JPWO2016194284A1 - Metal oxide and / or metal hydroxide-containing sheet - Google Patents

Abstract

Provision of a metal oxide and / or metal hydroxide-containing sheet having excellent antibacterial performance. A nonwoven fabric comprising a layer containing a metal component, wherein the metal component is present as a metal oxide and / or metal hydroxide.

Description

  The present invention relates to a sheet containing a metal oxide and / or a metal hydroxide, and more particularly to a nonwoven fabric containing calcium oxide and / or calcium hydroxide. The metal oxide and / or metal hydroxide-containing sheet of the present invention is used as a wet wiping sheet for wiping purposes such as cleaning and toilet cleaning, and for wiping purposes for sterilization, sterilization and antiviral purposes. It can be used for a sheet, a wiping sheet for preventing infection in a hospital, a kindergarten / nursery school, a public facility, a gym, etc., a wiping sheet after vomit treatment, and a towel. In addition, it can be used for food tray mats, food packaging sheets, beauty sheets, antibacterial sheets, insect repellent sheets, masks, cleaning sheets, etc. it can. Furthermore, it can be used as a desiccant, drying / mold-proofing sheet, deodorizing / mold-proofing sheet, packaging food, packaging it with food, and storing it together when storing food. .

Metal oxides such as calcium oxide (CaO) and magnesium oxide (MgO), and metal hydroxides such as calcium hydroxide (Ca (OH) ₂ ) and magnesium hydroxide (Mg (OH) ₂ ) It is known to have antibacterial activity and to enable sterilization and growth inhibition of microorganisms. Therefore, these metal oxides and metal hydroxides are used in the antibacterial processed product field, food field (sterilization / disinfection, food oxidation prevention, food freshness maintenance), fishery field (fresh fish fineness maintenance), agricultural field (soil It is used in various fields such as improvement, livestock), cosmetics / toiletries, sanitary products, pharmaceutical parts, cleaning products, clothing (deodorization), and miscellaneous goods.

  For example, Patent Document 1 discloses an antibacterial nanofiber nonwoven fabric using calcium oxide powder as an antibacterial agent that can be used in sanitary products such as diapers, sanitary napkins, and cloths. In Patent Document 1, a step of obtaining a calcium saturated aqueous solution of pH 12.0 to pH 14.0 by dissolving calcium oxide powder with purified water, dipping the nanofiber nonwoven fabric in the calcium saturated aqueous solution and impregnating the surface of the nanofiber nonwoven fabric with calcium And the step of drying the nanofiber nonwoven fabric impregnated with calcium, the antibacterial nanofiber nonwoven fabric is manufactured.

JP 2012-246595 A

The antibacterial mechanism of metal oxides and metal hydroxides has not yet been fully clarified, but generally, the main factor is that the metal oxides and metal hydroxides are alkaline when dissolved in water. It has been. There is also a theory that metal ions are sterilized by binding to -SH groups in proteins present in bacterial and mold cell substrates and inhibiting cellular respiration. In addition, it is presumed that hydroxy radicals (OH.) And hydroxy ions (OH ⁻ ) in an aqueous solution exhibit an antibacterial effect by decomposing organic substances by their oxidizing action.

However, in Patent Document 1, as described above, in the production process, calcium oxide is once dissolved in water to obtain a saturated calcium aqueous solution, and the nanofiber nonwoven fabric is immersed in this to obtain an antibacterial nanofiber nonwoven fabric. . In the case of this production method, most of the calcium oxide (CaO) (metal oxide) used as a raw material is calcium hydroxide (Ca (OH)) in the antibacterial nanofiber nonwoven fabric containing water before drying. ₂ ) It is considered to be contained as (metal hydroxide). The Ca (OH) ₂ seems to be liberated in water to Ca ²⁺ and OH · and OH ⁻ . Therefore, in the step of drying the antibacterial nanofiber nonwoven fabric containing water, CO ₂ in the atmosphere selectively reacts with Ca ²⁺ to obtain CaCO ₃ (metal carbonate) having no antibacterial properties. It is thought that it will be. As a result, the inventors have found that the desired antibacterial property cannot be obtained in the manufactured antibacterial nanofiber nonwoven fabric.

  An object of the present invention is to provide a metal oxide and / or metal hydroxide-containing sheet excellent in antibacterial performance.

  The present invention for solving the above-described problems has the following aspects.

  [1] A nonwoven fabric comprising a layer containing a metal component, wherein the metal component is present as a metal oxide and / or metal hydroxide.

  [2] The nonwoven fabric according to [1], wherein the layer includes fibers, and the metal oxide and / or metal hydroxide powder is held in voids formed by the fibers.

  [3] The layer contains a heat-fusible resin A, and the metal oxide and / or metal hydroxide powder present in the layer is part of the powder. The nonwoven fabric according to [1] or [2], which is fixed in a state of being covered with.

  [4] A layer adjacent to the layer contains the heat-fusible resin B, and the metal oxide and / or metal hydroxide powder present in the layer is a part of the powder. The nonwoven fabric according to any one of [1] to [3], which is fixed in a state of being covered with the adhesive resin B.

  [5] The nonwoven fabric according to any one of [1] to [4], which is heat-sealed.

  [6] The nonwoven fabric according to any one of [1] to [5], wherein an adhesive layer is provided adjacent to the layer.

  [7] The nonwoven fabric according to any one of [1] to [6], which is embossed.

[8] Metal in which the metal oxide and / or metal hydroxide is one or more of MO and / or M (OH) ₂ (wherein M is Mg, Ca, Sr or Ba) The nonwoven fabric according to any one of [1] to [7], which is an oxide and / or a metal hydroxide.

  [9] The nonwoven fabric according to any one of [1] to [8], wherein the metal oxide and / or metal hydroxide is calcium oxide and / or calcium hydroxide.

  The nonwoven fabric of this invention is a nonwoven fabric provided with the layer containing a metal component, and the said metal component exists as a metal oxide and / or a metal hydroxide.

  In the present invention, the metal component is present in the layer as a metal oxide and / or metal hydroxide. In the nonwoven fabric of the present invention, metal oxide and / or metal hydroxide can act as an antibacterial agent, and as a result, the nonwoven fabric of the present invention can have excellent antibacterial performance.

  Moreover, the nonwoven fabric of this invention can include a metal oxide and / or a metal hydroxide in the form of a powder. The metal oxide and / or metal hydroxide in the form of a powder can maintain its original form when added to the layer in the layer, so it can be easily applied to any part in the in-plane direction and thickness direction of the layer. A metal oxide and / or a metal hydroxide can be localized in this.

The nonwoven fabric provided with the layer in which the metal component is present as a metal oxide and / or metal hydroxide according to the present invention can be produced, for example, by a dry production method (dry method) that does not involve water. According to the dry production method, the metal oxide and / or metal hydroxide used as a raw material does not become calcium carbonate (Ca (CO ₃ ) in the nonwoven fabric production process, and thus the oxide and / or hydroxide. This is because it can be included in the layer as it is.

  When the layer containing the metal component is provided by a dry method, the metal oxide and / or metal hydroxide can be contained in the sheet without being dissolved, and therefore the metal oxide and / or metal hydroxide Can be efficiently blended in the layer.

It is a figure which shows the structural example of the metal oxide and / or metal hydroxide containing sheet | seat of this invention. It is a schematic diagram which shows the web formation apparatus which can be used in the manufacturing method of the metal oxide and / or metal hydroxide containing sheet | seat of this invention. It is a SEM photograph of the section of the metal oxide and / or metal hydroxide content sheet of the present invention (magnification 500 times). It is a table | surface which shows the result of the performance evaluation test about an Example and a comparative example. It is a table | surface which shows the result of the performance evaluation test about an Example and a comparative example. It is a table | surface which shows the result of the performance evaluation test about an Example and a comparative example. It is a table | surface which shows the result of the performance evaluation test about an Example and a comparative example. It is a table | surface which shows the result of the performance evaluation test about an Example and a comparative example.

(Metal oxide and / or metal hydroxide-containing sheet (nonwoven fabric))
The metal oxide and / or metal hydroxide-containing sheet of the present invention is a nonwoven fabric provided with a layer containing a metal component, wherein the metal component exists as a metal oxide and / or metal hydroxide. It is the characteristic nonwoven fabric.

  Here, the “sheet” can also be expressed as “nonwoven fabric”. That is, the sheet of the present invention includes a metal oxide and / or metal hydroxide-containing layer, and the metal oxide and / or metal hydroxide-containing layer is provided by a dry method. Or it can also be said to be a metal hydroxide-containing sheet.

  In this case, the “metal oxide and / or metal hydroxide-containing layer” corresponds to the “layer containing a metal component”, and the metal of the metal component is a metal that comes into contact with water and becomes a strong alkali. It is a metal constituting an oxide or a metal hydroxide, preferably a divalent metal, more preferably a metal of Group 2 element of the periodic table, and more preferably M (wherein M is Mg, Ca, Sr) Or Ba)), particularly preferably an alkaline earth metal.

  Hereinafter, in the present specification, “metal oxide and / or metal hydroxide” is also referred to as “metal (water) oxide”. Further, the “layer containing a metal component” is also referred to as a “metal oxide and / or metal hydroxide-containing layer” or a “metal (water) oxide-containing layer”. The nonwoven fabric of the present invention is also referred to as a metal oxide and / or metal hydroxide-containing sheet, a metal (water) oxide-containing nonwoven fabric, or a metal (water) oxide-containing sheet.

  With reference to FIG. 1, the structure of the metal (water) oxide containing sheet | seat contained in the range of this invention is demonstrated. FIG. 1 is a diagram showing the structure of the metal (water) oxide-containing sheet of the present invention for the purpose of illustration and not for the purpose of limitation. In the drawings, the same reference numerals indicate the same components. For the same component, a duplicate description may be omitted.

  FIG. 1 (a)-(c) shows a metal (water) oxide containing sheet | seat provided with the metal (water) oxide containing layer 100 based on this invention. FIG. 1A is a metal (water) oxide-containing sheet composed only of the metal (water) oxide-containing layer 100. FIGS. 1B and 1C are metal (water) oxide-containing sheets in which another layer 300 is laminated on one side or both sides of the metal (water) oxide-containing layer 100.

  As described above, the metal (water) oxide-containing sheet of the present invention may have a single layer structure, or may have a multilayer structure of two layers, three layers, or four or more layers not shown. . The metal (water) oxide-containing sheet may include two or more metal (water) oxide-containing layers 100. The other layer 300 is, for example, a metal (water) oxide for the purpose of modifying the surface of the metal (water) oxide-containing sheet or for imparting strength (rigidity) to the metal (water) oxide-containing sheet. It can be arranged for the purpose of imparting some functionality to the containing sheet. For the other layer 300, for example, a sheet of cloth, nonwoven fabric, paper, film, or the like can be used. The other layer 300 may contain a heat-fusible resin. When the metal (water) oxide-containing sheet includes a plurality of layers 300, these layers 300 may be the same material or different materials.

  The metal (water) oxide-containing layer 100 can contain only the metal (water) oxide D. At this time, it is not limited to one type, and a plurality of types of metal (water) oxides D can be included. The type of metal (water) oxide will be described later.

  In addition to the metal (water) oxide D, the metal (water) oxide-containing layer 100 may contain fibers, a heat-fusible resin, an effect accelerator, and the like.

  As an example of the configuration for preventing the metal (water) oxide D from falling off from the metal (water) oxide-containing sheet, specific modes as shown in the following first to sixth modes will be described.

(First aspect)
FIG. 1D shows an example in which the metal (water) oxide-containing layer 100 includes fibers F. In the metal (water) oxide-containing layer 110 containing the fibers F, the metal (water) oxide powder is held in the voids formed by the fibers F, that is, the voids in the fiber structure formed by the fibers F. This prevents powder falling off.

  The metal (water) oxide-containing layer 110 containing fibers can contain only metal (water) oxide D and fibers F. In addition to the metal (water) oxide D and the fiber F, the metal (water) oxide-containing layer 110 containing fibers may include a heat-fusible resin, an effect accelerator, and the like. Further, the fiber F itself may be a heat-fusible resin.

  In this embodiment, the metal (water) oxide-containing sheet is provided on one side or both sides of the metal (water) oxide-containing layer 110 containing the fibers F for the purpose of imparting functionality such as surface modification and strength (rigidity). It may have a multilayer structure (not shown) in which other layers 300 are stacked.

  Here, FIG. 3 is based on a scanning electron microscope (SEM) showing an example of a “metal (water) oxide-containing layer containing fibers” of the metal (water) oxide-containing sheet according to the first aspect of the present invention. It is a cross-sectional photograph (magnification 500 times). As is apparent from this photograph, in the CaO-containing layer, CaO is fixed by a heat-fusible resin (heat-fusible fiber). Thus, in the present invention, the metal (water) oxide powder in the metal (water) oxide-containing layer is a void formed by a heat-fusible resin (heat-fusible fiber), that is, heat-fusible. It is held in the voids in the structure formed by the resin (heat-fusible fiber).

(Second aspect)
FIG. 1E is an example in which the metal (water) oxide-containing layer 100 includes a heat-fusible resin A. The metal (water) oxide-containing layer 120 containing the heat-fusible resin A melts the heat-fusible resin A in the mixture containing the metal (water) oxide D powder and the heat-fusible resin A. It was obtained by this. In this example, the metal (water) oxide D powder in the metal (water) oxide-containing layer is fixed (bound or fixed) in a state where a part of the powder is coated with the heat-fusible resin A. Also called).

  In the metal (water) oxide-containing layer 120 containing the heat-fusible resin A, the metal (water) oxide D is partially covered when the molten heat-fusible resin A is solidified. By being fixed, powder fall-off is prevented. The heat-fusible resin A is blended in such an amount that does not cover the entire metal (water) oxide D, and the metal (water) oxide D is covered with the heat-fusible resin A. There is no part, and contact with water and elution are guaranteed when using the sheet.

  The metal (water) oxide-containing layer 120 containing the heat-fusible resin A can contain only the metal (water) oxide D and the heat-fusible resin A. Further, the metal (water) oxide-containing layer 120 containing the heat-fusible resin A contains fibers, an effect accelerator and the like in addition to the metal (water) oxide D and the heat-fusible resin A. It may be. Further, the heat-fusible resin A itself may be fibrous.

  In this embodiment, the metal (water) oxide-containing sheet is a metal (water) oxide-containing layer 120 containing the heat-fusible resin A for the purpose of imparting functionality such as surface modification and strength (rigidity). It may have a multilayer structure (not shown) in which another layer 300 is laminated on one side or both sides.

(Third aspect)
FIG. 1 (f) is an example in which a layer adjacent to the metal (water) oxide-containing layer 100 includes the heat-fusible resin B. The layer 200 containing the heat-fusible resin B adjacent to the metal (water) oxide-containing layer is disposed by placing the heat-fusible resin B on the surface of the metal (water) oxide-containing layer 100 and heat-sealing by heat. It is obtained by melting the functional resin B. In this example, the metal (water) oxide D powder in the metal (water) oxide layer is fixed in a state where a part of the powder is coated with the heat-fusible resin B.

  When the metal (water) oxide D contained in the metal (water) oxide-containing layer 100 is solidified, the heat-bondable resin B melted in the layer 200 containing the heat-bondable resin B adjacent thereto is solidified. By partly covering and fixing, powder falling is prevented. Moreover, the metal (water) oxide D has a part which is not coat | covered with the heat-fusible resin B, and the contact and elution with water at the time of sheet | seat use are ensured.

  The layer 200 containing the heat-fusible resin B can contain only the heat-fusible resin B. In addition to the heat-fusible resin B, the layer 200 containing the heat-fusible resin B may contain fibers, an effect accelerator, and the like. When these other components are included, the layer 200 containing the heat-fusible resin B is a mixture of the heat-fusible resin B and these other components on the surface of the metal (water) oxide-containing layer 100. It can be obtained by melting the heat-fusible resin B with heat.

  The metal (water) oxide-containing sheet of the example shown in FIG. 1 (f) is more specifically, a layer (200) containing the heat-fusible resin B, and metal (water) oxidation consisting of metal (water) oxide powder. It has a three-layer structure including the material-containing layer 100 and the metal (water) oxide-containing layer 120 containing the heat-fusible resin A. In the case of this example, the metal (water) oxide-containing layer 120 containing the heat-fusible resin A is also made of the metal (water) oxide contained in the metal (water) oxide-containing layer 100 positioned as the intermediate layer. Can contribute to prevention of powder falling. Also, here, the metal (water) oxide-containing layer 100 and the metal (water) oxide-containing layer 120 containing the heat-fusible resin A are shown and described as separate layers, but these two layers are integrated. A configuration in which the metal (water) oxide-containing layer 120 including one layer of the heat-fusible resin A is included in this embodiment. According to this aspect, in particular, in the metal (water) oxide-containing layer 120 containing the heat-fusible resin A, when the metal (water) oxide powder is unevenly distributed on the surface side, powder removal is effective. Can be prevented.

  In this embodiment, the layer 200 containing the heat-fusible resin B may be provided on both surfaces of the metal (water) oxide-containing layer. That is, for example, a configuration (not shown) including the layer 200 including the heat-fusible resin B, the metal (water) oxide-containing layer, and the layer 200 including the heat-fusible resin B in this order: It is the range of this aspect.

  In this embodiment, the metal (water) oxide-containing sheet includes a metal (water) oxide-containing layer and a heat-fusible resin B for the purpose of imparting functionality such as surface modification and strength (rigidity). You may have the multilayer structure (not shown) by which the other layer 300 was laminated | stacked on the single side | surface or both surfaces of the outer surface of the laminated body of the layer 200. FIG.

(Fourth aspect)
The metal (water) oxide-containing sheet according to the present invention may be formed by heat sealing. As an example, FIG. 1 (g) shows a configuration in which another layer 300 containing a heat-fusible resin is laminated on both surfaces of a metal (water) oxide-containing layer 100 and the four sides are heat-sealed.

(5th aspect)
FIG. 1H is an example in which an adhesive layer is provided adjacent to the metal (water) oxide-containing layer 100. Adhesive layer 500 adjacent to the metal (water) oxide-containing layer is obtained by disposing an adhesive layer on the surface of the metal (water) oxide-containing layer. The adhesive layer is not particularly limited as long as it is a layer that exhibits an adhesive function so as to prevent metal (water) oxide contained in the metal (water) oxide-containing layer 100 from falling off. Agents and the like.

  Specifically, the metal (water) oxide-containing sheet shown in FIG. 1H is a hot-melt adhesive such as a thermoplastic resin between the metal (water) oxide-containing layer 100 and another layer 300. A configuration in which an adhesive layer 500 made of an agent is interposed and interlayer bonding is performed by hot melt processing is shown.

  More specifically, the metal (water) oxide-containing sheet of the example shown in FIG. 1 (h) has a heat fusion property on the surface of the metal (water) oxide-containing layer 100 opposite to the adhesive layer 500. The metal (water) oxide-containing layer 120 containing the resin A is included. Also in the metal (water) oxide-containing sheet of the example shown in FIG. 1 (h), the metal (water) oxide-containing layer containing the heat-fusible resin A is the same as the case of the example shown in FIG. 120 can contribute to prevention of powder falling of the metal (water) oxide contained in the metal (water) oxide-containing layer 100 positioned as the intermediate layer. Also, here, the metal (water) oxide-containing layer 100 and the metal (water) oxide-containing layer 120 containing the heat-fusible resin A are shown and described as separate layers, but these two layers are integrated. A configuration in which the metal (water) oxide-containing layer 120 including one layer of the heat-fusible resin A is included in this embodiment. According to this aspect, in particular, in the metal (water) oxide-containing layer 120 containing the heat-fusible resin A, when the metal (water) oxide powder is unevenly distributed on the surface side, powder removal is effective. Can be prevented.

  In this embodiment, the other layer 300 via the adhesive layer 500 may be provided on both surfaces of the metal (water) oxide-containing layer. That is, for example, the configuration (not shown) including the other layer 300, the adhesive layer 500, the metal (water) oxide-containing layer, the adhesive layer 500, and the other layer 300 in this order is the present aspect. Range. At this time, the adhesive layers 500 and the other layers 300 provided on both surfaces may be the same or different from each other. The other layer 300 is a layer provided for the purpose of imparting functionality such as surface modification and strength (rigidity), and details thereof will be described later.

(Sixth aspect)
The metal (water) oxide-containing sheet according to the present invention may be formed by embossing. As an example, FIG. 1 (i) shows a configuration in which layers 300 are laminated on both surfaces of a metal (water) oxide-containing layer 120 containing a heat-fusible resin A, and the layers are bonded together by embossing.

  The configuration of the metal (water) oxide-containing sheet of the present invention has been described above with reference to FIGS. However, these are merely examples, and other configurations, for example, combinations of the exemplified embodiments are also included in the scope of the present invention. For example, a layer shown as a metal (water) oxide-containing layer 100 in the figure includes a metal (water) oxide-containing layer 110 containing fibers F or a metal (water) oxide containing heat-fusible resin A. The layer 120 may be sufficient, or the layer containing both the fiber F and the heat-fusible resin A may be sufficient. Similarly, configurations in which layers are replaced between these layers are included in the scope of the present invention.

  Below, the detail of the component of the metal oxide and / or metal hydroxide containing sheet | seat which concerns on this invention is demonstrated.

(Layer containing metal component (metal oxide and / or metal hydroxide-containing layer))
The nonwoven fabric of the present invention is provided with a layer containing a metal component. Here, the layer containing a metal component is also referred to as a metal component-containing layer, a metal oxide and / or metal hydroxide-containing layer, or a metal (water) oxide-containing layer. That is, the metal component exists as a metal oxide and / or a metal hydroxide. The metal oxide and / or metal hydroxide is included as a powder (particle). The metal oxide and / or metal hydroxide-containing layer can contain only metal oxide, can contain only metal hydroxide, and can contain metal oxide and metal water. Oxides can be included. Each of the metal oxide and the metal hydroxide is not limited to one type, and a plurality of types may be included. In addition to the metal oxide and / or metal hydroxide, the metal oxide and / or metal hydroxide-containing layer may contain fibers, a heat-fusible resin, an effect accelerator, and the like. Good.

(Metal oxide)
The metal oxide used in the present invention is a metal oxide that becomes a strong alkali upon contact with water, preferably a divalent metal oxide, more preferably a metal oxide of a Group 2 element of the periodic table More preferably, it is a metal oxide represented by MO (wherein M is Mg, Ca, Sr or Ba), and particularly preferably an oxide of an alkaline earth metal. As non-limiting examples, magnesium oxide (11.4), calcium oxide (12.7), strontium oxide (13.2), barium oxide (13.4), and manganese oxide (10.6) are preferably used. can do. The numerical value in parentheses after the substance name indicates the value of the acid dissociation constant pKa. The metal oxide to be used can be selected according to a use or a desired effect. For example, in applications that come into contact with food, calcium oxide is preferably used from the viewpoint of safety and the like. These metal oxides can be used alone or in combination.

(Metal hydroxide)
The metal hydroxide used in the present invention is a metal hydroxide that becomes strong alkali upon contact with water, preferably a divalent metal hydroxide, more preferably a metal of a Group 2 element of the periodic table. More preferably, it is a metal hydroxide represented by M (OH) ₂ (wherein M is Mg, Ca, Sr or Ba), and particularly preferably an alkaline earth metal It is a hydroxide. Non-limiting examples include magnesium hydroxide (11.4), calcium hydroxide (12.7), strontium hydroxide (13.2), barium hydroxide (13.4), and manganese hydroxide (10. 6) can be preferably used. The numerical value in parentheses after the substance name indicates the value of the acid dissociation constant pKa. The metal hydroxide to be used can be selected according to a use or a desired effect. For example, in applications that come into contact with food, calcium hydroxide is preferably used from the viewpoint of safety and the like. These metal hydroxides can be used alone or in combination.

  Thus, the layer containing the metal component is a layer containing a metal oxide and / or metal hydroxide, and the metal component constituting the metal oxide and / or metal hydroxide is the metal oxide. The metal component in which the product and / or metal hydroxide comes into contact with water and becomes strong alkali. The metal component is preferably a divalent metal, more preferably a metal of a Group 2 element of the periodic table, and still more preferably a metal represented by M (wherein M is Mg, Ca, Sr or Ba). Yes, particularly preferably an alkaline earth metal.

  The metal oxide and / or metal hydroxide used in the present invention is used in the form of powder (particles). The metal oxide and / or metal hydroxide in the form of powder (particles) can be obtained by any method known in the art, and can be purchased from the manufacturer. For example, in the case of calcium oxide, Okhotsk calcium manufactured by Natural Japan Co., Ltd., scallop shell baked powder manufactured by Unicera Co., Ltd., and the like can be suitably used. For example, in the case of calcium hydroxide, Scarlow (registered trademark) manufactured by Antibacterial Research Institute, Inc. and sold by Hishie Chemical Co., Ltd. can be suitably used. In the case of calcium oxide or calcium hydroxide, calcium (calcium carbonate) obtained from scallop shells can be suitably used as the calcium raw material, but is not limited to this, and shells of other shells (for example, oysters) For example, sea urchin shells), animal bones (for example, sea urchin shells), and minerals.

  The average particle diameter of the metal oxide and / or metal hydroxide powder (particles) is not limited, but is preferably 1-1000 μm, more preferably 2-800 μm. If the average particle size is too small, there are concerns such as dropping off from the sheet (nonwoven fabric) and reduction in work efficiency due to scattering in the production process. Moreover, when the said average particle diameter is too large, it may become difficult to mix | blend uniformly with the whole nonwoven fabric.

(fiber)
As the fibers, natural fibers such as pulp, rayon, hemp, cotton, silk, wool, and mineral fibers, and synthetic fibers such as polylactic acid, nylon, polyvinyl alcohol (PVA), and polymer absorbent fibers (SAF) can be used. . Since these fibers have water absorption, they can be blended as a water absorbing material to promote contact and dissolution of the metal (water) oxide with water when the metal (water) oxide-containing sheet is used. Moreover, a non-water-absorbing fiber can also be used as the fiber of the present invention. The heat-fusible resin described below may be used in the form of fibers. These fibers can be used, for example, in the form of a defibration shortcut fiber. Two or more of these fibers may be used in combination.

(Heat-fusion resin)
The heat-fusible resin in the present invention is a binder resin that binds the constituent components. The heat-fusible resin has an effect of imparting strength to the metal (water) oxide-containing sheet, and the shape of the metal (water) oxide-containing sheet is easily maintained by including the heat-fusible resin. .

  The heat-fusible resins A and B can bind metal (water) oxides and other components when they contain metal (water) oxides and other components. When the heat-fusible resins A and B are melted and solidified so as not to prevent contact and elution of the metal (water) oxide with water, the entire powder (particles) of the metal (water) oxide is removed. The amount is such that it does not cover.

  The heat-fusible resin may be fibrous or particulate. From the viewpoint of higher strength, the heat-fusible resin is preferably fibrous. The heat-fusible resin may be in the form of a shortcut fiber, for example.

  The heat-fusible resin includes polyethylene (PE), polypropylene, polyethylene terephthalate (PET) such as low melting point polyethylene terephthalate, ethylene / vinyl acetate copolymer (EVA), low melting point polyamide, low melting point polylactic acid, polybutylene succin And the like.

  The heat-fusible resin may be a composite of two or more kinds of resins. For example, a core-sheath fiber composed of a core part and a sheath part, a side-by-side fiber made of a resin in which a half on one side and a half on the other side are different in a cross section perpendicular to the longitudinal direction, and a core and a shell made of different resins Examples include core-shell particles. Among them, a core-sheath fiber is preferable when it is desired to improve the rigidity of the nonwoven fabric while exhibiting the performance of the heat-fusible resin.

As the core-sheath fiber, for example, a core portion made of polypropylene fiber (melting point 160 ° C.),
PP / PE composite core-sheath fiber provided with the sheath part which consists of polyethylene (melting | fusing point 130 degreeC) formed in the outer periphery of this core part is mentioned. Other core sheath fibers include PP / EVA composite core sheath fiber, PET / low melting point PET composite core sheath fiber, high density polyethylene / low density polyethylene composite core sheath fiber, PET / PE composite core sheath fiber, polyamide / Examples include low melting point polyamide composite core-sheath fibers, polylactic acid / low melting point polylactic acid composite core-sheath fibers, and polylactic acid / polybutylene succinate composite core-sheath fibers. Among core-sheath fibers, composite core-sheath fibers having a sheath portion made of polyethylene, such as PP / PE composite core-sheath fibers, PET / PE composite core-sheath fibers, and PE / PE composite core-sheath fibers, are preferable.

  As the heat-fusible resin, (1) PET heat-fusible fiber, (2) composite core-sheath fiber having a sheath portion made of PET, (3) polyethylene heat-fusible fiber, (4) made of polyethylene Preferably, at least one selected from the group consisting of a composite core-sheath fiber provided with a sheath part, (5) EVA heat-fusible fiber, and (6) a composite core-sheath fiber provided with a sheath part made of EVA. More preferred is at least one selected from the group consisting of fusible fibers and core-sheath fibers having a sheath portion made of polyethylene.

  Two or more kinds of heat-fusible resins may be used in combination. That is, the heat-sealable resins A and B may be the same heat-sealable resin or different heat-sealable resins. As the heat-fusible resin A and the heat-fusible resin B, one kind of heat-fusible resin may be used, or plural kinds of heat-fusible resins may be used in combination. When the metal (water) oxide-containing sheet includes another layer 300 to be described later and the other layer 300 includes a heat-fusible resin, the heat-fusible resin included in the other layer 300 May be the same as or different from the heat-fusible resins A and B, and may be one type or a combination of a plurality of types.

(Other layers)
In addition to the metal (water) oxide-containing layers 100, 110, and 120, the metal (water) oxide-containing sheet of the present invention is used for the purpose of imparting functionality such as surface modification and strength (rigidity). Layer 300 can be included.

  As the other layer 300, for example, any sheet having a property of passing moisture (water permeability) and / or a property of absorbing moisture (water absorption), such as a nonwoven fabric, cloth, and paper can be used. Moreover, arbitrary films can be used. The other layer 300 may contain a heat-fusible resin. When a film having relatively low water permeability is used on one surface of the metal (water) oxide-containing sheet, it is possible to prevent the antibacterial agent from eluting from the surface when the sheet is used. That is, it can promote that an antibacterial agent elutes from the other surface.

  The surface of the other layer 300 that is the outer layer of the metal (water) oxide-containing sheet may be subjected to surface processing such as concavity and convexity and processing such as formation of holes and slits. For example, in applications such as mats for food trays, a perforated film or slit in which a large number of holes such as a surface material of a sanitary material are formed on one or both surfaces of a metal (water) oxide-containing sheet. A film can be preferably used. With such a structure, when the sheet is used, the metal (water) oxide can be easily eluted by the holes and slits, and the drip from the food is layered inside the metal (water) oxide-containing sheet. Can suck.

(Effect promoter)
One or a plurality of effect accelerators can be blended in the metal (water) oxide-containing sheet of the present invention depending on its use.

  Examples of the effect promoter include: oily base, moisturizer, touch improver, surfactant, polymer, thickener / gelator, solvent, propellant, antioxidant, reducing agent, oxidizing agent, preservative , Antibacterial agents, chelating agents, pH adjusters, acids, carbonates, alkalis, powders, inorganic salts, UV absorbers, whitening agents, vitamins and their derivatives, anti-inflammatory agents, anti-inflammatory agents, hair growth agents, blood circulation Accelerator, Stimulant, Hormones, Anti-wrinkle agent, Anti-aging agent, Squeeze agent, Cool sensation agent, Warm sensation agent, Wound healing promoter, Stimulation mitigation agent, Analgesic agent, Cell activator, Plant / Animal / Microbe extract , Antipruritic agent, exfoliating / dissolving agent, antiperspirant, refreshing agent, astringent, enzyme, nucleic acid, fragrance, dye, colorant, dye, pigment, metal-containing compound, unsaturated monomer, polyhydric alcohol, high Molecular additives, anti-inflammatory analgesics, antifungal agents, antihistamines, hypnotic sedatives, tranquilizers, Antihypertensive, Antihypertensive diuretic, Antibiotic, Anesthetic agent, Antibacterial agent, Antiepileptic agent, Coronary vasodilator, Herbal medicine, Adjuvant, Wetting agent, Thickener, Tackifier, Antidiarrheal agent, Keratin softening release agent Oily raw materials, UV blockers, antiseptics, anti-oxidants, liquid matrices, fat-soluble substances, polymeric carboxylates, additives, metal soaps, water-absorbing materials, and the like.

  An effect promoter can be mix | blended with the metal (water) oxide content layer 100,110,120. In addition, when the metal (water) oxide-containing sheet has a multilayer structure including a metal (water) oxide-containing layer and another layer, it is blended in any one or a plurality of layers. can do.

(Heat seal processing)
Heat sealing is a method in which heat is applied by a heating means such as a heat sealer to bond the layers. In the present invention, for example, a metal (water) oxide-containing layer made of only a metal (water) oxide is used as an intermediate layer, and layers 200 including a heat-fusible resin are arranged on both sides thereof, and four sides are heated. By sealing, a metal (water) oxide-containing sheet having a multilayer structure can be formed.

(Adhesive layer)
The method for forming the adhesive layer is not particularly limited, but is preferably an adhesive layer obtained by hot melt processing. Hot melt processing is a processing method in which a thermoplastic resin is melted and extruded to bond the sheets. It can be used for interlayer adhesion when joining a metal (water) oxide-containing layer and another layer.

  Examples of the thermoplastic resin that can be used for hot-melt processing include ethylene / vinyl acetate copolymer (EVA), and resins generally known as hot-melt adhesives can be used.

(Embossing)
Embossing is a process in which heat is applied with a pressing die carved with uneven patterns. This method can also be used for interlayer adhesion of multilayer structures. This method can also be used for surface treatment such as irregularities on a single layer or multilayer structure metal (water) oxide-containing sheet.

(Content ratio of ingredients)
The amount of the metal (water) oxide in the metal (water) oxide-containing sheet varies depending on the use and desired effect, but from the viewpoint of the antibacterial performance of the metal (water) oxide, the powder occupies the total amount of the sheet Is preferably 0.01% by mass or more, more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Moreover, from the viewpoint of exhibiting deodorizing properties of the metal (water) oxide, the amount of powder in the total amount of the sheet is preferably 1% by mass or more, although it depends on the type of gas to be deodorized, preferably 3% by mass. More preferably, it is more preferably 5% by mass or more, still more preferably 8% by mass or more, and particularly preferably 10% by mass or more. From the viewpoint of preventing metal (water) oxide from falling off, the amount of the metal (water) oxide powder in the total amount of the metal (water) oxide-containing sheet is preferably 60% by mass or less, and 50% by mass. % Or less is more preferable, and 40% by mass or less is further preferable.

(Basis weight)
The basis weight of the metal (water) oxide-containing sheet can be appropriately set depending on the application. For example, 10 to 4000 g / m ² is preferable, 30 to 3000 g / m ² is more preferable, and 50 to 300 g / m ² is more preferable. When the basis weight is too small, it may be difficult to produce a uniform sheet (nonwoven fabric), and when the basis weight is too large, handling during use may be deteriorated.

(Formation of metal oxide and / or metal hydroxide-containing layer by dry method)
In the present invention, the metal (water) oxide-containing layer is a layer provided by a dry method. Dry methods that can be used in the present invention include any layer forming method that does not use water.

(Method for producing metal oxide and / or metal hydroxide-containing sheet)
For example, a metal (water) oxide-containing layer is produced by a web forming apparatus employing an airlaid method, and when another layer is included, the other layer is separately laminated on the metal (water) oxide-containing layer. Manufacturing methods can be used. As such a method, a heat-fusible resin B such as polyethylene (PE) is disposed on the surface of the metal (water) oxide-containing layer, and the heat-fusible resin B is melted by heat and bonded. There is a way. Alternatively, when a metal (water) oxide-containing layer (for example, the metal (water) oxide-containing layer 120 containing the heat-fusible resin A) is produced by a web forming apparatus employing an airlaid method, the metal (water ) By using the other layer 300 of the present invention in the carrier sheet for conveying the web layer to be the oxide-containing layer 120, a laminate of the other layer 300 and the metal (water) oxide-containing layer 120 is formed. And you may obtain the metal (water) oxide containing sheet | seat which has the layer structure which concerns on this invention. Moreover, you may join each layer of the metal (water) oxide containing sheet produced separately by embossing or heat seal processing. Also, a method of providing an adhesive layer (adhesive layer) with a hot melt adhesive such as a thermoplastic resin on at least one of the joining surfaces of the respective layers of the metal (water) oxide-containing sheet, and joining the layers by hot melt processing There are also. In order to prevent contact and dissolution of metal (water) oxide with water during production, in the present invention, these laminations are performed by a dry method.

(Method for producing metal oxide and / or metal hydroxide-containing sheet employing airlaid method)
The method for producing a metal (water) oxide-containing sheet according to this embodiment that employs the airlaid method optionally includes a defibrating step, a mixing step, a web forming step, and a binding step.

(Defibration process)
The defibrating step is a step of defibrating a material in the form of a shortcut fiber to obtain a defibrated shortcut fiber by airflow.

  In the defibrating method using the air flow of the shortcut fiber, an air flow is formed by a blower or the like, the shortcut fiber is supplied to the air flow, and the fiber is defibrated by the stirring effect of the air flow.

  As a defibrating method, it is preferable to defibrate with a swirling air flow. According to the defibrating method using the swirling air flow, the shortcut fiber can be sufficiently defibrated, and the dispersibility of the defibrated shortcut fiber can be further increased when forming the air laid web by the air laid method. .

  As a defibrating method using a swirling air flow, for example, a method of putting a shortcut fiber into the blower and defibrating with the blower can be mentioned. Further, there is a method in which air is sent along a circumferential direction in a cylindrical container by a blower to form a swirling flow, a shortcut fiber is supplied into the swirling flow, and stirring to defibrate.

  The flow rate of the air flow is appropriately selected according to the amount of the shortcut fiber, but is usually in the range of 10 to 150 m / sec.

(Mixing process)
The mixing step is a step of obtaining a web raw material by mixing metal (water) oxide powder (particles) and a material in the form of a defibrating shortcut fiber (if included). At this time, any other material can be mixed at the same time. The shape of any other material may be fibrous or particulate. Examples of optional other materials include auxiliary agents added as necessary, such as heat-fusible resins and effect accelerators. There is no particular limitation on the order of addition of these materials, and these materials can be added by, for example, spraying or the like in a step after the mixing step.

  In mixing, in order to improve the dispersibility of the defibrating shortcut fiber, it is preferable to stir the defibrating shortcut fiber and other materials. However, in order to prevent breakage of the defibration shortcut fiber, it is preferable to apply stirring using an air flow instead of stirring using mechanical shearing force.

  The mixing step may be after the defibrating step or at the same time as the defibrating step. When the mixing step is performed simultaneously with the defibration step, the defibration shortcut fiber and an arbitrary material are mixed using an air flow in the defibration step. In addition, a metal (water) oxide powder (particles) and / or arbitrary particles may be added to and mixed with the web forming line of the defibrating shortcut fiber in the particle dispersion step described later.

(Web forming process)
A web formation process is a process of obtaining an airlaid web from a web raw material by the airlaid method. Here, the airlaid method is a method of forming a web by randomly depositing fibers three-dimensionally using an air flow.

(Particle spraying process)
The particle spraying step is a step of blending a material in the form of powder (particles) into the web raw material by a known method. Either a system in which a material in the form of powder (particles) is mixed with fibers to form a web, or a system in which the material is dispersed on the surface of the web or a carrier sheet may be used.

  In the web forming process in the present embodiment, for example, a web forming apparatus 1 shown in FIG. 2 is used. The web forming apparatus 1 includes a conveyor 10, a gas permeable endless belt 20, a web material supply unit 30, a first carrier sheet supply unit 40, a second carrier sheet supply unit 50, and a suction box 60.

  Here, the conveyor 10 includes a plurality of rollers 11. The air permeable endless belt 20 is mounted on the conveyor 10 and rotates. The web raw material supply means 30 supplies the web raw material to the air permeable endless belt 20 together with the air flow. The first carrier sheet supply means 40 supplies the first carrier sheet 41 toward the gas permeable endless belt 20. The second carrier sheet supply means 50 supplies the second carrier sheet 51 toward the first carrier sheet 41 that has passed through the air-permeable endless belt 20. The suction box 60 sucks the air permeable endless belt 20 from the inside thereof.

  In the web forming apparatus 1, the web raw material supply means 30 is installed above the permeable endless belt 20, the first carrier sheet supply means 40 is installed upstream of the permeable endless belt 20, and the second carrier sheet. The supply means 50 is installed downstream of the air permeable endless belt 20.

  In the web forming process using the web forming apparatus 1, the rollers 10 are rotated in the same direction to drive the conveyor 10 and rotate the air permeable endless belt 20. Further, the first carrier sheet 41 is fed out from the first carrier sheet supply means 40 so as to come into contact with the permeable endless belt 20.

  Next, while sucking the permeable endless belt 20 by the suction box 60, the web material is lowered together with the air flow from the web material supply means 30, and the fiber mixture is dropped onto the first carrier sheet 41 on the permeable endless belt 20. , Deposit. Thereby, the air laid web W is formed.

  Next, the second carrier sheet 51 is supplied from the second carrier sheet supply means 50 on the air laid web W to obtain an air laid web-containing laminated sheet.

(Binding process)
As the binding method, it is preferable to use a thermal bond method from the viewpoint of binding without using water. The binding step by the thermal bond method is a step of heat-treating the air laid web and binding the defibrating shortcut fibers with a heat-fusible resin.

  Examples of the heat treatment of the air laid web include hot air treatment and infrared irradiation treatment, and hot air treatment is preferable from the viewpoint of low cost of the apparatus.

  As the hot air treatment, a method in which the air laid web is heat-treated by bringing it into contact with a through air dryer provided with a rotating drum having air permeability on the peripheral surface (hot air circulation rotary drum method), and the air laid web is passed through a box type dryer. Examples include a method of heat treatment by passing hot air through an air laid web (hot air circulation conveyor oven method).

  When the air laid web is sandwiched between the first carrier sheet and the second carrier sheet as in the present embodiment to form a laminated sheet, the laminated sheet may be subjected to hot air treatment. The first carrier sheet and the second carrier sheet can be peeled from the air laid web after the hot air treatment. The heat treatment temperature may be a temperature at which the heat-fusible resin melts.

  After the binding step, the metal (water) oxide-containing sheet may be compressed through a heating roll for the purpose of finely adjusting the thickness and density of the sheet.

(Function and effect)
In the above production method, the metal (water) oxide powder (particles) can be contained in the metal (water) oxide-containing layer in the form of powder (particles) without using water. Therefore, the possibility of the metal (water) oxide becoming a metal carbonate is prevented by the manufacturing process, and the manufactured sheet can contain the metal (water) oxide as an antibacterial agent and has good antibacterial performance. be able to. The manufactured sheet also has good antiviral performance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example. In the following examples, calcium oxide is used as the metal (water) oxide. That is, a calcium component is used as the metal component.

[Example 1]
<Manufacture of calcium oxide-containing sheet>
Short-cut polyethylene (PE) heat-fusible fiber (melting point: about 135 ° C.) and short-cut polyethylene terephthalate (PET) fiber (fineness: 3.3 dtex, fiber length: 5 mm), respectively, using a swirling jet airflow defibrating device The defibration shortcut fiber was obtained.

  Polyethylene (PE) powder and calcium oxide obtained by baking shells (Okhotsk Calcium F-015, Natural Japan Co., Ltd., average particle size of about 15 μm) are mixed at a ratio (mass ratio) of 80/20 to obtain PE powder. And a mixture of calcium oxide particles.

  Next, a 50/50/5 ratio of polyethylene (PE) heat-fusible fiber in the form of defibration shortcut fiber, PET fiber in the form of defibration shortcut fiber, and a particle mixture of PE powder and calcium oxide ( The web raw material containing PE / PET / calcium oxide was obtained by uniformly mixing by air flow at a mass ratio).

  Next, an airlaid web-containing sheet was formed from the web raw material using the web forming apparatus 1 shown in FIG.

  Specifically, the first carrier sheet 41 was fed out by the first carrier sheet supply means 40 on the air-permeable endless belt 20 that is mounted on the conveyor 10 and travels.

While sucking the air-permeable endless belt 20 by the suction box 60, the web material was dropped and deposited on the first carrier sheet 41 together with the air flow from the web material supply means 30. At that time, the web raw material was supplied so that the basis weight of the shortcut fiber per air-laid web portion was 100 g / m ² . The second carrier sheet 51 was laminated thereon to obtain an airlaid web-containing sheet. For the carrier sheet, a PET spunbonded nonwoven fabric (basis weight 15 g / m ² ) was used for both the first and second.

The obtained air-laid web-containing sheet was passed through a hot air circulating conveyor oven type box type dryer and treated with hot air at 150 ° C. After the treatment, both the first and second carrier sheets were peeled off. A calcium oxide-containing sheet having a basis weight of 105 g / m ² was obtained.

[Example 2]
A calcium oxide-containing sheet was obtained in the same manner as in Example 1 except that calcium oxide was changed to Okhotsk calcium F-2000, manufactured by Natural Japan Co., Ltd., and a particle size of 2000 μm or less.

[Example 3]
Short-cut, core-sheath type heat-fusible composite fiber (PET / PE composite core-sheath fiber, fineness 3.3 dtex, fiber length 5 mm, core part is polyethylene terephthalate (PET) and sheath part is polyethylene (PE), The sheath melting point 130 ° C. was defibrated using a swirling jet airflow defibrating device to obtain a defibrated shortcut fiber (web raw material).

Next, in the web forming apparatus 1 shown in FIG. 2, a first carrier made of tissue (basis weight 14 g / m ² ) made of wood pulp on a gas-permeable endless belt 20 that is mounted on the conveyor 10 and travels. The first carrier sheet 41 was fed out by the sheet supply means 40.

While sucking the air-permeable endless belt 20 by the suction box 60, the PE powder is spread on the first carrier sheet 41 so as to be 5 g / m ^2, and the air flow is supplied from the web raw material supply means 30 thereon. At the same time, the web raw material was dropped and deposited. In that case, the web raw material was supplied so that the basic weight of the shortcut fiber per air laid web part might be 110 g / m < ² >. A second carrier sheet 51 made of tissue (basis weight: 14 g / m ² ) made of wood pulp is laminated thereon by spreading a particle mixture of PE powder and calcium oxide to 7.5 g / m ² thereon. Thus, an airlaid web-containing sheet having a basis weight of 150.5 g / m ² was obtained.

  At this time, as the particle mixture, polyethylene (PE) powder and calcium oxide obtained by baking shells (Okhotsk calcium F-015, natural Japan Co., Ltd., average particle size of about 15 μm) are in a ratio of 80/20. A particle mixture mixed at (mass ratio) was used.

The obtained air-laid web-containing sheet was passed through a hot air circulating conveyor oven type box type dryer and subjected to hot air treatment at 150 ° C. to obtain a calcium oxide-containing sheet having a basis weight of 150.5 g / m ² . After the hot air treatment, the first and second carrier sheets were left as they were without peeling off.

[Example 4]
A calcium oxide-containing sheet was obtained in the same manner as in Example 3 except that calcium oxide was changed to Okhotsk calcium F-2000, manufactured by Natural Japan Co., Ltd., and a particle size of 2000 μm or less.

[Example 5]
A web raw material containing a particle mixture by pre-mixing a defibration shortcut fiber, a particle mixture of PE powder and calcium oxide, and then this is applied onto the PE powder sprayed on the first carrier sheet 41, Along with the air flow from the web supply means 30, it was dropped and deposited. At that time, a basis weight of 137 g / m ² of shortcut fibers per airlaid web portion, as particle mixture is 75 g / m ^2, mixing the web material and particle mixture, was fed a web material containing particle mixture. On top of that, PE powder was sprayed at 5 g / m ² . At this time, as the particle mixture, polyethylene (PE) powder and calcium oxide obtained by baking shells (Okhotsk calcium F-015, manufactured by Natural Japan Co., Ltd., average particle size of about 15 μm) are in a ratio of 20/10. A particle mixture mixed at (mass ratio) was used. Other than that was carried out similarly to Example 3, and obtained the calcium oxide containing sheet | seat of basic weight 250g / m < ² >.

[Example 6]
A calcium oxide-containing sheet was obtained in the same manner as in Example 5 except that calcium oxide was changed to Okhotsk calcium F-2000, manufactured by Natural Japan Co., Ltd., and a particle size of 2000 μm or less.

[Example 7]
50/50/35 ratio (mass ratio) of polyethylene (PE) heat-fusible fiber in the form of defibration shortcut fiber, PET fiber in the form of defibration shortcut fiber, and a particle mixture of PE powder and calcium oxide ) To obtain a web raw material containing PE / PET / calcium oxide and obtain an airlaid web-containing sheet having a basis weight of 135 g / m ^2. Similarly, a calcium oxide-containing sheet having a basis weight of 135 g / m ² was obtained.

[Example 8]
<Manufacture of calcium hydroxide-containing sheet>
PE powder obtained by mixing polyethylene (PE) powder and calcium hydroxide obtained by baking shells (Okhotsk calcium OH-I, manufactured by Natural Japan Co., Ltd.) at a ratio (mass ratio) of 80/20; A calcium hydroxide-containing sheet was obtained in the same manner as in Example 1 except that the calcium hydroxide particle mixture was used.

[Example 9]
A calcium hydroxide-containing sheet was obtained in the same manner as in Example 8, except that the calcium hydroxide was Okhotsk calcium OH manufactured by Natural Japan Corporation.

[Example 10]
Instead of PET / PE composite core-sheath fiber, heat-fusible composite fiber (PP / PE composite core-sheath fiber, fineness 1.7 dtex, fiber whose core part is polypropylene (PP) and whose sheath part is polyethylene (PE)) A calcium oxide-containing sheet was obtained in the same manner as in Example 3 except that a length of 5 mm and a sheath melting point of 130 ° C. were used.

[Example 11]
When PET spunbond nonwoven fabric (basis weight 15 g / m ² ) is used for the first carrier sheet and the second carrier sheet, and the defibrating shortcut fiber (web raw material) is dropped and deposited from the web raw material supply means 30 together with the air flow. the basis weight of the shortcut fiber airlaid web portions, except that so as to be 107.5 g / m ^2, in the same manner as in example 3 to yield calcium oxide containing sheet having a basis weight of 150 g / m ^2.

[Example 12]
A calcium oxide-containing sheet was obtained in the same manner as in Example 11 except that calcium oxide was changed to Okhotsk calcium F-2000, manufactured by Natural Japan Co., Ltd., and a particle size of 2000 μm or less.

[Example 13]
A PET spunbonded nonwoven fabric (basis weight 15 g / m ² ) is used for the first carrier sheet and the second carrier sheet, and a defibration shortcut fiber, a particle mixture of PE powder and calcium oxide are mixed in advance to form particles The web raw material containing the mixture was then dropped and deposited from the web supply means 30 with an air stream. At that time, the web raw material and the particle mixture were mixed so that the basis weight of the shortcut fiber per air-laid web portion was 140 g / m ² and the particle mixture was 75 g / m ^2, and the web raw material containing the particle mixture was supplied. On top of that, PE powder was sprayed at 5 g / m ² . Other than that was carried out similarly to Example 3, and obtained the calcium oxide containing sheet | seat of basic weight 250g / m < ² >.

[Example 14]
When the web raw material containing the particle mixture is dropped and deposited together with the air flow from the web raw material supply means 30, the web is adjusted so that the basis weight of the shortcut fiber per air-laid web portion is 65 g / m ² and the particle mixture is 150 g / m ^2. The raw material and the particle mixture were mixed and the web raw material was supplied. Otherwise in the same manner as in Example 13, a calcium oxide-containing sheet having a basis weight of 250 g / m ² was obtained.

[Example 15]
A calcium oxide-containing sheet was obtained in the same manner as in Example 13 except that calcium oxide was changed to Okhotsk calcium F-2000, manufactured by Natural Japan Co., Ltd., and a particle size of 2000 μm or less.

[Example 16]
A calcium oxide-containing sheet was obtained in the same manner as in Example 14 except that calcium oxide was changed to Okhotsk calcium F-2000, manufactured by Natural Japan Co., Ltd., and a particle size of 2000 μm or less.

[Example 17]
Defibrinated shortcut fiber (web raw material): fluff pulp defibrated fiber and shortcut heat-fusible composite fiber (PET / PE composite core-sheath fiber, fineness 3.3 dtex, fiber length 5 mm, sheath melting point 130 ° C.) A calcium oxide-containing sheet having a basis weight of 150 g / m ² was obtained in the same manner as in Example 11, except that a fiber obtained by defibration was mixed at 70/30.

[Example 18]
When the defibrated shortcut fiber (web raw material) is dropped and deposited from the web supply means 30 together with the air flow, the web raw material is supplied so that the basis weight of the shortcut fiber per air laid web portion is 60 g / m ^2. A calcium oxide-containing sheet having a basis weight of 100 g / m ² was obtained in the same manner as in Example 17 except that a particle mixture of PE powder and calcium oxide was supplied to 5 g / m ² .

[Example 19]
When the defibrating shortcut fiber (web raw material) is dropped and deposited from the web supply means 30 together with the air flow, the web raw material is supplied so that the basis weight of the shortcut fiber per air-laid web portion is 40 g / m ^2. A powder mixture of PE powder and calcium oxide was supplied to 75 g / m ² . Otherwise in the same manner as in Example 17, a calcium oxide-containing sheet having a basis weight of 150 g / m ² was obtained.

[Example 20]
A tissue (basis weight: 14 g / m ² ) was used as the first carrier sheet. When the web raw material was dropped and deposited together with the air flow from the web raw material supply means 30, the web raw material was supplied so that the basis weight of the shortcut fiber per air-laid web portion was 84 g / m ² . A dry nonwoven fabric (basis weight 40 g / m ² , KS-40, manufactured by Oji Kinocross Co., Ltd.) was used as the second carrier sheet. A particle mixture of PE powder and calcium hydroxide obtained by mixing polyethylene (PE) powder and calcium hydroxide (Okhotsk calcium OH, manufactured by Natural Japan Co., Ltd.) at a ratio (mass ratio) of 80/20 as a particle mixture. Was used. Otherwise in the same manner as in Example 17, a calcium hydroxide-containing sheet having a basis weight of 150.5 g / m ² was obtained.

[Example 21]
When the web raw material is dropped and deposited together with the air flow from the web raw material supply means 30, the web raw material and the particle mixture are adjusted so that the basis weight of the shortcut fiber per air laid web portion is 41 g / m ² and the particle mixture is 100 g / m ² . And the web raw material was supplied. Otherwise in the same manner as in Example 20, a calcium hydroxide-containing sheet having a basis weight of 200 g / m ² was obtained.

[Example 22]
When the web raw material is dropped and deposited from the web raw material supply means 30 together with the air flow, the basis weight of the shortcut fiber per air laid web portion is 77.5 g / m ^2, and the second carrier sheet is made of tissue (basis weight 14 g / m ²⁾ and was a polyethylene Fi Mul on the second carrier sheet (basis weight 26 g / m ^2, except that stuck in Yamatogawa polymeric) a hot-melt resin (5 g / m ^2), example 17 In the same manner as above, a calcium oxide-containing sheet having a basis weight of 150 g / m ² was obtained.

[Example 23]
When the first carrier sheet is a dry nonwoven fabric (basis weight 40 g / m ² , KS-40, manufactured by Oji Kinocross Co., Ltd.) and the web raw material is dropped and deposited together with the air flow from the web raw material supply means 30, except that the basis weight of the shortcut fiber and 52.5 g / m ^2, the same procedure as in example 22, to give a calcium oxide-containing sheet having a basis weight of 150 g / m ^2.

[Example 24]
When the first carrier sheet is a rayon spun lace (basis weight 28 g / m ² , # 7128, manufactured by Shinwa Co., Ltd.) and the web raw material is dropped and deposited from the web raw material supply means 30 together with the air flow, a shortcut per airlaid web portion except that the basis weight of the fiber was 64.5 g / m ^2, the same procedure as in example 22, to give a calcium oxide-containing sheet having a basis weight of 150 g / m ^2.

[Example 25]
When the web raw material is dropped and deposited from the web raw material supply means 30 together with the air flow, the basis weight of the shortcut fiber per air laid web portion is set to 91.5 g / m ^2, and a particle mixture of PE powder and calcium oxide is formed thereon. Was sprayed to 7.5 g / m ^2, and the airlaid web-containing sheet thus obtained was subjected to the same heat treatment as in Example 3 without using the second carrier sheet. Contains calcium oxide with a basis weight of 150 g / m ^{2 in} the same manner as in Example 22 except that fimul (basis weight 26 g / m ² , manufactured by Yamatogawa Polymer) was bonded with a hot melt resin (5 g / m ² ). A sheet was obtained.

[Example 26]
When the web raw material is dropped and deposited together with the air flow from the web raw material supply means 30, the basis weight of the shortcut fiber per air laid web portion is 66.5 g / m ^2, and a particle mixture of PE powder and calcium oxide is further added thereto. The airlaid web-containing sheet obtained by spraying to 5 g / m ² was subjected to the same heat treatment as in Example 3 without using the second carrier sheet, and was directly subjected to polyethylene film ( A calcium oxide-containing airlaid web sheet having a basis weight of 150 g / m ^{2 in} the same manner as in Example 23 except that a basis weight of 26 g / m ² , manufactured by Yamatogawa Polymer) was bonded with a hot melt resin (5 g / m ² ). Got.

[Example 27]
When the web raw material is dropped and deposited together with the air flow from the web raw material supply means 30, the basis weight of the shortcut fiber per air laid web portion is 78.5 g / m ^2, and the obtained air laid web-containing sheet includes The same heat treatment as in Example 3 was carried out without using the carrier sheet of No. ^2, and the particle mixture of PE powder and calcium oxide was sprayed on it as it was so as to be 7.5 g / m ^2, and polyethylene was coated on it. A calcium oxide-containing sheet having a basis weight of 150 g / m ² was obtained in the same manner as in Example 24 except that fimul (26 g / m ² , manufactured by Yamatogawa Polymer) was bonded with a hot melt resin (5 g / m ² ). Obtained.

[Comparative Example 1]
A sheet having a basis weight of 100 g / m ² was obtained in the same manner as in Example 1 except that the particle mixture was not blended.

[Comparative Example 2]
A sheet having a basis weight of 100 g / m ² was obtained in the same manner as in Example 1 except that the particle mixture was not blended. Then, the sheet | seat of the comparative example 2 was obtained by apply | coating 0.6 mass% calcium oxide containing aqueous solution with a spray with respect to the said sheet | seat, and then drying. In addition, the application by the spray is performed such that the application amount of the calcium oxide-containing aqueous solution is 200 g / m ² (that is, the application amount of calcium oxide as a solid content is 1.2 g / m ² ). went. It was confirmed that the sheet of Comparative Example 2 contained CaCO ₃ (metal carbonate).

[Comparative Example 3]
A sheet was obtained in the same manner as in Example 3 except that PE powder was used alone instead of the particle mixture of PE powder and calcium oxide.

[Comparative Example 4]
A sheet was obtained in the same manner as in Comparative Example 2, except that the 0.6 mass% calcium oxide-containing aqueous solution was impregnated (dipped) instead of spray coating. From the weight after drying, it was confirmed that a solid content of 1.5 g / m ² was applied. It was confirmed that the sheet of Comparative Example 4 contained CaCO ₃ (metal carbonate).

[Comparative Example 5]
A sheet was obtained in the same manner as in Example 17 except that PE powder was used alone instead of the PE powder and calcium oxide particle mixture dispersed on the web material.

[Comparative Example 6]
A sheet was obtained in the same manner as in Example 20 except that PE powder was used alone instead of the particle mixture of PE powder and calcium hydroxide dispersed on the web raw material.

[Comparative Example 7]
A sheet was obtained in the same manner as in Example 25 except that PE powder was used alone instead of the particle mixture of PE powder and calcium oxide dispersed on the web raw material.

<Performance evaluation test>
About the metal (water) oxide containing sheet | seat of an Example, and the sheet | seat of a comparative example, the following test was done and performance was evaluated.

(Antimicrobial test)
Bactericidal activity value calculated by applying the properties (antibacterial properties) to suppress the growth of bacteria in accordance with the Japanese Industrial Standards JIS L1902 “Methods for testing antibacterial properties and antibacterial effects of textile products” for various test bacteria. It was evaluated by the size. It shows that antimicrobial property is so high that a bactericidal activity value is large. As test bacteria, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Serratia, O-157, MRSA, Salmonella, and Vibrio parahaemolyticus were used.

Specifically, as shown in the following table, antibacterial properties are ranked in five levels according to the magnitude of the bactericidal activity value, and symbols of ◎, ○, Δ, ×, XX are in descending order of antibacterial properties. I guessed.

  In this example, when the antibacterial property was greater than or equal to ○ (that is, the rank indicated by the symbol ○ or ◎), the sample was evaluated as having good antibacterial properties (bactericidal properties) that can be used as an antibacterial sheet.

(Antiviral test)
The antiviral property was evaluated by the antiviral activity value calculated by applying the international standard ISO18184 “Antiviral Test Method for Textile Products”. It shows that antiviral property is so high that an antiviral activity value is large. As a test virus, feline calicivirus was used as an alternative to norovirus.

Specifically, as shown in the following table, antiviral properties are ranked in three levels according to the magnitude of the antiviral activity value, and symbols ◎, ○, and X are assigned in descending order of antiviral properties. It was.

  In this example, the sample was evaluated as having good antiviral properties that could be used as an antiviral sheet when the antiviral properties were ◯ or higher (that is, the rank indicated by ◯ or ◎).

(Deodorization test)
The deodorizing property was evaluated by a method defined by the SEK mark fiber product certification standard of the Japan Fiber Evaluation Technology Council. As the evaluation gas, acetic acid gas and hydrogen sulfide gas were used. The larger the odor reduction rate, the higher the deodorizing property (gas removal performance).

Specifically, as shown in the table below, the deodorant was ranked in four stages according to the odor reduction rate, and the symbols ◎, ○, Δ, and X were assigned in descending order of deodorant. .

(Mold resistance test)
The mold resistance was evaluated based on the fiber product test (wet method and dry method) of “Must Resistance Test Method” of Japanese Industrial Standard JIS Z2911. In the wet method, the treatment performed under running water for 24 hours was omitted, and JIS Z2911 was applied mutatis mutandis. The dry method was performed in accordance with JIS Z2911.

Specifically, as shown in the following table, the mold resistance was ranked in three stages according to the state of mycelial growth, and symbols ◎, ○, and X were assigned in descending order of mold resistance.

(Food mold resistance test)
Mold resistance to food was evaluated by placing the sample together with the food in a plastic bag with a chuck, leaving it at room temperature, and visually checking for the growth of mold every week. As the food, commercially available rice cake (Iliveli, Maruzen Co., Ltd.) and bread (super-ripe, Shikishima Bread Co., Ltd.) were used. The number of inspections was 3, and only food was put in a plastic bag with a chuck without putting a sample as a blank.

  Evaluation was performed as follows. First, when a little mold was confirmed in one of the three in the blank, a sample in which even a slight mold was observed was evaluated as x. After checking for mold on the blank, the sample was further left for 1 week, and a sample in which slight mold was observed was evaluated as Δ. At this time, the sample in which mold was not observed was further left to stand, and a sample in which mold was observed 4 weeks after the start of the test was evaluated as ◯, and a sample in which mold was not observed was evaluated as ◎. By the way, in the bowl, mold was confirmed in one of three blanks one week after the start of the test, and in bread, mold was deposited in one of three blanks two weeks after the start of the test. confirmed.

Specifically, as shown in the table below, according to the state of mold growth in food, the resistance to food is ranked in four stages, and the order of highest resistance to food is ◎, ○ The symbols △, △, and X were applied.

(Sterilization test)
The sterilization property was evaluated based on the “bacteria disinfection performance test” defined by the Japan Sanitary Materials Industry Association. A wet wiper was prepared by applying 6 times or 10 times the weight of the sample to the sample of Example and Comparative Example and infiltrating the whole over 3 minutes. E. coli was used as a test bacterium.

Specifically, as shown in the following table, sterilization was ranked in two stages according to the sterilization activity value, and symbols ◎ and × were assigned in descending order of sterilization.

(Antimicrobial test of chemicals)
The antibacterial properties of the chemicals were evaluated as follows. First, samples of Examples and Comparative Examples were cut into dimensions of 100 × 150 mm, 6 times the weight of water was infiltrated throughout, left for 3 minutes, and then squeezed to obtain a chemical solution. To 2 ml of this chemical solution, 0.02 ml of a bacterial solution adjusted to about 10 ⁸ viable bacteria / ml was added and allowed to stand for 5 minutes. The chemical solution after standing was used as a test solution, 1 ml of the test solution was inactivated with 9 ml of SCDLP broth medium, and the viable cell count was measured by pour plate culture. The common logarithm of the number of viable bacteria was taken, and the difference of the common logarithm was calculated by subtracting the common logarithm of the number of viable bacteria of the specimen from the common logarithm of the number of viable bacteria of the control (distilled water). As test bacteria, Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa were used.

Specifically, as shown in the table below, the antibacterial properties of chemical solutions are ranked in four levels according to the difference in the common logarithm of viable cell counts or the presence or absence of detection of viable cell counts. The symbols ◎, ○, △, and × were applied in descending order.

<Results of performance evaluation test>
4 to 8 and Table 5 below show the results of performance evaluation tests on the metal (water) oxide-containing sheets of the examples and the sheets of the comparative examples. In each table showing the test results, the symbol “-” indicates that the test was not performed.

Table 5.

  The metal oxide and / or metal hydroxide-containing sheet according to the example of the present invention is more antibacterial (bactericidal), antiviral, deodorant, mold resistant, and food than the sheet of the comparative example. The mold resistance, sterilization and antibacterial properties of the chemicals were all good. Further, the metal oxide and / or metal hydroxide-containing sheet according to Examples 5 to 7 containing a relatively large amount of metal oxide and / or metal hydroxide has good antibacterial properties (bactericidal properties) and In addition to antiviral properties, it had significant to good deodorizing properties.

DESCRIPTION OF SYMBOLS 1 Web forming apparatus 30 Web raw material supply means 41 1st carrier sheet 51 2nd carrier sheet W Airlaid web A Thermally fusible resin B Thermally fusible resin D Metal (water) Oxide F Fiber 100 Metal (water) Oxide-containing layer 110 Metal (water) oxide-containing layer 120 containing fibers Metal (water) oxide-containing layer 200 containing heat-fusible resin A Layer 300 containing heat-fusible resin B Other layers 500 Adhesive layer

Claims (9)

  A nonwoven fabric comprising a layer containing a metal component, wherein the metal component is present as a metal oxide and / or a metal hydroxide. The layer comprises fibers;
The metal oxide and / or metal hydroxide powder is held in voids formed by the fibers,
The nonwoven fabric according to claim 1. The layer includes a heat-fusible resin A,
The metal oxide and / or metal hydroxide powder present in the layer is fixed in a state where a part of the powder is coated with the heat-fusible resin A,
The nonwoven fabric according to claim 1 or 2. The layer adjacent to the layer contains the heat-fusible resin B,
The metal oxide and / or metal hydroxide powder present in the layer is fixed in a state where a part of the powder is coated with the heat-fusible resin B,
The nonwoven fabric in any one of Claims 1-3.   The nonwoven fabric according to any one of claims 1 to 4, which is heat-sealed.   The nonwoven fabric in any one of Claims 1-5 by which the contact bonding layer is provided adjacent to the said layer.   The nonwoven fabric according to any one of claims 1 to 6, which is embossed. The metal oxide and / or metal hydroxide is represented by one or more kinds of MO and / or M (OH) ₂ (wherein M is Mg, Ca, Sr or Ba) and The nonwoven fabric according to any one of claims 1 to 7, which is / or a metal hydroxide.   The nonwoven fabric according to any one of claims 1 to 8, wherein the metal oxide and / or metal hydroxide is calcium oxide and / or calcium hydroxide.