WO2022145243A1 - Corps absorbant composite et article d'hygiène - Google Patents

Corps absorbant composite et article d'hygiène Download PDF

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Publication number
WO2022145243A1
WO2022145243A1 PCT/JP2021/046341 JP2021046341W WO2022145243A1 WO 2022145243 A1 WO2022145243 A1 WO 2022145243A1 JP 2021046341 W JP2021046341 W JP 2021046341W WO 2022145243 A1 WO2022145243 A1 WO 2022145243A1
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Prior art keywords
absorbent
polymer
water absorption
absorber
composite
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PCT/JP2021/046341
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English (en)
Japanese (ja)
Inventor
響 菊池
章恵 木下
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ユニ・チャーム株式会社
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Publication of WO2022145243A1 publication Critical patent/WO2022145243A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis

Definitions

  • the present invention relates to a composite absorber and a sanitary product having the same.
  • Patent Document 1 describes an absorbent article using an absorbent body formed by combining absorbent resin particles (highly absorbent polymer) having an excellent absorption amount and hydrophilic fibers such as pulp fibers having an excellent absorption rate. Is disclosed.
  • SAP highly absorbent polymer
  • a conventional absorber when body fluids such as urine and menstrual blood are discharged from the wearer of sanitary goods, the body fluids are quickly absorbed by the pulp in the absorber, temporarily held in the pulp, and then retained in water. It will be handed over to a highly capable SAP and will be retained within the SAP.
  • the present invention has been made in view of such a problem, and an object of the present invention is to provide an absorber having high absorption efficiency.
  • One aspect (aspect 1) of the present invention is a composite absorber for hygiene products for absorbing body fluids.
  • the polymer absorbent has an initial water absorption of 5 g / g or more 5 seconds after a load of 40 g / cm 2 is applied, and the water absorption after 20 seconds or more is 110 of the initial water absorption.
  • It is a complex absorber characterized by being% or more.
  • the composite absorber of the first aspect is absorbed because the polymer absorbent capable of taking in the body fluid into the continuous pores by the capillary phenomenon has the above-mentioned specific initial absorption amount and the absorption amount after 20 seconds or more.
  • the amount of absorption in the initial stage is large, and the body fluid can be temporarily retained, and the body fluid can be absorbed even after a lapse of a predetermined time.
  • the composite absorber of the first aspect can exhibit high absorption efficiency as an absorber.
  • aspects 2 is characterized in that, in the composite absorber of the above aspect 1, the composite absorber further contains a highly absorbent polymer.
  • the composite absorber of the second aspect contains a highly absorbent polymer (SAP) together with the above-mentioned polymer absorbent, the body fluid is quickly absorbed by the polymer absorbent in the composite absorbent and temporarily retained. , It can be handed over to a SAP with high water retention capacity and held in the SAP. As a result, the composite absorber of the second aspect can exhibit higher absorption efficiency.
  • SAP highly absorbent polymer
  • the liquid transfer amount from the polymer absorbent to the highly absorbent polymer is 5.0 g / g or more.
  • the composite absorber of the third aspect has a liquid transfer amount from the polymer absorbent to the SAP of 5.0 g / g or more, the body fluid temporarily held by the polymer absorbent is more reliably received by the SAP. Can be passed. As a result, the composite absorber of the third aspect can more reliably exhibit high absorption efficiency.
  • the polymer absorbent in the composite absorber of the above aspect 2 or 3, is characterized in that the liquid discharge rate of the absorbed water is 65% or more. ..
  • the liquid discharge rate of the polymer absorbent is 65% or more, and the water absorbed by the polymer absorbent is easily released. Therefore, the body liquid temporarily held by the polymer absorbent. Can be more easily delivered to the SAP.
  • the polymer absorbent is a monolithic absorbent.
  • the polymer absorbent is a monolithic absorbent, the body fluid can be quickly absorbed and the temporarily held body fluid can be more steadily transferred to the SAP. ..
  • the polymer absorbent in any of the composite absorbers of aspects 1-5, is a (meth) acrylic acid ester and two or more in one molecule. It is a hydrolyzate of a crosslinked polymer of a compound containing a vinyl group, and is characterized by containing at least one -COONa group.
  • the hydrophilic continuous skeleton is likely to be elongated and the continuous pores are likely to be expanded when absorbing the body fluid. A large amount of body fluid can be taken into the continuous pores more quickly, and more excellent absorption efficiency can be exhibited as an absorber.
  • yet another aspect (aspect 7) of the present invention is a hygienic product characterized by having the complex absorber according to any one of the above aspects 1 to 6.
  • the hygienic product of the present aspect 7 has the composite absorber according to any one of the above-mentioned aspects 1 to 6, it can exhibit excellent absorption efficiency as a hygienic product.
  • FIG. 1 is a schematic plan view of the light incontinence pad 1 in the deployed state as viewed from the skin facing surface side in the thickness direction.
  • FIG. 2 is a diagram illustrating a manufacturing process of the absorbent A, which is an example of the polymer absorbent.
  • FIG. 3 is an SEM photograph of the absorbent A at a magnification of 50 times.
  • FIG. 4 is an SEM photograph of the absorbent A at a magnification of 100 times.
  • FIG. 5 is an SEM photograph of the absorbent A at a magnification of 500 times.
  • FIG. 6 is an SEM photograph of the absorbent A at a magnification of 1000 times.
  • FIG. 7 is an SEM photograph of the absorbent A at a magnification of 1500 times.
  • a preferred embodiment of the composite absorber of the present invention will be described in detail using a light incontinence pad 1 which is an example of a hygienic product to which the composite absorber is applied.
  • a light incontinence pad 1 which is an example of a hygienic product to which the composite absorber is applied.
  • an object placed on a horizontal plane in a deployed state for example, a light incontinence pad, a composite absorber, etc.
  • the object is a sanitary product.
  • looking in the thickness direction of the object from the surface sheet side is simply called "planar view”.
  • the "longitudinal direction” refers to "the direction in which the length of a vertically long object (for example, a light incontinence pad in a deployed state, a composite absorber, etc.) in a plan view is long" and is “the width direction”.
  • the short direction of the length of the vertically long object in the plan view and “the thickness direction” refers to "the direction perpendicular to the object placed on the horizontal plane in the unfolded state", and their longitudinal directions.
  • the direction, width direction, and thickness direction are orthogonal to each other.
  • skin is relatively proximal to the wearer's skin surface when the light incontinence pad 1 is worn in the thickness direction of the light incontinence pad 1. It is referred to as “opposing surface side", and "when the light incontinence pad 1 is worn, the side relatively distal to the wearer's skin surface” is referred to as “non-skin facing surface side”.
  • FIG. 1 is a schematic plan view of a light incontinence pad 1 in a deployed state to which the composite absorber 4 according to the embodiment of the present invention is applied.
  • the light incontinence pad 1 has a longitudinal direction L and a width direction W in a plan view, and two longitudinal end edges project in an arc shape toward the outward side in the longitudinal direction. It has a vertically long outer shape.
  • the external shape of the light incontinence pad 1 is not limited to such a mode, and any shape (for example, oval shape, rectangular shape, etc.) according to various uses, usage modes, etc., as long as it is a vertically long shape. Hourglass shape, etc.) can be adopted.
  • the light incontinence pad 1 has a liquid-permeable surface sheet 2 that forms the surface of the light incontinence pad 1 on the skin-facing surface side and a back surface that forms the surface of the light incontinence pad 1 on the non-skin-facing surface side.
  • a sheet 3 and a composite absorber 4 located between these sheets are provided as a basic configuration.
  • an adhesive portion (not shown) which is arranged on the surface of the back surface sheet 3 on the non-skin facing surface side and adhesively fixes the light incontinence pad 1 to the inner surface of clothing such as the wearer's underwear is further provided. I have.
  • the light incontinence pad 1 is not limited to such a configuration, and is, for example, located at both ends of the light incontinence pad 1 in the width direction W at a position on the skin facing surface side of the surface sheet 2 and in the longitudinal direction.
  • a pair of side sheets for forming a leak-proof wall arranged so as to extend to L, and a plurality of elastic members arranged along the longitudinal direction L in each of the pair of side sheets are provided. May be.
  • the composite absorber 4 is located between the front surface sheet 2 and the back surface sheet 3, and can absorb body fluids such as urine discharged from the wearer and permeated through the front surface sheet 2.
  • body fluids such as urine discharged from the wearer and permeated through the front surface sheet 2.
  • a composite absorber 4 Formed by a sex member, such a composite absorber 4 comprises a polymer absorbent with a hydrophilic continuous skeleton and continuous vacancies. Further, this polymer absorbent has an initial water absorption amount of 5 g / g or more 5 seconds after a load of 40 g / cm 2 is applied, and the water absorption amount after 20 seconds or more is the initial water absorption amount. It has a specific water absorption of 110% or more of.
  • Such a polymer absorbent can take in body fluid into continuous pores by capillarity, and further has the above-mentioned specific initial absorption amount and absorption amount after 20 seconds or more, so that it can be absorbed. Since the amount of absorption in the initial stage is large, the body fluid can be temporarily retained, and the body fluid can be absorbed even after a lapse of a predetermined time, the composite absorber 4 containing such a polymer absorbent is an absorber. High absorption efficiency can be exhibited.
  • the light incontinence pad 1 provided with such a composite absorber 4 can also exhibit excellent absorption efficiency as a light incontinence pad.
  • the load of 40 g / cm 2 is a load assuming a general body pressure, and the amount of water absorbed after 20 seconds or more is 20 seconds after the load is applied under predetermined temperature conditions. It means the amount of water absorption (mass; g / g) at any timing after the lapse (for example, any timing after 20 seconds, 60 seconds, 300 seconds, 3600 seconds, etc.). .. The method for measuring the amount of water absorbed by the polymer absorbent under the specific load will be described later.
  • the water absorption after 20 seconds or more is 110% or more of the initial water absorption, which is 110% of the initial water absorption when the water absorption after 5 seconds is 100%. It means that it is the above.
  • the surface sheet 2 extends from one side edge of the light incontinence pad 1 in the longitudinal direction L to the other side edge in a plan view, and
  • the light incontinence pad 1 has a vertically long outer shape extending from the vicinity of one side edge of the width direction W to the vicinity of the other side edge.
  • the surface sheet 2 is arranged at a position on the skin facing surface side in the thickness direction of the light incontinence pad 1 and forms a contact surface that can come into contact with the wearer's skin, that is, the surface of the light incontinence pad 1 on the skin facing surface side. It is composed of a liquid-permeable sheet-like member.
  • the surface sheet 2 has a size slightly larger in the longitudinal direction L and the width direction W than the composite absorber 4 arranged on the non-skin facing surface side of the surface sheet 2. It is joined to the back surface sheet 3 located on the non-skin facing surface side in the peripheral portion.
  • the outer shape, various dimensions, basis weight, etc. of the surface sheet are not particularly limited as long as they can be used as the surface sheet of sanitary products, depending on desired liquid permeability, touch, flexibility, strength, and the like. Any external shape, various dimensions, basis weight, etc. can be adopted.
  • the back surface sheet 3 extends from one side edge of the light incontinence pad 1 in the longitudinal direction L to the other side edge and extends in the width direction W of the light incontinence pad 1 in a plan view. It has a vertically long outer shape extending from one side edge to the other side edge.
  • the back sheet 3 is arranged at a position on the non-skin facing surface side in the thickness direction of the light incontinence pad 1 to form the non-skin facing surface of the light incontinence pad 1 and urine that has permeated the composite absorber 4. It is composed of a liquid-impermeable sheet-like member that prevents body fluids such as those from leaking to the outside of the light incontinence pad 1.
  • the outer shape, various dimensions, basis weight, etc. of the back sheet are not particularly limited as long as they can be used as the back sheet of sanitary goods, and are arbitrary according to desired leakage-proof performance, breathability, strength, and the like. It is possible to adopt the outer shape, various dimensions, basis weight, etc.
  • the composite absorber 4 is one of the longitudinal directions L centered on the central portion of the light incontinence pad 1 in the longitudinal direction L and the width direction W in a plan view. It extends over a wide area in the longitudinal direction L extending from the vicinity of the side edge to the vicinity of the other side edge, and also in the width direction W, a wide area extending from the vicinity of one side edge of the width direction W to the vicinity of the other side edge. Further, it has a vertically long outer shape in which two longitudinal end edges project in an arc shape toward the outward side in the longitudinal direction.
  • the composite absorber 4 has a constricted portion in the central portion in the longitudinal direction in a plan view, which is relatively smaller in width direction than the other portions, and further, the constricted portion. It has a minimum width portion having a minimum width of the composite absorber 4 and a maximum width portion having a maximum width of the composite absorber 4 on the outer side in the longitudinal direction of the constricted portion.
  • the composite absorber 4 is arranged between the front surface sheet 2 and the back surface sheet 3 in the thickness direction of the light incontinence pad 1, and can absorb and retain body fluid such as urine that has permeated the front surface sheet 2.
  • the water-absorbent member is formed of a water-absorbent material such as a polymer absorbent, a hydrophilic fiber, and a highly absorbent polymer, which will be described later, and a sheet such as a tissue holding the water-absorbent material.
  • the composite absorber means a water-absorbent member composed of a water-absorbent material capable of absorbing and holding a body fluid and a sheet holding the water-absorbent material.
  • the composite absorber 4 is bonded to each of the front surface sheet 2 and the back surface sheet 3 with an arbitrary adhesive such as a hot melt type adhesive.
  • the composite absorber 4 contains a polymer absorbent having a specific water absorption, which has a hydrophilic continuous skeleton and continuous pores as described above. This polymer absorbent will be described later.
  • the composite absorber 4 further contains a water-absorbing material known in the art in addition to the above-mentioned polymer absorbent.
  • a water-absorbent material include hydrophilic fibers and highly absorbent polymers, and more specifically, cellulosic fibers such as pulp fibers (for example, crushed pulp), cotton, rayon, acetate and the like.
  • SAP highly absorbent polymer
  • the composite absorbent 4 has a structure in which such a polymer absorbent or a water-absorbent material is covered with a wrap sheet such as a tissue having hydrophilicity.
  • the outer shape, various dimensions, basis weight, etc. of the composite absorber are not particularly limited as long as the effects of the present invention are not impaired, and any outer shape according to desired water absorption, flexibility, strength, etc. Various dimensions, basis weight, etc. can be adopted.
  • the polymer absorbent is a polymer absorbent having a hydrophilic continuous skeleton and continuous pores, and has an initial water absorption of 5 g / g or more 5 seconds after a load of 40 g / cm 2 is applied. It is not particularly limited as long as it has a specific water absorption such that the water absorption after 20 seconds or more is 110% or more of the initial water absorption, and includes, for example, at least (meth) acrylic acid ester. It is a hydrolyzate of a crosslinked polymer of two or more monomers, and examples thereof include polymer compounds having at least one hydrophilic group as a functional group.
  • a hydrolyzate of a (meth) acrylic acid ester and a crosslinked polymer of a compound containing two or more vinyl groups in one molecule, and a polymer compound having at least a -COONa group can be mentioned.
  • a polymer absorbent is an organic porous body having at least one -COONa group in one molecule, and may further have a -COOH group. -COONa groups are distributed substantially uniformly in the skeleton of the porous body.
  • the polymer absorbent is a hydrolyzate of such a (meth) acrylic acid ester and a crosslinked polymer of a compound containing two or more vinyl groups in one molecule, and at least one -COONa. If it contains a group, as will be described later, when absorbing body fluids such as urine, the hydrophilic continuous skeleton tends to elongate and the continuous pores also tend to expand, so that more body fluids can be continuously expanded more quickly. It can be taken into the pores and can exhibit even better absorption efficiency as an absorber.
  • the (meth) acrylic acid ester means an acrylic acid ester or a methacrylic acid ester.
  • a hydrophilic continuous skeleton is formed by an organic polymer having at least a -COONa group. , It has a communication hole (continuous pore) that serves as an absorption field for the liquid to be absorbed (that is, body fluid such as urine) between the skeletons. Since the hydrolysis treatment changes the -COOR group (that is, the carboxylic acid ester group) of the crosslinked polymer to a -COONa group or a -COOH group (see FIG. 2), the polymer absorbent is-. It may have a COOR group.
  • FIG. 2 is a diagram illustrating a manufacturing process of the absorbent A, which is an example of the polymer absorbent.
  • the upper figure shows the constituent raw materials for the polymerization
  • the middle figure shows the monolith A which is a crosslinked polymer of (meth) acrylic acid ester and divinylbenzene
  • the lower figure shows the monolith A in the middle figure.
  • the absorbent A obtained by hydrolysis and drying treatment is shown.
  • an absorbent A formed by a hydrolyzate of a crosslinked polymer of (meth) acrylic acid ester and divinylbenzene, which is an example of a polymer absorbent, will be described.
  • the polymer absorbent is not limited to such a absorbent A, but is a hydrolyzate of a (meth) acrylic acid ester and a crosslinked polymer of a compound having two or more vinyl groups in one molecule, or , It may be a hydrolyzate of a crosslinked polymer of two or more kinds of monomers containing at least (meth) acrylic acid ester.
  • “monolith A” is an organic porous body composed of a crosslinked polymer of (meth) acrylic acid ester and divinylbenzene before hydrolysis treatment, and is “monolithic organic porous”. Sometimes referred to as “polymer”. Further, the “absorbent A” is a hydrolyzate of a crosslinked polymer (monolith A) of (meth) acrylic acid ester and divinylbenzene after being hydrolyzed and dried. In the following description, the absorbent A is in a dry state.
  • the absorbent A has a hydrophilic continuous skeleton and continuous pores as described above.
  • the absorbent A which is an organic polymer having a hydrophilic continuous skeleton, was obtained by cross-linking and polymerizing a (meth) acrylic acid ester as a polymerization monomer and divinylbenzene as a cross-linking monomer. It is obtained by further hydrolyzing the crosslinked polymer (Monolith A).
  • the organic polymer forming a hydrophilic continuous skeleton has an ethylene group polymerization residue (hereinafter referred to as “constituent unit X”) and a crosslinked polymerization residue of divinylbenzene (hereinafter referred to as “constituent unit Y”) as constituent units. ”) And. Furthermore, the polymerization residue (constituent unit X) of the ethylene group in the organic polymer forming the hydrophilic continuous skeleton is the -COONa group or -COOH group and -COONa group generated by hydrolysis of the carboxylic acid ester group. It has both groups. When the polymerization monomer is a (meth) acrylic acid ester, the polymerization residue (constituent unit X) of the ethylene group has an —COONa group, a —COOH group and an ester group.
  • the ratio of the crosslinked polymerization residue (constituent unit Y) of divinylbenzene in the organic polymer forming the hydrophilic continuous skeleton is, for example, 0.1 to 30 mol% with respect to all the constituent units. , Preferably 0.1 to 20 mol%.
  • the ratio of the cross-linking polymerization residue (constituent unit Y) of divinylbenzene in the organic polymer forming a hydrophilic continuous skeleton is, for example, 0.1 to 30 mol% with respect to all the constituent units. , Preferably 0.1 to 20 mol%.
  • the ratio of the cross-linking polymerization residue (constituent unit Y) of divinylbenzene in the organic polymer forming a hydrophilic continuous skeleton is, for example, 0.1 to 30 mol% with respect to all the constituent units. , Preferably 0.1 to 20 mol%.
  • the ratio of the crosslinked polymerization residue of the divinylbenzene in the organic polymer forming the hydrophilic continuous skeleton is 0.1 mol% or more, the strength of the absorbent A is less likely to decrease, and the divinylbenzene is also difficult to decrease.
  • the ratio of the crosslinked polymerization residue of the above is 30 mol% or less, the absorption amount of the liquid to be absorbed is less likely to decrease.
  • the organic polymer forming the hydrophilic continuous skeleton may be composed of only the constituent unit X and the constituent unit Y, or in addition to the constituent unit X and the constituent unit Y, It may have a structural unit other than the structural unit X and the structural unit Y, that is, a polymerization residue of a monomer other than the (meth) acrylic acid ester and divinylbenzene.
  • Examples of the constituent units other than the constituent unit X and the constituent unit Y include styrene, ⁇ -methylstyrene, vinyltoluene, vinylbenzyl chloride, glycidyl (meth) acrylate, isobutene, butadiene, isoprene, chloroprene, vinyl chloride, and bromide.
  • Polymerization residues of monomers such as vinyl, vinylidene chloride, tetrafluoroethylene, (meth) acrylonitrile, vinyl acetate, ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropanetri (meth) acrylate Can be mentioned.
  • the ratio of the structural units other than the structural unit X and the structural unit Y in the organic polymer forming the hydrophilic continuous skeleton is, for example, 0 to 50 mol%, preferably 0 to 30 with respect to all the structural units. It is mol%.
  • the absorbent A preferably has a hydrophilic continuous skeleton having a thickness of 0.1 to 100 ⁇ m.
  • the thickness of the hydrophilic continuous skeleton of the absorbent A is 0.1 ⁇ m or more, the space (pores) for taking in the absorption target liquid (body fluid) in the porous body is less likely to be crushed during absorption, and the absorption amount is reduced. It becomes difficult to do.
  • the thickness of the hydrophilic continuous skeleton is 100 ⁇ m or less, an excellent absorption rate can be easily obtained.
  • the thickness of the continuous skeleton is measured by using the skeleton cross section appearing on the test piece for electron microscope measurement as the evaluation point of the thickness. ..
  • the continuous skeleton is often formed in a polygonal shape because it is formed at intervals between water (water droplets) that are removed by dehydration / drying treatment after hydrolysis. Therefore, the thickness of the continuous skeleton is the average value of the diameters ( ⁇ m) of the circles circumscribing the polygonal cross section. Also, in rare cases, there may be a small hole in the polygon, in which case the circumscribed circle of the cross section of the polygon surrounding the small hole is measured.
  • the absorbent A preferably has an average diameter of continuous pores of 1 to 1000 ⁇ m.
  • the average diameter of the continuous pores of the absorbent A is 1 ⁇ m or more, the space (pores) for taking in the absorption target liquid (body fluid) of the porous body is less likely to be crushed during absorption, and the absorption rate is less likely to decrease. ..
  • the average diameter of the continuous pores is 1000 ⁇ m or less, an excellent absorption rate can be easily obtained.
  • the average diameter ( ⁇ m) of the continuous pores of the absorbent A can be measured by the mercury intrusion method, and the maximum value of the pore distribution curve obtained by the mercury intrusion method is adopted.
  • a sample for measuring the average diameter of the continuous pores a sample dried for 18 hours or more in a vacuum dryer set at a temperature of 50 ° C. is used regardless of the ionic form of the absorbent A.
  • the final ultimate pressure is 0 Torr.
  • FIG. 3 is an SEM photograph having a magnification of 50 times for the absorbent A
  • FIG. 4 is an SEM photograph having a magnification of 100 times for the absorbent A
  • FIG. 5 is an SEM photograph having a magnification of 500 for the absorbent A. It is a double SEM photograph
  • FIG. 6 is an SEM photograph having a magnification of 1000 times for the absorbent A
  • FIG. 7 is an SEM photograph having a magnification of 1500 times for the absorbent A.
  • the absorbent A shown in FIGS. 3 to 7 is an example of an absorbent having butyl methacrylate as a polymerization monomer and divinylbenzene as a cross-linking monomer, and each has a cubic structure of 2 mm square.
  • the absorbent A shown in FIGS. 3 to 7 has a large number of bubble-shaped macropores, and further has a portion where these bubble-shaped macropores overlap each other.
  • the absorbent A has an open cell structure in which the overlapping portions of the macropores have a common opening (mesopore), that is, an open cell structure (continuous macropore structure).
  • the portion where the macropores overlap each other has a common opening (mesopore) having an average diameter of 1 to 1000 ⁇ m, preferably 10 to 200 ⁇ m, particularly preferably 20 to 100 ⁇ m in a dry state, and most of them have an open pore structure. It has become.
  • the average diameter of the mesopore in a dry state is 1 ⁇ m or more, the absorption rate of the liquid to be absorbed becomes better.
  • the average diameter of the mesopore in a dry state is 1000 ⁇ m or less, the absorbent A is less likely to become brittle. It should be noted that the number of such macropores overlapped with each other is about 1 to 12 for one macropore, and about 3 to 10 for most macropores.
  • the absorbent A has such an open cell structure, the macropore group and the mesopore group can be uniformly formed, and the particle aggregation type as described in Japanese Patent Application Laid-Open No. 8-252579 etc. can be formed uniformly. Compared to the porous body, there is an advantage that the pore volume and the specific surface area can be significantly increased.
  • the total pore volume of the pores (pores) of the absorbent A is preferably 0.5 to 50 mL / g, more preferably 2 to 30 mL / g.
  • the total pore volume of the absorbent A is 0.5 mL / g or more, the space (pores) for taking in the absorption target liquid (body fluid) of the porous body is less likely to be crushed during absorption, and the absorption amount and absorption rate Is less likely to decrease.
  • the total pore volume of the absorbent A is 50 mL / g or less, the strength of the absorbent A is less likely to decrease.
  • the total pore volume can be measured by the mercury intrusion method.
  • a sample dried for 18 hours or more in a vacuum dryer set at a temperature of 50 ° C. is used regardless of the ionic form of the absorbent A.
  • the final ultimate pressure is 0 Torr.
  • body fluid a liquid such as a body fluid
  • the mass of the absorbed body fluid is substantially proportional to the amount of the body fluid, the mass of the body fluid may be simply referred to as "the amount of the body fluid" in the following description.
  • the continuous pores included in the absorbent A shown in FIGS. 3 to 7 are pores in which a plurality of pores (pores) communicate with each other, and a large number of pores are provided from the appearance. Can be visually recognized with the naked eye.
  • a certain amount of the body fluid enters the large number of pores and is absorbed by the absorbent A due to the capillary phenomenon.
  • some of the body fluids absorbed by the absorbent A are absorbed into the hydrophilic continuous skeleton by osmotic pressure, and the continuous skeleton is elongated.
  • the body fluids that are not absorbed in the hydrophilic continuous skeleton are absorbed in a state of being retained in the pores.
  • the absorbent A has a property that the hydrophilic continuous skeleton is elongated when the body fluid is absorbed. This extension of the continuous skeleton occurs in almost all directions. Further, as the outer shape of the absorbent A becomes larger due to the extension of the continuous skeleton, the size of each pore also becomes larger. As the size of the vacancies increases in this way, the volume inside the vacancies increases, so that the amount of body fluid that can be retained in the vacancies also increases. That is, the absorbent A, which has become larger by absorbing a certain amount of body fluid, can further absorb a predetermined amount of body fluid into the enlarged pores by the capillary phenomenon. Further, since the absorbent A absorbs the body fluid by the capillary phenomenon, the body fluid can be quickly absorbed.
  • the amount of body fluid absorbed by the absorbent A is larger than that absorbed in the hydrophilic continuous skeleton. Since most of the absorption of body fluid by the absorbent A is performed by retaining the body fluid in the pores by capillarity, the porosity (absorbent A) which is the ratio of the volume of the voids in the pores (total pore volume). The larger the volume of the voids in the pores relative to the volume of the pores), the more body fluid can be absorbed.
  • the porosity is preferably 85% or more.
  • the porosity of the absorbent A shown in FIGS. 3 to 7 described above is as follows.
  • the specific surface area of the absorbent A obtained by the mercury intrusion method is 400 m 2 / g, and the pore volume is 15.5 mL / g.
  • This pore volume of 15.5 mL / g means that the volume of the pores in 1 g of the absorbent A is 15.5 mL.
  • the specific gravity of the absorbent A is 1 g / mL
  • the volume occupied by the pores in 1 g of the absorbent A that is, the pore volume is 15.5 mL
  • the volume of the absorbent A of 1 g. Becomes 1 mL.
  • the total volume (volume) of 1 g of the absorbent A becomes 15.5 + 1 (mL), and the ratio of the pore volume thereof becomes the porosity. Therefore, the porosity of the absorbent A is 15.5 / (. 15.5 + 1) ⁇ 100 ⁇ 94%.
  • the absorbent A having such a hydrophilic continuous skeleton and continuous pores that is, the polymer absorbent is in the form of particles, sheets, etc., and the above-mentioned light incontinence pad 1 is used. It is applied to a complex absorber for absorbing body fluid such as urine, such as the complex absorber 4 of the above. Further, as described above, this polymer absorbent has an initial water absorption amount of 5 g / g or more 5 seconds after a load of 40 g / cm 2 is applied, and a water absorption amount after 20 seconds or more. It has a specific water absorption of 110% or more of the initial water absorption.
  • Such a polymer absorbent can take in body fluid into continuous pores by capillarity, and further has the above-mentioned specific initial absorption amount and absorption amount after 20 seconds or more, so that it is in the initial stage of absorption.
  • the amount of absorption is large, and the body fluid can be temporarily retained, and the body fluid can be absorbed even after a lapse of a predetermined time.
  • the composite absorber of the present invention containing such a polymer absorbent can exhibit high absorption efficiency as an absorber.
  • the initial water absorption amount of the polymer absorbent and the water absorption amount after a lapse of a predetermined time can be measured as follows.
  • ⁇ Measurement method of water absorption under specific load > 25 g of physiological saline (0.9% sodium chloride aqueous solution) with a pedestal (inner diameter: 85 mm, depth: 20 mm, pedestal arrangement: two pedestals at the center of the bottom surface (inner surface side) at intervals of 24 mm Arranged in parallel, pedestal width: 2 mm, pedestal height: 2 mm, pedestal length: 25 mm). This measuring method is performed under the conditions of a temperature of 25 ° C. and a humidity of 60%.
  • Nylon mesh material on the bottom surface N-NO255HD 115 manufactured by NBC Mesh Tech Co., Ltd.
  • a cylindrical plastic piston (diameter: 25 mm, mass: 5 g) is placed on a sample in a cylinder, and a weight having a predetermined mass (200 g; for a load of 40 g / cm 2 ) is further placed on the plastic piston. Place and measure the mass (g) of the cylinder.
  • a cylinder containing a sample, a plastic piston and a weight is placed on a pedestal in the center of a petri dish, the bottom surface of the cylinder is immersed in physiological saline, and the physiological saline is absorbed by the sample in the cylinder.
  • the cylinder is pulled up, the cylinder is tilted 45 ° and drained for 1 minute. Then, the mass (g) of the cylinder is measured.
  • the water absorption amount (g / g) when the predetermined time (that is, the water absorption time) of the above (5) is 5 seconds is "the initial water absorption amount 5 seconds after the load of 40 g / cm 2 is applied”.
  • the water absorption amount (g / g) when the water absorption time is 20 seconds or more is the "water absorption amount after 20 seconds or more have elapsed”.
  • ⁇ Method of recovering sample (polymer absorbent) for measurement> Peel off the surface sheet or the like from the hygienic product to expose the composite absorber.
  • the magnification of the simple loupe is not particularly limited as long as the pores of the porous body can be visually recognized, and examples thereof include a magnification of 25 to 50 times.
  • (4) The measurement object thus recovered is used as a sample for measurement in various measurement methods.
  • a polymer absorbent as an example of the present invention a pulp fiber (fluff pulp) as a comparative example, an Infinity particle body as a comparative example, and a highly absorbent polymer (SAP) as a comparative example are used.
  • a pulp fiber (fluff pulp) as a comparative example
  • an Infinity particle body as a comparative example
  • SAP highly absorbent polymer
  • the measurement results of this water absorption amount are shown in Table 1 below.
  • the Infinity particle body is an absorbent manufactured by P & G, and although it has a structure (foaming structure) similar to that of a polymer absorbent, it absorbs liquid unlike a polymer absorbent. It does not have the
  • the polymer absorbent has a larger absorption amount in the initial stage of absorption than SAP, as in the case of pulp fibers and Infinity particles, under a specific load and under a non-load. There is. Further, in the absorption amount after 20 seconds or more, both the pulp fiber and the Infinity particle body have reached the saturation amount, whereas the polymer absorbent has a further water absorption amount even after such a predetermined time has elapsed. It is increasing, and it can be seen that it has excellent water absorption peculiar to conventional pulp fibers, Infinity particles, SAP and the like.
  • the composite absorber further contains a conventional highly absorbent polymer (SAP) in addition to the above-mentioned polymer absorbent.
  • SAP highly absorbent polymer
  • the amount of liquid transferred from the polymer absorbent to SAP is preferably 5.0 g / g or more.
  • the amount of liquid transferred from the polymer absorbent to SAP is 5.0 g / g or more, the body fluid temporarily held by the polymer absorbent can be more reliably delivered to SAP, so that it can be used as an absorber. , High absorption efficiency can be exhibited more reliably.
  • the amount of liquid transferred from the polymer absorbent to SAP is more preferably 23.0 g / g or more, further preferably 27.0 g / g or more, and particularly preferably 33.0 g / g or more.
  • the amount of liquid transferred from this polymer absorbent to SAP can be measured as follows.
  • Nylon mesh material on the bottom surface N-NO255HD 115 manufactured by NBC Mesh Tech Co., Ltd. (standard width: 115 cm, 255 mesh / 2.54 cm, opening: 57 ⁇ m, wire diameter: 43 ⁇ m, thickness: 75 ⁇ m))
  • a plastic cylinder inner diameter: 60 mm, outer diameter: 70 mm, height: 52 mm, mass: 64 g
  • 0.3 g of a sample for measurement (polymer absorbent) is placed uniformly. Break in and measure the mass (g) of the cylinder. This measuring method is performed under the conditions of a temperature of 25 ° C. and a humidity of 60%.
  • the sample for measurement (polymer absorbent) is recovered from the product of sanitary goods and used, it can be obtained according to the above-mentioned ⁇ Method for recovering the sample for measurement (polymer absorbent)>.
  • a plastic cylinder (inner diameter: 60 mm, outer diameter: 70 mm, height: 52 mm, mass: 64 g) is placed in a petri dish (inner diameter: 85 mm, depth: 20 mm), and a highly absorbent polymer (SAP) is placed. After evenly sprinkling 0.3 g into the cylinder, remove the cylinder and measure the mass (g) of the petri dish.
  • Chloride with pedestal (inner diameter: 85 mm, depth: 20 mm, pedestal arrangement: two pedestals arranged in parallel at 24 mm intervals in the center of the bottom surface (inner surface side), pedestal width: 2 mm, pedestal height: 2 mm , Pedestal length: 25 mm), add 60 mL of physiological saline (0.9% sodium chloride aqueous solution).
  • the cylinder after draining in (5) above is placed on a petri dish containing SAP, and the sample in the cylinder and the SAP in the petri dish are passed through the bottom surface (mesh material) of the cylinder. Make contact.
  • the cylinder is removed and the mass (g) of the petri dish is measured.
  • the water absorption amount (g) of the SAP is calculated by subtracting the mass (g) of the dome measured in (8) above by the mass (g) of the planet measured in (2) above, and the water absorption amount is further calculated.
  • the water absorption amount of SAP per unit mass of the sample (g / g), that is, the amount of liquid transferred to the SAP per unit mass of the sample (g / g) is obtained. ..
  • the polymer absorbent when the composite absorber contains the above-mentioned polymer absorbent and SAP, the polymer absorbent preferably has a liquid discharge rate of 65% or more of the absorbed water.
  • the liquid discharge rate of the polymer absorbent is 65% or more, the water absorbed by the polymer absorbent is easily released, so that the body liquid temporarily held by the polymer absorbent is more easily received by the SAP. Can be passed.
  • the liquid discharge rate of the polymer absorbent is more preferably 70% or more, and particularly preferably 75% or more.
  • the liquid discharge rate of this polymer absorbent can be measured as follows.
  • ⁇ Measurement method of liquid discharge rate of polymer absorbent> (1) Mesh bag obtained by cutting 1 g of a sample (polymer absorbent) for measurement into 10 cm squares (manufactured by NBC Meshtec Inc., N-NO255HD 115 (standard width: 115 cm, 255 mesh / 2.54 cm, opening:) Enclose in 57 ⁇ m, wire diameter: 43 ⁇ m, thickness: 75 ⁇ m)). The mass (g) of the mesh bag is measured in advance. Further, this measuring method is carried out under the conditions of a temperature of 25 ° C. and a humidity of 60%.
  • the sample for measurement (polymer absorbent) is recovered from the product of sanitary goods and used, it can be obtained according to the above-mentioned ⁇ Method for recovering the sample for measurement (polymer absorbent)>.
  • (2) Immerse the mesh bag containing the sample in physiological saline (0.9% sodium chloride aqueous solution) for 1 hour.
  • (3) The mass (g) after hanging the mesh bag for 5 minutes and draining it is measured.
  • the mesh bag after draining in (3) above is subjected to centrifugation at 150 G for 90 seconds, and the mass (g) of the mesh bag after the centrifugation is measured.
  • the liquid discharge amount (g / g) per unit mass of the sample (polymer absorbent) is obtained.
  • the sample (polymer absorbent) is obtained by dividing the liquid discharge amount per unit mass obtained in (6) above by the water absorption amount per unit mass obtained in (4) above and multiplying by 100.
  • the liquid discharge amount with respect to the water absorption amount, that is, the liquid discharge rate (%) is obtained.
  • the above-mentioned absorbent A can be obtained by undergoing a cross-linking polymerization step and a hydrolysis step. Hereinafter, each of these steps will be described.
  • Cross-link polymerization step First, an oil-soluble monomer for cross-linking polymerization, a cross-linking monomer, a surfactant, water, and, if necessary, a polymerization initiator are mixed to obtain a water-in-oil emulsion.
  • This water-in-oil emulsion is an emulsion in which the oil phase becomes a continuous phase and water droplets are dispersed therein.
  • butyl methacrylate which is a (meth) acrylic acid ester
  • divinylbenzene is used as the crosslinkable monomer
  • surfactant is used.
  • Crosslink polymerization is carried out using sorbitan monooleate as an activator and isobutyronitrile as a polymerization initiator to obtain monolith A.
  • this emulsion is immediately transferred to a reaction vessel, sealed, and polymerized at 60 ° C. for 24 hours under the static condition. After completion of the polymerization, the contents are taken out, extracted with methanol, and dried under reduced pressure to obtain Monolith A having a continuous macropore structure.
  • the monolith A had an open cell structure and the thickness of the continuous skeleton was 5.4 ⁇ m.
  • the average diameter of the continuous pores measured by the mercury intrusion method was 36.2 ⁇ m, and the total pore volume was 15.5 mL / g.
  • the content of divinylbenzene with respect to all the monomers is preferably 0.3 to 10 mol%, more preferably 0.3 to 5 mol%. Further, the ratio of divinylbenzene to the total of butyl methacrylate and divinylbenzene is preferably 0.1 to 10 mol%, more preferably 0.3 to 8 mol%. In the above-mentioned absorbent A, the ratio of butyl methacrylate to the total of butyl methacrylate and divinylbenzene is 97.0 mol%, and the ratio of divinylbenzene is 3.0 mol%.
  • the amount of the surfactant added can be set according to the type of the oil-soluble monomer and the size of the desired emulsion particles (macropores), and is about 2 to 70 with respect to the total amount of the oil-soluble monomer and the surfactant. It is preferably in the range of%.
  • alcohols such as methanol and stearyl alcohol
  • carboxylic acids such as stearic acid
  • hydrocarbons such as octane, dodecane and toluene
  • cyclic ethers such as tetrahydrofuran and dioxane are used. It may coexist in the polymerization system.
  • the mixing method for forming the water-in-oil emulsion is not particularly limited.
  • a method of mixing each component at once, an oil-soluble monomer, a surfactant, and an oil-soluble polymerization initiator, which are oil-soluble can be adopted.
  • the mixing device for forming the emulsion is not particularly limited, and any device such as a normal mixer, a homogenizer, or a high-pressure homogenizer can be adopted depending on the desired emulsion particle size, and further, the object to be treated can be used.
  • a so-called planetary stirrer or the like can also be used, in which an object is placed in a mixing container and the mixture is rotated while revolving around a revolving axis in an inclined state to stir and mix the object to be processed.
  • the mixing conditions are not particularly limited, and the stirring rotation speed, stirring time, etc. can be arbitrarily set according to the desired emulsion particle size.
  • water droplets in the W / O emulsion can be uniformly generated, and the average diameter thereof can be arbitrarily set in a wide range.
  • Various conditions can be adopted for the polymerization conditions of the water-in-oil emulsion depending on the type of monomer and initiator.
  • the polymerization is carried out by heating at a temperature of 30 to 100 ° C. for 1 to 48 hours in a sealed container under an inert atmosphere.
  • hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, etc. are used as the polymerization initiator, they should be placed in a sealed container under an inert atmosphere at a temperature of 0 to 30 ° C. for 1 to 48 hours. It may be polymerized.
  • the unreacted monomer and the residual surfactant can be removed by taking out the contents and performing Soxhlet extraction with a solvent such as isopropanol to obtain Monolith A shown in the middle figure of FIG. ..
  • monolith A is immersed in dichloroethane containing zinc bromide, stirred at 40 ° C. for 24 hours, and hydrolyzed by contacting it with methanol, 4% hydrochloric acid, 4% sodium hydroxide aqueous solution and water in this order. After that, it is dried to obtain a block-shaped absorbent A. Further, the block-shaped absorbent A is pulverized to a predetermined size to obtain a particulate absorbent A.
  • the form of the absorbent A is not limited to particles, and may be formed into a sheet during or after drying, for example.
  • the method for hydrolyzing Monolith A is not particularly limited, and various methods can be adopted.
  • aromatic solvents such as toluene and xylene
  • halogen solvents such as chloroform and dichloroethane
  • ether solvents such as tetrahydrofuran and isopropyl ether
  • amide solvents such as dimethylformamide and dimethylacetamide
  • alcohol solvents such as methanol and ethanol.
  • P-solvented acid such as toluenesulfonic acid or Lewis acid such as zinc bromide, aluminum chloride, aluminum bromide, titanium chloride (IV), cerium chloride / sodium iodide, magnesium iodide, etc. Be done.
  • the (meth) acrylic acid ester is not particularly limited, but the (meth) acrylic acid has C1 to C10 (that is, the number of carbon atoms). Alkyl esters of 1 to 10) are preferable, and C4 (that is, 4 carbon atoms) alkyl esters of (meth) acrylic acid are particularly preferable.
  • the C4 alkyl ester of (meth) acrylic acid include (meth) acrylic acid t-butyl ester, (meth) acrylic acid n-butyl ester, and (meth) acrylic acid iso-butyl ester.
  • the monomer used for the cross-linking polymerization may be only (meth) acrylic acid ester and divinylbenzene, and in addition to (meth) acrylic acid ester and divinylbenzene, other than (meth) acrylic acid ester and divinylbenzene. It may contain other monomers. In the latter case, the other monomer is not particularly limited, but for example, styrene, ⁇ -methylstyrene, vinyltoluene, vinylbenzyl chloride, glycidyl (meth) acrylate, diethylhexyl (meth) acrylate, isobutene, butadiene, isobrene.
  • the proportion of the monomers other than the (meth) acrylic acid ester and divinylbenzene in all the monomers used for the cross-linking polymerization is preferably 0 to 80 mol%, more preferably 0 to 50 mol%.
  • the surfactant is not limited to the above-mentioned sorbitan monooleate, and may be any one that can form a water-in-oil (W / O) emulsion when the cross-linking polymerization monomer and water are mixed. ..
  • surfactants include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene group nonylphenyl ether, polyoxyethylene group stearyl ether, and polyoxyethylene group sorbitan.
  • Nonionic surfactants such as monooleate, anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, sodium dioctyl sulfosuccinate, cationic surfactants such as distearyldimethylammonium chloride, lauryldimethylbetaine and the like. Androgynous surfactants can be mentioned. These surfactants may be used alone or in combination of two or more.
  • the polymerization initiator a compound that generates radicals by heat and light irradiation is preferably used.
  • the polymerization initiator may be water-soluble or oil-soluble, and may be, for example, azobis (4-methoxy-2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, etc.
  • Azobiscyclohexanecarbonitrile azobis (2-methylpropionamidine) dihydrochloride
  • benzoyl peroxide potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, tetramethylthium disulfide, etc.
  • the polymerization proceeds only by heating or light irradiation without adding the polymerization initiator, so that it is not necessary to add the polymerization initiator in such a system.
  • the composite absorber of the present invention includes, for example, a pants-type disposable diaper, a tape-type disposable diaper, a sanitary napkin, an absorbent liner, and an absorbent pad (for example, a decubitus pad or a decubitus pad).
  • an absorbent pad for example, a decubitus pad or a decubitus pad.
  • Applicable to various hygiene products such as (pads, etc.), absorbent sheets, breast milk pads, disposable diapers for pets, absorbent pads for pets, excrement disposal sheets for pets, wet sheets, wet wipes, cosmetic wipes, masks, etc. can do. Therefore, the body fluid to be absorbed by the composite absorber is a liquid discharged from the wearer of the sanitary goods, and examples thereof include urine, sweat, stool, menstrual blood, cage, breast milk, blood, and exudate. Be done.
  • present invention is not limited to the above-described embodiments and the like, and can be appropriately combined, substituted, modified, etc. within the range not deviating from the object and purpose of the present invention.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Vascular Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epidemiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un corps absorbant ayant une efficacité d'absorption élevée.　Un corps absorbant composite (4) selon la présente invention est destiné à des articles d'hygiène qui sont destinés à absorber des fluides corporels, et est caractérisé en ce qu'il comprend un absorbant polymère doté d'un squelette continu hydrophile et de pores continus, l'absorbant polymère présentant une quantité initiale d'absorption d'eau non inférieure à 5 g/g lorsque 5 secondes se sont écoulées depuis l'application d'une charge de 40 g/cm2, et, après 20 ou plus de 20 secondes, une quantité d'absorption d'eau qui est égale ou supérieure à 110 % de la quantité d'absorption d'eau initiale.
PCT/JP2021/046341 2020-12-29 2021-12-15 Corps absorbant composite et article d'hygiène WO2022145243A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002505702A (ja) * 1997-06-19 2002-02-19 エスシーエー ハイジーン プロダクツ アーベー 吸収材料構造体、その製造方法及び用途、及びかかる材料構造体を含む使い捨て吸収物品
JP2010522008A (ja) * 2007-03-23 2010-07-01 キンバリー クラーク ワールドワイド インコーポレイテッド 高透過率の超吸水性ポリマー組成物を含む吸収性物品
WO2011129314A1 (fr) * 2010-04-13 2011-10-20 和光純薬工業株式会社 Procédé de deutération ou tritiation de saccharide
JP2013000696A (ja) * 2011-06-20 2013-01-07 Fujifilm Corp 水の浄化方法
WO2020261929A1 (fr) * 2019-06-28 2020-12-30 オルガノ株式会社 Échangeur d'ions poreux organique monolithique
WO2020262343A1 (fr) * 2019-06-28 2020-12-30 ユニ・チャーム株式会社 Absorbeur et article absorbant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002505702A (ja) * 1997-06-19 2002-02-19 エスシーエー ハイジーン プロダクツ アーベー 吸収材料構造体、その製造方法及び用途、及びかかる材料構造体を含む使い捨て吸収物品
JP2010522008A (ja) * 2007-03-23 2010-07-01 キンバリー クラーク ワールドワイド インコーポレイテッド 高透過率の超吸水性ポリマー組成物を含む吸収性物品
WO2011129314A1 (fr) * 2010-04-13 2011-10-20 和光純薬工業株式会社 Procédé de deutération ou tritiation de saccharide
JP2013000696A (ja) * 2011-06-20 2013-01-07 Fujifilm Corp 水の浄化方法
WO2020261929A1 (fr) * 2019-06-28 2020-12-30 オルガノ株式会社 Échangeur d'ions poreux organique monolithique
WO2020262343A1 (fr) * 2019-06-28 2020-12-30 ユニ・チャーム株式会社 Absorbeur et article absorbant

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