CN109219425B - Physiological articles - Google Patents

Abstract

A sanitary product (10) comprises a top sheet (20) positioned on the skin-contact surface side, a back sheet (30) positioned on the non-skin-contact surface side, and an absorbent body (40) interposed therebetween. A blood cell coagulant-containing region containing a blood cell coagulant and a liquid film cracking agent-containing region containing a liquid film cracking agent are disposed on the absorbent body (40) or on the skin contact surface side of the absorbent body (40). For example, the liquid film-containing dehiscent agent region may be provided in the topsheet (20), and the blood cell aggregate-containing region may be provided in the core-covering sheet (42) constituting the absorbent body (40).

Description

Physiological articles

Technical Field

The present invention relates to a sanitary article for absorbing menstrual blood.

Background

Sanitary products are used for the treatment of menstrual blood, vaginal discharge, and the like in women. In general, a sanitary product has a structure in which an absorbent body capable of absorbing and retaining excretions such as menstrual blood is provided between a topsheet on the skin contact surface side and a backsheet on the non-skin contact surface side.

Techniques for improving various properties of such physiological articles by applying a cationic polymer material thereto are known. For example, patent document 1 describes a personal care absorbent article such as a sanitary napkin or a tampon comprising a porous nonwoven web material treated with a treatment agent for blocking or dissolving red blood cells in blood. In the same document, as the treatment agent, a polycationic material which is a polymer having a strong positive charge is used. The treatment agent causes red blood cells in blood to aggregate or lyse when the blood enters or passes through the absorbent article.

Patent document 2 discloses a top sheet containing a blood modifying agent for improving the texture of the top sheet after menstrual blood absorption. The blood modifying agent can reduce the viscosity and surface tension of blood, stabilize blood cells, and make absorption body easily absorb menstrual blood.

[ Prior art documents ]

[ patent document ]

Patent document 1: japanese Kohyo publication 2002-528232

Patent document 2: japanese patent laid-open publication No. 2013-063245

Disclosure of Invention

The invention provides a sanitary article having a topsheet on the skin-contact surface side, a backsheet on the non-skin-contact surface side, and an absorbent body sandwiched therebetween. The sanitary article of the present invention is characterized in that a blood cell coagulant-containing region containing a blood cell coagulant and a liquid film-forming agent-containing region containing a liquid film-forming agent are disposed on the skin contact surface side of the absorbent body or the absorbent body.

The present invention also provides a sanitary article having a topsheet on the skin-contact surface side, a backsheet on the non-skin-contact surface side, and an absorbent body interposed therebetween. The sanitary article of the present invention comprises a cationic polymer-containing region containing a cationic polymer and a compound-containing region containing the following compound C1, disposed on the absorbent body or on the skin contact surface side of the absorbent body.

[ Compound C1]

A compound having an expansion coefficient of 15mN/m or more with respect to a liquid having a surface tension of 50 mN/m.

The present invention also provides a sanitary article having a topsheet on the skin-contact surface side, a backsheet on the non-skin-contact surface side, and an absorbent body interposed therebetween. The sanitary article of the present invention comprises a cationic polymer-containing region containing a cationic polymer and a compound-containing region containing the following compound C2, disposed on the absorbent body or on the skin contact surface side of the absorbent body.

[ Compound C2]

A compound having an expansion coefficient of more than 0mN/m with respect to a liquid having a surface tension of 50mN/m and an interfacial tension of 20mN/m or less with respect to a liquid having a surface tension of 50 mN/m.

Drawings

FIG. 1 is a schematic view showing the mechanism of absorption of menstrual blood in the sanitary product of the present invention.

Fig. 2(a) and 2(b) are schematic diagrams showing a mechanism of absorption of menstrual blood in a conventional sanitary product.

Fig. 3 is a schematic view showing a liquid film formed in gaps between fibers of a nonwoven fabric.

Fig. 4 is an explanatory view of the liquid film splitting process by the liquid film splitting agent of the present invention, in which (a1) to (a4) are schematic side views of the liquid film gradually split and (B1) to (B4) are schematic perspective views seen from above the same liquid film.

Fig. 5 is a plan view schematically showing a skin-contacting surface of a sanitary napkin according to an embodiment of the sanitary product of the present invention.

Fig. 6 is a cross-sectional view schematically showing a cross-section taken along line I-I of fig. 5.

Fig. 7 is a perspective view showing only the topsheet of the sanitary napkin shown in fig. 5.

Detailed Description

It is known that the rate or amount of absorption of moisture by a super absorbent polymer varies depending on the type of moisture. For example, when a superabsorbent polymer is made to absorb a physiological saline solution and made to absorb blood, the absorption rate of blood is slower and the amount of blood absorbed is smaller than that of a physiological saline solution. Therefore, in order to improve the performance of the sanitary products, it is important to improve various absorption properties of the super absorbent polymer to blood. Patent document 1 or patent document 2 discloses a blood modifying agent, but it is insufficient for improving the absorption performance of a super absorbent polymer and reducing the amount of liquid returned from a physiological product.

Further, since the surface sheet of the sanitary product on the skin contact surface side is normally white in an unused state, the user of the sanitary product can feel a sense of reassurance on the absorption performance because the used sanitary product removed from the surface sheet side is white in surface. Therefore, it is required that the surface whiteness after use is further excellent. Patent document 1 or patent document 2 does not describe the degree of surface whiteness, and no study is made as to which part of a physiological product the modified blood should be retained in this point.

The present inventors have conducted various studies with the object of improving the absorption capacity of menstrual blood in a sanitary product, and as a result, have found that: when the surface of the super absorbent polymer is covered with red blood cells contained in menstrual blood, the absorption performance (absorption rate, absorption amount) of menstrual blood by the super absorbent polymer is reduced, and the amount of fluid returned from the sanitary article is increased. The following insights were obtained: in order to prevent such a problem, it is effective to reduce the amount of rewet of the sanitary product by disposing a water-soluble cationic polymer having the ability to aggregate red blood cells at a site in the sanitary product which can come into contact with menstrual blood excreted by the user earlier than the superabsorbent polymer. However, it is known that when aggregates of red blood cells are formed on the topsheet side of a sanitary product by a water-soluble cationic polymer, there is room for improvement in appearance seen from the topsheet side after use.

The present inventors have made various studies with a view to improving the surface whiteness of a used sanitary product, and as a result, have found that: menstrual blood in nonwoven fabrics such as topsheet forms a liquid film between fibers and stays there, which is a factor of reducing surface whiteness after use. The following insights were obtained: in order to prevent such a problem, it is effective to dispose a liquid film-splitting agent having an ability to split a liquid film with respect to menstrual blood excreted by a user on a surface sheet or the like, and to improve the surface whiteness of a used sanitary product. It is found that the liquid film in the top sheet disappears, and thus the amount of the return liquid is also reduced, but there is still room for improvement in order to achieve further reduction.

Accordingly, the present invention relates to a sanitary article which has a reduced amount of liquid returned and has an excellent surface whiteness even after use.

The present invention will be described below based on preferred embodiments thereof. The sanitary article of the present invention generally comprises an absorbent material having liquid-retaining properties. The absorbent body is preferably a super absorbent polymer comprising a hydrogel material capable of absorbing and retaining water. A liquid-permeable topsheet can be disposed on the skin-contact surface side of the user in the absorbent body. Further, a back sheet may be disposed on the non-skin contact surface side of the absorbent body. In the present specification, the "skin contact surface" refers to a surface of the sanitary product or a constituent member thereof which faces the skin of the user when the sanitary product is used, that is, a surface which is relatively closer to the skin of the user. In the present specification, the "non-skin contact surface" refers to a surface of the sanitary product or a component thereof which faces the side opposite to the skin of the user when the sanitary product is used, that is, a surface facing clothes such as shorts, in other words, a surface which is relatively distant from the skin of the user than the skin contact surface.

The sanitary article of the present invention has a blood cell coagulant-containing region containing a blood cell coagulant described in detail below and a liquid film tearing agent region containing a liquid film tearing agent described in detail below. The present invention provides a sanitary article having a reduced amount of back-flow and excellent surface whiteness after use, which comprises a highly absorbent polymer having an increased absorption amount by a blood cell coagulant and a liquid film-splitting agent for controlling the diffusion of liquid in an absorbent.

(hemagglutinating agent)

The present inventors have made various studies on the reason why the rate of absorption or the amount of absorption of moisture by a super absorbent polymer differs depending on the type of moisture, and as a result, have found the following fact. Blood is roughly divided into a liquid component such as plasma and a non-liquid component such as red blood cells, and the component absorbed by the super absorbent polymer is a liquid component such as plasma. As shown in fig. 2(a), when menstrual blood 1 contacts the super absorbent polymer 4, only the liquid component 2 in the menstrual blood 1 is absorbed by the super absorbent polymer 4, and red blood cells as the non-liquid component 3 are not absorbed by the super absorbent polymer 4. When the absorption of the liquid component 2 into the super absorbent polymer 4 continues, as shown in fig. 2(b), the non-liquid component 3 which is not absorbed into the super absorbent polymer 4 accumulates on the surface of the super absorbent polymer 4 to form a film 5. The formation of the coating 5 inhibits the absorption of liquid by the super absorbent polymer 4, and the absorption rate decreases. Further, the formation of the coating 5 also inhibits swelling of the super absorbent polymer 4, and the absorption amount decreases.

As a result of various studies by the present inventors with respect to a method for preventing the occurrence of the phenomenon shown in fig. 2(b) and preventing the decrease in absorption performance, it has been found that it is effective to aggregate red blood cells, which are a major component of menstrual blood, which is a non-liquid component, as shown in fig. 1, to form an aggregate 6. By forming the aggregates 6 of red blood cells, a film of the aggregates 6 is less likely to be formed on the surface of the super absorbent polymer 4, or even if a film of the aggregates 6 is formed, a space through which the liquid component 2 can permeate remains in the film, and thus absorption of the liquid component 2 is less likely to be inhibited. As a result, the super absorbent polymer 4 can sufficiently exhibit the original absorption performance. In this way, in order to further improve the absorption performance, the larger the particle size of the agglomerate of red blood cells, the better the hardness of the agglomerate.

When this hemagglutinating agent comes into contact with menstrual blood, which is a typical excrement, the hemagglutinating agent is eluted into the menstrual blood, and anionic erythrocytes contained in the menstrual blood are aggregated to form hemagglutinated masses, thereby modifying the menstrual blood. Since the blood cell aggregates generated by the blood cell aggregation effect are larger than red blood cells, even when the blood cell aggregates adhere to a part of the surface of the super absorbent polymer, a defect that most of the surface of the super absorbent polymer is covered with the blood cell aggregates is unlikely to occur, and thus the absorption performance inherent to the super absorbent polymer is stably exhibited.

As the blood cell aggregating agent used in the sanitary product of the present invention, an aggregating agent having an action of aggregating red blood cells in blood is used. The red blood cells aggregated by the hemagglutinating agent become an aggregate. The blood cell aggregating agent may be a fluid treatment agent as described in Japanese patent application laid-open No. 2002-528232 or a blood gelling agent as described in Japanese patent application laid-open No. 57-153648, and according to the findings of the present inventors, a cationic polymer is useful as the blood cell aggregating agent. The reason for this is as follows. The red blood cells have a red blood cell membrane on their surface. The erythrocyte membrane has a double-layer structure. The bilayer structure includes a lower erythrocyte membrane skeleton and an upper lipid membrane. The lipid membrane exposed to the surface of the red blood cells contains a protein called glycophorin. Glycophorin has a sugar chain to which an anionically charged sugar called sialic acid is linked at its terminal. As a result, the red blood cells can be treated as colloid particles having an anionic charge. A coagulant is generally used for coagulating the colloidal particles. In view of the fact that red blood cells are anionic colloidal particles, it is advantageous to use a cationic material as a coagulant in terms of neutralizing the electric double layer of red blood cells. Further, if the aggregating agent has a polymer chain, the polymer chains of the aggregating agent adsorbed on the surface of the red blood cells are likely to entangle with each other, thereby promoting aggregation of the red blood cells. Further, when the aggregating agent has a functional group, aggregation of red blood cells is also promoted by interaction between the functional groups, which is preferable. By the above mechanism of action, a cationic polymer can form an aggregate of erythrocytes in menstrual blood.

(property of forming aggregate)

The blood cell coagulant used in the present invention functions to coagulate red blood cells in blood and separate plasma components from aggregates formed by coagulation of the red blood cells.

Examples of the desired hemagglutinating agent include those having the following properties.

That is, when 1000ppm of a measurement sample agent is added to the simulated blood, at least 2 or more red blood cells aggregate to form an aggregate while the fluidity of the blood is maintained.

The "state in which the fluidity of blood is maintained" means the following state: 10g of mock blood containing 1000ppm of a measurement sample agent was put into a spiral vial (product number "spiral tube No. 4", port diameter 14.5mm, cylinder diameter 27mm, full length 55mm, manufactured by Maruemu Co., Ltd.) and when the spiral vial containing the mock blood was inverted by 180 degrees, 60% or more of the mock blood fell within 20 seconds. The "mock blood" was obtained by adjusting the blood cell/plasma ratio of defibrinated horse blood (manufactured by Nippon Bio-Test Laboratories, Inc.) so that the viscosity at 25 ℃ was 8 mPas, as measured with a B-type viscometer (model TVB-10M, manufactured by Toyobo industries Co., Ltd., measurement conditions: spindle No.19, 30rpm, 60 seconds).

Whether or not the above-mentioned "2 or more red blood cells aggregate to form an aggregate" is achieved is determined as follows. That is, the simulated blood to which 1000ppm of the measurement sample agent was added was diluted 4000 times with physiological saline, and it was judged that "2 or more red blood cells were aggregated to form an aggregate" when the median diameter of the volume particle diameter average measured at 25 ℃ was 10 μm or more, which corresponds to the size of an aggregate formed by aggregating 2 or more red blood cells, by a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution measuring apparatus (model LA-950V2, manufactured by horiba ltd., measurement conditions: flow cytometry, circulation rate 1, no ultrasonic wave).

The hemagglutinating agent used in the present invention is a single compound satisfying the above properties, a mixture of a plurality of single compounds satisfying the above properties, or a preparation satisfying the above properties (capable of achieving the agglutination of red blood cells) by a combination of a plurality of compounds. That is, the hemagglutinating agent is limited to a preparation having a hemagglutination action defined as above. Thus, the compounds used in the physiological articles are distinguished from hemagglutinating agents in the case where they comprise a third component not meeting the above definition. The term "single compound" as used herein is a concept including compounds having the same composition formula but different molecular weights depending on the number of repeating units.

As the hemagglutinating agent, any hemagglutinating agent described in International publication No. 2016/093233 can be used.

The hemagglutination agent preferably has a blood coagulation rate of 0.75 mPas/s or less. The blood coagulation rate is a measure of the ability of a blood cell coagulant to coagulate blood to form a coagulated lump, and a smaller value indicates a smaller size of a coagulated lump after a certain time has elapsed. That is, when blood is coagulated with a blood cell coagulant, if the size of the resulting coagulated masses is large after a certain period of time has elapsed, the liquid permeability may be impaired by clogging of the components of the sanitary article due to the coagulated masses, and therefore, by controlling the coagulation rate, the liquid permeability may not be reduced due to the coagulated masses, and the absorption capacity of the super absorbent polymer can be increased. Thus, the contradictory requirements for improving the liquid permeability and the absorption capacity of the super absorbent polymer are satisfied at the same time. From this viewpoint, the aggregation rate is more preferably 0.32 mPas/s or less, and still more preferably 0.15 mPas/s or less. The lower limit of the aggregation rate is preferably 0.001 mPas/s or more, and more preferably 0.01 mPas/s or more.

The above-mentioned agglomeration rate is measured by the following method. The blood used for measuring the coagulation rate was the above-described simulated blood. 200. mu.L of blood previously dispensed on a carrier was added dropwise to 2. mu.L of physiological saline in which 5% of a hemagglutinating agent was dissolved in advance, using a rheometer (manufactured by Thermo Fisher Scientific, Inc., HAAKE RheoStress 6000), and the mixture was heated at a temperature of 35 mm. phi. with a cone plate (gradient 1 degree): 30 degrees, shear rate: 10¹(second)^-1) The change in viscosity was measured under the conditions of (1). The change in viscosity was measured over 50 seconds, the obtained curve was approximated by a straight line, and the coagulation rate was calculated from the slope of the straight line.

The hemagglutinating agent used in the present invention preferably contains a cationic polymer. The cationic polymer may be disposed in the absorbent body or any portion closer to the skin contact surface side than the absorbent body, but if the cationic polymer having an opposite charge is not present in the vicinity of the anionic superabsorbent polymer, elution of the cationic polymer into menstrual blood is not inhibited, red blood cells are easily aggregated, and a sufficient aggregating effect can be obtained before the superabsorbent polymer absorbs liquid, which is preferable.

Examples of the cationic polymer include: cationized cellulose, and cationized starch such as hydroxypropyltrimethylammonium chloride starch. The blood cell coagulant used in the present invention may contain a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer, or a quaternary ammonium salt polycondensate as the cationic polymer. In the present invention, the "quaternary ammonium salt" includes a compound having a positive monovalent charge at a nitrogen atom position or a compound generating a positive monovalent charge at a nitrogen atom position by neutralization, and specific examples thereof include: salts of quaternary ammonium cations, neutralized salts of tertiary amines, and tertiary amines with cations in aqueous solution. The "quaternary ammonium site" mentioned below is also used in the same meaning, and is a site positively charged in water. In the present invention, the "copolymer" is a polymer obtained by copolymerizing 2 or more polymerizable monomers, and includes both binary copolymers and ternary or more copolymers. In the present invention, the "polycondensate" is a polycondensate obtained by polymerizing a condensate composed of 2 or more monomers.

When the blood cell coagulating 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 blood cell coagulating agent may contain any one of a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer and a quaternary ammonium salt polycondensate, or may contain any combination of 2 or more thereof. The quaternary ammonium salt homopolymer may be used alone in 1 kind or in combination of 2 or more kinds. Likewise, the quaternary ammonium salt copolymer may be used alone in 1 kind or in combination of 2 or more kinds. Further, similarly, 1 kind of the quaternary ammonium salt polycondensate may be used alone or 2 or more kinds may be used in combination.

Among the various cationic polymers, quaternary ammonium salt homopolymers, quaternary ammonium salt copolymers or quaternary ammonium salt polycondensates are particularly preferably used in terms of adsorption to red blood cells. 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 1 kind of polymerizable monomer having a quaternary ammonium moiety. On the other hand, the quaternary ammonium salt copolymer is obtained by copolymerizing at least 1 polymerizable monomer having a quaternary ammonium moiety and, if necessary, at least 1 polymerizable monomer having no quaternary ammonium moiety. That is, the quaternary ammonium salt copolymer is obtained by copolymerizing 2 or more kinds of polymerizable monomers having a quaternary ammonium moiety, or is obtained by copolymerizing 1 or more kinds of polymerizable monomers having a quaternary ammonium moiety and 1 or more kinds of 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 a condensate comprising 1 or more kinds of monomers having a quaternary ammonium moiety. That is, the quaternary ammonium salt polycondensate is obtained by polymerizing a condensate of 2 or more monomers having a quaternary ammonium moiety, or by polycondensation of 1 or more monomers having a quaternary ammonium moiety and 1 or more monomers having no quaternary ammonium moiety.

The quaternary ammonium salt polymer is a cationic polymer having a quaternary ammonium moiety. The quaternary ammonium sites can be generated by quaternization of the tertiary amine with an alkylating agent. Alternatively, the tertiary amine may be formed by dissolving in an acid or water and neutralizing. Or may be formed by quaternization by nucleophilic reactions including condensation reactions. Examples of alkylating agents include: halogenated alkyl groups, or dialkyl sulfates such as dimethyl sulfate. Among these alkylating agents, dialkyl sulfates are preferred because the corrosion problem that may occur when halogenated alkyl groups are 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, hyaluronic acid, and the like. In particular, the use of a quaternary ammonium salt polymer obtained by quaternizing a tertiary amine site with an alkylating agent is preferable because it can surely neutralize the electrical double layer of red blood cells. The quaternization by the nucleophilic reaction including the condensation reaction can be performed as a ring-opening polycondensation reaction of dimethylamine and epichlorohydrin, or a cyclization reaction of dicyandiamide and diethylenetriamine.

The molecular weight of the cationic polymer is preferably 2000 or more, more preferably 1 ten thousand or more, and even more preferably 3 ten thousand or more, from the viewpoint of efficiently generating an aggregate of red blood cells. When the molecular weight of the cationic polymer is not less than these values, the cationic polymer is sufficiently entangled with each other between erythrocytes, or the cationic polymer is sufficiently crosslinked between erythrocytes. The upper limit of the molecular weight is preferably 1000 ten thousand or less, more preferably 500 ten thousand or less, and further preferably 300 ten thousand or less. When the molecular weight of the cationic polymer is less than these values, the cationic polymer is favorably dissolved in menstrual blood. The molecular weight of the cationic polymer is preferably 2000 to 1000 ten thousand, more preferably 2000 to 500 ten thousand, even more preferably 2000 to 300 ten thousand, even more preferably 1 to 300 ten thousand, and particularly preferably 3 to 300 ten thousand. The molecular weight referred to in the present invention is a weight average molecular weight. The molecular weight of the cationic polymer can be controlled by appropriately selecting the polymerization conditions. The molecular weight of the cationic polymer can be measured by the following method.

The cationic polymer is preferably water-soluble from the viewpoint of efficiently generating an aggregate of red blood cells. The term "water-soluble" as used herein means that the water-solubility is 100g or more as measured by the following method.

The cationic polymer preferably has a structure comprising a main chain and a plurality of side chains connected to the main chain. In particular, the quaternary ammonium salt polymer is preferably one having a main chain and a plurality of side chains connected to the main chain. The quaternary ammonium sites are preferably present as side chains. In this case, if the main chain and the side chain are linked at1 point, the flexibility of the side chain is not easily impaired, and the quaternary ammonium moiety present in the side chain can be smoothly adsorbed on the surface of the red blood cell. Of course, in the present invention, the main chain and the side chain of the cationic polymer may be linked at 2 or more points. In the present invention, "linked at1 point" means that 1 carbon atom of the carbon atoms constituting the main chain and 1 carbon atom at the end of the side chain are linked by a single bond. The term "linked at 2 or more points" means that 2 or more carbon atoms among the carbon atoms constituting the main chain and 2 or more carbon atoms at the end of the side chain are each linked by a single bond.

When the cationic polymer has a structure having a main chain and a plurality of side chains linked to the main chain, for example, when the quaternary ammonium salt polymer has a structure having a main chain and a plurality of side chains linked to the main chain, the number of carbon atoms in 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 number of carbon atoms is preferably 10 or less, more preferably 9 or less, and further preferably 8 or less. For example, the number of carbon atoms of the side chain is preferably 4 or more and 10 or less, more preferably 5 or more and 9 or less, and further preferably 6 or more and 8 or less. The number of carbon atoms in the side chain is the number of carbon atoms in the quaternary ammonium moiety (cationic moiety) in the side chain, and even if carbon is contained in the anion as the counter ion, the carbon is not included in the number of carbon atoms. In particular, if the number of carbon atoms including the carbon atom bonded to the main chain and the carbon atom bonded to the quaternary nitrogen among the carbon atoms of the side chain is in the above range, the steric hindrance when the quaternary ammonium salt polymer is adsorbed on the surface of red blood cells is lowered, which is preferable.

When the quaternary ammonium salt polymer is a quaternary ammonium salt homopolymer, the homopolymer may be a polymer of a vinyl monomer having a quaternary ammonium moiety or a tertiary amine moiety, for example. When a vinyl monomer having a tertiary amine moiety is polymerized, the tertiary amine moiety is quaternized with an alkylating agent before and/or after the polymerization to form a quaternary ammonium salt homopolymer, or the tertiary amine moiety is neutralized with an acid before and/or after the polymerization to form a tertiary amine neutralized salt, or the tertiary amine having a cation in an aqueous solution after the polymerization. Examples of alkylating agents or acids are as described above.

The quaternary ammonium salt homopolymer particularly preferably has a repeating unit represented by the following formula 1.

In the formula, R₁Represents H or CH₃。

R₂To represent

n represents an integer of 1 to 10 inclusive.

Represents a halide ion,

Specific examples of the quaternary ammonium salt homopolymer include polyethyleneimine. Further, examples of the side chain having a quaternary ammonium moiety and the main chain linked at1 point include: poly (2-methacryloyloxyethyldimethylamine quaternary salt), poly (2-methacryloyloxyethyltrimethylamine quaternary salt), poly (2-methacryloyloxyethyldimethylethylammonium ethylsulfate), poly (2-acryloyloxyethyldimethylamine quaternary salt), poly (2-acryloyloxyethyltrimethylamine quaternary salt), poly (2-acryloyloxyethyldimethylethylammonium ethylsulfate), poly (3-dimethylaminopropylacrylamide quaternary salt), dimethylaminoethyl methacrylate, polyallylamine hydrochloride, cationized cellulose, polyethyleneimine, polydimethylaminopropyl acrylamide, polyamidine and the like. On the other hand, examples of homopolymers in which a side chain having a quaternary ammonium moiety is linked to a main chain at 2 or more points include: poly (diallyldimethylammonium chloride), poly (diallylamine hydrochloride).

In the case where the quaternary ammonium salt polymer is a quaternary ammonium salt copolymer, as the copolymer, the following can be used: a copolymer obtained by copolymerizing 2 or more polymerizable monomers used for the polymerization of the quaternary ammonium salt homopolymer. As the quaternary ammonium salt copolymer, the following may be used: a copolymer obtained by copolymerizing 1 or more polymerizable monomers used for the polymerization of the quaternary ammonium salt homopolymer and 1 or more polymerizable monomers having no quaternary ammonium moiety. Further, other polymers may be usedSynthetic monomers, e.g. -SO₂And the like are used together with or in place of the vinyl polymerizable monomer. The quaternary ammonium salt copolymer may be a binary copolymer or a ternary or higher copolymer, as described above.

The quaternary ammonium salt copolymer is particularly preferably a copolymer having a repeating unit represented by the above formula 1 and a repeating unit represented by the following formula 2, from the viewpoint of efficiently generating an aggregate of red blood cells.

In the formula, R₃Represents H or CH₃。

R₄To represent

m represents an integer of 1 to 10 inclusive.

Y^⊕Represents Na^⊕Or K^⊕。

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, cationic polymerizable monomers or nonionic polymerizable monomers are used, and therefore, the quaternary ammonium moiety in the quaternary ammonium salt copolymer is not electrically charged, and therefore, the coagulation of red blood cells can be efficiently caused. Examples of the cationically polymerizable monomer include: and a condensation compound of dicyandiamide and diethylenetriamine, which is a linear compound having a nitrogen atom having a cation under a specific condition in the main chain. 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 the nonionic polymerizable monomer include: vinyl alcohol, acrylamide, dimethylacrylamide, ethylene glycol, propylene glycol, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, and the like. One of these cationically polymerizable monomers, anionically polymerizable monomers, or nonionically polymerizable monomers may be used, or any 2 or more thereof may be used in combination. Further, 2 or more kinds of cationically polymerizable monomers may be used in combination, 2 or more kinds of anionically polymerizable monomers may be used in combination, or 2 or more kinds of nonionicpolymerizable monomers may be used in combination. The quaternary ammonium salt copolymer obtained by copolymerization using a cationically polymerizable monomer, an anionically polymerizable monomer and/or a nonionic polymerizable monomer as a polymerizable monomer has a molecular weight of preferably 1000 ten thousand or less, particularly preferably 500 ten thousand or less, and particularly preferably 300 ten thousand or less, as described above (the same applies to the quaternary ammonium salt copolymer exemplified below).

As the polymerizable monomer having no quaternary ammonium moiety, a polymerizable monomer having a functional group capable of forming a hydrogen bond may also be used. When such polymerizable monomers are used for copolymerization and the thus obtained quaternary ammonium salt copolymer is used to aggregate red blood cells, a hard aggregate is easily formed, and the absorption performance of the super absorbent polymer is less likely to be hindered. Examples of the functional group capable of forming a hydrogen bond include: -OH, -NH₂CHO, -COOH, -HF, -SH, etc. Examples of the polymerizable monomer having a functional group capable of forming a hydrogen bond include: hydroxyethyl methacrylate, vinyl alcohol, acrylamide, dimethylacrylamide, ethylene glycol, propylene glycol, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like. In particular, hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, hydroxyethyl acrylate, dimethylacrylamide and the like, which strongly act as hydrogen bonds, are preferable because a stable adsorption state of the quaternary ammonium salt polymer to erythrocytes can be achieved. These polymerizable monomers may be used alone in 1 kind, or in more than 2 kindsCan be used together.

As the polymerizable monomer having no quaternary ammonium moiety, a polymerizable monomer having a functional group capable of hydrophobic interaction may also be used. By using such a polymerizable monomer for copolymerization, the same advantageous effect as in the case of using a polymerizable monomer having a functional group capable of forming a hydrogen bond, that is, the effect of easily forming a hard erythrocyte aggregate, is exhibited. Examples of the functional group capable of producing hydrophobic interaction include: alkyl groups such as methyl, ethyl and butyl, phenyl, alkylnaphthyl and fluorinated alkyl groups. Examples of the polymerizable monomer having a functional group capable of producing hydrophobic interaction include: methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, butyl methacrylate, butyl acrylate, styrene, and the like. In particular, methyl methacrylate, methyl acrylate, butyl methacrylate, butyl acrylate, and the like, which exert a strong hydrophobic interaction and do not significantly reduce the solubility of the quaternary ammonium salt polymer, are preferable because a stable adsorption state of the quaternary ammonium salt polymer to red blood cells can be achieved. These polymerizable monomers may be used alone in 1 kind, or in combination of 2 or more kinds.

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

In the case where the quaternary ammonium salt polymer is a quaternary ammonium salt polycondensate, as the polycondensate, the following can be used: a condensation polymer obtained by polymerizing a condensation product of 1 or more of the monomers having a quaternary ammonium moiety. Specific examples thereof include: dicyandiamide/diethylenetriamine polycondensates, dimethylamine/epichlorohydrin polycondensates, and the like.

The quaternary ammonium salt homopolymer and the quaternary ammonium salt copolymer can be obtained by a homopolymerization method or a copolymerization method of a vinyl polymerizable monomer. Examples of the polymerization method include radical polymerization, living cationic polymerization, living anionic polymerization, coordination polymerization, ring-opening polymerization, polycondensation, and the like. The polymerization conditions are not particularly limited as long as the conditions capable of obtaining a quaternary ammonium salt polymer having a target molecular weight, flow potential, and/or IOB value are appropriately selected.

For example, the flow potential of the quaternary ammonium salt polymer is preferably 1500. mu. eq/L or more, more preferably 2000. mu. eq/L or more, still more preferably 3000. mu. eq/L or more, and still more preferably 4000. mu. eq/L or more, from the viewpoint of more efficiently forming an aggregated mass of red blood cells. When the flow potential of the quaternary ammonium salt polymer is not less than these values, the electric double layer of the red blood cell can be sufficiently neutralized. The upper limit of the flow potential is preferably 13000. mu. eq/L or less, more preferably 8000. mu. eq/L or less, and still more preferably 6000. mu. eq/L or less. When the flow potential of the quaternary ammonium salt polymer is less than these values, the quaternary ammonium salt polymer adsorbed on red blood cells can be effectively prevented from generating an electrical repulsive force therebetween.

The flow potential of the quaternary ammonium salt polymer can be controlled by adjusting, for example, the molecular weight of the cationic monomer itself constituting the copolymer and the copolymerization molar ratio of the cationic monomer and the anionic monomer or the nonionic monomer constituting the copolymer. The flow potential of the quaternary ammonium salt polymer was measured using a flow potential measuring instrument (PCD04) manufactured by Spectris corporation. Specific measurement conditions are as follows. First, a commercially available sanitary product is decomposed into a surface sheet, an absorbent body, a back sheet, and the like by deactivating a hot melt for bonding members using a dryer or the likeAnd (3) a component. Subjecting each decomposed part to a multi-stage solvent extraction from a nonpolar solvent to a polar solvent, and separating the treating agent used in each part to obtain a solution containing a single composition. Drying and solidifying the obtained solution to obtain¹The structure of the treating agent is identified by a combination of H-NMR (nuclear magnetic resonance), IR (infrared spectroscopy), LC (liquid chromatography), GC (gas chromatography), MS (mass spectrometry), GPC (gel permeation chromatography), fluorescent X-ray, and the like. A measurement sample was obtained by dissolving 0.001g of a treatment agent (quaternary ammonium salt polymer) to be measured in 10g of physiological saline, and a 0.001N aqueous solution of sodium polyvinylsulfonate (0.001N aqueous solution of polydiallyldimethylammonium chloride when the measurement sample has a negative charge) was titrated against the measurement sample to measure a titration amount X mL required until the potential difference between the electrodes disappeared. Thereafter, the flow potential of the quaternary ammonium salt polymer was calculated according to the following formula.

Streaming potential (X + 0.190)^※)×1000

The dosage required by the corresponding solvent of the physiological saline solution

In order to allow the quaternary ammonium salt polymer to be smoothly adsorbed on the surface of erythrocytes, it is advantageous that the quaternary ammonium salt polymer easily interacts with the sialic acid. From this viewpoint, the present inventors have conducted studies and, as a result, have judged that the degree of interaction between the sialic acid conjugate and the cationic polymer can be evaluated on the basis of the Inorganic value/Organic value (hereinafter referred to as "IOB (Inorganic Organic Balance) value") which is the ratio of the Inorganic value to the Organic value of the substance.

In general, the behavior of a substance is largely governed by various intermolecular forces, which mainly include Van Der Waals (Van Der Waals) force based on molecular mass and electric affinity based on molecular polarity. If each of van der waals force and electric affinity which greatly affect a change in a property of a substance can be grasped, the properties of an unknown substance or a mixture thereof can be predicted from the combination. This idea is a theory known to the public as "organic concept graph theory". Organic conceptual diagram theory is described, for example, in "organic analysis" by rattan moore (Kaniya Shoten, 1930), and "organic qualitative analysis" by rattan moore: the systematic pure substance section (co-pending publication, 1953), the "adapted chemistry and organic chemistry section" by the rattan moor (heshu studios, 1971), the "systematic organic qualitative analysis (mixture section) by the rattan moor/akatsu political practices, the" wind room studios, 1974), and the "new organic conceptual diagram basis and application" by the shantian shansheng/zuoguang/shankunfu (triple co-pending publication, 2008), and the like are described in detail. According to the theory of organic conceptual diagrams, the degree of physical properties based mainly on van der waals forces is referred to as "organic properties", the degree of physical properties based mainly on electric affinity is referred to as "inorganic properties", and the physical properties of a substance are determined as a combination of "organic properties" and "inorganic properties". Further, 1 carbon (C) is defined as organic 20, and the inorganic and organic values of the various polar groups are defined as described in table 1 below, and the sum of the inorganic values and the sum of the organic values are obtained, and the ratio of the two is defined as IOB value. In the present invention, the IOB value of the sialic acid conjugate is determined based on the organic value and the inorganic value, and the IOB value of the cationic polymer is determined based on the determined IOB value.

[ Table 1]

Specifically, it is considered to be advantageous to use a cationic polymer having an IOB value equal to or similar 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 linked to a terminal of a glycolipid such as a galactolipid. The IOB value of sialic acid was 4.25 based on sialic acid monomer and 3.89 based on sialic acid conjugate. The sialic acid conjugate is a product in which a sugar chain in a glycolipid is linked to sialic acid, and the sialic acid conjugate has a higher ratio of organic value and a lower IOB value than a sialic acid monomer.

Therefore, the IOB value of the quaternary ammonium salt polymer is preferably 0.6 or more, more preferably 1.8 or more, more preferably 2.1 or more, and further preferably 2.2 or more. The IOB value of the cationic polymer is preferably 4.6 or less, more preferably 3.6 or less, and still more preferably 3 or less. The IOB value is more preferably 1.8 or more and 3.6 or less, more preferably 2.1 or more and 3.6 or less, and still more preferably 2.2 or more and 3 or less.

In the case where the quaternary ammonium salt polymer is a copolymer, the IOB value is calculated according to the following procedure based on the molar ratio of the monomers used for copolymerization. That is, the copolymer is obtained from a monomer A and a monomer B, and the monomer A has an organic value of OR_AInorganic value is IN_AThe organic value of the monomer B is OR_BInorganic value is IN_BThe molar ratio of monomer A/monomer B being M_A/M_BIn the case of (3), the IOB value of the copolymer is calculated by the following equation.

The blood cell coagulation agent used in the present invention may be in the form of a composition (blood cell coagulation agent composition) containing 1 or more third components, for example, other components such as a solvent, a plasticizer, a perfume, an antibacterial/deodorant agent, and a skin care agent, in addition to the polycation (cationic polymer). 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-butylene glycol, and the like can be used. As the flavor, a flavor having a fragrance like green herbs, an extract of a plant, an extract of citrus, and the like described in Japanese patent laid-open No. 2007-244764 can be used. As the antibacterial/deodorant agent, a cancrinite-like mineral containing an antibacterial metal as described in Japanese patent application laid-open No. 2004-244789, a porous polymer obtained by polymerizing a polymerizable monomer having a phenyl group as described in Japanese patent application laid-open No. 2007-097953, a quaternary ammonium salt, an activated carbon, a clay mineral, and the like as described in Japanese patent application laid-open No. 2006-191966 can be used. As skin care agents, plant extracts, collagen, natural moisturizing components, moisturizers, keratolytic agents, anti-inflammatory agents, and the like described in Japanese patent application laid-open No. 2004-255164 can be used.

The proportion of the cationic polymer in the blood cell coagulant composition is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. Further, it is preferably 99% by mass or less, more preferably 80% by mass or less, and still more preferably 60% by mass or less. By setting the ratio of the cationic polymer in the blood cell coagulant composition within this range, an effective amount of the cationic polymer can be provided to the physiological article.

The content of the blood cell aggregating agent contained in the physiological product is preferably 0.01g/m from the viewpoint of reliably functioning by elution into blood and forming a large aggregate²Above, more preferably 0.5g/m²The above. The content of the hemagglutinating agent contained in the physiological article is preferably 20g/m from the viewpoint of not impairing the liquid permeability²Hereinafter, more preferably 10g/m²The following. Specifically, the content of the hemagglutinating agent contained in the physiological article is preferably 0.01g/m²Above and 20g/m²Hereinafter, more preferably 0.5g/m²Above and 10g/m²The following.

(liquid film cracking agent)

The liquid film-splitting agent is an agent for splitting a liquid film formed between fibers or on the surface of fibers of a nonwoven fabric by bringing a liquid, for example, a highly viscous excretory fluid such as menstrual blood into contact with the nonwoven fabric, or for suppressing the formation of a liquid film, and has an action of splitting the formed liquid film and an action of suppressing the formation of a liquid film. The former may be called a primary role and the latter may be called a secondary role. The liquid film is cracked by the action of the liquid film cracking agent which pushes apart a part of the liquid film layer to destabilize the liquid film layer. The liquid film-splitting agent allows the liquid to easily pass through the nonwoven fabric without being retained in a narrow space between fibers of the nonwoven fabric. Namely, a nonwoven fabric having excellent liquid permeability is obtained. Thus, even if the fibers constituting the nonwoven fabric are thinned and the distance between the fibers is narrowed, soft touch feeling and suppression of residual liquid can be achieved at the same time. In the present invention, the use of the blood cell aggregating agent stably exerts the absorption performance inherent in the super absorbent polymer and effectively suppresses the rewet, while the color of the surface (skin contact surface) of the used sanitary article tends to significantly decrease the surface whiteness of the article when not used and increase the red color derived from blood, but the use of the blood cell aggregating agent in combination with the liquid film cracking agent suppresses the decrease in the surface whiteness due to the blood cell aggregating agent by the action of the liquid film cracking agent, and thus the reduction in the rewet amount and the improvement in the surface whiteness after use can be achieved at the same time.

The liquid film splitting effect is not limited to being generated only between fibers of the nonwoven fabric as long as the liquid film splitting agent is disposed in a portion where a liquid film is likely to be present. For example, in an absorbent body having fluff pulp or a super absorbent polymer, a liquid film splitting effect can be produced even for a liquid film formed between fibers of the fluff pulp, between particles of the super absorbent polymer, between the fluff pulp and the super absorbent polymer particles, or the like.

In the present invention, the term "material constituting the sanitary article" mainly means a material attached to the surface of the material, which contains or contains a liquid film-splitting agent. In the case where the fibers contain the liquid film-splitting agent, the liquid film-splitting agent may be, for example, one contained in the fibers or one contained in the fibers by internal addition, as long as the liquid film-splitting agent remains on the surface of the fibers.

In order to provide the liquid film-splitting agent of the present invention with the following liquid film-splitting effect in a physiological article, the liquid film-splitting agent should be present in a liquid state when it comes into contact with a body fluid. In this respect, the melting point of the liquid film cracking agent of the present invention is preferably 40 ℃ or lower, more preferably 35 ℃ or lower. Further, the melting point of the liquid film cracking agent of the present invention is preferably-220 ℃ or higher, more preferably-180 ℃ or higher.

(property of disappearing liquid film)

The liquid film breaking agent used in the present invention has a property of breaking a liquid film, and by this property, a liquid film breaking effect can be exhibited when the liquid film breaking agent is applied to a test solution mainly containing a plasma component. The liquid film disappearing effect mentioned here includes both an effect of suppressing the formation of a liquid film of a structure in which air is included in a plurality of liquid films formed from a test liquid and an effect of disappearing the formed structure, and a preparation exhibiting at least one effect may be said to have a property capable of exhibiting the liquid film disappearing effect.

The Test solution was a liquid component obtained by extraction from defibrinated horse blood (manufactured by Nippon Bio-Test Laboratories, Inc.). Specifically, when 100mL of horse blood is allowed to stand at 22 ℃ and 65% humidity for 1 hour, the horse blood is separated into an upper layer and a lower layer, and the upper layer is the test solution. The upper layer contains mainly plasma components and the lower layer contains mainly blood cell components. For example, a pipette (manufactured by NIPPON MICRO corporation) may be used to extract only the upper layer from the defibered horse blood separated into the upper layer and the lower layer.

Whether or not a certain agent has the "property of disappearing a liquid film" is determined based on the amount of a liquid film, which is a structure formed by enclosing air in a liquid film formed by the test liquid to which the agent is applied, in a case where the structure is in a state in which the structure is likely to be generated. That is, the temperature of the test solution was adjusted to 25 ℃ and 10g of the test solution was put into a spiral tube (No. 5, manufactured by Maruemu Co., Ltd., cylinder diameter 27mm, full length 55mm) to obtain a standard sample. The same sample as the standard sample was added with 0.01g of the preparation to be measured previously adjusted to 25 ℃ to obtain a measurement sample. The standard sample and the measurement sample were rapidly placed on a horizontal surface after being strongly vibrated by reciprocating the sample 2 times in the vertical direction of the spiral tube. By the vibration of the sample, a liquid layer (lower layer) having no structure and a structural body layer (upper layer) including a plurality of structures formed on the liquid layer are formed in the vibrated spiral tube. Immediately after the vibration, the height of the structure layer (height from the liquid surface of the liquid layer to the upper surface of the structure layer) was measured for both samples after 10 seconds. Further, when the height of the structural layer of the measurement sample is 90% or less of the height of the structural layer of the standard sample, it is judged that the preparation to be measured has a liquid film cracking effect.

The liquid film breaking agent used in the present invention is a single compound satisfying the above properties, a mixture of a plurality of single compounds satisfying the above properties, or a preparation satisfying the above properties (capable of breaking a liquid film) by a combination of a plurality of compounds. That is, the liquid film breaking agent is limited to those having the liquid film breaking effect defined above. Thus, the compounds used in the physiological articles are distinguished from liquid film-splitting agents in the case of comprising a third component which does not meet the above definition. In the present specification, the term "single compound" is a concept including compounds having the same composition formula but different molecular weights depending on the number of repeating units.

As the liquid film breaking agent, any of the liquid film breaking agents described in International publication No. 2016/098796 can be used.

Hereinafter, preferred embodiments of the liquid film cracking agent of the present invention will be described. The liquid film cracking agent of the present invention is preferably used in both embodiments 1 and 2.

The liquid film cracking agent of embodiment 1 is compound C1. Compound C1 has a coefficient of expansion of 15mN/m or more with respect to a liquid having a surface tension of 50mN/m, and a water solubility of 0g or more and 0.025g or less.

The "coefficient of expansion to a liquid having a surface tension of 50 mN/m" possessed by the liquid film-cleaving agent of embodiment 1 refers to the coefficient of expansion when assuming an excretory fluid such as menstrual blood as described above. The "expansion coefficient" is a value obtained based on the following formula (1) from a measurement value obtained by the following measurement method in an environmental region at a temperature of 25 ℃ and a Relative Humidity (RH) of 65%. Further, γ of the formula (1)_wAnd gamma_woThe "liquid film" in (1) means a liquid phase of "a liquid having a surface tension of 50 mN/m", and includes both a liquid in a state in which a film has been formed between fibers or on the surface of the fibers and a liquid in a state before the film is formed, and is also simply referred to as a liquid. Also, γ of the following formula (1)_wAnd gamma_oThe "surface tension" in (1) means the interfacial tension at the interface of the liquid film and the liquid film-cleaving agent with the gas phase, which is different from the liquid film-cleaving between the liquid phasesInterfacial tension of the cracking agent and the liquid film. This difference is also the same as in other descriptions in this specification.

S＝γ_w－γ_o－γ_wo·····(1)

γ_w: surface tension of liquid film (liquid)

γ_o: surface tension of liquid film cracking agent

γ_wo: interfacial tension of liquid film cracking agent and liquid film

As is apparent from the above formula (1), the coefficient of expansion (S) of the liquid film cracking agent is determined by the surface tension (gamma) of the liquid film cracking agent_o) Becomes smaller and larger, and is caused by the interfacial tension (gamma) between the liquid film-splitting agent and the liquid film_wo) Becoming smaller and larger. Since the spreading coefficient is 15mN/m or more, the liquid film cracking agent of embodiment 1 has high mobility, i.e., high diffusibility, on the surface of the liquid film formed in the narrow region between fibers. From this viewpoint, the spreading factor of the liquid film cracking agent according to embodiment 1 is more preferably 20mN/m or more, still more preferably 25mN/m or more, and particularly preferably 30mN/m or more. On the other hand, the upper limit is not particularly limited, but according to the above formula (1), for example, the upper limit is 50mN/m in the case of using a liquid having a surface tension of 50mN/m, 60mN/m in the case of using a liquid having a surface tension of 60mN/m, and 70mN/m in the case of using a liquid having a surface tension of 70mN/m, and thus the surface tension of the liquid forming the liquid film becomes the upper limit. Therefore, in the present invention, the liquid film cracking agent of embodiment 1 has an expansion coefficient of 50mN/m or less from the viewpoint of using a liquid having a surface tension of 50 mN/m.

The liquid film cracking agent of embodiment 1 has a water solubility of 0g or more and 0.025g or less, and is less likely to dissolve in an aqueous liquid and form an interface with a liquid film, thereby making the above-mentioned diffusibility more effective. From the same viewpoint, the water solubility of the liquid film cracking agent of embodiment 1 is preferably 0.025g or less, more preferably 0.0017g or less, and still more preferably less than 0.0001 g. The lower the water solubility, the better, and more than 0g, from the viewpoint of the diffusibility into a liquid film, practically 1.0X 10^-9g is above. Furthermore, the above-mentioned water solubility is also considered to be suitableCan be used for menstrual blood containing water as main component. The water solubility of the liquid film cracking agent can be measured by the following method.

Surface tension (gamma) of the liquid film (liquid having a surface tension of 50 mN/m)_w) Surface tension (gamma) of liquid film cracking agent_o) And interfacial tension (gamma) between the liquid film cracking agent and the liquid film_wo) Is measured by the following method.

(surface tension of liquid film (liquid) (. gamma.)_w) Method of measuring (1)

The measurement can be carried out by a plate method (Wilhelmy method) using a platinum plate in an environment region of 25 ℃ and 65% Relative Humidity (RH). As a measuring apparatus in this case, an automatic surface tensiometer "CBVP-Z" (trade name, manufactured by Kyowa Kagaku K.K.) can be used. The platinum plate used had a purity of 99.9% and a size of 25mm in length/10 mm in width.

The "liquid having a surface tension of 50 mN/m" is a solution prepared by adding polyoxyethylene sorbitan monolaurate (trade name: RHEODOL SUPER TW-L120, manufactured by Kao corporation) as a nonionic surface active material to deionized water by the above-mentioned measurement method to adjust the concentration to 50. + -.1 mN/m.

(surface tension (. gamma.) of liquid film-splitting agent_o) Method of measuring (1)

Surface tension (gamma) with liquid film_w) Similarly, the measurement can be carried out by a plate method using the same apparatus in an environment at a temperature of 25 ℃ and a Relative Humidity (RH) of 65%. In this measurement, when the obtained liquid film cracking agent is a solid, the liquid film cracking agent is heated to the melting point +5 ℃ to cause phase transition to a liquid, and the measurement is performed while maintaining the temperature condition.

(interfacial tension (. gamma.) between the liquid film-cleaving agent and the liquid film_wo) Method of measuring (1)

The measurement can be carried out by the pendant drop method in an environmental region at a temperature of 25 ℃ and a Relative Humidity (RH) of 65%. As the measuring apparatus in this case, an automatic interfacial viscoelasticity measuring apparatus (trade name THE TRACKER manufactured by TECLIS-ITCONCEPT, or DSA25S manufactured by KRUSS) can be used. In the pendant drop method, the adsorption of a nonionic surface active material contained in a liquid having a surface tension of 50mN/m is started simultaneously with the formation of a liquid drop, and the interfacial tension gradually decreases with the passage of time. Therefore, the interfacial tension at the time of droplet formation (at 0 second) was read. In the measurement, when the obtained liquid film cracking agent is a solid as described above, the liquid film cracking agent is heated to the melting point +5 ℃ to cause phase transition to a liquid, and the measurement is performed while maintaining the temperature condition.

Further, the following may be the case when the interfacial tension is measured: when the difference in density between the liquid film breaking agent and the liquid having a surface tension of 50mN/m is very small, or when the viscosity is significantly high, or when the interfacial tension value is not more than the measurement limit of the pendant drop method, it is difficult to measure the interfacial tension by the pendant drop method. In this case, the measurement can be performed by the spin drop method in an environmental region at a temperature of 25 ℃ and a Relative Humidity (RH) of 65%. As a measuring apparatus in this case, a spinning drop interfacial tension meter (product name SITE100, manufactured by KURUSS) can be used. In addition, for the measurement, the interfacial tension at the time of stabilizing the droplet shape was also read, and when the obtained liquid film cracking agent was a solid, the liquid film cracking agent was heated to the melting point thereof +5 ℃ to cause phase transition to a liquid, and the measurement was carried out while maintaining the temperature condition.

In the case where the interfacial tension can be measured by both measuring apparatuses, a smaller value of the interfacial tension is used as the measurement result.

The liquid film cracking agent of embodiment 1 has the above expansion coefficient and water solubility, and thus can diffuse on the surface of the liquid film without dissolving, and push away the liquid film layer from the vicinity of the center of the liquid film. This destabilizes the liquid film and causes cracking.

Here, the above-described liquid film splitting effect of the liquid film splitting agent in the absorbent body of embodiment 1 will be specifically described with reference to fig. 3 and 4, taking as an example a case where the liquid film splitting agent is disposed in a nonwoven fabric.

Fig. 3 shows a state in which a liquid film 8 is formed in gaps between fibers 7 constituting a nonwoven fabric, and fig. 4 shows a process in which the liquid film 8 is split by a liquid film splitting agent 9. As shown in fig. 3, in a narrow region between fibers, excretory fluid having high viscosity such as menstrual blood is likely to form a liquid film 8. On the other hand, the liquid film-cracking agent 9 destabilizes and cracks the liquid film 8 as described below, suppresses the formation of the liquid film 8, and promotes the discharge of the liquid from the nonwoven fabric. First, as shown in fig. 4(a1) and (B1), the liquid film cracking agent 9 attached to the surface of the fibers 7, which the fibers 7 of the nonwoven fabric have, moves from above the fibers 7 to the liquid film 8, and further moves above the surface of the liquid film 8 while maintaining the interface with the liquid film 8. Then, as shown in fig. 4(a2) and (B2), the liquid film cracking agent 9 pushes apart a part of the liquid film 8 and penetrates into the inside in the thickness direction of the liquid film 8, and as shown in fig. 4(A3) and (B3), the liquid film 8 is gradually changed into an uneven thin film. As a result, as shown in fig. 4(a4) and (B4), the liquid film 8 is broken as it bursts open and is split. The liquid such as menstrual blood formed into the liquid film 8 thus split becomes droplets and easily passes through the space between fibers of the nonwoven fabric, and therefore the amount of residual liquid decreases.

The liquid film splitting agent acts to split the liquid film not only in the case of the liquid film between mutually intersecting fibers as shown in fig. 3, but also in the case of the liquid film adhering to the fiber surface. That is, the liquid film-splitting agent moves on the liquid film adhered to the fiber surface to push away a part of the liquid film, thereby splitting the liquid film. In this case, the liquid film splitting agent can split a liquid film adhering to the fiber surface by its hydrophobic effect to suppress the formation of the liquid film even if the liquid film splitting agent itself does not move on the fiber surface toward the liquid film.

In embodiment 1, the liquid film cracking agent more preferably has an interfacial tension of 20mN/m or less with respect to a liquid having a surface tension of 50 mN/m. That is, the variable "interfacial tension (γ) between the liquid film cracking agent and the liquid film" which determines the value of the expansion coefficient (S) in the above formula (1)_wo) "preferably 20mN/m or less. By "interfacial tension (gamma) of the liquid film cleavage agent and the liquid film_wo) "the effect is more clearly understood by the fact that the suppression is low, the expansion coefficient of the liquid film cracking agent is increased, and the liquid film cracking agent easily moves from the fiber surface to the vicinity of the center of the liquid film. From this viewpoint, "interfacial tension against liquid having surface tension of 50 mN/m" of the liquid film-cleaving agent is more preferably 17mN/m or less, more preferably 13mN/m or less, still more preferably 10mN/m or less, particularly preferably 9mN/m or less, and particularly preferably 1mN/m or less. On the other hand, the lower limit is not particularly limited, and from the viewpoint of insolubility in a liquid film, it may be more than 0 mN/m. Further, when the interfacial tension is 0mN/m, that is, when the liquid film breaking agent is dissolved in the liquid film, an interface cannot be formed between the liquid film and the liquid film breaking agent, and therefore the above formula (1) does not hold, and the agent does not expand.

From the above equation (1), the value of the expansion coefficient changes depending on the surface tension of the liquid to be treated. For example, when the surface tension of the object liquid is 72mN/m, the surface tension of the liquid film opener is 21mN/m, and the interfacial tension thereof is 0.2mN/m, the spreading factor is 50.8 mN/m.

When the surface tension of the target liquid was 30mN/m, the surface tension of the liquid film opener was 21mN/m, and the interfacial tension thereof was 0.2mN/m, the spreading factor was 8.8 mN/m.

In any case, the larger the expansion coefficient, the greater the liquid film-cracking effect of the formulation.

In the present specification, the numerical value in the case of a surface tension of 50mN/m is defined, but even if the surface tensions are different, the magnitude relationship of the expansion coefficients of the respective substances is not changed, and therefore even if the surface tension of the body fluid is changed by daily physical conditions or the like, the preparation having a larger expansion coefficient exhibits an excellent liquid film breaking effect.

In embodiment 1, the surface tension of the liquid film cleavage agent is preferably 32mN/m or less, more preferably 30mN/m or less, still more preferably 25mN/m or less, and particularly preferably 22mN/m or less. The lower the surface tension, the more preferable the lower the surface tension, the lower the surface tension is not particularly limited. The liquid film cracking agent is actually 1mN/m or more in terms of durability.

Next, the liquid film cracking agent of embodiment 2 will be described.

The liquid film cracking agent of embodiment 2 is compound C2. Compound C2 has a coefficient of expansion of more than 0mN/m for a liquid having a surface tension of 50mN/m, i.e., a positive value, a water solubility of 0g to 0.025g, and an interfacial tension of 20mN/m or less for a liquid having a surface tension of 50 mN/m. Setting the "interfacial tension against a liquid having a surface tension of 50 mN/m" to 20mN/m or less means that the diffusibility of the liquid film cracking agent in the liquid film is improved as described above. Accordingly, even when the "coefficient of expansion with respect to a liquid having a surface tension of 50 mN/m" is relatively small, the liquid film cracking agent is dispersed in a large amount from the fiber surface into the liquid film due to high diffusibility, and the liquid film is pushed away at a plurality of positions, whereby the same liquid film cracking effect as in the case of embodiment 1 can be exhibited.

The "coefficient of expansion to a liquid having a surface tension of 50 mN/m", "water solubility" and "interfacial tension to a liquid having a surface tension of 50 mN/m" of the liquid film-cleaving agent are the same as those defined in embodiment 1, and the measurement method thereof is also the same.

In embodiment 2, the "interfacial tension with respect to a liquid having a surface tension of 50 mN/m" is preferably 17mN/m or less, more preferably 13mN/m or less, even more preferably 10mN/m or less, even more preferably 9mN/m or less, and particularly preferably 1mN/m or less, from the viewpoint of more effectively making the above-described action of the liquid film cracking agent. The lower limit value is not particularly limited as in embodiment 1, and is actually greater than 0mN/m from the viewpoint of insolubility in a liquid film (a liquid having a surface tension of 50 mN/m).

Further, the "coefficient of expansion with respect to a liquid having a surface tension of 50 mN/m" is preferably 9mN/m or more, more preferably 10mN/m or more, and still more preferably 15mN/m or more, from the viewpoint of more effectively making the above-described action of the liquid film opener. The upper limit is not particularly limited, and from the viewpoint that the surface tension of the liquid forming the liquid film is the upper limit, the upper limit is substantially 50mN/m or less according to the above formula (1).

Further, more preferable ranges of the surface tension and water solubility of the liquid film cracking agent are the same as those of embodiment 1.

The liquid film breaking agent according to embodiment 1 and embodiment 2 preferably further contains a phosphate ester type anionic surfactant when the liquid film breaking agent is contained in a nonwoven fabric containing synthetic resin fibers, paper containing cellulose fibers, or an absorbent core. Accordingly, the hydrophilicity of the fiber surface is improved, the wettability is improved, the contact area between the liquid film and the liquid film cracking agent is increased, and the blood contains a surfactant having a phosphate group derived from a living body, and therefore, the surfactant having a phosphate group is used in combination, and further, the affinity with the phospholipid contained in the blood is good due to the compatibility of the surfactant, so that the liquid film cracking agent is easily moved to the liquid film, and the cracking of the liquid film is further promoted. The content ratio of the liquid film cracking agent to the phosphate ester type anionic surfactant is set as the former: the latter, preferably 1: 1-19: 1, more preferably 2: 1-15: 1, more preferably 3: 1-10: 1. the content ratio is the former in terms of mass ratio: the latter, in particular, is preferably 5: 1-19: 1, more preferably 8: 1-16: 1, more preferably 11: 1-13: 1.

the phosphate ester type anionic surfactant can be used without particular limitation. Specific examples thereof include: alkyl ether phosphates, dialkyl phosphates, alkyl phosphates, and the like. Among them, alkyl phosphate is preferable from the viewpoint of enhancing the affinity of the liquid film cleavage agent containing the same with a liquid film and imparting a function of imparting processability to the nonwoven fabric.

Next, specific examples of the liquid film cracking agent according to embodiment 1 and embodiment 2 will be described. They have the property of being insoluble in water or water and exert the liquid film splitting effect by being in the above-specified numerical range. On the other hand, a surfactant or the like conventionally used as a fiber treatment agent is used by being dissolved in water in actual use, and is substantially water-soluble, and is not the liquid film breaking agent of the present invention.

The liquid film cracking agent according to embodiment 1 and embodiment 2 is preferably a compound having a weight average molecular weight of 500 or more. This weight average molecular weight has a large influence on the viscosity of the liquid film cracking agent. By maintaining a high viscosity, the liquid is less likely to flow down when passing through the constituent material, and the continuity of the liquid film cracking effect can be maintained. The weight average molecular weight of the liquid film cracking agent is more preferably 1000 or more, still more preferably 1500 or more, and particularly preferably 2000 or more, from the viewpoint of achieving a viscosity that sufficiently sustains the liquid film cracking effect. On the other hand, the viscosity at which the liquid film cracking agent is allowed to move from the constituent material provided with the liquid film cracking agent to the liquid film, that is, the diffusibility is maintained is preferably 50000 or less, more preferably 20000 or less, and still more preferably 10000 or less.

The liquid film cracking agent according to embodiment 1 is preferably a compound having at least 1 structure selected from the group consisting of structures X, X-Y and Y-X-Y. The structure X and the structure Y mentioned here are specifically the following structures. In the following structures, "C" represents a carbon atom, and "<", ">" and "-" each represent a connecting bond.

Structure X represents > C (A) -, -C (A)₂-、-C(A)(B)-、＞C(A)-C(R¹)＜、＞C(R¹)-、-C(R¹)(R²)-、-C(R¹)₂-, > C <, and-Si (R)¹)₂O-、-Si(R¹)(R²) A siloxane chain having a structure in which any one of the basic structures of O-is repeated or 2 or more kinds of O-are combined, or a mixed chain thereof. Having a terminal end of structure X selected from hydrogen atoms, or-C (A)₃、-C(A)₂B、-C(A)(B)₂、-C(A)₂-C(R¹)₃、-C(R¹)₂A、-C(R¹)₃or-OSi (R)¹)₃、-OSi(R¹)₂(R²)、-Si(R¹)₃、-Si(R¹)₂(R²) At least one group of (1).

R is as defined above¹Or R²Each independently represents various substituents such as a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms; for example, preferably a methyl group, an ethyl group, or a propyl group), an alkoxy group (preferably having 1 to 20 carbon atoms; for example, preferably a methoxy group or an ethoxy group), an aryl group (preferably having 6 to 20 carbon atoms; for example, preferably a phenyl group), a halogen atom (for example, preferably a fluorine atom), or the like. A. B independently represents a hydroxyl group or a carboxylic acid group, an amino group, an amide group, an imino group, a phenol group or the likeA substituent containing an oxygen atom or a nitrogen atom. In structure X R¹、R²When there are a plurality of A, B, these may be the same or different. The bond between consecutive C (carbon atom) or Si is usually a single bond, but may contain a double bond or a triple bond, and the bond between C or Si may contain an ether group (-O-), an amide group (-CONR)^A-：R^AA hydrogen atom or a monovalent group), an ester group (-COO-), a carbonyl group (-CO-), a carbonate group (-OCOO-), and the like. The number of the C and Si linked to one C or Si is 1 to 4, and there may be a case where a long silicone chain (siloxane chain) or a mixed chain has a branch or has a radial structure.

The structure Y represents a hydrophilic group containing an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom and having hydrophilicity. Examples of the hydrophilic group include a single hydrophilic group or a combination thereof, such as a hydroxyl group, a carboxylic acid group, an amino group, an amide group, an imine group, a phenol group, and a polyoxyalkylene group (the number of carbon atoms of the oxyalkylene group is preferably 1 to 4; for example, a Polyoxyethylene (POE) group or a polyoxypropylene (POP) group), a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, a sulfobetaine group, a carbonylbetaine group, a phosphobetaine group (these betaine groups refer to betaine residues obtained by removing 1 hydrogen atom from each betaine compound), and a quaternary ammonium group. In addition to these, the following compounds relating to M may be mentioned¹The radicals and functional groups mentioned. Further, when there are a plurality of Y's as in the structure Y-X-Y, the plurality of Y's may be the same or different from each other.

In the structures X-Y and Y-X-Y, Y is a group bonded to X or to the end of X. In the case where Y is a group bonded to the terminal of X, the group bonded to Y is bonded to Y, for example, by removing hydrogen atoms or the like in an amount equal to the number of bonds to Y.

In this structure, the hydrophilic group Y, A, B may be selected from the specifically described groups to satisfy the above expansion coefficient, water solubility, interfacial tension. Thus, the target liquid film cracking effect is exhibited.

The liquid film cracking agent of embodiment 1 is preferably a compound in which structure X is a siloxane structure. Further, the liquid film cracking agent of embodiment 1 is preferably a compound composed of a siloxane chain in which structures represented by the following formulae (1) to (11) as specific examples of the structure X, X-Y, Y-X-Y are arbitrarily combined. Further, from the viewpoint of the liquid film cracking effect, the compound preferably has a weight average molecular weight within the above range.

In the above formulae (1) to (11), M¹、L¹、R²¹And R²²Represents the following 1-valent or multi-valent (2-valent or more) group. R²³And R²⁴Represents a group having 1 or more valences (2 or more valences) below, or a single bond.

M¹The functional group is a group having a polyoxyethylene group, a polyoxypropylene group, a polyoxybutenyl group, or a polyoxyalkylene group in which these groups are combined, or a hydrophilic group having a plurality of hydroxyl groups such as an erythritol group, a xylitol group, a sorbitol group, a glyceryl group, or a glycol group (a hydrophilic group obtained by removing 1 hydrogen atom from the above-mentioned compound having a plurality of hydroxyl groups such as erythritol), a hydroxyl group, a carboxylic acid group, a mercapto group, or an alkoxy group (preferably having 1 to 20 carbon atoms, for example, a methoxy group), an amino group, an amide group, an imino group, a phenol group, a sulfonic acid group, a quaternary ammonium group, a sulfobetaine group, a hydroxysulfobetaine group, a phosphobetaine group, an imidazolium betaine group, a carbonylbetaine group, an epoxy group, a primary alcohol (carbinol) group, a (meth) acryloyl group, or a combination thereof. Furthermore, in M¹In the case of a polyvalent radical, M¹Each group or functional group is further a group obtained by removing 1 or more hydrogen atoms.

L¹Represents an ether group or an amino group (which may be L)¹And amino groups employed in the formula > NR^C(R^CHydrogen atom or monovalent group), an amide group, an ester group, a carbonyl group, or a carbonate group.

R²¹、R²²、R²³And R²⁴Each independently represents an alkyl group (preferably having 1 to 20 carbon atoms; for example, preferably a methyl group)Ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, decyl), alkoxy (preferably 1 to 20 carbon atoms; for example, preferably methoxy group, ethoxy group), aryl group (preferably, C6-20; for example, preferably a phenyl group), a fluoroalkyl group or an aralkyl group, or a hydrocarbon group containing these in combination, or a halogen atom (for example, preferably a fluorine atom). Further, in R²²And R²³The polyvalent group means a polyvalent hydrocarbon group obtained by further removing 1 or more hydrogen atoms or fluorine atoms from the hydrocarbon group.

And, in R²²Or R²³And M¹In the case of connection, R may be defined as²²Or R²³Examples of the group to be used include M in addition to the above-mentioned groups, the above-mentioned hydrocarbon group and halogen atom¹And the imine group is used.

Among the liquid film cracking agents according to embodiment 1, preferred is a compound having a structure represented by any one of the above formulae (1), (2), (5), and (10) as a structure X, and having a structure represented by any one of the above formulae other than those formulae as an end of X or a group composed of an end of X and Y. More preferably, the compound is a compound composed of a siloxane chain in which X or a group composed of the end of X and Y has at least 1 of the structures represented by any of the above formulae (2), (4), (5), (6), (8), and (9).

Specific examples of the liquid film cracking agent of embodiment 1, which is the above-mentioned compound, include organically modified silicones (polysiloxanes) as silicone surfactants. Examples of the organic modified silicone modified with a reactive organic group include amino-modified, epoxy-modified, carboxyl-modified, glycol-modified, primary alcohol (carbinol) -modified, (meth) acryloyl-modified, mercapto-modified, and phenol-modified silicones. Examples of the organic modified silicone modified with a non-reactive organic group include polyether modified (including polyoxyalkylene modified), methyl styrene modified, long chain alkyl modified, higher fatty acid ester modified, higher alkoxy modified, higher fatty acid modified, and fluorine modified silicones. Depending on the type of the organic modification, for example, the molecular weight of the silicone chain, the modification ratio, the number of moles of the modifying group added, and the like are appropriately changed, whereby the coefficient of expansion which exerts the above-mentioned liquid film cracking effect can be obtained. Here, the term "long chain" means a carbon atom number of 12 or more, preferably 12 to 20. The term "higher" means a carbon atom number of 6 or more, preferably 6 to 20.

Among these, the liquid film cleavage agent of a modified silicone such as a polyoxyalkylene-modified silicone, an epoxy-modified silicone, a primary alcohol (carbinol) -modified silicone, or a glycol-modified silicone is preferably a modified silicone having a structure in which the modified group contains at least one oxygen atom, and particularly preferably a polyoxyalkylene-modified silicone. The polyoxyalkylene-modified silicone has a polysiloxane chain, and when a liquid film cracking agent is contained in a synthetic resin fiber, the silicone is less likely to penetrate into the fiber and is likely to remain on the surface. Further, addition of a hydrophilic polyoxyalkylene chain is preferable because affinity with water is improved and interfacial tension is low, and thus migration on the surface of the liquid film is easy. Even when the polyoxyalkylene-modified silicone is subjected to hot melt processing such as embossing, the polyoxyalkylene-modified silicone is likely to remain on the fiber surface, and the liquid film cracking effect is less likely to be reduced. In particular, it is preferable that the embossed portion where liquid is likely to be retained sufficiently exhibit a liquid film splitting effect.

Examples of the polyoxyalkylene-modified silicone that can be used as the liquid film cracking agent in embodiment 1 include those represented by the following formulas [ I ] to [ IV ]. Further, the polyoxyalkylene-modified silicone preferably has a weight average molecular weight in the above range from the viewpoint of the liquid film cracking effect.

The above formula [ I]～[IV]In, R³¹Represents an alkyl group (preferably having 1 to 20 carbon atoms; for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, decyl) is preferable. R³²Represents a single bond or an alkylene group (preferably having 1 to 20 carbon atoms; for example, preferably a phenylene group)Methyl, ethylene, propylene, butylene), preferably represents the above alkylene group. Plural R³¹A plurality of R³²May be the same or different from each other. M¹¹Represents a group having a polyoxyalkylene group, and is preferably a polyoxyalkylene group. Examples of the polyoxyalkylene group include: polyoxyethylene groups, polyoxypropylene groups, polyoxybutenyl groups, and the like, which are obtained by copolymerizing these constituent monomers. m and n are each independently an integer of 1 or more. Further, the symbols of these repeating units are in the formula [ I]～[IV]The terms (a) and (b) do not necessarily denote the same integer, but may be different.

The polyoxyalkylene-modified silicone that can be used as the liquid film cracking agent in embodiment 1 may have either one or both of a polyoxyethylene-modified silicone and a polyoxypropylene-modified silicone. In addition, in order to be insoluble in water and have a low interfacial tension, the alkyl group R of the silicone chain is preferably³¹Having a methyl group therein. The modified group and the silicone chain are not particularly limited, and there is, for example, a paragraph [0006 ] of Japanese patent laid-open publication No. 2002-]And [0012]]The method is described. More specifically, there may be mentioned: polyoxyethylene (POE) polyoxypropylene (POP) modified silicone, Polyoxyethylene (POE) modified silicone, polyoxypropylene (POP) modified silicone, and the like. Examples of the POE-modified silicone include POE (3) modified dimethyl silicone to which 3 moles of POE are added. Examples of the POP-modified silicone include POP (10) -modified dimethylsilicone, POP (12) -modified dimethylsilicone, and POP (24) -modified dimethylsilicone, to which 10, 12, or 24 moles of POP are added.

The spreading factor and the water solubility of the liquid film cracking agent of embodiment 1 can be set to specific ranges in the case of the polyoxyalkylene-modified silicone, for example, by the number of moles of polyoxyalkylene added (the number of oxyalkylene groups forming a polyoxyalkylene bond per 1 mole of the polyoxyalkylene-modified silicone), the following modification ratio, and the like. The surface tension and the interfacial tension of the liquid film cleavage agent can be set to specific ranges in the same manner.

From the above viewpoint, the polyoxyalkylene-modified silicone that can be used as the liquid film cracking agent of embodiment 1 is preferably one in which the number of moles of added polyoxyalkylene is 1 or more. From the viewpoint of enhancing the liquid film cracking effect by reducing the interfacial tension and increasing the expansion coefficient, the number of moles added is more preferably 3 or more, and still more preferably 5 or more. On the other hand, from the viewpoint of preventing the water solubility from becoming too high due to the hydrophilicity, the number of moles added is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less.

The modification ratio of the modified silicone is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more, in order to ensure necessary hydrophilicity. In order to make it insoluble in water, it is preferably 95% or less, more preferably 70% or less, and still more preferably 40% or less. The modification ratio of the modified silicone is a ratio of the number of repeating units of the modified siloxane bond to the total number of repeating units of the siloxane bond in the molecule of the modified silicone 1. For example, (n/m + n) × 100% in the above formulae [ I ] and [ IV ], (2/m) × 100% in the formula [ II ], and (1/m) × 100% in the formula [ III ].

In the case of polyoxyalkylene-modified silicone, the specific ranges may be set by using a water-soluble polyoxyethylene group and a water-insoluble polyoxypropylene group and a water-insoluble polyoxybutenyl group as the modifying groups in combination, in addition to the above-described modes; changing the molecular weight of the water-insoluble silicone chains; as the modifying group, in addition to polyoxyalkylene modification, an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a primary alcohol (carbinol) group, or the like is introduced.

When the nonwoven fabric contains the polyalkylene-modified silicone which can be used as the liquid film-splitting agent in embodiment 1, the content of the polyalkylene-modified silicone is preferably 0.02 mass% or more and 8 mass% or less in terms of the content ratio (Oil Per Unit) with respect to the mass of the fiber. The content ratio (OPU) of the polyalkylene-modified silicone is more preferably 5% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.4% by mass or less. Thus, the nonwoven fabric has a good touch. From the viewpoint of sufficiently exerting the liquid film splitting effect by the polyalkylene-modified silicone, the content ratio (OPU) is more preferably 0.0005 mass% or more, and still more preferably 0.0015 mass% or more.

The content of the polyalkylene-modified silicone contained in the sanitary article is preferably 0.00001g/m from the viewpoint of acting on the liquid film reliably, not limited to the nonwoven fabric²Above, more preferably 0.0001g/m²Above, more preferably 0.0003g/m²The above. The content of the polyalkylene-modified silicone contained in the sanitary article is preferably 10g/m from the viewpoint of ensuring liquid permeability²Hereinafter, more preferably 7g/m²Hereinafter, it is more preferably 5g/m²The following. Specifically, the content of the polyalkylene-modified silicone as the liquid film-splitting agent according to embodiment 1 contained in the physiological article is preferably 0.00001g/m²Above and 10g/m²Hereinafter, more preferably 0.0001g/m²Above and 7g/m²Hereinafter, more preferably 0.0003g/m²Above and 5g/m²The following.

The liquid film cracking agent according to embodiment 2 is preferably a compound having at least 1 structure selected from the following structures Z, Z-Y and Y-Z-Y, as described below. The structure Z and the structure Y mentioned here are specifically the following structures. In the following structures, "C" represents a carbon atom, and "<", ">" and "-" each represent a connecting bond.

Structure Z represents > C (A) -, -C (A)₂-、-C(A)(B)-、＞C(A)-C(R³)＜、＞C(R³)-、-C(R³)(R⁴)-、-C(R³)₂A hydrocarbon chain having a structure in which any one of the basic structures-, > C < is repeated or 2 or more kinds are combined. Having at the terminus of structure Z a hydrogen atom, or-C (A)₃、-C(A)₂B、-C(A)(B)₂、-C(A)₂-C(R³)₃、-C(R³)₂A、-C(R³)₃At least one group of (1).

R is as defined above³Or R⁴Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms, for example, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, a nonyl group, a decyl group),Alkoxy (preferably having 1 to 20 carbon atoms; for example, preferably methoxy or ethoxy), aryl (preferably having 6 to 20 carbon atoms; for example, preferably phenyl), fluoroalkyl, aralkyl, a hydrocarbon group containing these, or a fluorine atom. A. Each B independently represents a substituent containing an oxygen atom or a nitrogen atom, such as a hydroxyl group, a carboxylic acid group, an amino group, an amide group, an imine group, or a phenol group. In structure Z R³、R⁴When there are a plurality of A, B, these may be the same or different. The bond between consecutive C (carbon atoms) is usually a single bond, but may contain a double bond or a triple bond, and the bond between C may contain a linking group such as an ether group, an amide group, an ester group, a carbonyl group, or a carbonate group. The number of the C-linked units is 1 to 4, and the long hydrocarbon chain may be branched or have a radial structure.

The structure Y represents a hydrophilic group containing an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom and having hydrophilicity. Examples of the hydrophilic group include a hydroxyl group, a carboxylic acid group, an amino group, an amide group, an imide group, a phenol group, a polyoxyalkylene group (the number of carbon atoms of the oxyalkylene group is preferably 1 to 4; for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, or a polyoxyalkylene group in combination thereof), a hydrophilic group having a plurality of hydroxyl groups such as an erythritol group, a xylitol group, a sorbitol group, a glycerin group, or an ethylene glycol group, and a hydrophilic group including one kind of a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, a sulfobetaine group, a carbonylbetaine group, a phosphobetaine group, a quaternary ammonium group, an imidazolium betaine group, an epoxy group, a primary alcohol (carbinol) group, a methacryl group, or the like, or a combination thereof. When a plurality of Y are used, they may be the same or different.

In the structures Z-Y and Y-Z-Y, Y is bonded to Z or to a group at the end of Z. In the case where Y is bonded to the terminal group of Z, the terminal group of Z is bonded to Y, for example, by removing a hydrogen atom or the like in an amount equal to the number of bonds to Y.

In this structure, the hydrophilic group Y, A, B may be selected from the specifically described groups to satisfy the above expansion coefficient, water solubility, interfacial tension. Thus, the target liquid film cracking effect is exhibited.

The liquid film cracking agent of embodiment 2 is preferably a compound in which structures represented by the following formulae (12) to (25), which are specific examples of the above structures Z, Z-Y, Y-Z-Y, are arbitrarily combined. Further, from the viewpoint of the liquid film cracking effect, the compound preferably has a weight average molecular weight within the above range.

In the above formulae (12) to (25), M²、L²、R⁴¹、R⁴²And R⁴³Represents the following 1-valent or polyvalent group (2-valent or more).

M²The functional group is a group having a polyoxyethylene group, a polyoxypropylene group, a polyoxybutenyl group, or a polyoxyalkylene group in combination with these groups, or a hydrophilic group having a plurality of hydroxyl groups such as an erythritol group, a xylitol group, a sorbitol group, a glyceryl group, or an ethylene glycol group, a hydroxyl group, a carboxylic acid group, a mercapto group, an alkoxy group (preferably having 1 to 20 carbon atoms; for example, preferably a methoxy group), an amino group, an amide group, an imino group, a phenol group, a sulfonic acid group, a quaternary ammonium group, a sulfobetaine group, a hydroxysulfobetaine group, a phosphobetaine group, an imidazolium betaine group, a carbonylbetaine group, an epoxy group, a primary alcohol (carbinol) group, (meth) acryloyl group, or a combination of these functional groups.

L²Represents an ether group, an amino group, an amide group, an ester group, a carbonyl group, a carbonate group, or a linking group such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutenyl group, or a polyoxyalkylene group in which these groups are combined.

R⁴¹、R⁴²And R⁴³Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms; for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, decyl), an alkoxy group (preferably having 1 to 20 carbon atoms; for example, methoxy, ethoxy), an aryl group (preferably having 6 to 20 carbon atoms; for example, methoxy, ethoxy), or a salt thereofPhenyl group), fluoroalkyl group, aralkyl group, or various substituents in which a hydrocarbon group or a halogen atom (for example, a fluorine atom) is combined.

At R⁴²In the case of a polyvalent radical, R⁴²Represents a group obtained by further removing 1 or more hydrogen atoms from each of the above substituents.

The terminal of the bond described in each structure may be optionally bonded to another structure or a hydrogen atom may be introduced.

Further, specific examples of the liquid film cracking agent of embodiment 2, which is the above-mentioned compound, include, first, a polyether compound and a nonionic surfactant, and second, a hydrocarbon compound having 5 or more carbon atoms, but are not limited thereto.

Specific examples of the polyether compound and the nonionic surfactant as specific example 1 of the liquid film cleavage agent according to embodiment 2 include: polyoxyalkylene alkyl (POA) ether represented by any one of the following formulas [ V ], polyoxyalkylene glycol having a weight average molecular weight of 1000 or more represented by the following formula [ VI ], steareth, beheneth, PPG myristic ether, PPG stearyl ether, PPG behenyl ether, and the like. The polyoxyalkylene alkyl ether is preferably lauryl ether to which POP is added in an amount of 3 to 24 moles, preferably 5 moles. The polyether compound is preferably polypropylene glycol to which 17 to 180 moles, preferably about 50 moles, of polypropylene glycol are added, and the weight average molecular weight of the polypropylene glycol is 1000 to 10000, preferably 3000. The weight average molecular weight can be measured by the following measurement method.

When the nonwoven fabric contains the polyether compound or the nonionic surfactant that can be used as the liquid film-splitting agent in embodiment 2, the content ratio (Oil Per Unit) with respect to the mass of the fibers is preferably 0.1 mass% or more and 8 mass% or less. The content ratio (OPU) of the polyether compound or the nonionic surfactant is more preferably 5% by mass or less, still more preferably 1.0% by mass or less, and particularly preferably 0.4% by mass or less. Thus, the nonwoven fabric has a good touch. From the viewpoint of sufficiently exerting the liquid film splitting effect by the polyether compound or the nonionic surfactant, the content ratio (OPU) is more preferably 0.0005 mass% or more, and still more preferably 0.0015 mass% or more.

In addition, not limited to the nonwoven fabric, the content of the polyether compound or the nonionic surfactant contained in the physiological article is preferably 0.00001g/m from the viewpoint of reliably acting on the liquid film²Above, more preferably 0.0001g/m²Above, more preferably 0.0003g/m²The above. The content of the polyether compound or the nonionic surfactant contained in the sanitary article is preferably 10g/m from the viewpoint of ensuring liquid permeability²Hereinafter, more preferably 7g/m²Hereinafter, it is more preferably 5g/m²The following. Specifically, the content of the polyether compound or the nonionic surfactant contained in the physiological article as the liquid film cleavage agent of embodiment 2 is preferably 0.00001g/m²Above and 10g/m²Hereinafter, more preferably 0.0001g/m²Above and 7g/m²Hereinafter, more preferably 0.0003g/m²Above and 5g/m²The following.

The above formula [ V ]]In, L²¹Represents a linking group such as an ether group, an amino group, an amide group, an ester group, a carbonyl group, a carbonate group, a polyoxyethylene group, a polyoxypropylene group, a polyoxybutenyl group, or a polyoxyalkylene group in which these groups are combined. The above formula [ V ]]And [ VI)]In, R⁵¹And represents various substituents containing a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a methoxy group, an ethoxy group, a phenyl group, a fluoroalkyl group, an aralkyl group, or a hydrocarbon group containing these in combination, or a fluorine atom. And a, b, m and n are each independently an integer of 1 or more. Here, C_mH_nRepresents alkyl (n ═ 2m +1), C_aH_bRepresents an alkylene group (a ═ 2 b). Further, the number of carbon atoms and the number of hydrogen atoms are in the formula [ V ]]And [ VI)]Are determined independently of each other and do not necessarily represent phasesThe same integer or different. The following formula [ VII]～[XV]The same applies to m, m ', n ', and n ' in (1). Furthermore, - (C)_aH_bO)_m"m" of (A) is an integer of 1 or more. The value of the repeating unit is in the formula [ V ]]And [ VI)]Each of (1) is independently determined, and does not necessarily represent the same integer, but may be different.

The coefficient of expansion, surface tension and water solubility of the liquid film breaking agent according to embodiment 2 are set to specific ranges, for example, by the number of moles of the polyoxyalkylene group in the case of the polyether compound or the nonionic surfactant. From this viewpoint, the number of moles of the polyoxyalkylene group is preferably 1 or more and 70 or less. From the viewpoint of enhancing the liquid film cracking effect by reducing the interfacial tension and increasing the expansion coefficient, the number of moles is more preferably 5 or more, and still more preferably 7 or more. On the other hand, the number of addition mols is preferably 70 or less, more preferably 60 or less, and still more preferably 50 or less, from the viewpoint of preventing the entanglement of molecular chains from becoming too strong and decreasing the diffusibility into a liquid film.

In the case of the polyether compound or the nonionic surfactant, the expansion coefficient, the surface tension, the interfacial tension, and the water solubility can be set to specific ranges by using a water-soluble polyoxyethylene group in combination with a water-insoluble polyoxypropylene group and a polyoxybutenyl group to change the chain length of a hydrocarbon chain, using a hydrocarbon chain having a branched chain, using a hydrocarbon chain having a double bond, using a hydrocarbon chain having a benzene ring or a naphthalene ring, or by appropriately combining the above-mentioned ranges.

Specific example 2 of the liquid film cracking agent according to embodiment 2 will be described with respect to a hydrocarbon compound having 5 or more carbon atoms. The number of carbon atoms of the hydrocarbon compound is preferably 100 or less, more preferably 50 or less, from the viewpoint that the liquid state is more likely to spread on the surface of the liquid film. The hydrocarbon compound does not include polyorganosiloxane, and is not limited to linear, but may be branched, and the chain is not particularly limited to saturated or unsaturated. Further, the compound may have a substituent such as an ester or an ether in the middle or at the end. Among them, those which are liquid at ordinary temperature can be preferably used alone. When the hydrocarbon compound is contained in the nonwoven fabric, the content ratio (Oil Per Unit) to the mass of the fiber is preferably 0.1 mass% or more and 5 mass% or less. The content ratio (OPU) of the hydrocarbon compound is preferably 1% by mass or less, more preferably 0.99% by mass or less, and still more preferably 0.4% by mass or less. Thus, the nonwoven fabric has a good touch. From the viewpoint of sufficiently exerting the liquid film cracking effect by the hydrocarbon compound, the content ratio (OPU) is more preferably 0.0005 mass% or more, and still more preferably 0.0015 mass% or more.

The content of the hydrocarbon compound having 5 or more carbon atoms contained in the sanitary article is preferably 0.00001g/m from the viewpoint of acting on the liquid film reliably, not limited to the nonwoven fabric²Above, more preferably 0.0001g/m²Above, more preferably 0.0003g/m²The above. The content of the hydrocarbon compound having 5 or more carbon atoms contained in the physiological article is preferably 10g/m from the viewpoint of not impairing the liquid permeability²Hereinafter, more preferably 7g/m²Hereinafter, it is more preferably 5g/m²The following. Specifically, the content of the hydrocarbon compound having 5 or more carbon atoms as the liquid film cracking agent of embodiment 2 contained in the physiological article is preferably 0.00001g/m²Above and 10g/m²Hereinafter, more preferably 0.0001g/m²Above and 7g/m²Hereinafter, more preferably 0.0003g/m²Above and 5g/m²The following.

Examples of the hydrocarbon compound that can be used as the liquid film cracking agent of embodiment 2 include oils and fats, for example, natural oils and natural fats. Specific examples thereof include: coconut oil, camellia oil, castor oil, coconut (cocout) oil, corn oil, olive oil, sunflower oil, tall oil, mixtures of these, and the like.

Further, as hydrocarbon compounds that can be used as the liquid film cracking agent of embodiment 2, there can be mentioned: fatty acids represented by the following formula [ VII ], such as caprylic acid, capric acid, oleic acid, lauric acid, palmitic acid, stearic acid, myristic acid, behenic acid, and mixtures thereof.

C_mH_n-COOH [VII]

The above formula [ VII]Wherein m and n are each independently an integer of 1 or more. Here, C_mH_nThe hydrocarbon group of each of the above fatty acids is represented.

Specific examples of the hydrocarbon compound (fatty acid) that can be used as the liquid film cracking agent of embodiment 2 include linear or branched, saturated or unsaturated, substituted or unsubstituted polyol fatty acid esters or a mixture of polyol fatty acid esters, and examples thereof include glycerin fatty acid esters or pentaerythritol fatty acid esters represented by the following formulas [ VIII-I ] or [ VIII-II ], and specific examples thereof include: tricaprylin, tripalmitin, mixtures thereof, and the like. Furthermore, mixtures of glycerol fatty acid esters or pentaerythritol fatty acid esters typically contain some mono-, di-, and triesters. Preferred examples of the glycerin fatty acid ester include: mixtures of tricaprylin, tricaaprolin, and the like. In addition, from the viewpoint of reducing the interfacial tension and obtaining a higher expansion coefficient, a polyol fatty acid ester into which a polyoxyalkylene group has been introduced to such an extent that water insolubility can be maintained may also be used.

The above formula [ VIII-I]And [ VIII-II]Wherein m, m ', n ' and n ' are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same or different from each other. Here, C_mH_n、C_m'H_n' and C_m”H_n"represents a hydrocarbon group of each of the above-mentioned fatty acids.

Specific examples of the hydrocarbon compound (fatty acid) that can be used as the liquid film cracking agent of embodiment 2 include a fatty acid or a fatty acid mixture in which a linear or branched saturated or unsaturated fatty acid forms an ester with a polyhydric alcohol having a plurality of hydroxyl groups and a part of the hydroxyl groups remain without being esterified, and examples thereof include any of the following formulas [ IX ], any of the following formulas [ X ], a glycerin fatty acid ester represented by any of the following formulas [ XI ], a sorbitan fatty acid ester, and a partial ester of a pentaerythritol fatty acid ester. Specifically, there may be mentioned: ethylene glycol monomyristate, ethylene glycol dimyristate, ethylene glycol palmitate, ethylene glycol dipalmitate, glycerol dimyristate, glycerol dipalmitate, glycerol monooleate, sorbitan monostearate, sorbitan dioleate, sorbitan tristearate, pentaerythritol monostearate, pentaerythritol dilaurate, pentaerythritol tristearate, mixtures thereof, and the like. Further, a mixture containing a partial ester of a glycerin fatty acid ester, a sorbitan fatty acid ester, a pentaerythritol fatty acid ester, or the like typically contains a certain amount of a completely esterified compound.

The above formula [ IX]Wherein m and n are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same or different from each other. Here, C_mH_nThe hydrocarbon group of each of the above fatty acids is represented.

The above formula [ X]In, R⁵²Represents a linear or branched, saturated or unsaturated hydrocarbon group (such as an alkyl group, an alkenyl group, or an alkynyl group) having 2 to 22 carbon atoms. Specifically, there may be mentioned: 2-ethylhexyl, lauryl, myristyl, palmityl, stearyl, behenyl, oleyl, linoleyl, and the like.

The above formula [ XI]Wherein m and n are each independently an integer of 1 or more. The plurality of m and the plurality of n may be the same or different from each other. Here, C_mH_nThe hydrocarbon group of each of the above fatty acids is represented.

Further, as hydrocarbon compounds that can be used as the liquid film cracking agent of embodiment 2, there can be mentioned: sterols, phytosterols, and sterol derivatives. Specific examples thereof include cholesterol, sitosterol, stigmasterol, ergosterol, and mixtures thereof having a sterol structure represented by the following formula [ XII ].

Examples of the hydrocarbon compound that can be used as the liquid film cracking agent in embodiment 2 include alcohols. Specific examples of the alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, cetearyl alcohol, and behenyl alcohol represented by the following formula [ XIII ], and mixtures thereof.

C_mH_n-OH [XIII]

The above formula [ XIII]Wherein m and n are each independently an integer of 1 or more. Here, C_mH_nRepresents a hydrocarbon group of each of the above-mentioned alcohols.

Specific examples of the fatty acid ester usable as the liquid film breaking agent in embodiment 2 include isopropyl myristate, isopropyl palmitate, cetyl ethylhexanoate, glyceryl triisooctanoate, octyldodecyl myristate, ethylhexyl palmitate, ethylhexyl stearate, butyl stearate, myristyl myristate, stearyl stearate, cholesterol isostearate, and mixtures thereof represented by the following formula [ XIV ].

C_mH_n-COO-C_mH_n [XIV]

The above formula [ XIV]Wherein m and n are each independently an integer of 1 or more. Here, 2C_mH_nMay be the same or different. C_mH_nC of-COO-_mH_nThe hydrocarbon group of each of the above fatty acids is represented. -COO-C_mH_nC of (A)_mH_nRepresents a hydrocarbon group derived from an ester-forming alcohol.

Examples of the compound that can be used as the liquid film cracking agent in embodiment 2 include wax. Specific examples of the wax include ozokerite, paraffin, vaseline, mineral oil, and liquid isoparaffin represented by the following formula [ XV ].

C_mH_n [XV]

In the formula [ XV ], m and n are each independently an integer of 1 or more.

The coefficient of expansion, surface tension, water solubility and interfacial tension of the liquid film breaking agent of embodiment 2 can be set to specific ranges in the case of the hydrocarbon compound having 5 or more carbon atoms, for example, by introducing a small amount of hydrophilic polyoxyethylene groups to such an extent that water insolubility can be maintained, introducing polyoxypropylene groups or polyoxybutylene groups which are hydrophobic but can reduce interfacial tension, changing the chain length of the hydrocarbon chain, using those having a branched chain on the hydrocarbon chain, using those having a double bond on the hydrocarbon chain, and using those having a benzene ring or naphthalene ring on the hydrocarbon chain.

The sanitary article of the present invention has the liquid film-containing cleavage agent region containing the liquid film cleavage agent, and the liquid film cleavage agent region or other regions may contain other components as necessary in addition to the liquid film cleavage agent. In addition, either one of the liquid film cracking agent of embodiment 1 and the liquid film cracking agent of embodiment 2 may be used, or both of the formulations may be used in combination, and in the latter case, both of the formulations may be mixed in one liquid film cracking agent-containing region. The same applies to the specific examples 1 and 2 of the liquid film cracking agent of embodiment 2.

(basic constitution of physiological articles)

As described above, the sanitary product of the present invention includes the absorbent body, and the topsheet can be disposed on the skin contact surface side and the backsheet can be disposed on the non-skin contact surface side of the absorbent body. The back sheet may be liquid impermeable, liquid impermeable or water repellent. A liquid-permeable sheet called a second sheet may be disposed between the topsheet and the absorbent body. When the sanitary product is, for example, a sanitary napkin, the sanitary napkin generally has a long shape having a longitudinal direction and a width direction perpendicular thereto. A pair of leakage preventing cuffs extending in the longitudinal direction may be disposed on both sides in the width direction of the skin-contacting surface of a sanitary napkin. The leakage-preventing cuff has a rising property to the skin side of a wearer of the sanitary napkin, thereby preventing leakage of menstrual blood discharged to the skin contact surface of the sanitary napkin.

The absorbent body preferably contains a super absorbent polymer, and may contain an absorbent fibrous material instead of or in addition to the super absorbent polymer. Alternatively, the absorbent body may be composed of only the super absorbent polymer. A typical example of the absorbent body is a member which is also called an absorbent core material and is generally contained in such a sanitary product, and specifically, for example, the absorbent body is constituted by containing a fibrous material such as a fluff pulp including wood pulp, a synthetic fiber subjected to a hydrophilization treatment, and a particulate highly absorbent polymer. In the absorbent core having such a configuration, the super absorbent polymer is usually held in the aggregate of the fibrous materials by the adhesive force of the super absorbent polymer in a wet state or by a separately added binder or a binder such as a cohesive fiber. The absorbent core may be a fiber stack in which fluff pulp and a super absorbent polymer are mixed, and the fluff pulp and the super absorbent polymer may be uniformly mixed or non-uniformly mixed in the fiber stack, or these materials may be partially different in basis weight.

The super absorbent polymer used in the present invention is preferably a polymer capable of absorbing and holding a liquid of 20 times or more the weight of itself and capable of being gelled. Examples of such super absorbent polymers include: starch or crosslinked carboxymethylated cellulose, polymers or copolymers of acrylic acid or alkali metal salts of acrylic acid, polyacrylic acid and salts thereof, and polyacrylate grafted polymers. As the polyacrylate salt, a sodium salt can be preferably used.

The absorbent member may have an absorbent core and a core-covering sheet covering the absorbent core. The core-wrapped sheet may be a form of covering not only the entire absorbent core but also a form of covering only a part of the skin-contact surface side of the absorbent core. In the present invention, the absorbent body is a concept including an absorbent core and a core-wrapped sheet optionally used. The core-spun sheet may use crepe paper (crepe paper), spunbond-meltblown-spunbond (SMS) nonwoven fabric, or the like.

The surface sheet is not particularly limited as long as it is a liquid-permeable sheet, and for example, a material known in the art, such as a through-air nonwoven fabric, a spunbond nonwoven fabric, or a spunlace nonwoven fabric, can be arbitrarily used. These nonwoven fabrics can be formed from fibers made of resins such as polyethylene, polypropylene, and polyethylene terephthalate, and it is preferable to apply a hydrophilic fiber treatment agent to these fibers. The surface sheet may include 1 layer or 2 or more layers. The surface sheet may be one having a flat skin-contacting surface or a non-flat skin-contacting surface, one having irregularities on either or both surfaces, or one having various variations in basis weight or density of fibers. In the case where the surface sheet comprises a plurality of layers, the hemagglutinating agent and the liquid film-breaking agent may be contained in all of the layers or may be contained in some of the layers.

When the back sheet is liquid-permeable, the same back sheet as the front sheet can be used. When the back sheet is liquid-impermeable, liquid-impermeable or water-repellent, a spunbonded nonwoven fabric, SMS nonwoven fabric, moisture-permeable film or the like may be used, or a laminate of a nonwoven fabric and a moisture-permeable film may be used.

Fig. 5 and 6 show a sanitary napkin 10 as an embodiment of the sanitary product of the present invention. The sanitary napkin 10 has a longitudinal direction X corresponding to the front-back direction of the user and a transverse direction Y perpendicular thereto, and has a longitudinal shape in which the maximum length in the longitudinal direction X is larger than the maximum length in the transverse direction Y in a plan view, as shown in fig. 5.

The sanitary napkin 10 includes a liquid-permeable topsheet 20 forming a skin-contacting surface of the sanitary napkin 10, a water-repellent backsheet 30 forming a non-skin-contacting surface of the sanitary napkin 10, and a liquid-retentive absorbent member 40 interposed between the two sheets 20, 30, and these are integrated by a known joining method such as an adhesive. The topsheet 20 and the backsheet 30 extend from the periphery of the absorber 40, and the end portions of these extending portions are joined to each other by a known joining method such as an adhesive or heat sealing to form the end seal 50. A leakage preventing groove 60 having a ring shape in a plan view, which is formed by integrally recessing the top sheet 20 and the absorber 40, is formed on the skin contact surface of the sanitary napkin 10. A pair of side sheets 70, 70 are disposed on both left and right sides of the skin contact surface of the sanitary napkin 10 in the longitudinal direction X over substantially the entire length of the sanitary napkin 10 in the longitudinal direction X. The absorber 40 includes an absorbent core 41 having liquid retention properties, and a core-wrapped sheet 42 covering both the skin contact surface and the non-skin contact surface of the absorbent core 41. The absorbent core 41 is composed of a fibrous material and a particulate superabsorbent polymer.

Fig. 7 shows a topsheet 20 provided in the sanitary napkin 10. In the surface sheet 20, the surface-1-20A side as a skin-contacting surface is formed into a concavo-convex shape, and the surface-2-20B side as a non-skin-contacting surface is formed into a flat or concavo-convex shape, but the degree of the concavo-convex is extremely small compared with the surface-1-20A side. Specifically, the uneven shape on the 1 st surface 20A side includes a plurality of protrusions 21 and linear recesses 22 surrounding the protrusions. The plurality of projections 21 are raised toward the 1 st surface 20A. The linear recessed portions 22 are arranged in a grid pattern, the 1 st surface 20A of the top sheet 20 is divided into a plurality of regions by the recessed portions 22 arranged in the grid pattern, and 1 protruding portion 21 is arranged in each region. That is, a plurality of projections 21 are scattered on the 1 st surface 20A of the top sheet 20, which is a skin contact surface.

The surface sheet 20 contains thermally extensible fibers whose length is extended by heating. Examples of the heat-extensible fiber include: fibers that elongate by changing the crystalline state of the resin upon heating, fibers that elongate by being subjected to crimping processing and that elongate in apparent length by being heated to eliminate crimping, and the like. When a fiber web mainly composed of unheated heat-extensible fibers, which is an intermediate product in the production of the topsheet 20, is subjected to a heating treatment such as hot air processing by blowing hot air after forming the lattice-shaped depressions 22 by embossing or the like, the heat-extensible fibers present in each region divided by the depressions 22 are extended, and thus each region becomes bulkier than the depressions 22. The fluffy portion thus formed is the convex portion 21. Due to the manufacturing process of the topsheet 20, the convex portions 21 have a solid structure filled with the constituent fibers, but have a bulky portion with a lower fiber density than the concave portions 22. On the other hand, the concave portion 22 has a pressure-bonded portion in which the constituent fibers of the surface sheet 20 are pressure-bonded or bonded, and the heat-extensible fibers present in the concave portion 22 are in a non-extended state even after being subjected to a heat treatment because the heat-extensible fibers are damaged by the pressure-bonding.

The top sheet 20 has a two-layer structure including an upper layer on the 1 st surface 20A side and a lower layer on the 2 nd surface 20B side. The upper layer on the 1 st surface 20A side is a layer having an uneven shape including projections 21 and mainly composed of a thermally extensible fiber. The proportion of the thermally extensible fibers in the entire constituent fibers of the upper layer is preferably 30 mass% or more, more preferably 50 mass% or more, and is preferably 100 mass% or less, more preferably 80 mass% or less. On the other hand, the lower layer on the 2 nd surface 20B side contains no thermally extensible fiber or contains a smaller amount of thermally extensible fiber than the upper layer on the 1 st surface 20A side having the uneven shape. The two layers constituting the surface sheet 20 are preferably joined to each other by the press-joining portion of the concave portion 22. The top sheet 20 is not limited to the two-layer structure, and may have a single-layer structure or a multilayer structure having 3 or more layers.

By using the surface sheet 20 having such an uneven shape, the contact area with the skin of the user is controlled, and stuffiness and skin rash are effectively prevented. The convex portions 21 contacting the skin are fluffy due to thermal elongation of the thermally extensible fibers, and the skin feels soft.

The surface sheet 20 can be produced by the following method, for example. First, a fiber web containing thermally extensible fibers is subjected to a heat embossing process to form linear depressions 22. At this time, the heat-stretchable fibers are fixed in the recesses 22 without being thermally stretched by pressure bonding or welding. Then, the web is subjected to hot air processing. As a result, the heat-extensible fibers present in the regions other than the recessed portions 22, that is, the regions surrounded by the lattice-shaped recessed portions 22 are extended, and the portions are raised toward the 1 st surface 20A side, whereby the raised portions 21 are formed, and the surface sheet 20 is obtained. As the constituent fibers of the top sheet 20, only the heat-extensible fibers may be used, or in addition to the heat-extensible fibers, non-heat-extensible heat-fusible fibers may be further used. As the constituent fibers of the top sheet 20, for example, those described in paragraphs [0013] and [0037] to [0040] of japanese patent application laid-open No. 2005-350836, and those described in paragraphs [0012] and [0024] to [0046] of japanese patent application laid-open No. 2011-1277258, can be used.

(blood cell flocculant-containing region and liquid film-cleaving agent-containing region)

The inventor finds that: by using a blood cell coagulant in combination with a liquid film-splitting agent, the surface whiteness of the used sanitary article can be maintained. And found that: as described below, the amount of returned liquid is significantly reduced in the case of using only the hemagglutinating agent and the liquid film-breaking agent in combination. This phenomenon will be described by taking a case where the sanitary napkin 10 is used as an example.

First, a sanitary napkin (hereinafter referred to as a sanitary napkin 10A) in which a blood cell coagulant-containing region is provided in the core-covering sheet 42 on the skin contact surface side of the absorbent core 41 and a liquid film tearing agent-containing region is not provided will be described. The sanitary napkin 10A does not contain a liquid film-splitting agent, and is a sanitary product outside the scope of the present invention.

When blood is discharged into the sanitary napkin 10A, the blood reaching the blood cell coagulant-containing region of the core-spun sheet 42 starts to form red blood cell coagulation masses at the positions, and is separated from the plasma components. In this manner, the aggregates of red blood cells are held on the skin contact surface side of the absorber 40, and the plasma components gradually diffuse into the absorber, as in the case of filtration through the gaps in the absorber 40. Further, the plasma component reaches the non-skin contact surface side of the absorber 40, and is mainly held on the non-skin contact surface side of the absorbent core 41. The liquid containing the plasma components held here tends to flow back toward the skin contact surface side when the sanitary napkin 10A is pressed, but is inhibited by the aggregated red blood cells present on the skin contact surface side of the absorber 40 and hardly reaches the topsheet 20. Thereby achieving a reduction in the amount of liquid returned.

However, since the sanitary napkin 10A forms a coagulated erythrocyte lump at a position close to the topsheet 20, there is room for improvement in appearance seen from the skin contact surface side after use.

Next, a sanitary napkin (hereinafter referred to as sanitary napkin 10B) having a liquid film-cleaving agent-containing region and a blood cell coagulation agent-free region provided on the topsheet 20 will be described. The sanitary napkin 10B does not contain a blood cell aggregating agent, and is a sanitary product outside the scope of the present invention.

When blood is excreted into the sanitary napkin 10B, the blood that has reached the liquid film-containing cleavage agent region of the topsheet 20 cannot form a liquid film continuously in the topsheet 20 due to the action of the liquid film cleavage agent that pushes away a part of the liquid film layer and destabilizes the liquid film, and flows toward the absorbent member 40 under its own weight. Thus, in the absorber 40, blood, more specifically, blood passing through the liquid film-containing dehiscent agent region diffuses in the planar direction while flowing from the skin contact surface side to the non-skin contact surface side. As a result, in the absorber 40, the blood diffusion area on the non-skin contact surface side is larger than the blood diffusion area on the skin contact surface side. Therefore, the effect of not holding liquid in the topsheet 20 and the effect of reducing the diffusion area on the skin contact surface side of the absorbent body 40 act in a complementary manner, and the surface whiteness of the sanitary napkin 10B after use is extremely excellent. Further, since no liquid film is present in the region from the absorbent 40 to the skin contact surface side of the topsheet 20, a liquid passage is not easily formed, and the amount of return liquid is reduced.

However, in the sanitary napkin 10A containing a blood cell coagulation agent, when pressure is applied, blood that tends to flow back toward the skin contact surface side is inhibited by the aggregated red blood cells present on the skin contact surface side of the absorbent body and is less likely to return to the top layer, as compared with the sanitary napkin 10B containing no blood cell coagulation agent, and therefore the amount of returned liquid is small, and there is room for improvement in the blood absorption performance of the sanitary napkin 10B.

The sanitary napkin 10A or 10B of the present invention contains two agents, respectively, as compared with the sanitary napkins containing only one of the hemagglutinating agent and the liquid film-breaking agent. Further, the sanitary article of the present invention is provided with a blood cell coagulant-containing region containing a blood cell coagulant and a liquid film cleavage agent-containing region containing a liquid film cleavage agent, and both the regions are disposed at the absorbent body or on the skin contact surface side of the absorbent body. By providing the blood cell coagulant-containing region and the liquid membrane-containing dehiscent agent region on the skin contact surface side of the absorbent body, the effects of these effects can be sufficiently utilized to achieve the effects of reducing the amount of return liquid and improving the surface whiteness after use.

As embodiment 1 of the sanitary product of the present invention, there can be mentioned a sanitary napkin (hereinafter referred to as sanitary napkin 10C) in which a blood cell coagulation agent and a liquid film-tearing agent are mixed and disposed in a core-covering sheet 42 positioned on the skin contact surface side of an absorbent core 41, that is, a region containing a blood cell coagulation agent and a region containing a liquid film-tearing agent are overlapped in both the thickness direction and the planar direction.

When blood is excreted into the sanitary napkin 10C and reaches the core-covering sheet 42, the blood is first introduced into the absorbent core 41 quickly without continuously forming a liquid film due to the effect of the liquid film cleavage agent. At the same time, the effect of the hemagglutinating agent gradually forms an erythrocyte aggregate. The formed red blood cell aggregates no longer pass through the gaps in the absorbent core 41, and are held in the middle of the absorbent body 40 in the thickness direction. On the other hand, the plasma component in the blood is further diffused and held on the non-skin contact surface side of the absorbent core 41. During this entire process, the blood passing through the area containing the liquid film-disrupting agent diffuses in the planar direction. As a result, in the absorber 40, the blood diffusion area on the non-skin contact surface side is larger than the blood diffusion area on the skin contact surface side.

According to the above phenomenon, first, the liquid held on the non-skin contact surface side of the absorber 40 is inhibited by the aggregate of red blood cells with respect to the amount of return liquid, and is less likely to move to the skin contact surface side. Further, since no liquid film is formed in the core sheet 42, a liquid passage reaching the topsheet 20 is not easily formed. By the above-described complementary effects, the amount of return liquid of the sanitary napkin 10C is significantly reduced as compared with the sanitary napkins 10A and 10B.

Next, regarding the surface whiteness, the red blood cell aggregates are held in the middle of the abdomen in the thickness direction of the absorber 40, and thus are less likely to appear through the topsheet 20 side. Further, since the diffusion area on the skin contact surface side of the absorber 40 is small, the sanitary napkin 10C exhibits excellent whiteness compared to the sanitary napkin 10A.

As embodiment 2 of the sanitary product of the present invention, there is exemplified a sanitary napkin (hereinafter referred to as sanitary napkin 10D) in which a liquid film-containing cleavage agent region is provided to a topsheet 20 and a blood cell coagulation agent-containing region is provided to a core sheet 42 positioned on the skin contact surface side of an absorbent core 41. In the sanitary napkin 10D, the liquid-containing film cleavage agent region of the topsheet 20 and the blood cell coagulation agent-containing region of the core-spun sheet 42 overlap at least partially, preferably entirely, in a plan view.

In the sanitary napkin 10D, the same phenomenon as in the sanitary napkin 10C occurs, but there is a difference not only in the core sheet 42 but also in that no liquid film is formed on the topsheet 20. This improves the whiteness of the topsheet 20 itself as compared with the sanitary napkin 10C, and therefore improves the ability to shield the absorbent member 40 from the aggregated red blood cells. As a result, the sanitary napkin 10D had a more excellent surface whiteness than the sanitary napkin 10C.

In the sanitary article of the present invention, the blood cell aggregating agent and the liquid film disrupting agent may be disposed on the skin contact surface side of the absorbent body or on any part of the absorbent body. In the case of being disposed in the absorbent body, the core-covering sheet is preferably disposed in the skin contact surface side of the absorbent body or in the skin contact surface side of the absorbent body for each preparation. That is, it is preferable that each agent is disposed on the skin contact surface side of the higher absorbent polymer. Thus, the blood cells can be coagulated before the blood is absorbed by the super absorbent polymer. Further, this makes it possible to reduce the surface tension of blood before the blood diffuses into the absorbent body.

In the sanitary product of the present invention, the blood cell coagulant-containing region is not disposed on the topsheet 20 but on the non-skin contact surface side with respect to the topsheet, and it is preferable that a coagulation mass of a non-liquid component in menstrual blood represented by red blood cells is generated in the sanitary product to prevent the non-liquid component from adhering to the skin of the user. In both of the sanitary napkins 10C and 10D, the region containing the hemagglutinating agent is disposed in the covering sheet 42. The blood cell coagulant-containing region may be disposed in the absorbent core 41.

In the sanitary product of the present invention, the blood cell aggregate-containing region and the liquid-containing membrane-cracking agent region may be disposed at the same position in the thickness direction of the sanitary product as in the sanitary napkin 10C, but in terms of easily obtaining the complementary effect of the two agents, it is preferable that the two regions are disposed at different positions, and it is particularly preferable that the liquid-containing membrane-cracking agent region is disposed on the skin contact surface side than the blood cell aggregate-containing region as in the sanitary napkin 10D. In the case where the "liquid-containing membrane cracking agent region is disposed on the skin contact surface side relative to the blood cell aggregate-containing region" as used herein, the overlapping portions may be formed when the two regions overlap each other in a plan view of the sanitary product.

On the other hand, the blood cell coagulation agent-containing region and the liquid membrane-containing cleavage agent-containing region may be spaced apart from each other without overlapping in the planar direction of the sanitary napkin, but from the viewpoint of easily obtaining the complementary effect of the two agents, it is preferable that the two regions overlap in the planar direction as in the sanitary napkins 10C and 10D.

In the case where the sanitary product of the present invention is a sanitary napkin as shown in fig. 5 and 6, the blood cell aggregating agent-containing region and the liquid membrane-containing dehiscent agent-containing region are preferably provided in the excretory opening abutment region from the viewpoint of facilitating contact between both regions with blood. The excretory opening abutment region is the central portion in the width direction and the longitudinal direction of the sanitary napkin for daily use, and the central portion in the width direction and the longitudinal direction of the divided region located at the 2 nd position from the front side (the abdominal side of the user) when the sanitary napkin for night use is divided into 4 parts in the longitudinal direction.

The distribution pattern of the blood cell aggregating agent in the blood cell aggregating agent-containing region in the planar direction and the distribution pattern of the liquid film tearing agent in the liquid film tearing agent-containing region in the planar direction are not particularly limited, and any pattern may be employed.

For example, in the case where the blood cell coagulant-containing region is provided in the core sheet as in the sanitary napkins 10C and 10D, the blood cell coagulant may be continuously attached to the entire surface of one surface of the core sheet, or may be continuously attached only to a part of one surface of the core sheet. The former method has an advantage of coping with excretion occurring at any position, and the latter method has an advantage of suppressing a decrease in sheet flexibility due to adhesion of a blood cell coagulation agent. The adhesion pattern of the blood cell coagulation agent is not limited to a continuous adhesion pattern of the non-adhesion portion of the non-blood cell coagulation agent, and may be a discontinuous adhesion pattern in which the adhesion portion and the non-adhesion portion of the blood cell coagulation agent are present in a mixture. Examples of the discontinuous adhesion pattern include: 1) a stripe pattern in which linear blood cell coagulation agent adhesion portions are intermittently arranged in a direction orthogonal to the longitudinal direction thereof in a plan view, 2) a lattice pattern formed by a plurality of intersecting linear blood cell coagulation agent adhesion portions in a plan view, and 3) a dot pattern in which blood cell coagulation agent adhesion portions having a specific shape such as a circular shape are scattered in a plan view. The pattern of 1) has an advantage of diffusing the excretory fluid in the longitudinal direction of the linear blood cell coagulation agent-attached portion, and for example, if the longitudinal direction of the linear blood cell coagulation agent-attached portion is aligned with the longitudinal direction of the sanitary product (the front-back direction of the user), diffusion of the excretory fluid such as menstrual blood in the longitudinal direction is promoted. The patterns 2) and 3) both have an advantage of reducing the surface redness due to the remaining erythrocyte aggregates, and the pattern 2) also has an advantage of further improving the certainty of the effect of the action of the hemagglutinating agent. The liquid membrane-disrupting agent-containing region may also have the same agent attachment pattern as the blood cell aggregating agent-containing region.

In the sanitary article of the present invention, the area of the region containing the blood cell coagulation agent may be the same as or different from the area of the region containing the liquid membrane cleavage agent.

From the viewpoint of large-area blood contact, the total area of the blood cell coagulant-containing regions in the physiological article is preferably 30cm²Above, more preferably 70cm²Above, more preferably 100cm²The above. The larger the total area of the blood cell coagulant-containing region in the physiological article, the better the total area, but the more the total areaThe distance between the grooves is 350cm²The following.

From the viewpoint of large-area blood contact, the total area of the liquid-containing membrane cleavage agent regions in the physiological article is preferably 10cm²Above, more preferably 30cm²Above, more preferably 50cm²The above. The larger the total area of the liquid film-containing cleavage agent region in the sanitary napkin, the better, but the total area is actually 350cm²The following.

(analysis method)

The methods for analyzing the hemagglutinating agent, the liquid film-breaking agent and the third component from commercially available physiological products are as follows.

First, a hot melt adhesive for bonding members to a physiological product to be analyzed is weakened by a heating device such as a dryer, and then decomposed into members such as a topsheet, an absorber, and a backsheet. Then, the decomposed parts were subjected to a multi-stage solvent extraction from a nonpolar solvent to a polar solvent, the solvent was dried, and the mixture to be measured was taken out. After selecting an appropriate column and solvent according to the composition of the substance to be removed, each component is separated by high performance liquid chromatography, and the structure of each component is identified by further performing NMR (nuclear magnetic resonance), IR (infrared spectroscopy), MS (mass spectrometry), elemental analysis, and the like on each component. At the same time, the weight of each component was measured. When the polymer compound is contained, the constituent components can be identified more easily by a method such as Gel Permeation Chromatography (GPC).

When the amount of the obtained constituent component is not sufficient for each measurement, the substance is purchased as a commercial product, or synthesized as a non-commercial product.

Thus, when the obtained constituent component is a cationic polymer or a substance having the above-described (property of forming aggregates), it is judged as a blood cell aggregating agent. The liquid film cracking agent is determined to be a liquid film cracking agent when the obtained component has an expansion coefficient of 15mN/m or more with respect to a liquid having a surface tension of 50mN/m, or has an expansion coefficient of more than 0mN/m with respect to a liquid having a surface tension of 50mN/m and an interfacial tension of 20mN/m or less with respect to a liquid having a surface tension of 50mN/m, or has the above-described property (property of causing a liquid film to disappear). The third component was judged to be one that did not belong to either the hemagglutinating agent or the liquid film cracking agent.

(measurement of molecular weight)

The molecular weight of the cationic polymer (hemagglutinating agent) can be measured by HLC-8320GPC manufactured by Tosoh corporation. Specific measurement conditions are as follows.

The case of a copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate

Separating the tubular column: protective column alpha and analysis column alpha-M series connection of the pipe column (Tosoh corporation manufacturing)

Eluent: an eluent containing 150mmol/L sodium sulfate and 1% by mass acetic acid dissolved in water

Flow rate of solvent: 1.0ml/min

Injection amount: 100 μ L

Temperature of the separation column: 40 deg.C

Other than copolymers containing water-soluble polymerizable monomers such as hydroxyethyl methacrylate

Separating the tubular column: protective column alpha and analysis column alpha-M series connection of the pipe column (Tosoh corporation manufacturing)

Eluent: in the presence of ethanol: water 3: 7 (volume ratio) was dissolved with an eluent of 50mmol/L lithium bromide and 1 mass% acetic acid

Flow rate of solvent: 0.6ml/min

Injection amount: 100 μ L

Temperature of the separation column: 40 deg.C

The detector uses RI (refractive index). As a sample to be measured, 1mg of the cationic polymer to be measured was dissolved in 1mL of the eluent. As for the copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate, an amylopectin mixture obtained by dissolving 2.5mg each of amylopectin having a molecular weight of 5900, amylopectin having a molecular weight of 47300, amylopectin having a molecular weight of 21.2 ten thousand and amylopectin having a molecular weight of 78.8 ten thousand in 10mL of an eluent was used as a molecular weight standard. In addition to the copolymer containing a water-soluble polymerizable monomer such as hydroxyethyl methacrylate, a PEG-PEO mixture obtained by dissolving 10mg each of polyethylene glycol (PEG) having a molecular weight of 106, PEG having a molecular weight of 400, PEG having a molecular weight of 1470, PEG having a molecular weight of 6450, polyethylene oxide (PEO) having a molecular weight of 5 ten thousand, PEO having a molecular weight of 23.5 ten thousand, and PEO having a molecular weight of 87.5 ten thousand in 20mL of an eluent was used as a molecular weight standard.

The weight average molecular weight of the polymer compound other than the cationic polymer was measured using a Gel Permeation Chromatograph (GPC) "CCPD" (trade name, manufactured by Tosoh corporation). The measurement conditions are as follows. The calculation of the converted molecular weight was performed based on polystyrene.

Separating the tubular column: GMHHR-H + GMHHR-H (cation)

Eluent: l Farmin DM20/CHCl3

Flow rate of solvent: 1.0ml/min

Temperature of the separation column: 40 deg.C

(Water solubility)

In the present specification, the term "water solubility" refers to a mass of a blood cell coagulant or a liquid film breaking agent that can be dissolved in 100g of deionized water. The term "water-soluble" as used herein means having a water solubility of 10g or more.

In an environmental region at a temperature of 25 ℃ and a Relative Humidity (RH) of 65%, a compound to be measured was gradually dissolved while stirring 100g of deionized water with a stirrer, the degree of dissolution was visually observed, and the amount of the dissolved compound at a time point when the compound was no longer dissolved, that is, at a time point when any of suspension, precipitation, and cloudiness was visually observed was taken as water solubility. Specifically, the measurement was carried out by adding 0.0001g of the reagent. As a result, the sample was rated as "less than 0.0001 g" when 0.0001g was not dissolved, and the sample was rated as "0.0001 g" when 0.0001g was dissolved but 0.0002g was not dissolved. In the case where the compound to be measured is a surfactant, "dissolution" means both monodispersed dissolution and micellar dispersed dissolution, and the amount of dissolution at the time when suspension, precipitation, or cloudiness is observed is water solubility.

(production method)

The blood cell flocculant-containing region and the liquid-containing film-splitting agent-containing region can be formed by impregnating synthetic fibers constituting a nonwoven fabric, pulp fibers constituting an absorbent, a super absorbent polymer, or the like with these agents alone or in a solution containing the above agents in advance, and then producing a sanitary napkin. Further, there may be mentioned a method in which synthetic fibers are nonwoven-woven and then nonwoven-woven, or pulp fibers are formed into an absorbent core or a core-wrapped sheet and then these absorbent core or core-wrapped sheet are coated with these agents alone or a solution containing the above agents. Examples of the solution include a solution obtained by diluting a hemocyte coagulant or a liquid film breaking agent with a solvent (hereinafter, this solution is also referred to as an agent solution). Further, the phosphate ester type anionic surfactant may be mixed in a solution containing a liquid film-splitting agent. In this case, the content ratio of the liquid film cracking agent to the phosphate ester type anionic surfactant is preferably as described above. The solvent is not particularly limited, and those capable of being suitably dissolved or dispersed and emulsified in the solvent to facilitate coating can be used. For example, examples of the hemocyte coagulant include: alcohol such as ethanol and methanol, or water. As the liquid film-splitting agent, an organic solvent such as ethanol, methanol, acetone, hexane or the like can be used, or when an emulsion is prepared, water can be used as a solvent or a dispersion medium, and as the emulsifier used for emulsification, various surfactants including alkyl phosphate, fatty acid amide, alkyl betaine, sodium alkyl sulfosuccinate or the like can be cited. The solvent for dissolving the hemagglutinating agent and the liquid film-cracking agent at the same time is a mixed solvent of water and alcohol.

As a method for attaching the blood cell coagulation agent and the liquid film cleavage agent to the surface of the constituent material, various methods generally used can be employed without particular limitation. Examples thereof include: coating using a sprayer, coating using a slit coater, dipping, and the like. When these agents are applied to a nonwoven fabric, these treatments may be performed on the fibers before the fibers are formed into a web, or may be performed after the fibers are formed into a web by various methods. When these agents are applied to an absorbent body, these treatments may be performed on fluff pulp or absorbent polymer before forming into the absorbent body shape, or may be performed on an absorbent core or core sheet after forming into the absorbent body shape. The treatment is carried out using a solution of the above agents in a solvent, or an emulsion or dispersion of the above agents, as required. In this case, the constituent material having these agents adhered to the surface thereof is preferably dried at a temperature sufficiently lower than the melting point or the ignition point of the constituent material (for example, 120 ℃ or lower) by, for example, a hot air blowing dryer.

The sanitary product of the present invention is not limited to sanitary napkins, and can be applied to other sanitary products such as sanitary pads as long as there is a possibility of blood absorption.

The present invention further discloses the following embodiments with respect to the above embodiments.

＜1＞

A sanitary article comprising a topsheet on the skin-contacting surface side, a backsheet on the non-skin-contacting surface side, and an absorbent member interposed therebetween, and

the absorbent body or the skin contact surface side of the absorbent body is provided with

A hemagglutinating agent-containing region containing hemagglutinating agent, and

a liquid film cracking agent-containing region containing a liquid film cracking agent.

＜2＞

The sanitary article according to the above <1>, wherein the blood cell coagulant is a cationic polymer.

＜3＞

The physiological article according to <1> or <2 > above, wherein the liquid film cleavage agent has a spreading factor of 15mN/m or more with respect to a liquid having a surface tension of 50 mN/m.

＜4＞

A sanitary article comprising a topsheet on the skin-contacting surface side, a backsheet on the non-skin-contacting surface side, and an absorbent member interposed therebetween, and

the absorbent body or the skin contact surface side of the absorbent body is provided with

Cationic polymer-containing region containing cationic polymer, and

a compound-containing region containing the following compound C1.

[ Compound C1]

A compound having an expansion coefficient of 15mN/m or more with respect to a liquid having a surface tension of 50 mN/m.

＜5＞

The sanitary article according to any one of the above <1> to < 4 >, wherein the liquid film opener or the compound C1 has an extension coefficient of 15mN/m or more, preferably 20mN/m or more, more preferably 25mN/m or more, further preferably 30mN/m or more, and 50mN/m or less with respect to a liquid having a surface tension of 50 mN/m.

＜6＞

The sanitary article according to any one of the above items <1> to < 5 >, wherein the liquid film-splitting agent or the compound C1 contains a compound having at least 1 structure selected from the group consisting of the following structures X, X-Y and Y-X-Y.

The structure X represents > C (A) -C represents a carbon atom. And <, > and-represent a bond. The same as, -C (A)₂-、-C(A)(B)-、＞C(A)-C(R¹)＜、＞C(R¹)-、-C(R¹)(R²)-、-C(R¹)₂-, > C <, and-Si (R)¹)₂O-、-Si(R¹)(R²) A siloxane chain having a structure in which any one of the basic structures of O-is repeated or 2 or more kinds of O-are combined, or a mixed chain thereof. Having a terminal end of structure X selected from hydrogen atoms, or-C (A)₃、-C(A)₂B、-C(A)(B)₂、-C(A)₂-C(R¹)₃、-C(R¹)₂A、-C(R¹)₃or-OSi (R)¹)₃、-OSi(R¹)₂(R²)、-Si(R¹)₃、-Si(R¹)₂(R²) At least one group of (1).

R is as defined above¹Or R²Each independently represents a hydrogen atomAlkyl, alkoxy, aryl or halogen atoms. A. Each B independently represents a substituent containing an oxygen atom or a nitrogen atom. In structure X R¹、R²When there are a plurality of A, B, these may be the same or different.

Y represents a hydrophilic group having hydrophilicity and containing an atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. When a plurality of Y's are used, they may be the same or different.

＜7＞

The sanitary article according to any one of the above items <1> to < 6 >, wherein the liquid film cleavage agent or the compound C1 is an organically modified silicone, and the organic modification is one or more selected from the group consisting of amino modification, epoxy modification, carboxyl modification, glycol modification, primary alcohol (carbinol) modification, (meth) acryl modification, mercapto modification, phenol modification, polyether modification (including polyoxyalkylene modification), methyl styrene modification, long-chain alkyl modification, higher fatty acid ester modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.

＜8＞

The sanitary article according to any one of the above <1> to < 6 >, wherein the liquid film-splitting agent or the compound C1 is a polyoxyalkylene-modified silicone represented by the following formulas [ I ] to [ IV ].

＜9＞

The physiological article according to the above <1> or <2 >, wherein the liquid film-disrupting agent has a spreading factor of more than 0mN/m with respect to a liquid having a surface tension of 50mN/m, and

the liquid film cleavage agent has an interfacial tension of 20mN/m or less with respect to a liquid having a surface tension of 50 mN/m.

＜10＞

A sanitary article comprising a topsheet on the skin-contacting surface side, a backsheet on the non-skin-contacting surface side, and an absorbent member interposed therebetween, and

the absorbent body or the skin contact surface side of the absorbent body is provided with

Cationic polymer-containing region containing cationic polymer, and

a compound-containing region containing the following compound C2.

[ Compound C2]

A compound having an expansion coefficient of more than 0mN/m with respect to a liquid having a surface tension of 50mN/m and an interfacial tension of 20mN/m or less with respect to a liquid having a surface tension of 50 mN/m.

＜11＞

The sanitary article according to the above <1>, <2 >, < 9 > or < 10 >, wherein the liquid film opener or the compound C2 has an expansion coefficient of more than 0mN/m, preferably 9mN/m or more, more preferably 10mN/m or more, further preferably 15mN/m or more, and further preferably 50mN/m or less with respect to a liquid having a surface tension of 50 mN/m.

＜12＞

The article according to any one of the above <1>, <2 >, < 9 > to < 11 >, wherein the liquid film cleavage agent or the compound C2 contains a compound having at least 1 structure selected from the group consisting of the following structures Z, Z-Y and Y-Z-Y.

Structure Z represents > C (a) -C: carbon atom >, -C (A)₂-、-C(A)(B)-、＞C(A)-C(R³)＜、＞C(R³)-、-C(R³)(R⁴)-、-C(R³)₂A hydrocarbon chain having a structure in which any one of the basic structures-, > C < is repeated or 2 or more kinds are combined. Having at the terminus of structure Z a hydrogen atom, or-C (A)₃、-C(A)₂B、-C(A)(B)₂、-C(A)₂-C(R³)₃、-C(R³)₂A、-C(R³)₃At least one group of (1).

R is as defined above³Or R⁴Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group, an aralkyl group, a hydrocarbon group containing these groups in combination, or a fluorine atom. A. Each B independently represents a substituent containing an oxygen atom or a nitrogen atom.

Y represents a hydrophilic group having hydrophilicity and containing an atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom. When a plurality of Y's are used, they may be the same or different.

＜13＞

The sanitary article according to any one of the above items <1>, <2 >, < 9 > to < 12 >, wherein the liquid film opener or the compound C2 is one or more selected from polyoxyalkylene alkyl (POA) ether represented by any one of the following formulas [ V ], polyoxyalkylene glycol having a mass average molecular weight of 1000 or more represented by the following formula [ VI ], steareth, beheneth, PPG myristic ether, PPG stearyl ether or PPG behenyl ether.

＜14＞

The sanitary article according to any one of the above items <1>, <2 >, < 9 > to < 12 >, wherein the liquid film opener or the compound C2 is one or more selected from a fatty acid represented by the following formula [ VII ], a glycerin fatty acid ester or pentaerythritol fatty acid ester represented by the following formula [ VIII-I ] or [ VIII-II ], a glycerin fatty acid ester, sorbitol anhydride fatty acid ester, or partial ester of pentaerythritol fatty acid ester represented by the following formula [ IX ], the following formula [ X ] or the following formula [ XI ], a sterol represented by the following formula [ XII ], an alcohol represented by the following formula [ XIII ], a fatty acid ester represented by the following formula [ XIV ], or a wax represented by the following formula [ XV ].

＜15＞

The sanitary article according to any one of the above items <1> to < 14 >, wherein the melting point of the liquid film-splitting agent or the compound C1 or the compound C2 is preferably 40 ℃ or lower, more preferably 35 ℃ or lower, further preferably-220 ℃ or higher, more preferably-180 ℃ or higher.

＜16＞

The physiological article according to any one of the above <1> to < 15 >, wherein the water solubility of the liquid film-splitting agent, the compound C1 or the compound C2 is 0g or more, preferably 1.0X 10^-9g or more, 0.025g or less, preferably 0.0017g or less, and more preferably less than 0.0001 g.

＜17＞

The sanitary article according to any one of the above-mentioned <1> to < 16 >, wherein the interfacial tension of the liquid film opener, the compound C1 or the compound C2 with respect to a liquid having a surface tension of 50mN/m is preferably 20mN/m or less, more preferably 17mN/m or less, further preferably 13mN/m or less, particularly preferably 10mN/m or less, further particularly preferably 9mN/m or less, most preferably 1mN/m or less, and further more than 0 mN/m.

＜18＞

The sanitary article according to any one of the above items <1> to < 17 >, wherein the surface tension of the liquid film opener, the compound C1 or the compound C2 is preferably 32mN/m or less, more preferably 30mN/m or less, still more preferably 25mN/m or less, particularly preferably 22mN/m or less, and further preferably 1mN/m or more.

＜19＞

The sanitary article according to any one of the above-mentioned <1> to < 18 >, wherein the weight average molecular weight of the liquid film opener, the compound C1 or the compound C2 is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, particularly preferably 2000 or more, and further preferably 50000 or less, more preferably 20000 or less, further preferably 10000 or less.

＜20＞

The physiological article according to any one of the above <1> to < 19 >, wherein the blood cell coagulation agent or the cationic polymer is a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer or a quaternary ammonium salt polycondensate.

＜21＞

The sanitary article according to any of the above-mentioned <1> to < 20 >, wherein the weight average molecular weight of the blood cell coagulation agent or the cationic polymer is preferably 2000 or more, more preferably 1 ten thousand or more, further preferably 3 ten thousand or more, further preferably 1000 ten thousand or less, more preferably 500 ten thousand or less, further preferably 300 ten thousand or less.

<22>

The sanitary article according to any one of the above <1> to <21>, wherein the blood cell coagulant or the cationic polymer is a quaternary ammonium salt homopolymer having a structure comprising a main chain and a side chain connected to the main chain and having a repeating unit represented by the following formula 1, or a quaternary ammonium salt copolymer having a structure comprising a main chain and a side chain connected to the main chain and having a repeating unit represented by the following formula 1 and a repeating unit represented by the following formula 2, and the main chain and the side chain of the blood cell coagulant or the cationic polymer are connected at1 point, and the side chain has a quaternary ammonium moiety.

In the formula, R₁Represents H or CH₃。

R₂To represent

n represents an integer of 1 to 10 inclusive.

Represents a halide ion,

In the formula, R₃Represents H or CH₃。

R₄To represent

m represents an integer of 1 to 10 inclusive.

Y^⊕Represents Na^⊕Or K^⊕。

＜23＞

The sanitary article according to any one of the above <1> to < 22 >, wherein the blood cell coagulant or the cationic polymer is a water-soluble cationic polymer having a flow potential of 1500. mu. eq/L or more and containing a quaternary ammonium salt homopolymer or a quaternary ammonium salt copolymer.

＜24＞

The sanitary article according to any one of the above-mentioned <1> to < 23 >, wherein the blood cell coagulant or the cationic polymer has a coagulation rate of 0.75 mPas/s or less.

＜25＞

The physiological article according to any one of the above <1> to < 24 >, wherein the ratio of the inorganic value to the organic value of the blood cell coagulation agent or the cationic polymer is 0.6 or more and 4.6 or less in the value of the inorganic value/organic value, and the blood cell coagulation agent or the cationic polymer is a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer or a quaternary ammonium salt polycondensate.

＜26＞

The sanitary article according to any one of the above items <1> to < 25 >, wherein the absorbent material comprises a super absorbent polymer.

＜27＞

The sanitary article according to any one of the above items <1> to < 26 >, wherein the absorbent member has a fiber stack in which fluff pulp and a super absorbent polymer are mixed.

＜28＞

The sanitary article according to the above < 26 > or < 27 >, wherein the blood cell coagulant-containing region or the cationic polymer-containing region and the liquid film disruptive agent-containing region or the compound-containing region are disposed on the skin contact surface side of the super absorbent polymer.

＜29＞

The sanitary article according to any one of the above items <1> to < 28 >, wherein the blood cell aggregate-containing region or the cationic polymer-containing region is disposed on the non-skin contact surface side of the topsheet.

＜30＞

The physiological article according to any one of the above <1> to < 29 >, wherein the liquid film-disruptive agent-containing region or the compound-containing region is disposed on the skin contact surface side of the blood cell-aggregating agent-containing region or the cationic polymer-containing region.

＜31＞

The sanitary article according to any one of the above <1> to < 30 >, wherein the liquid film-containing dehiscent agent region or the compound-containing region overlaps with the blood cell coagulant-containing region or the cationic polymer-containing region in a planar direction.

＜32＞

The sanitary article according to any one of the above items <1> to < 31 >, wherein the liquid film-containing cleavage agent region or the compound-containing region is provided on the top sheet.

＜33＞

The sanitary article according to any one of the above items <1> to < 32 >, wherein the absorbent member has an absorbent core and a core-wrapped sheet covering the absorbent core.

＜34＞

The sanitary product according to < 33 > above, wherein the blood cell coagulation agent-containing region or the cationic polymer-containing region is provided on the core-covering sheet located on the skin contact surface side of the absorbent core.

＜35＞

The article according to any one of the above <1> to < 34 >, wherein one or both of the blood cell coagulant-containing region or the cationic polymer-containing region and the liquid film cleavage agent-containing region or the compound-containing region is disposed in an excretory opening abutment region of the article.

[ examples ]

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. Further, the coefficient of expansion, the interfacial tension, the surface tension and the water solubility were measured in an environmental region at a temperature of 25 ℃ and a Relative Humidity (RH) of 65% as described above. The flow potential and IOB value of the blood cell coagulation agent and the surface tension, water solubility and interfacial tension of the liquid film breaking agent in the following examples were measured or calculated by the above-mentioned measuring methods or calculating methods. In the following table, "-" means that the agent indicated by the item name is not used, that the value corresponding to the item does not exist, or the like. The OPU of the liquid film cracking agent is a content ratio of the fiber mass of the nonwoven fabric as a whole.

[ example 1]

A sanitary napkin having the same structure as the sanitary napkin 10 shown in fig. 5 was produced according to a conventional method. Specifically, a commercially available sanitary napkin ("LAURIER HADA-KIREI Guard type common for daily use manufactured by kao corporation in 2015") was used, in which a hot-melt adhesive for bonding the members was weakened by a dryer, and a top sheet, a back sheet, and an absorbent body, which were obtained by decomposition, were used. This absorbent body is obtained by covering an absorbent core material (hereinafter, also referred to as an absorbent body X) comprising a mixed fiber accumulation body of fluff pulp and a super absorbent polymer with a core-spun sheet.

The whole of the core-wrapped sheet (skin-side core-wrapped sheet) positioned on the skin contact surface side of the absorber X was coated with diallyldimethylammonium chloride (Merquat 100, manufactured by Lubrizol Japan corporation) (hereinafter, also referred to as agent a) as a hemagglutination agent, and then further coated with Polyoxyethylene (POE) modified dimethyl silicone (KF-6015, manufactured by shin-shi chemical industries, co., ltd.) (hereinafter, also referred to as agent G) as a liquid film cracking agent. The specific coating method of the two agents is described below.

The absorbent body X having the blood cell aggregating agent and the liquid film tearing agent laminated on the whole surface thereof, which was thus formed as the skin-facing surface, was laminated with the topsheet on the skin-facing surface, and the topsheet and the backsheet were integrated by applying pressure, and further laminated on the non-skin-facing surface of the absorbent body X, to obtain the sanitary napkin of example 1.

The coating method of formulation a in example 1 is as follows. The agent a was dissolved in ethanol as a solvent to prepare a 0.06 mass% diluted solution as a coating solution, the coating solution was applied to the entire skin-contact surface of the core sheet on the skin side of the absorbent body X by a spray, and the solvent was dried.

The coating method of formulation G in example 1 is as follows. The agent G was dissolved in ethanol as a solvent to prepare a diluted solution containing 0.06 mass% of the active ingredient of the liquid film cracking agent as a coating solution, the coating solution was applied to the entire skin-contacting surface of the core sheet on the skin side of the absorbent body X by a spray, and the solvent was dried. With respect to the agent G, X in the above-mentioned structure X-Y contains a group comprising-Si (CH)₃)₂A dimethylsilone chain of O-, Y contains a group consisting of- (C)₂H₄POE chain of O) -, the end group of the POE chain being methyl (CH)₃) The modification rate was 20% and the number of moles of polyoxyethylene added was 3.

In the measurement of the expansion coefficient and interfacial tension of the Polyoxyethylene (POE) -modified dimethylsilicone, the "liquid having a surface tension of 50 mN/m" was a solution prepared by adding 3.75. mu.L of polyoxyethylene sorbitan monolaurate (trade name: RHEODOL SUPER TW-L120, manufactured by Kao corporation) as a nonionic surface active material to 100g of deionized water with a micropipette (ACURA825, manufactured by Socorex Isba SA), and adjusting the surface tension to 50. + -. 1 mN/m.

[ example 2]

A sanitary napkin of example 2 was obtained in the same manner as in example 1, except that the core sheet (absorbent body) was not coated with the coating liquid of the liquid film cracking agent but with the surface sheet.

[ examples 3 to 7]

Sanitary napkins of examples 3 to 7 were obtained in the same manner as in example 1 except that the blood cell aggregating agent was changed to the following agents B to F.

Agent B (example 3): diallyl dimethyl ammonium chloride (PAS-H-5L manufactured by Nittobo Medical Co., Ltd.)

Agent C (example 4): polymethacryloxyethyldimethylammonium diethyl sulfate (prepared by dissolving diethylaminoethyl methacrylate diethyl sulfate in ethanol as a solvent, adding 2,2'-Azobis (2-methylpropionamidine) dihydrazide (2,2' -Azobis (2-methylpropionamidine) dihydrochloride) as an oil-soluble azo initiator (and V-65B manufactured by Wako pure chemical industries, Ltd.) and heating to polymerize the mixture, thereby obtaining a water-soluble quaternary ammonium salt homopolymer)

Agent D (example 5): polymethacryloxyethyldimethylammonium diethylsulfate/dimethylacrylamide copolymer (a water-soluble quaternary ammonium salt copolymer was obtained by dissolving diethylaminosulfate of dimethylaminoethyl methacrylate and dimethylacrylamide in a molar ratio of 56: 44 in ethanol as a solvent, adding 2,2' -Azobis (2-methylproprionamide) dihydrate (V-65B, manufactured by Wako pure chemical industries, Ltd.) as an oil-soluble azo initiator, and heating and copolymerizing the mixture)

Agent E (example 6): polymethacryloxyethyltrimethylammonium sulfate (manufactured by SENKA)

Agent F (example 7): polymethacryloxyethyltrimethylammonium methyl hydrochloride (a water-soluble quaternary ammonium salt homopolymer is obtained by dissolving a methyl chloride salt of dimethylaminoethyl methacrylate in ethanol as a solvent, adding 2,2' -Azobis (2-methylproprionidine) dihydride (V-65B manufactured by Wako pure chemical industries, Ltd.) as an oil-soluble azo initiator, heating, and polymerizing

[ examples 8 to 9]

Sanitary napkins of examples 8 to 9 were obtained in the same manner as in example 1 except that the liquid film splitting agent was changed to agents H to I described below.

Agent H (example 8): polyoxypropylene (POP) alkyl ether (antifoaming agent No.8, available from Kao corporation)

Agent I (example 9): tricaprylin octanoate (COCONARD MT, manufactured by Kao corporation)

[ example 10]

A commercially available sanitary napkin ("Laurier Slim Guard type 25 cm" manufactured by kao corporation in 2015) was used, and a surface sheet, a back sheet, and an absorbent body, each of which was obtained by decomposing and removing a hot-melt adhesive used for bonding the respective members, were used by a dryer. This absorbent body is obtained by covering an absorbent core (hereinafter, also referred to as absorbent body Y) comprising 5 sheets of a laminated sheet in which a super absorbent polymer is sandwiched between two sheets of crepe paper with a core sheet. Except for the above, a sanitary napkin of example 10 was obtained in the same manner as in example 1.

[ reference example 1]

A sanitary napkin of reference example 1 was obtained in the same manner as in example 1 except that the liquid film-splitting agent was not applied.

[ reference example 2]

A sanitary napkin of reference example 2 was obtained in the same manner as in example 1, except that no hemagglutinating agent was applied.

[ reference example 3]

A sanitary napkin of reference example 3 was obtained in the same manner as in example 10, except that the liquid film-splitting agent was not applied.

[ reference example 4]

A sanitary napkin of reference example 4 was obtained in the same manner as in example 10, except that no hemagglutinating agent was applied.

Comparative example 1

As the sanitary napkin of comparative example 1, a commercially available sanitary napkin ("LAURIER HADA-KIREI Guard type common for daily use manufactured by Kao corporation, 2015) itself, that is, a sanitary napkin containing no blood cell coagulation agent and no liquid film cracking agent was used.

The return liquid amount, the diffusion area, and the surface whiteness (L value) of each of the examples, reference examples, and comparative examples were evaluated by the following methods. The results are shown in tables 2 to 5 below.

< method for evaluating amount of returned liquid >

A sanitary napkin to be evaluated was developed into a flat shape, placed horizontally with the skin-facing surface side (topsheet side) facing upward, and an acrylic resin injection plate integrally molded so that a cylindrical part made of an acrylic resin and having a cylinder inner diameter of 22mm phi and a cylinder height of 50mm was positioned on an injection opening part of 10mm phi was stacked on the sanitary napkin so that the injection hole was positioned at the center of the excretion part-facing region in the skin-facing surface (topsheet side) of the sanitary napkin, and a weight (including the injection plate itself) was appropriately placed so as to adjust the load to 5g/m². 3g of the above-described simulated blood was weighed into a 10cc liquid-injection beaker. The blood was quickly injected into the cylinder of the liquid injection plate at one time, and then left to stand for 3 minutes, after which 3g was injected again, and the sanitary napkin was left to stand for 3 minutes in this state. Immediately thereafter, 10 pieces of weighed absorbent paper (Advantec 5A, 55 mm. phi.) and a rectangular parallelepiped weight having a weight of 960g were placed on the portion of the sanitary napkin into which blood had been injected, and left for 10 seconds, and the amount (g) of blood absorbed by the absorbent paper was calculated from the weight of the absorbent paper after 10 seconds. The measurement was performed 3 times, and the average value was taken as the return liquid amount of the sanitary napkin. The smaller the value of the amount of the returned liquid, the more excellent the absorption performance of the sanitary napkin.

< evaluation method of diffusion area >

From the sanitary napkin immediately after the evaluation method of < amount of return liquid > was performed, the topsheet was removed, and an OHP sheet (KOKUYO corporation, regenerated OHP film, a4 size, transparent VF-1300N) was superimposed on the skin-contact surface side and the non-skin-contact surface side of the absorbent body, respectively, to trace the wet range. Thereafter, the OHP sheet was read by a scanner and taken into Image software (Image-Pro 6.2J, manufactured by Nippon rose) to calculate the area. The measurement was performed 3 times, and the average value was taken as each diffusion area.

The ratio (former/latter) of the diffusion area on the non-skin contact surface side of the absorber to the diffusion area on the skin contact surface side of the absorber was calculated. When the ratio exceeds 1, that is, when the diffusion area on the non-skin contact surface side is larger than the diffusion area on the skin contact surface side, it means that blood (the above-mentioned dummy blood) diffuses in the planar direction when moving from the skin contact surface side to the non-skin contact surface side in the absorbent body, and when the ratio exceeds 1 and becomes larger, it means that the diffusion is promoted. Further, if the diffusion of the blood is promoted, the user who sees the skin contact surface side of the used sanitary product may be concerned with giving a feeling of reliability and a feeling of security to the absorption performance of the sanitary product and also with improving the surface whiteness after use because the amount of blood remaining on the skin contact surface side is relatively small compared to the non-skin contact surface side. That is, the larger the above ratio is, the higher the evaluation is.

< method for evaluating surface whiteness (L value) >

Immediately after the evaluation method < amount of return liquid > was performed, a color difference meter (SPECTRO PHOTOMETER NF333, manufactured by Nippon Denshoku industries Co., Ltd.) was placed on the topsheet, and the measurement was performed from the injection site of blood (the above-mentioned simulated blood). The measurement was performed 3 times, and the average value was taken as the L value. The larger the L value, the more excellent the surface whiteness after use.

[ Table 4]

[ Table 5]

As shown in tables 2 to 4, in examples 1 to 9, since they contained both the blood cell coagulation agent and the liquid film cracking agent, the amount of the returned liquid was 1/10 or less of that of comparative example 1. Example 1 contains both the blood cell aggregating agent and the liquid film breaking agent, and therefore compared with reference examples 1 and 2 containing only one dose, the amount of the return liquid was 1/5 or less, the L value was larger than that of reference example 1, and the whiteness was excellent. In examples 2 to 9, the liquid film cracking agent was contained in the surface sheet, so that the L value was higher than that in comparative example 1 and reference example 1, and the whiteness was very excellent.

Further, as shown in Table 5, example 10, in which the absorbent body was changed from the absorbent body X to the absorbent body Y and which contained the hemagglutinating agent and the liquid film-breaking agent, had a smaller amount of returned liquid and a larger value of L than those of reference examples 3 and 4, which contained only one dose.

[ Industrial passability ]

The physiological article of the present invention has a small amount of returned liquid and has excellent surface whiteness after use.

Claims (29)

1. A sanitary article comprising a topsheet on the skin-contacting surface side, a backsheet on the non-skin-contacting surface side, and an absorbent member interposed therebetween, and

the absorbent body or a skin contact surface side of the absorbent body is provided with:

a region containing a hemagglutinating agent containing hemagglutinating agent, and

a liquid film cracking agent-containing region containing a liquid film cracking agent,

wherein the content of the first and second substances,

the hemagglutinating agent is a cationic polymer,

the cationic polymer is a quaternary ammonium salt homopolymer having a structure comprising a main chain and a side chain connected to the main chain and having a repeating unit represented by the following formula 1, or a quaternary ammonium salt copolymer having a structure comprising a main chain and a side chain connected to the main chain and having a repeating unit represented by the following formula 1 and a repeating unit represented by the following formula 2, wherein the main chain and the side chain of the cationic polymer are connected at1 point and the side chain has a quaternary ammonium moiety,

in the formula 1, R₁Represents H or CH₃，

R₂To represent

n represents an integer of 1 or more and 10 or less,

represents a halide ion,

In the formula 2, R₃Represents H or CH₃，

R₄To represent

m represents an integer of 1 to 10 inclusive,

to represent

The liquid film cracking agent has an expansion coefficient of more than 0mN/m to a liquid with a surface tension of 50mN/m, and

the interfacial tension of the liquid film cracking agent to the liquid with the surface tension of 50mN/m is less than or equal to 20mN/m,

the liquid membrane disruptive agent-containing region overlaps the hemagglutinating agent-containing region in a planar direction.

2. The physiological article according to claim 1, wherein the liquid film-splitting agent has an extension coefficient of 15mN/m or more with respect to a liquid having a surface tension of 50 mN/m.

3. The physiological article according to claim 1 or 2, wherein the liquid film-splitting agent has an expansion coefficient of 15mN/m or more and 50mN/m or less with respect to a liquid having a surface tension of 50 mN/m.

4. The physiological article according to claim 1 or 2, wherein the liquid film breaking agent is composed of a compound having at least 1 structure selected from the group consisting of X, X-Y and Y-X-Y,

structure X represents > C (A) -, -C (A)₂-、-C(A)(B)-、＞C(A)-C(R¹)＜、＞C(R¹)-、-C(R¹)(R²)-、-C(R¹)₂-, > C <, and-Si (R)¹)₂O-、-Si(R¹)(R²) A siloxane chain having a structure in which any one of the basic structures of O-is repeated or 2 or more kinds of O-are combined, or a mixed chain thereof; having a hydrogen atom at the terminus of structure X, or-C (A)₃、-C(A)₂B、-C(A)(B)₂、-C(A)₂-C(R¹)₃、-C(R¹)₂A、-C(R¹)₃、-OSi(R¹)₃、-OSi(R¹)₂(R²)、-Si(R¹)₃、-Si(R¹)₂(R²) At least one group of (a); wherein C represents a carbon atom, and <, > and-represent a bond, the same as defined below,

the R is¹And R²Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom; A. each B independently represents a substituent containing an oxygen atom or a nitrogen atom; in structure X R¹、R²A, B, which may be the same or different from each other,

y represents a hydrophilic group having hydrophilicity and containing an atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom; when a plurality of Y's are present, they may be the same or different.

5. The physiological article according to claim 1 or 2, wherein the liquid film cleavage agent is an organically modified silicone which is one or more selected from the group consisting of amino modification, epoxy modification, carboxyl modification, glycol modification, primary alcohol modification, (meth) acryl modification, mercapto modification, phenol modification, polyether modification, methyl styrene modification, long-chain alkyl modification, higher fatty acid ester modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification, wherein the polyether modification includes polyoxyalkylene modification.

6. The physiological article according to claim 1 or 2, wherein the liquid film-splitting agent is a polyoxyalkylene-modified silicone represented by the following formulas [ I ] to [ IV ],

the formula [ I]～[IV]The method comprises the following steps: r³¹Represents an alkyl group; r³²Represents a single bond or an alkylene group; plural R³¹A plurality of R³²Are respectively the same or different from each other; m¹¹Represents a group having a polyoxyalkylene group; m and n each independently represent an integer of 1 or more.

7. The physiological article according to claim 1, wherein the liquid film-splitting agent has an extension coefficient of more than 0mN/m and 50mN/m or less with respect to a liquid having a surface tension of 50 mN/m.

8. The physiological article according to claim 1, wherein the liquid film breaking agent is composed of a compound having at least 1 structure selected from the group consisting of the following structures Z, Z-Y and Y-Z-Y,

structure Z represents > C (A) -, -C (A)₂-、-C(A)(B)-、＞C(A)-C(R³)＜、＞C(R³)-、-C(R³)(R⁴)-、-C(R³)₂A hydrocarbon chain having a structure in which any one of the basic structures-, > C < is repeated or 2 or more kinds are combined; having a hydrogen atom at the terminus of structure Z, or-C (A)₃、-C(A)₂B、-C(A)(B)₂、-C(A)₂-C(R³)₃、-C(R³)₂A、-C(R³)₃At least one group of (a); wherein C represents a carbon atom,

the R is³And R⁴Each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group, an aralkyl group, a hydrocarbon group in which these are combined, or a fluorine atom; A. each B independently represents a substituent containing an oxygen atom or a nitrogen atom,

y represents a hydrophilic group having hydrophilicity and containing an atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a phosphorus atom, and a sulfur atom; when a plurality of Y's are present, they may be the same or different.

9. The physiological article according to claim 1, wherein the liquid film opener is one or more selected from polyoxyalkylene alkyl ethers represented by any one of the following formulas [ V ], polyoxyalkylene glycols represented by the following formula [ VI ] and having a mass average molecular weight of 1000 or more, steareth, beheneth, PPG myristic ether, PPG stearyl ether, and PPG behenyl ether,

the formula [ V]In, L²¹A linking group such as an ether group, an amino group, an amide group, an ester group, a carbonyl group, a carbonate group, a polyoxyethylene group, a polyoxypropylene group, a polyoxybutenyl group, or a polyoxyalkylene group in which these groups are combined; the formula [ V]And [ VI)]In, R⁵¹Represents various substituents containing a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a methoxy group, an ethoxy group, a phenyl group, a fluoroalkyl group, an aralkyl group, or a hydrocarbon group containing these in combination, or a fluorine atom; a. b, m and n are each independently an integer of 1 or more; c_mH_nRepresents an alkyl group, wherein n is 2m +1, C_aH_bRepresents an alkylene group, wherein a is 2b, and the number of carbon atoms and the number of hydrogen atoms are represented by the formula [ V]And [ VI)]Each of (1) is independently determined, and does not necessarily represent the same integer, but may be different.

10. The physiological article according to claim 1, wherein the liquid film breaking agent is one or more selected from the group consisting of a fatty acid represented by the following formula [ VII ], a glycerin fatty acid ester or pentaerythritol fatty acid ester represented by the following formula [ VIII-I ] or [ VIII-II ], a glycerin fatty acid ester, a sorbitan fatty acid ester, or a partial ester of pentaerythritol fatty acid ester represented by the following formula [ IX ], the following formula [ X ] or the following formula [ XI ], a sterol represented by the following formula [ XII ], an alcohol represented by the following formula [ XIII ], a fatty acid ester represented by the following formula [ XIV ], and a wax represented by the following formula [ XV ],

C_mH_n-COOH [VII]

C_mH_n-OH [XIII]

C_mH_n-COO-C_mH_n [XIV]

C_mH_n [XV]

in the respective formulae: m and n are each independently an integer of 1 or more; m, m ', n ' and n ' are each independently an integer of 1 or more; a plurality of m and a plurality of n are respectively the same or different; r⁵²Represents a linear or branched, saturated or unsaturated hydrocarbon group having 2 to 22 carbon atoms.

11. The physiological article according to claim 1 or 2, wherein the liquid film breaking agent has a melting point of 40 ℃ or lower and-220 ℃ or higher.

12. The physiological article according to claim 1 or 2, wherein the water solubility of the liquid film-splitting agent is 0g or more and 0.025g or less.

13. The physiological article according to claim 1 or 2, wherein the liquid film-splitting agent has an interfacial tension of 20mN/m or less and more than 0mN/m with respect to a liquid having a surface tension of 50 mN/m.

14. The physiological article according to claim 1 or 2, wherein the surface tension of the liquid film cleavage agent is 32mN/m or less and 1mN/m or more.

15. The sanitary article according to claim 1 or 2, wherein the liquid film-cracking agent has a weight-average molecular weight of 500 or more and 50000 or less.

16. The physiological article according to claim 1 or 2, wherein the cationic polymer is a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer or a quaternary ammonium salt polycondensate.

17. The sanitary article according to claim 1 or 2, wherein the weight average molecular weight of the cationic polymer is 2000 or more and 1000 ten thousand or less.

18. The sanitary article according to claim 1 or 2, wherein the cationic polymer is a water-soluble cationic polymer having a flow potential of 1500 μ eq/L or more and comprising a quaternary ammonium salt homopolymer or a quaternary ammonium salt copolymer.

19. The sanitary article according to claim 1 or 2, wherein the cationic polymer has a coagulation rate of 0.75 mPas/s or less.

20. The physiological article according to claim 1 or 2, wherein the cationic polymer has an inorganic value/organic value ratio of an inorganic value to an organic value of 0.6 or more and 4.6 or less, and the cationic polymer is a quaternary ammonium salt homopolymer, a quaternary ammonium salt copolymer or a quaternary ammonium salt polycondensate.

21. The sanitary article according to claim 1 or 2, wherein said absorbent comprises a super absorbent polymer.

22. The sanitary article according to claim 1 or 2, wherein the absorbent member has a fiber stack in which fluff pulp and a super absorbent polymer are mixed.

23. The sanitary article according to claim 22, wherein said blood cell coagulant-containing region and said liquid membrane disruptive agent-containing region are disposed on the skin contact surface side of said superabsorbent polymer.

24. The sanitary product according to claim 1 or 2, wherein said hemagglutinating agent-containing region is disposed on the non-skin contact surface side of said top sheet.

25. The sanitary article according to claim 1 or 2, wherein the liquid film-disruptive agent-containing region is disposed on the skin contact surface side of the blood cell aggregate-containing region.

26. The sanitary article according to claim 1 or 2, wherein the liquid film-disrupting agent-containing region is provided in the topsheet.

27. The sanitary article according to claim 1 or 2, wherein the absorbent member has an absorbent core and a core-wrapped sheet covering the absorbent core.

28. The sanitary article according to claim 27, wherein the blood cell coagulant-containing region is provided on the core-covering sheet on the skin contact surface side of the absorbent core.

29. The physiological article according to claim 1 or 2, wherein one or both of the blood cell coagulant-containing region and the liquid membrane cleavage agent-containing region are disposed in an excretory opening abutment region of the physiological article.

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