JP6802078B2 - Absorbent article - Google Patents

Description

The present invention relates to an absorbent article comprising a sheet having a red blood cell agglutinating action.

There is known a technique of applying a cationic polymer material to an absorbent article to improve various performances of the absorbent article. For example, Patent Document 1 describes a technique in which polylysine, which is a cationic polymer, is placed between a cover sheet of a personal care absorbent article and a liquid-impermeable backing material, and red blood cells in menstrual blood are aggregated by polylysine. Has been done.

As another technique, Patent Document 2 discloses an absorbent article provided with an antibacterial sheet that exerts an antibacterial effect when in contact with a body fluid. The antibacterial sheet described in Patent Document 2 is formed by adhering an antibacterial composition having an antibacterial agent and a thermoplastic water-soluble polymer, and Patent Document 2 describes the molecular weight as the thermoplastic water-soluble polymer. It is described that a plurality of different types of polyethylene glycol are preferably used.

Special Table 2002-528232 Japanese Unexamined Patent Publication No. 2008-142464

According to the technique described in Patent Document 1, menstrual blood absorbed in an absorbent article is aggregated by polylysine, which makes it difficult for menstrual blood to revert. However, agglutination of menstrual blood may contribute to impeding the permeability of menstrual blood excreted from the second time onward, which may slow down the absorption rate of menstrual blood in the absorber.

The technique described in Patent Document 2 does not use a cationic polymer material, and no study has been made on compatibility between menstrual blood reversion utilizing menstrual blood aggregation and menstrual blood absorption rate. ..

Therefore, an object of the present invention is to improve a material for treating menstrual blood, and more specifically, to provide an absorbable article that achieves both difficulty in reversing menstrual blood and improvement in absorption rate of menstrual blood. ..

The present invention is an absorbent article containing a blood cell flocculant, wherein the blood cell flocculant has a total weight average molecular weight of 100,000 or more as measured by a gel permeation chromatography method, and the total weight average molecular weight is adjusted to the total weight average molecular weight. On the other hand, a first cationic polymer having a molecular weight of 50% or more and a second cationic polymer having a molecular weight of 15% or less with respect to the total weight average molecular weight are contained, and the amount D1 of the first cationic polymer is determined. It provides an absorbent article in which the ratio D2 / D1 to the amount D2 of the second cationic polymer on a mass basis is 35/65 or more and 80/20 or less.

The present invention is an absorbent article containing a cationic polymer, wherein the cationic polymer has a total weight average molecular weight of 100,000 or more as measured by a gel permeation chromatography method, and the total weight average molecular weight is 100,000 or more. A first cationic polymer having a molecular weight of 50% or more and a second cationic polymer having a molecular weight of 15% or less with respect to the total weight average molecular weight are contained, and the amount of the first cationic polymer is D1. The present invention provides an absorbent article in which the ratio D2 / D1 to the amount D2 of the second cationic polymer on a mass basis is 35/65 or more and 80/20 or less.

According to the present invention, there is provided an absorbable article that achieves both the difficulty of reversing menstrual blood and the improvement of the absorption rate of menstrual blood.

FIG. 1 is a plan view showing an embodiment of the absorbent article of the present invention. 2 (a) and 2 (b) are schematic views showing the absorption mechanism of menstrual blood in a conventional absorbent article. FIG. 3 is a schematic view showing the absorption mechanism of menstrual blood in the absorbable article of the present invention.

Hereinafter, the present invention will be described based on its preferred embodiment. The absorbable article of the present invention contains a blood cell flocculant. In this embodiment, the absorbent article contains a cationic polymer. In the present embodiment, as described later, a cationic polymer or the like can be mentioned as the hemagglutination agent. FIG. 1 shows a sanitary napkin 1 (hereinafter, also simply referred to as “napkin 1”), which is an embodiment of an absorbent article of the present invention. The napkin 1 has a vertical direction X corresponding to the front-back direction of the wearer and a horizontal direction Y orthogonal to the vertical direction X, and is arranged on an absorber 4 capable of absorbing menstrual blood and a side facing the skin of the absorber 4. A surface sheet 2 that can come into contact with the wearer's skin when worn is provided as a constituent member.

In the present specification, the "skin facing surface" is a surface of the absorbent article or its constituent members (for example, the absorber 4) that is directed toward the skin side of the wearer when the absorbent article is worn, that is, relatively of the wearer. The side closer to the skin, the "non-skin facing surface" is the side of the absorbent article or its constituents that is opposite to the skin side when the absorbent article is worn, that is, toward the side relatively far from the wearer's skin. It is the surface to be. The term "when worn" as used herein means a state in which the normal proper wearing position, that is, the correct wearing position of the absorbent article is maintained, and the absorbent article is in a state deviated from the wearing position. Does not include.

The napkin 1 includes an absorbent main body 10 including a front surface sheet 2 forming a skin facing surface, a back surface sheet 3 forming a non-skin facing surface, and an absorber 4 interposed between both sheets 2 and 3. .. The absorbent body 10 is arranged on the ventral side, that is, the front side of the wearer from the excretion portion facing portion 1B, which is a region facing the wearer's liquid excretion portion (vaginal opening, etc.) when worn, and the excretion portion facing portion 1B. The front portion 1A to be formed and the rear portion 1C arranged on the back side, that is, the rear side of the wearer from the excretion portion facing portion 1B are provided in the vertical direction X. That is, the napkin 1 or the absorbent body 10 is divided into three regions in the vertical direction X in order from the ventral side of the wearer: the front portion 1A, the excretion portion facing portion 1B, and the rear portion 1C. The vertical direction X corresponds to the longitudinal direction of the napkin 1 and the absorbent body 10, and the lateral direction Y corresponds to the width direction orthogonal to the longitudinal direction of the napkin 1 and the absorbent body 10.

The surface sheet 2 covers the entire surface of the absorber 4 facing the skin, and its side edges along the vertical direction X are substantially at the same positions as the side edges of the absorber 4 along the vertical direction X. On the other hand, the back surface sheet 3 covers the entire non-skin facing surface of the absorber 4, and further extends outward from both side edges along the vertical direction X of the absorber 4 in the horizontal direction Y, and the side sheet 6 described later. Together with this, the side flap portion 10S is formed. The back surface sheet 3 and the side sheet 6 are bonded to each other by known bonding means such as an adhesive, a heat seal, and an ultrasonic seal at the extending portions from both side edges of the absorber 4 along the vertical direction X. Further, the front surface sheet 2 and the back surface sheet 3 are joined to each other by known joining means at the extending portions from both ends of the absorber 4 in the vertical direction X. Each of the front surface sheet 2 and the back surface sheet 3 and the absorber 4 may be bonded by an adhesive.

As the front surface sheet 2 and the back surface sheet 3, various materials conventionally used for absorbent articles such as sanitary napkins can be used without particular limitation. For example, as the back surface sheet 3, a resin film having low liquid permeability and moisture permeability, a laminated sheet of the resin film and a non-woven fabric, or the like can be used. On the other hand, as the surface sheet 2, a non-woven fabric having a single-layer or multi-layer structure, a perforated film, or the like can be used. The surface sheet 2 can be coated with various oil agents for improving liquid permeability, for example, various surfactants. When the surface sheet 2 has a multi-layer structure, the surface sheet 2 includes a first fiber layer located on the side closer to the wearer's skin and a second fiber layer located on the side farther from the wearer's skin. Both fiber layers are integrated in the thickness direction by a large number of partially formed joints, and a portion of the first fiber layer located between the plurality of joints is convex. A concavo-convex sheet that is raised to form the concavo-convex convex portion can be used. The convex portion in the concave-convex sheet may have a solid structure in which the entire surface is filled with fibers, or may have a hollow structure having a space inside. As the uneven sheet having the convex portion having a solid structure, for example, those described in JP-A-2007-1826662 and JP-A-2002-187228 can be used.

The surface sheet 2 may be embossed. The embossing pattern is not particularly limited, and various patterns can be formed depending on the specific use of the napkin 1. For example, a so-called round embossing having a closed shape along the peripheral edge can be formed at a position inside the peripheral edge of the absorber 4. In this round embossing, it is preferable that the portion corresponding to the side edge of the absorber 4 has a shape that bulges outward in the width direction of the absorber 4. This round embossing may be composed of a collection of discontinuous embossing patterns within a range that can be regarded as continuous when viewed as a whole.

The absorbent body 10 includes a second sheet 5. The second sheet 5 is liquid permeable and is arranged between the surface sheet 2 and the absorber 4. The second sheet 5 is a constituent member of an absorbent article, which is also called a sublayer sheet or the like in the present technical field, and improves the permeability of the liquid from the surface sheet 2 to the absorber 4, and the surface of the liquid absorbed by the absorber 4. It plays a role of reducing liquid return to the sheet 2. In the present embodiment, the second sheet 5 covers substantially the entire area of the absorber 4 facing the skin. As the second sheet 5, a hydrophilic non-woven fabric or a hydrophilic fiber aggregate can be used, and examples of the non-woven fabric include an air-through non-woven fabric, a point-bonded non-woven fabric, a resin-bonded non-woven fabric, a spunlace non-woven fabric, and an air-laid non-woven fabric. The basis weight of the second sheet 5 is preferably 10 g / m ² or more, more preferably 15 g / m ² or more, and preferably 50 g / m ² or less, still more preferably 40 g / m ² or less. The thickness of the second sheet 5 is preferably 0.1 mm or more and 5 mm or less.

A pair of both side portions of the absorbent body 10 on the skin-facing surface, that is, the skin-facing surface of the surface sheet 2 along the vertical direction X, so as to overlap the left and right side portions of the absorber 4 along the vertical direction X in a plan view. The side sheets 6 and 6 are arranged over substantially the entire length of the absorbent body 10 in the vertical direction X. The pair of side sheets 6 and 6 are joined to the surface sheet 2 by known joining means at a joining line 61 extending in the vertical direction X, respectively.

In addition to the absorbent main body 10, the napkin 1 is a pair of wing portions 10W and 10W extending outward in the horizontal direction Y from both side portions of the absorbent main body 10 along the vertical direction X of the excretion portion facing portion 1B. have.

When the napkin 1 has the wing portion 10W, the excretion portion facing portion 1B is along the region having the wing portion 10W (the vertical direction X of one wing portion 10W) in the vertical direction (X direction in the drawing) of the napkin 1. It means a region sandwiched between the base and the base along the vertical direction X of the other wing portion 10W). When the napkin 1 does not have a wing portion, the excretion portion facing portion 1B crosses the napkin 1 in the lateral direction (Y direction in the drawing), which is generated when the napkin 1 is folded into a tri-fold individual packaging form. For two bending lines (not shown), it means a region surrounded by the first bending line and the second bending line counting from the front end of the napkin 1 in the vertical direction X.

The side flap portion 10S projects greatly outward in the lateral direction Y at the excretion portion facing portion 1B, whereby a pair of wing portions 10W and 10W are provided on both the left and right sides of the absorbent main body 10 along the vertical direction X. It has been extended. The wing portion 10W has a substantially trapezoidal shape in which the lower base (the side longer than the upper base) is located on the side side of the napkin 1 in a plan view as shown in FIG. 1, and the wing portion 10W has a substantially trapezoidal shape on the non-skin facing surface thereof. , A wing portion adhesive portion (not shown) for fixing the wing portion 10W to clothes such as shorts is formed. The wing portion 10W is used by being folded back toward the non-skin facing surface (outer surface) side of the crotch portion of clothing such as shorts. Before its use, the adhesive portion of the wing portion is covered with a release sheet (not shown) made of a film, a non-woven fabric, paper or the like.

The absorber 4 contains a highly absorbent polymer. As the highly absorbent polymer contained in the absorber 4, a particulate polymer is generally used, but a fibrous polymer may also be used. When a particulate high-absorbent polymer is used, its shape may be spherical, lumpy, bale-shaped or amorphous. As the highly absorbent polymer, a polymer or copolymer of acrylic acid or an alkali metal salt of acrylic acid can generally be used. Examples thereof include polyacrylic acid and salts thereof, and polymethacrylic acid and salts thereof. As the polyacrylic acid salt and the polymethacrylate, a sodium salt can be preferably used. In addition, acrylic acid or methacrylic acid, maleic acid, itaconic acid, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2-hydroxyethyl (meth) acrylate, styrenesulfonic acid, etc. A copolymer obtained by copolymerizing the above comonomers without deteriorating the performance of the highly absorbent polymer can also be used.

The absorber 4 further contains hydrophilic fibers in addition to the highly absorbent polymer. Examples of the hydrophilic fibers contained in the absorber 4 include those obtained by hydrophilizing the hydrophobic fibers and those that are hydrophilic in themselves, and one of these fibers may be used alone or in combination of two or more thereof. Can be used. In particular, those that are hydrophilic and have water retention are preferable. As the latter hydrophilic fiber, natural fiber, cellulosic regenerated fiber or semi-synthetic fiber are preferable examples. As the hydrophilic fiber, pulp and rayon are particularly preferable, and pulp is more preferable. Examples of the pulp include wood pulp such as coniferous kraft pulp and broadleaf kraft pulp, as well as non-wood pulp such as cotton pulp and straw pulp, but the pulp is not particularly limited. Further, a crosslinked cellulose fiber obtained by cross-linking the inside and / or between the molecules of the cellulose fiber, or a bulky cellulose fiber obtained by marcelifying wood pulp may be used.

The absorber 4 can be embossed. The embossing may be performed only on the absorber 4, or may be performed on the surface sheet 2 and the absorber 4 described above together. By embossing the surface sheet 2 and the absorber 4 together, these members are joined by heat fusion and / or crimping at the embossed portion. When the surface sheet 2 is subjected to the round embossing described above, the round embossing can also be applied to the absorber 4 together, and the absorber 4 and the surface sheet 2 can be joined by the round embossing. ..

The absorber 4 includes an absorbent core composed of a lower absorbent core 41 and an upper absorbent core 42 containing hydrophilic fibers and a highly absorbent polymer. Specifically, the absorber 4 is superposed on the lower absorbent core 41, which is arranged to face the excretory portion of the wearer when worn, and the lower absorbent core 41, and the lower absorbent core 4 is superposed on the lower absorbent core 41 in a plan view as shown in FIG. It has a laminated structure including an upper absorbent core 42 having a portion 42E extending outward from at least a part of the peripheral edge of the core 41. The "periphery of the central absorbent sheet" as used herein means the peripheral edge of the lower absorbent core 41 in a state of being incorporated in the napkin 1. In the napkin 1 shown in FIG. 1, the upper absorbent core 42 extends outward from the entire peripheral edge of the lower absorbent core 41. Due to the fact that the absorber 4 has such a structure, the central portion in the lateral direction Y of the excretion portion facing portion 1B is a so-called middle and high portion which is thicker than the peripheral portion. ..

At least the upper and lower surfaces of the absorbent core including the lower absorbent core 41 and the upper absorbent core 42 are covered with a coating sheet (not shown). Preferably, the entire absorbent core is covered with a coating sheet. The coating sheet is liquid permeable. As an example of the coating sheet, thin paper using cellulose fiber as a main material, a non-woven fabric subjected to a hydrophilic treatment, or the like is used.

The blood cell flocculant contained in napkin 1 has a total weight average molecular weight of 100,000 or more as measured by a gel permeation chromatography method (GPC method), and has a molecular weight of 50% or more of the total weight average molecular weight. It contains a monocationic polymer and a second cationic polymer having a molecular weight of 15% or less based on the total weight average molecular weight. Here, the total weight average molecular weight refers to the weight average molecular weight in a state where all the blood cell flocculants contained in the napkin 1 are mixed. The total weight average molecular weight is preferably 100,000 or more, preferably 2 million or less, more preferably 1 million or less, and particularly preferably 600,000 or less. Within this range, the high molecular weight hemagglutination agent and the low molecular weight hemagglutination agent can suitably exert their respective functions.

In the present embodiment, the cationic polymer contained in the napkin 1 has a total weight average molecular weight of 100,000 or more as measured by a gel permeation chromatography method (GPC method), and is 50% of the total weight average molecular weight. It contains a first cationic polymer having the above molecular weight and a second cationic polymer having a molecular weight of 15% or less with respect to the total weight average molecular weight. Here, the total weight average molecular weight refers to the weight average molecular weight in a state where all the cationic polymers contained in the napkin 1 are mixed. The total weight average molecular weight is preferably 100,000 or more, preferably 2 million or less, more preferably 1 million or less, and particularly preferably 600,000 or less. Within this range, the high molecular weight cationic polymer and the low molecular weight cationic polymer can suitably exhibit their respective functions.

The first cationic polymer preferably has a molecular weight of 50% or more with respect to the total weight average molecular weight, and particularly preferably 55% or more with respect to the total weight average molecular weight. Further, the second cationic polymer preferably has a molecular weight of 15% or less with respect to the total weight average molecular weight, and particularly preferably 10% or less with respect to the total weight average molecular weight. Here, the "hemagglutinant" has an action of aggregating red blood cells in blood, and acts so as to separate the agglutinated agglomerates and plasma components. Further, as a hemagglutinant, when 1000 ppm of a measurement sample agent is added to simulated blood, at least two or more erythrocytes aggregate to form an agglutinin while the blood fluidity is maintained. It is preferable to have. The molecular weight referred to in the present invention is a weight average molecular weight. The cationic polymer means a strongly positively charged linear cationic polymer such as an acrylamide copolymer or polylysine. The molecular weight of the cationic polymer can be controlled by appropriately selecting the polymerization conditions thereof.

In the above-mentioned "state in which blood fluidity is maintained", 10 g of pseudo blood to which 1000 ppm of a measurement sample agent is added is added to a screw tube bottle (Maruemu Corporation product number "Screw tube No. 4", mouth inner diameter 14.5 mm, It means a state in which 80% or more of the simulated blood flows down within 5 seconds when the screw tube bottle containing the simulated blood is placed in a body diameter of 27 mm and a total length of 55 mm) and inverted 180 degrees. Pseudoblood has a viscosity of 8 mPa · s measured using a B-type viscometer (model number TVB-10M manufactured by Toki Sangyo Co., Ltd., measurement conditions: rotor No. 19, 30 rpm, 60 seconds, 25 ° C.). The blood cell / plasma ratio of defibered horse blood (manufactured by Japan Biotest Research Institute Co., Ltd.) was prepared.

Whether or not the above-mentioned "two or more red blood cells aggregate to form an agglutinating mass" is determined as follows. That is, the simulated blood to which 1000 ppm of the measurement sample agent was added was diluted 4000 times with physiological saline, and a laser diffraction / scattering type particle size distribution measuring device (manufactured by Horiba Seisakusho Co., Ltd., model number: LA-950V2, measurement condition: flow type). The average median diameter of the volume particle size measured at a temperature of 25 ° C. by the laser diffraction / scattering method using cell measurement (cell measurement, circulation speed 1, no ultrasonic waves) corresponds to the size of agglomerates in which two or more red blood cells have aggregated. When it is 10 μm or more, it is determined that “two or more erythrocytes aggregate to form an agglomerate”.

The hemagglutination agent used in the present invention is an agent that satisfies the above-mentioned properties (can express erythrocyte aggregation) by a plurality of combinations of a single compound that fits the above-mentioned properties, or a combination of a plurality of compounds. That is, the hemagglutination agent is an agent limited to those having a hemagglutination action as defined above. Therefore, when the hemagglutination agent contains a third component that does not meet the above definition, it is expressed as a hemagglutination agent composition to distinguish it from the hemagglutination agent. The term "single compound" as used herein is a concept that includes compounds having the same composition formula but different molecular weights due to different numbers of repeating units.

The blood cell aggregating agent used in the present invention preferably has a blood aggregation rate of 0.75 mPa · s / s or less. The blood agglutination rate is a measure of the ability of a hemagglutinant to agglutinate blood to form an agglutinin, and the smaller the value, the smaller the size of the agglutinin after a certain period of time. That is, when blood is aggregated by a hemagglutin, if the size of the aggregate generated after a certain period of time is large, the constituent members of the sanitary napkin are clogged by the aggregate, and the liquid permeates. Where the property may be hindered, by controlling the agglutination rate, it is possible to improve the absorption capacity of the highly absorbent polymer without causing a decrease in liquid permeability due to agglutination. As a result, the trade-off requirements of improving the permeability of the liquid and improving the absorption capacity of the highly absorbent polymer are simultaneously satisfied. From this viewpoint, the agglutination rate is more preferably 0.32 mPa · s / s or less, and even more preferably 0.15 mPa · s / s or less. The lower limit of the aggregation rate is preferably 0.001 mPa · s / s or more, and more preferably 0.01 mPa · s / s or more.

The aggregation rate is measured by the method described below. The blood used for measuring the aggregation rate is a sample obtained by adding 500 ppm of a hemagglutination agent to the above-mentioned simulated blood. Using a rheometer (Thermo Fisher Scientific, Inc. HAAKE RheoStress6000), 2 μL of physiological saline in which 5% of the blood cell flocculant was previously dissolved was added dropwise to 200 μL of blood previously developed on the stage, and a 35 mmΦ cone plate was used. (gradient 1 °) temperature: 30 °, shear rate: 10 viscosity changes were measured at ¹ (sec ^-1). The change in viscosity is measured for 50 seconds, the obtained plot is linearly approximated, and the aggregation rate is calculated from the slope of the straight line.

For the gel permeation chromatography method, for example, HLC-8320GPC manufactured by Tosoh Corporation can be used. The above-mentioned "total weight average molecular weight measured by the GPC method" is the weight average when a lysate in which all the blood cell flocculants contained in the napkin 1 are mixed is measured by a gel permeation chromatography method. Means molecular weight. The specific measurement conditions are as follows.

As the column, a guard column α manufactured by Tosoh Corporation and an analysis column α-M connected in series are used at a column temperature of 40 ° C. RI (refractive index) is used as the detector. As a measurement sample, 1 mg of the treatment agent to be measured (for example, a quaternary ammonium salt polymer) is dissolved in 1 mL of the eluent. For a copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate, an eluent obtained by dissolving 150 mmol / L sodium sulfate and 1% by mass of acetic acid in water is used. A copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate has a molecular weight of 5900 pullulan, a molecular weight of 47300 pullulan, a molecular weight of 212,000 pullulan, and a molecular weight of 788,000 per 10 mL of the eluent. Pullulan, a mixture of pullulan in which 2.5 mg each is dissolved, is used as a molecular weight standard. The copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate is measured at a flow rate of 1.0 mL / min and an injection amount of 100 μL. Except for copolymers containing water-soluble polymerizable monomers such as hydroxyethyl methacrylate, elution of 50 mmol / L lithium bromide and 1% by mass of acetic acid in ethanol: water = 3: 7 (volume ratio). Use liquid. Except for copolymers containing water-soluble polymerizable monomers such as hydroxyethyl methacrylate, polyethylene glycol (PEG) having a molecular weight of 106, PEG having a molecular weight of 400, PEG having a molecular weight of 1470, and PEG having a molecular weight of 6450 per 20 mL of eluent. , Polyethylene oxide (PEO) having a molecular weight of 50,000, PEO having a molecular weight of 235,000, PEO having a molecular weight of 875,000, and a mixture of PEG-PEO in which 10 mg each is dissolved are used as the molecular weight standard. Except for the copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate, the measurement is carried out at a flow rate of 0.6 mL / min and an injection amount of 100 μL.

The advantages of the napkin 1 including the hemagglutination agent are as described below.
The absorption rate and the amount of water absorbed by the highly absorbent polymer differ depending on the type of water, and when comparing physiological saline and blood, blood has a slower absorption rate and a smaller amount of absorption than physiological saline. When the present inventor examined various reasons for this, the facts described below were found. Blood is roughly classified into a liquid component such as plasma and a non-liquid component such as red blood cells, and the component absorbed by the highly absorbent polymer is a liquid component such as plasma. As shown in FIG. 2A, when the menstrual blood 11 comes into contact with the highly absorbent polymer 14, only the liquid component 12 in the menstrual blood 11 is absorbed by the highly absorbent polymer 14, and the red blood cells, which are the non-liquid component 13, are high. Not absorbed by the absorbent polymer 14. As the absorption of the liquid component 12 into the highly absorbent polymer 14 progresses, as shown in FIG. 2B, the non-liquid component 13 which is not absorbed by the highly absorbent polymer 14 accumulates on the surface of the highly absorbent polymer 14. A coating 15 is formed. Due to the formation of the coating film 15, the liquid absorption of the highly absorbent polymer 14 is inhibited, and the absorption rate is lowered. Further, due to the formation of the coating film 15, swelling inhibition of the highly absorbent polymer 14 also occurs, and the amount of absorption decreases.

As a result of various studies by the present inventor on means for preventing the occurrence of the phenomenon as shown in FIG. 2B and preventing the deterioration of absorption performance, the components occupying most of the non-liquid components in menstrual blood. As shown in FIG. 3, it was found that it is effective to agglutinate the red blood cells to form agglomerates 16. By generating agglomerates 16 of red blood cells, it becomes difficult to form a film of the agglomerates, or even if a film is formed by the agglutinates, a space through which the liquid component 12 can permeate remains in the film. Inhibition of absorption of component 12 is less likely to occur. As a result, the highly absorbent polymer 14 can sufficiently exhibit its original absorption performance. In order to further enhance the absorption performance, it is preferable that the erythrocyte aggregate particle size is large, and the hardness of the aggregate is preferable.

According to the findings of the present inventor, it is useful to contain a cationic polymer as the hemagglutination agent. The reason is as follows. Red blood cells have an erythrocyte membrane on their surface. The erythrocyte membrane has a two-layer structure. This two-layer structure consists of a lower erythrocyte membrane skeleton and an upper lipid membrane. The lipid film exposed on the surface of red blood cells contains a protein called glycophorin. Glycophorin has a sugar chain at the end of which an anion-charged sugar called sialic acid is bound. As a result, erythrocytes can be treated as anionic-charged colloidal particles. A flocculant is generally used for agglutination of colloidal particles. Considering that erythrocytes are anionic colloidal particles, it is advantageous to use a cationic substance as the flocculant from the viewpoint of neutralizing the electric double layer of erythrocytes. Further, when the flocculant has a polymer chain, the polymer chains of the flocculant adsorbed on the surface of the erythrocytes are likely to be entangled with each other, which promotes the aggregation of erythrocytes. Further, when the flocculant has a functional group, the interaction between the functional groups also promotes the aggregation of erythrocytes, which is preferable. According to the hemagglutination agent (cationic polymer), the above mechanism of action makes it possible to generate erythrocyte aggregates in menstrual blood.

Here, in the napkin 1, the blood cell flocculant contains a relatively high molecular weight first cationic polymer and a relatively low molecular weight second cationic polymer. Therefore, the relatively low molecular weight second cationic polymer acts on the blood before the relatively high molecular weight first cationic polymer, and it becomes easier to form small agglomerates. Further, after the second cationic polymer acts to form a small agglomerate, the relatively high molecular weight first cationic polymer acts on the blood to form a large agglomerate. When such a large agglomerate is formed, it becomes difficult for menstrual blood to revert. As described above, since it takes time to form a large agglomerate after forming a small agglomerate, a napkin 1 provided with a hemagglutinant containing a first cationic polymer and a second cationic polymer is used for menstrual blood. It is possible to achieve both the difficulty of reversion and the improvement of the absorption rate of menstrual blood.

In the napkin 1, the hemagglutination agent is a mixture of a first cationic polymer and a second cationic polymer having different weight average molecular weights. The weight average molecular weight of the relatively high molecular weight first cationic polymer is preferably 100,000 or more, more preferably 150,000 or more, from the viewpoint of difficulty in reversion of menstrual blood. It is more preferably 200,000 or more, and particularly preferably 250,000 or more. Further, it is preferably 10 million or less, more preferably 5 million or less, further preferably 1 million or less, and particularly preferably 600,000 or less. Specifically, the first cationic polymer is preferably 100,000 or more and 10 million or less, more preferably 150,000 or more and 5 million or less, and further preferably 200,000 or more and 1 million or less. It is particularly preferable that the amount is 250,000 or more and 600,000 or less.
On the other hand, the weight average molecular weight of the relatively low molecular weight second cationic polymer is lower than the weight average molecular weight of the relatively high molecular weight first cationic polymer from the viewpoint of improving the absorption rate of menstrual blood. On the condition that it is 2000 or more, it is preferable. Further, it is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less. Specifically, the second cationic polymer is preferably 2000 or more and 200,000 or less, more preferably 150,000 or less, and further preferably 100,000 or less.
The first cationic polymer and the second cationic polymer may be the same type of polymer having different weight average molecular weights, or may be polymers having different weight average molecular weights and different types. Here, the same type of polymer means polymers having the same main chain of the polymer, and different polymers mean the polymers having different main chains of the polymer.

In napkin 1, when the molecular weight distribution of the blood cell flocculant was measured by gel permeation chromatography (GPC method) and a differential molecular weight distribution curve was obtained, the first cationic polymer was difficult to reverse menstrual blood. From this point of view, it is preferable to have a peak or shoulder peak in the range of 50% or more, and a peak or shoulder peak in the range of 55% or more with respect to the total weight average molecular weight. More preferred. Further, when the molecular weight distribution curve is obtained, the second cationic polymer has a peak or a shoulder peak in the range of 15% or less with respect to the total weight average molecular weight from the viewpoint of improving the absorption rate of menstrual blood. It is preferable to have it, and it is more preferable to have a peak or a shoulder peak in the range of 10% or less. Here, the total weight average molecular weight means the weight average molecular weight in a state where all the blood cell flocculants contained in the above-mentioned napkin 1 are mixed. As described above, the hemagglutination agent which is a mixture of the first cationic polymer and the second cationic polymer having different weight average molecular weights may have two peaks or a main peak and a shoulder peak on the differential molecular weight distribution curve. preferable. In addition, when the differential molecular weight distribution curve of the hemagglutin has two peaks, or a main peak and a shoulder peak, the two peaks are compatible with the difficulty of reversing menstrual blood and the improvement of the absorption rate of menstrual blood. The difference in value, or the difference between the main peak value and the shoulder peak value, is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more. Further, it is preferably 2 million or less, more preferably 1 million or less, and further preferably 500,000 or less. Specifically, it is preferably 50,000 or more and 2 million or less, more preferably 100,000 or more and 1 million or less, and further preferably 150,000 or more and 500,000 or less.

The mass of the amount D1 of the first cationic polymer and the amount D2 of the second cationic polymer from the viewpoint of making both the difficulty of reversion of menstrual blood and the improvement of the absorption rate of menstrual blood even more remarkable. The reference ratio D2 / D1 is greater than or equal to 35/65 and less than or equal to 80/20.

The ratio D2 / D1 is measured as follows.
The molecular weight distribution of the blood cell flocculant is measured by gel permeation chromatography (GPC method), a differential molecular weight distribution curve is obtained, and the total weight average molecular weight is calculated. Area under the curve (D1) in the differential molecular weight distribution curve of the first cationic polymer which is 50% or more of the total weight average molecular weight, and the differential molecular weight of the second cationic polymer which is 15% or less of the total weight average molecular weight. The area under the curve (D2) in the distribution curve is calculated, and the ratio D2 / D1 is calculated. In the present embodiment, the molecular weight distribution of the cationic polymer is measured by a gel permeation chromatography method (GPC method), a differential molecular weight distribution curve is obtained, and the total weight average molecular weight is calculated. Area under the curve (D1) in the differential molecular weight distribution curve of the first cationic polymer which is 50% or more of the total weight average molecular weight, and the differential molecular weight of the second cationic polymer which is 15% or less of the total weight average molecular weight. The area under the curve (D2) in the distribution curve is calculated, and the ratio D2 / D1 is calculated.

As the hemagglutinant, in addition to a cationic polymer such as a first cationic polymer and a second cationic polymer (hereinafter, also simply referred to as “cationic polymer”), a triblock copolymer of polypropylene oxide and polyethylene oxide is further used. May be contained. An example of such a triblock copolymer is "Pluronic F-98" available from BASF.

Examples of the cationic polymer contained in the hemagglutin include cationized cellulose and cationized starch such as hydroxypropyltrimonium chloride starch. Further, the cationic polymer may include a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer, or a quaternary ammonium salt polycondensate. In the present invention, the "quaternary ammonium salt" includes a compound having a positive monovalent charge at the position of the nitrogen atom or a compound that generates a positive monovalent charge at the position of the nitrogen atom by neutralization. Specific examples thereof include a salt of a quaternary ammonium cation, a neutralized salt of a tertiary amine, and a tertiary amine having a cation in an aqueous solution. The "quaternary ammonium moiety" described below is also used with the same meaning, and is a site that is positively charged in water. Further, in the present invention, the "copolymer" is a polymer obtained by copolymerizing two or more kinds of polymerizable monomers, and is a binary copolymer and a ternary or more copolymer. Includes both things. In the present invention, the "polycondensate" is a polycondensate obtained by polymerizing a condensate composed of two or more kinds of monomers.

When the blood cell flocculant used in the present invention contains a quaternary ammonium salt homopolymer and / or a quaternary ammonium salt copolymer and / or a quaternary ammonium salt polycondensate as a cationic polymer, the blood cell flocculant. The agent may contain any one of a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer and a quaternary ammonium salt polycondensate, or any combination of two or more. May include. Further, the quaternary ammonium salt homopolymer may be used alone or in combination of two or more. Similarly, the quaternary ammonium salt copolymer may be used alone or in combination of two or more. Similarly, as the quaternary ammonium salt polycondensate, one type may be used alone or two or more types may be used in combination.

Among the various cationic polymers described above, the use of a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer, or a quaternary ammonium salt polycondensate is particularly effective in terms of adsorptivity to erythrocytes. preferable. In the following description, for the sake of simplicity, the quaternary ammonium salt homopolymer, the quaternary ammonium salt copolymer, and the quaternary ammonium salt polycondensate are collectively referred to as "quaternary ammonium salt polymer".

The quaternary ammonium salt homopolymer is obtained by using one kind of polymerizable monomer having a quaternary ammonium moiety and polymerizing the monomer. On the other hand, the quaternary ammonium salt copolymer uses at least one polymerizable monomer having a quaternary ammonium moiety and, if necessary, at least one polymerizable monomer having no quaternary ammonium moiety. It was obtained by using seeds and copolymerizing them. That is, the quaternary ammonium salt copolymer is obtained by using two or more kinds of polymerizable monomers having a quaternary ammonium moiety and copolymerizing them, or a quaternary ammonium moiety is used. It is obtained by copolymerizing one or more polymerizable monomers having one or more and one or more polymerizable monomers having no quaternary ammonium moiety. The quaternary ammonium salt copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. The quaternary ammonium salt polycondensate is obtained by using a condensate composed of one or more monomers having a quaternary ammonium moiety and polymerizing the condensate. That is, the quaternary ammonium salt polycondensate is obtained by using a condensate of two or more types of monomers having a quaternary ammonium moiety and polymerizing them, or the quaternary ammonium moiety. It is obtained by polycondensation of one or more monomers having a quaternary ammonium moiety and one or more monomers having no quaternary ammonium moiety.

The quaternary ammonium salt polymer is a cationic polymer having a quaternary ammonium moiety. The quaternary ammonium moiety can be generated by quaternary ammonium conversion of a tertiary amine with an alkylating agent. Alternatively, the tertiary amine can be dissolved in an acid or water and neutralized. Alternatively, it can be produced by quaternary ammonium conversion by a nucleophilic reaction including a condensation reaction. Examples of the alkylating agent include alkyl halides and dialkyl sulfates such as dimethyl sulfate and diethyl sulfate. Of these alkylating agents, dialkyl sulfate is preferable because it does not cause the problem of corrosion that may occur when alkyl halide is used. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid, phosphoric acid, fluorosulfonic acid, boric acid, chromium acid, lactic acid, oxalic acid, tartaric acid, gluconic acid, formic acid, ascorbic acid, hyaluronic acid and the like. .. In particular, it is preferable to use a quaternary ammonium salt polymer in which the tertiary amine moiety is quaternary ammoniumized with an alkylating agent because the electric double layer of erythrocytes can be reliably neutralized. Quaternary ammonium conversion by a nucleophilic reaction including a condensation reaction can occur as in the cycloaddition reaction of dimethylamine and epichlorohydrin and the cyclization reaction of dicyandiamide and diethylenetriamine.

From the viewpoint of effectively producing erythrocyte aggregates, the cationic polymer is preferably water-soluble. In the present invention, "water-soluble" means that 0.05 g of a powdery cationic polymer having a thickness of 1 mm or less or a film-like cationic polymer having a thickness of 0.5 mm or less is added to and mixed with 50 mL deionized water at 25 ° C. When this is done, a stirrer chip having a length of 20 mm and a width of 7 mm is inserted, and the entire amount is dissolved in water within 24 hours under stirring at 600 rpm using a magnetic stirrer HPS-100 manufactured by AS ONE Corporation. In the present invention, as the more preferable solubility, the total amount is preferably dissolved in water within 3 hours, and the total amount is more preferably dissolved in water within 30 minutes.

The cationic polymer preferably has a structure having a main chain and a plurality of side chains bonded thereto. In particular, the quaternary ammonium salt polymer preferably has a structure having a main chain and a plurality of side chains bonded thereto. The quaternary ammonium moiety is preferably present in the side chain. In this case, if the main chain and the side chain are bound at one point, the flexibility of the side chain is less likely to be inhibited, and the quaternary ammonium site present in the side chain is smoothly applied to the surface of the erythrocyte. It will be adsorbed. However, in the present invention, it is not prevented that the main chain and the side chain of the cationic polymer are bonded at two points or more. In the present invention, "bonded at one point" means that one of the carbon atoms constituting the main chain is single-bonded with one carbon atom located at the end of the side chain. .. "Bonded at two or more points" means that two or more of the carbon atoms constituting the main chain are single-bonded with two or more carbon atoms located at the ends of the side chains. Say.

When the cationic polymer has a structure having a main chain and a plurality of side chains bonded to the main chain, for example, a quaternary ammonium salt polymer has a structure having a main chain and a plurality of side chains bonded to the main chain. In the case of, the number of carbon atoms in each side chain is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. The upper limit of the number of carbon atoms is preferably 10 or less, more preferably 9 or less, and even more preferably 8 or less. For example, the number of carbon atoms in the side chain is preferably 4 or more and 10 or less, more preferably 5 or more and 9 or less, and further preferably 6 or more and 8 or less. The carbon number of the side chain is the carbon number of the quaternary ammonium moiety (cation moiety) in the side chain, and even if carbon is contained in the anion which is a counterion, the carbon is counted. Not included. In particular, among the carbon atoms in the side chain, the number of carbon atoms from the carbon atom bonded to the main chain to the carbon atom bonded to the quaternary nitrogen is in the above range, that is, the quaternary ammonium salt. It is preferable because the steric hindrance when the polymer is adsorbed on the surface of the erythrocyte is reduced.

When the quaternary ammonium salt polymer is a quaternary ammonium salt homopolymer, examples of the homopolymer include polymers of vinyl-based monomers having a quaternary ammonium moiety or a tertiary amine moiety. .. When polymerizing a vinyl-based monomer having a tertiary amine moiety, a quaternary ammonium salt homozygous in which the tertiary amine moiety is quaternary ammonium-modified with an alkylating agent before and / or after polymerization. It becomes a polymer, becomes a tertiary amine neutralizing salt in which the tertiary amine moiety is neutralized with an acid before and / or after polymerization, or becomes a tertiary amine having a cation in an aqueous solution after polymerization. .. Examples of alkylating agents and acids are as described above.

In particular, the quaternary ammonium salt homopolymer preferably has a repeating unit represented by the following formula 1.

Specific examples of the quaternary ammonium salt homopolymer include polyethyleneimine and the like. In addition, poly (2-methacryloxyethyl dimethylamine quaternary salt) and poly (2-methacryloxyethyl trimethylammonium salt) in which the side chain having a quaternary ammonium moiety is bonded to the main chain at one point. ), Poly (2-methacryloxyethyl dimethyl ethyl ammonium methyl sulfate), poly (2-methacryloxy ethyl dimethyl ethyl ammonium ethyl sulfate), poly (2-acrylic oxyethyl dimethylamine quaternary salt), poly (2- Acrylicoxyethyltrimethylamine quaternary salt), poly (2-acrylicoxyethyldimethylethylammonium ethyl sulfate), poly (3-dimethylaminopropylacrylamide quaternary salt), dimethylaminoethyl polymethacruate, polyallylamine hydrochloride, cationization Examples thereof include cellulose, polyethyleneimine, polydimethylaminopropylacrylamide, and polyamidine. On the other hand, examples of homopolymers in which the side chain having a quaternary ammonium moiety is bonded to the main chain at two or more points include polydiallyldimethylammonium chloride and polydialylamine hydrochloride.

When the quaternary ammonium salt polymer is a quaternary ammonium salt copolymer, two kinds of polymerizable monomers used for the polymerization of the above-mentioned quaternary ammonium salt homopolymer are used as the copolymer. The copolymer obtained by the above-mentioned copolymerization can be used. Alternatively, as the quaternary ammonium salt copolymer, one or more polymerizable monomers used for the polymerization of the above-mentioned quaternary ammonium salt homopolymer and a polymerizable single amount having no quaternary ammonium moiety. A copolymer obtained by copolymerizing using one or more kinds of bodies can be used. Further, in addition to or in place of the vinyl-based polymerizable monomer, another polymerizable monomer such as −SO ₂₋ can be used. As described above, the quaternary ammonium salt copolymer may be a binary copolymer or a ternary or higher copolymer.

In particular, the quaternary ammonium salt copolymer having a repeating unit represented by the above formula 1 and a repeating unit represented by the following formula 2 effectively produces agglomerates of erythrocytes. Preferred from the point of view.

Further, as the polymerizable monomer having no quaternary ammonium moiety, a cationically polymerizable monomer, an anionic polymerizable monomer, or a nonionic polymerizable monomer can be used. By using a cationically polymerizable monomer or a nonionic polymerizable monomer among these polymerizable monomers, charge cancellation with the quaternary ammonium moiety in the quaternary ammonium salt copolymer is performed. Can be effectively caused by the aggregation of erythrocytes. Examples of cationically polymerizable monomers include vinylpyridine as a cyclic compound having a cation-bearing nitrogen atom under specific conditions, and a linear compound having a cation-bearing nitrogen atom in the main chain under specific conditions. Examples thereof include a condensed compound of dicyandiamide and diethylenetriamine. Examples of anionic polymerizable monomers include 2-acrylamide-2-methylpropanesulfonic acid, methacrylic acid, acrylic acid, styrenesulfonic acid, and salts of these compounds. On the other hand, examples of nonionic polymerizable monomers include vinyl alcohol, acrylamide, dimethylacrylamide, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate and ethyl. Examples thereof include acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate and butyl acrylate. As these cationically polymerizable monomers, anionic polymerizable monomers, or nonionic polymerizable monomers, one of them can be used, or any two or more of them can be used in combination. Can be done. Further, two or more types of cationically polymerizable monomers can be used in combination, two or more types of anionic polymerizable monomers can be used in combination, or two or more types of nonionic polymerizable monomers can be used in combination. Can also be used. The quaternary ammonium salt copolymer copolymerized using a cationically polymerizable monomer, an anionic polymerizable monomer and / or a nonionic polymerizable monomer as a polymerizable monomer has a molecular weight thereof. However, as described above, it is preferably 10 million or less, particularly preferably 5 million or less, particularly preferably 3 million or less (the same applies to the quaternary ammonium salt copolymer exemplified below).

As the polymerizable monomer having no quaternary ammonium moiety, a polymerizable monomer having a functional group capable of hydrogen bonding can also be used. When such a polymerizable monomer is used for copolymerization, and when erythrocytes are aggregated using a quaternary ammonium salt copolymer obtained from the copolymer, hard agglomerates are likely to occur, and the highly absorbent polymer Absorption performance is less likely to be impaired. Examples of functional groups capable of hydrogen bonding include -OH, -NH ₂ , -CHO, -COOH, -HF, and -SH. Examples of polymerizable monomers having a functional group capable of hydrogen bonding include hydroxyethyl methacrylate, vinyl alcohol, acrylamide, dimethylacrylamide, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, hydroxyethyl methacrylate, and hydroxyethyl. Examples include acrylate. In particular, hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, dimethylacrylamide and the like, in which hydrogen bonds work strongly, are preferable because the adsorption state of the quaternary ammonium salt polymer to erythrocytes is stabilized. These polymerizable monomers may be used alone or in combination of two or more.

As the polymerizable monomer having no quaternary ammonium moiety, a polymerizable monomer having a functional group capable of having a hydrophobic interaction can also be used. By using such a polymerizable monomer for copolymerization, the same advantageous effect as that of using the above-mentioned polymerizable monomer having a functional group capable of hydrogen bonding, that is, the hardness of erythrocytes is obtained. The effect is that agglomerates are likely to occur. Examples of the functional group capable of having a hydrophobic interaction include an alkyl group such as a methyl group, an ethyl group and a butyl group, a phenyl group, an alkylnaphthalene group and an alkylfluoride group. Examples of polymerizable monomers having a functional group capable of having a hydrophobic interaction include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, and styrene. Can be mentioned. In particular, methyl methacrylate, methyl acrylate, butyl methacrylate, butyl acrylate, etc., which have a strong hydrophobic interaction and do not significantly reduce the solubility of the quaternary ammonium salt polymer, are in an adsorbed state of the quaternary ammonium salt polymer to red blood cells. Is preferable because it stabilizes. These polymerizable monomers may be used alone or in combination of two or more.

The molar ratio of the polymerizable monomer having a quaternary ammonium moiety to the polymerizable monomer having no quaternary ammonium moiety in the quaternary ammonium salt copolymer is the quaternary. It is preferable that the ammonium salt copolymer is appropriately adjusted so that the erythrocytes are sufficiently aggregated. In particular, the molar ratio of the polymerizable monomer having a quaternary ammonium moiety in the quaternary ammonium salt copolymer is preferably 10 mol% or more, more preferably 22 mol% or more, and 32 mol. It is more preferably% or more, and even more preferably 38 mol% or more. Further, it is preferably 100 mol% or less, more preferably 80 mol% or less, further preferably 65 mol% or less, and further preferably 56 mol% or less. Specifically, the molar ratio of the polymerizable monomer having a quaternary ammonium moiety is preferably 10 mol% or more and 100 mol% or less, and more preferably 22 mol% or more and 80 mol% or less. It is more preferably 32 mol% or more and 65 mol% or less, and further preferably 38 mol% or more and 56 mol% or less.

When the quaternary ammonium salt polymer is a quaternary ammonium salt polycondensate, a condensate composed of one or more monomers having the above-mentioned quaternary ammonium moiety is used as the polycondensate. The polycondensate obtained by polymerizing these condensates can be used. Specific examples include dicyandiamide / diethylenetriamine polycondensate, dimethylamine / epichlorohydrin polycondensate, and the like.

The above-mentioned quaternary ammonium salt homopolymer and quaternary ammonium salt copolymer can be obtained by a homopolymerization method or a copolymerization method of a vinyl-based polymerizable monomer. As the polymerization method, for example, radical polymerization, living radical polymerization, living cationic polymerization, living anion polymerization, coordination polymerization, ring-opening polymerization, polycondensation and the like can be used. The polymerization conditions are not particularly limited, and the conditions for obtaining a quaternary ammonium salt polymer having the desired molecular weight, flow potential, and / or IOB value may be appropriately selected.

For example, the flow potential of the quaternary ammonium salt polymer is preferably 1500 μeq / L or more, more preferably 2000 μeq / L or more, and 3000 μeq / L or more, from the viewpoint of more effectively generating erythrocyte aggregates. It is more preferably L or more, and even more preferably 4000 μeq / L or more. When the flow potential of the quaternary ammonium salt polymer is equal to or higher than these values, the electric double layer of erythrocytes can be sufficiently neutralized. The upper limit of the flow potential is preferably 13000 μeq / L or less, more preferably 8000 μeq / L or less, and even more preferably 6000 μeq / L or less. When the flow potential of the quaternary ammonium salt polymer is equal to or less than these values, it is possible to effectively prevent the electrical repulsion between the quaternary ammonium salt polymers adsorbed on the erythrocytes.

Further, in order for the quaternary ammonium salt polymer to be successfully adsorbed on the surface of erythrocytes, it is advantageous that the quaternary ammonium salt polymer easily interacts with the above-mentioned sialic acid. From this point of view, the present inventor proceeded with the study and found that the value of the inorganic value / organic value, which is the ratio of the inorganic value of the substance to the organic value (hereinafter referred to as "IOB (Inorganic Organic Balance) value"). It was found that the degree of interaction between the sialic acid bond and the cationic polymer can be evaluated using the above as a scale.

In detail, it has been found to be advantageous to use a cationic polymer having an IOB value equal to or close to the IOB value of the sialic acid bond. The sialic acid conjugate is a compound in which sialic acid can exist in a living body, and examples thereof include compounds in which sialic acid is bound to the end of a glycolipid such as galactolipid. The IOB value of sialic acid is 4.25 for sialic acid alone and 3.89 for sialic acid conjugates. The sialic acid conjugate is a bond of a sugar chain and sialic acid in a glycolipid, and the sialic acid conjugate has a higher proportion of organic value and a lower IOB value than sialic acid alone.

Therefore, the IOB value of the quaternary ammonium salt polymer is preferably 0.6 or more, more preferably 1.8 or more, further preferably 2.1 or more, and 2.2 or more. It is more preferable to have. The IOB value of the cationic polymer is preferably 4.6 or less, more preferably 3.6 or less, and even more preferably 3.0 or less.
When the quaternary ammonium salt polymer is a copolymer, the IOB value is calculated by the following procedure according to the molar ratio of the monomers used for the copolymerization. In other words, a copolymer was obtained from the monomers A and B, organic value of the monomer A is OR _A, inorganic value is IN _A, organic value of the monomer B is OR _B, inorganic value There is iN _B, when the molar ratio of the monomer a / monomer B is M _a / M _B, IOB value of copolymer is calculated from the following equation.

The first cationic polymer and the second cationic polymer constituting the blood cell flocculant may be contained in different members of the constituent members of the absorbent article (napkin 1), but in the napkin 1, they are the same member. A liquid-permeable sheet or a highly absorbent polymer is contained in a hydrophilic fiber sheet located on the skin contact surface side of the highly absorbent polymer sheet sandwiched between hydrophilic fiber sheets made of hydrophilic fibers. The liquid permeable sheet containing the first cationic polymer and the second cationic polymer (hereinafter, also referred to as “hemagglutination agent-containing sheet (in this embodiment, the cationic polymer-containing sheet)”) is liquid permeable. There is no limitation on the type of the material, and for example, a fiber sheet or a perforated film can be used as a base material. When a fiber sheet is used as a base material, the fiber sheet is preferably made of paper or a non-woven fabric, and is particularly preferably paper from the viewpoint of good compatibility with a blood cell flocculant. It is preferable that the fibers constituting the paper are wood pulp, which is mainly natural cellulose, from the viewpoint of retention of the blood cell flocculant. The basis weight of the base material is preferably 10 g / m ² or more, further preferably 12 g / m ² or more, and more preferably 15 g / m ² or more. Further, it is preferably 30 g / m ² or less, more preferably 25 g / m ² or less, and even more preferably 20 g / m ² or less. When the highly absorbent polymer sheet is used, the total basis weight containing the highly absorbent polymer is preferably 21 g / m ² or more, more preferably 30 g / m ² or more, and more preferably 50 g. It is more preferably / m ² or more. Further, it is preferably 500 g / m ² or less, more preferably 300 g / m ² or less, and even more preferably 200 g / m ² or less.

One of the features of the hemagglutination-containing sheet is that the one surface side contains a relatively large amount of the hemagglutination agent as compared with the other surface side. In addition to this, the blood cell flocculant-containing sheet is on the skin-facing surface side of the napkin 1 with respect to the position where the absorbent core is arranged, with one surface side facing the absorbent core containing the highly absorbent polymer. It also has one of the features in that it is arranged in.

The hemagglutin-containing sheet has an action of agglutinating red blood cells in blood by contacting with blood. The blood referred to here is generally human blood, but is not limited to this. Since the hemagglutination agent-containing sheet contains both the first cationic polymer and the second cationic polymer, as described above, it is necessary to achieve both the difficulty of reversing menstrual blood and the improvement of the absorption rate of menstrual blood. Is possible.

From the viewpoint of further enhancing the above advantages, the hemagglutination agent-containing sheet (cationic polymer-containing sheet) may be used, for example, as the surface sheet 2 forming the skin-facing surface as a constituent member of the napkin 1. preferable. Instead, a hemagglutin-containing sheet (cationic polymer-containing sheet) is placed between the absorbent core consisting of the lower absorbent core 41 and the upper absorbent core 42 containing the highly absorbent polymer and the surface sheet 2. It is also preferable to use it as the second sheet 5 to be arranged. It is also preferable that the hemagglutination agent-containing sheet is used as the coating sheet for coating the absorbent core containing the highly absorbent polymer. Alternatively, the hemagglutination agent-containing sheet may be the above-mentioned highly absorbent polymer sheet. When a plurality of highly absorbent polymer sheets are laminated, it is preferable that the layer on the side facing the skin is coated with a blood cell flocculant and contained. As described above, it is preferable that the hemagglutination agent-containing sheet is arranged on the skin-facing surface side of the position where the absorbent core containing the highly absorbent polymer is arranged. In this case, a hemagglutinant containing a first cationic polymer and a second cationic polymer may be contained over the entire plane direction of the coating sheet including the non-skin facing surface side of the absorber, or the coating sheet. Of these, the hemagglutination agent may be contained only in the portion of the absorbent core located on the skin-facing surface side. In either case, the hemagglutination agent is contained at least in the site of the absorptive core located on the skin-facing surface side. In this case, the hemagglutination agent may be partially contained or may be contained entirely in the portion of the absorbable core located on the skin-facing surface side. When the blood cell flocculant is partially contained, the blood cell flocculant can be contained, for example, in a stripe shape along the plane direction of the sheet. Alternatively, the hemagglutination agent can be contained in a scattered manner along the plane direction of the sheet.

The proportion of the blood cell flocculant contained in the blood cell flocculant-containing sheet is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 1.0% by mass or more. More preferred. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. The proportion of the blood cell flocculant contained in the blood cell flocculant-containing sheet is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 40% by mass or less. It is more preferably 0% by mass or more and 30% by mass or less.

The total amount and molecular weight distribution of the blood cell flocculant contained in the blood cell flocculant-containing sheet are measured by the following method.
Products such as napkins to be measured are separated into individual members by weakening the adhesive using a cold spray and carefully peeling them off. Each member is immersed in deionized water for 60 minutes to elute the hemagglutination composition. Then, the deionized water in which the obtained hemagglutination composition is eluted is dialyzed. The dialysis treatment is a treatment for removing water-soluble low molecular weight components such as solvents, plasticizers, fragrances, antibacterial / deodorants, and skin care agents. For example, a dialysis tube capable of removing components having a molecular weight of 2000 or less is used. .. After dialysis, evaporate to dryness or lyophilize. Then, ¹ H-NMR or mass spectrometry (MS) is used alone or in combination to identify the hemagglutination agent. By measuring the mass of the identified hemagglutination agent, the total amount of the hemagglutination agent can be determined. Based on the total amount of the hemagglutination agent thus obtained and the mass of the member before eluting the hemagglutination agent composition, the ratio of the hemagglutination agent contained in the hemagglutination agent-containing sheet can be obtained. .. In addition, a differential molecular weight distribution curve can be obtained by measuring the identified hemagglutination agent by a gel permeation chromatography method.

In addition to the polycation (cationic polymer), the hemagglutination agent used in the present invention contains one other component such as a solvent, a plasticizer, a fragrance, an antibacterial / deodorant, and a skin care agent. It may be in the form of the composition (hemagglutination agent composition) containing the above. As the solvent, water, a water-soluble organic solvent such as a saturated aliphatic monohydric alcohol having 1 to 4 carbon atoms, or a mixed solvent of the water-soluble organic solvent and water can be used. As the plasticizer, glycerin, ethylene glycol, 1,3-butanediol and the like can be used. As the fragrance, a fragrance having a green herbal-like aroma described in JP-A-2007-244764, a plant extract, a citrus extract and the like can be used. Examples of the antibacterial / deodorant include a canclinite-like mineral containing an antibacterial metal described in JP-A-2004-244789, and a phenyl group-containing polymerizable mineral described in JP-A-2007-097953. Porous polymers polymerized from monomers, quaternary ammonium salts described in JP-A-2006-191966, activated carbon, clay minerals and the like can be used. As the skin care agent, plant extracts, collagen, natural moisturizing ingredients, moisturizers, keratin softening agents, anti-inflammatory agents and the like described in JP-A-2004-255164 can be used.

The proportion of the cationic polymer in the hemagglutination composition is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. Further, it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 10% by mass or less. By setting the proportion of the cationic polymer in the hemagglutination composition within this range, an effective amount of the cationic polymer can be imparted to the absorbent article.

Although the present invention has been described above based on the preferred embodiment, the present invention is not limited to the above embodiment. For example, in the above embodiment, the present invention has been described by taking a sanitary napkin as an example, but application of the present invention to an absorbent article other than the sanitary napkin is not hindered at all.

With respect to the embodiments described above, the present invention further discloses an absorbable article containing the following hemagglutinant.

<1>
An absorbable article containing a blood cell flocculant, the blood cell flocculant has a total weight average molecular weight of 100,000 or more as measured by a gel permeation chromatography method, and is 50% of the total weight average molecular weight. An absorbent article containing a first cationic polymer having the above molecular weight and a second cationic polymer having a molecular weight of 15% or less based on the total weight average molecular weight.

<2>
The first cationic polymer preferably has a molecular weight of 50% or more with respect to the total weight average molecular weight, and particularly preferably 55% or more with respect to the total weight average molecular weight. The absorbent article according to 1>.
<3>
The second cationic polymer preferably has a molecular weight of 15% or less with respect to the total weight average molecular weight, and particularly preferably 10% or less with respect to the total weight average molecular weight. The absorbent article according to 1> or <2>.
<4>
The above-mentioned <1> to <3>, wherein the first cationic polymer and the second cationic polymer are contained in the same member among the constituent members of the absorbent article. Absorbent article.
<5>
When the molecular weight distribution of the blood cell flocculant was measured by a gel permeation chromatography method and a differential molecular weight distribution curve was obtained, the first cationic polymer was in the range of 50% or more with respect to the total weight average molecular weight. The absorbent article according to any one of <1> to <4>, which has a peak or a shoulder peak.
<6>
The absorbent article according to any one of <1> to <5>, wherein the second cationic polymer has a peak or a shoulder peak in a range of 15% or less with respect to the total weight average molecular weight. ..
<7>
The first cationic polymer preferably has a peak in the range of 50% or more, and more preferably 55% or more with respect to the total weight average molecular weight. The absorbent article according to any one of <1> to <6>.
<8>
The second cationic polymer preferably has a peak in the range of 15% or less, and more preferably 10% or less, with respect to the total weight average molecular weight. The absorbent article according to any one of <1> to <7>.
<9>
The differential molecular weight distribution curve of the hemagglutin has two peaks, or a main peak and a shoulder peak, and the difference between the two peak values or the difference between the main peak value and the shoulder peak value is preferably 50,000 or more. The absorbent article according to any one of <1> to <8>, wherein the amount is 100,000 or more, more preferably 150,000 or more.
<10>
The differential molecular weight distribution curve of the hemagglutin has two peaks, or a main peak and a shoulder peak, and the difference between the two peak values or the difference between the main peak value and the shoulder peak value is preferably 2 million or less. The absorbent article according to any one of <1> to <9>, wherein the amount is 1 million or less, and more preferably 500,000 or less.

<11>
The absorbent article contains a surface sheet forming a skin-facing surface, an absorbent core containing a highly absorbent polymer, and a hemagglutinant containing both the first cationic polymer and the second cationic polymer. The absorbable article according to any one of <1> to <10>, which has a sheet and the blood cell flocculant-containing sheet is arranged between the surface sheet and the absorbable core.
<12>
The hemagglutination agent-containing sheet containing the first cationic polymer and the second cationic polymer contains a relatively large amount of the hemagglutination agent on one surface side as compared with the other surface side. The absorbent article according to any one of <1> to <11>.
<13>
The hemagglutination agent-containing sheet containing the first cationic polymer and the second cationic polymer has the absorbent core with one surface side facing the absorbent core containing the highly absorbent polymer. The absorbent article according to any one of <1> to <12>, which is arranged on the skin-facing surface side of the napkin 1 from the arrangement position of.
<14>
The first cationic polymer and the second cationic polymer are hydrophilic fibers located on the skin contact surface side of the highly absorbent polymer sheet in which the highly absorbent polymer is sandwiched between hydrophilic fiber sheets made of hydrophilic fibers. The absorbent article according to any one of <1> to <13>, which is contained in the sheet.
<15>
The absorbent article has an absorbent core and a coating sheet covering the absorbent core, and even if the blood cell flocculant is contained in a portion of the covering sheet located on the skin-facing surface side of the absorbent core. Good, the absorbent article according to any one of <1> to <14>.
<16>
The ratio D2 / D1 of the amount D1 of the first cationic polymer to the amount D2 of the second cationic polymer on a mass basis is 35/65 or more and 80/20 or less, the above <1> to <15>. The absorbent article according to any one of.
<17>
The ratio D2 / D1 of the amount D1 of the first cationic polymer to the amount D2 of the second cationic polymer on a mass basis is preferably 35/65 or more, preferably <1> to <16>. The absorbent article according to any one of.
<18>
The ratio D2 / D1 of the amount D1 of the first cationic polymer to the amount D2 of the second cationic polymer on a mass basis is preferably 80/20 or less, the above <1> to <17>. The absorbent article according to any one of.
<19>
The total weight average molecular weight in a state in which all the contained blood cell flocculants are mixed is preferably 100,000 or more, preferably 2 million or less, further preferably 1 million or less, and 600,000. The absorbent article according to any one of <1> to <18>, which is particularly preferably as follows.
<20>
The weight average molecular weight of the first cationic polymer is preferably 100,000 or more, more preferably 150,000 or more, further preferably 200,000 or more, and more preferably 250,000 or more. The absorbent article according to any one of <1> to <19>, which is particularly preferable.

<21>
The weight average molecular weight of the first cationic polymer is preferably 10 million or less, more preferably 5 million or less, further preferably 1 million or less, and preferably 600,000 or less. The absorbent article according to any one of <1> to <20>, which is particularly preferable.
<22>
The second cationic polymer is preferably 2000 or more, provided that the weight average molecular weight is lower than the weight average molecular weight of the first cationic polymer having a relatively high molecular weight. The absorbent article according to any one of ~ <21>.
<23>
The second cationic polymer is preferably 200,000 or less, preferably 150,000 or less, provided that the weight average molecular weight is lower than the weight average molecular weight of the first cationic polymer having a relatively high molecular weight. The absorbent article according to any one of <1> to <22>, wherein the content is more preferably 100,000 or less.
<24>
The proportion of the blood cell flocculant contained in the blood cell flocculant-containing sheet containing the first cationic polymer and the second cationic polymer is preferably 0.1% by mass or more, preferably 0.5% by mass or more. The absorbent article according to any one of <1> to <23>, wherein the content is more preferably 1.0% by mass or more.
<25>
The proportion of the blood cell flocculant contained in the blood cell flocculant-containing sheet containing the first cationic polymer and the second cationic polymer is preferably 50% by mass or less, and preferably 40% by mass or less. The absorbable article according to any one of <1> to <24>, more preferably 30% by mass or less.
<26>
At least one of the first cationic polymer and the second cationic polymer has a structure having a main chain and a side chain bonded thereto, has a molecular weight of 2000 or more, and is a repeat represented by the following formula 1. A quaternary ammonium salt homopolymer having a unit, or a quaternary ammonium salt copolymer having a repeating unit represented by the above formula 1 and a repeating unit represented by the above formula 2. The absorbability according to any one of <1> to <25>, wherein the main chain and the side chain are bonded at one point, and the side chain has a quaternary ammonium moiety. Goods.
<27>
At least one of the primary cationic polymer and the secondary cationic polymer has a flow potential of 1500 μeq / L or more and a molecular weight of 2000 or more, and is a quaternary ammonium salt homopolymer or a quaternary ammonium salt copolymer. The absorbent article according to any one of <1> to <26>, which has 0.2 g / m ² or more and 20 g / m ² or less of a water-soluble cationic polymer composed of a substance.
<28>
The absorbent article according to any one of <1> to <27>, wherein at least one of the first cationic polymer and the second cationic polymer has an aggregation rate of 0.75 mPa · s / s or less.
<29>
At least one of the first cationic polymer and the second cationic polymer has an inorganic value / organic value value of 0.6 or more and 4.6 or less, which is a ratio of an inorganic value to an organic value. The absorbable article according to any one of <1> to <28>, which is a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer, or a quaternary ammonium salt polycondensate.
<30>
The absorbent article according to any one of <1> to <29> is an absorbent article that is a sanitary napkin.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, "%" means "mass%".

[Example 1]
As the cationic polymer constituting the hemagglutination agent, a first raw material cationic polymer and a second raw material cationic polymer were used. As the first raw material cationic polymer, polydiallyldimethylammonium chloride (DADMAC), which is a water-soluble quaternary ammonium salt homopolymer (Part No. 409030 (weight average molecular weight: 400,000-500,000) manufactured by Aldrich), is described below. The one purified by removing the low molecular weight by the dialysis treatment of No. 1 was used. Further, as the second raw material cationic polymer constituting the blood cell flocculant, polydiallyldimethylammonium chloride (DADMAC) (trade name "Markor 106" manufactured by Nippon Lubrizol Co., Ltd. (weight average molecular weight: 15,000)) Was purified by removing the monomer component by the following dialysis treatment from the viewpoint of safety. Mix so that the weight ratio of the first raw material cationic polymer: the second raw material cationic polymer is 50% by mass: 50% by mass, and prepare a 5% by mass aqueous solution of the hemagglutination agent using deionized water. It was applied to one surface of a pulp paper having an amount of 16 g / m ² using a spray gun to obtain a hemagglutin-containing sheet containing a total amount of the hemagglutin in Table 1 of 5 g / m ² . Separately, the surface sheet is taken out from a sanitary napkin (Kao Corporation: Laurier Super Absorption Guard 2015) using a cold spray. Next, the hemagglutination agent-containing sheet was cut out to a size of 80 mm (Cross Direction direction) × 80 mm (Macine Direction direction), and the surface sheet of the same shape and size was placed on one of the cut out surfaces and cut out. by disposing an absorbent core having the same shape and the same size (mixed fiber stacking of the superabsorbent polymer 50 g / m ² pulp 200 g / m ²⁾ on the other surface, topsheet, the hemagglutination-containing sheets and the absorbent The cores were overlapped. Then, the superposed material was compressed to a thickness of 4.5 mm (under a load of 0.5 g / cm ² ) using a mangle to prepare a sample of Example 1.

[Dialysis treatment method of product number 409030 manufactured by Aldrich]
100 g (about 20% by mass of solid content concentration) of polydiallyldimethylammonium chloride (DADMAC) (product number 409030) manufactured by Aldrich was diluted 5-fold to obtain a diluted sample solution of about 4% by mass and 500 g. Preliminary filtration was performed with a membrane for artificial kidneys (hollow fiber membrane module with a membrane area of 0.8 m ² ) having zero plasma albumin transmittance. When the weight of the 10% (50 g) sample solution was reduced, the operation of performing the same amount of replacement fluid (water) was repeated 40 times. The sample solution from which the solutes of low molecules were reduced by this prefiltration was subsequently subjected to automatic fluid replacement ultrafiltration 10% (50 g) × 40 times using a molecular weight fractionation membrane of 300 K. Subsequently, the solution in the molecular weight fractionation membrane was freeze-dried to obtain a high molecular weight cationic polymer from which the low molecular weight was removed. This was used as the first raw material cationic polymer of Example 1.

[Dialysis method of trade name "Markor 106" manufactured by Nippon Lubrizol Co., Ltd.]
Spectra / Pore 6 (manufactured by Funakoshi Co., Ltd., fractional molecular weight 1000) 700 g (solid content concentration of about 33% by mass) of "Markor 106" (weight average molecular weight: 15,000) manufactured by Nippon Lubrizol Co., Ltd. , Φ29 mm × 45 mm × 100 cm (6 bottles), and dialyzed in 45 L deionized water for 2 days (replacement of deionized water 4 times in 2 days). Subsequently, the solution was freeze-dried in the molecular weight fractionation membrane to obtain a cationic polymer from which the low molecular weight (molecular weight of about 1000 or less) was removed. This was used as the second raw material cationic polymer of Example 1.

[Reference Example 1]
A spray gun was used to coat one surface of a pulp paper having a basis weight of 16 g / m ² so that a total amount of a hemagglutin containing only one type of cationic polymer was 5 g / m ² . A hemagglutination agent-containing sheet was obtained in the same manner as in Example 1 except that only the same polymer as the second raw material cationic polymer of Example 1 was used, and the surface sheet, the same as in Example 1, said. A sample of Reference Example 1 was prepared by superimposing a hemagglutination agent-containing sheet and an absorbent core.

[Reference example 2]
A spray gun was used to coat one surface of a pulp paper having a basis weight of 16 g / m ² so that a total amount of a hemagglutin containing only one type of cationic polymer was 5 g / m ² . As the polymer, a hemagglutination agent-containing sheet was obtained in the same manner as in Example 1 except that only the same polymer as the first raw material cationic polymer of Example 1 was used, and the surface sheet, the same as in Example 1, said. A sample of Reference Example 2 was prepared by superimposing the hemagglutination agent-containing sheet and the absorbent core.

[Comparative Example 1]
Using a pulp paper having a basis weight of 16 g / m ^{2 in} a state where the hemagglutination agent was not yet applied, which was used for preparing a sample of the hemagglutination agent-containing sheet of Example 1, the same procedure as in Example 1 was used. , The surface sheet, the paper and the absorbent core were superposed to prepare a sample of Comparative Example 1.

[Examples 2 to 4]
As the cationic polymer constituting the hemagglutination agent, a first raw material cationic polymer and a second raw material cationic polymer were used. As the first raw material cationic polymer, the same one as that of the first raw material cationic polymer of Example 1 was used. Further, as the second raw material cationic polymer constituting the blood cell flocculant, the same one as that of the second raw material cationic polymer of Example 1 was used. Mix the first raw material cationic polymer: the second raw material cationic polymer so that the weight ratio is as shown in Table 2, prepare a 5% by mass aqueous solution of the blood cell flocculant using deionized water, and prepare the absorber F. using a spray gun was applied to one surface of (pulp ^{25g / m 2, SAP30g / m} 2, laminated body of pulp 20 g / m ^2), high total amount of hemagglutination agent present in Table 2 contained 3 g / m ² An absorbent polymer sheet was obtained. Separately, remove the surface sheet and sublayer from a sanitary napkin (Kao Corporation: Laurier Slim Guard for a long time and firmly for daytime 2015) using a cold spray. Next, the highly absorbent polymer sheet containing the hemagglutination agent was cut out to a size of 80 mm (CD direction) × 80 mm (MD direction), and the surface sheet having the same shape and the same size was arranged on one of the cut out surfaces. absorber F uncoated hemagglutination agent on the other surface cut as an absorbent core having the same shape and the same size (the pulp ^{25g / m 2, SAP30g / m} 2, laminated body of pulp 20 g / m ²⁾ Four layers were laminated, and the surface sheet, the sublayer, the absorber F containing the hemagglutination agent, and the absorber F4 layer uncoated with the hemagglutination agent were overlapped. Then, the superposed material was compressed to a thickness of 3.8 mm (under a load of 0.5 g / cm ² ) using a mangle to prepare a sample of Example 2.

[Example 5]
The same as the first raw material cationic polymer of Example 1 is used as the first raw material cationic polymer, and after being dissolved in deionized water, the absorber F (pulp 25 g / m ² , SAP 30 g / m ² , pulp 20 g / m). ^A spray gun was used to apply the coating amount to the coating amount shown in Table 2 on one surface of the laminate ( ² ), and then the same second raw material cationic polymer as that of Example 1 was applied as the second raw material cationic polymer. After being dissolved in deionized water, it was applied to one surface of the highly absorbent polymer sheet containing the first cationic polymer using a spray gun so as to have the coating amount shown in Table 2, and the total amount of the blood cell flocculant was applied. Obtained an absorber F containing 3 g / m ² . A sample of Example 5 was prepared in the same manner as in Examples 2 to 4 except for the above.

[Example 6]
As the first raw material cationic polymer constituting the hemagglutination agent, the same one as the first raw material cationic polymer of Example 1 was used. The secondary raw material cationic polymer constituting the blood cell flocculant is dimethylaminoethyl methacrylate diethylsulfate (MOEDES) (manufactured by Kao Corporation, trade name "Caosera"), which is a water-soluble quaternary ammonium salt homopolymer. "MD-P" (weight average molecular weight: 56,000)) was used. First-source cationic polymer: Highly absorbable polymer sheet containing first-source cationic polymer after mixing so that the weight ratio of the first-source cationic polymer is as shown in Table 2 and dissolving in deionized water. The polymer F was applied to one surface using a spray gun so as to have the coating amount shown in Table 2 to obtain an absorber F containing a total amount of blood cell flocculant of 3 g / m ² . A sample of Example 5 was prepared in the same manner as in Examples 2 to 4 except for the above.

[Reference Examples 3 to 4]
One cationic polymer only an absorber so that the basis weight in Table 2 hemagglutination agent in a total amount containing F (pulp ^{25g / m 2, SAP30g / m} 2, laminated body of pulp 20 g / m ²⁾ Reference is made in the same manner as in Examples 2 to 5 except that one surface is coated with a spray gun and only the same cationic polymer as the first raw material cationic polymer of Example 1 is used. Samples of Examples 3 to 4 were prepared.

[Reference Example 5]
One cationic polymer only an absorber so that the basis weight in Table 2 hemagglutination agent in a total amount containing F (pulp ^{25g / m 2, SAP30g / m} 2, laminated body of pulp 20 g / m ²⁾ Reference is made in the same manner as in Examples 2 to 5 except that one surface is coated with a spray gun and only the same cationic polymer as the second raw material cationic polymer of Example 1 is used. A sample of Example 5 was prepared.

[Comparative Example 2]
Absorbent F (pulp 25 g / m ² , SAP 30 g /) used in the preparation of a sample of the highly absorbent polymer sheet containing the blood cell flocculant of Examples 2 to 5 in a state where the blood cell flocculant has not been applied yet. m ^2, a laminated body of pulp 20 g / m ^2), in the same manner as in example 5 from example 2, the topsheet and sublayer, by overlapping the absorber F5 layers to prepare a sample of Comparative example 2.

[Evaluation]
The absorption rate and the amount of liquid return were evaluated by the following methods for the samples of Examples 1 to 6, the samples of Reference Examples 1 to 5 and the samples of Comparative Examples 1 to 2. The results are shown in Tables 1 and 2 below.

<Absorption time>
The absorption rate can be evaluated by measuring the absorption time. The samples obtained in Examples and Comparative Examples were placed horizontally with the surface sheet side facing vertically upward, and a cylindrical acrylic plate with an injection port having a diameter of 10 mm was placed on the bottom, and 3 g of pseudo blood was placed from the injection port. (Adjusted to a viscosity of 8 cPs) was injected twice at 3 minute intervals (6 g in total), and the time until the simulated blood accumulated in the cylinder disappeared from the surface sheet was measured. This time was evaluated as the absorption time of each sample. Each sample was measured twice (Table 1) or four times (Table 2), and the average value was taken as the absorption time of the sample. As described in the present specification, the simulated blood is measured using a B-type viscometer (model number TVB-10M manufactured by Toki Sangyo Co., Ltd., measurement conditions: rotor No. 19, 30 rpm, 25 ° C., 60 seconds). The blood cell / plasma ratio of deflated horse blood (manufactured by Nippon Biotest Research Institute Co., Ltd.) was adjusted so that the resulting viscosity would be 8 mPa · s.

<Amount of liquid return>
After measuring the absorption time, the state was maintained for 3 minutes after injection. Next, the acrylic plate with a cylinder was removed, and a pre-weighed liquid absorbent paper (10 sheets of 5A filter paper manufactured by Advantech Co., Ltd.) was placed on the surface sheet of the sample. Further, a weight was placed on the weight so that the pressure became 40 gf / cm ² , and the pressure was applied for 10 seconds. After pressurization, the absorbent paper was taken out, the weight of the absorbent paper before and after pressurization was measured, and the weight (g) of the simulated blood absorbed by the absorbent paper was calculated. Each sample was measured twice (Table 1) or four times (Table 2), and the average value was taken as the amount of liquid return of the sample.

As is clear from the results shown in Table 1, the sample of Example 1 had a faster absorption rate than the sample of Reference Example 2, and the amount of liquid return could be suppressed as compared with the sample of Reference Example 1. Further, the sample of Example 1 was able to significantly suppress the amount of liquid return while the absorption rate was about the same as that of the sample of Comparative Example 1. According to such a sample of Example 1, it can be expected that both the difficulty of reversion of menstrual blood and the improvement of the absorption rate of menstrual blood are compatible.

As is clear from the results shown in Table 2, the samples of Examples 2 to 6 had a faster absorption rate and could suppress the amount of liquid return as compared with the samples of Reference Examples 3 to 5 and Comparative Example 2. According to the samples of Examples 2 to 6, it can be expected that the difficulty of reversion of menstrual blood and the improvement of the absorption rate of menstrual blood are compatible with each other.

1 Sanitary napkin (absorbent article)
2 Front sheet 3 Back sheet 4 Absorber 41 Lower absorbent core 42 Upper absorbent core 5 Second sheet 6 Side sheet 10 Absorbent body 11 Menstrual blood 12 Liquid component 13 Non-liquid component 14 Highly absorbent polymer 15 Film 16 Aggregate

Claims (5)

An absorbable article containing a hemagglutination agent
The blood cell flocculant has a total weight average molecular weight of 100,000 or more as measured by a gel permeation chromatography method, and has a molecular weight of 50% or more of the total weight average molecular weight of the first cationic polymer and the total weight. It contains a secondary cationic polymer having a molecular weight of 15% or less with respect to the weight average molecular weight.
An absorbent article in which the ratio D2 / D1 of the amount D1 of the first cationic polymer to the amount D2 of the second cationic polymer on a mass basis is 35/65 or more and 80/20 or less. An absorbent article containing a cationic polymer
The cationic polymer has a total weight average molecular weight of 100,000 or more as measured by a gel permeation chromatography method, and has a molecular weight of 50% or more with respect to the total weight average molecular weight. Containing a secondary cationic polymer having a molecular weight of 15% or less with respect to the weight average molecular weight,
An absorbent article in which the ratio D2 / D1 of the amount D1 of the first cationic polymer to the amount D2 of the second cationic polymer on a mass basis is 35/65 or more and 80/20 or less. The absorbent article according to claim 1 or 2, wherein the first cationic polymer and the second cationic polymer are contained in the same member among the constituent members of the absorbent article. The absorbent article contained, as a constituent member, a surface sheet forming a skin-facing surface, an absorbent core containing a highly absorbent polymer, and both the first cationic polymer and the second cationic polymer. It has a hemagglutin-containing sheet and
The absorbable article according to claim 1 or 3, wherein the hemagglutin-containing sheet is arranged between the surface sheet and the absorbable core. The absorbent article contained, as a constituent member, a surface sheet forming a skin-facing surface, an absorbent core containing a highly absorbent polymer, and both the first cationic polymer and the second cationic polymer. With a cationic polymer-containing sheet,
The absorbent article according to claim 2 or 3, wherein the cationic polymer-containing sheet is arranged between the surface sheet and the absorbent core.