WO2009150984A1 - 吸収体及び吸収性物品 - Google Patents
吸収体及び吸収性物品 Download PDFInfo
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- WO2009150984A1 WO2009150984A1 PCT/JP2009/060185 JP2009060185W WO2009150984A1 WO 2009150984 A1 WO2009150984 A1 WO 2009150984A1 JP 2009060185 W JP2009060185 W JP 2009060185W WO 2009150984 A1 WO2009150984 A1 WO 2009150984A1
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- Prior art keywords
- water
- absorbing polymer
- polymer
- absorbent
- fiber
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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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
- A61F13/45—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 shape
- A61F13/47—Sanitary towels, incontinence pads or napkins
- A61F13/475—Sanitary towels, incontinence pads or napkins characterised by edge leakage prevention means
- A61F13/4751—Sanitary towels, incontinence pads or napkins characterised by edge leakage prevention means the means preventing fluid flow in a transversal direction
- A61F13/4756—Sanitary towels, incontinence pads or napkins characterised by edge leakage prevention means the means preventing fluid flow in a transversal direction the means consisting of grooves, e.g. channels, depressions or embossments, resulting in a heterogeneous surface level
-
- 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
- A61F13/534—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 having an inhomogeneous composition through the thickness of the pad
- A61F13/53409—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 having an inhomogeneous composition through the thickness of the pad having a folded core
- A61F13/53418—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 having an inhomogeneous composition through the thickness of the pad having a folded core having a C-folded cross-section
-
- 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
- A61F2013/530481—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials
- A61F2013/53051—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials being only in particular parts or specially arranged
- A61F2013/530547—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials being only in particular parts or specially arranged positioned in a separate layer or layers
- A61F2013/530554—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials being only in particular parts or specially arranged positioned in a separate layer or layers and being fixed to a web
-
- 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
- A61F2013/530481—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials
- A61F2013/530708—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the absorbency properties
- A61F2013/530737—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the absorbency properties by the absorbent capacity
-
- 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
- A61F2013/530481—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials
- A61F2013/530708—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the absorbency properties
- A61F2013/530737—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the absorbency properties by the absorbent capacity
- A61F2013/530744—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 having superabsorbent materials, i.e. highly absorbent polymer gel materials characterized by the absorbency properties by the absorbent capacity by the absorbency under load
Definitions
- the present invention relates to an absorbent body used for absorbent articles such as sanitary napkins and absorbent articles using the absorbent body, and more particularly, an absorbent body that can easily remove redness such as menstrual blood absorbed by washing with water after use. And an absorbent article.
- an absorbent body containing a water-absorbing polymer As an absorbent article such as a sanitary napkin or a disposable diaper, an absorbent body containing a water-absorbing polymer is known.
- a water-absorbing polymer water-absorbing polymers having carboxy groups and / or carboxylate groups such as polyacrylic acid-based water-absorbing polymers are mainly used, and various techniques for improving the water-absorbing polymers have been proposed. Yes.
- Patent Document 1 Japanese Patent No. 3461860 discloses a technique for improving a water-absorbing polymer, in which an unneutralized carboxy of a water-absorbing resin (water-absorbing polymer) having a predetermined degree of neutralization (50 to 85 mol%) is disclosed. A method is described in which a group is further neutralized with a water-soluble alkali compound containing an alkali metal and / or ammonium to adjust to a predetermined degree of neutralization (50.1 to 95 mol%). According to the method described in Patent Document 1, the amount of water absorption (water absorption ratio) under pressure of the water-absorbing polymer, which is one of the important performances in absorbent article applications, is increased, and the water absorption under pressure is improved. ing.
- sanitary napkins that have been mainly used in Malay ethnic territories are cloth napkins (for example, Patent Documents 2 to 4: Japanese Patent Laid-Open Nos. 2006-288868, 2001-353182, and 2004). No. 337204) and water-absorbing materials mainly composed of pulp fibers and containing no water-absorbing polymer, and thus can be washed with water, and absorbed menstrual blood can be washed away with water. Met.
- the sanitary napkin containing a water-absorbing polymer as described in Patent Document 1 adheres firmly to the water-absorbing polymer with coloring components such as hemoglobin in menstrual blood. It was difficult to wash away blood, and washing with water was difficult.
- a sanitary napkin that does not contain a water-absorbing polymer as described above has poor menstrual blood absorption and retention performance, and may cause so-called liquid return in which, for example, body fluid absorbed on the surface of the absorbent material oozes out. Therefore, in a conventional sanitary napkin that can be washed with water and does not contain a water-absorbing polymer, the use of a large amount of pulp fibers compensates for the lack of absorption performance.
- such sanitary napkins become thick due to the bulkiness of the pulp fibers, are particularly bulky when folded and packaged, are inconvenient to carry, and have a poor fit.
- the present invention relates to providing an absorbent body and an absorbent article that contain a water-absorbing polymer and can be easily washed with water.
- the present inventors have found that the water-absorbing polymer having a carboxy group and / or a carboxylate group such as a polyacrylic acid-based water-absorbing polymer as a water-absorbing polymer contained in the absorber.
- a polymer whose neutralization degree and centrifugal retention amount (water absorption ratio) are controlled within a specific range, the redness of the absorber due to absorbed menstrual blood and the like is greatly reduced by washing the absorber with water. And it was found that the absorption performance can be maintained. It was also found that the redness of absorbed menstrual blood increases when the amount of centrifugal retention (water absorption ratio) of the water-absorbing polymer increases.
- the present invention has been made on the basis of the above knowledge, and has a carboxy group and / or a carboxylate group, has a neutralization degree of 75 mol% or more, and has a water absorption capacity of 5 to 20 g / g according to JIS K 7223. It is an absorber containing a functional polymer.
- the present invention also relates to an absorber containing a water-absorbing polymer, wherein the absolute value of the difference between the zeta potential of the water-absorbing polymer in ion-exchanged water and the zeta potential of bovine hemoglobin in ion-exchanged water is 30 mV or less. is there.
- the present invention contains a water-absorbing polymer
- the water-absorbing polymer has a carboxy group and / or a carboxylate group and is neutralized with a neutralizing agent containing an alkali metal, and the degree of neutralization is
- the absorber is 75 mol% or more and the alkali metal is uniformly distributed throughout the water-absorbing polymer.
- the present invention is an absorbent article comprising the absorber.
- this invention is a manufacturing method of the water absorbing polymer which has the following process I and II.
- Step I Polymerizing a monomer containing (meth) acrylic acid and / or an alkali metal salt thereof to obtain a polymer, crosslinking the polymer with a crosslinking agent, or (meth) acrylic acid and / or an alkali metal salt thereof In the presence of a crosslinking agent to prepare a polymer having a centrifugal retention amount of 5 to 20 g / g in accordance with JIS K 7223, wherein the mass ratio of the crosslinking agent to the monomer [crosslinking Agent / monomer] is 0.15 / 100 to 40/100.
- Step II A step of bringing the polymer obtained in Step I above into contact with a basic compound and / or water and performing a neutralization treatment so that the degree of neutralization of the polymer is 75 mol% or more.
- the present invention is a water-absorbing polymer obtained by the above production method.
- the absorbent body and absorbent article of the present invention can be easily washed with water despite containing a water-absorbing polymer, and can remove redness caused by blood such as absorbed menstrual blood. It is suitable for people who have a habit of washing the article with water and then disposing it. Moreover, since the absorbent body and absorbent article of the present invention contain a water-absorbing polymer, the absorption performance is good, for example, liquid return can be effectively suppressed. Furthermore, since the thickness can be designed to be thin, it is possible to provide an absorbent article that is not bulky and has excellent portability and wearing feeling.
- FIG. 1 is a perspective view showing the skin contact surface side (surface sheet side) of one embodiment of the sanitary napkin of the present invention.
- FIG. 2 is a cross-sectional view schematically showing a cross section taken along line XX of FIG.
- FIG. 3 is a perspective view schematically showing one embodiment of the absorbent body of the present invention.
- FIG. 4 is a perspective view schematically showing another embodiment of the absorbent body of the present invention.
- FIG. 5 is a perspective view schematically showing still another embodiment of the absorbent body of the present invention.
- 6 is a cross-sectional view schematically showing a cross-section in the width direction of the polymer sheet used in the absorbent body shown in FIG.
- FIG. 7 is a view corresponding to FIG. 2 showing another embodiment of the sanitary napkin of the present invention.
- FIG. 8 is a view corresponding to FIG. 2 of the sanitary napkin of Example 5.
- FIG. 2 is a sectional view taken along line XX in FIG.
- the sanitary napkin 1 (hereinafter also referred to as napkin 1) of the present embodiment includes a front surface layer, a back surface layer, and an absorption layer that is disposed between both layers and contains a water-absorbing material. More specifically, the napkin 1 has a shape that is long in one direction as shown in FIG. 1, a top sheet 2 as a liquid-permeable surface layer, a back sheet 3 as a liquid-impermeable back layer, And the absorber 4 as a liquid holding
- the absorbent body 4 has a shape that is long in one direction, and the longitudinal direction of the absorbent body 4 coincides with the longitudinal direction of the napkin 1 so that the absorbent body 4 is disposed at the center in the width direction of the napkin 1.
- the top sheet 2 covers the entire skin contact surface of the absorber 4, and the back sheet 3 covers the entire non-skin contact surface of the absorber 4.
- the top sheet 2 and the back sheet 3 are joined to each other at an extended portion extending outward from the peripheral edge of the absorber 4 to form an end seal portion 6.
- An adhesive is applied on the non-skin contact surface of the back sheet 3 to form a fixing portion (not shown) for fixing the napkin 1 to shorts or the like.
- the top sheet 2 can be made of the same material as that conventionally known. For example, a hydrophilic nonwoven fabric or a perforated film is used.
- the back sheet 3 is made of, for example, a liquid-impermeable film sheet, and the liquid-impermeable film sheet may have water vapor permeability.
- the “longitudinal direction” is a direction along the long side direction of the absorbent article or its constituent members
- the “width direction” is a direction orthogonal to the longitudinal direction.
- the “skin contact surface” is a surface of the absorbent article or a component thereof that faces the wearer's skin when the absorbent article is worn
- the “non-skin contact surface” refers to the absorbent article or its It is a surface which is directed to the underwear side (the side opposite to the wearer's skin side) when the absorbent article is worn in the constituent member.
- the absorbent body 4 of the present embodiment includes thin absorbent sheets 4a and 4b containing a water-absorbing polymer or fiber. More specifically, the absorbent body 4 has a structure in which two absorbent sheets 4a and 4a are overlapped to form a laminate, and another absorbent sheet 4b and 4b is overlapped on the upper and lower surfaces of the laminate. It consists of a laminate of four thin absorbent sheets.
- the absorbent sheet 4a and the absorbent sheet 4b have the same composition and differ only in dimensions, and the absorbent sheet 4a positioned inward in the thickness direction of the absorbent body 4 absorbs in the thickness direction outward.
- the dimension (length in the longitudinal direction and width direction) in plan view is smaller than that of the conductive sheet 4b.
- the absorbent body 4 Since the absorbent body 4 has such a configuration, the absorption capacity at the center of the product is high, so that menstrual blood hardly spreads over the entire napkin, and a narrow range of washing is sufficient. Further, the absorbent body 4 is difficult to twist while the napkin is worn, and the absorbent body 4 is not easily biased when the napkin is washed, so that it is easy to squeeze.
- a composition may differ between the absorbent sheet 4a and the absorbent sheet 4b, and the arrangement
- the substantially entire absorber 4 may be covered with a covering sheet (not shown).
- a covering sheet When substantially the entire absorber is covered with a covering sheet, it is particularly effective for improving the shape stability of the absorber and preventing the water-absorbing polymer from falling off.
- the form of covering the absorbent body with the covering sheet is not particularly limited.
- the form in which the upper surface (skin contact surface) and the left and right side faces of the absorbent body are covered with the covering sheet, and in addition to these faces, the absorbent body The form by which the lower surface (non-skin contact surface) is covered with a covering sheet.
- the absorbent body 4 When the absorbent body 4 is coated with the covering sheet, extreme movement and dropping off of the water-absorbing polymer contained in the absorbent body 4 can be effectively prevented during wearing or washing of the absorbent article. . Furthermore, since the handling property as the absorber 4 as a whole becomes good, it can be easily transported alone. Moreover, since it can be easily cut or cut into a desired shape, an absorbent body corresponding to the shape of the absorbent article can be easily produced.
- the absorber 4 and the covering sheet may be joined by a predetermined means.
- covered with the coating sheet increases, and handling property becomes still more favorable by it.
- embossing performed on a normal sanitary napkin absorbing body from above the covering sheet or the top sheet 2) 4 is formed).
- the covering sheet a material that has a strength sufficient to prevent the water-absorbing polymer from falling off and that does not hinder the permeation of excreted liquid is appropriately used.
- a hydrophilic fiber sheet for example, a hydrophilic fiber sheet, a perforated film or the like is used.
- the hydrophilic fiber sheet include paper such as tissue paper and various nonwoven fabrics (spunbond nonwoven fabric, spunbond-meltblown-spunbond nonwoven fabric). , Spunbond-meltblown-meltblown-spunbond nonwoven fabric, thermal bond nonwoven fabric, needle punch nonwoven fabric, spunlace nonwoven fabric, airlaid nonwoven fabric, spunlace nonwoven fabric containing hydrophilic fibers such as acrylic and rayon, and the like.
- nonwoven fabrics may be subjected to a hydrophilic treatment or a hole opening treatment as necessary, and may further be formed with slits, or may be subjected to a softening process such as embossing.
- the constituent fibers of these nonwoven fabrics include fibers using a thermoplastic resin such as polyethylene, polypropylene, and polyethylene terephthalate alone, or composite fibers using these resins.
- hydrophilic fibers such as rayon, cotton, lyocell, tencel, acetate, and natural pulp, can coexist in these nonwoven fabrics.
- Examples of the absorbent sheets 4a and 4b include the absorbent sheet described in [Embodiment of the invention] of JP-A-9-156014.
- a sheet in which the water-absorbent polymer is fixed between two thin sheets of paper due to the adhesive or the water-absorbent polymer when wet including a laminated structure in which a plurality of layers of fiber assemblies are laminated, A sheet in which a water-absorbing polymer is interposed between one of the layers in the laminated structure); a water-absorbing polymer is dispersed at the time of manufacturing the nonwoven fabric, and the water-absorbing polymer is sprayed on the previously manufactured nonwoven fabric at the same time
- a sheet in which the water-absorbing polymer is immobilized; a sheet in which a water-absorbing polymer is directly polymerized and immobilized on a fiber assembly produced by a known card method or the like is preferably used as a thin absorbent sheet.
- the absorbent body 4 is not limited to the structure including the absorbent sheets 4a and 4b described above, and for example, a conventionally used mixed product of water absorbent polymer and pulp fiber or a water absorbent polymer. And a laminate of pulp fibers and the following absorbers A to C can also be used.
- Each of the following absorbers A to C has a laminated structure in which a plurality of layers made of fiber assemblies are laminated, and an absorption in which a water-absorbing polymer is interposed between one of the layers in the laminated structure. Is the body.
- Absorbent body A an absorbent body in which the water-absorbing polymer 41 is wrapped with one fiber sheet 40 (see FIG. 3).
- the absorbent body A shown in FIG. 3 has a rectangular shape in plan view, and is incorporated into the napkin 1 with its longitudinal direction coinciding with the longitudinal direction of the napkin 1.
- a non-existing region 50 of the water-absorbing polymer 41 is formed at the center in the width direction of the absorbent body A.
- the non-existing area 50 has a linear shape extending in the longitudinal direction of the napkin 1 in plan view, and extends over substantially the entire length of the absorbent body A in the longitudinal direction.
- the non-existing area 50 is a concave portion in which one surface side of the absorber A is recessed in the thickness direction.
- the recess may be directed to the skin contact surface side of the napkin 1 or may be directed to the non-skin contact surface side.
- the absorber A can be manufactured as follows, for example. The water-absorbing polymer is applied so that the non-existing area 50 is formed in the central region sandwiched between both sides of the fiber sheet by spreading the water-absorbing polymer in a stripe shape on one surface of the vertically long fiber sheet. Scatter. And the absorber A is obtained by wrapping the disperse
- the fiber sheet 40 a sheet containing pulp fiber, synthetic fiber, or the like can be used, and examples thereof include paper and nonwoven fabric. Moreover, as the fiber sheet 40, the hydrophilic sheet mentioned later can also be used.
- Adoption of the absorbent body A improves the absorption performance through effective use of the absorbent body, and also increases the drainage of the cleaning water and enables rapid cleaning.
- Absorber A has a non-existing region of the water-absorbing polymer in the center portion in the width direction, and the rigidity in the center portion in the width direction is lower than in other parts, so that the wearability is improved. It is done.
- Absorbent body B an absorbent body in which a water absorbent polymer 41 and a synthetic fiber nonwoven fabric 45 are interposed between two fiber sheets 40 and 40 (see FIG. 4).
- the absorbent body B shown in FIG. 4 has a rectangular shape in plan view, and is incorporated into the napkin 1 with its longitudinal direction coinciding with the longitudinal direction of the napkin 1.
- the water-absorbing polymer 41 in the absorbent body B is supported on the nonwoven fabric 45. That is, the water-absorbing polymer 41 enters the space formed by the constituent fibers (synthetic fibers) of the non-woven fabric 45, and even if stress is applied to the non-woven fabric 45 from the outside, extreme movement and dropout are unlikely to occur. .
- Adoption of the absorbent body B suppresses the movement of the water-absorbing polymer mainly due to the action of the nonwoven fabric, suppresses the twist of the absorbent body that occurs when the napkin is squeezed during wearing or washing, and exhibits stable absorption characteristics. This makes it easier to replace the washing water.
- Absorbent body C an absorbent body including a polymer sheet 46 in which a water-absorbing polymer 41 is interposed between two fiber sheets 40, 40, and absorbs water over at least one side of the polymer sheet 46.
- Fig. 6 is a schematic cross-sectional view in the width direction orthogonal to the longitudinal direction of the polymer sheet 46.
- the absorbent body C shown in FIG. 5 has a rectangular shape in plan view, and is incorporated into the napkin 1 with its longitudinal direction coinciding with the longitudinal direction of the napkin 1.
- the polymer sheet 46 in the absorbent body C does not include the water-absorbing polymer 41 over the entire longitudinal side portions 46s and 46s, and is C-shaped in a cross-sectional view in the width direction as shown in FIG.
- the both side portions 46s, 46s in the longitudinal direction are respectively located in the center portion in the width direction of the absorbent body C.
- the longitudinal side portions 46s and 46s may be abutted as shown in FIG. 5, or one may be overlaid on the other.
- both side portions 46s, 46s in the longitudinal direction of the polymer sheet 46 that are abutted or overlapped may be directed to the skin contact surface side of the napkin 1, and non-skin contact You may face to the surface side.
- the absorbent body C Since the absorbent body C has a relatively high liquid permeability in the thickness direction, the use of the absorbent body C increases the drainage of the washing water and enables rapid cleaning.
- absorber 4 include absorbers (hereinafter also referred to as absorber D) as described in, for example, Japanese Patent Application Laid-Open No. 2006-110329 and Japanese Patent Application Laid-Open No. 2007-283086.
- the absorber D is an absorber in which a water-absorbing polymer is supported on a fiber web.
- the water absorbent polymer is entangled in the fiber gap of the long fiber in the fiber web or the long fiber is cut to become a short fiber, or the water absorbent polymer is fixed to the fiber gap by hot melt or the like. Yes.
- the crimp rate (JIS L0208) of the constituent fibers (long fibers) is preferably 10 to 90%, more preferably 10 to 60%, and still more preferably 10 to 50%. Since the long fibers are crimped, the absorbent body D is easily deformed flexibly as a whole, and when the absorbent body D is incorporated into an absorbent article, it is deformed into a wearable fit or concave shape. Therefore, it is possible to improve the deformability to the concave shape when improving the leak-proof property.
- the adoption of the absorbent body D allows the water-absorbing polymer to easily get entangled in the constituent fibers of the absorbent body D even if a hand-holding operation is performed during cleaning of the absorbent article, so that the water-absorbing polymer flows out of the article during the cleaning. Is prevented.
- the crimp of the long fiber and the short fiber in the absorbent body D may be two-dimensional or three-dimensional.
- the absorber 4 preferably contains a specific water-absorbing polymer (hereinafter also referred to as a water-absorbing polymer A) as a water-absorbing material.
- a specific water-absorbing polymer hereinafter also referred to as a water-absorbing polymer A
- the main effect of the absorbent body 4 or napkin 1 of this embodiment is largely due to the action of the water-absorbing polymer A.
- the water-absorbing polymer A will be described.
- the absorbent body and absorbent article of the present invention preferably have a degree of neutralization and a centrifugal retention amount, which will be described later, in a specific range which will be described later, respectively, and preferably various other physical properties which will be described later in addition to these characteristics ( Water absorption polymer by vortex method, water absorption rate by DW method, bulk specific gravity, liquid flow rate under pressure at 2.0 kPa, absorption amount under pressure at 2.0 kPa, etc. are within the specific ranges described below ( It is preferred to contain a water-absorbing polymer A).
- the term “contains the water-absorbing polymer A” means that the average of the measured values of the degree of neutralization and the centrifugal retention amount of the water-absorbing polymer in at least a predetermined part of the absorbent body or the absorbent article is specified later. Means within range. It is even better if the average of the measured values of various properties described later other than the degree of neutralization and the centrifugal retention amount of the water-absorbing polymer at the predetermined site is within a specific range described later.
- the “predetermined part” for example, a part (excretion part facing part) facing the excretion part of the absorbent article wearer in the absorbent body or the absorbent article can be mentioned.
- the average of the measured values of the neutralization degree and the centrifugal retention amount of the water-absorbing polymer in the entire absorbent body or absorbent article as well as a predetermined part (excretion part facing part) is within a specific range described later.
- the average of measured values of various physical properties to be described later including the degree of neutralization and the retained centrifugal amount is within a specific range described later.
- the water-absorbing polymer A used in the present invention is a water-absorbing resin having a carboxy group and / or a carboxylate group in its structural unit.
- a water-absorbing polymer generally includes a polymer or copolymer of acrylic acid or an alkali metal acrylate, and examples thereof include polyacrylic acid and a salt thereof and polymethacrylic acid and a salt thereof.
- the polyacrylate and polymethacrylate sodium salts can be preferably used.
- a copolymer obtained by copolymerizing the above-mentioned comonomer within a range that does not deteriorate the performance of the water-absorbing polymer can also be preferably used as the water-absorbing polymer A.
- water-absorbing polymer having a carboxyl group and / or a carboxylate group include, for example, polyacrylic acid crosslinked polymers and copolymers, starch-acrylonitrile graft polymer hydrolysates, starch-acrylic acid graft crosslinked polymers, Examples thereof include saponified vinyl acetate-acrylic acid ester copolymers.
- polyacrylic acid-based water-absorbing polymers are polymers that contain at least 50 mol% of acrylic acid monomer units and are substantially insoluble in water, but have a high degree of swelling.
- the water-absorbing polymer having a carboxy group and / or a carboxylate group constituting the water-absorbing polymer A is a polymer of acrylic acid or an alkali metal acrylate.
- the water-absorbing polymer A is composed of such a water-absorbing polymer, it is particularly effective in terms of control of water-absorbing physical properties, production cost, safety and the like.
- the water-absorbing polymer A used in the present invention preferably has a neutralization degree of 75 mol% or more.
- the degree of neutralization is preferably 75 to 95 mol%, particularly 80 to 90 mol%.
- the reason for setting the neutralization degree of the water-absorbing polymer having a carboxy group and / or a carboxylate group as high as 75 mol% or higher is mainly in the menstrual blood absorbed by the absorbent body 4. This is to prevent hemoglobin, which is the main red component, from adhering to the water-absorbing polymer.
- the portion of the absorber 4 that absorbs blood such as menstrual blood is reddish, but the main cause of this redness is in hemoglobin in the blood. Therefore, in order to easily remove this redness by washing the napkin with water, it is effective to reduce the adhesion rate or adhesion strength of hemoglobin to the water-absorbing polymer.
- the water-absorbing polymer comprising an acrylic acid cross-linked polymer.
- the redness of the napkin caused by blood can be easily removed by washing with water by adjusting the neutralization degree of the polymer to 75 mol% or more.
- the neutralization degree of the water-absorbing polymer composed of the acrylic acid cross-linked polymer is 75 mol% or more.
- the adhesion rate or adhesion strength of hemoglobin to the water-absorbing polymer is reduced, and it is assumed that hemoglobin is easily detached by washing with water.
- the degree of neutralization is measured as follows.
- a neutralization titration curve of the main chain polymer of the water-absorbing polymer is prepared.
- the main chain polymer of the water absorbent polymer is polyacrylic acid.
- a sodium hydroxide solution was appropriately added dropwise to an ion exchange aqueous solution of polyacrylic acid (Wako Pure Chemical Industries, average molecular weight 250,000), and the pH of the solution was measured using a pH meter.
- the degree of neutralization was calculated from the molecular weight of polyacrylic acid and the number of moles of added sodium hydroxide, and the neutralization degree was plotted on the horizontal axis and the pH was plotted on the vertical axis to draw a neutralization titration curve.
- the degree of neutralization was in the range of 50 to 100%.
- As the pH meter Horiba pH ion meter D53 and electrode type 6583 were used.
- 0.1 g of the water-absorbing polymer was put into 20 ml of ion-exchanged water, and after stirring for 10 minutes, the pH of the stirred solvent was measured. From the obtained pH value, the neutralization titration curve was used for the purpose.
- the degree of neutralization was calculated. The measurement is performed at 23 ⁇ 2 ° C. and humidity 50 ⁇ 5%, and the sample is measured after being stored in the same environment for 24 hours or more.
- the amount of sodium in the water-absorbing polymer was quantified by elemental analysis, and the following theoretical structural formula (1) (theory applied to acrylic acid-based water-absorbing polymers)
- the target neutralization degree may be calculated based on the structural formula.
- a target neutralization degree may be calculated from a value measured by a method according to JIS K0113-1997.
- a method based on JIS K0113-1997 is a method in which a 0.1 N potassium hydroxide aqueous solution is used as a titrant to perform potentiometric titration, and an end point is determined by an inflection point method.
- Adjustment of the degree of neutralization of the water-absorbing polymer can be performed, for example, by neutralizing the water-absorbing polymer with an alkali compound. This neutralization process will be described later.
- the water-absorbing polymer A used in the present invention has a carboxy group and / or a carboxylate group and preferably has a degree of neutralization of preferably 75 mol% or more, and further, a centrifugal retention amount in accordance with JIS K 7223. Is preferably 5 to 20 g / g.
- the centrifugal retention amount of the water-absorbing polymer is a property related to the water absorption amount (water absorption magnification) of the water-absorbing polymer. Generally, a water-absorbing polymer having a large centrifugal retention amount has a large water absorption amount (water absorption magnification).
- the absorbent body in the absorbent article in order to improve the absorption performance of the absorbent body in the absorbent article, it can be said that it is effective to increase the value of the centrifugal retention amount of the water-absorbing polymer contained in the absorbent body.
- a method of blending a large amount of water-absorbing polymer into the absorbent body with a high basis weight is effective, but when such a method is employed in the absorbent article, When the absorbent article is washed with water, the absorbent polymer absorbs a large amount of washing water, which may cause the absorbent article to expand and rupture.
- the present inventors have controlled the water absorption ratio of the water-absorbing polymer, and further controlled the absorption rate, so that the absorbent article expands and bursts during washing. It was found that the operation of washing and squeezing absorbent articles becomes easier.
- the purpose of increasing the degree of neutralization of the water-absorbing polymer described in Patent Document 1 is to increase the osmotic pressure of the obtained water-absorbing polymer, increase the water absorption rate, or increase the water absorption ratio (under pressure). Because.
- an increase in the amount of the water-absorbing polymer centrifuged and the water absorption speed have undesirable effects. That is, when the centrifugal retention amount of the water-absorbing polymer increases, redness due to absorbed blood increases, and it becomes more difficult to remove such redness by washing with water.
- the increase in the water absorption rate facilitates the absorption of hemoglobin in the blood together with the washing water when the absorbent article is washed with water, and the swelling of the water-absorbing polymer causes the article to expand in a short period of time.
- the centrifugal retention amount of the water-absorbing polymer A is more preferably 7 to 15 g / g. The centrifugal retention amount is measured as follows.
- ⁇ Measuring method of centrifugal retention The measurement of the centrifugal retention amount is performed according to JIS K 7223 (1996).
- Nylon woven fabric (mesh opening 255, sold by Sanriku Manufacturing Co., Ltd., product name: nylon net, standard: 250 x mesh width x 30 m) is cut into a rectangle with a width of 10 cm and a length of 40 cm and folded in half at the center in the longitudinal direction. Both ends are heat-sealed to produce a nylon bag having a width of 10 cm (inner dimension: 9 cm) and a length of 20 cm. 1.00 g of the water-absorbing polymer as a measurement sample is precisely weighed and placed uniformly at the bottom of the produced nylon bag.
- the nylon bag containing the sample is immersed in physiological saline (0.9 mass% sodium chloride water) adjusted to 25 ° C. Thirty minutes after the start of soaking, the nylon bag is taken out from the physiological saline, suspended in a vertical state for 1 hour and drained, and then dehydrated using a centrifugal dehydrator (Kokusan Co., Ltd., model H-130C special model). The dehydration condition is 143 G (800 rpm) for 10 minutes. After dehydration, the mass of the sample is measured, and the target centrifugal retention amount is calculated according to the following formula.
- the amount of centrifugal retention of the water-absorbing polymer can be adjusted, for example, by adjusting the degree of surface crosslinking of the water-absorbing polymer.
- the centrifugal retention amount water absorption magnification
- the centrifugal retention amount can be adjusted to the above range. Is possible.
- the centrifugal retention amount can be adjusted by increasing the degree of crosslinking of the entire water-absorbing polymer regardless of whether or not surface crosslinking is performed.
- the degree of cross-linking of the water-absorbing polymer A used in the present invention (the degree of surface cross-linking or the degree of cross-linking of the whole water-absorbing polymer) is at a higher level than that of a normal water-absorbing polymer. In order to realize the degree, it is preferable to take a method such as increasing the amount of the crosslinking agent, raising the reaction temperature, or taking a longer reaction time.
- the water-absorbing polymer A used in the present invention preferably has a water absorption rate of 30 seconds or more, particularly 40 to 120 seconds, by the vortex method.
- the evaluation of the water absorption rate by the vortex method is evaluated by measuring time, the longer the measurement time, the lower the water absorption rate. If the water-absorbing polymer A is such a relatively slow water-absorbing polymer, the absorbent 4 (absorbent sheets 4a and 4b) is broken by preventing the water-absorbing polymer from swollen rapidly during washing. Can be prevented.
- the water-absorbing polymer whose water absorption rate by the vortex method is in the above range is, for example, the particle size of the water-absorbing polymer, the primary cross-linking density, the adjustment of the degree of surface cross-linking (post-crosslinking treatment), shape control, various surfactants and polyhydric alcohols. It can be obtained by surface treatment of a water-absorbing polymer with hydrophilic powder or the like.
- the water absorption rate by the vortex method is measured as follows.
- ⁇ Measurement method of water absorption rate by vortex method A 100 mL glass beaker, 50 mL of physiological saline (0.9% by mass sodium chloride water) and a magnetic stirrer chip (center diameter 8 mm, both ends diameter 7 mm, length 30 mm, surface coated with fluororesin ) And place the beaker on a magnetic stirrer (HPS-100 manufactured by ASONE). The rotational speed of the magnetic stirrer is adjusted to 600 ⁇ 60 rpm, and the physiological saline is stirred.
- the water absorption rate of the water-absorbing polymer A used in the present invention can also be evaluated by the measured value of the DW method generally used in the technical field.
- the water absorption rate by the vortex method serves as an index for the water-absorbing polymer to fix a certain amount of liquid
- the water absorption rate by the DW method expresses the behavior of the water-absorbing polymer to absorb and absorb the liquid. , Including the amount of water present in the gap between adjacent water-absorbing polymers.
- the water absorption rate according to the DW method is useful as an index of the shape retention of the absorbent body during production and after liquid absorption, particularly the shape retention after liquid absorption.
- the water absorption rate (unit: ml / 0.3 g ⁇ 30 sec) by the DW method is measured using a device (Demand Wettability Tester) generally known as a device for performing the DW method.
- a device Demand Wettability Tester
- the level of the physiological saline solution is set at the same level as the surface of the polymer spray table (70 mm ⁇ , a table in which No. 2 filter paper is placed on the glass filter No. 1), and the polymer spray table Sprinkle 0.3 g of the water-absorbing polymer to be measured on the surface.
- the water absorption at the time when the water-absorbing polymer is sprayed is set to 0, and the water absorption after 30 seconds is measured.
- the amount of water absorption is measured by a burette scale indicating the amount of decrease in the saline water level.
- the value of the water absorption obtained is taken as the water absorption rate by the DW method.
- the water absorption rate by the DW method can be designed by the shape, particle size, bulk specific gravity, degree of crosslinking, etc. of the water-absorbing polymer.
- the measurement is performed at 23 ⁇ 2 ° C. and humidity 50 ⁇ 5%, and the sample is measured after being stored in the same environment for 24 hours or more.
- the absorbent body 4 when the absorbent body 4 is produced by spreading a water-absorbing polymer on a water-containing fiber web and superimposing another fiber web on the spread water-absorbing polymer, the water-absorbing polymer
- the water absorption speed by the DW method is too high, the moisture content in the absorbent body 4 is increased, and drying defects are likely to occur.
- the water absorption rate by the DW method is too slow, the adhesiveness of the water-absorbing polymer does not work, and sufficient adhesion between the layers cannot be obtained. As a result, the water-absorbing polymer may come out of the absorber 4.
- the water absorption rate of the water-absorbing polymer used in the absorber 4 by the DW method is 2 to 20 ml / 0.3 g ⁇ 30 sec. In particular, it is preferably in the range of 4 to 15 ml / 0.3 g ⁇ 30 sec.
- the water-absorbing polymer A used in the present invention preferably has a bulk specific gravity of 0.5 to 0.8 g / cm 3 , particularly 0.55 to 0.7 g / cm 3 .
- Bulk specific gravity is useful as an index of various characteristics of the water-absorbing polymer, such as control of water absorption speed, maintenance of water absorption repeatedly, ease of discharge of blood and washing liquid when washing absorbent articles, and bulk specific gravity is in the above range. This gives good results for these properties.
- the bulk specific gravity is measured as follows.
- the bulk specific gravity was measured according to JIS K6219-2 2005.
- the water-absorbing polymer to be measured was poured into the center of a cylindrical container (a stainless steel container having a diameter of 100 mm, capacity 1000 ml) having a known mass and volume from a height of 50 mm or less from the lower end of the container. At this time, a sufficient amount of the water-absorbing polymer was poured into the cylindrical container so that the poured water-absorbing polymer formed a triangular pyramid above the upper end of the cylindrical container.
- the excess water-absorbing polymer above the upper end of the cylindrical container is wiped off using a spatula, the weight of the container is measured in this state, and the weight of the container is subtracted from the measured value.
- the measurement is performed at 23 ⁇ 2 ° C. and humidity 50 ⁇ 5%, and the sample is measured after being stored in the same environment for 24 hours or more.
- excretion fluid such as urine and menstrual blood is taken into the absorbent body through a surface layer (surface sheet), and a fiber material such as pulp forms in the absorbent body. It is absorbed and held by an absorption mechanism that is once held in the space and then fixed by the water-absorbing polymer in the absorbent body. That is, the absorption speed of the liquid in the absorbent article depends not only on the speed at which the water-absorbing polymer actually fixes the liquid, but also on the diffusion / permeation speed of the liquid in the absorbent body.
- the water absorption rate by the vortex method and the water absorption rate by the DW method mainly evaluate the “speed at which the water-absorbing polymer fixes the liquid”, and the “diffusion / permeation speed of the liquid in the absorber” It can be evaluated by the following pressure passing rate under pressure.
- the following water-absorbing polymer having a slow liquid passage speed under pressure small value of the liquid passage speed under pressure is likely to cause inhibition of liquid diffusion in the absorbent body due to gel blocking, especially in repeated absorption of liquid.
- the speed at which the liquid of the water-absorbing polymer itself is fixed (the water absorption speed evaluated by the vortex method or the DW method described above) is sufficiently high, the absorption speed of the liquid in the absorbent article using the water-absorbing polymer Is not enough and can be slow.
- the water-absorbing polymer A used in the present invention preferably has a liquid flow rate under pressure of 2.0 kPa of 150 ml / min or more, particularly 200 to 2000 ml / min, particularly 250 to 1500 ml / min.
- the load of 2.0 kPa substantially corresponds to the pressure applied to the absorbent body when the absorbent article is being washed.
- the absorbent article used in the absorbent article is adhered or absorbed.
- the liquid flow rate is effective as an index for evaluating the water-absorbing polymer from such a viewpoint.
- the liquid flow rate of the water-absorbing polymer is less than 150 ml / min, the water-absorbing polymer saturated and swollen by the liquid absorption They adhere to each other under load and prevent the liquid from passing through, so that gel blocking is likely to occur, and the washing water may not be easily drained from the napkin.
- the liquid-absorbing polymer flow rate By setting the liquid-absorbing polymer flow rate to 150 ml / min or more, gel blocking is less likely to occur, and dirty cleaning liquid is easily excreted from the absorbent article.
- the permeability of the liquid to the absorber I.e., the rate at which excretion fluid is taken into the napkin through the surface layer is increased), and adhesion to the skin is less likely to occur, or liquid leakage is less likely to occur.
- liquid flow rate is within the above range, improvement of the overall performance relating to the absorbability of the water-absorbing polymer can be expected, that is, urine or loose stool can be expected to have the same effect as that for blood.
- the “penetration of the liquid into the absorber” can be evaluated by ⁇ Measurement method of absorption time> described later.
- the larger the value of the liquid flow rate the more preferable from the viewpoint of preventing the occurrence of gel blocking.
- it is 2000 ml / min or less, particularly in a thin absorbent body having few hydrophilic fibers such as pulp.
- Can sufficiently fix the liquid in the absorber and can effectively prevent leakage from the end of the absorber.
- it is possible to effectively suppress the accumulation of liquid on the surface of the absorbent article at a portion where the liquid easily flows, such as the crotch portion in the standing position, the stomach side when lying on the back, and the back side when lying on the back.
- the thin absorber here is about 300 g / m 2 or less (preferably 250 g / m 2 or less, more preferably 200 g / m 2 or less) in terms of pulp basis weight, and the thickness under no load is less than 4 mm. It is an absorber satisfying at least one of the above. Moreover, the range of the liquid flow rate is an appropriate range for using the water-absorbing polymer most efficiently.
- the liquid passing speed is measured by using a measuring method and a measuring apparatus described in Japanese Patent Application Laid-Open No. 2003-235889. Specifically, the flow rate under pressure at 2.0 kPa is measured by the following procedure. The following measurement is performed at 23 ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5%. Before the measurement, the sample is stored in the same environment for 24 hours or more.
- ⁇ Measurement method of liquid flow rate under pressure In a 100 mL glass beaker, a sufficient amount of physiological saline (0.9% by mass sodium chloride water) to swell the measurement sample water-absorbing polymer 0.32 ⁇ 0.005 g, for example, the saturated absorption amount of the water-absorbing polymer. Immerse it in 5 times more saline and leave it for 30 minutes.
- physiological saline 0.9% by mass sodium chloride water
- a wire mesh mesh opening 150 ⁇ m, biocolumn sintered stainless steel filter 30SUS sold by Sansho Co., Ltd.
- a capillary with an inner diameter of 2 mm
- a filtration cylindrical tube having an inner diameter of 4 mm and a length of 8 cm is prepared, and the contents of the beaker including the swollen measurement sample are put into the cylindrical tube with the cock closed.
- a cylindrical rod having a diameter of 2 mm with a wire mesh having an opening of 150 ⁇ m and a diameter of 25 mm is inserted into the filtration cylindrical tube so that the wire mesh and the measurement sample are in contact with each other.
- T 1 the time until the liquid level in the filtration cylindrical tube reaches the 40 mL scale line from the 60 mL scale line (that is, 20 mL of liquid passes) (T 1 ) (Seconds).
- T 1 the time until the liquid level in the filtration cylindrical tube reaches the 40 mL scale line from the 60 mL scale line (that is, 20 mL of liquid passes) (T 1 ) (Seconds).
- T 1 the flow rate at 2.0 kPa is calculated from the following equation.
- T 0 (seconds) is a value obtained by measuring the time required for 20 ml of physiological saline to pass through the wire mesh without putting the measurement sample in the filtering cylindrical tube.
- the water-absorbing polymer A used in the present invention preferably has an absorbed amount under pressure at 2.0 kPa of 5 to 20 g / g, particularly 7 to 15 g / g.
- the amount of absorption under pressure is a measure of how much liquid can be absorbed by the water-absorbing polymer in the absorbent body when pressure such as body pressure is applied to the absorbent body by wearing the absorbent article.
- the higher the absorption amount under pressure of the water-absorbing polymer the better the absorption performance, but from the viewpoint of removing redness caused by absorbed blood, which is a specific object of the present invention, the increase in absorption amount under pressure is Undesirable effects.
- the absorption amount under pressure of the water-absorbent polymer A is measured as follows.
- ⁇ Measurement method of absorption under pressure The amount of absorption under pressure is measured using a measuring method and measuring apparatus described in JP-A-2003-235889. Measurement is performed as follows in an environment of 25 ⁇ 2 ° C. and a relative humidity of 50% ⁇ 5%. That is, 0.10 g of a sample (water-absorbing polymer) was weighed in a cylindrical plastic tube (inner diameter: 30 mm, height: 60 mm) with a nylon mesh (JIS Z8801-1: 2000) having a mesh size of 63 ⁇ m attached to the bottom surface.
- the mass of the cylindrical plastic tube and the weight that have been measured in advance is subtracted, and the mass of the physiological saline absorbed by the sample is calculated. .
- a value obtained by multiplying the mass of the absorbed physiological saline by 10 is defined as an absorbed amount under pressure (g / g).
- the measurement is performed at 23 ⁇ 2 ° C. and humidity 50 ⁇ 5%, and the sample is measured after being stored in the same environment for 24 hours or more.
- the preferable numerical range of the above-mentioned two characteristics is any 5 to 20 g / g, particularly 7 to 15 g / g, and the water-absorbing polymer A has a feature that the numerical ranges of these two characteristics coincide.
- the centrifugal retention amount indicates the liquid absorption amount of the water-absorbing polymer without pressure
- the numerical range of the centrifugal retention amount and the absorption amount under pressure at 2.0 kPa coincides, that is, both are
- the water-absorbing polymer A which is substantially the same, has a constant liquid absorption amount regardless of the pressure.
- the amount of centrifugal retention and the amount of absorption under pressure are closely related to the degree of crosslinking (gel strength) of the water-absorbing polymer. The lower the degree of crosslinking (the lower the degree of crosslinking), the higher the value of centrifugal retention.
- the value of the amount of absorption under pressure is low, and the amount of centrifugal retention and the amount of absorption under pressure are approximately inversely proportional.
- the water-absorbing polymer in which the centrifugal retention amount and the absorption amount under pressure show substantially the same value is considered to be a special water-absorbing polymer that is particularly well-crosslinked.
- a water-absorbing polymer having low gel strength is less likely to swell the polymer chain due to cross-linking, so that it easily swells under no pressure and increases the centrifugal retention, while constituting a water-absorbing polymer under pressure.
- the gel cannot withstand pressurization, and the absorption amount under pressure tends to be low.
- the water-absorbing polymer A used in the present invention can be produced, for example, as follows.
- the method for producing the water-absorbing polymer A described below has the following steps 1 to 3. That is, the water-absorbing polymer A preferably used in the present invention is produced by sequentially subjecting a water-absorbing polymer having a carboxy group and / or a carboxylate group to a surface cross-linking treatment to a surface cross-linking treatment and a neutralization treatment. It is a thing.
- Step 1 A step of producing a water-absorbing polymer having a carboxy group and / or a carboxylate group.
- Step 2 A step of subjecting the water-absorbing polymer obtained in Step 1 to surface cross-linking treatment.
- Step 3 A step of neutralizing the water-absorbing polymer obtained in Step 2.
- the step 1 can be performed using a conventionally known method for producing a polyacrylic acid-based water-absorbing polymer.
- Examples of the method for producing a water-absorbing polymer usable in Step 1 include (i) a reverse phase suspension polymerization method using an anionic surfactant described in Japanese Patent No. 2721658 as a dispersant, and (ii) An aqueous solution polymerization method described in JP-A-2003-235889 can be mentioned.
- the surface of the water-absorbent polymer particles obtained in step 1 may be crosslinked with a crosslinking agent. That is, the water-absorbing polymer obtained in step 1 may be a water-absorbing polymer whose particle surface is subjected to a crosslinking treatment.
- Examples of the water-absorbing polymer having a carboxy group and / or a carboxylate group produced in Step 1 include a polymer of a monomer containing (meth) acrylic acid and / or an alkali metal salt thereof prepared in Step I, which will be described later. Is mentioned.
- the degree of neutralization of the water-absorbing polymer obtained in Step 1 is preferably 50% or more, more preferably 65% or more and less than 75%, from the viewpoint of water absorption characteristics and reaction efficiency of the crosslinking agent.
- the degree of neutralization is measured by the measurement method described above.
- the surface of the water-absorbing polymer particles obtained in the step 1 is subjected to a crosslinking treatment (post-crosslinking treatment).
- a crosslinking treatment post-crosslinking treatment
- the degree of cross-linking in the vicinity of the surface of the water-absorbing polymer is increased compared to the case where no post-crosslinking treatment is performed, thereby making the molecular chain network finer and While preventing hemoglobin from penetrating into the deep part, the centrifugal retention amount of the water-absorbing polymer is lowered.
- the post-crosslinking treatment is effective as a method of adjusting the centrifugal retention amount according to JIS K 7223 of the water-absorbing polymer to the specific range (5 to 20 g / g).
- the post-crosslinking treatment can be performed by the same method as the surface cross-linking treatment performed in step 1.
- Examples of the crosslinking agent used for the surface crosslinking treatment performed in Step 2 include the crosslinking agent used in Step I described later.
- the crosslinking used in the surface crosslinking treatment performed in the step 2 is larger than the addition amount of the crosslinking agent used in the surface crosslinking treatment performed in the step 1. It is preferable to increase the addition amount of the agent.
- the type of the crosslinking agent used in step 1 or step 2 may be the same or different.
- the water-absorbing polymer obtained after the cross-linking treatment obtained in the step 2 is neutralized using a basic compound (neutralizing agent), and one of unneutralized carboxy group or carboxylate group is obtained. Neutralize part.
- the treatment conditions such as the amount of neutralizing agent used are adjusted so that the degree of neutralization of the finally obtained water-absorbing polymer is 75 mol% or more as described above.
- the neutralization process performed at the process 3 can be performed in the same procedure as the neutralization process of a conventionally well-known water absorbing polymer.
- the neutralization treatment is performed in the presence of water.
- the amount of water used in the neutralization treatment is 30 to 600 parts by mass with respect to 100 parts by mass of the water-absorbing polymer.
- a particularly preferable range of the amount of water used in the neutralization treatment in Step 3 (water content of the water-absorbing polymer) is 100 parts by mass or more, particularly 100 to 500 parts by mass with respect to 100 parts by mass of the water-absorbing polymer.
- mass means “mass at the time of drying” unless otherwise specified.
- the “mass at the time of drying” of the absorbent article and the constituent members of the absorbent article is measured as follows. Measuring method of mass at the time of drying: The object to be measured is left in an environment of constant temperature and humidity of 25 ° C. and 30% humidity for 24 hours, and then the mass is measured in the environment, and the measured value is measured. This is the “mass when dried” of the object.
- Examples of the basic compound (neutralizing agent) used in Step 3 include water-soluble carbonate compounds such as sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate; sodium hydroxide, potassium hydroxide, water glass, and the like.
- a water-soluble hydroxide compound is mentioned.
- sodium hydrogen carbonate and sodium carbonate are particularly preferably used in the present invention because they dissolve and exhibit weak alkalinity, and suppress an increase in water absorption capacity associated with the breakage of the crosslinking by alkali.
- a strongly basic compound such as sodium hydroxide can also be used as a neutralizing agent. In this case, the water content of the water-absorbing polymer is increased in advance before neutralization, or a low concentration aqueous solution is gradually added. Neutralization can be performed while keeping the water absorption factor low by appropriately selecting the conditions such as adding to the reaction temperature and performing the reaction at as low a temperature as possible.
- Examples of the neutralization method in Step 3 include a method of adding an aqueous solution in which a predetermined amount of a basic compound is dissolved in a water-absorbing polymer; a water-absorbing polymer and a predetermined amount of a powdered basic compound are mixed. Furthermore, the method of adding water etc. are mentioned. In addition, in order to suppress the power required for stirring in the reaction vessel, or to increase the stirring efficiency and perform the reaction as uniformly as possible, a predetermined amount of a basic compound is added to the water-absorbing polymer adjusted to a predetermined water content. A dissolved aqueous solution may be added, or a powdered basic compound may be added.
- the water-absorbing polymer When the water-absorbing polymer is pre-hydrated, 30 to 200 parts by mass of water is added to 100 parts by mass of the water-absorbing polymer.
- the amount of water combined with the water contained in the alkaline aqueous solution is used as the amount of water used in the neutralization treatment. From the viewpoint of water resistance, hydrolysis resistance of crosslinking, and drying efficiency of the water-absorbing polymer.
- a dispersant is used in addition to the neutralizing agent from the viewpoint of suppressing the power necessary for stirring of the reaction vessel or increasing the stirring efficiency and performing the reaction as uniformly as possible.
- Can do for example, sugar ester or the like can be used.
- the amount of the dispersant used is usually 0.2 to 5 parts by mass with respect to 100 parts by mass of the water-absorbing polymer.
- the water-absorbing polymer A used in the present invention is obtained by washing the water-absorbing polymer obtained as necessary to remove the dispersant and further drying and removing water. It is done.
- the water-absorbing polymer A obtained in this way is classified according to the particle size as necessary.
- the water-absorbing polymer A used in the present invention can also be produced by a production method having the following steps I and II. Hereinafter, this manufacturing method will be described.
- Step I Polymerizing a monomer containing (meth) acrylic acid and / or an alkali metal salt thereof to obtain a polymer, crosslinking the polymer with a crosslinking agent, or (meth) acrylic acid and / or an alkali metal salt thereof In the presence of a crosslinking agent to prepare a polymer having a centrifugal retention amount of 5 to 20 g / g in accordance with JIS K 7223, wherein the mass ratio of the crosslinking agent to the monomer [crosslinking Agent / monomer] is 0.15 / 100 to 40/100.
- Step II A step of bringing the polymer obtained in Step I above into contact with a basic compound and / or water and performing a neutralization treatment so that the degree of neutralization of the polymer is 75 mol% or more.
- the step I is publicly known except that a polymer having a specific centrifugal retention amount is prepared using a monomer containing (meth) acrylic acid and / or an alkali metal salt thereof and a crosslinking agent at a specific mass ratio.
- the polyacrylic acid-based water-absorbing polymer production method can be used. Examples of the known production method include the reverse phase suspension polymerization method (i) and the aqueous solution polymerization method (ii).
- the polymer obtained by polymerizing a monomer containing (meth) acrylic acid and / or an alkali metal salt thereof in the presence of a crosslinking agent may be further crosslinked with a crosslinking agent.
- the polymer of the monomer containing (meth) acrylic acid and / or its alkali metal salt prepared in the above step I is a single polymer of (meth) acrylic acid from the viewpoint of blood absorbability control, safety, production cost, and the like.
- Examples of the homopolymer of (meth) acrylic acid include polyacrylic acid and polymethacrylic acid.
- Examples of the copolymer of (meth) acrylic acid include acrylic acid or methacrylic acid, maleic acid, itaconic acid, acrylamide, Copolymers obtained by copolymerizing co-monomers such as 2-acrylamido-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2-hydroxyethyl (meth) acrylate, or styrenesulfonic acid, starch-acrylic acid Examples thereof include a graft copolymer.
- the amount of the comonomer of the copolymer is preferably in a range that does not deteriorate blood absorption performance.
- sodium salts such as polyacrylic acid and polymethacrylic acid, are preferable.
- a cross-linked polymer is more preferred. These polymers usually contain 50 mol% or more of acrylic acid monomer units, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and are substantially insoluble in water. Although it is a polymer having a high degree of swelling.
- the crosslinking agent used in the step I includes a compound having two or more polymerizable unsaturated groups in the molecule, or a reactive group capable of reacting with two or more carboxy groups and / or carboxylate groups in the molecule.
- a compound having two or more hydroxyl groups in the molecule, a compound having two or more polymerizable double bonds, a compound having two or more epoxy groups, and the like can be given.
- Examples of the compound having two or more hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, diethanolamine, polyoxypropylene, sorbitan fatty acid ester, trimethylolpropane, pentaerythridine. Trit, 1,3-propanediol, sorbitol and the like can be mentioned.
- Examples of the compound having two or more polymerizable double bonds in the molecule include bis (meth) acrylamide, allyl (meth) acrylamide, di- or polyester of (meth) acrylic acid by polyol (for example, diethylene glycol diacrylate, trimethylol).
- polyol for example, diethylene glycol diacrylate, trimethylol.
- Propane triacrylate, polyethylene glycol diacrylate, etc. unsaturated mono-or polyols derived from the reaction of C 1 -C 10 polyhydric alcohols with 2 to 8 C 2 -C 4 alkylene oxides per hydroxyl group, or Examples thereof include polycarboxylic acid di- or polyester (for example, ethoxylated trimethylolpropane triacrylate and the like).
- Compounds having two or more epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylol
- polyglycidyl ethers such as propane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether.
- crosslinking agents a compound having two or more polymerizable double bonds and a compound having two or more epoxy groups in the molecule are preferable, and a compound having two or more epoxy groups in the molecule is more preferable.
- ethylene glycol diglycidyl ether and trimethylolpropane polyglycidyl ether are particularly preferable.
- the amount of the crosslinking agent used is 0.15 / 100 to 40/100 in terms of mass ratio of [crosslinking agent / monomer] from the viewpoint of blood absorption performance and removal of redness caused by absorbed blood. 0.2 / 100 to 30/100 is preferable, and 0.3 / 100 to 20/100 is more preferable.
- Step II the polymer obtained in Step I is brought into contact with a basic compound and / or water, and the polymer is neutralized.
- the treatment conditions such as the amount of neutralizing agent used are adjusted so that the degree of neutralization of the finally obtained water-absorbing polymer is 75 mol% or more.
- the neutralization treatment in Step II can be performed in the presence of water in the same procedure as the known neutralization treatment.
- the water content of the water-absorbing polymer in this neutralization treatment is preferably 100% by mass or more, and more preferably 100 to 600% by mass with respect to the polymer obtained in Step I.
- the same basic compound (neutralizing agent) used in Step 3 can be used.
- water-soluble carbonate compounds such as sodium hydrogen carbonate and sodium carbonate
- water-soluble hydroxide compounds such as sodium hydroxide, potassium hydroxide and water glass are preferred.
- a water-soluble carbonate compound and a water-soluble hydroxide compound may be used in combination.
- Examples of the shape of the water-absorbing polymer A used in the present invention include particles and fibers.
- the particulate water-absorbing polymer includes an amorphous type, a block type, a bowl type, a spherical agglomeration type, a spherical type and the like due to the difference in shape, and any type can be used.
- the water-absorbing polymer used in the present invention (which is a general term for the water-absorbing polymer used in the absorbent or absorbent article of the present invention and includes the above-described water-absorbing polymer A. Hereinafter, the same unless otherwise specified). It is preferable to have the following characteristics in relation to hemoglobin which is the main red component. That is, the absolute value ⁇ V of the difference between the zeta potential V1 in the ion-exchanged water of the water-absorbing polymer used in the present invention and the zeta potential V2 in the ion-exchanged water of bovine hemoglobin is 30 mV or less, particularly 5 to 20 mV. It is preferable.
- the zeta potential is determined by the electrophoretic light scattering measurement method (also known as laser Doppler method), which is obtained from each migration velocity when an external electric field is applied to the water-absorbing polymer or bovine hemoglobin in ion-exchanged water. Means.
- the zeta potential measuring device for example, a device using the principle of electrophoretic light scattering measurement method such as “ELSZ-2 zeta potential / particle size measuring system” manufactured by Otsuka Electronics Co., Ltd. can be used.
- the zeta potential is measured as follows.
- ⁇ Method for measuring zeta potential In 10000 parts by mass of ion-exchanged water adjusted to pH 7.0, 5 parts by mass of the water-absorbing polymer to be measured or bovine hemoglobin (so that the concentration in the ion-exchanged water is 0.05% by mass) is dispersed, A water-absorbing polymer dispersion and bovine hemoglobin dispersion are prepared. The zeta potential of the bovine hemoglobin dispersion is measured by adjusting the pH so that the pH is equal to that of the water-absorbing polymer dispersion to be measured.
- hydrochloric acid or sodium hydroxide is used as necessary, and a commercially available pH meter (for example, Horiba pH ion meter D53, electrode type 6583) is used to measure pH. it can.
- a commercially available pH meter for example, Horiba pH ion meter D53, electrode type 6583
- a particulate polymer having passed through a sieve having an aperture of 106 ⁇ m is used as the water-absorbing polymer to be measured. If the water-absorbing polymer particles are too large to be measured (if the water-absorbing polymer particles are too large, the water-absorbing polymer will settle in the ion exchange water, making it difficult to measure the zeta potential).
- the opening of the sieve is adjusted as appropriate, and the size of the particles used for the measurement is adjusted.
- the zeta potential of a water-absorbing polymer or bovine hemoglobin is measured using a zeta potential measuring device.
- the water temperature of the dispersion is 23 ⁇ 2 ° C.
- the humidity of the measurement chamber is 50 ⁇ 5%.
- the measurement is repeated three times for each sample, and the average value thereof is taken as the zeta potential of the sample.
- the zeta potential V1 of the water-absorbing polymer used in the present invention is preferably ⁇ 40 to 5 mV, more preferably ⁇ 35 to ⁇ 5 mV.
- the zeta potential V2 of bovine hemoglobin is usually in the range of ⁇ 15 to 10 mV (showing a positive potential on the acidic side of the isoelectric point and a negative potential on the alkaline side of the isoelectric point).
- the water-absorbing polymer used in the present invention is preferably a polyacrylic acid-based water-absorbing polymer, that is, an acrylic acid-based resin.
- the water-absorbing polymer in which the zeta potential V1 is in the above range is, for example, a polyacrylic acid-based water-absorbing polymer, treated as follows. Can be obtained by applying Examples of the polyacrylic acid-based water-absorbing polymer include polymers of monomers containing the aforementioned (meth) acrylic acid and / or alkali metal salts thereof.
- the zeta potential V1 correlates with the charge density on the surface of the water absorbent polymer, and the charge density is closely related to the amount of centrifugal retention of the water absorbent polymer. That is, when the centrifugal retention amount of the water-absorbing polymer is reduced, the absolute value of the zeta potential V1 of the water-absorbing polymer tends to decrease. Using this, the zeta potential V1 can be adjusted. As described above, since the centrifugal retention amount of the water-absorbing polymer can be adjusted by the surface cross-linking degree of the water-absorbing polymer, the zeta potential V1 of the water-absorbing polymer can be set to a desired value by adjusting the surface cross-linking degree of the water-absorbing polymer. Can be adjusted to the range. For example, when the surface cross-linking degree of the water-absorbing polymer is increased, the centrifugal retention amount is decreased, and the absolute value of the zeta potential V1 is decreased.
- the zeta potential V1 can be adjusted by adjusting the neutralization degree of the water-absorbing polymer, for example.
- the degree of neutralization of the water-absorbing polymer is 70 to 95 mol%, particularly 75 to 90 mol%, more preferably 80 to 90 mol%. It is preferable that it is mol%.
- the degree of neutralization the explanation in the water-absorbing polymer A described above is appropriately applied.
- the zeta potential V1 can also be adjusted by treating the surface of the water-absorbing polymer with a cationic compound.
- the surface treatment of the water-absorbing polymer with a cationic compound is, for example, 1) a method of mixing a dry or water-containing water-absorbing polymer and a cationic compound in a dry state (dry blend method), or 2) a dry state.
- the water-absorbing polymer may be coated with an aqueous solution or dispersion of a cationic compound.
- the cationic compound examples include cationic polymer compounds such as cationized starch, cationic polyacrylamide, polyethyleneimine, and aminoalkyl (meth) acrylate / acrylamide copolymer; aluminum oxide, iron oxide, titanium oxide, and zinc oxide. And metal oxides such as
- the amount of the cationic compound used in the surface treatment is 0.01 to 5% by weight, particularly 0.02 to 3% by weight, especially 0.05 to 2% by weight, based on the dry water-absorbing polymer. preferable.
- Examples of the water-absorbing polymer in which the zeta potential V1 is in the above range include the above-mentioned “having a carboxyl group and / or a carboxylate group.
- a water-absorbing polymer (water-absorbing polymer A) having a neutralization degree of 75 mol% or more and a centrifugal retention amount of 5 to 20 g / g in accordance with JIS K 7223 is exemplified.
- the water-absorbing polymer used in the present invention is in the form of particles, has a carboxy group and / or a carboxylate group, and has been neutralized with a neutralizing agent containing an alkali metal such as sodium, It is preferable that the degree of neutralization is 75 mol% or more, preferably 75 to 95 mol%, more preferably 80 to 90 mol%, and the alkali metal is uniformly distributed throughout the water-absorbing polymer. .
- a neutralizing agent that can be used in the production of the water-absorbing polymer A described above can be used.
- water-absorbing polymer having such characteristics By using a water-absorbing polymer having such characteristics in an absorbent or absorbent article, the redness of the absorbent or absorbent article due to absorbed blood can be easily removed by washing the absorbent or absorbent article with water. It becomes possible to do.
- the above-mentioned “water-absorbing polymer having a carboxyl group and / or carboxylate group and having a neutralization degree of 75 mol% or more and a centrifugal retention amount of 5 to 20 g / g according to JIS K 7223” (water-absorbing polymer A) is: It has such characteristics.
- the alkali metal concentration ratio is such that the water-absorbing polymer particles are divided into two parts, a central part and a surface layer part located outside the central part, and the average alkali metal concentration in the surface part when the average alkali metal concentration in the central part is 1. Concentration.
- ⁇ Measurement method of alkali metal distribution state The distribution state of the alkali metal in the water-absorbing polymer particles is measured using an energy dispersive X-ray analyzer (EDX) attached to a scanning electron microscope (SEM) based on an enlarged cross-sectional image of the water-absorbing polymer particles. It can be measured by elemental analysis.
- EDX energy dispersive X-ray analyzer
- SEM scanning electron microscope
- the entire water-absorbing polymer particles are embedded with a resin (for example, epoxy resin, methacrylic acid resin, polyester resin) to form a resin layer.
- the amount of the resin forming the resin layer is set to a minimum amount necessary for embedding the entire water-absorbing polymer particles with the resin, and an excessive amount of resin is not used.
- the resin layer is cut into two in the thickness direction, thereby cutting the water-absorbing polymer particles in the resin layer. The intersection of the major axis and the minor axis on the cut surface of the water-absorbing polymer particles thus obtained is taken as the center of the water-absorbing polymer.
- mapping of the alkali metal is performed by EDX on the cut surface of the obtained water-absorbing polymer particles while being enlarged by SEM.
- the X-ray extraction angle is 30 °
- the X-ray folding time is 30 minutes
- a Si (Li) semiconductor detector can be used for X-ray detection.
- the center of the water-absorbing polymer particle and an arbitrary point on the surface of the particle are divided into approximately two equal parts so that the particle is separated from the center including the center and the center.
- Alkali metal concentration ratio (average alkali metal concentration in the surface layer / average alkali metal concentration in the center)
- the alkali metal concentration ratio is preferably 1 to 1.3, more preferably 1 to 1.2, and still more preferably 1 to 1.1.
- Such a water-absorbing polymer in which the alkali metal is uniformly distributed throughout the polymer is, for example, a water-absorbing polymer (carboxy group and / or Or a water-absorbing polymer having a carboxylate group) is sequentially subjected to a surface crosslinking treatment and a neutralization treatment using a neutralizing agent containing an alkali metal in the presence of a predetermined amount of water (so-called post-neutralization treatment). Obtained by.
- the amount of water used in the neutralization treatment (water content of the water-absorbing polymer) is determined by neutralization in the above-described method for producing the water-absorbing polymer A (manufacturing method having steps 1 to 3, manufacturing method having steps I and II). Similar to the treatment, it is preferable to control to 100% by mass or more, particularly 100 to 600% by mass with respect to the water-absorbing polymer.
- the content of the water-absorbing polymer A in the absorbent body 4 is 2 to 90 mass%, particularly 5 to 70 mass%, based on the total mass of the absorbent body 4. It is preferable in terms of the balance between softness and absorption performance during wearing.
- the content of the water-absorbing polymer A is 20 to 90% by mass, particularly 30 It is preferable to set it to 70 mass% in terms of the balance between thinness and absorption performance.
- the content of the water-absorbing polymer in the absorber 4 can be the same as the content of the water-absorbing polymer A.
- the distribution amount of the water-absorbing polymer (all the water-absorbing polymers in the absorber including the water-absorbing polymer A) in the absorbent body 4 is preferably 5 to 250 g / m 2 , more preferably 10 to 200 g / m 2 . is there.
- the ratio of the water-absorbing polymer and fibers can be appropriately adjusted and used.
- the water-absorbing polymer associated with the tearing of the fiber web preferably has an average particle size of 200 to 600 ⁇ m, particularly 250 to 450 ⁇ m, especially 250 to 400 ⁇ m.
- the content of the water-absorbing polymer having a particle size of less than 250 ⁇ m is less than 20% by mass, particularly less than 15% by mass, so that it can be worn for a long time.
- the absorption time of the liquid into the napkin 1 is short, it is difficult for leakage to occur, and redness is easily removed, which is preferable.
- the content of the water-absorbing polymer having a particle size of less than 150 ⁇ m is less than 5% by mass, particularly less than 3% by mass. This is preferable because the above-described effect can be more reliably exhibited.
- the “average particle size” and the “content of water-absorbing polymer having a particle size of less than 250 ⁇ m” and “content of water-absorbing polymer having a particle size of less than 150 ⁇ m” are measured by the following ⁇ Method for measuring particle size distribution>, respectively.
- the “water-absorbing polymer having a particle size of less than 250 ⁇ m or less than 150 ⁇ m” is not limited to a water-absorbing polymer having a spherical shape or a nearly spherical shape.
- the shape of the water-absorbing polymer is not limited.
- a sieve for example, a standard sieve manufactured by Tokyo Screen Co., Ltd.
- a tray sieving is performed using a shaker (for example, AS200 model manufactured by Lecce).
- the shaking condition is 50 Hz
- the amplitude is 0.5 mm
- the shaking time is 10 minutes.
- the measurement was performed 3 times, and the average value was defined as the mass on the sieve.
- the mass on each sieve obtained was divided by 50 to determine the relative frequency, and a particle size cumulative curve was drawn.
- the particle diameter corresponding to the central cumulative value (50%) of the cumulative curve was taken as the average particle diameter.
- the “water-absorbing polymer having a particle size of 250 ⁇ m or more” is placed on the sieve having an opening of 250, and the “water-absorbing polymer having a particle size of less than 250 ⁇ m” is screened under the sieve having an opening of 250, that is, a sieve having an opening of 150
- “water-absorbing polymer having a particle size of less than 150 ⁇ m” means what is on the saucer after passing through a sieve having 150 openings.
- the sieving was performed 3 times, and the average value of 3 times was defined as the mass on each sieve.
- the mass on each obtained sieve was calculated as a mass percentage with respect to the total mass, and the abundance ratio of each particle size was calculated.
- the measurement is performed at 23 ⁇ 2 ° C. and humidity 50 ⁇ 5%, and the sample is measured after being stored in the same environment for 24 hours or more.
- the napkin 1 can be made thin by containing the specific water-absorbing polymer described above.
- the thickness of the napkin 1 is preferably 1 to 10 mm, particularly 1 to 7 mm, and more preferably 1.5 to 5.5 mm, since it does not give a sense of incongruity while preventing leakage during wearing and is convenient for carrying.
- the thickness of the napkin here means the thickness of the napkin under a load of 7 g / cm 2 and is measured by the following method.
- ⁇ Method for measuring thickness Place the entire product to be measured (napkins) on a flat surface with the top sheet side up, without wrinkles or bending, and place 7 g / cm 2 on the upper surface of the area where the absorber is placed. Apply a load and measure the thickness under that condition.
- Thickness meter PEACOCK DIAL UPRIGHT GAUGES R5-C (manufactured by OZAKI MFG.CO.LTD.) Is used for measuring the thickness.
- a plate an acrylic plate having a thickness of about 5 mm
- the shape of the plate is circular or square.
- the measurement is performed at 23 ⁇ 2 ° C. and humidity 50 ⁇ 5%, and the sample is measured after being stored in the same environment for 24 hours or more.
- the absorbent body 4 contains fibers in addition to the water-absorbing polymer described above.
- fibers contained in the absorbent body 4 those normally used in the technical field can be appropriately used. Examples include natural fibers such as wood pulp and plant pulp such as softwood and hardwood pulp, regenerated fibers such as cupra and rayon, semi-synthetic fibers such as acetate, synthetic fibers such as polyolefins, polyamides, and polyesters. These 1 type can be used individually or in mixture of 2 or more types.
- the natural fiber includes a modified pulp obtained by subjecting the natural fiber to a crosslinking treatment. That is, the absorbent body 4 has a laminated structure in which a plurality of layers made of fiber assemblies are laminated, and a water-absorbing polymer is interposed between opposing layers in the laminated structure, and the fiber assemblies are modified. It is preferred to include pulp and natural fibers (preferably softwood and / or hardwood pulp). As a modified pulp, the below-mentioned crosslinked cellulose fiber and mercerized pulp can be used.
- the proportion of the modified pulp in the total fibers contained in the absorbent body 4 is preferably 20 to 100% by mass, more preferably 35 to 80% by mass.
- the ratio of the natural fibers such as softwood pulp in the total fibers contained in the absorbent body 4 is preferably 0 to 80% by mass, and more preferably 20 to 55% by mass.
- the fiber content in the absorbent body 4 is preferably 10 to 98 mass%, more preferably 30 to 95 mass%, based on the total mass of the absorbent body 4.
- an ultra-thin napkin having a thickness (thickness under a load of 7 g / cm 2 ) of 2.5 mm or less it is preferably 10 to 70% by mass, particularly preferably 30 to 60% by mass.
- the absorber 4 is mainly composed of a water absorbing material (in this embodiment, a water absorbing polymer and a fiber).
- the water-absorbing material includes not only a material that itself retains liquid but also a material that retains liquid in the gap.
- the content of the water-absorbing material in the absorber 4 is preferably 90% by mass or more, and more preferably 95% by mass with respect to the total mass of the absorber 4.
- the content of the water-absorbing material in the absorbent body 4 is preferably 100% by mass from the viewpoint of water-absorbing performance, but the absorbent body 4 contains a hygroscopic agent and a deodorant as necessary in addition to the absorbent material. Etc. can be contained.
- the hygroscopic agent include silica gel
- the deodorizer include activated carbon, activated clay, and a silver-containing compound.
- One preferred embodiment of the absorbent body 4 has a structure in which a plurality of hydrophilic sheets (layers of fiber aggregates) are overlapped and a water-absorbing polymer is sandwiched between the overlapping hydrophilic sheets.
- Absorbers having a laminated structure in which a plurality of layers made of fiber assemblies are laminated, and having a water-absorbing polymer interposed between at least one of the layers in the laminated structure will be described.
- the hydrophilic sheet is preferably an absorbent paper containing bulky cellulose fibers and hydrophilic fine fibers.
- This absorbent paper contains 30 parts by mass or more, particularly 40 to 90 parts by mass of bulky cellulose fibers, and less than 70 parts by mass of hydrophilic fine fibers with respect to 100 parts by mass of the absorbent paper.
- the content is preferably 103 to 60 parts by mass.
- the abundance ratio of these two kinds of fibers in the hydrophilic sheet may be different for each layer (hydrophilic sheet) constituting the absorber.
- the average fiber length is preferably 0.8 to 20 mm, more preferably 1.5 to 5 mm, and b) the molecules and the molecules are crosslinked ( Is a crosslinked cellulose fiber), or c) when the network of cellulose fibers is formed, the fiber itself is bulky, that is, thick as a structure.
- the fiber roughness is preferably 0.3 mg / m or more, More preferably, it is 0.3 to 2 mg / m, and more preferably 0.32 to 1 mg / m.
- Particularly preferred bulky cellulose fibers are those having all of a) to c).
- the average fiber length and fiber roughness in this specification are measured as follows. “Fiber roughness” is used as a measure of fiber thickness in fibers with non-uniform fiber thickness, such as wood pulp.
- the bulky cellulose fibers comprising the above a) and b) can maintain the bulky structure even in a wet state.
- the bulky cellulose fiber having the above c), that is, the bulky cellulose fiber having a fiber roughness of 0.3 mg / m or more is bulky in the fiber web because the cellulose fiber is accumulated in a bulky state. This is preferable because a network structure is easily formed. Further, it is preferable because the movement resistance of the body fluid is small and the passage speed of the body fluid is increased.
- Examples of bulky cellulose fibers with a fiber roughness of 0.3 mg / m or more include softwood kraft pulp (“ALBACEL” (trade name) made by Federal Paper Board Co. and “INDORAYON” made by PTInti Indorayon Utama (product) Name)).
- cross-linking cellulose fibers as in b) above (method for producing cross-linked cellulose fibers), and examples thereof include a fiber cross-linking method using a cross-linking agent.
- cross-linking agents include N-methylol compounds such as dimethylolethylene urea and dimethylol dihydroxyethylene urea; polycarboxylic acids such as citric acid, tricarballylic acid and butanetetracarboxylic acid; dimethylhydroxyethylene urea and the like Polyols; Examples include crosslinkers of polyglycidyl ether compounds.
- a crosslinking agent of a polycarboxylic acid or a polyglycidyl ether compound that does not generate formalin or the like harmful to the human body during crosslinking is preferable.
- the amount of the crosslinking agent used is preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the cellulose fiber. If the amount of the crosslinking agent used is less than 0.2 parts by mass, the crosslinking density of the cellulose fibers is low, so that the elastic modulus may be greatly reduced when wet. If the amount used exceeds 20 parts by mass, the cellulose fibers Is too stiff and the cellulose fiber may become brittle when stress is applied, so the above range is preferable.
- a cellulose fiber is impregnated into an aqueous solution of the cross-linking agent, if necessary, and the aqueous solution of the cross-linking agent becomes the design adhesion amount.
- the cellulose fiber is dehydrated, and then the cellulose fiber is heated to the crosslinking temperature, or 2) the aqueous solution of the crosslinking agent is sprayed on the cellulose fiber so as to have a designed adhesion amount by spraying, and then heated to the crosslinking temperature.
- cross-linking reaction examples include "High Bulk Additive" manufactured by Weyerhaeuser Paper Co.
- the bulky cellulose fiber has d) a round cross-sectional shape of the fiber.
- the roundness of the fiber cross-section is 0.5. More preferably, it is ⁇ 1, especially 0.55 ⁇ 1.
- Bulky cellulose fibers having a fiber cross-section roundness of 0.5 to 1 are preferred because they have a low body fluid movement resistance and a high body fluid permeation rate.
- Particularly preferred bulky cellulose fibers are those having all of a) to d).
- the roundness of the fiber cross section is measured as follows.
- ⁇ Measurement of roundness of fiber cross section The fiber to be measured is sliced in a cross-sectional direction orthogonal to the length direction. When slicing, be careful not to change the cross-sectional area of the fiber as much as possible.
- the cross section of the fiber obtained by slicing is imaged using an electron microscope, and the cross-sectional photograph is analyzed with an image analyzer (“Avio EXCEL” (trade name) manufactured by Nippon Avionics Co., Ltd.).
- the roundness of the target fiber cross section was obtained.
- 100 degrees of arbitrary fiber cross sections measured this roundness, and it was set as the average value.
- (Roundness of fiber cross section) 4 ⁇ ⁇ ⁇ (cross section area of measurement fiber) / (perimeter of cross section area of measurement fiber) 2
- wood pulp is preferably used as the fiber material of bulky cellulose fibers, but generally the cross section of wood pulp is flattened by delignification treatment, and most of its roundness is less than 0.5. It is.
- such wood pulp may be mercerized to swell the cross section of the wood pulp.
- Examples of commercially available mercerized pulp that can be used in the present invention include “FILTRANIER” (trade name) manufactured by ITT Rayonier Inc., “POROSANIER” (trade name) manufactured by the same company, and the like.
- hydrophilic ultrafine fibers examples include fibrillated pulp and hydrophilic regenerated and synthetic fibers having a specific fiber diameter.
- fibrillated pulp include those obtained by beatening chemically treated pulp such as softwood (NBKP), hardwood (LBKP) pulp, or crosslinked pulp.
- hydrophilic fibers such as regenerated cellulose fibers such as rayon, lyocell, and tencel, and synthetic fibers such as acetate and acrylic can be used.
- fibers that are as thin as possible that is, those that are molded as thin as possible in a range that does not exceed 1 dtex, or those that obtain a fiber that does not exceed 1 dtex as a result of split processing, such as split fibers.
- split fibers are preferred.
- tencel is preferable in that the fibers can be easily fibrillated with a relatively simple device, and can be refined by beating as in the case of pulp.
- the hydrophilic ultrafine fibers do not have to have the same fineness for all the fibers, and some of the fibers are thinned and thinned, such as fibrillated pulp, and some of the split fibers are It includes the case where it is divided and contains ultrafine fibers.
- the average fiber length of the hydrophilic ultrafine fibers is preferably 0.3 to 5 mm, more preferably 0.5 to 3 mm, and the diameter (fiber width) is preferably 5 to 100 ⁇ m. These can be measured using a pulp fiber length distribution measuring device (manufactured by Kajaani).
- the absorbent paper (hydrophilic sheet) preferably has a stable structure even when wet.
- the above-described bulky paper is added to the absorbent paper.
- heat-melting adhesive fibers, paper strength reinforcing agents, ordinary cellulose fibers (for example, wood pulp and non-wood pulp), etc. are blended, etc. It is effective to increase the wet strength.
- blending of a hot-melt adhesive fiber or a paper strength reinforcing agent is effective.
- hot-melt adhesive fibers fibers that are melted by heating and bonded to each other can be used.
- polyolefin fibers such as polyethylene, polypropylene, and polyvinyl alcohol, polyester fibers, and polyethylene-polypropylene composite fibers.
- polyethylene-polyester composite fibers low-melting point polyester-polyester composite fibers, polyvinyl alcohol-polypropylene composite fibers having a hydrophilic fiber surface, and polyvinyl alcohol-polyester composite fibers.
- any of a core-sheath type composite fiber and a side-by-side type composite fiber can be used.
- These hot-melt adhesive fibers can be used alone or in combination of two or more.
- the hot-melt adhesive fibers preferably used in the present invention include polyvinyl alcohol fibers that are dissolved in hot water, and core-sheath type polyester fibers.
- the absorbent paper (hydrophilic sheet) can be produced, for example, as follows.
- the concentration of bulky cellulose fibers is 0.16% by mass
- the concentration of hydrophilic fine fibers is 0.05% by mass
- the thickness is 1 denier and the average fiber length is 3 mm.
- PVA concentration of Kuraray Co., Ltd.
- This slurry was sprayed onto a papermaking wire having a wire opening diameter of 1.4 mm (12 mesh) to form a paper layer on the papermaking wire.
- the paper layer was dehydrated using a suction box.
- the dehydrated aqueous solution contained about 0.02% by mass of fibers, most of which were hydrophilic fine fibers.
- 10% crepe was applied to obtain an absorbent paper having a basis weight of 80 g / m 2 .
- This absorbent paper contained 80 parts by mass of bulky cellulose fibers, 15 parts by mass of hydrophilic fine fibers, and 5 parts by mass of PVA fibers with respect to 100 parts by mass of the absorbent paper. Further, this absorbent paper had a gradient in the existence ratio of hydrophilic fine fibers in the thickness direction.
- One of the other embodiments of the absorbent body 4 is one having a mixed fiber body of fibers and a water-absorbing polymer.
- This mixed product is obtained, for example, by mixing fibers and a water-absorbing polymer in an air stream.
- the water-absorbing polymer in this mixed fiber is distributed almost uniformly throughout the mixed fiber, and like the water-absorbing polymer in the absorber using the hydrophilic sheet described above, It is not unevenly distributed in the area of the part.
- an absorbent body having such a mixed product fiber will be described.
- the fiber constituting the mixed fiber natural pulp such as wood pulp or synthetic fiber can be used.
- the synthetic fiber has an average fiber length of preferably 0.1 to 30 mm, more preferably 0.5 to 25 mm, and even more preferably 1.5 to 15 mm, and belongs to a range generally referred to as a short fiber. Can be used.
- the fineness of the short fibers is preferably 0.1 to 7.8 dtex, more preferably 0.5 to 5.6 dtex, and still more preferably 0.9 to 3.4 dtex.
- a single synthetic fiber containing one kind of resin such as polyethylene, polypropylene, polyethylene terephthalate, or a composite synthetic fiber containing two or more kinds of these resins
- resin such as polyethylene, polypropylene, polyethylene terephthalate, or a composite synthetic fiber containing two or more kinds of these resins
- composite synthetic fibers in that various well-known functionalities can be imparted, or melt adhesion between fibers and bulkiness of a mixed fiber (absorber) can be imparted.
- the composite synthetic fiber include a core-sheath type and a side-by-side type.
- the cross-sectional shape of the composite synthetic fiber include a circular shape, an irregular shape, a C shape, and a hollow shape.
- Synthetic pulp can be used as the synthetic fiber.
- a material made of a thermoplastic resin such as polyethylene, modified polyethylene, or polypropylene is preferably used.
- Synthetic pulp has an average fiber length of preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, and even more preferably 0.9 to 1.5 mm, similar to natural pulp such as wood pulp. It is preferable because it can be handled easily.
- the liquid absorption capacity of the mixed fiber can be increased by using it as the main constituent fiber of the mixed fiber.
- the synthetic fiber is a material having a property of being melted by heating to a predetermined temperature, by using this as a main constituent fiber of the mixed product, the mixed product is produced in the manufacturing process of the mixed product.
- the strength of the entire mixed fiber body can be increased by a process such as heating the entire fiber body to melt the synthetic fiber.
- the mixed product is mainly composed of a nonwoven fabric such as an airlaid nonwoven fabric.
- the mixed fiber is a short fiber of natural or (semi) synthetic hydrophilic fiber such as rayon, cotton, lyocell, tencel, acetate, polyvinyl alcohol fiber, acrylic, etc. May be included.
- the mixed product is different in size, composition, etc. (for example, size, thickness, shape in plan view, mixing ratio of fibers and water-absorbing polymer, etc.) are laminated. May be formed, and may be divided into arbitrary shapes.
- the napkin 1 of the present embodiment is designed to be able to remove redness due to blood by washing with water by the action of the above-described water-absorbing polymer whose characteristics such as the degree of neutralization and the amount of centrifugal retention are in a specific range. Although it has sufficient water washability, the napkin 1 may further contain a metal ion scavenger in order to further improve the water washability.
- a metal ion scavenger will be described.
- metal ion scavenger examples include ethylenediaminetetraacetic acid (EDTA) tetrasodium, nitrilotriacetic acid (NTA) trisodium, diethylenetriaminepentaacetic acid (DTPA) pentasodium, hydroxyethylethylenediaminetriacetic acid (HEDTA) trisodium, L-glutamic acid.
- EDTA ethylenediaminetetraacetic acid
- NTA nitrilotriacetic acid
- DTPA diethylenetriaminepentaacetic acid
- HEDTA hydroxyethylethylenediaminetriacetic acid
- Aminocarboxylate-based metal ion scavengers such as tetraacetic acid (GLDA) tetrasodium; phosphonate-based metal ion scavengers such as hydroxyethylidene diphosphonic acid (HEDP) tetrasodium; sodium tripolyphosphate (STPP), sodium pyrophosphate (TSPP), polymer phosphate metal ion scavengers such as sodium hexametaphosphate; builders for polymer detergents such as sodium polyacrylate and acrylic acid / maleic acid copolymer; trisodium citrate, citric acid Other organic metal ion scavengers such as ammonium; Zeolite (crystalline aluminosilicate), inorganic metal ion scavengers such as sodium silicate, etc.
- GLDA tetraacetic acid
- HEDP hydroxyethylidene diphosphonic acid
- STPP sodium tripolyphosphat
- ethylenediaminetetraacetic acid (EDTA) tetrasodium, trisodium citrate, sodium tripolyphosphate, sodium acrylate, and zeolite are preferred.
- trisodium citrate is highly water-soluble, so It is easy to move to the location, has a high redness removal effect, and has excellent biodegradability.
- Trisodium citrate is preferable because it is effective in weakening the affinity between hemoglobin and the water-absorbing polymer contained in menstrual blood and has a high redness removal effect.
- Examples of the method of containing the metal ion scavenger in the napkin 1 include a method of spraying as a solid (powder); an aqueous solution obtained by dissolving or dispersing the metal ion scavenger in an appropriate solvent such as water, and the aqueous solution And a method of spraying or applying the sucrose onto a predetermined part of the napkin 1 (a part where the metal ion scavenger is to be contained).
- the above-described interior of the absorber 4 and its peripheral portion can be mentioned.
- the inside of the absorbent body between the absorbent sheet 4b disposed on the surface and the periphery of the water-absorbent polymer, and the position farthest from the skin (position closest to the back sheet 2) and the absorbent sheet 4a positioned immediately above the absorbent sheet 4b Is preferred.
- the content of the metal ion scavenger is preferably 0.001 to 30% by mass, more preferably 0.01%, based on the total mass of the absorber 4. ⁇ 10% by mass.
- the metal ion scavenger may be present at one location or may be present at a plurality of locations.
- the metal ion scavenger 10 may be disposed on the inside of the covering sheet, and may be disposed on the outside of the covering sheet. May be. That is, the metal ion scavenger 10 may be covered with the covering sheet together with the absorber 4, or may be disposed outside the covering sheet that covers the absorbing body 4.
- Particularly preferred locations for the presence of the metal ion scavenger are the surface and the periphery of the water-absorbing polymer, and B) the portion closer to the non-skin contact surface than the absorber 4. In this case, absorbed menstrual blood and the like could be washed away with water most clearly.
- FIG. 7 shows an embodiment in which B) is adopted as the location of the metal ion scavenger.
- the metal ion scavenger 10 exists between the inner sheet 11 and the back sheet 3 disposed adjacent to the non-skin contact surface of the absorber 4.
- the metal ion scavenger 10 is described as if it forms a layer, but it does not necessarily form a layer in practice. Due to the presence of the inner sheet 11, the absorber 4 and the metal ion scavenger are separated from each other, and the metal ion scavenger can be prevented from entering the absorber 4 beyond the design value.
- the inner sheet 11 the same sheet as the covering sheet can be used.
- the basis weight of the inner sheet 11 is preferably 10 to 20 g / m 2 and the thickness is 0.05 to 0.15 mm.
- the content of the metal ion scavenger is preferably 0.00 with respect to 100 parts by mass of the total water-absorbing polymer contained in the napkin 1 from the viewpoint of washing menstrual blood and the like more cleanly from the napkin.
- the amount is from 01 to 100 parts by weight, more preferably from 0.1 to 50 parts by weight, particularly preferably from 0.5 to 20 parts by weight.
- the napkin 1 of this embodiment can remove redness due to menstrual blood by simple water washing.
- the degree of redness removal can be evaluated by the redness degree a * value of the red portion stained red by blood in the napkin after blood is injected and washed according to the following procedures 1 to 3. The smaller the a * value, the lower the degree of red in the red part, which means that the blood has been washed away with water.
- Procedure 1 Inject 12 g of blood into the sanitary napkin from the surface layer side of the sanitary napkin, leave it in an environment of 25 ° C. for 30 minutes, and then remove the sanitary napkin with water having a water temperature of 25 ° C. and a hardness of 12 ° DH. The sanitary napkin is squeezed by hand, and the water contained in the napkin is squeezed out as much as possible.
- Procedure 2 On the surface layer side of the wet sanitary napkin obtained in the procedure 1, the red degree a * using a spectrocolorimeter for the five most reddish spots of the red part stained with blood . Measure the value.
- Procedure 3 The average of the three measured values obtained by removing the maximum value and the minimum value from the five measured values obtained in the procedure 2 is defined as the red degree a * value of the sanitary napkin.
- the a * value obtained according to the procedures 1 to 3 is a measure for evaluating the superiority or inferiority of the water-washing ability of the absorbent article.
- the napkin 1 of the present embodiment having the above-described configuration has an a * value of 7 or less, preferably 5 or less, and has a practically sufficient water washing ability.
- horse blood is used as blood to be injected into the napkin. More specifically, equine defibrinated blood manufactured by Japan Biotest Laboratory Co., Ltd. is used. The viscosity of this horse defibrinated blood is less than 15 mPa ⁇ S as measured with a (B) viscometer TVB-10M (measurement temperature 25 ° C., rotor L adapter) manufactured by Toki Sangyo Co., Ltd.
- the water used for washing the napkin is water prepared by dissolving calcium chloride and magnesium chloride in ion exchange water having an electric conductivity of 1 ⁇ S / cm or less.
- Water having an ion content ratio (calcium ion: magnesium ion) of 7: 3 and a German hardness of 12 ° DH is used.
- Indonesian water for daily use one of the customs of washing used sanitary napkins, has different hardness depending on the region, but the water with a German hardness of 12 ° DH used in steps 1 to 3 above. It is almost the same as domestic water used in at least part of Indonesia.
- the environment in which the napkin into which blood has been injected is allowed to stand for 30 minutes before washing is an air temperature of 25 ° C. and a humidity of 60%.
- the napkin is washed by hand, and “the operation of putting about 100 g of water on the napkin with one hand and squeezing the napkin with the other hand” is repeated three times in 10 seconds. That is, the operation performed for 10 seconds is “sprinkle water ⁇ squeeze the napkin ⁇ spread water ⁇ squeeze the napkin ⁇ spread water ⁇ squeeze the napkin”. Therefore, the amount of water used for washing the napkin for 3 minutes in the procedure 1 is approximately 100 g as described above because the amount of water used in one water application operation is approximately 100 g as described above.
- 100 ⁇ 3 corresponds to the amount of water used for 10 seconds
- 100 ⁇ 3 ⁇ 6 corresponds to the amount of water used for 1 minute.
- the pressure when the napkin is squeezed by hand that is, the grip strength of the hand is usually about 10 to 15 kg.
- the measurement sample and the spectral color difference meter are brought into close contact with each other so that external light does not enter.
- a simple spectral color difference meter “NF333” pen type detector
- each leakage prevention groove 5 is formed by compacting and integrating the topsheet 2 and the absorber 4 from the topsheet 2 side by pressing means such as embossing.
- Each leak-proof groove 5 has a substantially symmetric shape with respect to the vertical center line of the napkin 1.
- the leakage prevention grooves 5 are connected to each other at their front and rear ends, thereby forming a closed shape as a whole.
- leak-proof grooves 5 and 5 body fluids flowing outward in the napkin width direction are blocked, and leakage (lateral leakage) from the side of the napkin 1 is effectively prevented and cleaning is performed. Since the decomposition of the napkin at the time can be suppressed, it is easy to perform the washing operation and blood can be easily washed away. Furthermore, the fact that the leak-proof grooves 5 and 5 have reached the vicinity of the lower part of the absorber 4 in order to prevent water from flowing through the entire absorber during cleaning and to prevent blood from remaining due to the absorber being biased. preferable.
- An end seal portion 6 is formed on the periphery of the napkin 1 at a position spaced outward from the absorber 4.
- the end seal portion 6 in the present embodiment is formed by integrating the top sheet 2 and the back sheet 3. More specifically, in the present embodiment, the top sheet 2 and the back sheet 3 extend from the peripheral edge portion of the absorbent body 4, and are joined to each other by a heat embossing process at the extended portions. Is formed.
- the end seal portion 6 has an effect of preventing the water absorbent material constituting the absorbent body 4 from flowing out when the napkin 1 is washed (when wet).
- the end seal portion 6 is not provided with a material that causes swelling or the like due to water used for the absorbent body 4 from the viewpoint of not separating each sheet material that is a constituent material of the end seal portion during cleaning. Further, the end seal portion 6 is formed by heat embossing with an adhesive such as hot melt disposed at a predetermined portion of the sheet material, thereby improving and stabilizing the flexibility of the seal portion and the seal strength when wet. From the viewpoint of making it more preferable.
- the napkin 1 of this embodiment is used by being attached to underwear in the same manner as a normal sanitary napkin of this type. Since the napkin 1 of the present embodiment includes the absorber 4 containing the specific water-absorbing polymer described above, the napkin 1 can be easily washed with water while having practically sufficient absorption performance. It is easy to wash away the blood adhering to the napkin 1 with water. For this reason, it can be suitably used for people who have a habit of discarding the used napkin after washing with water. In addition, since the napkin 1 of the present embodiment contains a water-absorbing polymer, the napkin 1 can be designed to have a small thickness, is not bulky, and has excellent portability and wearing feeling.
- the absorbent article (sanitary napkin) of the present invention may not include the leak-proof groove 5, the adhesive portion (not shown), the wing portion, the rear flap portion, and the like included in the embodiment. good.
- Both the wing part and the rear flap part are parts extending outward from the both side edges of the absorbent body 4 in the longitudinal direction, and the wing part is normally opposed to the excretion part that is disposed to face the excretion part of the napkin wearer.
- the rear flap part is located behind the wing part in the napkin longitudinal direction.
- the absorbent article to which the absorbent body of the present invention can be applied or the absorbent article of the present invention is not limited to sanitary napkins, but is used for disposable diapers, incontinence pads, urine-absorbing pads, pet diapers, pet sheets, etc. Is also applicable.
- the water-absorbing polymer (water-absorbing polymer A) used in the present invention has a reduced water absorption ratio by adjusting the centrifugal retention amount to the specific range, and further has a liquid passing rate under pressure of 2.0 kPa. When adjusted to the specified range, the liquid flow rate under pressure is high, so the absorption rate under repetition or pressure is very fast, and the liquid can diffuse quickly to the details of the absorber. Moreover, even if it swells, there is little so-called gel feeling, which leads to an improvement in uncomfortable feeling when worn.
- the synthesis method is as follows: synthesis of a water-absorbing polymer (corresponding to the step 1), crosslinking treatment of the water-absorbing polymer (corresponding to the step 2), neutralization treatment of the water-absorbing polymer (corresponding to the step 3) Proceeded in the order.
- 2,2′-azobis (2-amidinopropane) dihydrochloride (Wako Pure Chemical Industries, trade name V-50) 0.05 g, polyethylene glycol (Kao, K-PEG6000 LA) 0.5 g, citric acid 4 g of ammonium iron (III) (manufactured by Kanto Chemical) and 10 g of ion-exchanged water were mixed and dissolved to prepare an initiator (A) solution. Further, 0.6 g of sodium persulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 10 g of ion-exchanged water to prepare an initiator (B) solution.
- a titanium citrate aqueous solution (50% citric acid and 7.6% (TiO 2 ) titanyl sulfate aqueous solution mixed at a mass ratio of 20/27) was prepared.
- To monomer aqueous solution A 12 g of initiator (A) solution is added to prepare monomer A.
- To monomer aqueous solution B 5 g of initiator (B) solution is added to prepare monomer B.
- To monomer aqueous solution C, initiator ( B) Monomer C was prepared by adding 5 g of the solution and 2 g of a titanium citrate aqueous solution (citric acid / Ti molar ratio 2, Ti amount 0.015% to acrylic acid mass).
- the monomer A, the monomer B, and the monomer C which were allowed to stand for 5 minutes or more, were dropped into the 5 L reaction vessel from the monomer dropping port using a microtube pump in this order for polymerization.
- azeotropic dehydration was performed using a dehydrating tube to adjust the water content of the water-absorbing polymer (hydrogel), and then ethylene glycol diglycidyl ether (manufactured by Nagase ChemteX, Sakai product name Denacol EX- 810) A solution of 0.5 g in 10 g of ion-exchanged water was added.
- Synthesis Examples 2 to 5 Five types of water-absorbent particles whose surfaces were crosslinked according to Synthesis Examples 2 to 5 according to [Synthesis of water-absorbing polymer], [Crosslinking of water-absorbing polymer] and [Neutralization of water-absorbing polymer] A polymer was obtained.
- Synthesis Examples 1 to 5 differ only in the amount of the crosslinking agent used in [Cross-linking of water-absorbing polymer], 5 g in Synthesis Example 2, 1 g in Synthesis Example 3, 0.2 g in Synthesis Example 4, and Synthesis Example 5 In this case, 0.05 g was used.
- Synthesis Examples 6 to 9 According to Synthesis Examples 6 to 8 according to Synthesis Example 1, three types of water-absorbing polymers whose particle surfaces were crosslinked were obtained. Synthesis Examples 6 to 8 differ only in the amount of neutralizing agent used in the above [Neutralization of water-absorbing polymer], 7.7 g in Synthesis Example 6, 17.5 g in Synthesis Example 7, and 26 in Synthesis Example 8 .8 g was used. Further, Synthesis Example 9 was carried out in the same manner as in Synthesis Example 1 except that [Neutralization treatment of water absorbent polymer] was not performed after [Crosslinking treatment of water absorbent polymer].
- a water-absorbing polymer was produced as follows. That is, in a 5 L reaction vessel (using a Foudra blade) similar to that used in Synthesis Example 1, sucrose fatty acid ester (manufactured by Mitsubishi Chemical Foods, trade name Ryoto Sugar Ester S-770) as a dispersant is 2% (relative to water absorption). The mass of the active polymer and the amount of the active ingredient) was added, and 2000 ml of cyclohexane was added. While stirring in a nitrogen atmosphere, the temperature was raised to 73 ° C.
- the monomer solution which left still for 5 minutes or more was dripped and polymerized in the said 5 L reaction container using the microtube pump from the monomer solution dripping port.
- a solution obtained by dissolving 74 g of 30% aqueous sodium hydroxide solution in 625 g of ion-exchanged water was further added using a dropping funnel from the dropping port. Thereafter, the water content was dehydrated to 35% by mass, and after cooling, cyclohexane was removed and dried to obtain a neutralized water-absorbing polymer.
- sucrose fatty acid ester product name: Ryoto Sugar Ester S-770, manufactured by Mitsubishi Chemical Foods
- sodium hydrogen carbonate manufactured by Wako Pure Chemical Industries, Ltd.
- the obtained water-absorbing polymer was washed with isopropanol, the dispersant was washed, filtered and dried to obtain a neutralized water-absorbing polymer.
- a water-absorbing polymer was produced using an aqueous solution polymerization method as follows. That is, 81.8 g of acrylic acid, 0.25 g of N, N′-methylenebisacrylamide and 241 g of deionized water were charged in a reaction vessel, and the temperature of the contents was kept at 1 to 2 ° C. while stirring and mixing.
- the obtained hydrogel containing the crosslinked polymer was shredded to a size of 3 to 7 mm with an internal mixer to obtain a shredded gel, and then 48% sodium hydroxide aqueous solution 67 was added to 325.0 g of the shredded gel. .5 g was added to neutralize 72 equivalent% of the carboxyl groups to obtain a neutralized chopped gel.
- this neutralized chopped gel is laminated to a thickness of about 5 cm on a stainless steel tray that is 20 cm long ⁇ 20 cm wide ⁇ 10 cm high, has no top plate, and has a 4 mm mesh wire mesh on the bottom plate.
- the dried product was pulverized and sieved using a sieve having an aperture of 150 ⁇ m and a sieve having the same size of 710 ⁇ m to obtain a water-absorbing polymer having a particle size of 150 to 710 ⁇ m.
- sucrose fatty acid ester product name: Ryoto Sugar Ester S-770, manufactured by Mitsubishi Chemical Foods
- sodium hydrogen carbonate manufactured by Wako Pure Chemical Industries, Ltd.
- the obtained water-absorbing polymer was washed with isopropanol, the dispersant was washed, filtered and dried to obtain a neutralized water-absorbing polymer.
- Neutralization degree of the water-absorbing polymer obtained in Synthesis Examples 1 to 13 amount retained by centrifugation, water absorption rate by vortex method, bulk specific gravity, liquid flow rate under pressure at 2.0 kPa, absorption amount under pressure at 2.0 kPa Were measured according to the measurement methods described above. The degree of neutralization was measured by the method using the neutralization titration curve described above. Further, for some of the water-absorbing polymers obtained in Synthesis Examples 1 to 13, the water absorption rate by the DW method, the zeta potential V1, and the absolute value ⁇ V of the zeta potential difference between the water-absorbing polymer and bovine hemoglobin. The alkali metal concentration ratio was measured according to the measurement methods described above. These results are shown in Table 1 below.
- the zeta potential V2 of bovine hemoglobin subjected to the measurement of the absolute value ⁇ V of the zeta potential difference is +10 mV in Synthesis Examples 9 and 13, respectively, ⁇ 9 mV in Synthesis Example 6, and in Synthesis Examples 1, 7, and 8-12, respectively. It was -12 mV.
- Example 1 70 parts by mass of a crosslinked pulp (Weyerhauser Paper “High Bulk Additive HBA-S”) having a fiber roughness of 0.32 mg / m and a fiber cross-section of 0.30, and a fiber roughness of 0.18 and a fiber cross-section of 30 parts by weight of softwood kraft pulp (Skeena Cellulose Co. “SKEENA PRIME”) having a roundness of 0.32 is dispersed and mixed in water, and further, a paper strength reinforcing agent (polyamide) is added to 100 parts by dry weight of the mixed pulp.
- a crosslinked pulp (Weyerhauser Paper “High Bulk Additive HBA-S”) having a fiber roughness of 0.32 mg / m and a fiber cross-section of 0.30, and a fiber roughness of 0.18 and a fiber cross-section of 30 parts by weight of softwood kraft pulp (Skeena Cellulose Co. “SKEENA PRIME”) having a roundness of 0.32 is dispersed and mixed
- Epichlorohydrin resin manufactured by Nippon PMC Co., Ltd., Kaimen WS-570 was dispersed and mixed with 1 part by weight of the resin component in water to obtain a predetermined concentration, and this dispersed mixture was dried at the forming part of a wet paper machine.
- the fiber web was formed so that the amount was 25 g / m 2 .
- the fiber web was dehydrated with a suction box until the water content became 100 parts by mass based on 100 parts by mass of the dry fiber web.
- the water-absorbing polymer of Synthesis Example 1 was sprayed almost uniformly at a spraying basis weight of 30 g / m 2 on the wet fiber web after dehydration.
- a pre-paper-absorbing absorbent paper (basis weight 25 g / m 2 ) having the same composition as that of the fiber web as a fiber aggregate is superposed on the surface of the fiber web where the water-absorbing polymer is dispersed.
- the laminated body of the fiber web and the absorbent paper was introduced into a dryer, and dried and integrated at a temperature of 130 ° C. to obtain an absorbent sheet having a water-absorbing polymer fixed therein.
- the two absorbent sheets (length 90 mm, width 35 mm) are overlaid, the two absorbent sheets (length 200 mm, width 75 mm) are arranged above and below, and the longitudinal front and rear ends are curved.
- the absorbent was cut into a shape.
- An adhesive was applied to the non-skin contact surface side of the obtained absorber, and a back sheet was fixed on the non-skin contact surface of the absorber via the adhesive.
- the entire surface of the skin contact surface of the absorbent is covered with a surface sheet, and the skin contact surface side of the surface sheet is embossed according to a conventional method to form a leak-proof groove, and a napkin precursor Got.
- An adhesive is applied to a predetermined portion of the non-skin contact surface (outer surface of the back sheet) of the napkin precursor obtained in this manner to form an adhesive part, and further, the extension from the peripheral part of the absorber in each of the front and back sheets.
- the end portion was subjected to end sealing according to a conventional method to obtain a napkin.
- an air-through nonwoven fabric (a perforated sheet used for a Kao Co., Ltd. Whyr Super Slim Guard) was used as the top sheet, and a polyethylene film having a thickness of 25 ⁇ m was used as the back sheet.
- the napkin generally has the structure shown in FIGS. The napkin thus obtained was used as a sample of Example 1.
- the content of the water-absorbing material (water-absorbing polymer and fiber) is 100% by mass with respect to the total mass of the absorber, and the water-absorbing property contained in the napkin (absorber). All of the polymers were the water-absorbing polymer A, and the content of the water-absorbing polymer A in the absorber was 40% by mass with respect to the total mass of the absorber.
- the thickness of the napkin of Example 1 (thickness under a load of 7 g / cm 2 ) was 1.8 mm.
- Example 1 a napkin was prepared in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 2 was used as the water-absorbing polymer, and this was used as a sample of Example 2. Further, in Example 1, a napkin was produced in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 3 was used as the water-absorbing polymer, and this was used as a sample of Example 3. Further, in Example 1, a napkin was prepared in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 4 was used as the water-absorbing polymer, and this was used as a sample of Example 4.
- Example 5 the napkin was prepared in the same manner as in Example 2 except that the absorber was replaced with the following, and the thickness of the napkin (thickness under a load of 7 g / cm 2 ) was 5.5 mm. A sample of Example 5 was obtained.
- a hot-melt adhesive (P-618B manufactured by Toyo Petrolite) was applied separately at a coating amount of 5 g / m 2 , and separately prepared on the adhesive-coated surface of a tissue paper (upper covering sheet) having a basis weight of 16 g / m 2.
- a pulp fiber fiber web (basis weight 240 g / m 2 , width 7 cm, length 17 cm) was placed. This tissue paper has larger dimensions than the fiber web.
- 0.13 g of the water-absorbing polymer of Synthesis Example 2 was uniformly spread over the entire fiber web.
- a tissue paper (basis weight 16 g / m 2 ) as a lower covering sheet in which a hot-melt adhesive is applied at a coating amount of 5 g / m 2 with the same size as the fiber web on the water-absorbing polymer spray surface of the fiber web.
- a tissue paper (basis weight 16 g / m 2 ) as a lower covering sheet in which a hot-melt adhesive is applied at a coating amount of 5 g / m 2 with the same size as the fiber web on the water-absorbing polymer spray surface of the fiber web.
- Example 6 In Example 3, except that 1 g of trisodium citrate (94 parts by mass with respect to 100 parts by mass of the total water-absorbing polymer contained in the napkin) was sprayed as a metal ion scavenger between the absorber and the back sheet. A napkin was produced in the same manner as in Example 3, and this was used as the sample of Example 6. The thickness of the napkin of Example 6 (thickness under a load of 7 g / cm 2 ) was 1.8 mm.
- Example 7 a napkin was produced in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 6 was used as the water-absorbing polymer, and this was used as a sample of Example 7. Further, in Example 1, a napkin was produced in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 7 was used as the water-absorbing polymer, and this was used as a sample of Example 8. Further, in Example 1, a napkin was produced in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 8 was used as the water-absorbing polymer, and this was used as a sample of Example 9.
- Example 10 In Example 1, a napkin was produced in the same manner as in Example 1 except that the absorber was replaced with the following (mixed fiber), and this was used as a sample of Example 10.
- Absorber of Example 10 100 parts by mass of defibrated pulp (fluff pulp) and 20 parts by mass of the water-absorbing polymer of Synthesis Example 1 are mixed in an air stream, and placed in a mold having a predetermined dimension (width 7 cm, length 17 cm) under the mold. Fibers were piled while suctioning from the inner surface of the metal mesh placed on the side. The basis weight of the mixed fiber thus obtained was 240 g / m 2 . The mixed fiber was wrapped with a tissue paper having a basis weight of 16 g / m 2 spray-coated with a hot melt adhesive to obtain an absorbent body.
- Example 10 a napkin was prepared in the same manner as in Example 10 except that the water-absorbing polymer of Synthesis Example 10 was used as the water-absorbing polymer used in the mixed fiber, and this was used as a sample of Example 11.
- a napkin was prepared in the same manner as in Example 10 except that the water-absorbing polymer of Synthesis Example 11 was used as the water-absorbing polymer used in the mixed fiber, and this was used as the sample of Example 12. did.
- a napkin was prepared in the same manner as in Example 10 except that the water-absorbing polymer of Synthesis Example 12 was used as the water-absorbing polymer used in the mixed fiber, and this was used as the sample of Example 13. did.
- Example 14 In Example 1, a napkin was produced in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 13 was used as the water-absorbing polymer, and this was used as a sample of Example 14.
- Example 1 A napkin was produced in the same manner as in Example 1 except that the water-absorbing polymer was changed to a commercially available water-absorbing polymer (manufactured by Nippon Shokubai Co., Ltd., trade name CAW4). Various characteristics such as the degree of neutralization and centrifugal retention of the commercially available water-absorbing polymer used in Comparative Example 1 were measured according to the measurement methods described above. In addition, regarding the commercially available water-absorbing polymer used in Comparative Example 1, the zeta potential V2 of bovine hemoglobin subjected to measurement of the absolute value ⁇ V of the zeta potential difference was +10 mV.
- Example 2 A napkin was prepared in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 5 was used as the water-absorbing polymer in Example 1, and this was used as a sample of Comparative Example 2. Further, in Example 1, a napkin was prepared in the same manner as in Example 1 except that the water-absorbing polymer of Synthesis Example 9 was used as the water-absorbing polymer, and this was used as a sample of Comparative Example 3.
- Example 4 In Example 1, a napkin was prepared in the same manner as in Example 1 except that the water-absorbing polymer was changed to a nonionic water-absorbing polymer (Sumitomo Seika, Aqua Coke). did. Various characteristics such as the centrifugal retention amount of the nonionic water-absorbing polymer used in Comparative Example 4 were measured according to the measurement methods described above.
- the injection part provided on the acrylic plate has a cylindrical shape with an inner diameter of 10 mm, and the central axis of the cylindrical injection part coincides with the central axis in the longitudinal direction and the width direction of the acrylic plate, and the cylindrical injection part A through-hole having an inner diameter of 10 mm is formed so as to communicate between the inside and the surface sheet facing surface of the acrylic plate.
- the acrylic plate is arranged so that the central axis of the cylindrical injection portion coincides with the central portion of the absorber in plan view, and 3 g of blood is injected from the cylindrical injection portion and absorbed by the sanitary napkin.
- the time (seconds) from when the blood reached the surface of the napkin until the total amount of 3 g was absorbed by the napkin was measured, and this was taken as the first absorption time.
- 3 minutes after the first blood injection the above procedure is repeated until 3 g of blood is further injected (a total of 6 g of blood is injected) until the total amount of the reinjected blood is absorbed by the napkin. Time (seconds) was measured, and this was taken as the second absorption time.
- Table 1 shows the absorption time for the second time (when 6 g of blood was injected).
- the first time when it exceeded 3 minutes until the total amount (3 g) of the injected blood was absorbed, the next 3 g was injected immediately after the total amount was absorbed.
- ⁇ Measurement method of liquid return amount> After 3 minutes from the third blood injection, the acrylic plate and the weight are removed, and the basis weight of 30 g / 7 cm ⁇ 7 cm is formed on the skin contact surface of the napkin (on the top sheet). Ten sheets of m 2 absorbent paper (commercial tissue paper) were placed on top of each other, and a load of 68 g / cm 2 was applied to the absorbent paper for 1 minute. After the loading, 10 sheets of absorbent paper were removed, and the weight of the 10 sheets of absorbent paper was measured.
- the mass (g) of blood absorbed in 10 sheets of absorbent paper is determined, and this mass is taken as the liquid return amount. did.
- each napkin of Examples 1 to 14 has a practically sufficient absorption performance and is sufficiently washed with water, even though the thickness is as thin as 5.5 mm or less. It is possible to remove redness.
- the napkin of Comparative Examples 1 and 3 mainly has a neutralization degree of the water-absorbing polymer of less than 75 mol%, so that the a * value is larger than that of the Example and it is difficult to remove redness by washing with water. It can be seen that it is. Further, in Comparative Example 1, since the centrifugal holding amount was as high as 25 g / g, the cleaning was broken.
- the napkin of Comparative Example 2 has an a * value substantially the same as that of the example, but since the centrifugal retention amount exceeds 20 g / g, the cleaning breakage occurs and it is difficult to wash with water. Recognize.
- the napkin of Comparative Example 4 is mainly a nonionic water-absorbing polymer and does not have a partially neutralized carboxy group, so that the absorption capacity by osmotic pressure is not sufficient. It can be seen that the absorption performance is inferior.
- a reference example does not contain a water absorbing polymer, since the thickness of an absorber is large, it turns out that it has practically sufficient absorption performance.
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Abstract
Description
工程I:(メタ)アクリル酸及び/又はそのアルカリ金属塩を含むモノマーを重合してポリマーを得、該ポリマーを架橋剤により架橋処理して、又は(メタ)アクリル酸及び/又はそのアルカリ金属塩を含むモノマーを、架橋剤の存在下で重合して、JIS K 7223に準拠した遠心保持量が5~20g/gのポリマーを調製する工程であって、該モノマーに対する架橋剤の質量比〔架橋剤/モノマー〕が0.15/100~40/100である工程。
工程II:前記工程Iで得られたポリマーに塩基性化合物及び/又は水を接触させて、該ポリマーの中和度が75モル%以上となるように中和処理を施す工程。
初めに、吸水性ポリマーの主鎖ポリマーの中和滴定曲線を作成する。例えば、吸水性ポリマーがアクリル酸架橋重合体である場合、該吸水性ポリマーの主鎖ポリマーはポリアクリル酸である。以下に、吸水性ポリマーがアクリル酸架橋重合体である場合を例にとって説明する。ポリアクリル酸(和光純薬工業、平均分子量25万)のイオン交換水溶液に対して、水酸化ナトリウム溶液を適宜滴下し、pHメーターを用いて該溶液のpHを測定した。この時、ポリアクリル酸の分子量と添加した水酸化ナトリウムのモル数とから中和度を算出し、横軸に中和度、縦軸にpHをプロットし、中和滴定曲線を描いた。中和度は50~100%の範囲で行った。pHメーターには、堀場pHイオンメーターD53、電極型式6583を用いた。次に、吸水性ポリマー0.1gをイオン交換水20ml中に投入し、10分攪拌後にこの攪拌した溶媒のpHを測定し、得られたpHの値から、前記中和滴定曲線を用いて目的とする中和度を算出した。尚、測定は23±2℃、湿度50±5%で行い、測定の前に試料を同環境で24時間以上保存した上で測定する。
「フローリィによれば、吸水力を付与する要因は、高分子電解質と水との親和力および可動イオン濃度がゲルの内側のほうが高いために発生する浸透圧、吸水力抑制意思としての網目構造に基づくゴム弾性力で決定される。
Q5/3(吸水力)={(1/2×i/Vu×1/S1/2)2+(1/2-X1)/V1}×V0/ν={(イオンの浸透圧)+(高分子電解質の水との親和性)}/橋架け密度
i/Vu:網目に固定された電荷濃度
1/S1/2:外部溶液の電解質のイオン強度
(1/2-X1)/V1:網目と水の親和力
V0/ν:橋架け密度」
遠心保持量の測定は、JIS K 7223(1996)に準拠して行う。ナイロン製の織布(メッシュ開き255、三力製作所販売、品名:ナイロン網、規格:250×メッシュ巾×30m)を幅10cm、長さ40cmの長方形に切断して長手方向中央で二つ折りにし、両端をヒートシールして幅10cm(内寸9cm)、長さ20cmのナイロン袋を作製する。測定試料である吸水性ポリマー1.00gを精秤し、作製したナイロン袋の底部に均一になるように入れる。試料の入ったナイロン袋を、25℃に調温した生理食塩水(0.9質量%塩化ナトリウム水)に浸漬させる。浸漬開始から30分後にナイロン袋を生理食塩水から取り出し、1時間垂直状態に吊るして水切りした後、遠心脱水器(コクサン(株)製、型式H-130C特型)を用いて脱水する。脱水条件は、143G(800rpm)で10分間とする。脱水後、試料の質量を測定し、次式に従って目的とする遠心保持量を算出する。
遠心保持量(g/g)=(a’-b-c)/c ;式中、a’は遠心脱水後の試料及びナイロン袋の総質量(g)、bはナイロン袋の吸水前(乾燥時)の質量(g)、cは試料の吸水前(乾燥時)の質量(g)を表す。測定は5回行い(n=5)、上下各1点の値を削除し、残る3点の平均値を測定値とした。尚、測定は23±2℃、湿度50±5%で行い、測定の前に試料を同環境で24時間以上保存した上で測定する。
100mLのガラスビーカーに、生理食塩水(0.9質量%塩化ナトリウム水)50mLとマグネチックスターラーチップ(中央部直径8mm、両端部直径7mm、長さ30mmで、表面がフッ素樹脂コーティングされているもの)を入れ、ビーカーをマグネチックスターラー(アズワン製HPS-100)に載せる。マグネチックスターラーの回転数を600±60rpmに調整し、生理食塩水を攪拌させる。測定試料である吸水性ポリマー2.0gを、攪拌中の食塩水の渦の中心部で液中に投入し、JIS K 7224(1996)に準拠して該吸水性ポリマーの吸水速度(秒)を測定する。具体的には、吸水性ポリマーのビーカーへの投入が完了した時点でストップウォッチをスタートさせ、スターラーチップが試験液に覆われた時点(渦が消え、液表面が平らになった時点)でストップウォッチを止め、その時間(秒)をボルテックス法による吸水速度として記録する。測定はn=5測定し、上下各1点の値を削除し、残る3点の平均値を測定値とした。尚、これらの測定は23±2℃、湿度50±5%で行い、測定の前に試料を同環境で24時間以上保存した上で測定する。
JIS K6219-2 2005に準じてかさ比重の測定を行った。測定対象の吸水性ポリマーを、質量及び体積既知の円筒容器(直径100mmのステンレス製容器、容量1000ml)の中心部へ該容器の下端から50mm以下の高さから注ぎ込んだ。このとき、注ぎ込まれた吸水性ポリマーが円筒容器の上端よりも上方で三角錐を形成するように、十分な量の吸水性ポリマーを円筒容器内に注ぎ込んだ。そして、へらを用いて円筒容器の上端よりも上方にある余剰の吸水性ポリマーを払い落とし、この状態で該容器の質量を測定し、その測定値から容器の質量を差し引くことで、吸水性ポリマーの質量を求め、これを容器の体積で除して、目的とするかさ比重を算出した。尚、測定は23±2℃、湿度50±5%で行い、測定の前に試料を同環境で24時間以上保存した上で測定する。
100mLのガラスビーカーに、測定試料である吸水性ポリマー0.32±0.005gを膨潤するに十分な量の生理食塩水(0.9質量%塩化ナトリウム水)、例えば吸水性ポリマーの飽和吸収量の5倍以上の生理食塩水に浸して30分間放置する。別途、垂直に立てた円筒(内径25.4mm)の開口部の下端に、金網(目開き150μm、株式会社三商販売のバイオカラム焼結ステンレスフィルター30SUS)と、コック(内径2mm)付き細管(内径4mm、長さ8cm)とが備えられた濾過円筒管を用意し、コックを閉鎖した状態で該円筒管内に、膨潤した測定試料を含む前記ビーカーの内容物全てを投入する。次いで、目開きが150μmで直径が25mmである金網を先端に備えた直径2mmの円柱棒を濾過円筒管内に挿入して、該金網と測定試料とが接するようにし、更に測定試料に2.0kPaの荷重が加わるようおもりを載せる。この状態で1分間放置した後、コックを開いて液を流し、濾過円筒管内の液面が60mLの目盛り線から40mLの目盛り線に達する(つまり20mLの液が通過する)までの時間(T1)(秒)を計測する。計測された時間T1(秒)を用い、次式から2.0kPaでの通液速度を算出する。尚、式中、T0(秒)は、濾過円筒管内に測定試料を入れないで、生理食塩水20mlが金網を通過するのに要する時間を計測した値である。 通液速度(ml/min)=20×60/(T1-T0) 前記式で得られた値を円筒内の膨潤した吸水性ポリマー層の厚みで除して、20mmあたりの値に換算して加圧下通液速度とする。測定は5回行い(n=5)、上下各1点の値を削除し、残る3点の平均値を測定値とした。尚、加圧下通液速度の更に詳細な測定方法は、特開2003-235889号公報の段落〔0008〕及び段落〔0009〕に記載されており、また測定装置は、同公報の図1及び図2に記載されている。
加圧下吸収量は、特開2003-235889号公報に記載されている測定方法及び測定装置を利用して測定される。25±2℃、相対湿度50%±5%の環境で次のようにして測定する。即ち、目開き63μmのナイロン網(JIS Z8801-1:2000)を底面に貼った円筒プラスチックチューブ(内径30mm、高さ60mm)内に、試料(吸水性ポリマー)0.10gを秤量し、円筒プラスチックチューブを垂直にしてナイロン網上に試料がほぼ均一厚さになるように整え、2.0kPaの加圧が試料にかかるように外径29.5mm×厚さ22mmの分銅を円筒プラスチックチューブ内に挿入する。円筒プラスチックチューブと分銅の質量はあらかじめ測定しておく。次いで、生理食塩水60mlの入ったシャーレ(直径:120mm)の中に試料及び分銅の入った円筒プラスチックチューブをナイロン網側を下面にして垂直に浸す。この時、シャーレの底面ぎりぎりの深さまで、円筒プラスチックチューブが浸漬するようにする。60分後に試料及び分銅の入った円筒プラスチックチューブを水中から引き上げて質量を計量し、あらかじめ測定しておいた円筒プラスチックチューブと分銅の質量を差し引き、試料が吸収した生理食塩水の質量を算出する。この吸収した生理食塩水の質量を10倍した値を加圧下吸収量(g/g)とする。尚、測定は23±2℃、湿度50±5%で行い、測定の前に試料を同環境で24時間以上保存した上で測定する。
工程II:前記工程Iで得られたポリマーに塩基性化合物及び/又は水を接触させて、該ポリマーの中和度が75モル%以上となるように中和処理を施す工程。
pH7.0に調整されたイオン交換水10000質量部中に、測定対象の吸水性ポリマー又は牛ヘモグロビンを5質量部(イオン交換水中の濃度が0.05質量%となるように)分散させて、吸水性ポリマー分散液、牛ヘモグロビン分散液を調製する。牛ヘモグロビン分散液のゼータ電位の測定は、測定対象の吸水性ポリマー分散液とpHが等しくなるように、pHを調整して行う。イオン交換水及び牛ヘモグロビン分散液のpH調整には、必要に応じ塩酸あるいは水酸化ナトリウムを用い、pHの測定には市販のpHメーター(例えば堀場pHイオンメーターD53、電極型式6583)を用いることができる。測定対象の吸水性ポリマーは、目開き106μmのふるいを通過した粒子状のものを用いる。吸水性ポリマー粒子が大きくて測定できない場合(吸水性ポリマー粒子が大きすぎると、イオン交換水中で該吸水性ポリマーが沈降してしまい、ゼータ電位の測定が困難になる)には、測定可能となるように適宜篩い分けの目開きを調整し、測定に供する粒子の大きさを調整する。得られた分散液について、ゼータ電位の測定装置を用いて吸水性ポリマー又は牛ヘモグロビンのゼータ電位を測定する。ゼータ電位の測定中、分散液の水温23±2℃、測定室の湿度50±5%とする。測定は、1つの試料につき3回繰り返し行い、それらの平均値を当該試料のゼータ電位とする。
吸水性ポリマー粒子におけるアルカリ金属の分布状態は、走査型電子顕微鏡(SEM)に付随されるエネルギー分散型X線分析装置(EDX)を用い、吸水性ポリマー粒子の拡大断面画像に基づいて微小領域の元素分析を行うことで測定することができる。先ず、測定対象の吸水性ポリマー粒子を複数、粘着層を設けた基板(例えば、ステンレスや銅等の基板の一面に、ニチバナイスタック両面紙NW-15S等の両面テープを貼り付けたもの)の該粘着層上に、該粒子が互いに重ならないように散布する。次いで、吸水性ポリマー粒子全体を樹脂(例えばエポキシ樹脂、メタクリル酸樹脂、ポリエステル樹脂)で包埋し、樹脂層を形成する。該樹脂層を形成する樹脂の量は、吸水性ポリマー粒子全体を樹脂で包埋するのに最低限必要な量とし、過剰量の樹脂は使用しないようにする。次いで、ミクロトームを用いて、該樹脂層をその厚み方向に二分するように切断し、これにより該樹脂層中の吸水性ポリマー粒子を切断する。こうして得られた吸水性ポリマー粒子の切断面における長軸と短軸との交点を、該吸水性ポリマーの中心とする。次いで、得られた吸水性ポリマー粒子の切断面について、SEMで拡大しながらEDXにてアルカリ金属のマッピングを行う。EDXの操作において、X線取り出し角度30°、X線折込時間30分とし、またX線の検出には、Si(Li)半導体検出器を用いることができる。このアルカリ金属のマッピングでは、吸水性ポリマー粒子の中心と該粒子の表面の任意の一点との間を略2等分することで、該粒子を、該中心を含む中心部と、該中心部よりも外側に位置する表層部とに2分割し、これら2つの領域それぞれについて、アルカリ金属原子固有のX線の量をカウントし、アルカリ金属濃度を測定する。斯かる操作を5回繰り返し、中心部及び表層部それぞれの平均アルカリ金属濃度を算出し、次式によりアルカリ金属濃度比を算出する。 アルカリ金属濃度比=(表層部の平均アルカリ金属濃度/中心部の平均アルカリ金属濃度)
吸収性物品、例えば、ナプキン1(吸収体4)に含有されている全ての吸水性ポリマー50gを、JIS Z 8801で規定された目開き850、600、500、355、300、250、150の標準篩(例えば東京スクリーン社製の標準篩)及び受け皿を用いて、振とう機(例えばレッチェ社製、AS200型)を用いて篩分けする。振とう条件50Hz、振幅0.5mm、振とう時間10分間とする。測定は3回行い、平均値をふるい上質量とした。得られた各ふるい上質量を50で除して相対頻度を求め、粒度累積曲線を描いた。累積曲線の中央累積値(50%)に相当する粒子径を平均粒径とした。篩い分け作業後、「粒径250μm以上の吸水性ポリマー」は目開き250の篩上に、「粒径250μm未満の吸水性ポリマー」は、目開き250の篩下、つまり、目開き150の篩上及びその下の受け皿上に、「粒径150μm未満の吸水性ポリマー」は目開き150の篩を通過して受け皿上にあるものをそれぞれ意味する。篩い分けは3回行い、3回の平均値を各篩上の質量とした。得られた各篩上の質量を全質量に対する質量百分率として計算し、各粒径の存在比率を算出した。尚、測定は23±2℃、湿度50±5%で行い、測定の前に試料を同環境で24時間以上保存した上で測定する。
測定対象の製品(ナプキン)の全体を、表面シート側を上にして平らな場所にシワや折れ曲がりがないように載置し、吸収体が配されている領域の上面に、7g/cm2の荷重を掛け、その状態下での厚みを測定する。厚みの測定には、厚み計 PEACOCK DIAL UPRIGHT GAUGES R5-C(OZAKI MFG.CO.LTD.製)を用いる。このとき、厚み計の先端部と製品との間の測定部分にプレート(厚さ5mm程度のアクリル板)を配置して、荷重が7g/cm2となるようにプレートの大きさを調整する。プレートの形状は、円形又は正方形とする。尚、測定は23±2℃、湿度50±5%で行い、測定の前に試料を同環境で24時間以上保存した上で測定する。
繊維粗度計FS-200(KAJAANI ELECTRONICS LTD.製)を用いて測定した。先ず、測定対象の繊維(セルロース繊維)の真の質量を求めるために、該繊維を真空乾燥機内にて100℃で1時間乾燥させ、繊維中に存在している水分を除去する。こうして乾燥させた繊維から1gを正確に量りとる(誤差±0.1mg)。次に、量り取った繊維を、該繊維に極力損傷を与えないように注意しつつ、前記繊維粗度計に付属のミキサーで150mlの水中に完全に離解させ、これを全量が5000mlになるまで水で薄めて希釈液を得た。得られた希釈液から50mlを正確に量りとってこれを繊維粗度測定溶液とし、前記繊維粗度計の操作手順に従って目的とする平均繊維長及び繊維粗度をそれぞれ算出した。尚、平均繊維長の算出には、前記操作手順に基づき下記式により計算された値を用いた。
測定対象の繊維を、その長さ方向と直交する断面方向にスライスする。スライスするときには、繊維の断面面積が極力変化しないように注意する。スライスして得られた繊維の断面を電子顕微鏡を用いて撮像し、その断面写真を画像解析装置(日本アビオニクス社製の「Avio EXCEL」(商品名))により解析し、下記に示す式を用いて目的とする繊維断面の真円度を求めた。尚、該真円度は、任意の繊維断面を100点測定し、その平均値とした。 (繊維断面の真円度)=4×π×(測定繊維の断面面積)/(測定繊維の断面面積の周囲長)2
手順2:前記手順1で得られた湿潤状態の生理用ナプキンの表面層側における、血液によって赤色に染まった赤色部分の最も赤みの強い点5箇所について、分光色差計を用いて赤色度合いa*値を測定する。
手順3:前記手順2で得られた5つの測定値から最大値及び最小値を除いた3つの測定値の平均を、生理用ナプキンの赤色度合いa*値とする。
また、前記手順1~3において、ナプキンの洗浄に用いる水としては、電気伝導度1μS/cm以下のイオン交換水に塩化カルシウムと塩化マグネシウムを溶解することにより調製される水で、カルシウムイオンとマグネシウムイオンとの含有比(カルシウムイオン:マグネシウムイオン)が7:3で且つドイツ硬度が12°DHの水を用いる。
尚、使用済みの生理用ナプキンを水洗する習慣がある国の一つである、インドネシアの生活用水は、地域によってその硬度が異なるが、前記手順1~3で用いるドイツ硬度12°DHの水は、少なくともインドネシアの一部で使用されている生活用水と略同じである。
ナプキンの洗浄は、手で行ない、「一方の手で100g程度の水をナプキンにかけ、他方の手で該ナプキンを絞る動作」を10秒間に3回繰り返す。即ち、10秒間に行う動作は、「水をかける→ナプキンを絞る→水をかける→ナプキンを絞る→水をかける→ナプキンを絞る」である。従って、前記手順1においてナプキンの3分間洗浄に使用する水の量は、水をかける動作1回で使用する水の量が前述したようにおよそ100gであるので、およそ(100×3×6×3=)5400gである。前記式において、100×3は、10秒間に使用する水の量、100×3×6は、1分間に使用する水の量に相当する。
ナプキンに水をかけるときはビーカー等を利用し、水をかけている最中はナプキンを絞らないようにする。
手順1において、ナプキンを3分間洗浄した後で該ナプキンを手で絞るときの圧力、即ち、手の握力は、通常、10~15kg程度である。
赤色部分の赤色度合いa*値を測定する際は、外光が入らないように、測定サンプルと分光色差計とを隙間なく密接させる。分光色差計としては、日本分光製の簡易型分光色差計「NF333」(ペン型検出器)を用いることができる。
ナプキン1の肌当接面側(表面シート2側)には、その長手方向左右両側部に、ナプキン1の長手方向へ延びる防漏溝5,5がそれぞれ形成されている。各防漏溝5は、表面シート2と吸収体4とが、表面シート2側からエンボス等の圧搾手段によって圧密化及び一体化されて形成されている。各防漏溝5は、ナプキン1の縦中心線に関してほぼ対称な形状になっている。各防漏溝5は、それらの前後端が互いに連結しており、これによって全体として閉じた形状をなしている。防漏溝5,5が形成されていることにより、ナプキン幅方向外方に流れる体液等が堰き止られ、ナプキン1の側部からの漏れ(横漏れ)が効果的に防止されると共に、洗浄時におけるナプキンの分解を抑えることができるため、洗浄操作がおこないやすく、血液の洗い流しが容易に行えるようになる。更に、防漏溝5,5が吸収体4の下部付近まで達していることが、洗浄時、吸収体全体に水がいきわたりやすく、且つ、吸収体が偏って血液が残留するのを防止するため好ましい。
〔吸水性ポリマーの合成〕
攪拌機、還流冷却管、モノマー滴下口、窒素ガス導入管、温度計を取り付けたSUS304製5L反応容器(アンカー翼使用)に分散剤としてポリオキシアルキレンエーテルリン酸エステル0.1%(対アクリル酸質量、有効成分量)を仕込み、ノルマルヘプタン1500mlを加えた。窒素ガスの雰囲気下に攪拌を行いながら90℃まで昇温した。一方、2L三つ口フラスコ中に、80%アクリル酸(東亞合成製、act.80.6%)とイオン交換水、48%苛性ソーダ水溶液(旭硝子製、act.49.7%)から、モノマー水溶液としてのアクリル酸ナトリウム(72%中和品)1000gを得た。このモノマー水溶液に、N-アシル化グルタミン酸ソーダ(味の素製、商品名アミソフトPS-11)0.25gをイオン交換水4.41gに溶解させたものを添加した後、550g(以下、モノマー水溶液Aという)、250g(以下、モノマー水溶液Bという)、250g(以下、モノマー水溶液Cという)に三分割した。
前記〔吸水性ポリマーの合成〕に用いたものと同様の反応容器(アンカー翼使用)に、前記〔吸水性ポリマーの合成〕で得られた吸水性ポリマー100gを仕込み、ノルマルヘプタン300mlを加えた。窒素雰囲気下、攪拌しながら、75℃まで昇温した。その後、滴下口から滴下ロートを用いて、イオン交換水60gを滴下し、続いて、イオン交換水10gに、架橋剤としてエチレングリコールジグリシジルエーテル(ナガセケムテックス製、商品名デナコールEX-810)3.0gを溶解したものを添加した。1.5時間還流させた後、ノルマルヘプタンを除去乾燥させることにより、粒子表面が架橋処理された吸水性ポリマーを得た。
前記〔吸水性ポリマーの合成〕に用いたものと同様の反応容器(アンカー翼使用)に、前記〔吸水性ポリマーの架橋処理〕で、得られた乾燥吸水性ポリマー100gに対して、分散剤としてショ糖脂肪酸エステル(三菱化学フーズ製、商品名リョートーシュガーエステルS-770)2%(対吸水性ポリマー質量、有効成分量)を仕込み、吸水性ポリマーの5倍量のイオン交換水に中和剤として炭酸水素ナトリウム(和光純薬製)12.5gを加え、徐々に滴下した。得られた吸水性ポリマーをイソプロパノールで洗浄し、分散剤を洗浄し、濾過、乾燥を行い、中和度が調整された吸水性ポリマーを得た。
前記の〔吸水性ポリマーの合成〕、〔吸水性ポリマーの架橋処理〕及び〔吸水性ポリマーの中和処理〕に従った合成例2~5により、粒子表面が架橋処理された5種類の吸水性ポリマーを得た。合成例1~5は前記〔吸水性ポリマーの架橋処理〕における架橋剤の使用量のみが異なっており、合成例2では5g、合成例3では1g、合成例4では0.2g、合成例5では0.05g用いた。
前記合成例1に従った合成例6~8により、粒子表面が架橋処理された3種類の吸水性ポリマーを得た。合成例6~8は前記〔吸水性ポリマーの中和処理〕における中和剤の使用量のみが異なっており、合成例6では7.7g、合成例7では17.5g、合成例8では26.8g用いた。また、〔吸水性ポリマーの架橋処理〕後に〔吸水性ポリマーの中和処理〕を行わなかった以外は合成例1と同様の手順で進めたものを合成例9とした。
前記工程I及びIIを有する吸水性ポリマーの製造方法に従って、以下のようにして吸水性ポリマーを製造した。即ち、合成例1で用いたものと同様の5L反応容器(ファウドラ翼使用)に、分散剤としてショ糖脂肪酸エステル(三菱化学フーズ製、商品名リョートーシュガーエステルS-770)2%(対吸水性ポリマー質量、有効成分量)を仕込み、シクロヘキサン2000mlを加えた。窒素雰囲気下、攪拌しながら、73℃まで昇温した。一方、2L三つ口フラスコ中に、80%アクリル酸とイオン交換水、48%苛性ソーダ水溶液から、モノマー水溶液としてのアクリル酸ナトリウム(85%中和品、濃度47%)1000gを得た。このモノマー水溶液に、過硫酸ナトリウム1.1g、及び架橋剤としてエチレングリコールジグリシジルエーテル(ナガセケムテックス製, 商品名デナコールEX-810)15g(モノマー(アクリル酸)質量に対して3.4%)を溶解した。次いで、前記の5L反応容器内に、モノマー溶液滴下口からマイクロチューブポンプを用いて、5分以上静置したモノマー溶液を滴下し重合した。1時間熟成の後、さらに滴下口から滴下ロートを用いて、イオン交換水625gに30%苛性ソーダ水溶液74g溶解したものを添加した。その後、含水率を35質量%まで脱水し冷却後、シクロヘキサンを除去・乾燥させることにより、中和処理された吸水性ポリマーを得た。
前記〔吸水性ポリマーの合成〕に用いたものと同様の反応容器(アンカー翼使用)に、市販の使い捨ておむつ(メリーズMサイズ、花王(株)製)から取り出した吸水性ポリマー100gを仕込み、ノルマルヘプタン300mlを加えた。窒素雰囲気下、攪拌しながら、90℃まで昇温した。その後、滴下口から滴下ロートを用いて、イオン交換水60gを滴下し、続いて、イオン交換水10gに、架橋剤としてエチレングリコールジグリシジルエーテル(ナガセケムテックス製、商品名デナコールEX-810) 5.0gを溶解したものを添加した。1.5時間還流させた後、ノルマルヘプタンを除去乾燥させることにより、粒子表面が架橋処理された吸水性ポリマーを得た。こうして得られた乾燥状態の吸水性ポリマー100gに対して、分散剤としてショ糖脂肪酸エステル(三菱化学フーズ製、商品名リョートーシュガーエステルS-770)2%(対吸水性ポリマー質量、有効成分量)を仕込み、吸水性ポリマーの5倍量のイオン交換水に中和剤として炭酸水素ナトリウム(和光純薬製)12.5gを加え、徐々に滴下した。得られた吸水性ポリマーをイソプロパノールで洗浄し、分散剤を洗浄し、濾過、乾燥を行い、中和処理された吸水性ポリマーを得た。
水溶液重合法を用い、以下のようにして吸水性ポリマーを製造した。即ち、反応容器にアクリル酸81.8g、N,N’-メチレンビスアクリルアミド0.25g及び脱イオン水241gを仕込み、攪拌・混合しながら内容物の温度を1~2℃に保った。次いで、内容物の液層中に窒素を流入し酸素濃度を0.02%未満にした後、密閉下、1%過酸化水素水溶液1g、0.2%アスコルビン酸水溶液1.2g及び2%の2,2’-アゾビスアミジノプロパンジハイドロクロライド水溶液2.8gを添加・混合して重合を開始させた(約5℃)。重合と共に温度が上昇し引き続き、密閉下で70~80℃ に約8時間温度管理しながら重合して、架橋重合体を含む含水ゲルを得た。得られた架橋重合体を含む含水ゲルをインターナルミキサーで3~7mm の大きさに細断して細断ゲルを得た後、この細断ゲル325.0gに48%の水酸化ナトリウム水溶液67.5gを添加してカルボキシル基の72当量%を中和して、中和細断ゲルを得た。次いで、縦20cm×横20cm×高さ10cmで、天板を有さず、底板に目開き4mmの金網を装着したステンレス製のトレイに、この中和細断ゲルを約5cmの厚さに積層し、150℃ 、風速2.0m/sの条件で、通気型バンド乾燥機(井上金属製)で乾燥して、乾燥体を得た。この乾燥体を粉砕した後、目開き150μmのふるいと同710μmのふるいを用いて篩い分けし、150~710μmの粒度である吸水性ポリマーを得た。
合成例9で得られた乾燥状態の吸水性ポリマー(カルボキシ基及び/又はカルボキシレート基を有し且つ中和度72モル%、JIS K 7223に準拠した遠心保持量10g/g)と、表面処理剤(カチオン性化合物)としての乾燥状態の酸化アルミニウム粉末(和光純薬製)とを混合し(ドライブレンド法)、前記ゼータ電位V1を所定範囲に調整した吸水性ポリマーを得た。酸化アルミニウム粉末の添加量は、吸水性ポリマーの質量に対して0.5質量%とした。
繊維粗度0.32mg/m、繊維断面の真円度0.30の架橋処理パルプ(Weyerhauser Paper製「High Bulk Additive HBA-S」)70質量部、及び繊維粗度0.18、繊維断面の真円度0.32の針葉樹クラフトパルプ(Skeena Cellulose Co.製「SKEENA PRIME」)30質量部を水中に分散混合し、更に前記混合したパルプの乾燥質量100部に対し、紙力補強剤(ポリアミドエピクロルヒドリン樹脂、日本PMC(株)製、カイメンWS-570)を樹脂成分で1質量部を水中に分散混合し、所定の濃度とした後、この分散混合液を湿式抄紙機のフォーミングパートで乾燥坪量が25g/m2になるように繊維ウエブを形成した。次いで、該繊維ウエブをサクションボックスにより、乾燥繊維ウエブ100質量部に基づき水分率100質量部になるまで、繊維ウエブを脱水した。次いで、プレスパート直前で、脱水後の湿潤した繊維ウエブ上に、前記合成例1の吸水性ポリマーを散布坪量30g/m2でほぼ均一に散布した。次いで、前記繊維ウエブの吸水性ポリマー散布面に、繊維集合体として、前記繊維ウエブと同様の配合組成を有する、予め抄紙しておいた吸収紙(坪量25g/m2)を重ね合わせ、かかる繊維ウエブと吸収紙との重ね合わせ体をドライヤーに導入し、130℃の温度にて乾燥、一体化することにより、内部に吸水性ポリマーが固定されている吸収性シートを得た。2枚の前記吸収性シート(長さ90mm、幅35mm)を重ね合わせた後、その上下に2枚の前記吸収性シート(長さ200mm、幅75mm)を配し、長手方向前後両端部を曲線状にカットして吸収体とした。
実施例1において、吸水性ポリマーとして合成例2の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを実施例2のサンプルとした。また、実施例1において、吸水性ポリマーとして合成例3の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを実施例3のサンプルとした。また、実施例1において、吸水性ポリマーとして合成例4の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを実施例4のサンプルとした。
実施例2において、吸収体を以下のものに置換し、ナプキンの厚み(7g/cm2荷重下における厚み)を5.5mmとした以外は実施例2と同様にしてナプキンを作製し、これを実施例5のサンプルとした。
ホットメルト接着剤(東洋ペトロライト製P-618B)が塗布量5g/m2で塗布された坪量16g/m2のティッシュペーパー(上側被覆シート)の該接着剤の塗布面上に、別途作製したパルプ繊維の繊維ウエブ(坪量240g/m2、幅7cm、長さ17cm)を載置した。このティッシュペーパーは、繊維ウエブよりも寸法が大きい。次いで、繊維ウエブの上から、前記合成例2の吸水性ポリマー0.13gを該繊維ウエブ全体に均一に散布した。更に、繊維ウエブの吸水性ポリマー散布面に、該繊維ウエブと同サイズでホットメルト接着剤が塗布量5g/m2で塗布された下側被覆シートとしてのティッシュペーパー(坪量16g/m2)を、その接着剤の塗布面が該繊維ウエブと対向するように重ね、前記上側被覆シートにおける該繊維ウエブからの延出部分を該下側被覆シートの上面に巻き上げた後、該繊維ウエブの上下を反転させて、吸収体の略全体がティッシュペーパー(被覆シート)で被覆されてなる平面視において矩形形状の吸収体を得た。実施例5のナプキンの断面模式図(図2相当図)を図8に示す。図8中、符号4は吸収体、符号41は吸水性ポリマー、符号42は繊維ウエブ、符号43は上側被覆シート、符号44は下側被覆シートである。
実施例3において、吸収体と裏面シートとの間に金属イオン捕捉剤としてクエン酸三ナトリウム1g(ナプキンに含有されている全吸水性ポリマー100質量部に対して94質量部)を散布した以外は実施例3と同様にしてナプキンを作製し、これを実施例6のサンプルとした。実施例6のナプキンの厚み(7g/cm2荷重下における厚み)は1.8mmであった。
実施例1において、吸水性ポリマーとして合成例6の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを実施例7のサンプルとした。また、実施例1において、吸水性ポリマーとして合成例7の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを実施例8のサンプルとした。また、実施例1において、吸水性ポリマーとして合成例8の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを実施例9のサンプルとした。
実施例1において、吸収体を以下のもの(混合積繊体)に置換した以外は実施例1と同様にしてナプキンを作製し、これを実施例10のサンプルとした。
解繊したパルプ(フラッフパルプ)100質量部と合成例1の吸水性ポリマー20質量部とを空気気流中に混合し、所定の寸法(幅7cm、長さ17cm)の型内に、型の下側に配した金属メッシュ内面から吸引を行いながら積繊した。こうして得られた混合積繊体の坪量は240g/m2であった。該混合積繊体をホットメルト粘着剤をスプレー塗工した坪量16g/m2のティッシュペーパーで包み込んで吸収体を得た。
実施例10において、混合積繊体に使用した吸水性ポリマーとして合成例10の吸水性ポリマーを用いた以外は実施例10と同様にしてナプキンを作製し、これを実施例11のサンプルとした。また、実施例10において、混合積繊体に使用した吸水性ポリマーとして合成例11の吸水性ポリマーを用いた以外は実施例10と同様にしてナプキンを作製し、これを実施例12のサンプルとした。また、実施例10において、混合積繊体に使用した吸水性ポリマーとして合成例12の吸水性ポリマーを用いた以外は実施例10と同様にしてナプキンを作製し、これを実施例13のサンプルとした。
実施例1において、吸水性ポリマーとして合成例13の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを実施例14のサンプルとした。
実施例1において、吸水性ポリマーを市販の吸水性ポリマー(日本触媒製、商品名CAW4)に変更した以外は実施例1と同様にしてナプキンを作製し、これを比較例1のサンプルとした。比較例1で用いた市販の吸水性ポリマーの中和度及び遠心保持量等の各種特性を、それぞれ前述した測定方法に従って測定した。尚、比較例1で用いた市販の吸水性ポリマーに関し、前記ゼータ電位差の絶対値ΔVの測定に供した牛ヘモグロビンの前記ゼータ電位V2は、+10mVであった。
実施例1において、吸水性ポリマーとして合成例5の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを比較例2のサンプルとした。また、実施例1において、吸水性ポリマーとして合成例9の吸水性ポリマーを用いた以外は実施例1と同様にしてナプキンを作製し、これを比較例3のサンプルとした。
実施例1において、吸水性ポリマーを非イオン性の吸水性ポリマー(住友精化製、アクアコーク)に変更した以外は実施例1と同様にしてナプキンを作製し、これを比較例4のサンプルとした。比較例4で用いた非イオン性の吸水性ポリマーの遠心保持量等の各種特性を、それぞれ前述した測定方法に従って測定した。
インドネシアで市販されている生理用ナプキン「スーパーマキシ」(花王(株)製)を、参考例のサンプルとした。このスーパーマキシは、吸水性ポリマーを含有していない。
実施例、比較例及び参考例の生理用ナプキンについて、前記測定方法に従って厚みを測定すると共に、前記手順1~3に従って赤色度合いa*値を測定した。また、手順3の終了後のナプキンの状態を目視で観察し、水洗いに起因するナプキンの破れ(洗浄破れ)の有無を確認した。また、これらの生理用ナプキンの吸収性能の評価として、下記の方法により吸収時間及び液戻り量を測定した。これらの結果を下記表2に示す。下記表1には、各生理用ナプキンで用いた吸水性ポリマーの特性を示した。尚、赤色度合いa*値に関し、測定値が1以下であった場合、測定の誤差を考慮すると該測定値は実質的に0とみなせるので、下記表2において「≒0」とした。
測定対象の生理用ナプキンを平面状に拡げ、表面シートを上に向けて水平面上に固定した状態で、吸収体の中心部における該表面シート上に、円筒状の注入部の付いたアクリル板をのせ、更にそのアクリル板上に錘をのせ、吸収体の中心部に対して、5g/m2の荷重を加える。アクリル板に設けられた注入部は、内径10mmの円筒状をなし、アクリル板には、長手方向及び幅方向の中心軸に、該円筒状注入部の中心軸線が一致し、該円筒状注入部の内部とアクリル板の表面シート対向面との間を連通する内径10mmの貫通孔が形成されている。次いで、円筒状注入部の中心軸が吸収体の平面視における中心部と一致するようにアクリル板を配置し、3gの血液を、円筒状注入部から注入し、生理用ナプキンに吸収させる。血液がナプキンの表面に到達した時点から3gの全量がナプキンに吸収されるまでの時間(秒)を計測し、これを1回目の吸収時間とした。また、最初の血液注入時から3分後に、前記手順を繰り返して3gの血液を更に注入(血液の注入量は合計6g)し、この再注入された血液の全量がナプキンに吸収されるまでの時間(秒)を計測し、これを2回目の吸収時間とした。これらの吸収時間の値が小さいほど、吸収速度が速く、高評価となる。下記表1には2回目(血液6g注入時)の吸収時間を示した。尚、1回目において、注入した血液の全量(3g)が吸収されるまでに3分を超えた場合は、全量を吸収後速やかに次の3gを注入した。
前記<吸収時間の測定方法>において、3回目の血液注入時から3分後に、アクリル板と錘を取り除き、ナプキンの肌当接面上(表面シート上)に、7cm×15cmで坪量30g/m2の吸収紙(市販のティッシュペーパー)を10枚重ねて載置し、該吸収紙の上から68g/cm2の荷重を1分間かけた。荷重後、吸収紙10枚を取り除き、該吸収紙10枚の重さを測定した。この測定値と、予め求めておいた荷重前の吸収紙10枚の重さの測定値とから、吸収紙10枚に吸収された血液の質量(g)を求め、該質量を液戻り量とした。該液戻り量が少ないほど、ナプキンの吸収性能が高く、高評価となる。
Claims (12)
- カルボキシ基及び/又はカルボキシレート基を有し且つ中和度75モル%以上、JIS K 7223に準拠した遠心保持量5~20g/gの吸水性ポリマーを含有する吸収体。
- 前記吸水性ポリマーは、ボルテックス法による吸水速度が30秒以上である請求の範囲第1項記載の吸収体。
- 前記吸水性ポリマーは、2.0kPaでの加圧下通液速度が150ml/分以上である請求の範囲第1項記載の吸収体。
- 繊維集合体からなる複数の層を積層してなる積層構造を備え、該積層構造における層間のうちの少なくとも1つの層間に前記吸水性ポリマーが介在されている請求の範囲第1項記載の吸収体。
- 前記繊維集合体が、改質パルプ及び天然繊維を含む請求の範囲第4項記載の吸収体。
- 吸水性ポリマーを含有し、該吸水性ポリマーのイオン交換水中でのゼータ電位と、牛ヘモグロビンのイオン交換水中でのゼータ電位との差の絶対値が30mV以下である吸収体。
- 吸水性ポリマーを含有し、該吸水性ポリマーが、カルボキシ基及び/又はカルボキシレート基を有し、アルカリ金属を含む中和剤で中和処理されており、その中和度が75モル%以上であり、且つ該吸水性ポリマー全体に該アルカリ金属が一様に分布している吸収体。
- 請求の範囲第1項、第6項及び第7項の何れかに記載の吸収体を具備する吸収性物品。
- 下記工程I及びIIを有する吸水性ポリマーの製造方法。
工程I:(メタ)アクリル酸及び/又はそのアルカリ金属塩を含むモノマーを重合してポリマーを得、該ポリマーを架橋剤により架橋処理して、又は(メタ)アクリル酸及び/又はそのアルカリ金属塩を含むモノマーを、架橋剤の存在下で重合して、JIS K 7223に準拠した遠心保持量が5~20g/gのポリマーを調製する工程であって、該モノマーに対する架橋剤の質量比〔架橋剤/モノマー〕が0.15/100~40/100である工程。
工程II:前記工程Iで得られたポリマーに塩基性化合物及び/又は水を接触させて、該ポリマーの中和度が75モル%以上となるように中和処理を施す工程。 - 前記塩基性化合物が、水溶性水酸化化合物及び/又は水溶性炭酸化合物である請求の範囲第9項記載の吸水性ポリマーの製造方法。
- 前記工程IIの中和処理において、吸水性ポリマーの含水率を、前記工程Iで得られたポリマーに対して100~600質量%にする請求の範囲第9項記載の吸水性ポリマーの製造方法。
- 請求の範囲第9項記載の製造方法により得られる吸水性ポリマー。
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US10323105B2 (en) | 2014-07-11 | 2019-06-18 | Sumitomo Seika Chemicals Co. Ltd. | Water-absorbent resin and absorbent article |
US11136420B2 (en) | 2014-07-11 | 2021-10-05 | Sumitomo Seika Chemicals Co. Ltd. | Water-absorbent resin and method of producing water-absorbent resin |
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CN107802410A (zh) * | 2017-11-06 | 2018-03-16 | 欣龙控股(集团)股份有限公司 | 一种折叠式吸收芯体 |
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US10323105B2 (en) | 2014-07-11 | 2019-06-18 | Sumitomo Seika Chemicals Co. Ltd. | Water-absorbent resin and absorbent article |
US11136420B2 (en) | 2014-07-11 | 2021-10-05 | Sumitomo Seika Chemicals Co. Ltd. | Water-absorbent resin and method of producing water-absorbent resin |
US20160222685A1 (en) * | 2015-01-31 | 2016-08-04 | Ramshorn Corporation | Concrete curing blanket |
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