HK1222212A1

HK1222212A1 - Antibacterial nonwoven sheet, liquid-containing sheet, and face mask

Info

Publication number: HK1222212A1
Application number: HK16110259.7A
Authority: HK
Inventors: 大前好信熊谷宗訓清岡純人中山和之; 大前好信; 熊谷宗训; 清冈纯人; 中山和之
Original assignee: 可乐丽股份有限公司
Priority date: 2013-09-27
Filing date: 2014-09-17
Publication date: 2017-06-23
Also published as: KR101906689B1; JPWO2015045982A1; CN105593421A; KR20160055928A; TWI632890B; TW201524448A; WO2015045982A1; JP6480335B2

Abstract

　In the present invention, an antibacterial nonwoven sheet is obtained by interlacing solvent-spun cellulose fibers and antibacterial fibers. In the antibacterial fibers, an antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial microparticles dispersed therein is present in at least a part of the fiber surface, the average particle size of the inorganic antibacterial particles being 0.01-20 µm, and the ethylene content of the antibacterial ethylene-vinyl alcohol copolymer being 10-70 mol%. It is thereby possible to provide an antibacterial nonwoven fabric sheet having excellent anticorrosion/antibacterial properties even in the absence of parabens or the like, having soft hand, having good impregnability and fluid retention when impregnated with various fluid compositions, having the capability of efficiently releasing the fluid compositions due to pressure or the like, and having excellent form stability because of low shrinkage or reduction in firmness due to the impregnation of the fluid compositions.

Description

Antibacterial nonwoven fabric sheet, liquid-containing sheet, and mask

Technical Field

The present invention relates to an antibacterial nonwoven fabric sheet as a base material effective for adsorption and absorption of a fluid composition to the skin, the fluid composition containing a cosmetic composition having functions of wiping, moisturizing, beautifying the skin, and the like, of excreta, sebum, cosmetics, and the like. The present invention also relates to a liquid-containing sheet impregnated with a fluid composition containing a cosmetic component, a medicinal component, and the like and integrated with an antibacterial nonwoven fabric sheet, and particularly to a facial mask having antibacterial properties, which is used by being stuck to the skin.

Background

Conventionally, as a water-containing sheet such as a wet tissue, a disposable wet tissue, or a sheet-like cosmetic material for covering the skin, in which water or an aqueous flowable composition is integrated with a nonwoven fabric sheet, a nonwoven fabric obtained by subjecting a fiber web composed of hydrophilic fibers such as rayon or a mixed cotton of hydrophilic fibers and a thermally fusible composite fiber to a high-pressure water flow treatment, or various nonwoven fabrics obtained by improving the functionality of the nonwoven fabric have been proposed. However, hydrophilic fibers such as rayon have the following problems: problems such as reduction in handling properties and reduction in form stability of liquid retention due to generation of wrinkles caused by reduction in stiffness of the fibers, shrinkage of the fibers, and the like when wet; the moisture is absorbed into the fibers, and the effect of the moisture cannot be effectively utilized. In order to solve the above-mentioned problems, a composite wet sheet has been proposed which contains 50 wt% or more of hydrophobic synthetic short fibers and is formed by laminating and holding a web containing 40 wt% or more of hydrophilic short fibers on both surfaces of a hot-melt-bonded nonwoven fabric in which constituent fibers are bonded to each other by local thermocompression bonding portions (for example, see japanese patent application laid-open No. 2001-336053 (patent document 1)).

However, in the sheet produced by melt-bonding the hot-melt adhesive component as in patent document 1, although the shrinkage during wetting is improved, the whole sheet becomes hard and the followability to the skin is reduced. Further, since the sheet surface is mainly composed of hydrophilic fibers, the impregnated chemical solution enters the fibers and cannot be sufficiently discharged to the wiping object. In addition, as the social demand expands, the function of absorbing various flowable compositions is further required.

In order to solve these problems, for example, as a water-containing sheet having a good feel to the skin and excellent water retention, release properties, and form stability, japanese patent application laid-open No. 2008-261067 (patent document 2) proposes a nonwoven fabric sheet in which solvent-spun cellulose fibers having a fiber length of 30 to 60mm and sheath-core composite fibers are interwoven, the sheath-core composite fibers being composed of a sheath portion and a core portion, the sheath portion being an ethylene-vinyl alcohol copolymer, the core portion being composed of a hydrophobic resin, and the core portion having a diameter of 5 to 15 μm.

In recent years, these nonwoven fabric sheets have been required to have antibacterial properties, and in particular, preservatives and antibacterial agents such as parabens have been used in large amounts. However, it is currently desired to achieve antisepsis and antisepsis without parabens (without using parabens) because of the fact that parabens are limited in use and the possibility of temporary irritation of the parabens as a whole is high, and the possibility of skin problems such as skin roughness and inflammation when they are adhered to the skin.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2001-336053

Patent document 2: japanese patent laid-open No. 2008-261067

Disclosure of Invention

Problems to be solved by the invention

That is, an object to be solved by the present invention is to provide an antibacterial nonwoven fabric sheet which has excellent antiseptic/antibacterial properties even if it does not contain paraben or the like, is soft and has a good feel to the skin, has good impregnation properties and liquid retention properties when impregnated with various fluid compositions, can effectively release the fluid composition by pressure or the like, and has excellent form stability because of reduced stiffness and less shrinkage due to impregnation with the fluid composition. The present invention also provides a liquid-containing sheet which has a good skin feel and is excellent in liquid retention, releasability and form stability of a fluid composition containing water or the like.

Means for solving the problems

The present inventors have made intensive studies in view of the above problems, and have completed the present invention.

That is, the invention of claim 1 provides an antibacterial nonwoven fabric sheet comprising antibacterial fibers and solvent-spun cellulose fibers which are entangled with each other, wherein the antibacterial fibers contain inorganic antibacterial fine particles dispersed therein, and an antibacterial ethylene-vinyl alcohol copolymer having an average particle diameter of 0.01 to 20 μm and an ethylene content of 10 to 70 mol% is present on at least a part of the fiber surface.

The invention of claim 2 is an antibacterial nonwoven fabric sheet characterized in that the antibacterial fiber of the invention of claim 1 and the solvent-spun cellulose fiber have a fiber length of 5 to 60mm and are formed by interlacing these fibers with each other.

The invention 3 is the antibacterial nonwoven fabric sheet according to the invention 1 and/or 2, wherein the antibacterial fiber is a sheath-core composite fiber, the sheath portion is an antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles having an average particle diameter of 0.01 to 20 μm dispersed therein, and the core portion is made of a hydrophobic resin and has a diameter of 5 to 15 μm.

The invention of claim 4 is the antibacterial nonwoven fabric sheet according to claims 1 to 3, characterized in that the surface of the antibacterial nonwoven fabric sheet has irregularities.

The invention of claim 5 is the antibacterial nonwoven fabric sheet of claims 1 to 4, which is characterized by containing 30 to 90 wt% of the antibacterial fiber.

The 6 th aspect of the present invention is the antibacterial nonwoven fabric sheet of the 5 th aspect of the present invention, which is characterized by containing 40 to 90 wt% of the antibacterial fibers, and the young's modulus of the antibacterial fibers is 25cN/dtex or more.

The 7 th aspect of the present invention is a liquid-containing sheet obtained by integrating the antibacterial nonwoven fabric sheet of the 1 st to 6 th aspects of the present invention with a flowable composition.

The 8 th aspect of the present invention is the liquid-containing tablet according to the 7 th aspect of the present invention, wherein the fluid composition contains water.

The 9 th aspect of the present invention is the liquid-containing sheet of the 7 th aspect of the present invention, wherein the flowable composition contains a cosmetic material.

The 10 th aspect of the present invention is the liquid-containing sheet of the 9 th aspect of the present invention, which is a skin care sheet.

The 11 th aspect of the present invention is the liquid-containing sheet according to the 9 th or 10 th aspect of the present invention, wherein the liquid-containing sheet is loaded at a load of 260g/cm with respect to 900 wt% of the flowable composition impregnated by weight of the sheet²When the load of (2) was removed again for 1 minute, the reduction of the compression in the thickness direction was not less than 35% for 5 minutes.

The 12 th invention is a facial mask using the liquid-containing sheet according to the 9 th to 11 th inventions.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention provides an antibacterial nonwoven fabric sheet as a base material effective for adsorbing and absorbing a fluid composition to the skin, the fluid composition containing a cosmetic material having functions of wiping, moisturizing, beautifying the skin such as excreta, sebum, and cosmetics, and also provides a liquid-containing sheet and a facial mask containing the antibacterial nonwoven fabric sheet.

In the invention 1, the antibacterial ethylene-vinyl alcohol copolymer containing the inorganic antibacterial fine particles dispersed therein is present on at least a part of the fiber surface, and the solvent-spun cellulose fiber both have hydrophilicity, and the nonwoven fabric sheet is formed by interlacing 2 types of fibers with each other, and therefore, is soft and has a good feel to the skin. In addition, both fibers in which the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface and solvent-spun cellulose fibers have high impregnation properties of the fluid composition, and the fluid composition such as water can be rapidly impregnated.

The antibacterial ethylene-vinyl alcohol copolymer has a hydrophobic portion, and various fluid compositions can be impregnated by adjusting the ethylene content thereof, adjusting the content of cellulose fibers spun with a solvent and fibers having the antibacterial ethylene-vinyl alcohol copolymer present on at least a part of the fiber surface, and the like.

In addition, solvent-spun cellulose fibers have high liquid retention properties with respect to hydrophilic fluid compositions such as water, aqueous solutions, polar solvents, and emulsions thereof. On the other hand, the liquid retention of the fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface is low. Therefore, the flowable composition in which the antibacterial ethylene-vinyl alcohol copolymer is present in the vicinity of at least a part of the fiber surface is easily exuded to the outside by pressure or the like. Furthermore, the fibers having the antibacterial ethylene-vinyl alcohol copolymer released from the flowable composition present on at least a part of the fiber surface have high impregnation properties, and the flowable composition is further deprived from the solvent-spun cellulose fibers, and therefore, the flowable composition continuously bleeds out at an appropriate rate. The antibacterial nonwoven fabric sheet of the present invention is obtained by interlacing at least a part of fibers in which an antibacterial ethylene-vinyl alcohol copolymer is present on the surface of the fibers with solvent-spun cellulose fibers, and therefore, the movement of the fluid composition can be rapidly performed. This improves the releasability of the impregnated fluid composition, and therefore, the fluid composition can be effectively used.

The antibacterial ethylene-vinyl alcohol copolymer is present in a state in which inorganic antibacterial fine particles having a specific particle diameter are dispersed therein, and therefore, the inorganic antibacterial fine particles can be prevented from falling off from the fibers and/or the nonwoven fabric sheet due to physical external factors such as abrasion, and antibacterial performance can be continuously exhibited.

In the invention of claim 2, the fibers in which the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the surface of the fibers and the solvent-spun cellulose-based fibers have a fiber length of 5 to 60mm, and thus the nonwoven fabric can have a soft skin touch and a feeling of following the skin while ensuring rigidity, appropriate softness and stretchability. In particular, when the nonwoven fabric sheet is produced by interlacing fibers under dry conditions, a bulky nonwoven fabric sheet having excellent impregnation with a fluid composition and excellent cushioning properties can be obtained.

In the case of the invention 3, the sheath-core type composite fiber having the antibacterial ethylene-vinyl alcohol copolymer as the sheath portion and the hydrophobic resin as the core portion is formed, and the diameter of the core portion is set to 5 to 15 μm, whereby the antibacterial nonwoven fabric sheet can be produced which is reduced in shrinkage due to impregnation with water, is less likely to wrinkle, and does not impair liquid retention and handling properties. Further, since the core can be made stiff when used, the core can provide a soft touch feeling, and the skin-friendly cosmetic composition can be improved in the following properties to the skin in applications such as a base material of a cosmetic material which is important to be in close contact with the skin.

In the invention 4, the surface of the antibacterial nonwoven fabric sheet is provided with the irregularities, so that an air layer can be formed between the sheet and the skin when the sheet is in close contact with the skin, and therefore the sheet is less likely to become stuffy. Further, the surface of the antibacterial nonwoven fabric sheet has irregularities, so that the surface area is increased, and the adhesiveness to the skin is improved. In applications such as wet tissues, disposable wet tissues, and liquid-containing sheets using a flowable composition containing a cosmetic material, which is impregnated with the flowable composition and released by pressure, the flowable composition is held in the concave portions, whereby the convex portions that easily contact the skin are dried and the flowable composition can be released well, and the feel of the skin is further improved. Further, the liquid retention effect of the fluid composition can be improved by the recessed portions, and the fluid composition can maintain a wide range of polarities without adjusting the overall polarity by the copolymerization ratio of the antibacterial ethylene-vinyl alcohol copolymer, and the like.

In the invention of claim 5, the antibacterial nonwoven fabric sheet of the present invention contains 30 to 90 wt% of the antibacterial fibers and 70 to 10 wt% of solvent-spun cellulose fibers, and thus the antibacterial nonwoven fabric sheet has a good skin feel, has good liquid retention of a fluid composition having impregnation properties, releasability and hydrophilicity when used after impregnation with the fluid composition, and has an excellent balance among shape stability and the like due to fiber shrinkage and reduced stiffness when not impregnated.

In the invention according to claim 6, the antibacterial nonwoven fabric sheet of the present invention contains 40 to 90 wt% of the antibacterial fiber, and the young's modulus of the antibacterial fiber is 25cN/dtex or more, so that the antibacterial nonwoven fabric sheet has antibacterial properties, is soft, has a good skin feel, can be rapidly impregnated with a fluid composition containing a cosmetic material such as a cosmetic liquid, and can be provided with appropriate stiffness and elasticity.

The 7 th aspect of the present invention is a liquid-containing sheet in which the antibacterial nonwoven fabric sheet of the present invention and the fluid composition are integrated, and therefore, the sheet has good skin feel and the fluid composition has excellent liquid retention, releasability and form stability, and is preferably suitable for use in wet wipes, disposable wet wipes, skin care sheets, facial masks and the like.

The 8 th aspect of the present invention is a liquid-containing sheet (water-containing sheet) containing water in a flowable composition, which has good feel to the skin and excellent water retention, releasability and form stability, and is preferably suitable for the above-mentioned applications.

The invention of claim 9 is a liquid-containing sheet comprising a flowable composition containing a cosmetic material, which is excellent in skin touch feeling, good in the release of the cosmetic material, and excellent in form stability, and therefore can be easily and satisfactorily adhered to the skin.

In the 10 th aspect of the present invention, the use of the liquid-containing sheet makes it possible to produce a skin care sheet excellent in impregnation property and liquid retention property of a fluid composition containing a cosmetic material.

In the 11 th aspect of the present invention, the cosmetic liquid (cosmetic material) is impregnated by its own weight at 900 wt% and the load is 260g/cm²When the load of (2) is removed again for 1 minute, the return to the compression in the thickness direction is 5 minutes to 35% or more, whereby a liquid-containing sheet capable of sufficiently holding the return of the cosmetic liquid of the pressing part can be produced.

In the 12 th aspect of the present invention, by using the liquid-containing sheet, a facial mask which can sufficiently permeate a cosmetic liquid (cosmetic material) into the skin can be produced.

Drawings

FIG. 1 is a schematic view for explaining a measuring method of the reset of the raw material in the example.

FIG. 2 is a schematic view for explaining a method of measuring a liquid-returning material in the examples.

Description of the symbols

1 laser displacement meter, 2, 5. load, 3, 6. sample, 4, 7. measuring table.

Detailed Description

< antimicrobial nonwoven Fabric sheet >

The antibacterial nonwoven fabric sheet of the present invention is a sheet formed by interlacing solvent-spun cellulose fibers with fibers in which an antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface (hereinafter, sometimes referred to as "antibacterial EVOH-containing fibers" or simply as "antibacterial fibers"), and the fibers uniformly mixed are nonwoven-woven by a water-flow holding method or the like, thereby realizing a soft and bulky fiber interlaced body.

The antibacterial fiber used in the present invention has an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles dispersed therein, which is present on at least a part of the surface of the fiber.

The antibacterial ethylene-vinyl alcohol copolymer used in the present invention has a proportion of ethylene units (copolymerization proportion) of 10 to 70 mol%, and the balance is a vinyl alcohol unit alone or a repeating unit of vinyl alcohol and another vinyl monomer. The ethylene unit is preferably 20 to 55 mol%, and more preferably 30 to 50 mol%. When the vinyl alcohol unit and the other vinyl monomer unit are used in combination, the ratio of the vinyl alcohol unit is not particularly limited, but is usually more than the other vinyl monomer unit, and preferably (vinyl alcohol unit): other vinyl monomer unit): 55: 45 to 99.9: 0.1, more preferably 70: 30 to 99.9: 0.1, and particularly preferably 80: 20 to 99.9: 0.1 in terms of molar ratio.

If the ethylene unit content in the ethylene-vinyl alcohol copolymer is less than 10 mol%, the spinnability during fiberization is poor, and single yarn breakage and yarn breakage during spinning are increased, and the flexibility is poor. Further, there is a problem that swelling occurs in water at a low temperature (20 to 60 ℃) and the form is changed.

On the other hand, if the proportion of the ethylene unit exceeds 70 mol%, the proportion of the vinyl alcohol unit, that is, the hydroxyl group is inevitably reduced, so that the hygroscopicity is lowered, and the effect of the inorganic antibacterial fine particles held in the copolymer cannot be sufficiently obtained, which is not preferable.

The ethylene-vinyl alcohol copolymer can be obtained by partially saponifying vinyl acetate of an ethylene/vinyl acetate copolymer, and the saponification degree of a vinyl alcohol unit in the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 90 to 99.99 mol%, more preferably 95 to 99.98 mol%, and particularly preferably 96 to 99.97 mol%. If the saponification degree is too small, not only the physical properties such as strength are reduced, but also the thermal stability is reduced, and the stability is reduced by thermal decomposition and saponification. On the other hand, if the saponification degree is too high, the production of the fiber itself becomes difficult.

The number average molecular weight of the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 5000 to 25000, more preferably 8000 to 20000. The number average molecular weight here is a value measured by GPC method.

The ethylene-vinyl alcohol copolymer is commercially available under the trade name "EVAL" manufactured by, for example, Coli corporation and under the trade name "SOARNOL" manufactured by Nippon synthetic chemical industries, Ltd. Further, an ethylene/vinyl acetate copolymer may be produced from commercially available ethylene and vinyl acetate by radical polymerization or the like, and may be used by saponifying the copolymer.

The type of the inorganic antimicrobial fine particles used in the present invention is not particularly limited, and any inorganic antimicrobial fine particles that do not volatilize, decompose, or deteriorate by heating or the like at the time of melt spinning of fibers and do not decrease in antimicrobial action in a short time can be used.

Examples of the inorganic antibacterial fine particles include: inorganic antibacterial fine particles obtained by encapsulating metal ions having antibacterial action such as silver ions, copper ions, zinc ions, tin ions, etc. in an inorganic carrier, titanium oxide inorganic antibacterial fine particles, etc. may be used in 1 kind or 2 or more kinds.

The inorganic carrier used in the present invention is not particularly limited as long as it contains antibacterial metal ions and can suppress the deterioration of the fibers, and for example, an inorganic carrier having an inclusion lattice can be preferably used as the inorganic carrier. The inclusion lattice means that the inorganic powder having the inclusion lattice has a property of enclosing molecules in a portion having a fine layered or cage-like hollow structure with gaps of the degree of atoms and molecules entering.

As the inorganic carrier having an inclusion lattice, there can be mentioned: zeolites, layered phosphates (zirconium phosphate, titanium phosphate, calcium phosphate, etc.), layered clay minerals, transition metal chalcogenides, graphite, transition metal oxides, layered oxysalts, and the like. These inorganic carriers may be used alone or in combination of two or more.

Among them, zeolites and zirconium phosphates having high ion exchange ability are particularly preferable. Among the inorganic antibacterial fine particles, inorganic antibacterial fine particles in which silver ions are held in the inorganic carrier are particularly preferably used in the present invention.

The average particle diameter of the inorganic antibacterial fine particles contained in the ethylene-vinyl alcohol copolymer used in the present invention is 0.01 to 20 μm, preferably 0.1 to 10 μm, and more preferably 0.3 to 6 μm. If the average particle size of the inorganic antibacterial fine particles is more than 20 μm, it is not preferable because yarn breakage or filter clogging is likely to occur during spinning and the inorganic antibacterial fine particles are likely to fall off from the fibers, and in addition, when a finer fiber is to be obtained, it is necessary to make the inorganic antibacterial fine particles smaller than the fiber diameter, and it is preferable that the ratio of the inorganic antibacterial fine particles/the fiber diameter is 0.8 or less. On the other hand, if the average particle diameter of the inorganic antibacterial fine particles is less than 0.01 μm, the inorganic antibacterial fine particles are not preferably dispersed uniformly in the ethylene-vinyl alcohol copolymer because aggregation and the like are likely to occur during kneading.

The amount of the inorganic antimicrobial fine particles contained in the antimicrobial ethylene-vinyl alcohol copolymer used in the present invention is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and particularly preferably 0.5 to 1.5% by weight, based on the weight of the ethylene-vinyl alcohol copolymer. Although the amount of the inorganic fine particles varies depending on the ion exchange capacity or the adsorption amount of the antibacterial metal ions in the inorganic fine particles, even when the inorganic fine particles (inorganic fine particles retaining antibacterial metal ions) in which the antibacterial metal ions are ion-exchanged or adsorbed at 90% or more of the ion exchange capacity or the metal adsorption capacity are used, it is difficult to impart sufficient antibacterial performance to the fibers, and particularly, it is difficult to obtain antibacterial performance having durability, when the amount of the inorganic fine particles retaining antibacterial metal ions is less than 0.01% by weight. On the other hand, when the amount of the inorganic fine particles holding the antibacterial metal ions exceeds 10% by weight, although the antibacterial performance is sufficient, aggregation of the inorganic antibacterial fine particles is likely to occur in the fiberizing step, and there is a risk of clogging of the filter and the like, which is not preferable.

The ethylene content (E: mol%) of the ethylene-vinyl alcohol copolymer used in the present invention and the proportion (W: weight%) of the inorganic antibacterial fine particles in the ethylene-vinyl alcohol copolymer may have the relationship represented by the following formula.

For example,

1≤(100－E)×W≤90，

preferably, the first and second liquid crystal materials are,

5≤(100－E)×W≤80。

the antibacterial EVOH-containing fiber of the present invention is not particularly limited as long as it has an antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles dispersed in the inside thereof on at least the outer surface, and may be a fiber composed of the antibacterial ethylene-vinyl alcohol copolymer alone or a composite fiber with another thermoplastic polymer.

The other thermoplastic polymer used in the present invention is not particularly limited as long as it can be combined with the antibacterial ethylene-vinyl alcohol copolymer, and a wide variety of polymers can be used depending on the purpose of the fiber. For example, as other thermoplastic polymers, there can be exemplified: thermoplastic polymers such as polyolefin-based resins, polyester-based resins, polyamide-based resins, polyvinyl chloride, polyvinylidene chloride, styrene-based resins, polyvinyl acetate-based resins, acrylic-based resins, polylactic acid-based resins, polycarbonate-based resins, and thermoplastic elastomers. As the other thermoplastic polymer, an ethylene-vinyl alcohol copolymer having no antibacterial property may be used.

Among the other thermoplastic polymers, polyolefin-based resins, polyester-based resins, and polyamide-based resins are preferably used, and more preferably hydrophobic resins such as polyolefin-based resins and polyester-based resins, from the viewpoints of heat resistance, fiber formability, and dimensional stability. This point will be described later.

The polyolefin-based resin is preferably polypropylene, polyethylene, or the like, and these polyolefin-based resins may contain other copolymerizable units.

As the polyester-based resin, preferred is poly C_2-4Aromatic polyester resins such as aromatic alkylene ester resins (e.g., polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), and particularly, polyethylene terephthalate resins such as PET are preferable. The polyethylene terephthalate resin may contain 20 mol% or more of ethylene terephthalate unitsThe following proportions contain units composed of other dicarboxylic acids (e.g., isophthalic acid, naphthalene-2, 6-dicarboxylic acid, phthalic acid, 4' -bibenzoic acid, bis (carboxyphenyl) ethane, sodium 5-sulfoisophthalate, etc.), diols (e.g., diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, cyclohexane-1, 4-dimethanol, polyethylene glycol, polytetramethylene glycol, etc.).

The polyamide-based resin is preferably an aliphatic polyamide such as polyamide 6, polyamide 6-10, polyamide 12 or polyamide 6-12, a copolymer thereof, or a semi-aromatic polyamide synthesized from an aromatic dicarboxylic acid and an aliphatic diamine. These polyamide-based resins may contain other copolymerizable units.

When the antibacterial EVOH-containing fiber of the present invention is a conjugate fiber, the ratio of the ethylene-vinyl alcohol copolymer to the other thermoplastic polymer is preferably 10: 90 to 90: 10 by weight. If the ratio is outside this range, the composition ratio becomes unbalanced, and therefore, there arises a problem such as bending of the discharged yarn after the discharge from the nozzle, and the spinning property becomes unfavorable, which is not preferable. The compounding ratio of the ethylene-vinyl alcohol copolymer to the other thermoplastic polymer is more preferably 30: 70 to 70: 30 in terms of weight ratio.

The composite form of the composite fiber may be an ethylene-ethylene copolymer having inorganic antibacterial fine particles contained in the fiber at least in a part of the outer surface, and examples thereof include: sheath-core type, sea-island type, bonded type, and mixed type thereof. In the case of the sheath-core type, the sheath-core type may be any of a 2-layer sheath-core type and a multilayer sheath-core type having 3 or more layers. In the case of the sea-island type, the shape, number, and dispersion state of the islands can be arbitrarily selected, and a part of the islands can be exposed to the surface of the fiber. In the case of the bonding type, the bonding surface may be in any state of a straight line, an arc shape, or any other random curved shape with respect to a fiber cross section perpendicular to the longitudinal direction of the fiber, and the plurality of bonded portions may be parallel, may be radial, or may have any other shape.

In the composite form, the sheath-core composite fiber is particularly preferred from the viewpoint of antibacterial performance because the ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles is disposed on the entire surface of the fiber. Further, in the case of producing the antibacterial nonwoven fabric sheet of the present invention, if a single fiber of an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles is used, the rigidity is liable to be lowered by liquid absorption (absorption of a flowable composition) and the sheet becomes soft, and in the steps of production, processing, packaging, and the like and use thereof, the sheet is compressed by the influence of liquid absorption, external force applied at the time, and the like, and it is difficult to maintain the space between the fibers, and as a result, it is sometimes difficult to ensure excellent liquid retention and handling properties. In contrast, since the sheath-core type composite fiber is made of the hydrophobic resin in the core portion, the core portion does not absorb liquid and does not change rigidity even if the sheath portion absorbs liquid, and therefore, the desired volume, that is, the void ratio can be maintained even in these processing steps, and the liquid absorption property can be simultaneously secured, and the stiffness of the antimicrobial nonwoven fabric sheet can be maintained even in a wet state, and the feeling when pressed against the skin can be maintained.

That is, in order to ensure a high porosity in the antibacterial nonwoven fabric sheet of the present invention, the antibacterial nonwoven fabric sheet is preferably made of fibers having a high young's modulus (initial tensile resistance strength) and high bending elasticity. In particular, even when the antibacterial nonwoven fabric sheet is in a state of having absorbed liquid in these processing steps, it is preferable that the fibers to be formed are made of a highly elastic resin in order to ensure high fiber elasticity. The higher the young's modulus, the more the porosity of the nonwoven fabric can be maintained, so that the liquid retention property can be maintained and the handling property can be improved.

In the antibacterial nonwoven fabric sheet of the present invention, when the content of the antibacterial EVOH-containing fiber described later is 40 to 90 wt%, the young's modulus of the antibacterial EVOH-containing fiber is preferably 25cN/dtex or more. In particular, the Young's modulus of the antibacterial EVOH-containing fiber is more preferably 25 to 90cN/dtex, still more preferably 30 to 70cN/dtex, and particularly preferably 35 to 60 cN/dtex. If the young's modulus of the antibacterial EVOH-containing fiber is too low, the stiffness and elasticity of the antibacterial nonwoven sheet obtained cannot be improved. The structure of the antibacterial EVOH-containing fiber is not particularly limited as long as it has the young's modulus, and may be a single fiber (single-phase fiber) of an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles, and is preferably a sheath-core composite fiber from the viewpoint of easy compatibility of elasticity, liquid retention, and liquid release.

When the antibacterial EVOH-containing fiber used in the present invention is a sheath-core type composite fiber, the sheath portion is preferably made of a hydrophilic resin in order to ensure wettability and liquid retention. When a fluid composition containing a cosmetic material (cosmetic liquid) or the like is applied to the antibacterial nonwoven fabric sheet, the sheath portion made of the hydrophilic resin plays an important role in absorbing the fluid composition into the antibacterial nonwoven fabric sheet, and when a large amount of the cosmetic material absorbed in the antibacterial nonwoven fabric sheet is used at a time, it plays a role in retaining the liquid during handling without dropping.

The resin having a higher young's modulus than the combination of the ethylene-vinyl alcohol copolymer and the ethylene-vinyl alcohol copolymer is excellent in spinnability, and the polyester resin is considered to be most suitable from the viewpoint of higher young's modulus, suppression of shrinkage of the antibacterial nonwoven fabric sheet, and good workability.

In order to maintain the porosity of the antibacterial nonwoven fabric sheet, to increase the liquid retention amount, to make the nonwoven fabric stiff, and to improve the handling properties when wet, a sheath-core type composite fiber is preferred, and the core portion preferably has a diameter of 5 to 15 μm. Further preferably, the diameter of the core is 8 to 12 μm. The core portion is preferably made of the above hydrophobic resin, and particularly preferably made of a polyester resin. If the diameter of the core part is less than 5 μm, the stiffness of the fibers is lowered, and as a result, the density of the nonwoven fabric is increased, and the impregnation amount of the fluid composition is lowered, which is not preferable. Further, the nonwoven fabric may have reduced stiffness, and in particular, may have reduced extensibility and wearability in a state of being impregnated with the fluid composition. On the other hand, when the diameter of the core portion exceeds 15 μm, the stiffness of the fibers becomes too large, and therefore, particularly in a liquid-containing sheet (described later) used for covering a face portion and impregnated with a fluid composition containing a cosmetic material, the following property to the face portion may be lowered, and the nonwoven fabric density is lowered due to the large stiffness of the fibers, so that the distance between the fibers in the nonwoven fabric becomes too long, and the cosmetic material cannot be held between the fibers, and the liquid is easily released unnecessarily.

The cross-sectional shape of the antibacterial EVOH-containing fiber of the present invention may be any shape, and may be a circular shape or a deformed shape. In the case of the irregular cross section, for example, any shape such as a flat shape, an oval shape, a triangular shape, a quadrangular shape, a pentagonal shape, a hexagonal shape, a heptagonal shape, an octagonal shape, a polygonal shape such as a T-shape, an H-shape, a V-shape, a dog bone shape (I-shape), a 3-8 petal shape, and the like may be formed, and these hollow cross sections may be formed.

The fineness of the antibacterial EVOH-containing fiber to be used in the present invention can be selected from, for example, 0.01 to 100dtex, preferably 0.5 to 30dtex, and more preferably 1.0 to 10dtex, depending on the application. When the fineness of the antibacterial EVOH-containing fibers is less than 0.01dtex, the inorganic antibacterial fine particles are liable to fall off from the fibers, and when the fineness of the antibacterial EVOH-containing fibers exceeds 100dtex, not only the performance of the antibacterial agent present in the resin is not sufficiently exhibited, but also the stiffness of the fibers is excessively high, so that the liquid-containing sheet used for coating the face portion impregnated with the cosmetic-containing fluid composition, particularly a face pack (described later), may have poor follow-up properties to the face portion, and the density of the nonwoven fabric is lowered due to the large stiffness of the fibers, so that the distance between the fibers in the nonwoven fabric becomes excessively long, and the cosmetic cannot be held between the fibers, and the liquid is liable to be released unnecessarily, which is not preferable.

The antibacterial EVOH-containing fiber used in the present invention or the fiber product using the fiber may further contain usual additives such as: stabilizers (heat stabilizers such as copper compounds, ultraviolet absorbers, light stabilizers, antioxidants, etc.), fine particles, colorants, fluorescent brighteners, antistatic agents, flame retardants, deodorants, plasticizers, lubricants, crystallization rate retarders, etc. These additives may be used alone or in combination of two or more. These additives may be contained in the fibers or may be carried on the surface of the fiber assembly.

The method for producing the antibacterial EVOH-containing fiber used in the present invention is not particularly limited, and for example, in the case of producing a composite fiber composed of two components with a hydrophobic resin, the respective resins may be melt-kneaded in separate extruders, and then the two resins may be introduced into a spinneret, and then the two resins may be discharged from the same spinning nozzle and drawn by a drawing roll.

The antibacterial EVOH-containing fiber used in the present invention is usually drawn and used, and the drawing method may be a 1-step method of drawing between hot rolls when drawing the fiber discharged from a nozzle at the time of spinning with a drawing roll, or a 2-step method of drawing once and then thermally drawing at a low speed in a water bath or a hot air oven.

The antibacterial EVOH-containing fiber is excellent in skin touch and hydrophilicity. However, for example, when an antibacterial nonwoven fabric sheet is produced using 100% of an antibacterial EVOH-containing fiber, the impregnation property is excellent when the sheet is impregnated with an aqueous fluid composition, but the water absorption of the fiber itself is low, so that the liquid absorption rate is slow, and it is difficult to hold the liquid-retained aqueous fluid composition in the sheet space. Therefore, when the sheet is used after impregnation with an aqueous fluid composition, it takes time to absorb liquid, which reduces the handling efficiency, and a part of the aqueous fluid composition is unnecessarily released from the sheet interior and lost, so that it is very important to combine and interlace solvent-spun cellulose fibers and antibacterial EVOH-containing fibers without using 100% of the antibacterial EVOH-containing fibers in the antibacterial nonwoven sheet of the present invention.

The antibacterial nonwoven fabric sheet of the present invention preferably contains 30 to 90% by weight of an antibacterial EVOH-containing fiber, more preferably 40 to 90% by weight. The lower limit of the content of the antibacterial EVOH-containing fiber is more preferably 50 wt% or more, particularly preferably 60 wt% or more, and the upper limit of the content of the antibacterial EVOH fiber is more preferably 80 wt% or less, and even more preferably 75 wt% or less, particularly preferably 70 wt% or less. The solvent-spun cellulose fiber preferably contains 10 to 70 wt%, more preferably 10 to 60 wt%. The lower limit of the content of the solvent-spun cellulose-based fibers is more preferably 20% by weight or more, and still more preferably 25% by weight or more, and particularly preferably 30% by weight or more, and the upper limit of the content of the solvent-spun cellulose-based fibers is more preferably 50% by weight or less, and particularly preferably 40% by weight or less.

If the content of the antibacterial EVOH-containing fiber is less than 30 wt%, the unique dry and astringent feeling of the cellulose-based fiber is enhanced particularly in the wet state, and the smoothness of the antibacterial nonwoven fabric sheet obtained is lowered. Further, if the content of the antibacterial EVOH-containing fiber is less than 30 wt%, the rate of absorption of the fluid composition into the fiber increases, and effective use of the skin is hindered. On the other hand, if the content of the antibacterial EVOH-containing fiber exceeds 90 wt%, impregnation ability, particularly impregnation speed, is lowered, and the ability to hold the fluid composition is lowered, so that the fluid composition is unnecessarily released from the inside of the sheet, runs off, and is wasted, which is not preferable.

The solvent-spun cellulose fiber used in the present invention means: unlike so-called regenerated cellulose fibers, such as conventional viscose rayon and cuprammonium rayon, in which cellulose is temporarily chemically converted to a cellulose derivative and then recovered to cellulose, cellulose is precipitated from a solution obtained by dissolving cellulose in a solvent without chemically changing the cellulose (purified cellulose fibers).

A preferable example of the solvent-spun cellulose fiber used in the present invention is a cellulose fiber produced by a method in which a spinning dope obtained by dissolving cellulose in an aminated oxygen is dry-wet spun in water, and the fiber obtained by precipitating cellulose is further drawn. A typical example of such fibers is Lyocell (Lyocell), which is sold under the trade name "TENCEL" (registered trademark) by Lenzing corporation of austria. Such a fiber is very preferable because it has a circular or elliptical cross-sectional shape, unlike regenerated cellulose fibers which are widely used, and therefore, when used in humans, the fiber is less likely to cause damage to the skin. In addition, since viscose rayon fibers have a reduced fiber strength under wet conditions, a sheet obtained by mixing the fibers is deformed in a wet state in which the sheet is impregnated with a fluid composition containing a chemical solution or the like, and the workability is reduced. Further, for example, when the liquid-containing sheet (described later) is used in which fibers and a fluid composition containing a cosmetic are integrated, the wearability is poor. In contrast, the antibacterial nonwoven fabric sheet of the present invention is very preferable because it hardly undergoes a decrease in strength even under wet conditions, and therefore does not undergo a morphological change and is excellent in wearability.

In general, the solvent-spun cellulose-based fibers are often fibrillated by beating with a beater, a refiner, a high-speed disintegrator, or the like, but in the present invention, it is preferable to use substantially non-fibrillated solvent-spun cellulose-based fibers in order to prevent fine fibers from adhering to the face due to fibrillation of the fibers.

The single fiber fineness of the solvent-spun cellulose fiber is not particularly limited, and is particularly preferably 1 to 3dtex, more preferably 1 to 2dtex, and further preferably 1.3 to 1.7dtex, because the feeling of softness when the fiber is in contact with the skin is often preferable. When the single fiber fineness exceeds 3dtex, the feeling to the skin may be deteriorated, and the liquid absorption and liquid retention properties of the fluid composition containing a cosmetic may be deteriorated. On the other hand, when the amount is less than 1dtex, the nonwoven fabric is undesirably increased in density and the gaps between fibers are reduced, so that the impregnation amount of the fluid composition is reduced.

Further, the mixing ratio of the antibacterial EVOH-containing fibers and the solvent-spun cellulose-based fibers and the resin polarity of the antibacterial ethylene-vinyl alcohol copolymer allow the polarity of the entire antibacterial nonwoven sheet to be adjusted, the impregnation amount of the fluid composition and the skin feel to be determined, and the skin feel to be adjusted without affecting the impregnation amount of the fluid composition by adjusting the thickness of each fiber. That is, if the cellulose-based fibers are solvent-spun to be thicker, the number of cellulose-based fibers decreases and the surface area decreases for the same weight per unit area, thereby decreasing the hydrophilicity of the antibacterial nonwoven fabric sheet to be produced. On the other hand, if the cellulose-based fibers are thinned, the hydrophilicity of the antimicrobial nonwoven fabric sheet increases. In addition, the cellulose-based fiber also becomes coarse as it becomes thicker with respect to the skin touch.

For example, when the mixing ratio of the antibacterial EVOH-containing fibers to the solvent-spun cellulose-based fibers is 60: 40, and the ethylene component of the antibacterial ethylene-vinyl alcohol copolymer is 50 mol% and the degree of saponification is 98%, the ratio of the thickness of the antibacterial EVOH-containing fibers to the thickness of the solvent-spun cellulose-based fibers is preferably in the range of 0.3 to 3.0, more preferably in the range of 0.3 to 2.0, in the application of a liquid-containing sheet (particularly a face film) (described later) in which an antibacterial nonwoven fabric sheet used for covering a surface portion or the like is integrated with a fluid composition containing a cosmetic material.

The fiber length of the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber is preferably in the range of 5 to 60 mm. If the fiber length of the antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber is too long, it is difficult to uniformly interlace the fibers with each other, and particularly if the interlacing of the two fibers is insufficient, the antibacterial nonwoven sheet has insufficient uniformity, and not only the feel to the skin is deteriorated, but also the efficiency of liquid absorption and release of the fluid composition is lowered, which is not preferable. Further, if the fiber length of the antibacterial EVOH-containing fiber or the solvent-spun cellulose-based fiber is too short, not only the fiber is likely to fall off from the antibacterial nonwoven fabric sheet, but also the flexibility and stretchability are reduced, which is not preferable. From the above viewpoint, the antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber used in the present invention preferably have a fiber length of 5 to 60mm, more preferably 10 to 50 mm. The ratio of the fiber length of the solvent-spun cellulose fiber to the antibacterial EVOH-containing fiber is preferably 0.5 to 2, and more preferably 0.8 to 1.5.

In the present invention, the antibacterial nonwoven fabric sheet of interest can be produced by uniformly mixing the antibacterial EVOH-containing fibers and solvent-spun cellulose fibers, then forming a web, and interlacing the web by hydroentanglement, and the web can be formed by a direct method such as a spunbond method or a melt-blown method, a dry method or a wet method such as a carding method using short fibers, an air-laid (airlay) method, or the like. Among them, from the viewpoint of easier mixing of fibers and securing a space for impregnation with the fluid composition, the dry method is most suitable as the method for producing the antibacterial nonwoven fabric sheet of the present invention. As the short fiber web in this case, an unoriented web, a semi-unoriented web, a parallel web, a cross-lapped web, or the like is preferably used. In forming the fiber web, it is preferable to blend the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber at the above-described blending ratio.

In the antibacterial nonwoven fabric sheet of the present invention, the surface preferably has irregularities, and the irregularities may be formed on the surface by interlacing the constituent fibers by subjecting the obtained fiber web to water-flow cohesion treatment as described above. The unevenness is formed on the surface of the antibacterial nonwoven fabric sheet by production under specific conditions during water holding. This makes it possible to hold the fluid composition in the recessed portions on the surface of the antibacterial nonwoven fabric sheet while maintaining the voids in the nonwoven fabric sheet, and thus to hold a large amount of cosmetic material on the surface without thickening the antibacterial nonwoven fabric sheet. In this case, the entire fiber absorbs water from the water flow, and a part of the solvent-spun cellulose-based fiber which easily moves with the force of the water flow is formed to be stretched in the direction of the water flow, that is, to be stretched in the direction of the height of the convex portion, and at the same time, an antibacterial EVOH-containing fiber which exhibits hydrophilicity and lipophilicity is formed, and particularly, in the case of a sheath-core composite fiber with a hydrophobic resin, the fiber is hardly moved in the direction of the height of the convex portion due to the hydrophobicity and rigidity of the core portion, and most of the fiber is formed to be stretched in the direction of the nonwoven fabric surface. Since these fibers are basically mixed with each other, the antibacterial nonwoven fabric sheet of the present invention has both hydrophilicity and lipophilicity, and therefore both hydrophilicity and lipophilicity of the fluid composition can be maintained in the uneven shape. In addition, since the fluid composition retained therein does not enter the tissue of the nonwoven fabric, the liquid-containing sheet in which the antimicrobial nonwoven fabric sheet of the present invention and the fluid composition containing a cosmetic material are integrated can be transferred to the skin very easily by the presence of the cosmetic material on the surface of the antimicrobial nonwoven fabric sheet, and exhibits extremely good transferability to the skin. In addition, even when the cosmetic material is present on the surface of the antibacterial nonwoven fabric sheet, since the fiber itself has both hydrophilic and lipophilic properties, the cosmetic material does not run off.

The irregularities preferably have a height difference between the recesses and the projections in the range of 0.1 to 0.4mm and are continuous in a predetermined direction at a pitch of 0.04 to 0.5 mm. If the height difference is less than 0.1mm, the nonwoven fabric surface becomes too smooth, and the fluid composition cannot be retained by the surface irregularities, so that impregnation property is lowered, which is not preferable. Further, the whole face is in contact with the skin in some cases, and therefore, the feeling of stuffiness and stickiness are generated when the mask is applied, which is not preferable. When the height difference exceeds 0.4mm, the portion holding the fluid composition becomes large, and therefore the liquid retention amount increases, but the ratio of solvent-spun cellulosic fibers in the vicinity of the top end of the projection tends to increase, and the liquid absorption behavior of this portion depends on the properties of the solvent-spun cellulosic fibers, and therefore the possibility of the liquid retention amount increasing but the liquid release property decreasing increases. Further, the smoothness of the surface is not preferable because it reduces the feeling of application by lowering the feeling of touch to the skin. On the other hand, if the pitch is less than 0.04mm, the concave portion becomes too narrow to allow the entry of the flowable composition containing the cosmetic, and it is difficult to effectively hold the flowable composition by the surface irregularities, which is not preferable. Further, if the pitch exceeds 0.5mm, the distance between fibers constituting the portion of the convex portion becomes too wide, and it becomes difficult to hold the fluid composition entering the concave portion, which is not preferable.

The unevenness on the surface of the nonwoven fabric may be treated by a sheet formed by entangling fibers with each other by preliminarily entangling the fiber web with a water stream. The pretreated aqueous stream cohesion may be preferably listed by: a method for treating a fiber web one or more times with a water flow of 1 to 6MPa water pressure, preferably 2 to 4MPa, from a water spray plate, which is a nozzle plate having nozzles arranged in 1 to 3 rows and having a nozzle diameter of 0.08 to 0.2mm and a nozzle pitch of 0.4 to 1mm, on a support of a metal perforated plate or a fabric structure.

The unevenness on the surface of the nonwoven fabric is preferably formed by water-jet treatment on the woven fabric structure of the fibers in at least the final treatment of the water-jet cohesion treatment. The support body of the fabric structure is preferably formed of monofilaments having a warp and a weft with a diameter of 0.01 to 1mm, more preferably 0.02 to 0.5mm, and the thickness of the fabric structure is 0.1 to 1 mm. If the monofilament diameter exceeds 1mm, the fibers move in the vicinity of the portion where the warp yarn exists above the weft yarn, and the surface of the nonwoven fabric is perforated to deteriorate the surface smoothness, which is not preferable. Further, a columnar water flow may be jetted from a nozzle having nozzles arranged at an interval of 0.4 to 1mm above the fabric structure to the fiber web after the fiber web is entangled to some extent in the preceding stage, the nozzle having a hole diameter of 0.05 to 0.3mm, preferably 0.08 to 0.2mm, and the columnar water flow having a water pressure of 6 to 15MPa, preferably 8 to 10 MPa.

By such a water-entangling treatment, an antibacterial nonwoven fabric sheet having irregularities suitable for holding a flowable composition on the surface can be obtained.

As described later, the antibacterial nonwoven fabric sheet of the present invention can be suitably used by being integrated with water to prepare a water-containing sheet and being integrated with a fluid composition containing a cosmetic material to prepare a liquid-containing sheet. When the antibacterial nonwoven fabric sheet of the present invention is used as a liquid-containing sheet, the impregnation property of the fluid composition containing the cosmetic material can be improved by adjusting the copolymerization composition of the ethylene-vinyl alcohol copolymer used in the present invention according to the polarity of the fluid composition.

That is, in the case of using the lipophilic fluid composition, it is preferable to use a copolymer having a high ethylene content, and in the case of using the hydrophilic fluid composition, it is preferable to use a copolymer having a low ethylene content. Similarly, the degree of saponification can be used to adjust the hydrophilicity. Further, not only the degree of saponification but also the affinity with various fluids can be adjusted depending on the type of unsaponifiable ester, the modification of the functional group of the hydroxyl group, and the like.

The impregnation property can also be improved by adjusting the proportion of the solvent-spun cellulose fibers. That is, in the case of using a lipophilic fluid composition, it is preferable to reduce the proportion of the solvent-spun cellulose-based fibers, and in the case of using a hydrophilic fluid composition, it is preferable to increase the proportion of the solvent-spun cellulose-based fibers.

The actual impregnation property varies depending on the viscosity of the fluid composition, and may be adjusted by the copolymerization composition of the ethylene-vinyl alcohol copolymer and/or the ratio of the solvent-spun cellulose-based fibers in consideration of the balance with the texture of the skin, the liquid retention property, and the like.

The antibacterial EVOH-containing fiber having the above properties and the solvent-spun cellulose fiber are uniformly mixed to be a single layer, and a water-entangled nonwoven fabric having a predetermined gap between fibers and a porosity of 80 to 95% is formed, whereby a lightweight fiber web having a high level of balance between hydrophilicity and lipophilicity as a whole and easily absorbing and releasing both an oil component and an aqueous component to the same extent can be obtained.

The antibacterial nonwoven fabric sheet of the present invention can follow a surface having a complicated shape by its flexibility, particularly in a wet state, which is related to the stress when the nonwoven fabric is elongated at 50% in a wet state in at least one direction, and the value is preferably 500g/50mm or less. More preferably 400g/50mm or less, and still more preferably 300g/50mm or less. If this value exceeds 500g/50mm, the base material is less likely to follow the irregularities of the face, and the cosmetic is less likely to be supplied to the entire face, which is not preferable. On the other hand, for example, in the case of a nonwoven fabric sheet or the like in a state of not being entangled or in a state of insufficient interlacing, when the stress at 50% elongation in wet state is less than 100g/50mm, the workability is not good at the time of producing a nonwoven fabric, and the problem of deterioration of the workability occurs, and therefore, the antimicrobial nonwoven fabric sheet is not suitable for the present invention.

The weight per unit area of the antibacterial nonwoven fabric sheet suitable for the present invention is preferably 30 to 100g/m²The range of (A) is preferably 40 to 70g/m from the viewpoints of adhesion to the skin and liquid absorption²The range of (1). The weight per unit area is less than 30g/m²In the case of the above-mentioned case, the amount of the liquid-absorbent composition which can be absorbed and held between the fibers is extremely small because the absolute fiber amount is decreased, which is not preferable. In addition, it exceeds 100g/m²In the case where the amount of the fibers is too large, the thickness of the antimicrobial nonwoven fabric sheet becomes too large, and the followability is lowered, which is not preferable.

The apparent density of the antibacterial nonwoven fabric sheet of the present invention is not particularly limited, but is preferably 0.03 to 0.20g/cm³More preferably 0.05 to 0.17g/cm³More preferably 0.06 to 0.15g/cm³Particularly preferably 0.08 to 0.12g/cm³. If the apparent density is too low, the liquid holding ability of the antibacterial nonwoven fabric sheet is lowered, and liquid dripping is likely to occur during handling during use. On the other hand, if the apparent density of the antibacterial nonwoven fabric sheet is too high, the liquid retention amount decreases.

The thickness of the antibacterial nonwoven fabric sheet of the present invention is not particularly limited, but is preferably 100 to 3000 μm, more preferably 200 to 2000 μm, even more preferably 300 to 1500 μm, even more preferably 400 to 1200 μm, and particularly preferably 500 to 1000 μm.

In addition, the antibacterial nonwoven fabric sheet of the present invention needs to ensure both the intended liquid absorption property and liquid release property. That is, the antibacterial nonwoven fabric sheet of the present invention is capable of absorbing and adsorbing and retaining liquids having both properties by using fibers having both hydrophilicity and lipophilicity as constituent fibers, and it is considered that in these liquids, the lipophilic component is retained mainly in the antibacterial EVOH-containing fiber portion, the hydrophilic component is retained partly in the antibacterial EVOH-containing fiber and mostly in the solvent-spun cellulose-based fiber. Further, the liquid is held on the fiber surface, and the liquid which cannot be directly held on the fiber surface is held in an amount of more than that, by filling in the fiber voids surrounded by the same kind of fibers (antibacterial EVOH-containing fibers or solvent-spun cellulose-based fibers), it is possible to secure a liquid amount of more than the adsorption amount of the nonwoven fabric-constituting fibers. For convenience of explanation, the porosity is used to clarify the existence of the voids filled with the liquid. The antibacterial nonwoven fabric sheet of the present invention preferably has a void volume of 80 to 95%. More preferably 85 to 93%. When the porosity exceeds 95%, the distance between fibers becomes too wide, and the fluid composition cannot be held by the hydrophilic portion of the fibers, which is not preferable. If the amount is less than 80%, the distance between fibers is too small, and the fluid composition does not enter the nonwoven fabric and the liquid absorption amount is undesirably reduced.

< liquid-containing tablet, mask >

The present invention also provides a liquid-containing sheet and a face mask which are excellent in antiseptic and antibacterial properties even when not containing parabens and the like, are soft and have a good skin feel, and which can be quickly returned even when pressed with a finger in a state in which a fluid composition containing a cosmetic material such as a cosmetic liquid is impregnated. That is, the present inventors have also found that, when an antibacterial EVOH-containing fiber containing a specific antibacterial ethylene-vinyl alcohol copolymer as one component and a solvent-spun cellulose-based fiber are entangled with each other to form an antibacterial nonwoven fabric sheet capable of absorbing a fluid composition, and the antibacterial nonwoven fabric sheet and the fluid composition are integrated to form a liquid-containing sheet, the liquid-containing sheet is subjected to controlled resetting of compression in the thickness direction, and the fluid composition can be rapidly returned to the liquid-containing sheet even by being pressed with a finger in a state in which the fluid composition containing a cosmetic material such as a cosmetic liquid is impregnated with the fluid composition

In the liquid-containing sheet of the present invention, the flowable composition may be water (in this case, referred to as "aqueous sheet") or may contain a cosmetic material. When a flowable composition containing a cosmetic material is used, it can be preferably used for a skin care sheet, particularly preferably used for a mask. That is, the antibacterial nonwoven fabric sheet of the present invention can be used for absorbing a flowable composition, for example, can be used for surface materials such as napkins and diapers, and body fluid absorbing sheets (or skin cleansing sheets) such as diaper liners and wet wipes, and has an excellent balance between liquid retention and release properties and can be easily adhered to the skin, the sheet (liquid-containing sheet) obtained by impregnating the antibacterial nonwoven fabric sheet of the present invention with a fluid composition containing a cosmetic ingredient, a medicinal ingredient, or the like is preferably used for application to the skin, for example, it is preferably used in various skin care sheets such as a face mask, a makeup removing sheet or cleansing sheet, a body cleansing sheet (sweat wiping sheet, oil absorbing sheet, etc.), a cooling sheet, a medicinal or therapeutic sheet (itch stopping sheet, compress, etc.), the use in a mask is particularly preferable because the return of the fluid composition is fast even when the fluid composition is pressed with a finger.

The liquid-containing sheet of the present invention may be a sheet used by impregnating the fluid composition at the time of use, or a sheet used by impregnating the fluid composition in advance (so-called wet sheet).

In the use of the antibacterial nonwoven fabric sheet of the present invention impregnated with the fluid composition, the fluid composition is not particularly limited. Mention may be made of: water, aqueous fluid compositions such as aqueous solutions and aqueous emulsions, organic solvents, solutions mediated by these, and mixtures thereof. In addition, it is also preferableA flowable composition is used which is obtained by dissolving and/or dispersing various solids, liquids, gases, and the like, which are well dissolved or dispersed, in the above flowable composition. The antibacterial nonwoven fabric sheet having excellent functionality can be produced by using a flowable composition in which various active ingredients are dissolved and/or dispersed. The flowable composition may also include a solution or dispersion (cosmetic, emulsion, cosmetic solution, etc.) containing an active ingredient such as a cosmetic ingredient or a pharmaceutically effective (functional) ingredient. Among them, hydrophilic fluid compositions including an aqueous fluid composition, a fluid composition containing a polar organic solvent, and the like are advantageous from the viewpoint of impregnation properties, and are also advantageous from the viewpoint of safety to the human body, and the like. In particular, the aqueous fluid composition is most advantageous from the viewpoint of liquid retention. The polar organic solvent includes various organic solvents having a polar functional group, and the polar functional group includes: hydroxyl, aldehyde, carboxyl, alkoxycarbonyl, ether, carbonyl, amine, nitro, thiol, and the like. Examples of the hydrophilic fluid composition include: water, lower aliphatic alcohol (e.g., C such as ethanol, isopropanol, etc.)_1-6Alkyl alcohols, etc.), alkylene glycols (e.g., ethylene glycol, diethylene glycol, propylene glycol, etc.), and the like. Further, unsaturated higher fatty acids (e.g., oleic acid, oleyl alcohol, etc.), animal and vegetable oils (e.g., jojoba oil, olive oil, coconut oil, camellia oil, macadamia nut oil, avocado oil, corn oil, sesame oil, wheat germ oil, linseed oil, castor oil, squalane, etc.), mineral oils (e.g., liquid paraffin, polybutene, silicone oil, etc.), synthetic oils (e.g., synthetic ester oils, synthetic polyether oils, etc.), and the like are preferably used.

These flowable compositions may be used alone or in combination of two or more. For example, a liquid oil may be used as an additive (oil component) in combination with a hydrophilic solvent such as water or ethanol. In these flowable compositions, water, lower alcohols or mixtures thereof may generally be used, preferably water and/or ethanol, more preferably water alone. For example, when water and a lower alcohol (particularly ethanol) are used in combination, the ratio of water/lower alcohol is 100/0 to 30/70, preferably 100/0 to 50/50, more preferably 100/0 to 70/30, and particularly preferably 99/1 to 80/20.

In the case of the flowable compositions, the additives usually used may be exemplified by: moisturizers or emollients (emolients) (e.g., dipropylene glycol, 1, 3-butylene glycol, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sucrose fatty acid ester, glycerin, sodium hyaluronate, polyoxymethyl glycoside (polyoxymethyl glycoside), polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose ethers (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc.), uv inhibitors, surfactants, astringents, enzymes, cooling agents, bactericides or antibacterial agents, skin softeners (e.g., salicylic acid or its derivatives, lactic acid, urea, etc.), antioxidants (e.g., tocopherol or its derivatives, polyphenols such as anthocyanin, etc.), whitening agents (e.g., ascorbic acid or its derivatives, etc.), skin lightening agents (e.g., vitamin c acid or its derivatives, vitamin c acid, etc.), and the like, Cysteine, placental peptide, ursolic acid, kojic acid, luminols (lucinol), ellagic acid, chamomile extract, etc.), antiperspirants (for example, aluminum compounds, zinc compounds, astringents such as tannic acid, etc.), skin roughness preventing agents (for example, glycyrrhetate, vitamins, etc.), anti-inflammatory agents (for example, allantoin, azulene, glycyrrhizic acid or its salt, glycyrrhetinic acid or its salt, -aminocaproic acid, tranexamic acid, ibuprofen, indomethacin (indomethacin), etc.), blood circulation promoting agents (for example, peony, rosemary, clove, etc.), vitamins (for example, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, vitamin K, etc.), amino acids (for example, tryptophan, cysteine, etc.), cell activating agents (for example, riboflavin, pyridoxine, nicotinic acid, pantothenic acid, alpha-tocopherol, or their derivatives, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, vitamin K, etc.), amino acids (for example, tryptophan, cysteine, etc.), cell activating agents (for example, vitamin A, plant extracts such as saxifrage extract), perfumes (e.g., synthetic perfumes, essential oils, essential oil components, etc.), etc. These additives may be used alone or in combination of two or more.

Among these additives, in the use of skin care sheets, for example, moisturizers, ultraviolet absorbers, surfactants, cooling agents, enzymes, astringents, bactericides, antibacterial agents, and the like are widely used. In particular, in a facial mask (facepack), for example, a moisturizer, an emollient, and the like may be blended in a hydrophilic solvent. The total proportion of the humectant and the emollient is, for example, 0.1 to 50 wt%, preferably 1 to 30 wt%, and more preferably 5 to 20 wt% in the solvent.

The proportion of these additives may be suitably selected depending on the application, and for example, the proportion of water, ethanol or the like is usually 30 to 99% by weight, preferably 40 to 95% by weight, and more preferably 50 to 90% by weight of the total amount of the flowable composition containing the additives.

The impregnation amount of the fluid composition to be used is not particularly limited as long as a predetermined effect can be obtained, and may be appropriately selected according to the purpose of the user, and for example, in the water-containing sheet and the liquid-containing sheet provided by the present invention, the amount is preferably 200 to 1000% by weight based on the weight of the base material, from the viewpoint of cost and performance, and the liquid-containing sheet is formed by integrating the fluid composition containing a cosmetic material and the antibacterial nonwoven fabric sheet.

In the liquid-containing sheet of the present invention comprising the antibacterial nonwoven fabric sheet and the fluid composition containing a cosmetic material, the antibacterial nonwoven fabric sheet is required to have a high liquid-absorbing performance capable of retaining a sufficient amount of the cosmetic material. In the present invention, the liquid-suction speed and the liquid retention rate are used to express this property.

First, the antibacterial nonwoven fabric sheet suitable for the liquid-containing sheet of the present invention is required to have excellent liquid-absorbing performance, and the liquid-absorbing rate is preferably 5 seconds or less. More preferably 3 seconds or less, still more preferably 2 seconds or less, and particularly preferably 1.5 seconds or less. If the liquid absorption rate exceeds 5 seconds, impregnation of the fluid composition containing a cosmetic material becomes difficult, and particularly, when the fluid composition containing a personal cosmetic material is used in a household, the fluid composition may run off from the surface, and as a result, the cosmetic material cannot be impregnated into the antimicrobial nonwoven fabric sheet and is wasted, which is not preferable. Since the liquid-absorbing rate of the liquid-absorbing composition containing a cosmetic is preferably 5 seconds or less in the former and 3 seconds or less in the latter, the liquid-absorbing rate is preferably 3 seconds or less in the latter.

An antibacterial nonwoven fabric sheet suitable for a liquid-containing sheet using a flowable composition containing a cosmetic material needs to be able to supply a sufficient amount of the cosmetic material to the skin. Therefore, it is necessary to increase the liquid retention rate, which is an index of the liquid retention amount of the antibacterial nonwoven fabric sheet containing the fluid composition of the cosmetic material, in a proportion of the liquid retention amount to the basis weight of the nonwoven fabric, preferably 900% or more, more preferably 1000% or more. In order to impregnate a fluid composition containing a desired amount of a cosmetic material into an antibacterial nonwoven fabric sheet having a low liquid retention rate, it is necessary to prepare various antibacterial nonwoven fabric sheets having different weights and compositions per unit area depending on the amount of impregnation, but the antibacterial nonwoven fabric sheet of the present invention can be used in various amounts of impregnation in 1 type.

In addition, when the liquid-containing sheet of the present invention is attached to the face, it is also important to avoid the problem that the fluid composition containing the cosmetic material flows in the nonwoven fabric along the face and finally drips from the chin to soil the clothes. In the present invention, the performance is expressed in terms of a liquid dropping rate, and the value is preferably 3.5% or less. More preferably 3% or less, and still more preferably 2.5% or less.

In addition, it is very important that the fluid composition containing a cosmetic material, which is impregnated in a large amount into the antibacterial nonwoven fabric sheet and is held so as to avoid dripping, be efficiently transferred to the skin by the above-described method. In the present invention, the release rate is preferably 95% or more. If the release rate is less than 95%, the effective cosmetic is absorbed into the fiber and cannot be effectively used for the skin. The ratio of the release of the fluid composition containing the cosmetic material, which retains the liquid and the liquid, is preferably 95% or more.

In particular, the liquid-containing sheet of the present invention can realize a liquid-containing sheet which has excellent suitability for use in a wet state and can supply a sufficient amount of a cosmetic material to the skin, without securing a high basis weight, by achieving a high-order balance among the impregnation properties, i.e., the liquid absorption rate and the liquid retention amount, and the dripping rate and the emission rate, of a fluid composition containing the cosmetic material.

The antibacterial nonwoven fabric sheet of the present invention is usually used by being impregnated with the fluid composition, and may be used by being impregnated with the fluid composition at the time of use, or may be impregnated with the fluid composition beforehand. In the former case, the following advantages are provided: in the case of the use of a liquid-containing sheet containing a cosmetic material, for example, a user can prepare a liquid-containing sheet in which a cosmetic material that the user desires is selected and impregnated. In addition, the product can be supplied in a dry state, and the packaging of the product is simplified.

In the case of using the above-mentioned liquid-containing sheet, the antibacterial nonwoven fabric sheet preferably has a wettability and a void for retaining liquid necessary for impregnating a flowable composition containing a cosmetic component or a pharmacologically effective (effective) component (for example, a moisturizing component, a cleansing component, an antiperspirant component, an aromatic component, a whitening component, a blood circulation-promoting component, a cooling component, an ultraviolet absorbing component, a skin itch-relieving component, etc.), does not drip during handling at the time of use, is retained to a predetermined site (for example, a face) covering the body, and has an action of gradually transferring the cosmetic material to the skin side as it is stuck or left to stand. The antibacterial nonwoven fabric sheet has excellent liquid retention properties, and also has appropriate stiffness and elasticity, and when impregnated with the fluid composition, the return to compression and the return of the fluid composition are rapid, and particularly when the antibacterial nonwoven fabric sheet is formed of high-elasticity fibers having a specific young's modulus as described above, the liquid retention properties of the fluid composition are excellent, and the thickness is rapidly restored, so that the antibacterial nonwoven fabric sheet can be restored to the same liquid retention state as that of an uncompressed portion in a short time.

The restoration of the compression is, specifically, impregnation 90 by its own weight0% by weight of a flowable composition, under a load of 260g/cm²When the load of (1) is removed again after 1 minute, the reduction of the compression in the thickness direction is preferably 5 minutes or more and 35% (for example, 35 to 100%), more preferably 50 to 99% (for example, 60 to 95%), and still more preferably 65 to 90% (particularly, 70 to 85%). If the reduction is less than 35%, the fluid composition such as a cosmetic liquid cannot be sufficiently returned to the pressing part. Specifically, the above-described reset can be measured by the method described in the examples described later.

Specifically, when a circular portion having a diameter of 1.2cm is subjected to a load of 620g for 1 minute and then removed from the circular portion impregnated with 900 wt% of the flowable composition by weight, the return rate of the cosmetic liquid after 5 minutes may be 45% or more, for example, 50 to 99%, preferably 60 to 98% (for example, 65 to 95%), and more preferably 70 to 92% (particularly, 80 to 90%). If the return rate is too low, the fluid composition after pressing is insufficient, and the facial mask cannot allow the cosmetic liquid to sufficiently permeate the skin. Specifically, the above-mentioned return rate can be measured by the method described in the examples described later.

When used in the liquid-containing sheet of the present invention, the antimicrobial nonwoven fabric sheet is suitably wrapped so as to have excellent flexibility when wetted and to be able to follow the skin such as the face, and the stress at 30% elongation when wetted (stress at 30% elongation when wetted) according to JISL1913 is preferably 0.5 to 10N/5cm, more preferably 1 to 8N/5cm, further preferably 1.5 to 5N/5cm, and particularly preferably 2 to 4N/5cm in at least one direction. If the stress is too small at 30% elongation upon wetting, the skin such as the face is excessively stretched and difficult to use, and if it is too large, the adhesiveness to the skin is lowered. In detail, the stress at 30% elongation can be measured by the method described in the examples described later.

When the fluid composition contains water, the water-containing sheet of the present invention may be provided with a function by containing at least one of the fluid composition and the active ingredient, for example, in addition to water. These fluid compositions and active ingredients do not need to be water-soluble, but substances having a high affinity for water can improve the homogeneity of the water-containing sheet, and the antibacterial nonwoven fabric sheet can be easily impregnated with the fluid compositions and active ingredients having additional functions at a high concentration. In addition, the antibacterial nonwoven fabric sheet is integrated with water in the state of an aqueous solution, dispersion, or emulsion, and the homogeneity of the aqueous sheet can be improved, which is advantageous in terms of production efficiency. In particular, the aqueous solution, aqueous dispersion, or aqueous emulsion has high affinity with the solvent-spun cellulose fibers of the antibacterial nonwoven fabric sheet of the present invention, and can be integrated with the antibacterial nonwoven fabric sheet at a high concentration, so that a strong function can be obtained, and the aqueous sheet is more advantageous in terms of uniformity and production efficiency.

The cosmetic-containing flowable composition used in the liquid-containing sheet of the present invention is in the form of, for example, a solution, a dispersion, an emulsion, or the like. Further, the liquid composition contains, for example, water or at least one of the above-mentioned flowable compositions. The cosmetic includes a substance having at least 1 cosmetic function, including a case where the cosmetic itself has fluidity and a case where the cosmetic is in a solid form or the like and has substantially no fluidity. When the cosmetic material itself has fluidity, the cosmetic material may be incorporated into the antibacterial nonwoven fabric sheet as a fluid composition alone, but the fluidity is generally improved by mixing with another liquid, thereby improving the productivity and the releasability when the fluid composition is incorporated. The liquid mixed with the cosmetic material has a high affinity with the cosmetic material, and thus can be integrated with the antibacterial nonwoven fabric sheet at a higher concentration, and therefore, a strong function can be obtained. The function of the cosmetic used is not particularly limited, and 1 type of cosmetic having various generally known functions may be used, or a mixture thereof may be used.

As described above, the present invention also provides a facial mask using the liquid-containing sheet, wherein the liquid-containing sheet is formed by integrating a fluid composition containing a cosmetic material and an antibacterial nonwoven fabric sheet. As described in patent document 1, the sheet produced by melt-bonding the hot-melt adhesive component improves the shrinkage during wetting, but the whole sheet becomes hard and the followability to the skin is lowered. Further, since the surface of the sheet is mainly composed of hydrophilic fibers, the impregnated chemical solution is absorbed into the fibers and is not sufficiently released to the object to be wiped, and in the case of a sheet covering the skin, such as a mask sheet, for example, a problem occurs in that the active ingredient such as a cosmetic solution is not sufficiently released. The nonwoven fabric sheet disclosed in patent document 2 is excellent in softness and liquid retention, but the sheet is low in stiffness (rigidity), and when the sheet is pressed with a finger to bring the mask film into close contact with the face, recovery of thickness and return of the cosmetic liquid (cosmetic material) are slow. Therefore, it is difficult to apply the cosmetic liquid to the entire face effectively. In particular, in the case of a mask pack, regardless of whether or not it is necessary to press a part requiring cosmetic liquid supply and a part difficult to adhere with fingers to adhere, in the case of a conventional mask pack, although the mask pack adheres to a target part, the supply of cosmetic liquid is insufficient. In order to improve the followability of the facial mask to the skin (face), facial masks having a layer made of ultrafine fibers on the side in contact with the skin, a three-dimensional structure, and the like have been developed. However, even these face masks still have insufficient skin-following properties, and it is necessary to repeat the operation of pressing once with a finger to adhere the attached face mask. Therefore, the cosmetic solution accumulated in the pressed portion is squeezed out every time the operation of pressing the skin is repeated, and as a result, the cosmetic solution becomes insufficient.

According to the present invention, there is also provided a facial mask which solves the above conventional problems. That is, the antibacterial nonwoven fabric sheet of the present invention is excellent in antibacterial properties and allows quick return of the fluid composition even when pressed with a finger in a state of being impregnated with a liquid component such as a cosmetic liquid, because the nonwoven fabric capable of absorbing the fluid composition is formed by using specific antibacterial fibers and solvent-spun cellulose fibers, and the return of the fluid composition to the thickness direction of the antibacterial nonwoven fabric sheet is controlled. Further, even if the fluid composition is impregnated and pressed with a finger, the thickness is quickly recovered. Therefore, for example, when used as a mask, the cosmetic liquid can be efficiently supplied to a desired site. Further, by using a sheath-core type composite fiber having a sheath portion formed of an ethylene-vinyl alcohol copolymer, flexibility, liquid retention property, and form stability can be improved.

The antibacterial nonwoven fabric sheet of the present invention is excellent in adhesion to the skin, and therefore, is suitable not only for a mask but also particularly as a liquid-containing sheet to be fixed to the skin such as a compress. For example, the liquid-containing sheet of the present invention can easily correct a floating part which is not in close contact with the skin, and therefore can be made to fit into a minute space such as the nasal root, and the active ingredient of the liquid-containing sheet can be made to effectively permeate into the skin.

The liquid-containing sheet of the present invention is also suitable for use in a cleaning sheet, a skin cleansing sheet, and the like. As described above, the liquid-containing sheet of the present invention can be brought into close contact with the surface of a human body even in a minute gap between the surfaces of the human body, and therefore, cosmetics (makeup cosmetics such as makeup base, powder, lipstick, and eye makeup) can be effectively removed. As described above, when the liquid-containing sheet of the present invention is used as a sheet for liquid-impregnated living organisms, the liquid-containing sheet is generally used by being impregnated with a fluid composition and being stuck to or brought into contact with the skin of the living organism, and therefore, the antibacterial property is very important. The liquid-containing sheet of the present invention may be laminated with other layers, for example, a non-porous film or sheet may be laminated on the side not in contact with the skin in order to promote absorption of the active ingredient.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The physical property values in the present example were measured by the following methods.

[ spinning Property ]

In the spinning step of fiber production, when the spun yarn is cooled and solidified and then drawn to a yarn take-up tube via a drawing roll, a case where the yarn can be drawn without being broken is defined as "a: good spinnability ", and the case where the yarn is broken and cannot be pulled and the case where a single yarn level end is generated and a burr is generated are defined as" b: the spinnability was not good ", and the spinnability was evaluated.

[ fineness ]

The evaluation was carried out according to JISL1015 "chemical fiber short fiber test method (8.5.1)".

[ Strength ]

The evaluation was carried out according to JISL1015 "chemical fiber short fiber test method (8.7.1)".

[ elongation ]

Evaluated according to JISL1015 "chemical fiber short fiber test method (8.7.1)".

[ Young's modulus ]

The evaluation of examples 7 to 11 and comparative examples 9 to 17 was carried out in accordance with JISL1015 "chemical short fiber test method (8.11)".

[ antibacterial Properties ]

150g of the antimicrobial nonwoven fabric sheet obtained in examples or comparative examples was put into a 20-liter bucket filled with water at 60 ℃ and then subjected to a 30-minute scouring treatment, followed by rinsing for 30 minutes and drying after dehydration. The antimicrobial property of the nonwoven fabric sheet after the refining treatment was tested by JISL1902 "antimicrobial property test method and antimicrobial effect of fiber product". The bactericidal activity value was calculated from the following formula using staphylococcus aureus and pneumococcus as test bacteria (bacterial suspension concentration 1/20NB, bacterial suspension dropping amount 0.2ml), and using cotton cloth as a non-processed sample. When the bactericidal activity value is 0 or more, the antibacterial effect is considered to be exhibited.

The bacteriostatic activity value: the difference between the number of viable bacteria before and after the action time is expressed as a logarithm

Log (A/B) antibacterial activity value

A is the number of bacteria dispersed and recovered immediately after inoculation of a non-processed specimen

B-number of bacteria dispersed and collected after 18 hours of culture of processed specimen

[ thickness ]

The thickness of the antibacterial nonwoven fabric sheets obtained in examples or comparative examples was measured according to JISL1096 "fabric test method for fabric and knit (8.5)". The thickness gauge was a digital micrometer (digimatic indicator) manufactured by Mitutoyo corporation, and the thickness gauge was used to probe a 1-inch (diameter) gauge with a load of 12g/cm²And (4) carrying out measurement.

[ weight per unit area ]

The weight per unit area of the antibacterial nonwoven fabric sheets obtained in examples and comparative examples was measured according to JISP8124 "method for measuring weight per unit area of paper and paperboard".

[ void fraction ]

The porosity (%) of the antimicrobial nonwoven fabric sheet obtained in examples or comparative examples was calculated from the basis weight (g/m) of the nonwoven fabric by the following equation²) Specific weight of fiber (g/cm)³) And calculating the thickness (cm) of the non-woven fabric.

The void ratio (%) (% of the formula of nonwoven fabric/fiber ratio/thickness of nonwoven fabric)/100 }

[ skin feel ]

The skin feel when the antibacterial nonwoven fabric sheets obtained in examples or comparative examples were contacted was evaluated organoleptically by 5 subjects according to the following criteria.

< evaluation Standard >

X: good skin touch feeling

Y: slightly poor skin feel

Z: bad skin touch

[ speed of liquid absorption ]

The liquid absorption rate of the antibacterial nonwoven fabric sheet obtained in the examples or comparative examples was measured according to JISL1907 "method for testing water absorption of fiber product (7.1.1 (dropping method))". The periphery was held, one drop of liquid was dropped from a 1cm upper part of the nonwoven fabric in a state of floating from the middle by a burette, and the time until the special light reflection of the drop on the surface disappeared was measured. The following tests I and II were carried out by dropping the liquid.

Test I: ion exchange water

Test II: edible blend oil manufactured by NisshinOilliOGroup

[ liquid retention rate ]

The liquid retention of the antibacterial nonwoven fabric sheets obtained in examples and comparative examples was measured according to JISL1907 "method for testing water absorption of fiber products (7.2 (water absorption method))". The test piece was cut into 5cm square and the weight C (g) was measured. The test piece was immersed in a flowable composition (Eisan Rolla Lotion manufactured by Eisan corporation) containing a cosmetic material for 30 seconds. Then, one side of the test piece was taken out of the liquid, and the weight d (g) after 10 seconds was measured, and the weight e (g) after 1 minute was further measured.

The liquid retention rate F (%) was calculated by the following equation.

Liquid retention rate F (%) { (E-C)/C } × 100

[ Release Rate ]

The release rates of the antibacterial nonwoven fabric sheets of examples 1 to 6 and comparative examples 1 to 8 were measured as follows. The sample having the measured liquid retention rate was sandwiched between filter papers (aligned filter paper No.2) cut 10cm square and about 2.5g as appropriate, and a 2kg weight was placed from above and left to stand for 1 minute. After 1 minute, the sample was taken out and the weight gain H (g) of the filter paper weight was determined.

The release rate G (%) of the flowable composition containing the cosmetic composition was calculated from the following formula.

G(％)＝{H/(E－C)}×100

[ reduction ]

The raw material pieces of the antibacterial nonwoven fabric sheets of examples 7 to 11 and comparative examples 9 to 17 were reset and measured as described below, a sample cut to 5cm in the MD direction 5cm × CD direction 5cm was prepared, 900% of a cosmetic liquid ("Freel essensenciclotionNA" manufactured by Kanebo cosmetics) was impregnated into the sample by weight, and as shown in FIG. 1, a sample 3 was spread and set on an acrylic plate (measuring table) 4, and the initial thickness was measured with a laser displacement meter 1, and then, the raw material piece (nonwoven fabric) was set at the center for 60 seconds at 260g/cm²The displacement was measured after removing the load until 300 seconds. When the thickness of the raw material sheet before measurement is I, the thickness after removal of the load is J, and the thickness after removal of the load for 300 seconds is K, the raw material sheet reset (%) is obtained according to the following equation.

Raw material piece reset (%) [ (I-K)/(I-J) ] × 100

[ liquid Return ]

The liquid return to the raw material sheet of the antibacterial nonwoven fabric sheets of examples 7 to 11 and comparative examples 9 to 17 was measured as follows. A sample cut into 5cm in the MD direction and 5cm in the CD direction was prepared, and the sample was impregnated with 900% of a cosmetic liquid (freshelesensensitionna manufactured by kanebo cosmetics corporation) with respect to the weight of the sample, and as shown in fig. 2, a sample 3 was spread and set on an acrylic plate (measuring table) 14, a load 12 of 620g was placed on a circular center portion having a diameter of 1.2cm for 60 seconds, and the width of a portion having no cosmetic liquid immediately after the load was removed was measured. Further, the width of the portion without the cosmetic liquid after the removal load for 300 seconds was measured. When the width of the portion without the cosmetic liquid immediately after the removal of the load is L and the width of the portion without the cosmetic liquid 300 seconds after the removal of the load is M, the return (%) of the liquid to the raw material sheet is obtained according to the following equation.

Return (%) of liquid to the starting sheet [ (L-M)/L ] × 100

[ uneven height Difference ]

The height differences between the concave portions and the convex portions on the surface of the antimicrobial nonwoven fabric sheet obtained in the examples or comparative examples were calculated by observing the cross section of the nonwoven fabric using MicroscopeVH-6300 manufactured by KEYENCE corporation, measuring and averaging the height differences between the concave portions and the convex portions adjacent to each other at 3 points.

[ stress at 50% elongation at Wet ]

The stress at 50% elongation in the wet state of the antibacterial nonwoven fabric sheets of examples 1 to 6 and comparative examples 1 to 8 was expressed as a strength value at a time when the elongation reached 50% when a tensile test was performed under conditions of a sample width of 50mm, a measurement length of 100mm, and a measurement speed of 200 mm/min using autograph ags-50D manufactured by shimadzu corporation.

[ 30% elongation stress at Wet ]

The stress at 30% elongation in wet of the antibacterial nonwoven fabric sheets of examples 7 to 11 and comparative examples 9 to 17 was measured by the method described in JISL1913 "general nonwoven fabric test method (6.3.2 (tensile strength and elongation test in wet))". Specifically, the sample is placed in water at 20 ℃. + -. 2 ℃ until it sinks by its own weight, or after sinking in water for 1 hour or more, taken out from the immersion fluid and the stress at 30% elongation is rapidly measured.

Reference example 1 Individual fibers

(1) To 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol%, 1 part by weight of silver-based inorganic antibacterial fine particles (substantially cubic with an average particle diameter of 2.5 μm, AV10D manufactured by sinannezeomic corporation) having silver ions supported on an inorganic ion exchanger was blended, and spun at a spinning temperature of 240 ℃ using a melt extruder. The spun yarn was cooled and solidified, and then drawn to a yarn take-up tube via a drawing roll.

(2) Subsequently, the wound yarn was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2 times, an oil agent was applied to the yarn in an oil agent bath, and then a crimping treatment was performed using a crimping device such as a stuffer type crimping device. After the crimping treatment, the fibers were dried with hot air at 100 ℃ and cut into 51mm, thereby obtaining antibacterial EVOH-containing fibers (1.7dtex, 51mm long, circular cross section). The spinnability and the drawability are good, the strength is 2.4cN/dtex, and the elongation is 33%. The evaluation results are shown in table 1.

(reference example 2: conjugate fiber)

(1) An ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% was blended with 99 parts by weight of silver-based inorganic antibacterial fine particles (AV 10D, average particle size 2.5 μm, substantially cubic) having silver ions supported on an inorganic ion exchanger to obtain a copolymer, and the copolymer was spun by using a composite spinning apparatus comprising a melt extruder with a circular cross-sectional nozzle at a spinning temperature of 280 ℃ and a sheath-core weight ratio of 50: 50, using a core portion of a thermoplastic polymer made of polyethylene terephthalate as a core portion, and with the core portion of the thermoplastic polymer as a core portion, the silver-based inorganic antibacterial fine particles having an average particle size of 2.5 μm and a substantially cubic shape, and having an ethylene content of 44 mol%. The spun yarn was cooled and solidified, and then drawn to a yarn take-up tube via a drawing roll.

(2) Next, the wound wire was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2 times, an oil agent was applied to the wire in an oil agent bath, and then a crimping treatment was performed using a crimping device such as a plug-type crimping device. After the crimping treatment, the fibers were dried with hot air at 100 ℃ and cut into 51mm, thereby obtaining antibacterial EVOH-containing fibers (3.4dtex, 51mm length, sheath-core weight ratio 50: 50, circular cross section, core diameter 12.5 μm). The spinnability and the drawability are good, the strength is 2.9cN/dtex, and the elongation is 27%.

Reference example 3 composite fiber

(1) The wound yarn of reference example 2 was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2 times, oil was applied to the yarn in an oil bath, and the yarn was cut into 10mm, thereby obtaining an antibacterial EVOH-containing fiber shown in table 1 below (3.4dtex, 10mm length, sheath-core weight ratio of 50: 50, circular cross section, core diameter of 12.5 μm). The spinning property and the tensile property are good, the strength is 2.9cN/dtex, and the elongation is 21%.

Reference example 4 Individual fibers

An antibacterial EVOH-containing fiber (1.7dtex, 51mm long, circular cross section) was obtained by spinning in the same manner as in reference example 1, with 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 85 mol% blended with 1 part by weight of silver-based inorganic antibacterial fine particles (AV 10D, average particle size 2.5gm, substantially cubic, manufactured by sinannezeomic corporation) having silver ions supported on an inorganic ion exchanger. The spinnability and the drawability are good, the strength is 3.1cN/dtex, and the elongation is 38%.

Reference example 5 composite fiber

An antibacterial EVOH-containing fiber (3.4dtex, 51mm long, sheath-core weight ratio 50: 50, circular cross section, core diameter 16.0 μm) was obtained by spinning in the same manner as in reference example 2 except that the discharge amount, drawing speed, and draw ratio of the resin were adjusted so that the fineness was 5.5 dtex. The spinning property and the tensile property are good, the strength is 2.9cN/dtex, and the elongation is 36%.

Reference example 6 composite fiber

(1) An ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% was used as a sheath portion, a thermoplastic polymer made of polyethylene terephthalate was used as a core portion, and a composite spinning device comprising a melt extruder was used to synthesize a sheath-core type by a circular cross-sectional nozzle at a spinning temperature of 280 ℃ and a sheath-core weight ratio of 50: 50, thereby carrying out spinning. The spun yarn was cooled and solidified, and then drawn to a yarn take-up tube via a drawing roll.

(2) Next, the wound wire was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2 times, an oil agent was applied to the wire in an oil agent bath, and then a crimping treatment was performed using a crimping device such as a plug-type crimping device. After the crimping treatment, the fibers were dried with hot air at 100 ℃ and cut into 51mm, thereby obtaining EVOH-containing fibers (3.4dtex, 51mm length, sheath-core weight ratio 50: 50, circular cross section, core diameter 12.5 μm). The spinning property and the tensile property are good, the strength is 3.6cN/dtex, and the elongation is 38%.

[ example 1]

70 wt% of the antibacterial EVOH-containing fiber of reference example 1 and 30 wt% of solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 38mm length manufactured by Lenzing Co.) were mixed to obtain a cotton blend having a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void content of 92%. The evaluation results are shown in table 1.

The sheet has sufficient liquid retention and release properties, and has good skin touch.

[ example 2]

70% by weight of the antibacterial EVOH-containing fiber of reference example 2 and 30% by weight of solvent-spun celluloseThe cotton was mixed with similar fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing Co., Ltd.) to obtain a cotton having a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void content of 95%. The evaluation results are shown in table 1. The sheet has sufficient liquid retention and release properties, and has good skin touch.

[ example 3]

The antibacterial EVOH-containing fiber of reference example 3 was dispersed in water at 70 wt% and solvent-spun cellulose-based fiber (Lyocell, 1.7dtex, 12mm length, manufactured by Lenzing Co., Ltd.) at 30 wt%, and the weight per unit area was made to be about 60g/m by a wet process²The wet process nonwoven fabric of (1).

Then, a water jet was applied to the wet-laid nonwoven fabric to carry out a cohesion treatment and obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void fraction of 90%. The evaluation results are shown in table 1. The sheet has sufficient liquid retention and release properties, and has good skin touch.

[ example 4]

70 wt% of the antibacterial EVOH-containing fiber of reference example 5 and 30 wt% of solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 38mm length manufactured by Lenzing Co.) were mixed to obtain a cotton blend having a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void fraction of 97%. The evaluation results are shown in table 1. The sheet has sufficient liquid retention and release properties, and has good skin touch.

[ example 5]

Water jet was applied to the card web obtained in example 2, and cohesion treatment was carried out to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having orifices with a diameter of 0.15mm provided at intervals of 0.6mm in the width direction of the wire were used, and the water pressure was 8MPa sprayed at each of the front and back surfaces at 2 stages to cause entanglement. The antibacterial nonwoven fabric sheet obtained had a porosity of 99%. The evaluation results are shown in table 1. As a result, the sheet had sufficient liquid retention and releasability, but had a slightly inferior feeling to the skin.

[ example 6]

A mixture of 10% by weight of the antibacterial EVOH-containing fiber obtained in reference example 2 and 90% by weight of solvent-spun cellulose-based fiber was prepared to have a basis weight of 60g/m²An antibacterial nonwoven fabric sheet was obtained in the same manner as in example 1, except for the carded web of (1). The antibacterial nonwoven fabric sheet obtained had a void fraction of 88%. The evaluation results are shown in table 1. The sheet had a slightly inferior liquid retention property and releasability, but had a good skin feel.

Comparative example 1

Yarn formation was carried out in the same manner as in reference example 2 except that silver-based inorganic antibacterial fine particles (having an average particle diameter of 0.008 μm and a substantially cubic shape, manufactured by SINANENZEOMIC Co., Ltd.) in which silver ions were supported on an inorganic ion exchanger were blended, but stable yarn formation could not be achieved due to poor spinning property.

Comparative example 2

Spinning was carried out in the same manner as in reference example 2 except that silver-based inorganic antibacterial fine particles (substantially cubic, having an average particle diameter of 25 μm, manufactured by SINANENZEOMIC) supporting silver ions on an inorganic ion exchanger were blended, but stable spinning was not possible due to poor spinning property.

Comparative example 3

A silver-based inorganic antibacterial fine particle (AV 10D; "average particle size 2.5 μm, substantially cubic" manufactured by SINANENZEOMIC) having silver ions supported on an inorganic ion exchanger was mixed with 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 8 mol% to produce a yarn in the same manner as in reference example 1, but the yarn could not be stably produced due to poor spinning properties.

Comparative example 4

70 wt% of the antibacterial EVOH-containing fiber of reference example 4 and 30 wt% of solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 38mm length manufactured by Lenzing Co.) were mixed to obtain a cotton blend having a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The water flow is bonded with the non-woven fabric to obtain the antibacterial non-woven fabric sheet. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void volume of 93%. The evaluation results are shown in table 2. Although this sheet has a good skin feel, it is difficult to use because of poor liquid retention and releasability and a slow water absorption rate.

Comparative example 5

Using 100% by weight of the antibacterial EVOH-containing fiber obtained in reference example 2, a 60g/m basis weight was prepared²An antibacterial nonwoven fabric sheet was obtained in the same manner as in example 1, except for the carded web of (1). The antibacterial nonwoven fabric sheet obtained had a void content of 96%. The evaluation results are shown in table 2. The sheet has excellent liquid retention and release properties, but is inconvenient to use because of its slow water absorption rate and has a slightly poor skin feel.

Comparative example 6

70 wt% of the antibacterial EVOH-containing fiber of reference example 2 and 30 wt% of cotton fiber manufactured by Mitsui corporation were mixed and kneaded to obtain a fiber having a basis weight of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The water flow is bonded with the non-woven fabric to obtain the antibacterial non-woven fabric sheet. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void volume of 94%. The evaluation results are shown in table 2. This sheet is unsatisfactory in terms of liquid retention, releasability, softness and suitability for the skin.

Comparative example 7

The wet-process nonwoven fabric obtained in example 3 was directly subjected to water-flow entangling treatment to prepare an antibacterial nonwoven fabric sheet. The evaluation results are shown in table 2. The nonwoven fabric sheet had a void ratio of 78%, and although it had a fairly good skin feel, it was inferior in liquid retention and releasability, and was unsatisfactory in handling properties.

Comparative example 8

The EVOH-containing fiber of reference example 6 was 50 wt% and a solvent-spun cellulose fiber (Lyocell, 1.7dtex, 38mm in length, manufactured by Lenzing Co.) were mixed together to prepare a unitArea weight of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The water flow is bonded with the non-woven fabric to obtain the non-woven fabric sheet. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The obtained nonwoven fabric sheet had a void ratio of 95%. The evaluation results are shown in table 2. The sheet has sufficient liquid retention, releasability and good skin feel, but remarkably poor antibacterial properties.

Reference example 7 Individual fibers

(1) To 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol%, 1 part by weight of silver-based antibacterial fine particles (substantially cubic with an average particle diameter of 2.5 μm, AV10D manufactured by sinannezeomic) having silver ions supported on an inorganic ion exchanger was blended, and spinning was performed at a spinning temperature of 240 ℃ using a melt extruder. The spun yarn was cooled and solidified, and then drawn to a yarn take-up tube via a drawing roll.

(2) Next, the wound wire was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2.4 times, an oil agent was applied to the wire in an oil agent bath, and then a crimping treatment was performed using a crimping device such as a plug-type crimping device. After the crimping treatment, the fibers were dried with hot air at 100 ℃ and then cut into an arbitrary cut length, thereby obtaining antibacterial EVOH-containing fibers (1.4dtex, circular cross section). The spinning property and the tensile property are good, the strength is 3.1cN/dtex, the elongation is 26%, and the Young modulus is 30.8 cN/dtex.

Reference example 8 composite fiber

(1) An ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% was blended with 99 parts by weight of silver-based antibacterial fine particles (AV 10D, average particle size 2.5 μm, substantially cubic) having silver ions supported on an inorganic ion exchanger to obtain a copolymer, and the copolymer was used as a sheath portion, a thermoplastic polymer made of polyethylene terephthalate was used as a core portion, and a composite spinning apparatus composed of a melt extruder was used to synthesize a sheath-core type at a spinning temperature of 280 ℃ and a sheath-core weight ratio of 50: 50 using a circular cross-sectional nozzle, thereby spinning. The spun yarn was cooled and solidified, and then drawn to a yarn take-up tube via a drawing roll.

(2) Next, the wound wire was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2.6 times, an oil agent was applied to the wire in an oil agent bath, and then a crimping treatment was performed using a crimping device such as a plug-type crimping device. After the crimping treatment, the fibers were dried with hot air at 100 ℃ and then cut to an arbitrary cut length, thereby obtaining antibacterial EVOH-containing fibers (1.7dtex, sheath-core weight ratio 50: 50, circular cross section, core diameter 8.9 μm) shown in Table 3 below. The fiber had good spinning property and tensile property, the strength was 3.6cN/dtex, the elongation was 31%, and the Young's modulus was 33.9 cN/dtex.

Reference example 9 composite fiber

(1) The wound yarn of reference example 8 was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2 times, oil was applied to the yarn in an oil bath, and the yarn was cut into 10mm, thereby obtaining an antibacterial EVOH-containing fiber (1.7dtex, 10mm length, sheath-core weight ratio of 50: 50, circular cross section, core diameter of 8.9gm) shown in table 3 below. The fiber had good spinning property and tensile property, the strength was 3.6cN/dtex, the elongation was 31%, and the Young's modulus was 33.9 cN/dtex.

Reference example 10 Individual fibers

An antibacterial EVOH-containing fiber (1.4dtex, 51mm long, circular cross section) was obtained by spinning an ethylene-vinyl alcohol copolymer having an ethylene content of 85 mol% with 1 part by weight of silver-based inorganic antibacterial fine particles (manufactured by SINANENZEOMIC, "AV 10D", average particle size 2.5 μm, substantially cubic) having silver ions supported on an inorganic ion exchanger, in the same manner as in reference example 7. The spinning property and the tensile property are good, the strength is 3.7cN/dtex, the elongation is 24%, and the Young modulus is 35.1 cN/dtex.

Reference example 11 composite fiber

An antibacterial EVOH-containing fiber (5.5dtex, 51mm long, sheath-core weight ratio 50: 50, circular cross section, core diameter 16.0 μm) was obtained by spinning in the same manner as in reference example 8, except that the discharge amount, drawing speed, and draw ratio of the resin were adjusted so that the fineness was 5.5 dtex. The spinning property and the tensile property are good, the strength is 2.7cN/dtex, the elongation is 36 percent, and the Young modulus is 28.7 cN/dtex.

Reference example 12 composite fiber

(2) Next, the wound wire was hot-drawn at a draw temperature of 80 ℃ at a draw ratio of 2 times, an oil agent was applied to the wire in an oil agent bath, and then a crimping treatment was performed using a crimping device such as a plug-type crimping device. After the crimp-imparting treatment, the fibers were dried with hot air at 100 ℃ and cut into 51mm, thereby obtaining EVOH-containing fibers (3.4dtex, 51mm length, sheath-core weight ratio 50: 50, circular cross section, core diameter 12.5 μm). The spinning property and the tensile property are good, the strength is 3.6cN/dtex, the elongation is 38%, and the Young modulus is 38.5 cN/dtex.

[ example 7]

50 wt% of the antibacterial EVOH-containing fiber of reference example 7 and 50 wt% of solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 38mm length, manufactured by Lenzing Co.) were mixed to obtain a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void fraction of 90%. The evaluation results are shown in table 3. The sheet has sufficient liquid retention property, liquid returning property to the raw material sheet, and good skin touch feeling.

[ example 8]

50 wt% of the antibacterial EVOH-containing fiber of reference example 8 and 50 wt% of solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 38mm length, manufactured by Lenzing Co.) were mixed to obtain a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void content of 92%. The evaluation results are shown in table 3. The sheet has sufficient liquid retention property, liquid returning property to the raw material sheet, and good skin touch feeling.

[ example 9]

The antibacterial EVOH-containing fiber of reference example 9 was 50 wt% and a solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 12mm length, manufactured by Lenzing Co., Ltd.) was 50 wt%, and the resulting fiber was dispersed in water to give a weight per unit area of about 60g/m by a wet method²The wet process nonwoven fabric of (1).

Then, a water jet was applied to the wet-laid nonwoven fabric to carry out a cohesion treatment and obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void fraction of 86%. The evaluation results are shown in table 3. The sheet has sufficient liquid retention property, liquid returning property to the raw material sheet, and good skin touch feeling.

[ example 10]

50 wt% of the antibacterial EVOH-containing fiber of reference example 11 and 50 wt% of solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 38mm length manufactured by Lenzing Co.) were mixed to obtain a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void volume of 94%. The evaluation results are shown in table 3. The sheet has sufficient liquid retention property, liquid returning property to the raw material sheet, and good skin touch feeling.

[ example 11]

Spraying to the card wire obtained in example 8Water flow, carrying out cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having orifices with a diameter of 0.15mm provided at intervals of 0.6mm in the width direction of the wire were used, and the water pressure was 8MPa sprayed at each of the front and back surfaces at 2 stages to cause entanglement. The antibacterial nonwoven fabric sheet obtained had a void content of 98%. The evaluation results are shown in table 3. As a result, the sheet had sufficient liquid retention and liquid-returning properties to the raw material sheet, but had a slightly inferior feeling to the skin.

Comparative example 9

Yarn formation was carried out in the same manner as in reference example 8 except that silver-based inorganic antibacterial fine particles (having an average particle diameter of 0.008 μm and a substantially cubic shape, manufactured by SINANENZEOMIC) in which silver ions were supported on an inorganic ion exchanger were blended, but stable yarn formation could not be achieved due to poor spinning property.

Comparative example 10

Spinning was carried out in the same manner as in reference example 8 except that silver-based inorganic antibacterial fine particles (having an average particle diameter of 25 μm and a substantially cubic shape, manufactured by SINANENZEOMIC) in which silver ions were supported on an inorganic ion exchanger were blended, but stable spinning was not possible due to poor spinning property.

Comparative example 11

A silver-based inorganic antibacterial fine particle (AV 10D; "average particle size 2.5 μm, substantially cubic" manufactured by SINANENZEOMIC) having silver ions supported on an inorganic ion exchanger was mixed with 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 8 mol% to produce a yarn in the same manner as in reference example 7, but the yarn could not be stably produced due to poor spinning properties.

Comparative example 12

50% by weight of the antibacterial EVOH-containing fiber of reference example 10 and 50% by weight of a solvent-spun cellulosic fiber (Lyocell, 1.7dtex manufactured by Lenzing Co., Ltd.),38mm long) cotton blend to a basis weight of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of about 60g/m²The water flow is bonded with the non-woven fabric to obtain the antibacterial non-woven fabric sheet. In addition, the water flow cohesion treatment was carried out by interlacing the net with a water pressure of 6MPa at 2 stages on the front and back surfaces of the net by using a nozzle having 0.1mm diameter nozzles provided at 0.6mm intervals in the width direction of the net. The obtained liquid retention sheet had a void ratio of 91%. The evaluation results are shown in table 4.

Although this sheet has a good skin feel, it has insufficient liquid retention properties and liquid-returning properties to the raw material sheet.

Comparative example 13

The antibacterial EVOH-containing fiber obtained in reference example 8 was made up to a basis weight of 60g/m using 100% by weight of the antibacterial EVOH²An antibacterial nonwoven fabric sheet was obtained in the same manner as in example 7, except for the carded web. The antibacterial nonwoven fabric sheet obtained had a void content of 96%. The evaluation results are shown in table 4.

The sheet has unsatisfactory properties of returning liquid to the raw material sheet, and is difficult to use because of slow water absorption rate, and also has poor skin touch.

Comparative example 14

35% by weight of the antibacterial EVOH-containing fiber of reference example 8 and 65% by weight of solvent-spun cellulosic fiber (Lyocell, 1.7dtex, 38mm long, manufactured by Lenzing Co.) were mixed to obtain a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The water flow is bonded with the non-woven fabric to obtain the antibacterial non-woven fabric sheet. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them.The antibacterial nonwoven fabric sheet obtained had a void content of 95%. The evaluation results are shown in table 4.

This sheet is not satisfactory in terms of liquid retention, liquid absorption speed, and properties of returning liquid to the raw material sheet.

Comparative example 15

70 wt% of the antibacterial EVOH-containing fiber of reference example 8 and 30 wt% of cotton fiber manufactured by Mitsui corporation were mixed and kneaded to obtain a fiber having a basis weight of about 60g/m²The carding cotton net of (1).

Then, a water jet was jetted to the card web to carry out a cohesion treatment to obtain a weight per unit area of 60g/m²The antibacterial nonwoven fabric sheet of the present invention is obtained by uniting the nonwoven fabric with the water flow. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void volume of 93%. The evaluation results are shown in table 4.

This sheet is unsatisfactory in terms of liquid retention, releasability, softness and suitability for the skin.

Comparative example 16

The wet-process nonwoven fabric obtained in example 9 was directly subjected to water-flow entangling treatment to prepare an antibacterial nonwoven fabric sheet. The antimicrobial nonwoven fabric sheet has a porosity of 74%, and although it has a very good skin feel, it has a low stress at 30% extension when wet, and is unsatisfactory in handling properties.

Comparative example 17

The EVOH-containing fiber of reference example 12 (50 wt.%) and a solvent-spun cellulose fiber (50 wt.%) (Lyocell, 1.7dtex, 38mm long, manufactured by Lenzing Co.) were mixed together to prepare a mixture having a weight per unit area of about 60g/m²The carding cotton net of (1).

Then, spraying to the card webWater flow, carrying out cohesion treatment to obtain a weight per unit area of 60g/m²The water flow is bonded with the non-woven fabric to obtain the antibacterial non-woven fabric sheet. In the water flow cohesion treatment, nozzles having 0.1mm diameter nozzles were provided at 0.6mm intervals in the width direction of the web, and the water pressure was applied to the front and back surfaces at 2 stages to interleave them. The antibacterial nonwoven fabric sheet obtained had a void content of 95%. The evaluation results are shown in table 4.

The sheet has sufficient liquid retention, releasability and good skin feel, but is significantly inferior in antibacterial property.

Industrial applicability

The antibacterial nonwoven fabric sheet of the present invention can be used for applications to absorb liquid components and contact the skin, for example, body fluid absorbing sheets (e.g., napkins, surface materials of diapers and the like, diaper pads, wet tissues and the like), skin care sheets (e.g., face masks, makeup removing sheets, cleansing sheets or body cleansing sheets (sweat wiping sheets, oil absorbing sheets, cooling sheets and the like)), medicinal sheets (itch relieving sheets, compresses and the like), and the like. In particular, the antibacterial nonwoven fabric sheet of the present invention is used as a face mask which is impregnated with a liquid component such as a cosmetic liquid (cosmetic) and which can quickly return the liquid component even when pressed with a finger, and thus can be used to impregnate functional components such as moisture retention and whitening of the whole face, nose, eyes, mouth corners, neck, and the like and has antibacterial properties.

Claims

1. An antibacterial nonwoven fabric sheet comprising antibacterial fibers and solvent-spun cellulose fibers interwoven with each other, wherein an antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles dispersed therein is present on at least a part of the fiber surface, the inorganic antibacterial fine particles have an average particle diameter of 0.01 to 20 [ mu ] m, and the antibacterial ethylene-vinyl alcohol copolymer has an ethylene content of 10 to 70 mol%.

2. The antimicrobial nonwoven fabric sheet according to claim 1, wherein the antimicrobial fibers and the solvent-spun cellulosic fibers have a fiber length of 5 to 60mm, and the antimicrobial nonwoven fabric sheet is formed by interweaving these fibers.

3. The antimicrobial nonwoven fabric sheet according to claim 1 or 2, wherein the antimicrobial fiber is a sheath-core composite fiber, the sheath portion is an antimicrobial ethylene-vinyl alcohol copolymer containing inorganic antimicrobial fine particles having an average particle diameter of 0.01 to 20 μm in a dispersed state, and the core portion is made of a hydrophobic resin and has a diameter of 5 to 15 μm.

4. The antimicrobial nonwoven fabric sheet according to any one of claims 1 to 3, wherein the surface of the antimicrobial nonwoven fabric sheet has irregularities.

5. The antimicrobial nonwoven fabric sheet according to any one of claims 1 to 4, which contains 30 to 90 wt% of the antimicrobial fiber.

6. The antimicrobial nonwoven fabric sheet according to claim 5, which contains 40 to 90 wt% of the antimicrobial fibers, and the Young's modulus of the antimicrobial fibers is 25cN/dtex or more.

7. A liquid-containing sheet obtained by integrating the antibacterial nonwoven fabric sheet according to any one of claims 1 to 6 with a flowable composition.

8. The liquid-containing tablet of claim 7, wherein the flowable composition comprises water.

9. The liquid-containing sheet according to claim 7, wherein the flowable composition contains a cosmetic material.

10. The liquid-containing sheet according to claim 9, which is a skin care sheet.

11. The liquid-containing sheet according to claim 9 or 10, wherein the sheet is loaded at 260g/cm with respect to 900 wt% of the flowable composition impregnated by weight²When the load of (2) was removed again for 1 minute, the reduction of the compression in the thickness direction was not less than 35% for 5 minutes.

12. A facial mask using the liquid-containing sheet according to any one of claims 9 to 11.