JP6220947B1 - Sanitary items - Google Patents

Abstract

[Problem] To provide a sanitary product that has excellent menstrual blood absorption performance and has less redness due to menstrual blood absorption when observed from the surface sheet side after use, and can give the wearer a sense of security with respect to the absorption performance. thing. SOLUTION: A sanitary product 1 is disposed between a liquid-permeable top sheet 2, a back sheet 3 disposed farther from the wearer's skin than the top sheet 2, and both sheets 2. The laminated structure 4 is provided. The laminated structure 4 includes a separating layer 41, a hemagglutinating agent layer 42, an aggregation promoting layer 43 and an absorbing layer 44 in the order closer to the top sheet 2. The hemagglutinating agent layer 42 does not contain a superabsorbent polymer but contains a hemagglutinating agent, and the absorbing layer 44 does not contain a hemagglutinating agent. The isolation layer 41 and the aggregation promoting layer 43 each contain fibers and do not contain a hemagglutinating agent and a superabsorbent polymer. [Selection] Figure 2

Description

  The present invention relates to a sanitary product used for absorption of menstrual blood.

  As a typical structure of a sanitary product used during menstruation such as a sanitary napkin, a liquid-permeable top sheet, a back sheet placed farther from the wearer's skin than the top sheet, and between the two sheets Are known, and hydrophilic fibers, superabsorbent polymers, and the like are used as a material for forming the absorber.

  A sanitary product has a high menstrual blood absorption capability, and it is desired to quickly absorb menstrual blood excreted on the top sheet into the absorbent body inside the article. However, menstrual menstrual blood may contain components such as endometrium, and is difficult to absorb because it has a higher viscosity than urine, which is the main absorption target of disposable diapers. Blood is not absorbed and remains on the top sheet, which may give the wearer a sticky feeling.

  In Patent Document 1, for the purpose of improving the menstrual blood absorption performance of sanitary products, a specific water-soluble property comprising a specific quaternary ammonium salt homopolymer or quaternary ammonium salt copolymer together with a superabsorbent polymer. It is described that a cationic polymer is used in combination. According to Patent Document 1, red blood cells in menstrual blood are aggregated by the action of this specific water-soluble cationic polymer, thereby effectively preventing swelling of the superabsorbent polymer by red blood cells. It is said that an improvement in blood absorption rate and absorption amount is realized.

  In addition, when the sanitary product surface sheet is normally white when not used, the user of the sanitary product can absorb menstrual blood when the sanitary product removed after use is viewed from the surface sheet side. As the resulting redness is less and the color of the topsheet is closer to the original white color, the absorption performance of the sanitary product tends to be more reliable and secure. Therefore, sanitary products are desired to have excellent surface whiteness after use.

Patent Document 2 discloses that a sanitary product can be given a sense of security with respect to the performance of the sanitary product when the menstrual blood absorbed by the sanitary product is confirmed when the sanitary product is replaced. The first sheet having liquid permeability and liquid holding ability in the order close to the surface sheet between the body and the body, and having the liquid permeability but not liquid holding ability, has been absorbed by the absorber. A document in which a second sheet for hiding the red color of blood is interposed is described. Patent Document 2 discloses that this sanitary product has a kinematic viscosity of 0.01 to 80 mm ² / s at 40 ° C., a water retention of 0.01 to 4.0% by mass, and a weight average molecular weight of less than 1000. And applying a blood slipperiness-imparting agent having an IOB of 0.00 to 0.60, and a surface sheet is exemplified as the application site ([0274] of Patent Document 2). According to Patent Document 2, since this blood slipperiness-imparting agent has a function of lowering the viscosity and surface tension of menstrual blood, a sanitary product to which the blood slipping agent is applied promptly passes menstrual blood from the surface sheet to the absorber. It can be migrated.

JP, 2006-107100, A JP 2014-68945 A

  By applying a so-called blood modifying agent such as a specific water-soluble cationic polymer described in Patent Document 1 or a blood slipperiness imparting agent described in Patent Document 2 to a sanitary product used for absorption of menstrual blood, Expected to improve blood absorption performance. However, depending on the type of blood modifying agent and the application site, absorption inhibition of the superabsorbent polymer may occur, leading to a decrease in absorption performance, or redness of the surface sheet of sanitary products after use. The appearance may be degraded. In particular, the sanitary product described in Patent Document 2 that uses surface whiteness after use as an effect can exhibit certain effects in menstrual blood absorption performance and surface whiteness after use, but there is still room for improvement. Moreover, since the sanitary product described in Patent Document 2 applies the blood slipperiness-imparting agent to the surface sheet that can come into contact with the skin of the wearer, there is a concern that the blood slipperiness-imparting agent may adhere to the skin and cause skin troubles. Is done.

  An object of the present invention relates to providing a sanitary product that is excellent in menstrual blood absorption and has less redness due to absorption of menstrual blood when observed from the surface sheet side after use.

The present invention is a sanitary product comprising a liquid-permeable top sheet, a back sheet disposed farther from the wearer's skin than the top sheet, and a laminated structure interposed between the two sheets. And
The laminated structure comprises a separating layer, a hemagglutinating agent layer, an aggregation promoting layer, and an absorbing layer in the order close to the top sheet,
The hemagglutinating agent layer contains a hemagglutinating agent without containing a superabsorbent polymer, and the absorbing layer does not contain a hemagglutinating agent,
The isolation layer and the aggregation-promoting layer each provide a sanitary product that contains fibers and does not contain a hemagglutinating agent and a superabsorbent polymer.

  ADVANTAGE OF THE INVENTION According to this invention, when it observes from the surface sheet side after use, it is excellent in the blood absorption capability, and the sanitary product with few redness resulting from absorption of menstrual blood is provided.

FIG. 1 is a plan view schematically showing a skin facing surface side (surface sheet side) of an example of a sanitary napkin that is an embodiment of the sanitary product of the present invention. FIG. 2 is a cross-sectional view schematically showing a cross section taken along line II of FIG. FIG. 3A and FIG. 3B are schematic views showing a menstrual blood absorption mechanism in a conventional sanitary product. FIG. 4 is a schematic diagram showing a menstrual blood absorption mechanism in the sanitary product of the present invention. FIG. 5 is a view corresponding to FIG. 2 (a cross-sectional view in the transverse direction along the thickness direction) of another embodiment of the sanitary product of the present invention.

  Hereinafter, a sanitary product of the present invention will be described based on preferred embodiments with reference to the drawings. 1 and 2 show a sanitary napkin 1 which is an embodiment of the sanitary product of the present invention. As shown in FIG. 1, the napkin 1 has a longitudinal direction X corresponding to the wearer's front-rear direction, extending from the wearer's abdomen side to the back side via the crotch portion, and a transverse direction Y orthogonal thereto. And an intermediate part M including a part facing the excretion part (vaginal opening or the like) of the wearer when worn, that is, an excretion part facing part, and positioned on the front side of the wearer on the abdomen side (front side) of the wearer. The front part F is divided into a rear part R positioned behind the intermediate part M and disposed on the back side (rear side) of the wearer. The excretory part-facing part is located at the center part in the lateral direction Y of the intermediate part M.

  As shown in FIG. 1, the napkin 1 extends outward in the lateral direction Y from the absorbent main body 10 having a shape that is long in the vertical direction X, and both side portions along the vertical direction X of the intermediate part M in the absorbent main body 10. It has a pair of wing portions 10W and 10W that come out. A wing adhesive portion (not shown) that fixes the wing 10W to clothes such as shorts is formed on the non-skin facing surface of the wing 10W. 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.

  When the sanitary product has a wing portion like the napkin 1, the intermediate portion M in the sanitary product of the present invention has a longitudinal direction X of the wing portion in the longitudinal direction (longitudinal direction, X direction in the figure) of the sanitary product. In the napkin 1 as an example, the pair of wing portions 10W and 10W are connected to each other in the longitudinal direction X by connecting the roots on the front side in the lateral direction. A virtual straight line extending in the Y direction is the front end of the intermediate part M, and a virtual straight line connecting the roots on the rear side and extending in the lateral direction Y is the rear end of the intermediate part M. Moreover, the intermediate part in the sanitary product which does not have a wing part is produced when the sanitary product is folded into the individual form, and the sanitary product crosses the sanitary product in the lateral direction (width direction, Y direction in the figure). About a fold line, the area | region enclosed by the 1st fold line and the 2nd fold line is counted from the front end of the vertical direction of this sanitary product.

  The absorbent main body 10 includes a liquid permeable top sheet 2, a back sheet 3 disposed farther from the wearer's skin than the top sheet 2, and a laminated structure disposed between both sheets 2 and 3. 4. The top sheet 2 and the back sheet 3 may be bonded to the laminated structure 4 with an adhesive. The absorbent main body 10 is divided into three regions of a front part A, an intermediate part M, and a 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 transverse direction Y coincides with the width direction orthogonal to the longitudinal direction.

  In the napkin 1, the left and right sides along the longitudinal direction X of the laminated structure 4 in a plan view as shown in FIG. 1 on both side portions along the longitudinal direction X of the skin facing surface of the absorbent main body 10, that is, the skin facing surface of the topsheet 2. A pair of side sheets 6, 6 are arranged over substantially the entire length in the longitudinal direction X of the absorbent main body 10 so as to overlap the part. The pair of side sheets 6 and 6 are joined to the topsheet 2 via linear joining portions 7 that are arranged at positions overlapping the laminated structure 4 in plan view and extend in the longitudinal direction X, respectively. The members arranged on the napkin 1 at the position closest to the skin of the wearer are the surface sheet 2 at the central portion in the lateral direction Y of the napkin 1 and the side sheets 6 at both sides thereof. May contact the wearer's skin. Each of the top sheet 2, the back sheet 3 and the side sheet 6 extends from the peripheral edge of the laminated structure 4, and at the end portions of at least two sheets of the extended portions, known adhesives, heat seals, and the like The end seal portion 8 is formed by being joined to each other by the joining means. A leak-proof groove in which the top sheet 2 and at least a part of the layers constituting the laminated structure 4 (isolation layer 41 closest to the top sheet 2) are integrally recessed on the skin facing surface of the napkin 1 (Not shown) may be provided.

  In the present specification, the “skin-facing surface” refers to a surface of the sanitary product or a component thereof (for example, the surface sheet 2) that is directed toward the wearer's skin when the sanitary product is worn, that is, relative to the wearer's skin. “Non-skin facing surface” is the near side, and the surface of the sanitary product or a component thereof facing the opposite side (clothing side) when the sanitary product is worn, that is, relatively from the skin of the wearer On the far side. In addition, "when wearing" here means a state in which a normal proper wearing position, that is, a correct wearing position of the sanitary product is maintained, and includes when the sanitary product is in a state of being deviated from the wearing position. Absent.

  The top sheet 2 is a liquid-permeable sheet that can be used without particular limitation for various types of absorbent articles such as sanitary napkins and disposable diapers, and can permeate bodily fluids such as menstrual blood. As a premise, a woven or non-woven fabric made of a synthetic fiber or natural fiber, a porous sheet, or the like can be used. As an example of the surface sheet 2, a non-woven fabric made of natural fibers such as cotton or a non-woven fabric made of various synthetic fibers subjected to hydrophilic treatment can be used. For example, a core-sheath structure type (including side-by-side type) composite fiber using polypropylene or polyester as the core component and polyethylene as the sheath component is made into a web by carding, and then nonwoven fabric (after this is opened at a predetermined location) by the air-through method That may be treated). From the viewpoint of high liquid permeability (dry feeling), an apertured sheet made of polyolefin such as low density polyethylene can also be preferably used.

  As the back sheet 3, various materials conventionally used for absorbent articles such as sanitary napkins and disposable diapers can be used without any particular limitation, and are hardly liquid permeable (including water repellency) and moisture permeable. Are preferably used. Specifically, in order to obtain sufficient water vapor permeability, a porous film having a fine hole formed by stretching a film made of a synthetic resin such as polyethylene in which fine powder made of a filler such as calcium carbonate is dispersed is a back sheet. 3 can be suitably used. As the side sheet 6, what can be used as the back sheet 3 can be used.

  The laminated structure 4 has a shape that is long in the longitudinal direction X in a plan view as shown in FIG. 1, and is arranged between the top sheet 2 and the back sheet 3 with its longitudinal direction coinciding with the longitudinal direction X. The laminated structure 4 is disposed at least in the intermediate part M which is a part facing the excretion part (such as the vaginal opening) of the wearer of the napkin 1. As shown in FIG. 1, the laminated structure 4 in the napkin 1 is continuous over the entire length in the longitudinal direction X of the intermediate part M, and further extends from the intermediate part M to the front part F and the rear part R, respectively. It occupies most of the total length of 10 longitudinal directions X.

  In the napkin 1, as shown in FIG. 2, in the napkin 1, the entire areas of the skin facing surface and the non-skin facing surface are covered with a covering sheet 5 that is separate from each layer constituting the laminated structure 4. . The covering sheet 5 serves to prevent leakage of the superabsorbent polymer particles and the like that can be included in the laminated structure 4 to the outside, and to increase the shape retention of the laminated structure 4. The covering sheet 5 in the napkin 1 is a single continuous liquid-permeable sheet having a width that is not less than 2 times and not more than 3 times the length of the laminated structure 4 in the lateral direction Y. As shown in FIG. 4 that covers the entire area of the skin facing surface 4 (the skin facing surface of the isolation layer 41) and extends outward from both side edges along the longitudinal direction X of the laminated structure 4 in the lateral direction Y. It is rolled down below the structure 4 to cover the entire area of the non-skin facing surface of the laminated structure 4 (the non-skin facing surface of the absorbent layer 44). The covering sheet 5 may not be such a single sheet. For example, one skin-side covering sheet that covers the skin-facing surface of the laminated structure 4 and the skin-side covering sheet are separate from each other. Moreover, you may be comprised including the non-skin side coating sheet which coat | covers the non-skin opposing surface of the laminated structure 4. FIG. The laminated structure 4 and the covering sheet 5 may be joined by a known joining means such as a hot melt adhesive.

The covering sheet 5 is preferably a liquid-permeable sheet that can permeate body fluid such as menstrual blood. For example, paper, woven fabric, nonwoven fabric, or the like made of synthetic fiber or natural fiber can be used. The thickness of the coating sheet 5 under a load of 0.5 g / cm ² is not particularly limited, but is usually smaller than the thickness of each layer constituting the laminated structure 4 under a load of 0.5 g / cm ² . From the viewpoint of the balance between liquid permeability and sheet strength, it is preferably 0.01 mm or more, more preferably 0.5 mm or more, and preferably 8 mm or less, more preferably 3 mm or less. The thickness of the sheet can be measured according to a method for measuring the thickness of the layer described later.

  As shown in FIG. 2, the laminated structure 4 includes an isolation layer 41, a hemagglutinating agent layer 42, an aggregation promoting layer 43, and an absorption layer 44 in order from the top sheet 2. That is, in the laminated structure 4, the isolation layer 41 is closest to the skin of the wearer of the napkin 1, and the absorption layer 44 is farthest from the wearer's skin. The hemagglutinating agent layer 42 is adjacent to the isolation layer 41 located on the skin surface side and the aggregation promoting layer 43 located on the non-skin surface side. It is preferable that no other layers other than these four layers are interposed between the layers in the laminated structure 4. Further, in the napkin 1, the four layers constituting the laminated structure 4 are simply overlapped and are not joined to each other by a joining means such as an adhesive or fusion, but the liquid permeability in the thickness direction The layers may be joined to each other as long as they do not interfere with the above.

  In the napkin 1, the four layers constituting the laminated structure 4 have the same shape and the same size in plan view, and the entire area of the surface facing the other layers in each of the four layers is covered with the other layers. Yes. The four layers constituting the laminated structure 4 are separated in the thickness direction without contacting the other two layers arranged on one side and the other side in the thickness direction of the napkin 1 with the layer interposed therebetween. Can do. That is, for example, the hemagglutinating agent layer 42 separates the isolation layer 41 and the aggregation promoting layer 43 adjacent to the hemagglutinating agent layer 42 in the thickness direction without contacting each other in the thickness direction. Separates the covering sheet 5 adjacent to the isolation layer 41 and the hemagglutinating agent layer 42 in the thickness direction without contacting each other. In order to achieve the effects of the present invention, the laminated structure according to the present invention only needs to have such a configuration at least in part, and such a configuration is not necessarily required for the entire laminated structure 4 like the napkin 1. There is no need to be.

  As one of the main features of the napkin 1, the hemagglutinating agent layer 42 of the four layers constituting the laminated structure 4 contains a hemagglutinating agent without containing a superabsorbent polymer (water-absorbing polymer) and absorbs it. The layer 44 does not contain a hemagglutinating agent. The absorbent layer 44 preferably contains a superabsorbent polymer, and is made as such in the napkin 1. The superabsorbent polymer plays a role in absorbing and holding body fluids such as menstrual blood, and is a member that forms the basis of the absorption performance of the napkin 1, and usually includes a hydrogel material capable of absorbing and holding moisture. Is done. On the other hand, the hemagglutinating agent means an agent capable of aggregating red blood cells in blood, and more specifically, a compound that meets the definition described later. Thus, in the laminated structure 4 arranged between the top sheet 2 and the back sheet 3, the hemagglutinating agent is arranged on the hemagglutinating agent layer 42 that is relatively close to the wearer's skin, and the wearer relatively By disposing the hemagglutinating agent in the absorption layer 44 far from the skin of the skin, preferably by arranging a superabsorbent polymer, the hemagglutinating agent of the hemagglutinating agent layer 42 that comes into contact with the body fluid prior to the absorbing layer 44 acts. In addition, the liquid absorption amount of the absorption layer 44 (when a superabsorbent polymer is arranged in the absorption layer 44, the liquid absorption amount of the superabsorbent polymer) can be improved. Hereinafter, with reference to FIG.3 and FIG.4, the effect of the hemagglutinating agent in the laminated structure 4 is demonstrated.

  In general, the absorption rate and amount of moisture absorbed by a superabsorbent polymer differ depending on the type of moisture, and when comparing saline (urine) and blood, blood absorbs slower than saline, Absorption is low. The reason is as follows. 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. 3 (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 by the inventor on the means for preventing the phenomenon as shown in FIG. 3B and preventing the decrease in absorption performance, most of the non-liquid component 13 in the menstrual blood 11 is obtained. It has been found that it is effective to agglomerate erythrocytes, which are components, to produce aggregate 16 as shown in FIG. By generating the erythrocyte aggregate 16, it becomes difficult to form a coating film of the aggregate 16, or even if the coating film 15 as shown in FIG. Since there remains a space through which the component 12 can permeate, absorption inhibition of the liquid component 12 is difficult to occur. As a result, the superabsorbent polymer 14 can sufficiently exhibit the 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.

  In the napkin 1, the hemagglutinating agent plays a role in generating an aggregate of red blood cells during menstrual blood. When this hemagglutinating agent comes into contact with menstrual blood, the hemagglutinating agent is eluted in menstrual blood, and anionic red blood cells contained in menstrual blood are aggregated to form a hemagglutinated clot, thereby altering menstrual blood. The hemagglutination resulting from the hemagglutination effect is larger than the red blood cells, so even though the hemagglutination may adhere to a part of the surface of the superabsorbent polymer, most of the surface of the superabsorbent polymer is hemagglutinated. The inconvenience of being covered with a lump is unlikely to occur, so that the absorption performance inherent to the superabsorbent polymer is stably exhibited.

  According to the knowledge of the present inventor, a cationic polymer is particularly useful as a hemagglutination agent for the following reason. 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. Furthermore, 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, it becomes possible to produce an aggregate of red blood cells during menstrual blood by the above mechanism of action.

  In the napkin 1, the hemagglutinating agent having such an effect is contained in the hemagglutinating agent layer 42 in the laminated structure 4 as described above, and is not contained in the absorbing layer 44 containing the superabsorbent polymer. . During wearing of the napkin 1 having such a configuration, menstrual blood excreted from the excretion part of the wearer to the intermediate part M sequentially passes through the top sheet 2 and the covering sheet 5 to reach the laminated structure 4, and further to the isolation layer 41, reaches the hemagglutinating agent layer 42, and contacts the hemagglutinating agent in the hemagglutinating agent layer 42. Thereby, menstrual blood is separated into red blood cells and plasma. The red blood cells that are hardly absorbed by the superabsorbent polymer form aggregates and remain in the hemagglutinating agent layer 42, and the plasma that is easily absorbed by the superabsorbent polymer diffuses in the plane direction in the hemagglutinating agent layer 42. However, it passes through the aggregation promoting layer 43 to reach the absorption layer 44 and is absorbed and held by the superabsorbent polymer contained in the absorption layer 44. In this way, the napkin 1 passes through the hemagglutinating agent contained therein at a position closer to the wearer's skin (hemagglutinating agent layer 42) than the absorbing layer 44 containing the superabsorbent polymer. The blood is separated into red blood cells and plasma, and only the separated plasma is preferentially drawn into the absorption layer 44 to be absorbed and held in the superabsorbent polymer. Therefore, the absorption layer 44 inhibits absorption by the red blood cells. The menstrual blood can be quickly absorbed without receiving, and the dry feeling of the topsheet 2 can be greatly improved.

  As described above, the laminated structure 4 mainly has a hemagglutinating agent layer 42 and an absorbing layer 44 that does not contain a hemagglutinating agent and preferably contains a superabsorbent polymer. Although the improvement is achieved, the two layers 42 and 44 alone do not provide the predetermined effect of the present invention, and the two layers 42 and 44 are closer to the wearer's skin than both the layers 42 and 44, and both layers. An aggregation promoting layer 43 disposed between 42 and 44 is required.

  In order to give the wearer who observes the napkin 1 from the side of the top sheet 2 after using the napkin 1 in order to give a sense of security to the absorption performance of the napkin 1, redness caused by absorption of menstrual blood on the top sheet 2 at the time of observation. It is important that the surface layer 2 has a color close to the original color (usually white), but the isolation layer 41 mainly plays a role of reducing redness during the observation. That is, as described above, red blood cell aggregates are generated in the hemagglutinating agent layer 42. The aggregates are the main factor that the topsheet 2 is reddish, and the position of the aggregates is close to the topsheet 2. The redness of the surface sheet 2 after use of the napkin 1 becomes stronger, and the appearance of the napkin 1 deteriorates. Therefore, the napkin 1 contains fibers and does not contain a hemagglutinating agent and a superabsorbent polymer between the surface sheet 2 to be observed and the hemagglutinating agent layer 42 in which a red aggregate is generated. By interposing the isolation layer 41, the degree of redness through the surface sheet 2 of the hemagglutinating agent layer 42 that has become red due to contact with menstrual blood is reduced, whereby the use of the napkin 1 is reduced. The wearer who observed the surface sheet 2 later gives an impression of less redness due to absorption of menstrual blood, and gives the wearer a sense of security with respect to absorption performance. That is, the isolation layer 41 in the laminated structure 4 is a layer that literally isolates the hemagglutinating agent layer 42 from the topsheet 2.

  The aggregation promoting layer 43 plays a role of promoting the formation of aggregates in the hemagglutinating agent layer 42 and further enhancing the improvement effect of menstrual blood absorption by the hemagglutinating agent. That is, in order to maximize the absorption performance of the superabsorbent polymer that is preferably contained in the absorption layer 44, before the non-liquid components such as red blood cells that can inhibit the absorption performance reach the absorption layer 44. In addition, it is important to agglomerate the non-liquid component. Therefore, in the napkin 1, the hemagglutination layer 43 containing fibers and not containing the hemagglutinating agent is interposed between the hemagglutination agent layer 42 and the absorption layer 44 containing the superabsorbent polymer, thereby allowing hemagglutination. The menstrual blood aggregation time by the hemagglutinating agent in the agent layer 42 is increased, and the action effect of the hemagglutinating agent is utilized to the maximum so that excellent absorption performance for menstrual blood can be expressed. That is, the aggregation promoting layer 43 in the laminated structure 4 is a layer that literally promotes aggregation of non-liquid components in the body fluid by the hemagglutinating agent.

  According to the napkin 1 having the laminated structure 4 having the above-described configuration, body fluid such as menstrual blood hardly stays in a portion corresponding to the excretion portion of the wearer and its peripheral portion, and the amount of excreted body fluid is relatively small. Even if there are many cases, this can be quickly absorbed, so-called liquid return in which the body fluid once absorbed in the absorption layer 44 returns to the top sheet 2 side, or so-called remaining soup in the top sheet 2 without absorbing body fluid. Liquid residue is effectively prevented. In addition, since the liquid component in menstrual blood such as plasma is efficiently absorbed by the absorption layer 44, the occurrence of inconveniences such as transpiration of the liquid component, stuffiness and skin fog due to the liquid component is effectively prevented. In addition, when the napkin 1 is observed from the surface sheet 2 side after use, there is little redness due to absorption of menstrual blood, and a sense of security with respect to absorption performance can be given to the wearer.

Hereinafter, each layer which comprises the laminated structure 4 is demonstrated.
The isolation layer 41 contains fibers and is typically made of a fiber assembly. The content of the fibers in the isolation layer 41 is preferably 50% by mass or more and 100% by mass with respect to the total mass of the isolation layer 41. As the fiber aggregate constituting the isolation layer 41, a sheet-like fiber aggregate having a liquid permeability capable of permeating body fluid such as menstrual blood in the thickness direction can be arbitrarily adopted. For example, the fiber aggregate can be obtained by nonwoven fabric or wet papermaking. Paper. Examples of the nonwoven fabric that can be used as the isolation layer 41 include air-through nonwoven fabric, air-laid nonwoven fabric, suction heat bond nonwoven fabric, spunlace nonwoven fabric, spunbond nonwoven fabric, meltblown nonwoven fabric, and chemical bond nonwoven fabric. From the viewpoint of maintaining the thickness in order to maintain the distance from the hemagglutinating agent layer 42, an air-through nonwoven fabric is preferably used as the isolation layer 41.

  Constituent fibers of the isolation layer 41 include wood fibers such as softwood and hardwood pulp, natural fibers such as non-wood pulp; modified pulps such as cationized pulp and mercerized pulp; regenerated fibers such as cupra and rayon; acetates and the like Semi-synthetic fibers; synthetic fibers made of synthetic resins such as polyethylene and polyethylene terephthalate can be used, and one of these can be used alone or in combination of two or more. The constituent fibers of the isolation layer 41 may be short fibers or long fibers, and core-sheath type or side-by-side type composite fibers, split fibers, irregular cross-section fibers, heat-shrinkable fibers, and the like can also be used.

  The isolation layer 41 is preferably mainly composed of hydrophilic fibers. As the hydrophilic fiber, in addition to the inherently hydrophilic fiber such as a natural fiber, a hydrophobic fiber (for example, a fiber made of a thermoplastic resin) subjected to a hydrophilization treatment can also be used. Examples of the fibers include fibers in which a hydrophilizing agent is kneaded, fibers having a hydrophilizing agent attached to the fiber surface, and fibers subjected to plasma treatment. The content of the hydrophilic fiber in the isolation layer 41 is preferably 50% by mass or more and may be 100% by mass with respect to the total mass of the isolation layer 41.

  As described above, the isolation layer 41 does not contain a hemagglutinating agent and a superabsorbent polymer. That is, although the hemagglutinating agent and the superabsorbent polymer are not intentionally contained in the isolation layer 41, both may be included in the isolation layer 41 unintentionally at the time of manufacture. In that case, the contents of the hemagglutinating agent and the superabsorbent polymer in the isolation layer 41 are very small, and are acceptable as long as they do not depart from the spirit of the present invention. Specifically, if the content of the hemagglutinating agent in the isolation layer 41 is 3% by mass or less, it can be said that “the isolation layer 41 does not contain the hemagglutinating agent”. Moreover, if content of the superabsorbent polymer in the isolation layer 41 is 3 mass% or less, it can be said that "the isolation layer 41 does not contain a superabsorbent polymer."

  The hemagglutinating agent layer 42 contains a hemagglutinating agent without containing a superabsorbent polymer. Here, the meaning of “not containing a superabsorbent polymer” is as described above. The hemagglutinating agent will be described later.

  The hemagglutinating agent layer 42 contains fibers and typically consists of a fiber assembly. As the fiber aggregate and the constituent fibers constituting the hemagglutinating agent layer 42, those usable for the isolation layer 41 can basically be arbitrarily adopted. A pulp fiber aggregate is preferably used as the hemagglutinating agent layer 42 from the viewpoint that the hemagglutinating agent can be efficiently impregnated and eluted efficiently.

  The hemagglutinating agent layer 42 can be produced by applying a hemagglutinating agent to a fiber assembly that does not contain the hemagglutinating agent. The method for applying the hemagglutinating agent is not particularly limited. For example, a coating solution is prepared by dissolving the hemagglutinating agent in an appropriate solvent (for example, ethanol), and the coating solution is formed into a sheet form constituting the hemagglutinating agent layer 42. The hemagglutinating agent layer 42 is obtained by applying or spraying on one or both sides of the fiber assembly and drying.

The hemagglutinating agent contained in the hemagglutinating agent layer 42 dissolves in blood and acts reliably to form a large aggregate, and the content thereof is preferably 0.01 g / m ² or more. More preferably, it is 1.5 g / m ² or more. Further, hemagglutination agent contained in the blood cell aggregating agent layer 42, from the viewpoint of not inhibiting the liquid-permeable, its content is preferably 20 g / m ^2, more preferably not more than 10 g / m ^2.

  Similar to the isolation layer 41, the aggregation promoting layer 43 contains fibers and does not contain a hemagglutinating agent and a superabsorbent polymer. The meaning of “not containing a hemagglutinating agent and a superabsorbent polymer” here is as described above.

  The aggregation promoting layer 43 contains fibers and is typically made of a fiber assembly. As the fiber aggregate and constituent fibers constituting the aggregation promoting layer 43, those usable for the isolation layer 41 can basically be arbitrarily adopted. The composition of the aggregation promoting layer 43 may be the same as the composition of the isolation layer 41. From the viewpoint of maintaining the thickness in order to promote aggregation, an air-through nonwoven fabric is preferably used as the aggregation promoting layer 43.

Regarding the isolation layer 41, the hemagglutinating agent layer 42, and the aggregation promoting layer 43, aggregation of the non-liquid component in the body fluid by the hemagglutinating agent of the hemagglutinating agent layer 42 is promoted, and the liquid component in the body fluid is released from the skin of the wearer. It is preferable to control characteristics such as density and thickness so that the absorption layer 44 can be quickly transferred to the farthest absorption layer 44.
Specifically, for example, the density of the isolation layer 41 is preferably the same as or lower than the density of the aggregation promoting layer 43. Thereby, in the isolation layer 41, since the isolation layer 41 may have a relatively low density, that is, the constituent fibers may be sparse, an improvement in liquid permeability can be expected. Further, in the aggregation promoting layer 43, since the aggregation promoting layer 43 can be relatively dense, that is, the constituent fibers can be dense, liquid convection occurs in the aggregation promoting layer 43, that is, body fluid such as menstrual blood is caused by gravity. In addition to flowing unilaterally toward the absorbing layer 44 side, it can flow toward the hemagglutinating agent layer 42 side against gravity, and as a result, formation of aggregates in the aggregation promoting layer 43 is promoted. Become so.

The ratio between the density of the isolation layer 41 and the density of the aggregation promoting layer 43 is preferably 0.1 or more, more preferably 0.2 or more, and preferably 0.7 or less, more preferably 1 as the former / the latter. It is as follows.
The density of the isolation layer 41 is preferably 0.01 g / m ³ or more, more preferably 0.02 g / m ³ or more, and preferably 0.5 g / m ³ or less, more preferably 0.2 g / m ³ or less. It is.
The density of the aggregation promoting layer 43 is preferably 0.01 g / m ³ or more, more preferably 0.02 g / m ³ or more, and preferably 0.5 g / m ³ or less, more preferably 0.2 g / m ^3. It is as follows.
The density of each layer in the laminated structure 4 is measured by the following method.

<Measurement method of layer density>
In sanitary products, if the layer to be measured (laminated structure) is bonded to another component with an adhesive such as a hot melt adhesive, the adhesive is invalidated using an organic solvent or cold spray. Then, the sanitary product is disassembled so that the shape of the layer to be measured is not deformed, and the layer is taken out. The layer to be measured taken out from the sanitary product is cut into a 5 cm square to obtain a sample, the weight (A) of the sample having an area of 25 cm ² is measured, and the thickness (X) is measured by the method described later. The volume (Y) is calculated from the thickness and area, and the density (Z) of the layer is calculated by the following equation. Z (g / cm ³ ) = A (g) / Y (cm ³ )

The thickness of 0.5 g / cm ² under a load of isolation layer 41 is preferably equal to or greater than the thickness of 0.5 g / cm ² under a load of hemagglutination agent layer 42. Thereby, the bodily fluid existing in the hemagglutinating agent layer 42 flows toward the isolation layer 41 against the gravity, and the disadvantage that a large amount of aggregates are generated in the isolation layer 41 is effectively prevented. That is, body fluid such as menstrual blood excreted from the wearer's body when the napkin 1 is worn when the thickness of the isolation layer 41 under a load of 0.5 g / cm ² is less than that of the hemagglutinating agent layer 42. In the process of moving to the side far from the wearer's skin due to gravity, even if convection occurs and body fluid moves toward the wearer's skin, Since the volume does not exceed the volume of the bodily fluid in the hemagglutinating agent layer 42, the bodily fluid is sufficiently retained in the hemagglutinating agent layer 42, and the formation of aggregates in the hemagglutinating agent layer 42 is promoted. .

The ratio between the thickness of the isolation layer 41 under a load of 0.5 g / cm ² and the thickness of the hemagglutinator layer 42 under a load of 0.5 g / cm ² is preferably 1 or more, more preferably 1 as the former / the latter. .5 or more, and preferably 7 or less, more preferably 4 or less.
The thickness of the isolation layer 41 under a load of 0.5 g / cm ² is preferably 1 mm or more, more preferably 1.5 mm or more, and preferably 8 mm or less, more preferably 5.2 mm or less.
The thickness of the hemagglutinating agent layer 42 under a load of 0.5 g / cm ² is preferably 0.1 mm or more, more preferably 0.5 mm or more, and preferably 3 mm or less, more preferably 1 mm or less.

The thickness of 0.5 g / cm ² under a load of aggregation promoting layer 43 is preferably equal to or greater than the thickness of 0.5 g / cm ² under a load of hemagglutination agent layer 42. Thereby, since the volume of the body fluid in the aggregation promoting layer 43 does not exceed the volume of the body fluid in the hemagglutinating agent layer 42, the body fluid is sufficiently retained in the hemagglutinating agent layer 42, and the hemagglutinating agent layer The formation of aggregates at 42 is promoted, and coupled with the presence of the aggregation promoting layer 43, the formation of aggregates before the body fluid reaches the absorption layer 44 is further promoted.

The ratio between the thickness of the aggregation promoting layer 43 under a load of 0.5 g / cm ² and the thickness of the hemagglutinating agent layer 42 under a load of 0.5 g / cm ² is preferably 0.8 or more as the former / the latter. Preferably it is 1 or more, preferably 10 or less, more preferably 4 or less.
The thickness of the aggregation promoting layer 43 under a load of 0.5 g / cm ² is preferably 0.5 mm or more, more preferably 1 mm or more, and preferably 8 mm or less, more preferably 5 mm or less.
The thickness of each layer in the laminated structure 4 is measured by the following method.

<Measurement method of layer thickness>
In sanitary products, if the layer to be measured (laminated structure) is bonded to another component with an adhesive such as a hot melt adhesive, the adhesive is invalidated using an organic solvent or cold spray. Then, the sanitary product is disassembled so that the shape of the layer to be measured is not deformed, and the layer is taken out. The thickness of the measurement target layer taken out from the sanitary product is measured using a laser thickness meter (two-dimensional CMOS laser type smart sensor (model number ZS-LD80) manufactured by OMRON Corporation). When measuring the thickness, a weight is arranged between the tip of the thickness meter and the layer to be measured, and the load on the layer to be measured is adjusted to 0.5 g / cm ^2. Measure the thickness of the layer to be measured under pressure.

  Further, the liquid retention of the isolation layer 41 is preferably the same as or lower than the liquid retention of the aggregation promoting layer 43. The relatively low liquid retention of the isolation layer 41 is effective in preventing liquid convection that may cause the formation of aggregates in the isolation layer 41. Further, when the liquid retention property of the aggregation promoting layer 43 is relatively high, menstrual blood can be efficiently retained in the aggregation promoting layer 43, thereby further promoting the generation of the aggregate. .

  As an example of a form in which the liquid retaining property of the separating layer 41 is lower than that of the aggregation promoting layer 43, a form in which the separating layer 41 having a relatively low liquid retaining property is configured to include a thermoplastic resin. In order to reduce the liquid retention of the isolation layer 41, it is important that the interfiber distance is wide and that the wide interfiber distance is maintained even when contacting with body fluid such as menstrual blood. Therefore, the isolation layer 41 is preferably configured to include a thermoplastic resin that hardly undergoes structural changes even when wet, and it is particularly preferable to include a fiber (thermoplastic fiber) made of a thermoplastic resin as a constituent fiber. . Examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate; polyamides such as nylon 6 and nylon 66; polyacrylic acid, polymethacrylic acid alkyl ester, polyvinyl chloride, and polyvinylidene chloride. These 1 type can be used individually or in combination of 2 or more types. The content of the thermoplastic resin (thermoplastic fiber) in the isolation layer 41 is preferably 50% by mass or more and 100% by mass with respect to the total mass of the isolation layer 41.

  On the other hand, it is preferable that the aggregation promoting layer 43 having a relatively high liquid retaining property has a smaller thermoplastic resin content than the separating layer 41 having a relatively low liquid retaining property. The content of the thermoplastic resin (thermoplastic fiber) in the aggregation promoting layer 43 is preferably 50% by mass or less with respect to the total mass of the aggregation promoting layer 43, and may be zero. Moreover, it is preferable that the aggregation promoting layer 43 is mainly composed of pulp fibers from the viewpoint of improving liquid retention, and the content of the pulp fibers is preferably 50% by mass or more with respect to the total mass of the aggregation promoting layer 43. Yes, it may be 100% by mass.

The basis weights of the isolation layer 41, the hemagglutinating agent layer 42, and the aggregation promoting layer 43 are preferably set as follows.
The basis weight of the separating layer 41 is preferably 50 g / m ² or more, more preferably 90 g / m ² or more, and preferably 300 g / m ² or less, more preferably 250 g / m ² or less.
The basis weight of the hemagglutinating agent layer 42 is preferably 10 g / m ² or more, more preferably 50 g / m ² or more, and preferably 100 g / m ² or less, more preferably 70 g / m ² or less.
The basis weight of the aggregation promoting layer 43 is preferably 50 g / m ² or more, more preferably 90 g / m ² or more, and preferably 300 g / m ² or less, more preferably 250 g / m ² or less.

The absorption layer 44 does not contain a hemagglutinating agent, and preferably contains a superabsorbent polymer. The meaning of “does not contain a hemagglutinating agent” here is as described above. The content of the superabsorbent polymer in the absorbent layer 44 is preferably 10 g / m ² or more, more preferably 30 g / m ² or more, and preferably 300 g / m ² or less, more preferably 200 g / m ² or less. . By setting the content of the superabsorbent polymer to 10 g / m ² or more, it is possible to ensure the absorption performance that the absorption layer 44 should have, and to absorb the content by setting the content to 300 g / m ² or less. The permeability of the liquid to be provided in the layer 44 can be ensured.

  The absorbent layer 44 may be configured to include only one of the fiber and the superabsorbent polymer, or may be configured to include both. As the fiber used in combination with the superabsorbent polymer, the above-mentioned hydrophilic fiber is preferably used. A typical example of the absorbent layer 44 is a form including a fiber aggregate mainly composed of hydrophilic fibers and a particulate high-absorbent polymer, and in such a form, the particulate super-absorbent polymer is usually used. Is held in the fiber assembly via an adhesive force generated in the superabsorbent polymer in a wet state or a binder such as a separately added adhesive or adhesive fiber.

An example of the absorbent layer 44 is a stacked fiber having a configuration in which fibers and a superabsorbent polymer are mixed. In the absorbent layer 44 made of this pile, the fibers and the superabsorbent polymer may be distributed uniformly, or the superabsorbent polymer may be unevenly distributed, or the basis weight of both may be partially May be different. The basis weight of the absorbent layer 44 made of the laminated fiber is preferably 10 g / m ² or more, more preferably 30 g / m ² or more, and preferably 300 g / m ² or less, more preferably 200 g / m ² or less. is there.

Another example of the absorbent layer 44 is an absorbent sheet having a configuration in which particulate superabsorbent polymers are distributed on at least one surface of a sheet-like fiber assembly. As a modified example of this absorbent sheet, there may be mentioned one in which particulate superabsorbent polymer is distributed between two sheet-like fiber assemblies. Such an absorbent sheet has a low thickness and a low rigidity compared with the above-described absorbent material stack, and therefore, a sanitary product including the absorbent sheet is thin and thin, and is flexible. It is easy to wear and can be folded compactly for excellent handling. From the standpoint of obtaining a sanitary product that is more effective in using the features of such an absorbent sheet and has sufficient liquid diffusibility and liquid retention and has a good wearing feeling, a sheet-like fiber assembly to which a superabsorbent polymer is dispersed. The thickness of the body under a load of 0.5 g / cm ² is preferably 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, more preferably 1.5 mm or less. As the absorbent sheet, for example, those described in Japanese Patent No. 2963647 and Japanese Patent No. 2955223 can be used.

  The superabsorbent polymer contained in the absorbent layer 44 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.

Hereinafter, the hemagglutinating agent used in the present invention will be described. The hemagglutinating agent used in the present invention refers to those having the following properties.
That is, when 1000 ppm of the measurement sample agent is added to the pseudo blood, when at least two blood cells aggregate to form an aggregate with the blood fluidity maintained, the measurement sample agent is added to the blood cell. Use a flocculant.
The simulated blood has a viscosity of 8 mPa · s measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., model number TVB-10M, measurement conditions: rotor No. 19, 30 rpm, 23 ° C., 60 seconds). The blood cell / plasma ratio of defibrinated horse blood (manufactured by Japan Biotest Laboratories, Inc.) was prepared.

Here, “the state in which the fluidity of blood is maintained” means that 10 g of the pseudo blood to which 1000 ppm of the measurement sample agent is added is a screw tube bottle (product number “Screw tube No. 4” manufactured by Maruemu Co., Ltd.) 5 mm, body diameter 27 mm, total length 55 mm), and when the screw tube bottle containing the pseudo blood is inverted 180 degrees, the pseudo menstrual blood of a volume of 60% or more flows down within 20 seconds. .
Further, 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 device (manufactured by Horiba, Ltd., model number: LA-950V2, measurement condition: flow) The average median diameter of the volume particle size measured at a temperature of 25 ° C. by the laser diffraction scattering method using the formula cell measurement (circulation speed 1, no ultrasonic wave) is the size of the aggregate where two or more blood cells are aggregated. When the thickness 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 is an agent that can satisfy the above definition (can express erythrocyte aggregation) by a compound that meets the above definition or a combination thereof, or a combination of compounds. 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.

  As the hemagglutinating agent used in the present invention, a cationic polymer is suitable. 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 kinds of condensates having a quaternary ammonium moiety, or quaternary ammonium moieties. 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 dimethyl 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 generating red blood cell aggregates, 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, further preferably 2000 or more and 3 million or less, and more preferably 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. Further, two or more kinds of cationic polymers having different molecular weights may be combined within the aforementioned molecular weight range. 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. A copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate uses an eluent in which 150 mmol / L sodium sulfate and 1% by mass acetic acid are dissolved in water. A copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate has a molecular weight of 5900, a pullulan with a molecular weight of 47300, a pullulan with 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 with 50 mmol / L lithium bromide and 1% by mass acetic acid 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, the flow rate is 0.6 mL / min and the injection amount is 100 μL.

  In the case of using a quaternary ammonium salt polymer as the cationic polymer, it is preferable that the quaternary ammonium salt polymer has a flow potential of 1500 μeq / L or more from the viewpoint of more effectively generating red blood cell aggregates. , More preferably 2000 μeq / L or more, still more preferably 3000 μeq / L or more, and still more preferably 4000 μeq / L or more. When the flow potential of the quaternary ammonium salt polymer is not less than these values, the electric double layer of erythrocytes can be sufficiently neutralized. The upper limit of the streaming 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 below these values, the electrical repulsion between the quaternary ammonium salt polymers adsorbed on the erythrocytes can be effectively prevented. The streaming potential of the quaternary ammonium salt polymer is preferably 1500 μeq / L or more and 13000 μeq / L, more preferably 2000 μeq / L or more and 13000 μeq / L or less, and 3000 μeq / L or more and 8000 μeq / L or less. Is more preferably 4000 μeq / L or more and 6000 μeq / L or less.

The flow potential of the quaternary ammonium salt polymer adjusts, for example, the molecular weight of the constituting cationic monomer itself, and the copolymerization molar ratio of the cationic monomer and the anionic monomer or nonionic monomer constituting the copolymer. Can be controlled. The streaming potential of the quaternary ammonium salt polymer can be measured using a streaming potential measuring device (PCD04) manufactured by Spectris Co., Ltd. Specific measurement conditions are as follows. First, hot melt bonding each member to a commercially available napkin is invalidated using a dryer or the like, and decomposed into members such as a top sheet, an absorber, and a back sheet. For each decomposed member, a multi-stage solvent extraction method from a nonpolar solvent to a polar solvent is performed to separate the treating agent used in each member to obtain a solution containing a single composition. The obtained solution was dried and solidified, and ¹ H-NMR (nuclear magnetic resonance), IR (infrared spectroscopy), LC (liquid chromatography), GC (gas chromatography), MS (mass spectrometry), GPC ( Gel permeation chromatography), fluorescent X-rays, etc. are combined to identify the structure of the treatment agent. With respect to a measurement sample in which 0.001 g of a treatment agent (quaternary ammonium salt polymer) to be measured is dissolved in 10 g of physiological saline, a 0.001N sodium polyethylene sulfonate aqueous solution (if the measurement sample has a negative charge) , 0.001N polydiallyldimethylammonium chloride aqueous solution) is titrated, and the titer XmL required until the potential difference between the electrodes disappears is measured. Thereafter, the streaming potential of the quaternary ammonium salt polymer is calculated by the following formula 1.
Streaming potential = (X + 0.190 *) × 1000 Equation 1
(* Titration required for the physiological saline solution)

  In order for the cationic polymer to be successfully adsorbed on the surface of erythrocytes, it is advantageous that the cationic polymer is likely to interact with sialic acid present on the surface of erythrocytes. From this point of view, the present inventors proceeded with studies, and as a result, inorganic value / organic value (hereinafter referred to as “IOB (Inorganic Organic Balance) value”), which is the ratio between the inorganic value and the organic value of the substance. It was found that the degree of interaction between the sialic acid conjugate and the cationic polymer can be evaluated on the basis of. Specifically, it has been found advantageous to use a cationic polymer having an IOB value that is the same as or close to that of the sialic acid conjugate. The sialic acid conjugate is a compound in which sialic acid can exist in a living body, and examples thereof include a compound in which sialic acid is bound to the end of a glycolipid such as galactolipid.

  In general, the properties of a substance are largely governed by various intermolecular forces between molecules, and this intermolecular force mainly consists of Van Der Waals force due to molecular mass and electrical affinity due to molecular polarity. If the Van Der Waals force, which has a great influence on changes in the properties of substances, and the electric affinity can be grasped individually, the properties of unknown substances or their mixtures can be predicted from the combination. be able to. This idea is a theory well known as “organic conceptual diagram”. Conceptual diagram of organic materials is, for example, “Organic analysis” written by Kei Fujita (Kanya Shoten, Showa 5), “Organic qualitative analysis: Systematic. Pure products” by Kyoda Fujita (Kyoritsu Shuppan, 1953), Jun Fujita "Reorganized Chemistry Experiments-Organic Chemistry" (Kawade Shobo, 1971), "Systematic Organic Qualitative Analysis (mixture)" written by Kei Fujita and Masami Akatsuka (Kazama Shobo, 1974), and Yoshio Koda It is described in detail in Shiro Sato and Yoshio Honma's “New Concept of Organic Conceptual Diagram Basics and Applications” (Sankyo Publishing, 2008). In the organic conceptual diagram, regarding the physicochemical properties of materials, the degree of physical properties mainly due to Van Der Waals force is called “organic”, and the degree of physical properties mainly due to electrical affinity is called “inorganic”. The physical properties of substances are considered as a combination of “organic” and “inorganic”. Then, one carbon (C) is defined as organic 20, and the inorganic and organic values of various polar groups are defined as shown in Table 1 below. The sum of the values is obtained, and the ratio between the two is defined as the IOB value. In the present invention, the IOB value of the sialic acid conjugate described above is determined based on these organic and inorganic values, and the IOB value of the cationic polymer is determined based on the value.

Specifically, when the cationic polymer is a homopolymer, the inorganic value and the organic value are determined based on the repeating unit of the homopolymer, and the IOB value is calculated. For example, in the case of polydiallyldimethylammonium chloride which is a cationic polymer used in Example 1 described later (trade name “Mercoat 106” manufactured by Nippon Lubrizol Co., Ltd.), an organic value of −C− × 8 = 160, Ammo and NH ₄ salt × 1 = 400 inorganic value, Ring (non-aromatic single ring) × 1 = 10 inorganic value, −Cl × 1 = 40 organic value and 10 inorganic value Therefore, the sum of the inorganic values is 400 + 10 + 10 = 420, and the sum of the organic values is 160 + 40 = 200. Therefore, the IOB value is 420/200 = 2.10.

On the other hand, when the cationic 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. That is, a copolymer is obtained from monomer A and monomer B, the organic value of monomer A is OR _A , the inorganic value is IN _A , the organic value of monomer B is OR _B , the 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 IOB value of the cationic polymer thus determined is preferably 0.6 or more, more preferably 1.8 or more, further preferably 2.1 or more, 2.2 It is still more preferable that it is above. Further, 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. Specifically, the IOB value of the cationic polymer is preferably 0.6 or more and 4.6 or less, more preferably 1.8 or more and 3.6 or less, and 2.1 or more and 3.6 or less. More preferably, it is 2.2 or more and 3.0 or less. The IOB value of sialic acid is 4.25 for sialic acid alone and 3.89 for sialic acid conjugate. The sialic acid conjugate is a glycolipid in which a sugar chain in a glycolipid and sialic acid are bound, and the sialic acid conjugate has a higher organic value ratio and a lower IOB value than sialic acid alone.

  The IOB value of the cationic polymer is as described above, and the organic value itself is preferably 40 or more, more preferably 100 or more, and further preferably 130 or more. Further, it is preferably 310 or less, more preferably 250 or less, further preferably 240 or less, and further preferably 190 or less. For example, the organic value is preferably 40 or more and 310 or less, more preferably 40 or more and 250 or less, further preferably 100 or more and 240 or less, and still more preferably 130 or more and 190 or less. By setting the organic value of the cationic polymer within this range, the cationic polymer is more successfully adsorbed to erythrocytes.

  On the other hand, the inorganic value of the cationic polymer is preferably 70 or more, more preferably 90 or more, still more preferably 100 or more, still more preferably 120 or more, and 250 or more. It is particularly preferred that Further, it is preferably 790 or less, more preferably 750 or less, still more preferably 700 or less, still more preferably 680 or less, and particularly preferably 490 or less. For example, the inorganic value is preferably from 70 to 790, more preferably from 90 to 750, even more preferably from 90 to 680, even more preferably from 120 to 680, It is especially preferable that it is 250 or more and 490 or less. By setting the inorganic value of the cationic polymer within this range, the cationic polymer can be more effectively adsorbed to erythrocytes.

  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 1 mm or less powdery or 0.5 mm or less film-form cationic polymer is added to and mixed with 50 mL of deionized water at 25 ° C. in a 100 mL glass beaker (5 mmΦ). 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 carbon number of each side chain is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. The upper limit of the carbon number is preferably 10 or less, more preferably 9 or less, and still 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, in addition to or instead of the vinyl polymerizable monomer, other polymerizable monomers 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 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 preferably 5 million or less, and particularly preferably 3 million or less (the same applies to quaternary ammonium salt copolymers 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, propylene glycol, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, Examples thereof include hydroxyethyl methacrylate and hydroxyethyl 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 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. Or it is preferable to adjust so that the streaming potential of a quaternary ammonium salt copolymer may become the value mentioned above. Or it is preferable to adjust so that IOB of a quaternary ammonium salt copolymer may become the value mentioned above. 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, 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, 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. The polymerization conditions are not particularly limited, and the conditions under which the quaternary ammonium salt polymer having the target 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. The composition may be applied in the form of the composition (hemocglutinating 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 sanitary product.

  FIG. 5 is a view corresponding to FIG. 2 of another embodiment of the sanitary product of the present invention. In other embodiments to be described later, constituent parts different from the above-described napkin 1 will be mainly described, and the same constituent parts will be denoted by the same reference numerals and description thereof will be omitted. The description of the napkin 1 is appropriately applied to components that are not particularly described.

  In the napkin 1, all four layers constituting the laminated structure 4 are integrally covered with the covering sheet 5. However, in the present invention, only a part of the laminated structure 4 is covered with the covering sheet 5. included. The napkin 1A shown in FIG. 5 is an example of such a form, and a part of the covering sheet 5, specifically, a portion interposed between the isolation layer 41 and the aggregation promoting layer 43 is a hemagglutinating agent layer. 42 is a portion that functions as 42, that is, a portion that does not contain a superabsorbent polymer but contains a hemagglutinating agent, and extends to the outside from the other portion (the isolation layer 41 or the aggregation promoting layer 43). Part) does not contain a superabsorbent polymer and a hemagglutinating agent, and integrally covers the aggregation promoting layer 43 and the absorption layer 44. The isolation layer 41 is not covered with the cover sheet 5 and is disposed between the top sheet 2 and the cover sheet 5. The isolation layer 41 in the napkin 1A has the same effect as a member called a sublayer sheet or a second sheet in this technical field in addition to the above-described effect as the isolation layer. It is possible to improve the performance and reduce the liquid return. The effect similar to that of the napkin 1 is achieved by the napkin 1A.

Although the present invention has been described above, the present invention is not limited to the above-described embodiments, and can be appropriately changed without departing from the spirit of the present invention.
The present invention can be applied to all articles used for absorption of menstrual blood. Examples of such articles include, but are not limited to, panty liners and tampons in addition to sanitary napkins as in the above embodiment.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to such examples.

[Examples 1 to 11 and Reference Example 2]
The laminated structure of the 4 layer structure of the structure shown in the following Table 2-Table 4 was produced. Specifically, four layers were separately prepared, and the prepared four layers were simply overlapped without being bonded to each other to form a laminated structure.
The hemagglutinating agent layer in the laminated structure was produced by the following procedure. That is, a hemagglutinating agent is dissolved in deionized water to prepare a 5% by weight diluted solution as a coating solution, and this coating solution is used as a skin-facing surface (sheet or non-woven fabric) serving as a base of the hemagglutinating agent layer ( It was applied by spraying over the entire area of the surface facing the isolation layer, and then drying the solvent.
As the absorption layer in the laminated structure, a layer (hereinafter, also referred to as “SAP layer”) composed of only a particulate superabsorbent polymer (hereinafter also referred to as “SAP”) or an absorbent sheet was used. As an absorbent sheet, as a sheet-like fiber aggregate, a commercially available sanitary napkin having a thickness of 0.8 mm under a weight of 75 g / m ² and 0.5 g / cm ² (manufactured by Kao Corporation, made in Japan in 2015 “ A Laurier slim guard was used. The absorber was taken out from a wing with a wing for a daytime using a cold spray. The absorber had a configuration in which SAP was sandwiched between two pulp sheets.

[Reference Example 1]
A laminated structure was produced in the same manner as in the example except that a laminated structure having a three-layer structure having no isolation layer was used.

[Reference Example 3]
A laminated structure was produced in the same manner as in Example except that a laminated structure having a three-layer structure having no aggregation promoting layer was used.

[Comparative Example 1]
A laminated structure having a total of two layers of a paper layer containing no hemagglutinating agent and an SAP layer was prepared in the order closest to the surface sheet.

In Examples and Reference Examples, any of the following agents A to D was used as a hemagglutinating agent.
Agent A: polydiallyldimethylammonium chloride (Mercoat 100 manufactured by Nippon Lubrizol Corporation)
Agent B: polymethacryloxyethyldimethylammonium diethylsulfate / dimethylacrylamide copolymer (diethylsulfate of dimethylaminoethyl methacrylate and dimethylacrylamide are used in a molar ratio of the former / the latter = 56: 44 and is a solvent. Dissolved in ethanol, added oil-soluble azo initiator 2,2'-Azobis (2-methylpropionamidine) dihydrochloride (V-65B manufactured by Wako Pure Chemical Industries, Ltd.), heated and copolymerized, water-soluble The quaternary ammonium salt copolymer was obtained.)
Agent C: Polymethacryloxyethyldimethylammonium diethylsulfate / dimethylacrylamide copolymer (diethylsulfate of dimethylaminoethyl methacrylate and dimethylacrylamide is used in a molar ratio of the former / the latter = 56: 44 and is a solvent. Dissolved in ethanol, added oil-soluble azo initiator 2,2'-Azobis (2-methylpropionamidine) dihydrochloride (V-65B manufactured by Wako Pure Chemical Industries, Ltd.), heated and copolymerized, water-soluble The quaternary ammonium salt copolymer was obtained.)
Agent D: Polymethacryloxyethyltrimethylammonium sulfate (Unisense FPV1000L manufactured by Senka Corporation)

〔Evaluation test〕
An evaluation sample is prepared by the following method using the laminated structure of each example, reference example, and comparative example, and the surface whiteness (L value), the liquid absorption amount of SAP, and the aggregate particle size are obtained for the evaluation sample immediately after the preparation. Were evaluated by the following methods. The results are shown in Tables 2 to 4 below.

(Evaluation sample preparation method)
Between the top sheet and the back sheet, the laminated structure to be evaluated was taken out from a commercially available sanitary napkin (Kao Co., Ltd., 2015 made in Japan, "Laurier slim guard with a firm wing for daytime 25cm") using a cold spray. It was sandwiched between two acrylic plates having a thickness of 3 mm from both sides in the thickness direction, and the pair of mangle rolls was reciprocated once in that state. The clearance of this pair of mangle rolls was set to 85 mm. And, when the laminated structure is incorporated into a sanitary product, the layer (isolation layer) disposed at the position closest to the wearer's skin is the uppermost layer (absorbing layer) farthest from the wearer's skin Is placed on a flat surface so as to be downward, and using a rotary pump (EYELA MP-1000, manufactured by Tokyo Rika Kikai Co., Ltd.), 3 g of the aforementioned pseudo blood is flowed from the top sheet at a flow rate of 0.125 g / sec. Immediately after injection, an 800 g weight was placed on the top sheet to pressurize the entire laminated structure, and the weight was removed after 3 minutes from the injection of pseudo blood. This series of operations over 3 minutes (injection of 3 g of simulated blood and subsequent pressurization) was repeated three times, and a total of 9 g of defibrinated horse blood was injected into the laminated structure as an evaluation sample.

<Method for evaluating surface whiteness (L value)>
A color difference meter (SPECTRO PHOTOMETER NF333 manufactured by Nippon Denshoku Industries Co., Ltd.) was applied to the surface on the blood injection side of the evaluation sample for measurement. The measurement was performed three times, and the average value was taken as the L value. It shows that it is excellent in the surface white after use, so that L value is large.

<Evaluation method of SAP liquid absorption>
After measuring the weight W1 of the wet SAP contained in the evaluation sample, the SAP was dried overnight at 105 ° C., and the weight W2 of the dry SAP was measured. And the liquid absorption amount (g / g) of SAP per unit weight was computed from both measured values by the following formula. It shows that it is excellent in the blood absorption performance, so that there is much liquid absorption amount of this SAP.
SAP absorption (g / g) = (W1-W2) / W2

<Evaluation method of aggregate particle size>
The blood stored in the laminated structure was taken out, transferred to a container, and diluted about 100 times with physiological saline. While circulating this blood dilution, the particle size of the aggregate contained therein was measured using a laser diffraction / scattering particle size distribution measuring apparatus (LA-350, Horiba, Ltd.). It shows that the larger the aggregate particle size, the more the aggregation of non-liquid components in blood such as erythrocytes, which is a factor that inhibits SAP absorption, and the easier the absorption performance inherent in SAP is.

1,1A Sanitary napkin (Sanitary products)
2 Top sheet 3 Back sheet 4 Laminated structure 41 Separating layer 42 Hemagglutinating agent layer 43 Aggregation promoting layer 44 Absorbing layer 5 Covering sheet 10 Absorbent body 11 Menstrual blood 12 Liquid component 13 Non-liquid component 14 Superabsorbent polymer 15 Film 16 Aggregation mass

Claims (9)

A sanitary product comprising a liquid-permeable top sheet, a back sheet disposed at a position farther from the wearer's skin than the top sheet, and a laminated structure disposed between both sheets,
The laminated structure comprises a separating layer, a hemagglutinating agent layer, an aggregation promoting layer, and an absorbing layer in the order close to the top sheet,
The hemagglutinating agent layer contains a hemagglutinating agent without containing a superabsorbent polymer, and the absorbing layer does not contain a hemagglutinating agent,
The isolation layer and the aggregation promoting layer each contain a fiber and do not contain a hemagglutinating agent and a superabsorbent polymer.   The sanitary product according to claim 1, wherein the density of the isolation layer is the same as or lower than the density of the aggregation promoting layer. The thickness at 0.5 g / cm ² under a load of isolation layer, sanitary article according to claim 1 or 2 same or greater than the thickness of 0.5 g / cm ² under a load of said blood cell aggregating agent layer. The thickness at 0.5 g / cm ² under a load of aggregation-promoting layer, wherein any one of hemagglutination agent layer of 0.5 g / cm ² or equal than larger claims 1-3 and thickness under load The sanitary products described in 1.   The sanitary product according to any one of claims 1 to 4, wherein the liquid retention of the isolation layer is the same as or lower than that of the aggregation promoting layer.   The sanitary product according to any one of claims 1 to 5, wherein the isolation layer includes a thermoplastic resin.   The hemagglutinating agent is a cationic polymer having a structure having a main chain and a plurality of side chains bonded thereto, and the cationic polymer includes a quaternary ammonium salt homopolymer and a quaternary ammonium salt copolymer. Or the sanitary product of any one of Claims 1-6 containing a quaternary ammonium salt polycondensate. The cationic polymer is a quaternary ammonium salt homopolymer having a repeating unit represented by the following formula 1, or a repeating unit represented by the following formula 1 and a repeating unit represented by the following formula 2. A quaternary ammonium salt copolymer having
The sanitary product according to claim 7, wherein the main chain and the side chain of the cationic polymer are bonded at one point, and the side chain has a quaternary ammonium moiety.
  The cationic polymer has a weight average molecular weight of 2000 or more, a streaming potential of 1500 μeq / L or more, and a ratio of inorganic value to organic value of 0.6 to 4.6 as an inorganic value / organic value. The sanitary product according to claim 7 or 8.