with liquid permeability (the surface sheet) and a substrate with liquid impermeability (the back sheet) , and 'mounting an elastic part, a diffusion layer, a pressure sensitive adhesive tape and the like as needed. 14717
35
[Examples]
The water absorbing resin composition of the present invention will be explained in more detail by way of Examples, however, the present invention is not any how limited by the following description. Any of the unit "%" represents % by mass (% by weight) unless otherwise stated, and any of the unit "part" represents part by mass (part by weight) unless otherwise stated.
(1) Centrifuge Retention Capacity (GVs/Gel Volume Saline)
A water absorbing resin in an amount of 0.2 g was uniformly put in a bag (60 mm x 60 mm) made of unwoven fabric and sealed. The bag was immersed in 100 g of a 0.9% aqueous sodium chloride solution at 25 (± 3) 0C. The bag was taken out of the solution 24 hours later, subjected to dewatering for 3 minutes at 250 G using a centrifuge, and then measured the weight Wl of the bag made of unwoven fabric. Weight W2 of the bag was measured after conducting similar operation without using any water absorbing resin. Absorption capacity was then calculated from the weight Wl and weight W2 according to the formula 1. When sampling of 0.2 g cannot be conducted due to the form or size of the water absorbing resin composition, the measurement may be performed after arbitrarily crushing to allow for the sampling of 0.2 g. Formula 1: GVs = (Wl-W2)/0.2 - 1
(2) Amount of Water Soluble Polymer (may be also referred to as extractable polymer content, and extractables)
A 0.90% by weight aqueous sodium chloride solution (physiological saline solution) was weighed to put 184.3 g in a plastic vessel with a lid having a capacity of 250 ml. Into the aqueous solution was added 1.00 g of the water absorbing resin, and extractables in the resin were extracted by stirring the mixture for 24 hours. The extracted liquid was filtrated with one sheet of filter paper (Advantec Toyo Kaisha, Ltd., trade name: (JIS P 3801, No. 2) , thickness: 0.26 mm, retaining particle size: 5 μm) , and 50.0 g of thus resulting filtrate was weighed to give a solution for the measurement.
First, the physiological saline solution alone was titrated with a 0.1 N aqueous NaOH solution to the pH of 10 and thereafter titrated with a 0.1 N aqueous HCl solution to the pH of 2.7 to thereby determine blank titers ( [bNaOH] ml,
[bHCl] ml) . The titers ( [NaOH] ml, [HCl] ml) were determined by carrying out a similar titration operation on the solution for the measurement. For example, in case of the water absorbing resin containing a known amount of acrylic acid and a sodium salt thereof, extractables ratio of the water absorbing resin can be calculated by the following formula 2 based on the average molecular weight of the monomers and the titers determined by the aforementioned operation. In case of the unknown amount, the average molecular weight of the monomer may be calculated using a neutralization ratio determined by the titration. The extractables thus extracted contain the extracted water soluble polymer as a principal component . Formula 2:
Extractables ratio (% by weight) = 0.1 x (average molecular weight) x 184.3 x 100 * ([HCl] - [bHCl])/ 1000/ 1.0/ 50.0
Formula 3 : Neutralization ratio (mol%) = (1- ([NaOH] - [bNaOH] ) / ([HCl] - [bHCl])) x 100 (3) Mass Median Particle Size (D50)
The water absorbing resin powder or the water absorbing resin composition was subjected to sieve classification using JIS standard sieves having a mesh opening size of 53 mm, 45 mm, 31.5 mm, 22.4 mm, 11.3 mm, 8 mm, 5.6 mm, 4 mm, 2.8 mm, 1.4 mm, 1 mm, 850 μm, 710 μm, 600 μm, 500 μm, 425 μm, 300 μm, 212 μm, 150 μm, 106 μm, 75 μm and the like (JIS Z8801-1 (2000) or equivalents thereof) , and the residual percentages were plotted on a logarithmic probability paper. Accordingly, the mass median particle size (D50) was read.
The sieve classification was carried out by charging 10 g of the water absorbing resin under the conditions at the room temperature (20 to 25°C) and relative humidity of 50 ± 5% RH in the aforementioned JIS standard sieve (The IIDA TESTING SIEVE: internal diameter : 80 mm) and conducting classification using a Ro-Tap sieve shaker (manufactured by Iida-seisakusho Japan Corporation, ES-65 sieve shaker) for 10 minutes. The mass median particle size (D50) is, as described in United States Patent No. 5051259 and the like, the particle diameter of the particles left on the standard sieve corresponding to 50% by weight of the entire particles among the standard sieves having a certain mesh opening size. Furthermore, in addition to the standard sieves having the aforementioned mesh opening size, any standard sieve described in JIS Z8801-1 may be arbitrarily selected for the measurement. [Absorbency Against Pressure]
According to United States Patent No. 6444744, absorbency against pressure for a physiological saline solution (0.9% by weight aqueous sodium chloride solution) under a pressure of 20 g/cm2 (0.3 psi) and a pressure of 50 g/cm2 (0.7 psi) was measured. (Reference Example 1)
To an aqueous monomer solution containing 340.6 parts of a 37% by weight aqueous sodium acrylate solution, 39.5 parts of acrylic acid, 1 part of a 10% aqueous polyethylene glycol diacrylate solution and 33.8 parts of ion exchanged water were added 1.9 parts of a 1% hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184; manufactured by Ciba Specialty Chemicals) solution in acrylic acid and 1.9 parts of a 3% aqueous sodium persulfate solution in a nitrogen atmosphere. Thereto was irradiated an ultraviolet ray in the state of the aqueous solution temperature being 5°C to execute the polymerization. After completing the polymerization, thus resulting hydro gel polymer (1) was crushed, and dried in a hot-air dryer at 120°C to obtain a water absorbing resin (1) . The water absorbing resin (1) had an mass median particle size of 1500 μm, and a ratio of the particles having a particle diameter of less than
150 μm of 0.1% by weight. Additionally, GVs (g/g) and extractables ratio (%) of the water absorbing resin (1) were 32 (g/g) and 7% by weight, respectively. (Reference Example 2)
To an aqueous monomer solution containing 340.6 parts of a 37% aqueous sodium acrylate solution, 39.5 parts of acrylic acid, 1 part of a 10% aqueous polyethylene glycol diacrylate solution and 33.8 parts of ion exchanged water were added 1.9 parts of a 1% hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184; manufactured by Ciba Specialty Chemicals) solution in acrylic acid and 1.9 parts of a 3% aqueous sodium persulfate solution in a nitrogen atmosphere. Thereto was irradiated an ultraviolet ray in the state of the aqueous solution temperature being 22°C to execute the polymerization. After completing the polymerization, thus resulting hydro gel polymer (2) was crushed, and dried in a hot-air dryer at 120°C to obtain a water absorbing resin (2). The water absorbing resin (2) had an mass median particle size of 1000 μm. In the water absorbing resin (2), ratio of the particles having a particle diameter of less than 150 μm was 0.1% by weight. Additionally, GVs (g/g) and extractables ratio (%) of the water absorbing resin (2) were 37 (g/g) and 9% by weight, respectively.
(Reference Example 3)
Polymerization of 400 parts of an aqueous monomer solution having a concentration of 39% which contains 74.5% by mole of sodium acrylate, 25% by mole of acrylic acid and 0.5% by mole of methylene bisacrylamide was carried out in a nitrogen atmosphere using 0.54 parts of sodium persulfate and 0.03 parts of L-ascorbic acid. A hydro gel polymer (3) obtained by this polymerization was finely crushed, and dried in a 180°C hot-air dryer. Thus resulting dried matter was pulverized with a pulverizer, and fractionated the matter that passes through a JIS standard sieve of 850 μm to obtain a water absorbing resin (3). The water absorbing resin (3) had an mass median particle size of 2000 μm. In the water absorbing resin (3) , ratio of the particles having a particle diameter of less than 150 μm was 0.5% by weight. Additionally, GVs (g/g) and extractables ratio (%) of the water absorbing resin (3) were 40 (g/g) and 9% by weight, respectively. (Example 1)
An aqueous solution containing 1.5 parts of a fragrant material (1) including 10% cis-3-hexenol, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 47 parts of ion exchanged water was produced. To this aqueous solution was added 1 part of the water absorbing resin (1) to obtain the water absorbing resin composition (1) of the present invention. The water absorbing resin composition (1) is a gelatinous composition. (Example 2) An aqueous solution containing 1 part of the fragrant material (1) including 10% cis-3-hexenol, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, and 180 parts of ion exchanged water was produced. To this aqueous solution was added 4.5 parts of the water absorbing resin (2) to obtain the water absorbing resin composition (2) of the present invention. The water absorbing resin composition (2) is a gelatinous composition. (Example 3)
An aqueous solution containing 1.5 parts of the fragrant material (1) including 10% cis-3-hexenol, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.0001 parts of Food Yellow No. 4 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 47 parts of ion exchanged water was produced. To this aqueous solution was added 1 part of the water absorbing resin (3) to obtain the water absorbing resin composition (3) of the present invention. The water absorbing resin composition (3) is a gelatinous composition. (Example 4) In a similar manner to Example 1 except that cis-3-hexenol was changed into trans-2-hexenal, the water absorbing resin composition (4) of the present invention was obtained. The water absorbing resin composition (4) is a gelatinous composition. (Example 5)
In a similar manner to Example 1 except that the fragrant material (1) was changed into a fragrant material including 5% cis-3-hexenol, 5% trans-2-hexenal, 15% citric acid triethyl ester and 75% ethyl alcohol as ingredients, the water absorbing resin composition (5) of the present invention was obtained. The water absorbing resin composition (5) is a gelatinous composition.
(Comparative Example 1)
In a similar manner to Example 1 except that cis-3-hexenol was not used, the comparative water absorbing resin composition (1) of the present invention was obtained. The comparative water absorbing resin composition (1) is a gelatinous composition.
(Comparative Example 2) In a similar manner to Example 1 except that the water absorbing resin (1) was not used, the comparative composition (2) of the present invention was obtained. (Example 6)
A water absorbing resin composition (6) was obtained by adding 1.5 parts of cis-3-hexenol to 100 parts of the water absorbing resin (1) followed by mixing. The water absorbing resin composition (6) is a powdery composition. (Evaluation 1)
The water absorbing resin compositions (1) to (5) in an amount of 20 g were each placed in a 500-ml glass beaker, and left to stand at room temperature. One month later, the weight of the aromatic compositions decreased by nearly half. However, they were still in a transparent gelatinous state without deposition onto the vessel, and also the aroma was maintained.
(Evaluation 2)
A test similar to Evaluation 1 was performed on the comparative water absorbing resin composition (1) and the comparative composition (2) . Accordingly, no aroma was left at all.
Specifications of the water absorbing resin compositions (1) to (6), the comparative water absorbing resin composition (1) and comparative composition (2) are shown in Table 1 below.
Table 1 Specifications of Water Absorbing Resin Composition, Comparative Water Absorbing Resin Composition and Comparative Composition
Composition Form Unsaturated organic Amount Water absorbing resin Amount Amount compound (parts by (parts by (parts by weight) weight) weight)
Water absorbing resin
Water absorbing resin composition (1) Blue gel cis-3-hexenol 0.15 1 Water 47 (D
Water absorbing resin
Water absorbing resin composition (2) Blue gel cis-3-hexenol 0.1 4.5 Water 180 (2)
Water absorbing resin
Water absorbing resin composition (3) Blue gel cis-3-hexenol 0.15 1 Water 47 (3)
Water absorbing resin
Water absorbing resin composition (4) Blue gel trans-2-hexenal 0.15 1 Water 47 (D
Water absorbing resin
Water absorbing resin composition (5) Blue gel cis-3-hexenol 0.075 1 Water 47 (D & trans-3-hexenal 0.075
Water absorbing resin
Water absorbing resin composition (6) Powder cis-3-hexenol 0.015 1 Water 0 (1)
Comparative water absorbing resin Water absorbing resin
Blue gel None 0 1 Water 47 composition (1) (D
Comparative composition (2) Blue liquid cis-3-hexenol 0.15 None 0 Water 47
(Example 7 )
An aqueous solution containing 1 part of the fragrant material (1) including 10% cis-3-hexenol, 15% triethyl citrate and 75% ethyl alcohol as ingredients, 2 parts of α-cyclodextrin and 180 parts of pure water was produced. To this aqueous solution was added 4.5 parts of the water absorbing resin (2) obtained in Reference Example 2 to obtain the water absorbing resin composition (7) of the present invention. The water absorbing resin composition (7) is a gelatinous composition. (Comparative Example 3)
In a similar manner to Example 7 except that the water absorbing resin was not added, a comparative composition (3) was obtained.
(Example 8) An aqueous solution containing 1.5 parts of the fragrant material (1) including 10% cis-3-hexenol, 15% triethyl citrate and 75% ethyl alcohol as ingredients, 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.2 parts of α-cyclodextrin and 47 parts of pure water was produced. To this aqueous solution was added 1 part of the water absorbing resin (1) obtained in Reference Example 1 to obtain the water absorbing resin composition (8) of the present invention. The water absorbing resin composition (8) is a gelatinous composition. (Example 9)
An aqueous solution containing 0.1 parts of citral A (manufactured by Takasago International Corporation), 0.2 parts of α-cyclodextrin and 100 parts of pure water was produced. To this aqueous solution was added 1 part of the water absorbing resin (2) to obtain the water absorbing resin composition (9) of the present invention. The water absorbing resin composition (9) is a gelatinous composition. (Comparative Example 4)
In a similar manner to Example 9 except that polyoxyethylene sorbitan monolaurate was used in place of α-cyclodextrin, a comparative composition (4) was obtained. The comparative composition (4) was apparently in a white turbid state. The comparative composition (4) is a gelatinous composition. (Example 10)
An aqueous solution containing 1.5 parts of the fragrant material (1) including 10% cis-3-hexenol, 15% triethyl citrate and 75% ethyl alcohol as ingredients, 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.0001 parts of Food Yellow No. 4 (manufactured by Tokyo
Chemical Industry Co., Ltd.), 0.2 parts of β-cyclodextrin and 47 parts of pure water was produced. To this aqueous solution was added 1 part of the water absorbing resin (3) obtained in Reference Example 3 to obtain the water absorbing resin composition (10) of the present invention. The water absorbing resin composition (10) is a gelatinous composition. (Example 11)
In a similar manner to example 7 except that cis-3-hexenol was changed into trans-2-hexenal, a water absorbing resin composition (11) was obtained. The water absorbing resin composition (11) is a gelatinous composition. (Reference Example 4)
The hydro gel polymer (1) obtained in Reference Example
1 was crushed, and subjected to hot-air drying at 18O0C to obtain a dried matter. Then, this dried matter was pulverized with a roll mill, and further classified with JIS standard sieves having a mesh opening size of 850 μm and a mesh opening size of 150 μm to obtain an irregularly crushed water absorbing resin (4) having a mass median particle size of 400 μm. The water absorbing resin (4) exhibited GVs (g/g) of 33 (g/g) . The extractables ratio (%) of the water absorbing resin (4) was 7% by weight. Absorbency against pressure of the water absorbing resin (4) for a physiological saline solution under a condition of the pressure being 20 g/cm2 was 7 (g/g) . Absorbency against pressure of the water absorbing resin (4) for a physiological saline solution under a condition of the pressure being 50 g/cm2 was 5 (g/g) . (Reference Example 5) A surface treatment agent composed of a mixed liquid of 0.4 parts by mass of 1, 4-butanediol, 0.6 parts by mass of propylene glycol and 3.0 parts by mass of pure water was homogenously mixed with 100 parts by mass of the water absorbing resin (4) obtained in Reference Example 4. This mixture was subjected to a heat treatment at 200°C for 30 minutes. A water absorbing resin (5) was obtained by pulverizing the particles thus subjected to the heat treatment into the particles that pass through a JIS standard sieve having a mesh opening size of 850 μm. The water absorbing resin (5) exhibited GVs (g/g) of 24 (g/g). The extractables ratio (%) of the water absorbing resin (4) was 7% by weight. Absorbency against pressure of the water absorbing resin (5) for a physiological saline solution under a condition of the pressure being 20 g/cm2 was 25 (g/g) . Absorbency against pressure of the water absorbing resin (5) for' a physiological saline solution under a condition of the pressure being 50 g/cm2 was 21 (g/g) . (Example 12 ) α-Cyclodextrin including the fragrant material (1) therein was obtained by mixing 1 part of the fragrant material (1) used in Example 1 and 2 parts of α-cyclodextrin to allow the fragrant material (1) to be absorbed to α-cyclodextrin. Next, an aqueous solution was produced by dissolving 3 parts of α-cyclodextrin including the fragrant material (1) in 180 parts of ion exchanged water. A water absorbing resin composition (12) was obtained by adding 4.5 parts of the water absorbing resin (2) to this aqueous solution. The water absorbing resin composition (12) is a gelatinous composition. (Example 13)
In a similar manner to Example 12 except that 1.5 parts of the fragrant material (1) and 0.0001 parts of Food Blue No. 1 (manufactured by Tokyo Chemical Industry Co., Ltd.) were allowed to be included in α-cyclodextrin, a water absorbing resin composition (13) was obtained. The water absorbing resin composition (13) is a gelatinous composition.
(Example 14) In a similar manner to Example 12, α-cyclodextrin including the fragrant material (1) therein was obtained. An aqueous solution (14) was obtained by dissolving 1 part of this α-cyclodextrin in 5 parts of ion exchanged water. This aqueous solution (14) was homogenously mixed with 100 parts of the water absorbing resin (5) obtained in Reference Example (5) . After mixing, this mixture was left to stand in a 600C windless oven for 1 hour. Thereafter, a powdery water absorbing resin composition (14) having a mass median particle size of 420 μm, and including 0.5% by weight of the particle ingredient having a particle diameter of less than 150 μm was obtained by passing through a JIS standard sieve having a mesh opening size of 850 μm. The water absorbing resin composition (14) exhibited GVs (g/g) of 23 (g/g) . The extractables ratio (%) of the water absorbing resin composition (14) was 7% by weight . Absorbency against pressure of the water absorbing resin composition (14) for a physiological saline solution under a condition of the pressure being 20 g/cm2 was 23 (g/g) . Absorbency against pressure of the water absorbing resin composition (14) for a physiological saline solution under a condition of the pressure being 50 g/cm2 was 20 (g/g) . (Example 15)
In a similar manner to Example 14 except that the fragrant material (1) was replaced with the fragrant material (2) , a particulate water absorbing resin composition (15) having a mass median particle size of 420 μm, and including 0.2% by weight of the particle ingredient having a particle diameter of less than 150 μm was obtained. The ingredients of the fragrant material (2) were 10% by weight trans-2-hexenal, 15% by weight citric acid triethyl ester and 75% by weight ethyl alcohol. The water absorbing resin composition (15) exhibited GVs (g/g) of 23 (g/g) . The extractables ratio (%) of the water absorbing resin composition (15) was 7% by weight . Absorbency against pressure of the water absorbing resin composition (15) for a physiological saline solution under a condition of the pressure being 20 g/cm2 was 23 (g/g) . Absorbency against pressure of the water absorbing resin composition (15) for a physiological saline solution under a condition of the pressure being 50 g/cm2 was 20 (g/g) . (Example 16) A powdery water absorbing resin composition (16) having a mass median particle size of 400 μm, and including 0.3% by weight of the particle ingredient having a particle diameter of less than 150 μm was obtained by homogenously mixing 1 part of the fragrant material (2) used in Example 15 with 100 parts of the water absorbing resin (5) obtained in Reference Example
5. The water absorbing resin composition (16) exhibited GVs
(g/g) of 24 (g/g) . The extractables ratio (%) of the water absorbing resin composition (16) was 7% by weight . Absorbency against pressure of the water absorbing resin composition (16) for a physiological saline solution under a condition of the pressure being 20 g/cm2 was 24 (g/g) . Absorbency against pressure of the water absorbing resin composition (16) for a physiological saline solution under a condition of the pressure being 50 g/cm2 was 21 (g/g) . (Evaluation 3)
Each 20 g of the water absorbing resin compositions (7) to (13) was placed in a 500-ml glass beaker, and left to stand at room temperature. One month later, the weight of the aromatic compositions decreased by nearly half . However, they were still in a transparent gelatinous state without deposition onto the vessel, and the aroma was also maintained. (Evaluation 4)
Evaluation was conducted similarly to Evaluation 3 except that the comparative composition (3) or (4) was used in place of the water absorbing resin compositions (7) to (13) . Consequently, no aroma was left at all. Additionally, a deposit was observed for the comparative composition (4). (Evaluation 5) Each 1-g of the water absorbing resin composition (6), the water absorbing resin composition (14), the water absorbing resin composition (15) and the water absorbing resin composition (16) was placed in a polypropylene vessel having an internal diameter of 60 mm and a height of 80 mm. Further, 50 g of ion exchanged water was added to 1 g of this water absorbing resin composition to produce a swollen gel.
Subsequently, the vessel charged with the swollen gel was covered with a lid, and left to stand in a 37°C dryer for one day.' After leaving to stand, the state of the gel was visually observed to reveal that any of the water absorbing resin compositions (6), (14), (15) and (16) kept a stable gelatinous state.
(Evaluation 6)
Evaluation was conducted in a similar manner to Evaluation 5 except that the water absorbing resin (4) obtained in Reference Example 4 was used in place of the water absorbing resin compositions (6) , (14) , (15) and (16) . The gel after leaving to stand exhibited a state in which a part thereof lysed to flow. As is proven from the comparison of Evaluation 5 with Evaluation 6, the water absorbing resin compositions (6), (14), (15) and (16) are more excellent in gel stability compared to the water absorbing resin (4) . (Evaluation 7)
Each 75 parts of the water absorbing resin compositions (14) to (16), and 25 parts of pulverized wood pulp as a hydrophilic fiber were subjected to dry blending using a mixer. Next, the resultant mixture was subjected to pneumatic molding on a wire screen of 400 mesh (mesh opening size: 38 μm) with a batch type pneumatic device. According to this pneumatic molding, a web having a size of 120 mm * 400 mm was formed. In addition, this web was pressed for 5 seconds under a pressure of 2 kg/cm2, thus obtaining an absorbent core having a basis weight of 0.047 g/cm2 and a core concentration of 75% by weight. A back sheet, the aforementioned absorbent core and a top sheet were attached to each other in this order with double-stick tapes, and two so-called tape fasteners were then provided to the resultant attached product, thus obtaining absorbent articles (1) to (3) that were disposable diapers. The aforementioned back sheet is constituted from liquid-impermeable polypropylene and has a so-called leg gather. The aforementioned top sheet is constituted from liquid-permeable polypropylene. Next, 50 ml of a physiological saline solution (0.9% by weight aqueous sodium chloride solution) was charged to the absorbing articles (1) to (3) from the side of the top sheet. Further, each 50 ml of the physiological saline solution was additionally charged at intervals of 20 minutes. Accordingly, the physiological saline solution of 250 ml in total was charged. Thereafter, the absorbing articles (1) to (3) charged with the physiological saline solution were left to stand in a windless at 37°C for 16 hours. When 50 ml of the physiological saline solution was charged again to the absorbing articles (1) to (3) after leaving to stand for 16 hours, the entire physiological saline solution was absorbed. (Evaluation 8) Evaluation was conducted in a similar manner to
Evaluation 7 except that the water absorbing resin (4) obtained in Reference Example 4 was used in place of the water absorbing resin compositions (14) to (16) . As a result, the physiological saline solution charged after leaving to stand for 16 hours was not absorbed from the top sheet due to clogging. Industrial Applicability
The water absorbing resin composition of the present invention provides sanitary goods and fragrances that are excellent in persistence of the aroma and stability of the aroma, and effective in relieving fatigue and stress. Still further, because the water absorbing resin composition of the present invention also exhibits a masking effect and an antibacterial effect resulting from the fragrant material ingredient, it can be also used as a deodorizing antimicrobial agent, which can be utilized, for example, as fragrances or deodorants for use in rooms and cars as well as sanitary goods. Stability of the fragrant material may be remarkably improved throughout the course of production over the article of trade. In addition, in case of use in sanitary goods such as disposable diapers, favorable deodorization effect, antibacterial effect and durability may be exhibited.

Claims

Claims :
1. A water absorbing resin composition which comprises: at least one substance selected from the group consisting of cyclodextrin including a fragrant material, a dextrin derivative including a fragrant material, unsaturated aliphatic aldehyde having 6 to 10 carbon atoms and unsaturated aliphatic alcohol having 6 to 10 carbon atoms; and a polycarboxylic acid type water absorbing resin.
2. The water absorbing resin composition according to claim 1 wherein said polycarboxylic acid type water absorbing resin is a polyacrylic acid (a salt thereof) cross-linked polymer.
3. The water absorbing resin composition according to claim 1 or 2 wherein the mass median particle size (defined by JIS standard sieve classification) is 100 to 20000 μm.
4. The water absorbing resin composition according to any one of claims 1 to 3 which is an aqueous gelling material.
5. The water absorbing resin composition according to any one of claims 1 to 4 wherein the amount of said water absorbing resin is within the range of 1 to 10000 parts by mass per 100 parts by mass of total amount of said cyclodextrin including the fragrant material, said dextrin derivative including the fragrant material, said unsaturated aliphatic aldehyde and unsaturated aliphatic alcohol.
6. The water absorbing resin composition according to any one of claims 1 to 5 which comprises 200 to 50000 parts by mass of an aqueous liquid per 100 parts by mass of total amount of said cyclodextrin including the fragrant material, said dextrin derivative including the fragrant material, said unsaturated ^aliphatic aldehyde, said unsaturated aliphatic alcohol and the water absorbing resin.
7. The water absorbing resin composition according to any one of claims 1 to 6 wherein said unsaturated aliphatic aldehyde is hexenal, or said unsaturated aliphatic alcohol is hexenol .
8. The water absorbing resin composition according to any one of claims 1 to 7 which comprises said cyclodextrin including the fragrant material and/or said dextrin derivative including the fragrant material, and a polyacrylic acid (a salt thereof) cross-linked polymer.
9. The water absorbing resin composition according to any one of claims 1 to 7 which comprises said unsaturated aliphatic aldehyde having 6 to 10 carbon atoms and/or said unsaturated aliphatic alcohol having 6 to 10 carbon atoms, and a polyacrylic acid (a salt thereof) cross-linked polymer.
10. A method for producing a water absorbing resin composition which comprises the steps of: mixing a fragrant material with cyclodextrin and/or a cyclodextrin derivative; allowing the mixture to be dissolved in water to prepare an aqueous solution; and allowing the aqueous solution to be absorbed to a water absorbing resin.
11. A method for producing a water absorbing resin composition which comprises the steps of: mixing cyclodextrin and/or a cyclodextrin derivative with a fragrant material to obtain an aqueous solution; and allowing the aqueous solution to be absorbed to a water absorbing resin.
12. A method for producing a water absorbing resin composition which comprises the steps of: mixing an aqueous liquid containing unsaturated aliphatic aldehyde having 6 to 10 carbon atoms and/or unsaturated aliphatic alcohol having 6 to 10 carbon atoms with a water absorbing resin.
13. A sanitary goods which comprises the water absorbing resin composition according to any one of claims 1 to 9.
14. A fragrance which comprises the water absorbing resin composition according to any one of claims 1 to 9.
PCT/JP2006/314717 2005-07-20 2006-07-19 Water absorbing resin composition WO2007011058A1 (en)

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