JP6345111B2 - Composite material and absorbent article using the same - Google Patents

Description

  The present invention relates to a composite material for an absorbent article and an absorbent article using the same.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 08-164159) discloses a liquid-permeable layer, a liquid-impermeable layer, a liquid-permeable layer disposed between the liquid-permeable layer and the liquid-impermeable layer, An absorbent article is described that includes a liquid permeable layer and a liquid diffusible layer disposed between the liquid absorbent layer.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2003-033390) includes a liquid-permeable layer, a liquid-impermeable layer, a liquid-permeable layer disposed between the liquid-permeable layer and the liquid-impermeable layer, An absorbent article is described that comprises a liquid diffusible layer disposed between a liquid absorbent layer and a liquid impermeable layer.

  As a method for supporting particles on the surface of a thermoplastic resin fiber, Patent Document 3 (Japanese Patent Application Laid-Open No. 6-341044) describes a method of fixing particles on the surface of a thermoplastic resin fiber with an adhesive (binder). In Patent Document 4 (Japanese Patent Laid-Open No. 2009-174114), particles heated to a temperature higher than the melting point of the thermoplastic resin fibers are brought into contact with the thermoplastic resin fibers, and particles are formed on the surface of the thermoplastic resin fibers. Is described.

  As a method for adsorbing child particles to mother particles, Patent Document 5 (Japanese Patent Application Laid-Open No. 2010-64945) discloses a polymer electrolyte (cationic polymer or charged polymer) that charges the surfaces of mother particles and child particles to opposite charges. And a method of adsorbing child particles to mother particles by electrostatic interaction.

Japanese Patent Laid-Open No. 08-164159 JP 2003-033390 A JP-A-6-341044 JP 2009-174114 A JP 2010-64945 A

  The liquid diffusible layer disposed between the liquid permeable layer and the liquid absorptive layer described in Patent Document 1 is based on the liquid diffusibility and cushioning property, and is from the liquid permeable layer to the liquid diffusible layer. The liquid diffusive layer disposed between the liquid-absorbing layer and the liquid-impermeable layer described in Patent Document 2 is useful in terms of improving the liquid transferability and cushioning properties of the absorbent article. This is useful in terms of improving the liquid absorbency in the liquid absorbent layer and the cushioning property of the absorbent article based on the diffusibility and the cushioning property. However, when the cushioning property of the liquid diffusible layer is improved, the liquid diffusible layer becomes bulky, so that the interfiber distance increases and the capillary force generated between the fibers decreases. This means a decrease in liquid diffusibility of the liquid diffusible layer. On the other hand, when the liquid diffusibility of the liquid diffusible layer is improved, the inter-fiber distance is decreased, so that the porosity of the liquid diffusible layer is decreased. This means a decrease in cushioning properties of the liquid diffusible layer. Thus, it is difficult to achieve both liquid diffusibility and cushioning properties of the liquid diffusible layer.

  On the other hand, in the method described in Patent Document 3, the surface of the particles is covered with an adhesive (binder) more than necessary, and the particles may not effectively exhibit a desired function. Further, in the method described in Patent Document 4, since the particles are buried in the fiber, there is a possibility that the particles cannot effectively exhibit a desired function.

  Accordingly, the present invention provides a composite material for an absorbent article, in which a guest material is composited with a host material, and a composite material capable of realizing both liquid diffusibility and cushioning properties. An object of the present invention is to provide an absorbent article using the above.

  In order to solve the above-described problems, the present invention provides a surface charged positively or negatively in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water. A composite material for an absorbent article, in which a guest material whose surface is charged to a charge opposite to the surface of the host material is adsorbed by electrostatic interaction in the predetermined solvent. The host material includes a nonwoven fabric substrate as a substrate, and the guest material has a plurality of hydrophilic particle substrates having an average particle diameter smaller than the average fiber diameter of the nonwoven fabric substrate or the nonwoven fabric substrate as the substrate. The composite comprising a plurality of hydrophilic fiber bases having an average fiber diameter smaller than the average fiber diameter, wherein at least one of the host material and the guest material has a polymer electrolyte layer covering the base To provide the material.

  The present invention also includes a liquid permeable layer, a liquid impermeable layer, a liquid permeable layer disposed between the liquid permeable layer and the liquid impermeable layer, the liquid permeable layer, and the liquid permeable layer. An absorbent article comprising a liquid diffusible layer disposed between liquid absorbent layers or between the liquid absorbent layer and the liquid impermeable layer, wherein the liquid diffusible layer is a composite of the present invention. The absorbent article containing a chemical material is provided.

  According to the present invention, a composite material in which a guest material is composited with a host material, which can realize both liquid diffusibility and cushioning properties, and an absorbent article using the composite material Is provided.

FIG. 1 is a plan view of a sanitary napkin according to an embodiment of the absorbent article of the present invention. 2 is a cross-sectional view taken along line AA in FIG. FIG. 3 is an electron micrograph (300 times) of the particle composite nonwoven fabric produced in Production Example 2. FIG. 4 is an electron micrograph (2000 times) of the nanofiber composite nonwoven fabric produced in Production Example 5. 5A is an electron micrograph (8000 times) of the nanofiber composite nonwoven fabric produced in Production Example 6, and FIG. 5B is an electron microscope photograph of the nanofiber composite nonwoven fabric produced in Production Example 5. It is a photograph (8000 times).

Hereinafter, embodiments included in the present invention will be described.
The composite material according to one embodiment of the present invention (hereinafter referred to as “embodiment 1A”) is in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water. Absorption, in which a guest material whose surface is charged to a charge opposite to that of the host material in the predetermined solvent is adsorbed by electrostatic interaction with the host material whose surface is positively or negatively charged. A composite material for an adhesive article, wherein the host material includes a nonwoven fabric substrate as a substrate, and the guest material has a plurality of hydrophilic materials having an average particle diameter smaller than the average fiber diameter of the nonwoven fabric substrate as a substrate. A plurality of hydrophilic fiber bases having an average fiber diameter smaller than the average fiber diameter of the conductive particle base or the nonwoven fabric base, and at least one of the host material and the guest material covers the base It has the quality layer, wherein a composite material.

  The host material is composed of a plurality of fibers (fibers covered with a polymer electrolyte layer and / or fibers not covered with a polymer electrolyte layer). When the host material does not have a polymer electrolyte layer covering the nonwoven fabric substrate, the average fiber diameter of the fibers constituting the host material is equal to the average fiber diameter of the nonwoven fabric substrate. When the host material has a polymer electrolyte layer that covers the nonwoven fabric substrate, the thickness of the polymer electrolyte layer that covers the nonwoven fabric substrate is negligibly small with respect to the average fiber diameter of the nonwoven fabric substrate. The average fiber diameter of the fibers can be approximated by the average fiber diameter of the nonwoven fabric substrate.

  The guest material may comprise a plurality of particles (particles coated with a polyelectrolyte layer and / or particles not coated with a polyelectrolyte layer) or a plurality of fibers (fibers coated with a polyelectrolyte layer and / or The fiber is not covered with a polymer electrolyte layer. The guest material may be composed of both particles and fibers. When the guest material does not have a polymer electrolyte layer covering the hydrophilic particle substrate or the hydrophilic fiber substrate, the average particle diameter or average fiber diameter of the particles or fibers constituting the guest material is the average particle of the hydrophilic particle substrate. Equal to the diameter or the average fiber diameter of the hydrophilic fiber substrate. When the guest material has a polymer electrolyte layer covering the hydrophilic particle substrate or hydrophilic fiber substrate, the thickness of the polymer electrolyte layer covering the hydrophilic particle substrate or hydrophilic fiber substrate is the average of the hydrophilic particle substrate. Since the particle diameter or the average fiber diameter of the hydrophilic fiber substrate is negligibly small, the average particle diameter or the average fiber diameter of the particles or fibers constituting the guest material is the average particle diameter or the hydrophilic fibers of the hydrophilic particle substrate. It can be approximated by the average fiber diameter of the substrate.

  As described above, the average fiber diameter of the fibers constituting the host material is the same as the average fiber diameter of the host material nonwoven substrate regardless of whether the host material nonwoven substrate is coated with the polymer electrolyte layer or not. The average particle diameter or average fiber diameter of the particles or fibers constituting the guest material is determined based on whether the hydrophilic particle base or the hydrophilic fiber base of the guest material is covered with the polymer electrolyte layer. Regardless, it can be considered to be the same as the average particle diameter or average fiber diameter of the hydrophilic particle substrate or hydrophilic fiber substrate of the guest material. The average particle diameter or average fiber diameter of the hydrophilic particle substrate or hydrophilic fiber substrate of the guest material is smaller than the average fiber diameter of the nonwoven fabric substrate of the host material. Therefore, the average particle diameter or average fiber diameter of the particles or fibers constituting the guest material is smaller than the average fiber diameter of the fibers constituting the host material. When such a guest material is combined with the host material, not only a capillary force is generated between the fibers constituting the host material, but also a capillary force is generated on the surface of the fibers constituting the host material.

  A polymer electrolyte layer in which at least one of a host material and a guest material covers a substrate (in the case of a host material, a non-woven substrate, and in the case of a guest material, a hydrophilic particle substrate or a hydrophilic fiber substrate) Therefore, the guest material is effectively adsorbed to the host material by electrostatic interaction. For this reason, the host material and the guest material are combined without depending on the adhesive, without being heated, and without being embedded in the host material. Therefore, the guest material combined with the host material can effectively exhibit a desired function (hydrophilicity based on a hydrophilic particle substrate or a hydrophilic fiber substrate).

  As described above, in the composite material according to aspect 1A, not only the capillary force is generated between the fibers constituting the host material, but also the capillary force is generated on the surface of the fiber constituting the host material. The guest material composited with the host material can effectively exhibit a desired function (hydrophilicity based on a hydrophilic particle substrate or a hydrophilic fiber substrate). Therefore, the composite material according to aspect 1A can achieve both liquid diffusibility and cushioning properties. That is, in the composite material according to aspect 1A, when a nonwoven fabric substrate having a high cushioning property (that is, bulky) is used as the nonwoven material substrate of the host material, the capillary force generated between the fibers constituting the host material is reduced. However, a decrease in the liquid diffusibility of the composite material is prevented by the capillary force generated on the surface of the fiber constituting the host material. However, in the composite material according to aspect 1A, it is not essential to use a nonwoven fabric substrate having a high cushioning property (that is, bulky) as the nonwoven material substrate of the host material. The cushioning property of the non-woven fabric substrate of the host material can be appropriately adjusted according to the use of the composite material. For example, when a nonwoven fabric substrate having a low cushioning property (that is, a low porosity) is used as the nonwoven material substrate of the host material, the capillary force generated between the fibers constituting the host material and the surface of the fibers constituting the host material Combined with the capillary force generated in the above, the liquid diffusibility of the composite material is improved.

  In a preferred embodiment of the composite material according to Embodiment 1A (hereinafter referred to as “Aspect 2A”), the ratio of the average particle diameter of the plurality of hydrophilic particle substrates to the average fiber diameter of the nonwoven fabric substrate (average of hydrophilic particle substrates) The particle diameter: the average fiber diameter of the nonwoven fabric substrate is 1: 4 to 1:50, and the ratio of the average fiber diameter of the plurality of hydrophilic fiber substrates to the average fiber diameter of the nonwoven fabric substrate (average of the hydrophilic fiber substrate) Fiber diameter: average fiber diameter of the nonwoven fabric substrate) is 1: 4 to 1: 2500. The composite material according to aspect 2A is preferable in that a capillary force can be effectively generated on the surface of the fiber constituting the host material.

  In a preferred embodiment of the composite material according to Embodiment 1A or Embodiment 2A (hereinafter referred to as “Aspect 3A”), the polymer electrolyte layer includes a plurality of laminated polymer electrolyte layers, and the plurality of polymer electrolyte layers , The polymer electrolyte layers charged to opposite charges in the predetermined solvent are adjacent to each other. The composite material according to aspect 3A is preferable in that a uniform surface coating can be achieved because the charge density of the polymer electrolyte layer becomes constant and the strength thereof increases.

  In a preferred embodiment of the composite material according to Embodiment 1A to Embodiment 3A (hereinafter referred to as “Aspect 4A”), the absolute value of the zeta potential of the host material and the guest material in the predetermined solvent is 20 mV or more. And it is balanced in charge. The composite material according to aspect 4A is preferable in that the guest material can be effectively adsorbed to the host material by electrostatic interaction.

In a preferred embodiment of the composite material according to any one of Embodiments 1A to 4A (hereinafter referred to as “Aspect 5A”), the host material includes the following steps (a ₁ ) and (a ₂ ):
(A ₁ ) In a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water, the surface is positively or negatively charged in the predetermined solvent. A step of producing a first coated body having a first polymer electrolyte layer as a surface layer by bringing a nonwoven fabric substrate into contact with a polymer electrolyte charged with a charge opposite to the surface of the nonwoven fabric substrate in the predetermined solvent. ;
(A ₂ ) kth positively or negatively charged in the predetermined solvent in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water a first k ₁ of the cover having a _first polyelectrolyte layer to the surface layer, contacting the polymer electrolyte charged to the predetermined charge opposite in a solvent and the second k ₁ polyelectrolyte layer, the ( The procedure for manufacturing the (k ₁ +1) -th covering having the k ₁ +1) polymer electrolyte layer as the surface layer is k ₁ = 1 to k ₁ = m (where m is an integer of 1 or more). ) M times, and the (m + 1) th covering manufactured by a method including a step of manufacturing a (m + 1) th covering having a (m + 1) th polymer electrolyte layer as a surface layer.

  In a preferred embodiment of the composite material according to Embodiment 5A (hereinafter referred to as “Aspect 6A”), the absolute value of the zeta potential of the (m + 1) th covering is 20 mV or more.

In a preferred embodiment of the composite material according to any of Embodiments 1A to 6A (hereinafter referred to as “Aspect 7A”), the guest material includes the following steps (b ₁ ) and (b ₂ ):
(B ₁ ) In a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water, the surface is positively or negatively charged in the predetermined solvent. A hydrophilic polymer substrate or a hydrophilic fiber substrate is contacted with a polyelectrolyte that is charged with a charge opposite to the surface of the hydrophilic particle substrate or the hydrophilic fiber substrate in the predetermined solvent, to thereby form a first polymer. Producing a first covering having an electrolyte layer as a surface layer;
(B ₂ ) kth positively or negatively charged in the predetermined solvent in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water a covering member of the k ₂ with ₂ polyelectrolyte layers on the surface layer, contacting the polymer electrolyte charged to the opposite charge as the polyelectrolyte layer of the first k ₂ at the predetermined solvent, the ( the procedure of manufacturing a covering member of the (k ₂ +1) with the polymer electrolyte layer of k ₂ +1) in the surface layer, the _{k 2 = 1 k 2 = n} ( where, n represents an integer of 1 or more. And (n + 1) -th coated body manufactured by a method including a step of manufacturing a (n + 1) -th coated body having a (n + 1) -th polymer electrolyte layer as a surface layer.

  In a preferable embodiment (hereinafter referred to as “embodiment 8A”) of the composite material according to Embodiment 7A, the absolute value of the zeta potential of the (n + 1) th covering is 20 mV or more.

  In a preferred embodiment of the composite material according to any of Embodiments 1A to 8A (hereinafter referred to as “Aspect 9A”), the hydrophilic particle substrate is silica particles.

  In a preferred embodiment of the composite material according to any of Embodiments 1A to 8A (hereinafter referred to as “Aspect 10A”), the hydrophilic fiber substrate is a cellulose fiber.

In a preferred embodiment of the composite material according to Embodiment 10A (hereinafter referred to as “Aspect 11A”), the composite material is a monohydric alcohol having 1 to 3 carbon atoms, and the guest material is mixed with the host material. It is obtained by adsorption by electrostatic interaction. The composite material according to the aspect 11A is preferable in that it becomes difficult to form hydrogen bonds between particles and / or fibers constituting the guest material in the drying step performed after the adsorption step, and the specific surface area of the guest material is increased. .
From the above viewpoint, the guest material is preferably cellulose fiber, and more preferably fibrillated cellulose fiber.

  An absorbent article according to an aspect of the present invention (hereinafter referred to as “Aspect 1B”) is disposed between a liquid-permeable layer, a liquid-impermeable layer, the liquid-permeable layer, and the liquid-impermeable layer. An absorbent article comprising: a liquid absorbent layer; and a liquid diffusible layer disposed between the liquid permeable layer and the liquid absorbent layer or between the liquid absorbent layer and the liquid impermeable layer. And it is the said absorbent article in which the said liquid diffusible layer contains the composite material which concerns on either of aspect 1A-aspect 11A. The absorbent article which concerns on aspect 1B can exhibit the effect according to the kind of composite material contained in a liquid diffusible layer.

  In a preferred aspect of the absorbent article according to aspect 1B (hereinafter referred to as “aspect 2B”), the liquid diffusible layer is in contact with the liquid absorbent layer. The absorbent article which concerns on aspect 2B is preferable at the point by which the liquid which diffused the liquid diffusible layer is rapidly absorbed by the liquid absorptive layer.

  The kind and use of the absorbent article which concerns on aspect 1B and aspect 2B are not specifically limited. Examples of the absorbent article include sanitary articles such as sanitary napkins, disposable diapers, and panty liners, and these may target humans and non-human animals such as pets. Examples of the liquid excrement to be absorbed by the absorbent article include menstrual blood, spillage, urine, and watery stool.

  Hereinafter, an embodiment of an absorbent article using the composite material of the present invention will be described based on the drawings, taking a sanitary napkin as an example.

  FIG. 1 is a plan view of a sanitary napkin 1 according to an embodiment of the absorbent article of the present invention, and FIG. 2 is a cross-sectional view taken along line AA of FIG.

  As shown in FIGS. 1 and 2, the sanitary napkin 1 has a length direction X, a width direction Y, and a thickness direction Z orthogonal to each other, and includes a liquid permeable layer 2, a liquid impermeable layer 3, and The liquid-absorbing layer 4 disposed between the liquid-permeable layer 2 and the liquid-impermeable layer 3, and the liquid-diffusible layer 5 disposed between the liquid-permeable layer 2 and the liquid-absorbing layer 4 Prepare.

  The sanitary napkin 1 is worn for the purpose of absorbing the liquid excretion (mainly menstrual blood) of the wearer. At this time, the liquid-permeable layer 2 is worn on the skin side of the wearer and the liquid-impermeable layer 3 is worn on the underwear side of the wearer. The liquid excrement of the wearer is transferred from the liquid permeable layer 2 to the liquid diffusible layer 5, temporarily stored in the liquid diffusible layer 5, and then transferred from the liquid diffusible layer 5 to the liquid absorbent layer 4. And is absorbed and retained by the liquid absorbent layer 4. Leakage of liquid excretion absorbed and retained by the liquid absorbent layer 4 is prevented by the liquid impermeable layer 3.

  The liquid permeable layer 2 is composed of a liquid permeable sheet through which liquid excretion excreted from the wearer can permeate. Examples of the liquid permeable sheet include a nonwoven fabric and a synthetic resin sheet in which liquid permeable holes are formed. Among these, the nonwoven fabric is preferable.

  The peripheral portion of the liquid permeable layer 2 is overlapped with the peripheral portion of the liquid impermeable layer 3 and joined by a seal portion (not shown). As a joining mode by a seal part, joining by heat emboss processing, joining by a hot-melt type adhesive agent, etc. are mentioned, for example.

  The liquid impervious layer 3 is composed of a liquid impervious sheet through which liquid excretion excreted from the wearer cannot permeate. Examples of the liquid impermeable sheet include a waterproof nonwoven fabric, a synthetic resin sheet, a composite sheet of a nonwoven fabric and a synthetic resin sheet, and the like.

  The liquid absorptive layer 4 contains an absorptive material that can absorb the liquid excretion excreted from the wearer. Examples of the absorbent material include hydrophilic fibers and superabsorbent polymers. Examples of hydrophilic fibers include cellulosic fibers such as wood pulp, non-wood pulp, regenerated cellulose, and semi-synthetic cellulose. Examples of the super absorbent polymer (SAP) include SAPs such as polyacrylates and polysulfonates.

  The liquid absorbent layer 4 includes, for example, an absorbent material layer and a core wrap that covers the absorbent material layer. The absorbent material layer may be a single layer or a plurality of layers. The core wrap is a liquid-permeable sheet through which liquid excretion excreted from the wearer can permeate. Examples of the core wrap include a nonwoven fabric and a synthetic resin sheet in which liquid permeation holes are formed, and a nonwoven fabric is preferable, and a tissue is more preferable.

  As shown in FIGS. 1 and 2, the liquid diffusible layer 5 is disposed so as to overlap both the liquid permeable layer 2 and the liquid absorbent layer 4 in the thickness direction Z. The liquid diffusible layer 5 is in contact with the liquid permeable layer 2 on one side in the thickness direction Z (upper side in FIG. 2), and the liquid absorbent layer 4 on the other side in the thickness direction Z (lower side in FIG. 2). It touches. The embodiment in which the liquid diffusible layer 5 is in contact with the liquid absorptive layer 4 is preferable in that the liquid excretion diffused through the liquid diffusible layer 5 is quickly absorbed by the liquid absorptive layer 4. However, in the present invention, the liquid diffusible layer 5 is in contact with only one of the liquid permeable layer 2 and the liquid absorbent layer 4, and the liquid diffusible layer 5 is the liquid permeable layer 2 and the liquid permeable layer 5. Embodiments that are not in contact with both absorbent layers 4 are included. In this embodiment, the liquid diffusible layer 5 is disposed between the liquid permeable layer 2 and the liquid absorbent layer 4, but the liquid diffusible layer 5 is composed of the liquid absorbent layer 4 and the liquid impermeable layer 3. It may be arranged between. In this case, the liquid diffusible layer 5 is preferably in contact with the liquid absorbent layer 4 on one side in the thickness direction Z.

  As shown in FIGS. 1 and 2, the sanitary napkin 1 has a pressing portion 6 that integrates the liquid permeable layer 2, the liquid diffusible layer 5, and the liquid absorbent layer 4 in the thickness direction Z. However, the present invention includes an embodiment in which the sanitary napkin 1 does not have the compressed portion 6. The pressing part 6 is a pressing groove formed around the central region of the skin side surface of the liquid permeable layer 2 by heat embossing. The central area of the skin-side surface of the liquid-permeable layer 2 is in contact with the excretion opening of the wearer (eg, small labia, large labia) when the sanitary napkin 1 is worn, and liquid excretion excreted from the wearer This is the area that is mainly supplied. A heat embossing process can be implemented in accordance with a conventional method.

  As shown in FIGS. 1 and 2, the sanitary napkin 1 includes a main body 11 in which the liquid absorbent layer 4 is incorporated, and one side in the width direction Y from the main body 11 (left side in FIGS. 1 and 2). And a second wing portion 13 extending from the main body portion 11 to the other side in the width direction Y (right side in FIGS. 1 and 2).

  As shown in FIGS. 1 and 2, the sanitary napkin 1 includes a first adhesive portion 71, a second adhesive portion 72, and a third adhesive portion 73 provided on the underwear side surface of the liquid impermeable layer 3. . However, the present invention includes an embodiment in which the sanitary napkin 1 does not include one or more of the first adhesive portion 71 to the third adhesive portion 73. The 1st adhesion part 71, the 2nd adhesion part 72, and the 3rd adhesion part 73 can prevent the shift | offset | difference of the sanitary napkin 1 at the time of wear.

Hereinafter, the liquid diffusible layer 5 will be described in detail.
The liquid diffusible layer 5 contains a composite material. The composite material contained in the liquid diffusible layer 5 is a composite material in which a guest material is adsorbed to the host material by electrostatic interaction.

The host material includes a nonwoven fabric substrate as the substrate. Examples of the nonwoven fabric substrate include an air-through nonwoven fabric, a spunbond nonwoven fabric, a point bond nonwoven fabric, a spunlace nonwoven fabric, a needle punched nonwoven fabric, a melt blown nonwoven fabric, and a combination thereof (for example, SMS), but an air-through nonwoven fabric is preferable. . The basis weight, thickness, and the like of the nonwoven fabric substrate are appropriately adjusted in consideration of liquid diffusibility, cushioning properties, and the like required for the liquid diffusible layer 5. When the nonwoven fabric substrate is an air-through nonwoven fabric, the basis weight is preferably 15 to 100 g / m ² , more preferably 20 to 60 g / m ² , and the thickness is preferably 0.1 to 3.0 mm, more preferably. Is 0.5 to 2.0 mm. In addition, the measurement of the basic weight (g / m < ² >) and thickness (mm) of a nonwoven fabric is implemented as follows.

[Basis weight]
The weight of three test pieces (10 mm × 10 mm) cut out from the nonwoven fabric conditioned by storage for 24 hours or more in a standard state (temperature 23 ± 2 ° C., relative humidity 50 ± 5%) is a direct balance (for example, , Measured by an electronic balance HF-300 manufactured by Kensei Kogyo Co., Ltd., and the mass per unit area of the nonwoven fabric calculated from the average value of the masses of the three test pieces was determined as the basis weight (g / m ² ) of the nonwoven fabric. To do. Regarding the measurement of the basis weight of the nonwoven fabric, the measurement conditions described in ISO 9073-1 or JIS L 1913 6.2 are adopted for the measurement conditions not particularly specified above. In addition, the basic weight of the nonwoven fabric used in the Example was also measured by the same method.

[Thickness]
Thickness gauges (for example, FS-manufactured by Daiei Kagaku Seisakusho Co., Ltd.) were prepared for three different parts of the nonwoven fabric that had been conditioned by storage for 24 hours or more in standard conditions (temperature 23 ± 2 ° C., relative humidity 50 ± 5%). 60 DS, measuring element area 15 cm ² ), pressurizing at a constant pressure of 3 g / cm ² , measuring the thickness after pressurization for 10 seconds in each part, and calculating the average thickness of the three parts as the thickness of the nonwoven fabric (mm) And In addition, the thickness of the nonwoven fabric used in the Example was also measured by the same method.

  Examples of fibers constituting the nonwoven fabric substrate include natural fibers (wool, cotton, etc.), regenerated fibers (rayon, acetate, etc.), thermoplastic resin fibers (polyethylene, polypropylene, polybutylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid). Polyolefins such as ethyl copolymers, ethylene-acrylic acid copolymers, and ionomer resins; polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyesters such as polylactic acid; polyamides such as nylon), surface modified products thereof, and the like However, a thermoplastic resin fiber or a surface modification product thereof is preferable. The fibers constituting the nonwoven fabric substrate are: single-component fibers; core-sheath fibers, side-by-side fibers, island / sea fibers, etc .; hollow fibers; flat, Y-shaped, C-shaped, etc. Atypical fibers; three-dimensional crimp fibers of latent crimp or actual crimp; split fibers that are split by a physical load such as water flow, heat, embossing, and the like.

  The guest material includes a plurality of hydrophilic particle substrates or a plurality of hydrophilic fiber substrates as a substrate. The guest material may include both a plurality of hydrophilic particle substrates and a plurality of hydrophilic fiber substrates as a substrate.

  The hydrophilic particle substrate is not particularly limited as long as the surface thereof is hydrophilic, and examples thereof include hydrophilic inorganic particles whose surface is hydrophilic and hydrophilic organic particles whose surface is hydrophilic. The hydrophilic particle substrate may be porous or non-porous, but is preferably porous. This is because when the hydrophilic particle substrate is porous, the specific surface area is increased and the chance of contact with the liquid is increased.

Examples of the hydrophilic inorganic particles include oxides or water of at least one element selected from beryllium, magnesium, aluminum, silicon, titanium, boron, germanium, tin, zirconium, iron, vanadium, antimony, and transition metals. Oxide particles may be mentioned, and silica (SiO ₂ ) particles are preferred.

  Examples of the hydrophilic organic particles include hydrophilic resin particles formed from a hydrophilic resin. The hydrophilic resin particles can be produced according to a conventional method. An example of a method for producing hydrophilic resin particles is as follows. A hydrophilic resin is dissolved in an organic solvent (for example, methyl ethyl ketone, methyl acetate, isopropyl acetate, tetrahydrofuran, acetone, isopropyl alcohol, dimethylformamide, a mixed solvent thereof), and an organic solvent in which the hydrophilic resin is dissolved as necessary. After neutralization (salt formation) treatment (for example, alkali treatment), a poor solvent (for example, water) is added to the organic solvent to carry out an emulsification treatment. Next, it is dried and granulated, and pulverized and classified as necessary. The hydrophilic resin is not particularly limited as long as it has a hydrophilic functional group. Examples of hydrophilic functional groups include weakly acidic functional groups such as hydroxyl groups, ethylene oxide groups, and carboxylic acid groups, and strongly acidic functional groups such as sulfonic acid groups.

The hydrophilic resin can be a homopolymer or copolymer of a hydrophilic monomer and can be a copolymer of a hydrophilic monomer and a hydrophobic monomer. Examples of the hydrophilic resin include (meth) acrylic acid esters, styrene / (meth) acrylic acid / (anhydrous) maleic acid copolymers, olefin polymers such as ethylene / propylene (or modified products thereof, or carboxyls by copolymerization). Acid unit introduced product), branched polyesters improved in acid value with trimellitic acid, polyamides, and the like.
The hydrophilic organic particles may be organic particles having a hydrophilic surface, for example, a copolymer of a hydrophobic monomer having a hydrophilic surface.

  Examples of the hydrophilic fiber substrate include hydrophilic fibers such as cellulosic fibers. Cellulosic fibers include, for example, wood pulp obtained from softwood or hardwood (for example, mechanical pulp such as groundwood pulp, refiner ground pulp, thermomechanical pulp, chemithermomechanical pulp; kraft pulp, sulfide pulp, alkaline pulp, etc. Chemical pulp; semi-chemical pulp, etc.]; mercerized pulp or crosslinked pulp obtained by chemically treating wood pulp; non-wood pulp such as bagasse, kenaf, bamboo, hemp, cotton (eg cotton linter); rayon, fibril Examples include regenerated cellulose such as rayon; semi-synthetic cellulose such as acetate and triacetate.

  A preferred hydrophilic fiber substrate is cellulose fiber. Examples of the cellulose fiber include cellulose nanofiber, cellulose nanocrystal, and pulverized pulp. A cellulose fiber may use a commercial item and what was manufactured in accordance with the conventional method may be used. Cellulose nanofibers can be produced by mechanical defibrating plant fibers such as pulp, and cellulose nanocrystals can be produced by acid hydrolysis of plant fibers such as pulp. The average fiber diameter of the cellulose fiber is usually 20 to 500 nm, preferably 20 to 300 nm, and the average fiber length is usually 0.50 to 10.00 μm, preferably 0.90 to 5.00 μm. The method for measuring the average fiber diameter of the cellulose fiber is the same as the method for measuring the average fiber diameter of the hydrophilic fiber substrate (described later). The average fiber length of the cellulose fiber means a weight-weighted average fiber length. The weight-weighted average fiber length is measured as an L (w) value by Kajaani Fiber Lab Fiber Properties (offline) [kajaani FiberLab properties (off-line)] manufactured by metso automation. In addition, the meaning of the average fiber length in an Example and the measuring method are also the same.

  At least one of the host material and the guest material is a polymer electrolyte layer that covers a substrate (in the case of a host material, a non-woven substrate, and in the case of a guest material, a hydrophilic particle substrate or a hydrophilic fiber substrate). Have Thereby, the guest material can be effectively adsorbed to the host material by electrostatic interaction. As long as one of the host material substrate and the guest material substrate is coated with the polymer electrolyte layer, the other may be coated with the polymer electrolyte layer, or may not be coated. From the viewpoint of effectively adsorbing the guest material to the material by electrostatic interaction, it is preferable that both the host material substrate and the guest material substrate are coated with a polymer electrolyte. When the substrate of the host material is coated with the polymer electrolyte layer, the host material includes a fiber not having the polymer electrolyte layer in the surface layer in addition to the coated fiber having the polymer electrolyte layer in the surface layer. Also good. In the plurality of coated fibers included in the host material, the types of the polymer electrolyte layers may be the same or different. When the base of the guest material is coated with the polymer electrolyte layer, the guest material includes particles or fibers that do not have the polymer electrolyte layer in the surface layer in addition to the coated particles or coated fibers that have the polymer electrolyte layer in the surface layer. May be included. In the plurality of coated particles or the plurality of coated fibers included in the guest material, the types of the polymer electrolyte layers may be the same or different.

  The average particle diameter of the hydrophilic particle substrate included in the guest material is smaller than the average fiber diameter of the nonwoven fabric substrate included in the host material, and the average fiber diameter of the hydrophilic fiber substrate included in the guest material is included in the host material. It is smaller than the average fiber diameter of the nonwoven fabric substrate. The ratio of the average particle diameter of the hydrophilic particle substrate to the average fiber diameter of the nonwoven fabric substrate (average particle diameter of the hydrophilic particle substrate: average fiber diameter of the nonwoven fabric substrate) is preferably 1: 4 to 1:50, and is hydrophilic. The ratio of the average fiber diameter of the hydrophilic fiber substrate to the average fiber diameter of the nonwoven fabric substrate (average fiber diameter of the hydrophilic fiber substrate: average fiber diameter of the nonwoven fabric substrate) is preferably 1: 4 to 1: 2500. The said range is preferable at the point which can generate | occur | produce a capillary force effectively in the surface of the fiber which comprises host material.

  The average fiber diameter of the nonwoven fabric substrate contained in the host material is measured as follows. The liquid diffusible layer is magnified 300 times with an electron microscope (for example, VE-8800 manufactured by Keyence Corporation), and among the fibers present in the magnified image, the fiber diameter of the fibers constituting the host material (distance between two points) ). The same measurement is performed on any 30 fibers (n = 30), and an average value is obtained. When the nonwoven fabric substrate is not covered with the polymer electrolyte layer, this average value is taken as the average fiber diameter of the nonwoven fabric substrate. Similarly, when the nonwoven fabric substrate is covered with the polymer electrolyte layer, this average value is taken as the average fiber diameter of the nonwoven fabric substrate. This is because the thickness of the polymer electrolyte layer covering the nonwoven fabric substrate is negligibly small relative to the average fiber diameter of the fibers constituting the nonwoven fabric substrate. This is because it can be approximated by the average fiber diameter before coating with the degradable layer. When enlarging the liquid diffusible layer, if only a few (for example, about 3 to 5) fibers are shown in one enlarged image, change the part to be enlarged with an electron microscope, and take an enlarged image multiple times, n = 30. The average fiber diameter of the nonwoven fabric substrate thus measured is usually 10 to 50 μm, preferably 12 to 48 μm, and more preferably 14 to 46 μm.

  The average particle diameter of the hydrophilic particle base contained in the guest material is measured as follows. The liquid diffusible layer is magnified 1000 times with an electron microscope (for example, VE-8800 manufactured by Keyence Corporation), and the particle diameter (distance between two points) of particles present in the enlarged image is measured. The same measurement is performed on arbitrary 100 particles (n = 100), and an average value is obtained. When the hydrophilic particle substrate is not coated with the polymer electrolyte layer, this average value is taken as the average particle size of the hydrophilic particle substrate. Similarly, when the hydrophilic particle substrate is covered with the polymer electrolyte layer, this average value is taken as the average particle size of the hydrophilic particle substrate. This is because the thickness of the polymer electrolyte layer covering the hydrophilic particle substrate is negligibly small relative to the average particle size of the hydrophilic particle substrate. This is because it can be approximated by the average particle diameter before coating with the degradable layer. When enlarging the liquid diffusive layer, if only a few (for example, about 3 to 5) particles appear in one magnified image, change the area to be magnified with an electron microscope, and take a magnified image multiple times, Let n = 100. The average particle diameter of the hydrophilic particle substrate thus measured is usually 1.0 to 12.0 μm, preferably 3.0 to 10.0 μm, and more preferably 5.0 to 8.0 μm.

  The average fiber diameter of the hydrophilic fiber base contained in the guest material is measured as follows. The liquid diffusible layer is magnified 8000 times with an electron microscope (manufactured by Keyence Corporation, VE-8800), and among the fibers present in the enlarged image, the fiber diameter of the fiber constituting the guest material (distance between two points) Measure. The same measurement is performed on any 30 fibers (n = 30), and an average value is obtained. When the hydrophilic fiber substrate is not covered with the polymer electrolyte layer, this average value is taken as the average fiber diameter of the hydrophilic fiber substrate. Similarly, when the hydrophilic fiber substrate is covered with the polymer electrolyte layer, this average value is taken as the average fiber diameter of the hydrophilic fiber substrate. This is because the thickness of the polymer electrolyte layer covering the hydrophilic fiber substrate is negligibly small relative to the average fiber diameter of the hydrophilic fiber substrate. This is because it can be approximated by the average fiber diameter before coating with the degradable layer. When enlarging the liquid diffusible layer, if only a few (for example, about 3 to 5) fibers are shown in one enlarged image, change the part to be enlarged with an electron microscope, and take an enlarged image multiple times, n = 30. The average fiber diameter of the hydrophilic fiber substrate thus measured is usually 0.02 to 1.00 μm, preferably 0.05 to 0.50 μm, more preferably 0.10 to 0.30 μm.

  The guest material is preferably surface-treated with a surfactant. When the guest material substrate (hydrophilic particle substrate or hydrophilic fiber substrate) is coated with a polymer electrolyte layer, the treatment with the surfactant increases the substrate (hydrophilic particle substrate or hydrophilic fiber substrate). It is carried out after coating with a molecular electrolyte layer. Examples of the surfactant include DK ester (Daiichi Kogyo Seiyaku Co., Ltd.). DK ester is a surfactant in which a fatty acid is ester-bonded to a hydroxyl group of sucrose. Since there are eight hydroxyl groups in one sucrose molecule, sucrose fatty acid esters are monoesters in which one molecule of fatty acid is bonded to one molecule of sucrose to octaesters in which eight molecules of fatty acid are bonded to one molecule of sucrose. Exists. DK ester is a mixture of these sucrose fatty acid esters having different degrees of esterification.

  The host material is positively or negatively charged in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water. The surface is charged to the opposite charge to the surface of the host material in the solvent. The charge on the surface of the material covered with the polymer electrolyte layer is determined by the charge of the polymer electrolyte layer located on the surface layer. For example, a material having a polymer electrolyte layer that is positively charged in a predetermined solvent as a surface layer is a material that has a positively charged surface in a predetermined solvent, and is negatively charged in a predetermined solvent. Is a material whose surface is negatively charged in a predetermined solvent.

  The absolute value of the zeta potential of the host material and the guest material in the predetermined solvent is preferably 20 mV or more, and more preferably 50 mV or more. That is, the zeta potential when positively charged is preferably +20 mV or higher, more preferably +50 mV or higher, and the zeta potential when negatively charged is preferably −20 mV or lower, more preferably −50 mV or lower. In addition, it is preferable that the absolute values of the zeta potentials of the host material and the guest material in a predetermined solvent are in charge balance. Here, “charge-balanced” means that the absolute values of the zeta potentials of the host material and the guest material are equal or substantially equal, and “absolute values are substantially equal” means the absolute value of the zeta potential of the host material. The difference between the absolute value and the absolute value of the zeta potential of the absorbent material (difference obtained by subtracting the smaller absolute value from the larger absolute value) is 20% or less, preferably It means 15% or less, more preferably 10% or less. The upper limit value of the zeta potential is usually +100 mV, preferably +70 mV when positively charged, and is usually −100 mV, preferably −70 mV when negatively charged.

  The zeta potential of the host material and the guest material is measured in an environmental atmosphere of 20 ° C. using a zeta potential measurement system ELSZ-1 manufactured by Otsuka Electronics. At this time, in the measurement of the zeta potential of the particles, the mode is measurement using a flow cell, and the measurement principle is based on the laser Doppler method (electrophoretic light scattering measurement method). In the measurement of the zeta potential of the fiber, the mode is measurement using a flat sample cell, and the measurement principle is based on the electroosmotic flow generated in the liquid in contact with the sample surface.

  As a host material, it is possible to use a coated body having a nonwoven fabric substrate and one or more polymer electrolyte layers covering the substrate, and one of the polymer electrolyte layers is located on the surface layer. The covering used as a host material has a plurality of laminated polymer electrolyte layers, and in the plurality of polymer electrolyte layers, polymer electrolyte layers that are oppositely charged in a predetermined solvent are adjacent to each other. It is preferable. The number of polymer electrolyte layers included in the covering is not particularly limited, but the absolute value of the zeta potential in a predetermined solvent is 20 mV or more (that is, +20 mV or more when positively charged). In order to be negatively charged, it is preferably adjusted so as to be −20 mV or less, and negatively so as to be 50 mV or higher (that is, when charged positively, +50 mV or higher). It is more preferable that the charge is adjusted so that the charge is -50 mV or less. In addition, the number of polymer electrolyte layers included in the covering is preferably adjusted so that the absolute values of the zeta potentials of the host material and the guest material are balanced in charge. Here, “balance in charge” has the same meaning as described above.

  The guest material has a hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) and one or more polymer electrolyte layers covering the substrate, and one of the polymer electrolyte layers is a surface layer. Can be used. The covering used as a guest material has a plurality of laminated polymer electrolyte layers, and in the plurality of polymer electrolyte layers, polymer electrolyte layers that are oppositely charged in a predetermined solvent are adjacent to each other. It is preferable. The number of polymer electrolyte layers included in the covering is not particularly limited, but the absolute value of the zeta potential in a predetermined solvent is 20 mV or more (that is, +20 mV or more when positively charged). In order to be negatively charged, it is preferably adjusted so as to be −20 mV or less, and negatively so as to be 50 mV or higher (that is, when charged positively, +50 mV or higher). It is more preferable that the charge is adjusted so that the charge is -50 mV or less. In addition, the number of polymer electrolyte layers included in the covering is preferably adjusted so that the absolute values of the zeta potentials of the host material and the guest material are balanced in charge. Here, “balance in charge” has the same meaning as described above.

  The composite material has a surface charged positively or negatively in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water. A method comprising an adsorption step of bringing a host material into contact with a guest material whose surface is charged to a charge opposite to the surface of the host material in the predetermined solvent and adsorbing the guest material to the host material by electrostatic interaction Can be manufactured.

  In the adsorption step, a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water is used. The kind of the nonpolar organic solvent and the polar organic solvent is not particularly limited as long as the ionization of the polymer electrolyte is possible. Common polyelectrolytes ionize in polar solvents, but there are polyelectrolytes designed to ionize in nonpolar solvents (eg, ACS Macro Lett. 2012, 1, 1270-1273). When the polymer electrolyte is ionized in a polar solvent, the solvent used in the adsorption step is water, a polar organic solvent or a mixed solvent of a polar organic solvent and water, and the polymer electrolyte is ionized in a nonpolar solvent. In some cases, the solvent used in the adsorption step is a nonpolar organic solvent. Since the organic solvent can be easily volatilized, the composite material produced through the adsorption step can be easily dried by natural drying or by a small heating amount in the case of forced drying. Therefore, changes in the structure and properties of the host material and guest material that may occur in the drying process performed after the adsorption process can be prevented.

When cellulose fiber is used as the guest material, it is preferable to use a polar organic solvent in the adsorption step, and it is more preferable to use a monohydric alcohol having 1 to 3 carbon atoms. When water is used in the adsorption process, there is a tendency that hydrogen bonds are easily formed between the cellulose fibers in the drying process performed after the adsorption process. For example, when cellulose fibers are fibrillated, Fibrils tend to form hydrogen bonds with cellulose fibers.
On the other hand, when a polar organic solvent (particularly a monohydric alcohol having 1 to 3 carbon atoms) is used in the adsorption step, it becomes difficult to form hydrogen bonds between the cellulose fibers in the drying step performed after the adsorption step. And when the cellulose fiber is fibrillated, since the fibril tends to remain, the specific surface area of the cellulose fiber increases.

  Examples of water include tap water, ion exchange water, and distilled water, and ion exchange water is preferable. Examples of the polar organic solvent include monohydric alcohols, polyhydric alcohols, and ketones. Examples of the monohydric alcohol include methanol, ethanol, propyl alcohol, and isopropyl alcohol. Examples of the ketone include acetone, ethyl methyl ketone, and diethyl ketone. The polar organic solvent is preferably an alcohol, more preferably a monohydric alcohol having 1 to 3 carbon atoms. The ratio of the polar organic solvent in the mixed solvent of the polar organic solvent and water is not particularly limited, but the higher the ratio of the organic solvent, the longer the time required for drying the composite material produced through the adsorption process, the heating amount, etc. Can be reduced. Therefore, the higher the ratio of the organic solvent in the mixed solvent, the better. The ratio of the organic solvent in the mixed solvent is usually 95.0% by weight or more, preferably 97.0% by weight or more, and more preferably 99.5% by weight or more.

  Examples of the nonpolar organic solvent include methylene chloride, ethyl acetate, chloroform, diethyl ether, toluene, benzene, hexane and the like.

  In the adsorption step, when the host material and guest material are contacted in a solvent, the contact time is usually 1 to 60 minutes, preferably 3 to 20 minutes, more preferably 5 to 15 minutes, and the temperature of the solvent is usually It is 0-50 degreeC, Preferably it is 10-40 degreeC, More preferably, it is 20-30 degreeC, and pH of a solvent is 4-10 normally, Preferably it is 5-9, More preferably, it is 6-8. When the guest material is a particle (that is, a coated particle having a hydrophilic particle substrate and a polymer electrolyte layer provided on the surface layer), the particle in the solvent when the host material and the guest material are contacted in the solvent. A density | concentration is 0.1-20 vol% normally, Preferably it is 0.2-10 vol%, More preferably, it is 0.5-5 vol%.

In the adsorption step, the host material is adsorbed by the host material by electrostatic interaction, whereby a composite material in which the host material and the guest material are combined can be manufactured. After the adsorption process, a drying process may be performed to dry the composite material. Examples of the drying step include natural drying or forced drying, for example, drying with a dryer. In the forced drying, the drying temperature needs to be lower than the melting points of the host material and the guest material. When the melting point of the host material and guest material exceeds 100 ° C, it is usually 30 to 100 ° C, preferably 40 to 90 ° C, and more preferably 50 to 80 ° C. In the forced drying, the drying time can be appropriately adjusted according to the drying temperature, but is usually 1 to 30 minutes, preferably 5 to 25 minutes, and more preferably 10 to 20 minutes.
The forced drying is preferable when the predetermined solvent contains water, and the natural drying is preferable when the predetermined solvent is an organic solvent.

A coated body having a nonwoven fabric substrate and one polymer electrolyte layer covering the substrate can be produced by the following step (a ₁ ), and the thus produced coated body is used as a host material in the adsorption step. Can be used. A coated body having a nonwoven fabric substrate and two or more polymer electrolyte layers covering the substrate can be produced by the following steps (a ₁ ) and (a ₂ ). m + 1)) can be used as a host material in the adsorption step.

(A ₁ ) In a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water, the surface is positively or negatively charged in the predetermined solvent. A step of producing a first covering body having a first polymer electrolyte layer as a surface layer by bringing a nonwoven fabric substrate into contact with a polymer electrolyte charged with a charge opposite to the surface of the nonwoven fabric substrate in the predetermined solvent.

(A ₂ ) kth positively or negatively charged in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water. the k ₁ of the cover having a _first polyelectrolyte layer on the surface layer (here, k ₁ is an integer of 1 or more.) and, of the k ₁ in the predetermined solvent opposite the polymer electrolyte layer contacting the polymer electrolyte is charged to the charge, the procedure for making a coated body of the first (k ₁ +1) with the polymer electrolyte layer of the (k ₁ +1) in the surface layer, k ₁ = 1 from k ₁ = The step of producing m (m + 1) -th coated bodies having m (m + 1) -th polymer electrolyte layer as a surface layer, carried out m times up to m (where m is an integer of 1 or more).

Hereinafter, the steps (a ₁ ) and (a ₂ ) will be described.
<Process (a ₁ )>
The nonwoven fabric substrate whose surface is positively charged in a predetermined solvent is not particularly limited as long as it has a cationic group on the surface. The cationic group is a group that is positively charged by ionization in a predetermined solvent. For example, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, or a quaternary group. A phosphonium group, a sulfonium group, a pyridinium group, etc. are mentioned. The cationic group may be a group that the substrate originally has, or may be a group introduced artificially. The nonwoven fabric substrate whose surface is positively charged in a predetermined solvent may have some anionic groups on the surface as long as the surface is positively charged as a whole.

  The nonwoven fabric substrate whose surface is negatively charged in a predetermined solvent is not particularly limited as long as it has an anionic group on the surface. The anionic group is a group that is negatively charged by ionization in a predetermined solvent, and examples thereof include a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphoric acid group. The anionic group may be a group that the substrate originally has, or may be a group introduced artificially. The nonwoven fabric substrate whose surface is negatively charged in a predetermined solvent may have some cationic groups on the surface as long as the surface is negatively charged as a whole.

  Surface modification of the nonwoven fabric substrate (introduction of a cationic group or an anionic group) can be performed according to a conventional method.

In the step (a ₁ ), when a nonwoven fabric substrate whose surface is positively charged in a predetermined solvent is used, a polymer electrolyte that is negatively charged in the predetermined solvent is used. Examples of the polymer electrolyte that is negatively charged in a predetermined solvent include polystyrene sulfonic acid (PSS), polyvinyl sulfate (PVS), polyacrylic acid (PAA), polymethacrylic acid (PMA), and polycarboxylic acid (PCA). Anionic polymers such as

In the step (a ₁ ), when a nonwoven fabric substrate whose surface is negatively charged in a predetermined solvent is used, a polymer electrolyte that is positively charged in the predetermined solvent is used. Examples of the polymer electrolyte that is positively charged in a predetermined solvent include poly (diallyldimethylammonium chloride) (PDDA), polyethyleneimine (PEI), polyvinylamine (PVAm), and poly (vinylpyrrolidone N, N-dimethyl). And cationic polymers such as aminoethylacrylic acid) copolymerization.

The predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water is not particularly limited as long as the polymer electrolyte can be ionized. When the polymer electrolyte is ionized in a polar solvent, the solvent used in the step (a ₁ ) is water, a polar organic solvent or a mixed solvent of a polar organic solvent and water, and the polymer electrolyte is in a nonpolar solvent. When ionizing with, the solvent used in step (a ₁ ) is a nonpolar organic solvent. Specific examples of water, polar organic solvent, and nonpolar organic solvent are the same as those in the adsorption step.

  When the nonwoven fabric substrate and the polymer electrolyte are contacted in a predetermined solvent, the concentration of the polymer electrolyte in the solvent is usually 0.05 to 10 wt%, preferably 0.1 to 5 wt%, more preferably 0.2 to 0.2 wt%. The contact time is usually 1 to 60 minutes, preferably 3 to 20 minutes, more preferably 5 to 15 minutes, and the solvent temperature is usually 0 to 50 ° C., preferably 10 to 40 ° C. More preferably, it is 20-30 degreeC, and pH of a solvent is 4-10 normally, Preferably it is 5-9, More preferably, it is 6-8.

In one embodiment of the step (a ₁ ), in a predetermined solvent, a nonwoven fabric substrate whose surface is positively charged in the predetermined solvent is contacted with a polymer electrolyte that is negatively charged in the predetermined solvent. Thereby, the 1st coating body by which the nonwoven fabric base | substrate positively charged was coat | covered with the polymer electrolyte layer negatively charged can be manufactured. In another embodiment of the step (a ₁ ), in a predetermined solvent, a non-woven substrate whose surface is negatively charged in the predetermined solvent is contacted with a polymer electrolyte that is positively charged in the predetermined solvent. By doing so, it is possible to produce a first coated body in which a negatively charged nonwoven fabric substrate is coated with a positively charged polymer electrolyte layer.

After the step (a ₁ ), it is preferable to carry out a washing step and wash the first covering with an organic solvent to remove excess polymer electrolyte adhering to the first covering. After the cleaning process, a drying process may be performed to dry the first covering. The drying process may be natural drying or forced drying.

<Process (a ₂ )>
In one embodiment of step (a _2), in a given solvent, the said predetermined first k ₁ which is positively charged in a solvent and coating of the k ₁ having a polymer electrolyte layer on the surface layer, of the predetermined by contacting the polymer electrolyte negatively charged in a solvent, coating of the (k ₁ +1) with the polymer electrolyte layer of the (k ₁ +1) to negatively charged at the predetermined solvent in the surface layer The body can be manufactured.

In another embodiment of step (a _2), in a given solvent, a coating of the k ₁ having a polymer electrolyte layer of the k ₁ negatively charged at the predetermined solvent in the surface layer, the predetermined A polymer electrolyte that is positively charged in the solvent of (k ₁ +1) and having a (k ₁ +1) th polymer electrolyte layer that is positively charged in the predetermined solvent as a surface layer. A covering can be produced.

Specific examples of the polymer electrolyte, a specific example of a given solvent, the contact conditions between the covering body and the polyelectrolyte of the k ₁ in a given solvent is the same as step (a _1).

The step (a ₂ ) is performed m times from k ₁ = 1 to k ₁ = m (where m is an integer equal to or greater than 1), whereby the substrate and the first to (m + 1) th coatings of the substrate are covered. ) Polymer electrolyte layer, and the (m + 1) th coating body in which the (m + 1) th polymer electrolyte layer is located on the surface layer can be produced. The first to (m + 1) th polymer electrolyte layers are laminated so that polymer electrolyte layers charged to opposite charges in a predetermined solvent are adjacent to each other. For example, when a substrate whose surface is positively charged in a predetermined solvent is used and m is 3, a first polymer electrolyte layer that is negatively charged and a second polymer electrolyte that is positively charged are formed on the substrate. 4th body is manufactured by laminating a layer, a negatively charged third polymer electrolyte layer, and a positively charged fourth polymer electrolyte layer, and the fourth polymer electrolyte layer is located on the surface layer can do. In addition, when a substrate whose surface is negatively charged in a predetermined solvent is used and m is 3, the first polymer electrolyte layer that is positively charged and the second polymer electrolyte that is negatively charged are formed on the substrate. 4th body which manufactures the 4th coating body in which the 4th polymer electrolyte layer which the layer, the 3rd polymer electrolyte layer positively charged, and the 4th polymer electrolyte layer negatively charged are laminated | stacked, and is located in the surface layer can do.
In addition, when m is 1, the 2nd covering body which has a base | substrate and the 1st and 2nd polymer electrolyte layer which coat | covers this base | substrate, and a 2nd polymer electrolyte layer is located in a surface layer Is manufactured.

  Although m is not particularly limited as long as it is an integer of 1 or more, it is preferably 2 to 5, and more preferably 3 to 4. Thereby, the charge density of the polymer electrolyte layer becomes constant and the strength thereof increases, so that uniform surface coating can be achieved. M is adjusted so that the polymer electrolyte layer located on the surface layer of the (m + 1) th covering is charged to a charge opposite to the surface of the guest material to be brought into contact with the (m + 1) th covering in the adsorption step. Is done.

In one embodiment of the steps (a ₁ ) and (a ₂ ), a non-woven substrate whose surface is positively charged in a predetermined solvent is alternately immersed in an anionic polymer solution and a cationic polymer solution. Thus, a coated body in which an anionic polymer layer and a cationic polymer layer are laminated on a nonwoven fabric substrate can be produced.

In another embodiment of steps (a ₁ ) and (a ₂ ), a non-woven substrate whose surface is negatively charged in a predetermined solvent is alternately immersed in a cationic polymer solution and an anionic polymer solution. By this, the coating body by which the cationic polymer layer and the anionic polymer layer were laminated | stacked on the nonwoven fabric base | substrate can be manufactured.

A coated body having a hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) and one polymer electrolyte layer covering the substrate can be produced by the following step (b ₁ ). The manufactured covering can be used as a guest material in the adsorption step. A coated body having a hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) and two or more polymer electrolyte layers covering the substrate is produced by the following steps (b ₁ ) and (b ₂ ). The coated body thus manufactured ((n + 1) th coated body) can be used as a guest material in the adsorption step.

(B ₁ ) In a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water, the surface is positively or negatively charged in the predetermined solvent. A hydrophilic polymer substrate or a hydrophilic fiber substrate is contacted with a polymer electrolyte that is charged to a charge opposite to the surface of the hydrophilic particle substrate or hydrophilic fiber substrate in the predetermined solvent, and the first polymer electrolyte layer For producing first covering body having surface layer

(B ₂ ) kth positively or negatively charged in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water. the k ₂ of the cover with _two polyelectrolyte layers on the surface layer (here, k ₂ is an integer of one or more.) and, of the k ₂ in the predetermined solvent opposite the polymer electrolyte layer contacting the polymer electrolyte is charged to the charge, the procedure for making a coated body of the first (k ₂ +1) with the polymer electrolyte layer of the (k ₂ +1) in the surface layer, k ₂ = 1 from k ₂ = Step of manufacturing n times (where n is an integer equal to or greater than 1), and manufacturing a (n + 1) th covering having a (n + 1) th polymer electrolyte layer as a surface layer

Hereinafter, the steps (b ₁ ) and (b ₂ ) will be described.
<Process (b ₁ )>
The hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) whose surface is positively charged in a predetermined solvent is not particularly limited as long as it has a cationic group on the surface. The cationic group is a group that is positively charged by ionization in a predetermined solvent. For example, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, or a quaternary group. A phosphonium group, a sulfonium group, a pyridinium group, etc. are mentioned. The cationic group may be a group that the material of the substrate originally has, or may be a group introduced artificially. The hydrophilic substrate whose surface is positively charged in a predetermined solvent may have some anionic groups on the surface as long as the surface is positively charged as a whole.

  The hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) whose surface is negatively charged in a predetermined solvent is not particularly limited as long as it has an anionic group on the surface. The anionic group is a group that is negatively charged by ionization in a predetermined solvent, and examples thereof include a hydroxyl group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, and a phosphoric acid group. The anionic group may be a group that the base material originally has, or may be a group introduced artificially. The hydrophilic substrate whose surface is negatively charged in a predetermined solvent may have some cationic groups on the surface as long as the surface is negatively charged as a whole.

  Surface modification (introduction of a cationic group or an anionic group) of a hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) can be performed according to a conventional method.

Specific examples of the polymer electrolyte, specific examples of the predetermined solvent, contact conditions between the base particles and the polymer electrolyte in the predetermined solvent are the same as those in the step (a ₁ ).

In one embodiment of the step (b ₁ ), in a predetermined solvent, a hydrophilic substrate (a hydrophilic particle substrate or a hydrophilic fiber substrate) whose surface is positively charged in the predetermined solvent, and the predetermined solvent By contacting the negatively charged polymer electrolyte with the negatively charged polymer electrolyte, a first coated body in which a positively charged hydrophilic substrate is coated with a negatively charged polymer electrolyte layer can be produced. In another embodiment of the step (b ₁ ), in a predetermined solvent, a hydrophilic substrate whose surface is negatively charged in the predetermined solvent, and a polymer electrolyte positively charged in the predetermined solvent, By contacting, a first coated body in which a negatively charged hydrophilic substrate is coated with a positively charged polymer electrolyte layer can be produced.

After the step (b ₁ ), it is preferable to carry out a washing step and wash the first covering with an organic solvent to remove excess polymer electrolyte adhering to the first covering. After the cleaning process, a drying process may be performed to dry the first covering. The drying process may be natural drying or forced drying.

<Process (b ₂ )>
In one embodiment of the step (b ₂ ), in a predetermined solvent, the k ₂ -th covering body having, as a surface layer, the k ₁ -th polymer electrolyte layer that is positively charged in the predetermined solvent; A (k ₂ +1) -th coating having, as a surface layer, a negative (k ₂ +1) -th polymer electrolyte layer that is negatively charged in the predetermined solvent by contacting a negatively-charged polymer electrolyte in the solvent. The body can be manufactured.

In another embodiment of step (b _2), in a given solvent, and the k ₂ coating having a polymer electrolyte layer of the k ₂ for negatively charged at the predetermined solvent in the surface layer, the predetermined A polymer electrolyte that is positively charged in the solvent of (k ₂ +1) and having a (k ₂ +1) th polymer electrolyte layer that is positively charged in the predetermined solvent as a surface layer. A covering can be produced.

Specific examples of the polymer electrolyte, a specific example of a given solvent, the contact conditions between the covering body and the polyelectrolyte of the k ₂ in a given solvent is the same as step (a _1).

The step (b ₂ ) is performed n times from k ₂ = 1 to k ₂ = n (where n is an integer of 1 or more), whereby the substrate and the first to (n + 1) th coatings of the substrate are applied. ) Polymer electrolyte layer, and the (n + 1) th coating body in which the (n + 1) th polymer electrolyte layer is located on the surface layer can be produced. The first to (n + 1) th polymer electrolyte layers are laminated so that polymer electrolyte layers charged to opposite charges in a predetermined solvent are adjacent to each other. For example, when a substrate whose surface is positively charged in a predetermined solvent is used and n is 3, the substrate is provided with a first polymer electrolyte layer that is negatively charged, and a second polymer electrolyte that is positively charged. 4th body is manufactured by laminating a layer, a negatively charged third polymer electrolyte layer, and a positively charged fourth polymer electrolyte layer, and the fourth polymer electrolyte layer is located on the surface layer can do. In addition, when a substrate whose surface is negatively charged in a predetermined solvent is used and n is 3, the substrate is provided with a first polymer electrolyte layer that is positively charged, and a second polymer electrolyte that is negatively charged. 4th body which manufactures the 4th coating body in which the 4th polymer electrolyte layer which the layer, the 3rd polymer electrolyte layer positively charged, and the 4th polymer electrolyte layer negatively charged are laminated | stacked, and is located in the surface layer can do.
In addition, when n is 1, it has the 1st and 2nd polymer electrolyte layer which coat | covers a base | substrate, and this 2nd polymer electrolyte layer is located in the surface layer. Is manufactured.

  Although n is not particularly limited as long as it is an integer of 1 or more, it is preferably 2 to 5, and more preferably 2 to 3. Thereby, the charge density of the polymer electrolyte layer becomes constant and the strength thereof increases, so that uniform surface coating can be achieved. Note that n is adjusted so that the polymer electrolyte layer located on the surface layer of the covering body is charged with a charge opposite to the surface of the host material to be brought into contact with the covering body in the adsorption step.

In one embodiment of the steps (b ₁ ) and (b ₂ ), a hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) whose surface is positively charged in a predetermined solvent, an anionic polymer solution, By alternately immersing in a cationic polymer solution, a covering in which an anionic polymer layer and a cationic polymer layer are laminated on a hydrophilic substrate can be produced.

In another embodiment of the steps (b ₁ ) and (b ₂ ), a hydrophilic substrate (hydrophilic particle substrate or hydrophilic fiber substrate) whose surface is negatively charged in a predetermined solvent is treated with a cationic polymer solution. By alternately immersing in an anionic polymer solution, a covering in which a cationic polymer layer and an anionic polymer layer are laminated on a hydrophilic substrate can be produced.

  In the composite material contained in the liquid diffusible layer 5, the average fiber diameter of the fibers constituting the host material is the same regardless of whether the nonwoven fabric substrate of the host material is coated with the polymer electrolyte layer or not. The average particle diameter or average fiber diameter of the particles or fibers constituting the guest material is the same as that of the guest material hydrophilic particle base or hydrophilic fiber base. Regardless of whether or not it is coated with an electrolyte layer, it can be considered to be the same as the average particle diameter or average fiber diameter of the hydrophilic particle substrate or hydrophilic fiber substrate of the guest material. The average particle diameter or average fiber diameter of the hydrophilic particle substrate or hydrophilic fiber substrate of the guest material is smaller than the average fiber diameter of the nonwoven fabric substrate of the host material. Therefore, the average particle diameter or average fiber diameter of the particles or fibers constituting the guest material is smaller than the average fiber diameter of the fibers constituting the host material. When such a guest material is combined with the host material, not only a capillary force is generated between the fibers constituting the host material, but also a capillary force is generated on the surface of the fibers constituting the host material.

  In the composite material contained in the liquid diffusive layer 5, at least one of the host material and the guest material is a substrate (in the case of a host material, a non-woven substrate, and in the case of a guest material, a hydrophilic particle substrate or a hydrophilic material). The guest material is effectively adsorbed to the host material by electrostatic interaction. For this reason, the host material and the guest material are combined without depending on the adhesive, without being heated, and without being embedded in the host material. Therefore, the guest material combined with the host material can effectively exhibit a desired function (hydrophilicity based on a hydrophilic particle substrate or a hydrophilic fiber substrate).

  As described above, in the composite material contained in the liquid diffusible layer 5, not only capillary force is generated between the fibers constituting the host material, but also capillary force is generated on the surface of the fibers constituting the host material. . The guest material composited with the host material can effectively exhibit a desired function (hydrophilicity based on a hydrophilic particle substrate or a hydrophilic fiber substrate). When the liquid diffusible layer 5 contains such a composite material, it is possible to achieve both liquid diffusibility and cushioning properties in the liquid diffusible layer 5. That is, when a nonwoven fabric substrate having a high cushioning property (that is, a bulky material) is used as the nonwoven material substrate of the host material, the cushioning property of the liquid diffusible layer 5 is improved, but occurs between fibers constituting the host material. Although the capillary force is reduced, a decrease in liquid diffusibility in the liquid permeable layer 5 is prevented by the capillary force generated on the surface of the fiber constituting the host material. However, in the composite material contained in the liquid diffusible layer 5, it is not essential that a nonwoven fabric substrate having a high cushioning property (that is, bulky) is used as the nonwoven material substrate of the host material. The cushioning property of the non-woven substrate of the host material can be appropriately adjusted according to the function required for the liquid diffusible layer 5 and the like. For example, when the liquid diffusible layer 5 is required to improve liquid diffusibility rather than cushioning, a non-woven base having a low cushioning property (that is, a low porosity) may be used as the non-woven base of the host material. it can. In this case, the capillary force generated between the fibers constituting the host material and the capillary force generated on the surface of the fibers constituting the host material combine to improve the liquid diffusibility of the liquid diffusible layer 5.

In the following production examples, the following materials, reagents, conditions and the like were adopted unless otherwise specified.
Centrifugation was performed using a centrifuge (manufacturer: Kubota Manufacturing Co., Ltd., distributor: Kubota Shoji Co., Ltd., model: universal cooling centrifuge 5922), and the centrifugation conditions were 8.5 × g. 5 minutes.
Ion exchange water was used as water.
As methanol, methanol with a purity of 99.5% manufactured by Wako Pure Chemical Industries, Ltd. was used.
As poly (diallyldimethylammonium chloride) (hereinafter referred to as “PDDA”), PDDA manufactured by Aldrich with a weight average molecular weight (Mw) of 100,000 to 200,000 was used.
As polyacrylic acid (hereinafter referred to as “PAA”), PAA manufactured by Aldrich with a weight average molecular weight (Mw) of 25,000 to 50,000 was used.
As silica particles, silica particles (trade name: Silicia 440, median diameter (d50): 5.96 μm) manufactured by Fuji Silysia Chemical Co., Ltd. were used.
As a first nonwoven fabric (hereinafter referred to as “nonwoven fabric F ₁ ”), a through sheath composed of a core-sheath type composite fiber (average fiber diameter: 30 μm, average fiber length: 51 mm) having PET as a core component and PE as a sheath component An air nonwoven fabric (basis weight: 20 g / m ² , thickness: 0.98 mm, density: 0.020 g / cm ³ ) was used.
As a second nonwoven fabric (hereinafter referred to as “nonwoven fabric F ₂ ”), a through sheath composed of core-sheath type composite fibers (average fiber diameter: 30 μm, average fiber length: 51 mm) having PET as a core component and PE as a sheath component An air nonwoven fabric (basis weight: 38 g / m ² , thickness: 0.51 mm, density: 0.074 g / cm ³ ) was used.
As cellulose nanofiber, it was used as cellulose nanofiber (average fiber diameter: 20.0 nm, average fiber length: 2.0 μm) manufactured by Sugino Machine.

[Production Example 1] The first production of particles combined non-woven fabric (1) Production of coated nonwoven fabric coated with the polymer electrolyte layer Step A _1: put nonwoven F ₁ to the container.
Step B ₁ : After Step A _1, an aqueous PDDA solution (PDDA concentration: 0.5% by weight) in which the non-woven fabric F ₁ is sufficiently immersed was added and allowed to stand for 15 minutes, and then the PDDA aqueous solution was removed.
Step C _1: after the step B _1, the amount of water the nonwoven fabric F ₁ is fully immersed addition, it was thoroughly shaken to remove water. This washing was repeated twice.
Step D ₁ : After Step C ₁ , an amount of PAA aqueous solution (PAA concentration: 0.5% by weight) in which the non-woven fabric F ₁ is sufficiently immersed was added and allowed to stand for 15 minutes, and then the PAA aqueous solution was removed.
Step E _1: after step D _1, the amount of water the nonwoven fabric F ₁ is fully immersed addition, it was thoroughly shaken to remove water. This washing was repeated twice.
Step F ₁ : After Step E ₁ , an amount of PDDA aqueous solution (PDDA concentration: 0.5 wt%) in which the non-woven fabric F ₁ is sufficiently immersed was added and allowed to stand for 15 minutes, and then the PDDA aqueous solution was removed.
Step G _1: after the step F _1, the amount of water the nonwoven fabric F ₁ is fully immersed addition, it was thoroughly shaken to remove water. This washing was repeated twice.

The first coated nonwoven fabric (hereinafter referred to as “coated nonwoven fabric CF ₁ ”), in which the nonwoven fabric F _{1 as} a substrate is sequentially coated with the PDDA layer, the PAA layer, and the PDDA layer, and the PDDA layer is located on the surface layer by the steps A ₁ to G _1. Manufactured). As a non-woven fabric, a through-air non-woven fabric (basis weight: 38 g / m) composed of a core-sheath type composite fiber (4.4 dtex × 38 mm) having PET as a core component and PE as a sheath component instead of the non-woven fabric F ₁ ² and a thickness of 1.4 mm), and a coated nonwoven fabric except that ethanol with a purity of 99.5% manufactured by Wako Pure Chemical Industries, Ltd. was used instead of water as the solvent for the PDDA solution and the solvent for the PAA solution. Regarding the coated nonwoven fabric produced in the same manner as CF ₁ , the zeta potential of the coated nonwoven fabric in ethanol was measured in an environmental atmosphere of 20 ° C. using the zeta potential measurement system ELSZ-1 manufactured by Otsuka Electronics. The zeta potential of was 40 mV. In addition, regarding the measurement of the zeta potential of the coated nonwoven fabric, the mode is measurement using a flat sample cell, and the measurement principle is based on the electroosmotic flow generated in the liquid in contact with the sample surface. Based on this result, an environment atmosphere 20 ° C., using a zeta potential measurement system ELSZ-1 made by Otsuka Electronics, when measuring the zeta potential of the coated nonwoven CF ₁ in water, the zeta potential of the coated nonwoven CF ₁ Is predicted to be +20 mV or higher.

(2) Production of coated silica particles coated with a polymer electrolyte layer Step A ₂ : 10 mL of water and 0.5 g of silica particles were added to a centrifuge tube attached to a centrifuge, centrifuged, and the centrifugal supernatant was removed.
Step B ₂ : After Step A ₂ , 10 mL of an aqueous PDDA solution (PDDA concentration: 0.5 wt%) was added to the centrifuge tube, left for 15 minutes, centrifuged, and the centrifugal supernatant was removed.
Step C ₂ : After Step B ₂ , 10 mL of water was added to the centrifuge tube, and after sufficient stirring, the mixture was centrifuged and the centrifugal supernatant was removed. This washing was repeated twice.
Step D ₂ : After Step C ₂ , 10 mL of a PAA aqueous solution (PAA concentration: 0.5% by weight) was added to the centrifuge tube, allowed to stand for 15 minutes, and then centrifuged to remove the centrifugal supernatant.
Step E ₂ : After Step D ₂ , 10 mL of water was added to the centrifuge tube, and after sufficient stirring, the mixture was centrifuged and the centrifugal supernatant was removed. This washing was repeated twice.

By the steps A ₂ to E ₂ , the silica particles as the substrate were coated with the PDDA layer and the PAA layer, and coated silica particles in which the PAA layer was located on the surface layer were produced. In addition, instead of silica particles, SAP particles manufactured by Sumitomo Seika Co., Ltd. (trade name: SA55SX-II) are used as the particles, and as a solvent for the PDDA solution and a solvent for the PAA solution, Wako Jun With respect to the coated SAP particles produced in the same manner as the coated silica particles, except that 99.5% purity ethanol manufactured by Yakuhin Co., Ltd. was used, a zeta potential measurement system ELSZ-1 manufactured by Otsuka Electronics in an environmental atmosphere at 20 ° C. Was used to measure the zeta potential of the coated SAP particles in ethanol, and the zeta potential of the coated SAP particles was −40 mV. In addition, regarding the measurement of the zeta potential of the coated SAP particle, the mode is measurement using a flow cell, and the measurement principle is based on the laser Doppler method (electrophoretic light scattering measurement method). Based on this result, when the zeta potential of the coated silica particles in water is measured using the zeta potential measurement system ELSZ-1 manufactured by Otsuka Electronics in an environmental atmosphere of 20 ° C., the zeta potential of the coated silica particles is − It is predicted to be 20 mV or less.

(3) Production of Particle Composite Nonwoven Fabric The coated nonwoven fabric CF ₁ and the coated silica particles are mixed in water, and the coated silica particles are adsorbed on the coated nonwoven fabric CF ₁ by electrostatic interaction. “Particulate composite nonwoven fabric M ₁ ”) was manufactured.

[Production Example 2] Production of second particle composite nonwoven fabric (1) Production of coated nonwoven fabric coated with polymer electrolyte layer Same as Production Example 1 except that nonwoven fabric F ₂ was used instead of nonwoven fabric F ₁ Then, the steps A ₁ to G ₁ are carried out, and the second coated nonwoven fabric (hereinafter referred to as “coated nonwoven fabric”) in which the nonwoven fabric F ₂ as the substrate is sequentially coated with the PDDA layer, the PAA layer and the PDDA layer, and the PDDA layer is located on the surface layer. was produced) of CF ₂ ". Incidentally, under environmental atmosphere of 20 ° C., using a zeta potential measurement system ELSZ-1 made by Otsuka Electronics, when measuring the zeta potential of the coated nonwoven CF ₂ in water, the zeta potential of the coated nonwoven CF ₂ is coated nonwoven Similarly as CF _1, it is expected to be + 20 mV or more.

(2) Production of coated silica particles coated with polymer electrolyte layer Steps A ₂ to E ₂ were carried out in the same manner as in Production Example 1, and the silica particles as the substrate were coated with the PDDA layer and the PAA layer. Coated silica particles in which the PAA layer was located were prepared.

(3) Production of Particle Composite Nonwoven Fabric The coated nonwoven fabric CF ₂ and the coated silica particles are mixed in water, and the coated silica particles are adsorbed on the coated nonwoven fabric CF ₂ by electrostatic interaction, whereby a second particle composite nonwoven fabric (hereinafter referred to as “second particle composite nonwoven fabric”). “Particulate composite nonwoven fabric M ₂ ”) was manufactured. Figure 3 is an electron micrograph of the particles combined non-woven fabric M ₂ (300-fold). Is determined based on FIG. 3, an average particle diameter of the coated silica particles CF _2, the ratio to the average fiber diameter of the coated nonwoven CF ₂ (average particle diameter of the coated silica particles CF _2: average fiber diameter of the coated nonwoven CF ₂₎ is 1:10.

[Production Example 3] Production of third particle composite nonwoven fabric (1) Production of coated nonwoven fabric coated with polymer electrolyte layer Same as Production Example 1 except that nonwoven fabric F ₂ was used instead of nonwoven fabric F ₁ and carrying out step a ₁ ~ step G ₁ in the nonwoven fabric F ₂ is PDDA layer is the substrate, is sequentially coated with PAA layer and PDDA layer, PDDA layer on the surface layer was prepared a coated nonwoven CF ₂ located.

(2) Production of coated silica particles coated with polymer electrolyte layer Steps A ₂ to E ₂ were carried out in the same manner as in Production Example 1, and the silica particles as the substrate were coated with the PDDA layer and the PAA layer. Coated silica particles in which the PAA layer was located were prepared. Thereafter, DK ester (Daiichi Kogyo Seiyaku Co., Ltd.) was sprayed on the coated silica particles. At this time, an aqueous solution of DK ester (DK ester concentration: 1.0% by weight) was sprayed using a spray bottle. The spray amount was 0.5% by weight based on the weight of the non-woven fabric after the particles were combined.

(3) Production of particle composite non-woven fabric Coated non-woven fabric CF ₂ and DK ester-treated coated silica particles are mixed in water, and DK ester-treated coated silica particles are adsorbed on coated non-woven fabric CF ₂ by electrostatic interaction. 3 particle composite nonwoven fabric (hereinafter referred to as “particle composite nonwoven fabric M ₃ ”) was produced.

[Production Example 4] first nanofiber composite nonwoven production (1) of the coated nonwoven fabric coated with the polymer electrolyte layer production process A _3: put nonwoven F ₁ to the container.
Step B ₃ : After Step A ₃ , an amount of PDDA methanol solution (PDDA concentration: 0.5 wt%) in which the non-woven fabric F ₁ is sufficiently immersed was added and left for 15 minutes, and then the PDDA methanol solution was removed. .
Step C ₃ : After step B ₃ , methanol was added in an amount sufficient to immerse the nonwoven fabric F ₁ , and after sufficient shaking, the methanol was removed. This washing was repeated twice.
Step D ₃ : After Step C ₃ , a PAA methanol solution (PAA concentration: 0.5 wt%) in an amount sufficient to immerse the nonwoven fabric F ₁ was added and left for 15 minutes, and then the PAA methanol solution was removed. .
Step E ₃ : After step D ₃ , methanol was added in an amount sufficient to immerse the nonwoven fabric F ₁ , and after sufficient shaking, the methanol was removed. This washing was repeated twice.
Step F ₃ : After Step E ₃ , an amount of PDDA methanol solution (PDDA concentration: 0.5% by weight) in which the non-woven fabric F ₁ is sufficiently immersed was added and allowed to stand for 15 minutes, and then the PDDA methanol solution was removed. .
Step G ₃ : After step F ₃ , methanol was added in an amount sufficient to immerse the nonwoven fabric F ₁ , and after sufficient shaking, the methanol was removed. This washing was repeated twice.

A _third coated nonwoven fabric (hereinafter referred to as “coated nonwoven fabric CF ₃ ”) in which the nonwoven fabric F _{1 as} a substrate is sequentially coated with a PDDA layer, a PAA layer, and a PDDA layer, and the PDDA layer is located on the surface layer by the steps A ₃ to G _3. Manufactured). Incidentally, under environmental atmosphere of 20 ° C., using a zeta potential measurement system ELSZ-1 made by Otsuka Electronics, when measuring the zeta potential of the coated nonwoven CF ₃ in water, the zeta potential of the coated nonwoven CF _3, the coating nonwoven Similarly as CF _1, it is expected to be + 20 mV or more.

(2) Production of coated cellulose nanofiber coated with polymer electrolyte layer Step A ₄ : Add 5.0 mL of methanol and 1.0 g of cellulose nanofiber to a centrifuge tube attached to a centrifuge, centrifuge, and centrifuge supernatant Was removed.
Step B ₄ : After Step A ₄ , 10 mL of a PDDA methanol solution (PDDA concentration: 0.5 wt%) was added to the centrifuge tube, left for 15 minutes, and then centrifuged to remove the centrifugal supernatant.
Step C _4: After step B _4, after methanol was added 10 mL, and stirred sufficiently to centrifuge tube, and centrifuged to remove the supernatant. This washing was repeated twice.
Step D ₄ : After Step C ₄ , 10 mL of a PAA methanol solution (PAA concentration: 0.5% by weight) was added to the centrifuge tube, allowed to stand for 15 minutes, and then centrifuged to remove the centrifugal supernatant.
Step E ₄ : After Step D ₄ , 10 mL of methanol was added to the centrifuge tube, and after sufficient stirring, the mixture was centrifuged and the supernatant was removed. This washing was repeated twice.

The Step A ₄ ~ Step E _4, the cellulose nanofiber is a substrate coated with PDDA layer and PAA layer, to produce a coated cellulose nanofibers PAA layer is located on the surface layer. In addition, when measuring the zeta potential of the coated cellulose nanofiber nonwoven fabric CF ₂ in methanol using the zeta potential measurement system ELSZ-1 manufactured by Otsuka Electronics in an environmental atmosphere of 20 ° C., the zeta potential of the coated cellulose nanofiber is measured. Is predicted to be -20 mV or less, similar to the coated silica particles.

(3) Production of nanofiber composite nonwoven fabric The coated nonwoven fabric CF ₃ and the coated cellulose nanofiber are mixed in methanol, and the coated cellulose nanofiber is adsorbed to the coated nonwoven fabric CF ₃ by electrostatic interaction, so that the first nanofiber A composite nonwoven fabric (hereinafter referred to as “nanofiber composite nonwoven fabric N ₁ ”) was produced.

[Production Example 5] Production of second nanofiber composite nonwoven fabric (1) Production of coated nonwoven fabric coated with polymer electrolyte layer Production Example 4 except that nonwoven fabric F ₂ was used instead of nonwoven fabric F ₁ Similarly, Step A ₃ to Step G ₃ are performed, and a nonwoven fabric F ₂ as a substrate is sequentially coated with a PDDA layer, a PAA layer, and a PDDA layer, and a PDDA layer is positioned on the surface layer (hereinafter referred to as “fourth coated nonwoven fabric”). Coated nonwoven fabric CF ₄ ”) was produced. Incidentally, under environmental atmosphere of 20 ° C., using a zeta potential measurement system ELSZ-1 made by Otsuka Electronics, when measuring the zeta potential of the coated nonwoven CF ₄ in water, the zeta potential of the coated nonwoven CF ₄ is coated nonwoven Similarly as CF _1, it is expected to be + 20 mV or more.

(2) Production of coated cellulose nanofibers coated with a polymer electrolyte layer Steps A ₄ to E ₄ were carried out in the same manner as in Production Example 4, and the cellulose nanofibers as the substrate were coated with the PDDA layer and the PAA layer. A coated cellulose nanofiber having a PAA layer on the surface layer was produced.

(3) Manufacture of nanofiber composite nonwoven fabric The coated nonwoven fabric CF ₄ and the coated cellulose nanofiber are mixed in methanol, and the coated cellulose nanofiber is adsorbed to the coated nonwoven fabric CF ₄ by electrostatic interaction, and the second nanofiber. A composite nonwoven fabric (hereinafter referred to as “nanofiber composite nonwoven fabric N ₂ ”) was produced. FIG. 4 is an electron micrograph (2000 × magnification) of the nanofiber composite nonwoven fabric N ₂ .

[Production Example 6] Production of third nanofiber composite nonwoven fabric (1) Production of coated nonwoven fabric coated with polymer electrolyte layer In the same manner as in Production Example 5, the nonwoven fabric F ₂ serving as the substrate is a PDDA layer and a PAA layer. Then, a coated nonwoven fabric CF ₄ was manufactured, which was sequentially coated with the PDDA layer and the PDDA layer was located on the surface layer.

(2) Production of coated cellulose nanofibers coated with a polymer electrolyte layer In the same manner as in Production Example 5, the cellulose nanofiber as a substrate is coated with a PDDA layer and a PAA layer, and the coated cellulose has a PAA layer on the surface layer. Nanofibers were produced.

(3) Manufacture of nanofiber composite non-woven fabric The coated non-woven fabric CF ₄ and the coated cellulose nanofiber are mixed in water, and the coated cellulose nanofiber is adsorbed on the coated non-woven fabric CF ₄ by electrostatic interaction to form a third nanofiber composite. A non-woven fabric (hereinafter referred to as “nanofiber composite non-woven fabric N ₃ ”) was produced. FIG. 5A is an electron micrograph (8000 times) of the nanofiber composite nonwoven fabric N ₃ , and FIG. 5B is an electron micrograph (8000 times) of the nanofiber composite nonwoven fabric N ₂ . The ratio of the average fiber diameter of the coated cellulose nanofibers to the average fiber diameter of the coated nonwoven fabric CF ₄ obtained based on FIG. 5A (average fiber diameter of the coated cellulose nanofibers: average fiber diameter of the coated nonwoven fabric CF ₄ ) Is 1: 1000, and the ratio of the average fiber diameter of the coated cellulose nanofibers to the average fiber diameter of the coated nonwoven fabric CF ₄ obtained based on FIG. 5B (average fiber diameter of the coated cellulose nanofibers: coated nonwoven fabric) The average fiber diameter of CF ₄ was 1: 2000.

[Test Example 1] Measurement of artificial menstrual brushing time Non-woven fabrics F ₁ and F ₂ before coating with a polymer electrolyte layer, particle-composited nonwoven fabrics M _{1 to} M ₃ and nano-fiber composite nonwoven fabrics N _{1 to} N ₃ From this, a test piece of 150 mm × 60 mm was cut out. An absorbent article sample was manufactured by stacking a top sheet (using a surface sheet of Sophia Hamooi) on each test piece, and an absorber on the bottom side of each test piece. As the absorbent, after the upper and lower sides of a pulp laminate having a basis weight of 300 g / m ² are sandwiched between tissues having a basis weight of 15 g / m ² , the thickness is adjusted so that the density is 0.1 g / cm ³ (after adjustment) The thickness was about 3.0 mm). A perforated acrylic plate (40 mm × 10 mm hole, 200 mm (length) × 100 mm (width)) was stacked on the surface sheet of the absorbent article sample. Using autoburet (Shibata Chemical Instruments Co., Ltd., Multidojimat E725-1 type), artificial menstrual blood (80 g of glycerin, 1 liter of ion-exchanged water, sodium carboxymethylcellulose) toward the hole in the acrylic plate 8 g, sodium chloride 10 g, sodium hydrogen carbonate 4 g, red No. 102 8 g, red No. 2 2 g and yellow No. 5 2 g were used, and 3 mL was injected at 90 mL / min (first time). After the start of injection, the time until the artificial menstrual blood staying in the hole of the acrylic plate disappeared was measured, and this was defined as the first artificial menstrual blood brushing time (second). The first artificial menstrual brushing time (seconds) was calculated as an average value of the measurement values obtained by the five measurements.

Two minutes after the start of the first injection, 3 mL of artificial menstrual blood was injected at a dropping rate of 90 mL / second (second time). After the start of the second injection, the time until the artificial menstrual blood staying in the hole in the acrylic plate disappeared was measured, and this was taken as the second artificial menstrual brushing time (seconds). The second artificial menstrual brushing time (seconds) was calculated as an average value of measurement values obtained by five measurements.
The results are shown in Table 1.

[Test Example 2] Measurement of liquid uptake height Test of 100 mm length x 25 mm width from nonwoven fabric F ₁ before coating with polymer electrolyte layer, particle composite nonwoven fabric M ₁ and nanofiber composite nonwoven fabric N ₁ A piece was cut out, and one end in the length direction of the test piece was fixed to a bar whose height was adjustable. A container containing pigment-containing water (type of pigment: blue No. 1, pigment concentration: 0.01% by weight) was placed below the test piece. The height of the bar was adjusted, and the other end of the test piece in the longitudinal direction was immersed in the dye-containing water in the container. At this time, the height of the bar was adjusted so that the portion from the other end in the length direction of the test piece to about 30 mm was immersed in the dye-containing water. Ten minutes after immersing the test piece in the dye-containing water, the distance from the surface of the dye-containing water in the container to the edge of the dye-containing water sucked up by the test piece is measured, and this is measured as the liquid suction height. (Mm). The liquid suction height (mm) was calculated as an average value of the measurement values obtained by five measurements. As a result, the liquid suction height of the nonwoven fabric F ₁ was 0 mm, the liquid suction height of the particle composite nonwoven fabric M ₁ was 10 mm, and the liquid suction height of the nanofiber composite nonwoven fabric N ₁ was 20 mm.

Claims (13)

In a predetermined solvent for a host material whose surface is positively or negatively charged in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water. A composite material for an absorbent article, wherein a guest material whose surface is charged to a charge opposite to the surface of the host material is adsorbed by electrostatic interaction,
The host material includes a nonwoven fabric substrate as a substrate,
The guest material as a substrate, a plurality of hydrophilic particle substrates having an average particle diameter smaller than the average fiber diameter of the nonwoven fabric substrate, or a plurality of hydrophilic fibers having an average fiber diameter smaller than the average fiber diameter of the nonwoven fabric substrate Including a substrate,
The composite material, wherein at least one of the host material and the guest material has a polymer electrolyte layer covering the substrate.   The ratio of the average particle diameter of the plurality of hydrophilic particle substrates to the average fiber diameter of the nonwoven fabric substrate (average particle diameter of the hydrophilic particle substrate: average fiber diameter of the nonwoven fabric substrate) is 1: 4 to 1:50, The ratio of the average fiber diameter of the plurality of hydrophilic fiber substrates to the average fiber diameter of the nonwoven fabric substrate (average fiber diameter of the hydrophilic fiber substrate: average fiber diameter of the nonwoven fabric substrate) is 1: 4 to 1: 2500. The composite material according to claim 1.   The polymer electrolyte layer includes a plurality of laminated polymer electrolyte layers, and in the plurality of polymer electrolyte layers, polymer electrolyte layers that are oppositely charged in the predetermined solvent are adjacent to each other. The composite material according to claim 1 or 2.   The composite according to any one of claims 1 to 3, wherein absolute values of zeta potentials of the host material and the guest material in the predetermined solvent are 20 mV or more and are in charge balance. Material. The host material comprises the following steps (a ₁ ) and (a ₂ ):
(A ₁ ) In a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water, the surface is positively or negatively charged in the predetermined solvent. A step of producing a first coated body having a first polymer electrolyte layer as a surface layer by bringing a nonwoven fabric substrate into contact with a polymer electrolyte charged with a charge opposite to the surface of the nonwoven fabric substrate in the predetermined solvent. ;
(A ₂ ) kth positively or negatively charged in the predetermined solvent in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water a first k ₁ of the cover having a _first polyelectrolyte layer to the surface layer, contacting the polymer electrolyte charged to the predetermined charge opposite in a solvent and the second k ₁ polyelectrolyte layer, the ( The procedure for manufacturing the (k ₁ +1) -th covering having the k ₁ +1) polymer electrolyte layer as the surface layer is k ₁ = 1 to k ₁ = m (where m is an integer of 1 or more). And (m + 1) -th coated body manufactured by a method including a step of manufacturing a (m + 1) -th coated body having a (m + 1) -th polymer electrolyte layer as a surface layer. Item 5. The composite material according to any one of Items 1 to 4.   The composite material according to claim 5, wherein an absolute value of a zeta potential of the (m + 1) -th covering is 20 mV or more. The guest material comprises the following steps (b ₁ ) and (b ₂ ):
(B ₁ ) In a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water, the surface is positively or negatively charged in the predetermined solvent. A hydrophilic polymer substrate or a hydrophilic fiber substrate is contacted with a polyelectrolyte that is charged with a charge opposite to the surface of the hydrophilic particle substrate or the hydrophilic fiber substrate in the predetermined solvent, to thereby form a first polymer. Producing a first covering having an electrolyte layer as a surface layer;
(B ₂ ) kth positively or negatively charged in the predetermined solvent in a predetermined solvent selected from water, a nonpolar organic solvent, a polar organic solvent, and a mixed solvent of a polar organic solvent and water a covering member of the k ₂ with ₂ polyelectrolyte layers on the surface layer, contacting the polymer electrolyte charged to the opposite charge as the polyelectrolyte layer of the first k ₂ at the predetermined solvent, the ( the procedure of manufacturing a covering member of the (k ₂ +1) with the polymer electrolyte layer of k ₂ +1) in the surface layer, the _{k 2 = 1 k 2 = n} ( where, n represents an integer of 1 or more. And (n + 1) -th coated body manufactured by a method including a step of manufacturing a (n + 1) -th coated body having a (n + 1) -th polymer electrolyte layer as a surface layer. Item 7. The composite material according to any one of Items 1 to 6.   The composite material according to claim 7, wherein an absolute value of a zeta potential of the (n + 1) th covering is 20 mV or more.   The composite material according to claim 1, wherein the hydrophilic particle base is silica particles.   The composite material according to claim 1, wherein the hydrophilic fiber base is a cellulose fiber.   The composite material according to claim 10, which is obtained by adsorbing the guest material to the host material by electrostatic interaction in a monohydric alcohol having 1 to 3 carbon atoms.   A liquid-permeable layer, a liquid-impermeable layer, a liquid-absorbing layer disposed between the liquid-permeable layer and the liquid-impermeable layer, and between the liquid-permeable layer and the liquid-absorbing layer Or it is an absorbent article provided with the liquid diffusible layer arrange | positioned between the said liquid absorptive layer and the said liquid impermeable layer, Comprising: The said liquid diffusible layer is any one of Claims 1-11. The said absorbent article containing the composite material of description.   The absorbent article according to claim 12, wherein the liquid diffusible layer is in contact with the liquid absorbent layer.