JP6228630B1 - Hemagglutinating fiber - Google Patents

Abstract

An object of the present invention is to provide a hemagglutinating fiber that immediately exhibits a blood cell aggregating effect upon contact with menstrual blood, and is less likely to reduce the agglutinating effect upon repeated contact with menstrual blood. The hemagglutinating fiber of the present invention has a hemagglutinating agent on the fiber surface, and the fractal dimension of the fiber surface is 1.0170 or more. It is preferable that the fiber is a hydrophilic fiber. It is also preferred that the fibers are fibrillated. It is also preferable that the beating degree of the fiber is 810 ml or less. [Selection] Figure 3

Description

  The present invention relates to a fiber having a blood cell aggregation action.

  A technique for improving various performances of an absorbent article by applying a cationic polymer material to the absorbent article is known. For example, Patent Document 1 describes a sanitary napkin containing a blood gelling agent comprising a polycation and a liquid absorbent material. Patent Document 2 describes a method for producing an antibacterial substance in which a cellulose material such as cotton or wood pulp and an antibacterial cationic polyelectrolyte are mixed to form a non-leaching bond therebetween. . This antibacterial substance is used for sanitary napkins and tampons. For example, polydiallyldimethylammonium chloride is used as the antibacterial cationic polyelectrolyte.

JP-A-57-153648 JP 2009-506056 A

  In the techniques described in Patent Documents 1 and 2, when a cationic polymer material is applied to the surface of a fiber that is one of the liquid-absorbing materials, when the fiber comes into contact with menstrual blood, the polymer material The surface area derived from the solubility of the fiber and the surface of the fiber becomes the rate-determining stage of effect expression, and there are cases where a high effect cannot be instantly expressed.

  Therefore, the object of the present invention is to improve the material for treating menstrual blood. More specifically, the function of the agent is immediately exerted by contact with menstrual blood, and the function of the agent is also lowered by repeated contact with menstrual blood. It is in providing the fiber which is hard to carry out, and the articles | goods containing it.

  The present invention provides a hemagglutinating fiber having a hemagglutinating agent on the fiber surface and a fractal dimension of the fiber surface of 1.0170 or more.

  The present invention also includes a base material impregnated with a solution containing a hemagglutinating agent and having a viscosity at coating of 100 mPa · s or more and a dried raw fiber, and then the raw material from the base material. The present invention provides a method for producing a hemagglutinating fiber, including a step of peeling the fiber.

  Moreover, this invention provides the fiber sheet and absorbent article containing the hemagglutinating fiber mentioned above.

  Furthermore, this invention provides the manufacturing method of a hemagglutination fiber including the process of spraying the solution containing a hemagglutination agent on raw material fiber.

  According to the present invention, there is provided a hemagglutinating fiber that immediately exhibits a blood cell aggregating effect upon contact with menstrual blood, and is less likely to deteriorate even when repeatedly contacted with menstrual blood.

FIG. 1 is a plan view showing an embodiment of an absorbent article including the hemagglutinating fiber of the present invention. Fig.2 (a) and FIG.2 (b) are the schematic diagrams which show the absorption mechanism of the menstrual blood in the conventional absorbent article. FIG. 3 is a schematic diagram showing a menstrual blood absorption mechanism in an absorbent article including the hemagglutinating fiber of the present invention.

  Hereinafter, the present invention will be described based on preferred embodiments thereof. The hemagglutinating fiber of the present invention has an action of aggregating red blood cells in blood by contacting with blood. The blood mentioned here is generally human blood, but is not limited thereto. The hemagglutinating fiber is obtained by applying a hemagglutinating agent to the fiber.

  The fiber used for the hemagglutinating fiber of the present invention has an elongated shape having a large length with respect to the thickness. The thickness is the diameter of a circle when the cross section of the fiber is a circle, and the diameter of a circle having the same area as the area of the cross section when the cross section is a shape other than a circle. . The length of the fiber is generally at least 5 times the thickness, and there is no limit on the upper limit.

  The thickness of the fiber used for the hemagglutinating fiber of the present invention can be appropriately selected according to the specific use of the hemagglutinating fiber. When the hemagglutinating fiber is used for a menstrual absorbent article such as a sanitary napkin, the thickness of the fiber is 0 from the viewpoint of providing a strength that can be formed as a fiber sheet and can be endured as an absorbent article. It is preferably 1 μm or more, more preferably 1 μm or more, and even more preferably 10 μm or more. Moreover, it is preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably 200 μm or less from the viewpoint of having a texture that does not feel uncomfortable when used in absorbent articles. The thickness of the fiber is preferably from 0.1 μm to 1000 μm, more preferably from 1 μm to 500 μm, and even more preferably from 10 μm to 200 μm. In the present invention, the thickness of the hemagglutinating fiber and the thickness of the fiber constituting the hemagglutinable fiber can be substantially identical. Therefore, the thickness of the hemagglutinating fiber is preferably in the range as described above. Moreover, the said fiber sheet is the concept also including the nonwoven fabric and paper which consist of synthetic fibers.

  The thickness of the hemagglutinating fibers and the thickness of the fibers constituting the hemagglutinating fibers are measured by magnified observation with a scanning electron microscope. The length in which the fiber crosses the line segment along the direction orthogonal to the longitudinal direction of the fiber is defined as the fiber thickness. The measurement is performed at 10 or more positions in the same or different fibers, and the calculated average value is defined as the fiber thickness, that is, the fiber diameter. When the fiber thickness is not constant along the length direction as in pulp fiber, the fiber thickness is the longest side of the line segment that crosses the cross section of the fiber, and the shortest side. The long side is the short side.

  The hemagglutinating fiber of the present invention is characterized by the presence of a hemagglutinating agent applied to the fiber. Specifically, the hemagglutinating agent is present on the fiber surface with an irregular thickness. That is, in the hemagglutinating agent, a portion having a large thickness and a portion having a small thickness are irregularly present on the surface of the fiber. As a result, the hemagglutinating agent exists so that irregularities are formed on the surface of the fiber.

  The hemagglutinating agent may be present throughout the fiber surface without exposing the fiber surface. Alternatively, the hemagglutinating agent may be discontinuously present on the surface of the fiber so that the fiber surface is partially exposed. The hemagglutinating agent only needs to be present at least on the surface of the fiber, and it is not prevented that the hemagglutinating agent is additionally present inside the fiber.

  The presence of the hemagglutinating agent on the surface of the fiber with an irregular thickness has the following advantages. That is, when the hemagglutinating fiber comes into contact with blood, the hemagglutinating agent aggregates red blood cells in the blood. In this case, if the hemagglutinating agent is present on the fiber surface with a uniform thickness, there is a limit to securing a large contact area between the hemagglutinating agent and the blood, and the hemagglutinating agent is present in the blood. It is not easy to elute instantly and in a sufficient amount. Also, if the hemagglutinating agent is present on the fiber surface with a uniform thickness, most of the hemagglutinating agent will be washed away after repeated contact with blood, making it difficult to exert sustained release properties. On the other hand, if the hemagglutinating agent is present on the surface of the fiber with an irregular thickness, the surface area of the hemagglutinating agent on the surface of the fiber increases, resulting in the hemagglutinating agent and blood It is easy to ensure a large contact area with the hemagglutinating agent, and the hemagglutinating agent is instantly and sufficiently eluted in the blood. In addition, the blood cell agglutination effect continues even when repeatedly contacted with blood. In other words, there is sustained release. Thus, the hemagglutinating fiber of the present invention improves the elution of the hemagglutinating agent into the blood and has a sustained release property. Therefore, the hemagglutinating agent of the present invention exhibits an agglutinating action of blood cells instantly and the action lasts for a long time.

The presence state of the hemagglutinating agent on the surface of the fiber can be quantitatively displayed using the fractal dimension as a scale. The higher the fractal dimension, the hemagglutinating agent has a larger surface area on the surface of the fiber. The fractal dimension is a concept that represents the complexity of the fractal view shape. When an entire figure is composed of M miniatures of similar shapes reduced to 1 / N, the fractal dimension D of this figure is defined by D = log ₁₀ M / log ₁₀ N.

In the present invention, the box count method is used to calculate the fractal dimension. The box count method is a method of dividing a target figure into a plurality of boxes and calculating the fractal dimension by counting the number of boxes containing the fractal figure. It is known that the relationship of N (d) ∝d− ^D is established, where D is the fractal dimension, d is the width of the box, and N (d) is the number of boxes including the fractal figure. Then, N (d) was counted for various values of d, log ₁₀ d and log ₁₀ N (d) were plotted on a graph, and the linear regression calculation was performed. The slope was calculated by the box count method. Fractal dimension D.

  In the hemagglutinating fiber of the present invention, an excellent effect is exhibited when the fractal dimension of the fiber surface is 1.0170 or more. As a result of the study by the present inventors, it has been found that an effect is recognized in the fractal dimension after the inflection point. From the viewpoint of sufficiently increasing the surface area of the hemagglutinating agent, the above-described fractal dimension is 1.0170 or more, preferably 1.0900 or more, more preferably 1.1500 or more on the fiber surface. The fractal dimension described above is preferably as large as possible. However, since the contour line of the projection image is regarded as a fractal figure and the contour image is two-dimensional, the upper limit is 2.000 or less.

When obtaining the fractal dimension of a hemagglutinating fiber, an enlarged projection image obtained by viewing the hemagglutinating fiber from a direction orthogonal to its longitudinal direction is acquired. The upper and lower contour lines of the acquired projection image are regarded as fractal figures, and the fractal dimension is obtained by the method described above. Specifically, the following procedure is performed. First, the cross section of a fiber is imaged with a scanning electron microscope. Imaging is performed at a magnification of 800 times so that the projected image of the fiber cross section falls within the imaging field. At this time, it is preferable to take an image so that the contrast of the image becomes strong. Then, the cross-sectional image is subjected to image processing with “ImageJ” which is image processing software. Image processing is performed in the following order (1)-(4).
(1) Binarization of cross-sectional image.
(2) Convert the binarized image into an outline.
(3) Extraction of attention area. The cutout range is set to Width: 250 pixels and Height: 500 pixels.
(4) Calculation of fractal dimension.

  As the fiber used for the hemagglutinating fiber, either natural fiber or synthetic fiber may be used. Examples of natural fibers include plant-derived cellulose fibers and rayon fibers. As a synthetic fiber, the fiber which consists of a thermoplastic resin which has fiber formation ability, for example is mentioned. Examples of the thermoplastic resin having fiber forming ability include various polyolefin fibers such as polyethylene and polypropylene, various polyester fibers such as polyethylene terephthalate and polybutylene terephthalate, and various acrylic fibers such as polyacrylic acid and polymethyl methacrylate. And various vinyl fibers such as polystyrene and polyvinyl chloride. These fibers can be used alone or in combination of two or more. Regardless of whether natural fibers or synthetic fibers are used, it is preferable to use hydrophilic fibers because the hemagglutinating agent can be easily attached to the surface of the fibers. When the surface of the fiber is hydrophobic, a hydrophilizing agent or the like may be treated. In particular, it is preferable to use a cellulose fiber because it is a hydrophilic fiber and the surface of the fiber itself has a complicated shape and has a large surface area.

  When cellulose fibers are used as the fibers, it is preferable to use those having a high degree of beating because the surface area of the fibers becomes even larger. Beating is an operation in which cellulose fibers such as pulp are mechanically beaten and ground in the presence of water. When cellulose fibers are mechanically ground and crushed, they swell and fibrillate. Fibrilization is a phenomenon in which cellulose fibers branch into fine branches. When the cellulose fiber is fibrillated, the surface area of the fiber increases.

  The degree of beating of cellulose fibers can be quantitatively expressed by the beating degree (also called the freeness). The degree of beating of the cellulose fiber expressed by the beating degree is more preferably 600 ml or less, and still more preferably 400 ml or less, from the viewpoint of increasing the surface area of the fiber. The lower limit of the beating degree is preferably 100 ml or more, more preferably 200 ml or more, and even more preferably 300 ml or more from the viewpoint of maintaining the fiber length and maintaining the workability. The beating degree is preferably 100 ml or more and 780 ml or less, more preferably 200 ml or more and 600 ml or less, and further preferably 300 ml or more and 400 ml or less. In addition, even after the hemagglutinating agent is applied to the fiber, there is no substantial change in the beating degree of the fiber, so that the preferred beating degree value of the hemagglutinating fiber is within the above range. In the case of synthetic fibers, the freeness measured using the same method is defined as the beating degree. The beating degree can be measured in accordance with Japanese Industrial Standards JIS P8121 / 2: 2012 Pulp-Freeness Test Method-Part 2: Canadian Standard Freeness Method.

  As the hemagglutinating agent used in the hemagglutinating fiber of the present invention, those having an action capable of aggregating erythrocytes in blood are used. The “hemagglutinating agent” has an action of aggregating red blood cells in blood, and acts to separate the aggregated aggregate and plasma components. Red blood cells aggregated by the hemagglutinating agent become aggregates. As the hemagglutinating agent, for example, a strongly positively charged linear cationic polymer such as acrylamide copolymer or polylysine can be used. Alternatively, a triblock copolymer of polypropylene oxide and polyethylene oxide can be used. An example of such a triblock copolymer is “Pluronic F-98” available from BASF.

  According to the knowledge of the present inventors, a cationic polymer is useful as a hemagglutinating agent. The reason is as follows. Red blood cells have a red blood cell membrane on their surface. The erythrocyte membrane has a two-layer structure. This two-layer structure is composed of a red blood cell membrane skeleton as a lower layer and a lipid membrane as an upper layer. The lipid film exposed on the surface of erythrocytes contains a protein called glycophorin. Glycophorin has a sugar chain to which a sugar having an anionic charge called sialic acid is bonded at its end. As a result, erythrocytes can be treated as colloidal particles having an anionic charge. In general, an aggregating agent is used for aggregating the colloidal particles. Considering that erythrocytes are anionic colloidal particles, it is advantageous to use a cationic substance as an aggregating agent from the viewpoint of neutralizing the electric double layer of erythrocytes. Further, if the aggregating agent has a polymer chain, the polymer chains of the aggregating agent adsorbed on the surface of the erythrocyte tend to be entangled with each other, thereby promoting the aggregation of erythrocytes. Further, when the aggregating agent has a functional group, it is preferable because the aggregation of erythrocytes is promoted by the interaction between the functional groups. According to the hemagglutinating agent (cationic polymer), it becomes possible to produce an aggregate of red blood cells during menstrual blood by the above mechanism of action.

  The hemagglutinating agent used in the present invention has the property that, when 1000 ppm of a measurement sample is added to simulated blood, at least two blood cells aggregate to form an aggregate in a state in which the blood fluidity is maintained. It is what has.

  The above-mentioned “state in which the fluidity of blood is maintained” means that 10 g of simulated blood to which a measurement sample agent is added 1000 ppm is screw tube bottle (manufactured by Maruemu Co., Ltd., product number “Screw tube No. 4”, mouth inner diameter 14.5 mm, When the screw tube bottle containing the simulated blood is turned 180 degrees, it is in a state where 80% or more of the simulated blood flows down within 5 seconds. Simulated blood is a viscosity 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) at 8 ° C. at 25 ° C. The blood cell / plasma ratio of defibrinated horse blood (manufactured by Japan Biotest Laboratories) is adjusted.

  Whether or not “two or more blood cells aggregate to form an aggregate” is determined as follows. That is, the simulated blood to which the measurement sample agent was added at 1000 ppm was diluted 4000 times with physiological saline, and a laser diffraction / scattering type particle size distribution measuring apparatus (manufactured by Horiba, Ltd., model number: LA-950V2, measurement condition: flow type). The median diameter of volume average particle diameter measured at a temperature of 25 ° C. by a laser diffraction scattering method using cell measurement, circulation rate 1 and no ultrasonic wave corresponds to the size of an aggregate obtained by agglomeration of two or more blood cells. If it is 10 μm or more, it is determined that “two or more blood cells aggregate to form an aggregate”.

  The hemagglutinating agent used in the present invention satisfies the above-mentioned properties by a single compound that meets the above-described properties, a plurality of combinations of single compounds that meet the above-mentioned properties, or a combination of a plurality of compounds (aggregation of erythrocytes). Agent). That is, the hemagglutinating agent is an agent limited to those having a hemagglutinating action as defined above. Therefore, when the hemagglutinating agent contains a third component that does not meet the above definition, it is expressed as a hemagglutinating agent composition and is distinguished from the hemagglutinating agent. The term “single compound” as used herein is a concept including compounds having the same composition formula but having different molecular weights due to different numbers of repeating units.

  As the hemagglutinating agent used in the present invention, those containing a cationic polymer are preferable. Examples of the cationic polymer include cationized cellulose and cationized starch such as hydroxypropyltrimonium chloride. The hemagglutinating agent used in the present invention can also contain a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer or a quaternary ammonium salt polycondensate as a cationic polymer. In the present invention, the “quaternary ammonium salt” includes a compound having a plus monovalent charge at the nitrogen atom position, or a compound that generates a plus monovalent charge at the nitrogen atom position 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 in the same meaning and is a moiety that is positively charged in water. Further, in the present invention, the “copolymer” is a polymer obtained by copolymerization of two or more kinds of polymerizable monomers, and is a binary copolymer or a ternary copolymer or more. Includes both things. In the present invention, the “polycondensate” is a polycondensate obtained by polymerizing a condensate composed of two or more monomers.

  When the hemagglutinating agent 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 the cationic polymer, the hemagglutination 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 be included. Moreover, a quaternary ammonium salt homopolymer can be used individually by 1 type or in combination of 2 or more types. Similarly, the quaternary ammonium salt copolymer can be used alone or in combination of two or more. Furthermore, similarly, a quaternary ammonium salt polycondensate can be used individually by 1 type or in combination of 2 or more types.

  Of the various cationic polymers described above, in particular, the use of a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer or a quaternary ammonium salt polycondensate from the viewpoint of adsorptivity to erythrocytes. preferable. In the following description, for convenience, 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 polymerizing one type of polymerizable monomer having a quaternary ammonium moiety. 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 polymerizable monomers having a quaternary ammonium moiety and copolymerizing them, or having a quaternary ammonium moiety. It is obtained by copolymerizing one or more polymerizable monomers having 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 polymerizing these condensates using a condensate composed of one or more monomers having a quaternary ammonium moiety. That is, the quaternary ammonium salt polycondensate is obtained by polymerizing two or more condensates having two or more monomers having a quaternary ammonium moiety, or the quaternary ammonium moiety. And a condensate comprising one or more monomers having quaternary ammonium moieties and one or more monomers having no quaternary ammonium moiety, and obtained by condensation polymerization.

  A quaternary ammonium salt polymer is a cationic polymer having a quaternary ammonium moiety. A quaternary ammonium moiety can be generated by quaternary ammoniumation of a tertiary amine using an alkylating agent. Alternatively, the tertiary amine can be dissolved in acid or water and generated by neutralization. Or it can produce | generate by the quaternary ammonium formation by the nucleophilic reaction containing 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, the use of dialkyl sulfate is preferable because the problem of corrosion that may occur when an alkyl halide is used does not occur. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid, phosphoric acid, fluorosulfonic acid, boric acid, chromic acid, lactic acid, oxalic acid, tartaric acid, gluconic acid, formic acid, ascorbic acid, and hyaluronic acid. . In particular, it is preferable to use a quaternary ammonium salt polymer in which a tertiary amine moiety is quaternized with an alkylating agent, because the electric double layer of erythrocytes can be reliably neutralized. Quaternary ammoniumation by a nucleophilic reaction including a condensation reaction can be caused by a ring-opening polycondensation reaction of dimethylamine and epichlorohydrin or a cyclization reaction of dicyandiamide and diethylenetriamine.

  From the viewpoint of effectively producing an aggregate of erythrocytes, the cationic polymer preferably has a molecular weight of 2000 or more, more preferably 10,000 or more, and even more preferably 30,000 or more. When the molecular weight of the cationic polymer is not less than these values, the entanglement of the cationic polymers between the erythrocytes and the crosslinking of the cationic polymer between the erythrocytes are sufficiently caused. The upper limit of the molecular weight is preferably 10 million or less, more preferably 5 million or less, and even more preferably 3 million or less. When the molecular weight of the cationic polymer is not more than these values, the cationic polymer dissolves well into menstrual blood. The molecular weight of the cationic polymer is preferably 2000 or more and 10 million or less, more preferably 2000 or more and 5 million or less, still more preferably 2000 or more and 3 million or less, and 10,000 or more and 3 million or less. It is even more preferable, and it is particularly preferably 30,000 to 3,000,000. The molecular weight referred to in the present invention is a weight average molecular weight. The molecular weight of the cationic polymer can be controlled by appropriately selecting the polymerization conditions. The molecular weight of the cationic polymer can be measured using HLC-8320GPC manufactured by Tosoh Corporation. Specific measurement conditions are as follows.

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

  The cationic polymer is also preferably a mixture of two or more cationic polymers having different weight average molecular weights. This further improves the blood cell aggregation effect. Specifically, a relatively low molecular weight cationic polymer plays a role in neutralizing the blood cell surface charge, while a relatively high molecular weight cationic polymer plays a role in forming blood cell aggregates. To do. From this viewpoint, when the cationic polymer is a mixture of two kinds of cationic polymers having different weight average molecular weights, the relatively low molecular weight cationic polymer has a weight average molecular weight of 2,000 to 150,000. It is preferably 10,000 or more and 100,000 or less, more preferably 30,000 or more and 80,000 or less. On the other hand, the relatively high molecular weight cationic polymer may have a weight average molecular weight of 150,000 or more and 3 million or less, provided that the weight average molecular weight is higher than that of the relatively low molecular weight cationic polymer. Preferably, it is 300,000 or more and 2 million or less, and more preferably 500,000 or more and 1 million or less. When the cationic polymer is a mixture of two or more kinds of cationic polymers having different weight average molecular weights, for example, a mixture of a cationic polymer A having a relatively low molecular weight and a cationic polymer B having a relatively high molecular weight. In some cases, the cationic polymer A and the cationic polymer B may be the same type of polymers having different weight average molecular weights, or may be polymers having different weight average molecular weights and different types.

  When the cationic polymer is a mixture of two or more kinds of cationic polymers having different weight average molecular weights, it is also preferable to have two peaks in the molecular weight distribution. This further improves the sustained release properties of the hemagglutinating agent. Specifically, the relatively low molecular weight cationic polymer elutes early in contact with blood, while the relatively high molecular weight cationic polymer elutes later in contact with blood. From this viewpoint, when the cationic polymer is a mixture of two kinds of cationic polymers having different weight average molecular weights, the difference in peak of the molecular weight distribution is preferably 300,000 or more, and more preferably 500,000 or more. More preferably, it is more preferably 700,000 or more, more preferably 3 million or less, further preferably 2 million or less, and further preferably 1 million or less. The difference in peak of the molecular weight distribution is preferably from 300,000 to 3,000,000, more preferably from 500,000 to 2,000,000, and even more preferably from 700,000 to 1,000,000. The difference in the peak of the molecular weight distribution is the difference between the weight average molecular weight of the relatively high molecular weight cationic polymer and the weight average molecular weight of the relatively low molecular weight cationic polymer. When the cationic polymer is a mixture of two or more kinds of cationic polymers having different weight average molecular weights, for example, a mixture of a cationic polymer A having a relatively low molecular weight and a cationic polymer B having a relatively high molecular weight. In some cases, the cationic polymer A and the cationic polymer B may be the same type of polymers having different weight average molecular weights, or may be polymers having different weight average molecular weights and different types.

  From the viewpoint of effectively producing red blood cell aggregates, the cationic polymer is preferably water-soluble. In the present invention, “water-soluble” means that 0.05 g of a 1 mm or less powdery or 0.5 mm or less film-like cationic polymer is added to a 100 mL glass beaker (5 mmΦ) and mixed with 50 mL ion-exchanged water at 25 ° C. In this case, a stirrer chip having a length of 20 mm and a width of 7 mm is added, and the whole amount is dissolved in water within 24 hours under stirring at 600 rpm using a magnetic stirrer HPS-100 manufactured by ASONE Co., Ltd. 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, when the main chain and the side chain are bonded at one point, the flexibility of the side chain is difficult to be hindered, and the quaternary ammonium moiety present in the side chain is smoothly formed on the surface of the erythrocyte. Adsorbs. However, in the present invention, it is not hindered 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. . “Connected at two or more points” means that two or more of the carbon atoms constituting the main chain are each single-bonded with two or more carbon atoms located at the end of the side chain. say.

  When the cationic polymer has a structure having a main chain and a plurality of side chains bonded thereto, for example, a quaternary ammonium salt polymer has a structure having a main chain and a plurality of side chains bonded thereto. In this case, 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 carbon number 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 still more 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 that is the counter ion, 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 within the aforementioned range, so that the quaternary ammonium salt. This 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 a polymer of a vinyl monomer having a quaternary ammonium moiety or a tertiary amine moiety. . In the case of polymerizing a vinyl monomer having a tertiary amine moiety, a quaternary ammonium salt homopolymer in which the tertiary amine moiety is quaternized with an alkylating agent before and / or after polymerization. Becomes a polymer, becomes a tertiary amine neutralized salt obtained by neutralizing a tertiary amine site with an acid before and / or after polymerization, or becomes a tertiary amine having a cation in an aqueous solution after polymerization. . Examples of the alkylating agent and the acid 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. Further, poly (2-methacryloxyethyldimethylamine quaternary salt), poly (2-methacryloxyethyltrimethylammonium salt) in which the side chain having a quaternary ammonium moiety is bonded to the main chain at one point. ), Poly (2-methacryloxyethyldimethylethylammonium methylsulfate), poly (2-acryloxyethyldimethylamine quaternary salt), poly (2-acryloxyethyltrimethylamine quaternary salt), poly (2-acryloxy) Ethyldimethylethylammonium ethyl sulfate), poly (3-dimethylaminopropylacrylamide quaternary salt), dimethylaminoethyl polymethacrylate, polyallylamine hydrochloride, cationized cellulose, polyethyleneimine, polydimethylaminopropylacrylamide, polyamidine, etc. And the like. On the other hand, examples of the homopolymer 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 polydiallylamine hydrochloride.

When the quaternary ammonium salt polymer is a quaternary ammonium salt copolymer, two kinds of polymerizable monomers used for the polymerization of the quaternary ammonium salt homopolymer described above are used as the copolymer. A copolymer obtained by the above copolymerization can be used. Alternatively, as a quaternary ammonium salt copolymer, one or more polymerizable monomers used for the polymerization of the quaternary ammonium salt homopolymer described above and a polymerizable monomer having no quaternary ammonium moiety The copolymer obtained by copolymerizing using 1 or more types of bodies can be used. Furthermore, other polymerizable monomers such as —SO ₂ — can be used in addition to or in place of the vinyl polymerizable monomer. As described above, the quaternary ammonium salt copolymer can be a binary copolymer or a ternary or higher copolymer.

  In particular, the quaternary ammonium salt copolymer has a repeating unit represented by the above-described formula 1 and a repeating unit represented by the following formula 2 to effectively produce an agglomerate of erythrocytes. It is preferable from the viewpoint.

  Further, as the polymerizable monomer having no quaternary ammonium moiety, a cationic polymerizable monomer, an anionic polymerizable monomer, or a nonionic polymerizable monomer can be used. Among these polymerizable monomers, in particular, by using a cationic polymerizable monomer or a nonionic polymerizable monomer, charge cancellation with a quaternary ammonium moiety in a quaternary ammonium salt copolymer is achieved. Therefore, erythrocyte aggregation can be effectively generated. Examples of cationic polymerizable monomers include linear compounds having a cation-carrying nitrogen atom in the main chain, such as vinylpyridine as a cyclic compound having a cation-carrying nitrogen atom under a particular condition And a condensed compound of dicyandiamide and diethylenetriamine. Examples of the anionic polymerizable monomer include 2-acrylamido-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, ethyl Examples include acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, and butyl acrylate. One of these cationic polymerizable monomers, anionic polymerizable monomers, or nonionic polymerizable monomers can be used, or any two or more of them can be used in combination. Can do. Also, two or more cationic polymerizable monomers can be used in combination, two or more anionic polymerizable monomers can be used in combination, or two or more nonionic polymerizable monomers can be used in combination. Can also be used. A quaternary ammonium salt copolymer copolymerized using a cationic polymerizable monomer, an anionic polymerizable monomer and / or a nonionic polymerizable monomer as a polymerizable monomer has a molecular weight of However, as described above, it is preferably 10 million or less, particularly 5 million or less, and particularly preferably 3 million or less (the same applies to the quaternary ammonium salt copolymer exemplified below).

A polymerizable monomer having a functional group capable of hydrogen bonding can also be used as the polymerizable monomer having no quaternary ammonium moiety. When such a polymerizable monomer is used for copolymerization, and when erythrocytes are aggregated using a quaternary ammonium salt copolymer obtained therefrom, a hard aggregate is likely to be formed. Absorption performance is less likely to be disturbed. Examples of the functional group capable of hydrogen bonding include —OH, —NH ₂ , —CHO, —COOH, —HF, —SH, and the like. Examples of polymerizable monomers having functional groups capable of hydrogen bonding include hydroxyethyl methacrylate, vinyl alcohol, acrylamide, dimethylacrylamide, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxyethyl An acrylate etc. are mentioned. 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 quaternary ammonium salt polymers on erythrocytes is stabilized. These polymerizable monomers can be used individually by 1 type or in combination of 2 or more types.

  As the polymerizable monomer having no quaternary ammonium moiety, a polymerizable monomer having a functional group capable of hydrophobic interaction can also be used. By using such a polymerizable monomer for copolymerization, the same advantageous effect as that in the case of using the polymerizable monomer having a functional group capable of hydrogen bonding described above, that is, the hardness of erythrocytes The effect that it becomes easy to produce an agglomerate is produced. Examples of functional groups capable of hydrophobic interaction include alkyl groups such as methyl, ethyl, and butyl groups, phenyl groups, alkylnaphthalene groups, and fluorinated alkyl groups. Examples of polymerizable monomers having functional groups capable of hydrophobic interaction include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, styrene, etc. Is 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 adsorbed to erythrocytes by the quaternary ammonium salt polymer. Is preferable because of stabilization. These polymerizable monomers can be used individually by 1 type or in combination of 2 or more types.

  The molar ratio of the polymerizable monomer having a quaternary ammonium moiety and the polymerizable monomer having no quaternary ammonium moiety in the quaternary ammonium salt copolymer is the quaternary ammonium salt. It is preferable that the red blood cells are appropriately adjusted so as to be sufficiently aggregated by the ammonium salt copolymer. 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. % Or more, more preferably 38 mol% or more. Further, it is preferably 100 mol% or less, more preferably 80 mol% or less, still more preferably 65 mol% or less, and even more 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, more preferably 22 mol% or more and 80 mol% or less, More preferably, it is 32 mol% or more and 65 mol% or less, and more preferably 38 mol% or more and 56 mol% or less.

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

  The above-described quaternary ammonium salt homopolymer and quaternary ammonium salt copolymer can be obtained by a homopolymerization method or a copolymerization method of a vinyl polymerizable monomer. As the polymerization method, for example, radical polymerization, living radical polymerization, living cation polymerization, living anion polymerization, coordination polymerization, ring-opening polymerization, polycondensation and the like can be used. There are no particular limitations on the polymerization conditions, and the conditions under which a quaternary ammonium salt polymer having the desired molecular weight, streaming potential, and / or IOB value can be obtained may be appropriately selected.

  In addition to the polycation (cationic polymer), the hemagglutinating agent used in the present invention includes one third component such as a solvent, a plasticizer, a fragrance, an antibacterial / deodorant, and a skin care agent. It may be in the form of a composition (hemagglutinating agent composition) contained 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, polyethylene glycol, propylene glycol, ethylene glycol, 1,3-butanediol, or the like can be used. As a fragrance | flavor, the fragrance | flavor which has the green herbal-like fragrance | flavor described in Unexamined-Japanese-Patent No. 2007-244762, a plant extract, a citrus extract, etc. can be used. As the antibacterial / deodorant, a cancrinite-like mineral containing a metal having antibacterial properties described in JP-A-2004-244789, and a polymerizable group having a phenyl group 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, moisturizing agents, keratin softening agents, anti-inflammatory agents and the like described in JP-A No. 2004-255164 can be used.

  The proportion of the cationic polymer in the hemagglutinating agent 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 still more preferably 10% by mass or less. By setting the proportion of the cationic polymer in the hemagglutinating agent composition within this range, an effective amount of the cationic polymer can be imparted to the absorbent article.

  The ratio of the hemagglutinating agent contained in the hemagglutinating fiber of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of expressing sufficient hemagglutination. More preferably, it is 30 mass% or more. Further, from the viewpoint of being able to be present on the fiber surface, the content is preferably 90% by mass or less, more preferably 70% by mass or less, and further preferably 50% by mass or less. The proportion of the hemagglutinating agent contained in the hemagglutinating fiber is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 70% by mass or less, and 30% by mass or more and 50% by mass or less. More preferably, it is as follows.

The total amount and molecular weight distribution of the hemagglutinating agent contained in the hemagglutinating fiber are measured by the following method.
A napkin or the like to be measured is weakened with a cold spray, and carefully peeled off to separate each member. Each member is immersed in deionized water for 60 minutes to elute the hemagglutinating agent composition. Thereafter, the deionized water from which the resulting hemagglutinating agent composition has been eluted is dialyzed. The dialysis treatment is a treatment for removing water-soluble low molecular weight components such as solvents, plasticizers, fragrances, antibacterial / deodorants, skin care agents, etc. For example, a dialysis tube that can remove components having a molecular weight of 2000 or less is used. . After dialysis, evaporate to dryness or freeze-dry. Thereafter, ¹ H-NMR, mass spectrometry (MS) or the like is used alone or in combination to identify the hemagglutinating agent. By measuring the mass of the identified hemagglutinating agent, the total amount of hemagglutinating agent can be determined. Based on the total amount of the hemagglutinating agent thus determined and the mass of the fiber before the hemagglutinating agent composition is eluted, the proportion of the hemagglutinating agent contained in the hemagglutinating agent fiber can be obtained. Moreover, a differential molecular weight distribution curve can be obtained by measuring the identified hemagglutinating agent by gel permeation chromatography.

In the present invention, various methods can be employed for allowing the hemagglutinating agent to exist on the surface of the fiber in a high fractal dimension. For example, the following methods (1) and (2) can be employed.
Method (1) A base material impregnated with a solution containing a hemagglutinating agent and having a viscosity of 100 mPa · s or more applied at the time of application is brought into contact with dried raw material fibers, and then the raw material is supplied from the base material. A method comprising a step of peeling fibers.
-Method (2) The method including the process of spraying the solution containing a hemagglutinating agent on a raw material fiber.

  In the method (1), by using the solution having a high viscosity, a hemagglutinating agent is used when the raw material fibers are peeled off after contacting the base material impregnated with the solution and the dry raw material fibers. Is held on the surface of the raw fiber so as to fuzz. In particular, the higher the viscosity of the solution impregnated in the base material, the easier it is to form a complex structure on the fiber surface at the time of peeling, and the fractal dimension becomes higher. From this viewpoint, the viscosity of the solution is more preferably 200 mPa · s or more, and more preferably 300 mPa · s or more at the time of application. From the viewpoint of applicability of the solution, the upper limit of the viscosity is preferably 100000 mPa · s or less, more preferably 50000 mPa · s or less, and still more preferably 10,000 mPa · s or less. The viscosity of the solution is preferably 100 mPa · s or more at the time of coating, more preferably 200 mPa · s or more, and further preferably 300 mPa · s or more.

  The viscosity of the solution containing the hemagglutinating agent is measured using a B-type viscometer (model number TVB-10M manufactured by Toki Sangyo Co., Ltd.) using a rotor suitable for the target solution viscosity at 30 ° C. for 60 seconds at 25 ° C. Asked.

  The solvent used in the solution is not particularly limited as long as it can dissolve the hemagglutinating agent. For example, water can be used conveniently. From the viewpoint of exfoliating the raw material fibers in a highly viscous state after impregnating the substrate with the solution, it is desirable to shorten the drying time of the solution. From this viewpoint, the solvent is preferably an organic solvent that can dissolve the hemagglutinating agent. Examples of such organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, tetrahydrofuran, acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, acetic acid and formic acid. These organic solvents can be used individually by 1 type or in combination of 2 or more types. Alternatively, one or more of these organic solvents can be used in combination with water. From the viewpoint of safety, high volatility, and economical efficiency, it is preferable to use ethanol.

  As the base material impregnated with the solution, a hydrophilic material is preferably used from the viewpoint of improving the impregnation property of the solution. For example, it is preferable to use a fiber sheet made of hydrophilic fibers, specifically paper, but is not limited thereto.

  Until now, generally, when the solution has a high viscosity, the solution has not been successfully wetted and spread on the substrate during transfer, and it has been difficult to uniformly apply the solution. On the other hand, according to the present invention, an elastic material capable of absorbing the uneven shape present on the surface of the raw material fiber is used as the base material, and the base material made of the elastic material and the raw material fiber are brought into contact with each other. Thus, the solution can be applied uniformly.

  The raw fiber may be brought into contact with the base material in the state of the fiber, or may be brought into contact with the base material in the state of a web or a fiber sheet. When contacting in the state of a web or a fiber sheet, you may perform a defibration process after that as needed.

  After the base material impregnated with the solution and the raw fiber are brought into contact with each other, the raw fiber is preferably peeled off before the solvent is completely volatilized from the solution. The period when it is in a state is preferable. However, depending on the viscosity of the solution, the raw fibers may be peeled immediately after the two are brought into contact with each other.

  In the method (2), the solution containing the hemagglutinating agent is in the form of droplets, and the solvent is likely to volatilize. As a result, the viscosity of the droplet increases, and it becomes easy to adhere to the surface of the fiber in the state of the droplet. Thereby, an uneven structure is formed by a hemagglutinating agent on the surface of the fiber. In particular, the higher the volatility of the organic solvent is, the more preferable it is because the solution after spraying becomes solid before it takes a flat structure and the fractal dimension becomes high.

  Examples of the solution containing the hemagglutinating agent include the same ones as used in the method (1). In particular, it is preferable to use an organic solvent solution in order to easily volatilize the solvent. A typical method for spraying the solution onto the raw fiber is a method using a spray nozzle, but is not limited thereto. The viscosity of the solution when this solution is sprayed onto the raw fiber is more preferably 1 mPa · s or more, and still more preferably 3 mPa · s or more. The upper limit of the viscosity of the solution is preferably 100 mPa · s or less, more preferably 80 mPa · s or less, and even more preferably 50 mPa · s or less. By using a solution having this viscosity, spraying can be easily performed, and a droplet size in which the solvent is easily volatilized can be realized.

  When a highly volatile organic solvent is used as the organic solvent, generally, clogging is likely to occur in the spray nozzle due to the volatilization of the organic solvent, and uniform application has not been easy. In contrast, according to the present invention, by setting the concentration of the solution within the above range, the organic solvent is less likely to volatilize in the spray nozzle, and the thickened state when the droplets land on the raw fiber. The ideal behavior can be easily realized.

  The raw fiber may be sprayed with the solution as it is, or may be sprayed with the web or fiber sheet. When contacting in the state of a web or a fiber sheet, you may perform a defibration process after that as needed.

  The hemagglutinating fiber of the present invention can be used, for example, in the form of a fiber stack formed by separately stacking the fibers, or can be used in the form of a fiber stack formed by mixing with other fibers. it can. In addition, the hemagglutinating fiber of the present invention can be used alone or mixed with other fibers and used in the form of a fiber sheet containing the hemagglutinating fiber. These piles and fiber sheets can be suitably used as constituent members of menstrual absorbent articles such as sanitary napkins. Below, an example of the absorbent article which has the member containing the hemagglutination fiber of this invention is demonstrated.

  A sanitary napkin 1 is shown in FIG. The napkin 1 has a longitudinal direction X corresponding to the wearer's front-rear direction and a transverse direction Y orthogonal thereto, and is disposed on the skin facing surface side of the absorbent body 4 and capable of absorbing menstrual blood. And a top sheet 2 that can come into contact with the wearer's skin when worn.

  In the present specification, the “skin-facing surface” is a surface of the absorbent article or a component thereof (for example, the absorbent body 4) that is directed toward the wearer's skin when the absorbent article is worn, that is, relative to the wearer's skin. The side close to the skin, and the “non-skin facing surface” is directed to the side opposite to the skin side when the absorbent article is worn, that is, the side that is relatively far from the wearer's skin. It is the surface to be. In addition, "at the time of wearing" said here means the state where the normal appropriate wearing position, that is, the correct wearing position of the absorbent article is maintained, and the absorbent article is in a state of being deviated from the wearing position. Is not included.

  The napkin 1 includes an absorbent main body 10 including a top sheet 2 that forms a skin facing surface, a back sheet 3 that forms a non-skin facing surface, and an absorbent body 4 interposed between both sheets 2 and 3. . The absorbent main body 10 is disposed on the abdomen side, that is, the front side of the wearer from the excretion part facing part B, which is an area disposed opposite to the wearer's liquid excretion part (such as the vaginal opening) when worn. The front portion A and the rear portion C arranged on the back side of the wearer, that is, the rear side of the excretory portion facing portion B are provided in the vertical direction X. That is, the napkin 1 or the absorbent main body 10 is divided into three regions of the front part A, the excretory part facing part B, and the rear part C in order from the wearer's stomach side in the longitudinal direction X. The longitudinal direction X coincides with the longitudinal direction of the napkin 1 and the absorbent main body 10, and the lateral direction Y coincides with the width direction orthogonal to the longitudinal direction of the napkin 1 and the absorbent main body 10.

  The top sheet 2 covers the entire skin facing surface of the absorbent body 4, and both side edges along the longitudinal direction X are substantially at the same position as both side edges along the longitudinal direction X of the absorbent body 4. On the other hand, the back sheet 3 covers the entire area of the non-skin facing surface of the absorbent body 4 and further extends outward in the lateral direction Y from both side edges along the longitudinal direction X of the absorbent body 4 to be described later. In addition, a side flap portion 10S is formed. The back sheet 3 and the side sheet 6 are joined to each other by known joining means such as an adhesive, heat seal, ultrasonic seal, and the like at the extended portions from both side edges along the longitudinal direction X of the absorber 4. Moreover, the surface sheet 2 and the back surface sheet 3 are joined to each other by a known joining means at the extending portions from both ends in the longitudinal direction X of the absorber 4. The top sheet 2 and the back sheet 3 may be bonded to the absorber 4 with an adhesive.

  As the top sheet 2 and the back sheet 3, various kinds of materials conventionally used for absorbent articles such as sanitary napkins can be used without particular limitation. For example, as the back sheet 3, a liquid hardly permeable and moisture permeable resin film, a laminated sheet of the resin film and a nonwoven fabric, or the like can be used. On the other hand, as the surface sheet 2, a single layer or multilayer nonwoven fabric, a perforated film, or the like can be used. The top sheet 2 can be coated with various oil agents for improving liquid permeability, for example, various surfactants. When the topsheet 2 has a multilayer structure, the topsheet 2 includes a first fiber layer located on the side close to the wearer's skin and a second fiber layer located on the side far from the wearer's skin. And both fiber layers are integrated in the thickness direction by a number of joints formed in part, and a portion of the first fiber layer located between the joints is convex. It is possible to use a concavo-convex sheet that protrudes and forms the concavo-convex convex portion. The convex portion of the concavo-convex sheet may have a solid structure that is entirely filled with fibers, or may have a hollow structure having a space inside. As the concavo-convex sheet in which the convex portion has a solid structure, for example, those described in Japanese Patent Application Laid-Open No. 2007-182626 and Japanese Patent Application Laid-Open No. 2002-187228 can be used.

  The top sheet 2 may be embossed. There is no restriction | limiting in particular in an embossing pattern, According to the specific use of the napkin 1, a various pattern can be formed. For example, a so-called round emboss having a closed shape along the periphery can be formed at a position inside the periphery of the absorbent body 4. In this round embossing, it is preferable that a portion corresponding to the side edge of the absorbent body 4 has a shape that bulges outward in the width direction of the absorbent body 4. This round embossing may be composed of an assembly of discontinuous embossing patterns within a range that can be considered continuous when viewed as a whole.

The absorbent main body 10 includes a second sheet 5. The second sheet 5 is liquid permeable and is disposed between the top sheet 2 and the absorber 4. The second sheet 5 is a constituent member of an absorbent article that is also called a sublayer sheet or the like in this technical field, and improves the permeability of the liquid from the top sheet 2 to the absorbent body 4, and the surface of the liquid absorbed by the absorbent body 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 skin facing surface of the absorbent body 4. As the second sheet 5, a hydrophilic nonwoven fabric or a hydrophilic fiber aggregate can be used. Examples of the nonwoven fabric include an air-through nonwoven fabric, a point bond nonwoven fabric, a resin bond nonwoven fabric, a spunlace nonwoven fabric, and an airlaid nonwoven fabric. The basis weight of the second sheet 5 is preferably 10 g / ^{m 2,} more preferably 15 g / ^{m 2} or more and, preferably 50 g / ^{m 2} or less, 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 skin facing surfaces of the absorbent main body 10, that is, both side portions along the longitudinal direction X of the skin facing surface of the topsheet 2, so as to overlap both left and right side portions along the longitudinal direction X of the absorbent body 4 in plan view. The side sheets 6 and 6 are arranged over substantially the entire length in the longitudinal direction X of the absorbent main body 10. The pair of side sheets 6 and 6 are joined to the top sheet 2 by a known joining means at joining lines 61 extending in the longitudinal direction X.

  In addition to the absorbent main body 10, the napkin 1 further includes a pair of wing portions 10 </ b> W and 10 </ b> W that extend outward in the lateral direction Y from both side portions along the vertical direction X of the excretory part facing portion B of the absorbent main body 10. have. That is, the napkin 1 has the absorptive main body 10 and a pair of wing parts 10W and 10W.

  When the napkin 1 has the wing part 10W, the excretion part opposing part B is a region having the wing part 10W in the longitudinal direction (X direction in the drawing) of the napkin 1 (along the longitudinal direction X of one wing part 10W). Means a region sandwiched between the base and the base along the longitudinal direction X of the other wing portion 10W. The excretion part facing part B when the napkin 1 does not have a wing part traverses the napkin 1 in the lateral direction (Y direction in the figure) generated when the napkin 1 is folded into a three-fold individual form. With respect to two fold lines (not shown), it means a region surrounded by a first fold line and a second fold line as counted from the front end in the longitudinal direction X of the napkin 1.

  The side flap portion 10 </ b> S projects greatly outward in the lateral direction Y at the excretory portion facing portion B, whereby a pair of wing portions 10 </ b> W and 10 </ b> W are provided on both left and right sides along the longitudinal direction X of the absorbent main body 10. It is extended. The wing portion 10W has a substantially trapezoidal shape in which the lower base (side longer than the upper base) is located on the side of the napkin 1 in a plan view as shown in FIG. The wing part adhesion part (not shown) which fixes the wing part 10W to clothes, such as shorts, is formed. The wing part 10W is folded and used on the non-skin facing surface (outer surface) side of the crotch part of clothes such as shorts. The wing adhesive section is covered with a release sheet (not shown) made of a film, nonwoven fabric, paper, or the like before use.

  The absorber 4 contains a superabsorbent polymer. The superabsorbent polymer contained in the absorbent body 4 is generally a particulate polymer, but may be a fibrous polymer. When the particulate superabsorbent polymer is used, the shape thereof may be any of a spherical shape, a block shape, a bowl shape, and an amorphous shape. As the superabsorbent polymer, generally, a polymer or copolymer of acrylic acid or an alkali metal acrylate can be used. Examples thereof include polyacrylic acid and salts thereof and polymethacrylic acid and salts thereof. As the polyacrylate and polymethacrylate, sodium salts can be preferably used. In addition, acrylic acid or methacrylic acid, maleic acid, itaconic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, 2-hydroxyethyl (meth) acrylate, styrenesulfonic acid, etc. It is also possible to use a copolymer obtained by copolymerizing the above-mentioned comonomer within a range that does not deteriorate the performance of the superabsorbent polymer.

  The absorber 4 further contains hydrophilic fibers in addition to the superabsorbent polymer. Examples of the hydrophilic fiber contained in the absorbent body 4 include those obtained by hydrophilizing hydrophobic fibers and those that are hydrophilic per se, and these are used alone or in combination of two or more. Can be used. Particularly preferred are those which are themselves hydrophilic and have water retention. Preferred examples of the latter hydrophilic fibers include natural fibers, cellulosic regenerated fibers, and semi-synthetic fibers. As the hydrophilic fiber, pulp and rayon are particularly preferable, and pulp is more preferable. In addition to wood pulp such as softwood kraft pulp and hardwood kraft pulp, pulp includes non-wood pulp such as cotton pulp and straw pulp, but is not particularly limited. Moreover, you may use the crosslinked cellulose fiber which bridge | crosslinked the molecule | numerator of the cellulose fiber and / or the molecule | numerator, and the bulky cellulose fiber obtained by carrying out the mercerization process of wood pulp.

  The absorber 4 can be embossed. Embossing may be performed only on the absorbent body 4 or may be performed together on the top sheet 2 and the absorbent body 4 described above. By embossing the top sheet 2 and the absorbent body 4 together, these members are joined at the embossed portion by thermal fusion and / or pressure bonding. When the above-described round embossing is performed on the top sheet 2, the round embossing can also be performed on the absorbent body 4 and the absorbent body 4 and the top sheet 2 can be joined by round embossing. .

  The absorbent body 4 includes an absorbent core composed of a lower absorbent core 41 and an upper absorbent core 42 containing hydrophilic fibers and a superabsorbent polymer. Specifically, the absorbent body 4 is superposed on the lower absorbent core 41 disposed opposite to the excretion part of the wearer when worn, and the lower absorbent core 41, and in the 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 periphery of the core 41. Here, the “periphery of the central absorbent sheet” 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 periphery of the lower absorbent core 41. Due to the absorber 4 having such a structure, the central portion in the lateral direction Y of the excretory portion-facing portion B is a so-called middle-high portion that is thicker than the peripheral portion. .

  The absorbent core composed of the lower absorbent core 41 and the upper absorbent core 42 is covered at least at the upper and lower surfaces thereof by a covering sheet (not shown). Preferably, the entire absorbent core is covered with a covering sheet. That is, in this embodiment, the absorber 4 has a structure in which an absorbent core containing a superabsorbent polymer and / or hydrophilic fibers is covered with a covering sheet. The covering sheet is liquid permeable. As an example of the covering sheet, a thin paper mainly composed of cellulose fibers, a non-woven fabric subjected to a hydrophilic treatment, or the like is used.

  The napkin 1 includes a hemagglutinating agent because any one of its constituent members includes a hemagglutinating fiber. The hemagglutinating fiber is advantageously present in the napkin 1 in such a manner as to come into contact with menstrual blood excreted by the napkin 1. From this point of view, the hemagglutinating fiber is preferably present on the skin facing surface side of the back sheet 3 or on the skin facing surface side of the back sheet 3, and the absorbent body 4 or the skin facing surface thereof. It is more preferable that it exists in the site | part of the surface side, and it is still more preferable that it exists in the site | part of the skin opposing surface side rather than the coating sheet (not shown) in the absorber 4. For example, the hemagglutinating fiber is any one member or any two of the covering sheet in the absorbent body 4, the top sheet 2, or the second sheet disposed between the covering sheet and the top sheet 2. It is preferable to be contained in the above members. When these members contain hemagglutinating fibers, the menstrual blood comes into contact with the hemagglutinating fibers before the menstrual blood reaches the absorbent core, which is the site containing the superabsorbent polymer. This is advantageous because it can cause aggregation of red blood cells in the menstrual blood before the menstrual blood reaches the absorbent core. Even when hemagglutinating fibers are included in the absorbent core, the agglutination effect of erythrocytes is observed. In particular, it is preferable to include hemagglutinating fibers in the cover sheet, the top sheet 2 and / or the second sheet 5 because the effect of erythrocyte aggregation is enhanced. When these sheets contain hemagglutinating fibers, the fibers may exist throughout the sheet, or may exist only in a part of the sheet.

Advantages of using a sheet containing hemagglutinating fibers as constituent members of various absorbent articles including the sanitary napkin 1 shown in FIG. 1 are as described below.
The absorption rate and absorption amount of moisture by the superabsorbent polymer vary depending on the type of moisture. When comparing physiological saline and blood, blood absorbs slower and absorbs less than physiological saline. As a result of various studies by the inventor on the reason, the following facts have been found. Blood is roughly divided into liquid components such as plasma and non-liquid components such as red blood cells, and the components absorbed by the superabsorbent polymer are liquid components such as plasma. As shown in FIG. 2 (a), when menstrual blood 11 comes into contact with superabsorbent polymer 14, only liquid component 12 in menstrual blood 11 is absorbed by superabsorbent polymer 14, and red blood cells that are non-liquid component 13 are high. It is not absorbed by the absorbent polymer 14. When the absorption of the liquid component 12 into the superabsorbent polymer 14 proceeds, the non-liquid component 13 that is not absorbed by the superabsorbent polymer 14 accumulates on the surface of the superabsorbent polymer 14 as shown in FIG. A film 15 is formed. Due to the formation of the coating film 15, the liquid absorption inhibition of the superabsorbent polymer 14 occurs, and the absorption rate decreases. In addition, due to the formation of the coating 15, swelling inhibition of the superabsorbent polymer 14 also occurs, and the amount of absorption decreases.

  As a result of various studies conducted by the present inventors on the means for preventing the phenomenon as shown in FIG. 2 (b) from occurring and preventing the decrease in absorption performance, a component occupying most of the non-liquid components in menstrual blood It has been found that it is effective to aggregate the erythrocytes as shown in FIG. By generating the erythrocyte aggregate 16, it becomes difficult to generate a film of the aggregate, or even if a film is generated by the aggregate, a space through which the liquid component 12 can permeate remains in the film. Absorption inhibition of component 12 is less likely to occur. As a result, the superabsorbent polymer 14 can sufficiently exhibit the original absorption performance. Thus, in order to further improve the absorption performance, the larger the aggregate particle size of red blood cells, the better, and the harder the aggregate hardness, the more preferable. Here, the absorption performance is expressed on the basis of the absorption amount and the absorption rate. The amount of absorption can be expressed as the ratio of the volume of the superabsorbent polymer 14 before absorption to the volume of the superabsorbent polymer 14 after absorption, that is, the volume swelling magnification described later. Further, the absorption rate can be expressed as the slope of the volume swell ratio of the superabsorbent polymer 14 over time.

  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 a hemagglutinating agent comprising a quaternary ammonium salt polymer, polydiallyldimethylammonium chloride, which is a water-soluble quaternary ammonium salt homopolymer (Nippon Lubrizol Co., Ltd., trade name “Mercoat 100”, weight average molecular weight 150,000). Was used. This was dissolved in ethanol to prepare a solution having a concentration of 5% and a viscosity of 10.4 mPa · s.
As the fiber, fibrillated pulp fiber having a beating degree of 550 ml was used. This pulp fiber was spray-coated with the above solution. The coating basis weight was 1.5 g / m ² . Ethanol was dried to obtain hemagglutinating fibers. The ratio of the hemagglutinating agent in the hemagglutinating fiber was 9%.

[Example 2]
As a hemagglutinating agent comprising a quaternary ammonium salt polymer, polymethacrylic acid dimethylaminoethyl diethyl sulfate (manufactured by Kao Corporation, weight average molecular weight 160,000), which is a water-soluble quaternary ammonium salt homopolymer, was used. . This was dissolved in ethanol to prepare a solution having a concentration of 5% and a viscosity of 5.5 mPa · s.
As the fiber, fibrillated pulp fiber having a beating degree of 550 ml was used. This pulp fiber was spray-coated with the above solution. The coating basis weight was 5 g / m ² . Ethanol was dried to obtain hemagglutinating fibers. The ratio of the hemagglutinating agent in this hemagglutinating fiber was 31%.

Example 3
As a hemagglutinating agent comprising a quaternary ammonium salt polymer, a water-soluble quaternary ammonium salt copolymer, poly [dimethylaminoethyldiethylsulfate methacrylate / methyl methacrylate] copolymer (manufactured by Kao Corporation, weight average) Molecular weight 350,000.) Was used. This was dissolved in water to prepare a solution having a concentration of 20% and a viscosity of 235 mPa · s.
This solution was applied to OHP paper (Kokuyo Co., Ltd., Recycled OHP film A4 size VF-1300N transparent) as a base material. The coating basis weight was 5 g / m ² .
As the fiber, fibrillated pulp fiber having a beating degree of 550 ml was used. This pulp fiber was arrange | positioned on the said base material, the pressure was applied, and the said solution impregnated in the base material was transcribe | transferred to the pulp fiber. As a result, hemagglutinating fibers were obtained. The ratio of the hemagglutinating agent in this hemagglutinating fiber was 31%.

[Reference Example 1]
In Example 1, a hemagglutinating agent was dissolved in deionized water to prepare a solution having a concentration of 5% and a viscosity of 18 mPa · s. Other than this, hemagglutinating fibers were obtained in the same manner as in Example 3. The ratio of the hemagglutinating agent in the hemagglutinating fiber was 9%.

[Reference Example 2]
In Example 2, a hemagglutinating agent was dissolved in ion-exchanged water to prepare a solution having a concentration of 5% and a viscosity of 18 mPa · s. Other than this, hemagglutinating fibers were obtained in the same manner as in Example 3. The ratio of the hemagglutinating agent in this hemagglutinating fiber was 31%.

[Reference Example 3]
In Example 3, the concentration of the hemagglutinating agent was lowered and the viscosity of the solution was 18 mPa · s. Other than this, hemagglutinating fibers were obtained in the same manner as in Example 3. The ratio of the hemagglutinating agent in this hemagglutinating fiber was 31%.

[Evaluation]
About the fiber obtained by the Example and the reference example, the fractal dimension of the fiber surface was calculated | required by the above-mentioned method. Further, the volume swelling ratio of the superabsorbent polymer was measured over time by the following method. The volume swelling ratio is a scale representing the amount of absorption of the superabsorbent polymer. The change with time of the volume swelling ratio is a measure of the release of the hemagglutinating agent from the fiber, and means that the hemagglutinating agent is gradually released as the volume swelling ratio increases even after the elapse of time. The results are shown in Table 1 below.

[Volume swelling ratio of superabsorbent polymer]
Wet paper making was carried out using the fibers obtained in Examples and Reference Examples as raw materials, respectively, to produce a 10 mm × 50 mm fiber sheet (basis weight 16 g / m ² ). After this fiber sheet was immersed in 1 g of simulated blood for 20 seconds, the fiber sheet was pulled up and again immersed in 1 g of simulated blood different from the previous one for 20 seconds. This dipping / pulling operation was repeated 10 times, the blood after each pulling was collected, and the superabsorbent polymer was swollen by the following procedure using each collected blood.
One superabsorbent polymer having a diameter of about 400 μm was placed on a glass slide, and 3 drops of each collected blood was dropped onto the superabsorbent polymer with a Pasteur pipette. Was absorbed and swollen. As the superabsorbent polymer, cross-linked sodium polyacrylate was used. After dripping the blood, the superabsorbent polymer was sealed using a small screw cap to prevent moisture transpiration. After 10 minutes, the lid was removed, and an excess amount of simulated blood was absorbed and removed using absorbent paper. Subsequently, the diameter of the superabsorbent polymer was measured with an optical microscope. When the diameter of the superabsorbent polymer before swelling is R ₁ (μm) and the diameter after swelling is R ₂ (μm), the volume swelling ratio is defined by (R ₂ / R ₁ ) ³ . The simulated blood was 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) as described in this specification. The blood cell / plasma ratio of defibrinated horse blood (manufactured by Nippon Biotest Co., Ltd.) was adjusted so that the obtained viscosity was 8 mPa · s.

  As is clear from the results shown in Table 1, the hemagglutinating fiber obtained in each example has a higher volume swelling ratio of the superabsorbent polymer from the first contact with simulated blood than in the reference example. It can also be seen that the volume swelling ratio is difficult to decrease over time.

1 Sanitary napkin (absorbent article)
2 Top 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 Superabsorbent polymer 15 Coating 16 Agglomerate

Claims (10)

A hemagglutinating fibers have a hemagglutination agent on the fiber surface, hemagglutinating fractal dimension of the fiber surface viewed blood lymphocytes coherent fibrous from a direction perpendicular to the longitudinal direction is 1.0 90 0 or more fiber.   The hemagglutinating fiber according to claim 1, wherein the fiber is a hydrophilic fiber.   The hemagglutinating fiber according to claim 1 or 2, wherein the fiber is fibrillated. The hemagglutinating fiber according to claim 1 or 2, wherein the beating degree of the fiber is 780 ml or less.   A fiber sheet comprising the hemagglutinating fiber according to any one of claims 1 to 4.   An absorbent article comprising the hemagglutinating fiber according to any one of claims 1 to 4 or the fiber sheet according to claim 5.   A step of bringing a base material impregnated with a solution containing a hemagglutinating agent and having a viscosity of 100 mPa · s or more into contact with a dried raw material fiber, and then peeling the raw material fiber from the base material A method for producing a hemagglutinating fiber, comprising:   The manufacturing method according to claim 7, wherein the substrate is hydrophilic. A method for producing a hemagglutinating fiber comprising a step of spraying a solution containing a hemagglutinating agent on a raw fiber ,
The solution comprises an organic solvent or comprises an organic solvent and water;
A method for producing a hemagglutinating fiber, wherein the viscosity of the solution at the time of spraying is 3 mPa · s or more . The manufacturing method according to any one of claims 7 to 9 , wherein the raw fiber is a cellulose fiber.