WO2015045982A1

WO2015045982A1 - Antibacterial nonwoven sheet, liquid-containing sheet, and face mask

Info

Publication number: WO2015045982A1
Application number: PCT/JP2014/074532
Authority: WO
Inventors: 大前　好信; 宗訓熊谷; 純人清岡; 和之中山
Original assignee: 株式会社クラレ
Priority date: 2013-09-27
Filing date: 2014-09-17
Publication date: 2015-04-02
Also published as: HK1222212A1; TW201524448A; KR101906689B1; CN105593421A; KR20160055928A; JP6480335B2; JPWO2015045982A1; TWI632890B

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 sheet, liquid-containing sheet, and face mask

The present invention is a substrate effective for adsorbing and absorbing a fluid composition containing a cosmetic composition having functions of wiping, wiping, moisturizing, and beauty of skin such as excrement, sebum, and cosmetics. It relates to an antibacterial nonwoven sheet. The present invention also relates to a liquid-containing sheet impregnated with a fluid composition containing a cosmetic ingredient, a medicinal ingredient, etc., and integrated with an antibacterial nonwoven sheet, in particular, an antibacterial face that is used by being attached to the skin. Regarding masks.

Conventionally, water-containing sheets such as wet tissues, disposable towels, and sheet-like cosmetics that coat the skin with water and aqueous fluid compositions integrated with nonwoven fabric sheets, hydrophilic fibers such as rayon, or hydrophilic fibers There have been proposed non-woven fabrics in which a high-pressure water flow treatment is applied to a fiber web made of mixed cotton and heat-adhesive conjugate fibers, or various non-woven fabrics obtained by functionally improving the non-woven fabric. However, when hydrophilic fibers such as rayon are wet, wrinkles occur due to decrease in fiber stiffness and fiber shrinkage, leading to problems such as reduced form stability that impairs workability and liquid retention. There is a problem that moisture is taken into the fiber and the effect of moisture cannot be used effectively. In order to remedy the above problem, the hydrophobic synthetic short fibers are contained in an amount of 50% by weight or more, and the hydrophilic fibers are contained in an amount of 40% by weight or more on both surfaces of the heat-bonded nonwoven fabric in which the constituent fibers are joined by the partial thermocompression bonding parts. There has been proposed a composite wet sheet obtained by laminating and intertwining fiber webs (see, for example, JP-A-2001-336053 (Patent Document 1)).

However, the sheet produced by fusing the heat-adhesive component as in Patent Document 1 is improved in shrinkage when wet, but the entire sheet becomes hard and the conformity to the skin is lowered. Further, since the surface of the sheet is mainly composed of hydrophilic fibers, the chemical liquid impregnated in the fibers is taken in and cannot be sufficiently released to the object to be wiped off. In addition, due to the spread of social needs, a function of incorporating various fluid compositions has been required.

In order to solve these problems, for example, Japanese Patent Application Laid-Open No. 2008-261667 (Patent Document 2) describes a fiber length of 30 to 60 mm as a water-containing sheet that has a good touch and is excellent in water retention, release and form stability. A nonwoven fabric sheet in which a solvent-spun cellulose-based fiber and a sheath-core type composite fiber are entangled with each other, the sheath-core type composite fiber comprising a sheath part and a core part, and the sheath part is ethylene-vinyl There has been proposed a non-woven fabric sheet which is an alcohol copolymer and has a core made of a hydrophobic resin and having a diameter of 5 to 15 μm.

In recent years, antibacterial properties have been required for these nonwoven fabric sheets, and in particular, many antiseptics and antibacterial agents such as parabens have been used. However, there are situations that should be restricted to the use of parabens, such as suspected endocrine disrupting effects in butylparaben, high possibility of transient irritation throughout the paraben, and rough skin, rash, etc. when attached to the skin Therefore, it is desired that antibacterial and antibacterial activities should be made paraben-free (without parabens).

JP 2001-336053 A JP 2008-261067 A

That is, the problem to be solved by the present invention is that it has excellent antiseptic and antibacterial properties without containing parabens, is soft and soft to the touch, and has good impregnation properties when impregnated with various fluid compositions. To provide an antibacterial non-woven fabric sheet that has liquid retention properties, can efficiently release the fluid composition by pressure, etc., and is excellent in form stability due to less deterioration and shrinkage due to impregnation of the fluid composition. It is in. Moreover, this invention is providing the liquid-containing sheet | seat which is good in the touch and excellent in the liquid retention property of a fluid composition containing water etc., discharge | release property, and form stability.

We have intensively studied in view of the above problems and have arrived at the present invention.
That is, in the first invention, an antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles dispersed therein is present on at least a part of the fiber surface, and the average particle size of the inorganic antibacterial fine particles The antibacterial fiber having a diameter of 0.01 to 20 μm and the ethylene content of the antibacterial ethylene-vinyl alcohol copolymer is 10 to 70 mol% and the solvent-spun cellulose fiber are entangled with each other. It is an antibacterial nonwoven fabric sheet characterized by being formed.

The second invention is an antibacterial nonwoven fabric sheet characterized in that the antibacterial fibers of the first invention and the solvent-spun cellulosic fibers have a fiber length of 5 to 60 mm and are entangled with each other.

In a third invention, the antibacterial fiber of the first invention and / or the second invention is a sheath-core type composite fiber, and the sheath part is an inorganic antibacterial having an average particle diameter of 0.01 to 20 μm. An antibacterial non-woven fabric sheet comprising an antibacterial ethylene-vinyl alcohol copolymer containing fine particles dispersed therein, wherein the core is made of a hydrophobic resin and has a diameter of 5 to 15 μm It is.

The fourth invention is the antibacterial nonwoven sheet according to the first to third inventions, wherein the antibacterial nonwoven sheet has an uneven surface.

The fifth invention is the antibacterial nonwoven sheet of the first to fourth inventions, characterized in that it contains 30 to 90% by weight of the antibacterial fiber.

A sixth invention is the antibacterial nonwoven fabric sheet of the fifth invention, comprising 40 to 90% by weight of the antibacterial fiber, and the Young's modulus of the antibacterial fiber is 25 cN / dtex or more. Antibacterial nonwoven sheet.

The seventh invention is a liquid-containing sheet in which the antibacterial nonwoven sheet of the first to sixth inventions and the fluid composition are integrated.

The eighth invention is the liquid-containing sheet of the seventh invention, wherein the fluid composition contains water.

The ninth invention is the liquid-containing sheet of the seventh invention, wherein the fluid composition contains a cosmetic.

The tenth invention is a liquid-containing sheet according to the ninth invention, which is a skin care sheet.

The eleventh invention is the liquid-containing sheet of the ninth or tenth invention, wherein the flowable composition is impregnated with 900% by weight with respect to its own weight and removed by applying a load of 260 g / cm ² for 1 minute. In this case, the liquid-containing sheet is characterized in that the repositioning with respect to compression in the thickness direction is 35% or more in 5 minutes.

The twelfth invention is a face mask using the liquid-containing sheet of the ninth to eleventh inventions.

By the means described above, the present invention can be used to adsorb and absorb fluid compositions containing cosmetics having functions such as wiping, wiping, moisturizing, and beauty such as excrement, sebum, and cosmetics. The present invention provides an antibacterial nonwoven sheet serving as an effective substrate, and a liquid-containing sheet and a face mask containing the antibacterial nonwoven sheet.

According to a first aspect of the present invention, a fiber in which an antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles dispersed therein is present in at least a part of the fiber surface and a solvent-spun cellulose fiber are both hydrophilic. In addition to having properties, the non-woven fabric sheet is formed by entanglement of two fibers with each other, so that it is soft and soft to the touch. In addition, both the fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface and the solvent-spun cellulose fiber are highly impregnated with the fluid composition, and the fluid composition such as water is promptly used. Can be impregnated.

Further, the antibacterial ethylene-vinyl alcohol copolymer has a hydrophobic portion, and the ethylene content thereof is adjusted, or the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface. Various fluid compositions can be impregnated by adjusting the fiber and solvent-spun cellulosic fiber content.

Furthermore, solvent-spun cellulose fibers have high liquid retention properties of hydrophilic fluid compositions such as water, aqueous solutions, polar solvents, and emulsions thereof. On the other hand, a fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface has low liquid retention. For this reason, the fluid composition near the fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface easily oozes out due to pressure or the like. Furthermore, since the antibacterial ethylene-vinyl alcohol copolymer released from the fluid composition is present in at least a part of the fiber surface, the fiber composition is highly impregnated and further deprives the fluid composition from the solvent-spun cellulose fiber. The flowable composition oozes out continuously at an appropriate rate. The antibacterial nonwoven fabric sheet of the present invention has a fluid composition by having a fiber in which an antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface and a solvent-spun cellulose fiber entangled with each other. Objects can be moved quickly. Since the discharge | release property of the fluid composition impregnated by these becomes high, a fluid composition can be used effectively.

For antibacterial ethylene-vinyl alcohol copolymers, fibers and / or non-woven sheets are caused by physical external factors such as abrasion by allowing inorganic antibacterial fine particles having a specific particle size to be dispersed inside. Therefore, it is possible to prevent the inorganic antibacterial fine particles from falling off and to continuously develop the antibacterial performance.

According to a second aspect of the present invention, the fiber having the antibacterial ethylene-vinyl alcohol copolymer present on at least a part of the fiber surface and the fiber length of the solvent-spun cellulosic fiber is 5 to 60 mm. Appropriate flexibility and elasticity can be secured, and a soft touch and fit to the skin can be realized. In particular, in production by fiber entanglement under dry conditions, a bulky nonwoven fabric sheet excellent in impregnation with a fluid composition and excellent in cushioning properties can be obtained.

According to a third aspect of the present invention, there is provided a sheath-core type composite fiber having an antibacterial ethylene-vinyl alcohol copolymer as a sheath and a hydrophobic resin as a core, and the core has a diameter of 5 to 15 μm. The antibacterial nonwoven fabric sheet is less likely to wrinkle due to less moisture impregnation, and does not impair liquid retention and workability. In addition, since the core can be felt on the skin during use, the skin feels soft, and, for example, in the use of a cosmetic base material that is important to be closely adhered to the skin, the conformity to the skin is increased.

In the fourth invention, since the surface of the antibacterial nonwoven sheet has irregularities, an air layer is formed between the antibacterial nonwoven fabric sheet and the skin when it is in close contact with the skin, so that it is difficult to get stuffy. Moreover, since the surface area of the antibacterial non-woven fabric sheet has irregularities, the surface area increases, and thus the adhesion to the skin increases. In applications such as wet tissues, disposable towels, and liquid-containing sheets using fluid compositions containing cosmetics that are impregnated with a fluid composition and released by pressure, the fluid composition is retained in the recesses, so that the skin Since the good fluid composition can be released while the convex portions that are easy to touch are smooth, the touch is even better. The liquid retaining effect of the fluid composition is enhanced by the recess, and the fluid composition having a wide range of polarities can be retained without adjusting the overall polarity depending on the copolymerization ratio of the antibacterial ethylene-vinyl alcohol copolymer. .

According to a fifth aspect of the present invention, the antibacterial nonwoven sheet of the present invention contains 30 to 90% by weight of the antibacterial fiber and 70 to 10% by weight of solvent-spun cellulosic fiber. When impregnated with a composition, the liquid retention property of the impregnable, releasable, and hydrophilic fluid composition is good, and the form stability due to the absence of fiber shrinkage and stiffness reduction during impregnation It is possible to obtain an antibacterial non-woven sheet having an excellent balance.

The sixth invention is the antibacterial nonwoven sheet of the present invention, comprising 40 to 90% by weight of antibacterial fibers, and having an antibacterial property when the Young's modulus of the antibacterial fibers is 25 cN / dtex or more. In addition, it is soft and soft to the touch, and can be rapidly impregnated with a flowable composition containing cosmetics such as a cosmetic liquid, and an antibacterial nonwoven sheet with appropriate stiffness and elasticity can be obtained.

The seventh invention is a liquid-containing sheet in which the antibacterial nonwoven sheet of the present invention and the fluid composition are integrated, so that the touch is good and the fluid composition has liquid retention, release and form stability. It is suitable for applications such as wet tissue, disposable towels, skin care sheets, face masks.

The eighth invention is a liquid-containing sheet (water-containing sheet) in which the fluid composition contains water, has a good touch, is excellent in water retention, release, and form stability, and is suitable for the above-described uses. .

The ninth invention is a liquid-containing sheet in which the flowable composition contains a cosmetic, which has a good touch, good release of the cosmetic, and excellent form stability, so that it can be easily and cleanly applied to the skin.

In the tenth aspect of the invention, by using the liquid-containing sheet described above, a skin care sheet excellent in impregnation property and liquid retention property of a fluid composition containing cosmetics can be obtained.

In an eleventh aspect of the present invention, when a cosmetic liquid (cosmetic material) is impregnated with 900% by weight with respect to its own weight and a load of 260 g / cm ² is applied and removed for 1 minute, the repositioning to compression in the thickness direction is 5 minutes. By being 35% or more, it can be set as the liquid containing sheet | seat which can fully maintain the return of the cosmetic liquid of a press part.

In the twelfth aspect of the invention, by using the liquid-containing sheet described above, a face mask that can sufficiently penetrate the cosmetic liquid (cosmetic material) into the skin can be obtained.

It is the schematic for demonstrating the measuring method of the original repeating position in an Example. It is the schematic for demonstrating the measuring method of the liquid return to the original fabric in an Example.

<Antimicrobial nonwoven sheet>
The antibacterial nonwoven sheet of the present invention is a fiber (hereinafter referred to as “antibacterial EVOH-containing fiber” or simply “antibacterial fiber”) in which an antibacterial ethylene-vinyl alcohol copolymer is present on at least a part of the fiber surface. And a solvent-spun cellulose fiber are entangled with each other, and the above-mentioned uniformly mixed fibers are made into a non-woven fabric by a hydroentanglement method or the like, whereby soft and bulky fiber entanglement The body is realized.

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

The antibacterial ethylene-vinyl alcohol copolymer used in the present invention has an ethylene unit ratio (copolymerization ratio) of 10 to 70 mol%, and the remainder is a vinyl alcohol unit alone, or vinyl alcohol and other vinyls. It consists of repeating units of a monomer. The proportion of ethylene units is preferably 20 to 55 mol%, more preferably 30 to 50 mol%. In the case where a vinyl alcohol unit and other vinyl monomer units are used in combination, the ratio of the vinyl alcohol unit is not particularly limited, but is usually larger than other vinyl monomer units, preferably in a molar ratio. Is (vinyl alcohol unit): (other vinyl monomer units) = 55: 45 to 99.9: 0.1, more preferably 70:30 to 99.9: 0.1, particularly preferably 80:20 to 99.9: 0.1.

When the proportion of ethylene units in the ethylene-vinyl alcohol copolymer is less than 10 mol%, the spinnability at the time of fiberization becomes poor, and the single yarn breakage at the time of spinning and the breakage of the yarn increase. Moreover, it becomes inflexible. Furthermore, there is a problem that the shape changes due to swelling with water at a low temperature (20 to 60 ° C.).

On the other hand, when the proportion of ethylene units exceeds 70 mol%, the proportion of vinyl alcohol units, that is, hydroxyl groups inevitably decreases, so that the hygroscopicity is reduced and the effect of inorganic antibacterial fine particles held inside the copolymer is reduced. Is not preferable because it cannot be sufficiently obtained.

The ethylene-vinyl alcohol copolymer can be obtained by saponifying the vinyl acetate portion of the ethylene / vinyl acetate copolymer, and the saponification of vinyl alcohol units in the ethylene-vinyl alcohol copolymer. The degree 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%. When the degree of saponification is too small, not only physical properties such as strength are lowered, but also thermal stability is lowered, and stability is lowered due to thermal decomposition and gelation. On the other hand, if the degree of saponification is too large, it is difficult to produce the fiber itself.

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

The ethylene-vinyl alcohol copolymer is commercially available, for example, under the trade name “EVAL” from Kuraray Co., Ltd. and under the trade name “Soarnol” from Nippon Synthetic Chemical Industry Co., Ltd. It is. Further, an ethylene / vinyl acetate copolymer may be produced from commercially available ethylene and vinyl acetate by radical polymerization or the like and saponified.

The type of inorganic antibacterial fine particles used in the present invention is not particularly limited, and any of the inorganic antibacterial fine particles that do not cause volatilization, decomposition, alteration, etc. due to heating at the time of melt spinning of the fiber and whose antibacterial action does not decrease in a short period of time. Can also be used.

Examples of the inorganic antibacterial fine particles include inorganic antibacterial fine particles in which metal ions having an antibacterial action such as silver ions, copper ions, zinc ions and tin ions are encapsulated in an inorganic carrier, and titanium oxide inorganic antibacterial fine particles. 1 type, or 2 or more types of these can be used.

The type of the inorganic carrier used in the present invention is not particularly limited as long as it contains metal ions having antibacterial properties and can suppress the degradation effect of the fiber. For example, such an inorganic carrier has an inclusion lattice. An inorganic carrier is preferably used. The inclusion lattice is a gap that allows atoms and molecules to enter, and the inorganic powder having the inclusion lattice has a property of trapping molecules in a structure having a minute layered or cage-like cavity.

Examples of inorganic carriers having an inclusion lattice include zeolites, layered phosphates (zirconium phosphate, titanium phosphate, calcium phosphate, etc.), layered clay minerals, transition metal chalcogenides, graphite, transition metal oxides, layered oxyacid salts, etc. Is mentioned. These inorganic carriers may be used alone or in combination of two or more.

Among them, zeolite having a high ion exchange capacity and zirconium phosphate are particularly preferable. Among the inorganic antibacterial fine particles described above, in the present invention, inorganic antibacterial fine particles in which silver ions are held on the above-described inorganic carrier are particularly preferably used.

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, preferably 0.3 to 6 μm. It is more preferable that If the average particle size of the inorganic antibacterial fine particles is larger than 20 μm, it is not preferable because spinning, filter clogging are likely to occur during spinning, and the inorganic antibacterial fine particles are liable to fall off from the fibers. When trying to obtain finer fibers, the inorganic antibacterial fine particles must be smaller than the fiber diameter, and the ratio of the inorganic antibacterial fine particle diameter / fiber diameter is desirably 0.8 or less. On the other hand, if the average particle size of the inorganic antibacterial fine particles is less than 0.01 μm, aggregation between the inorganic antibacterial fine particles is likely to occur during kneading, and the inorganic antibacterial fine particles are uniformly dispersed in the ethylene-vinyl alcohol copolymer. Since it becomes difficult, it is not preferable.

The addition amount of the inorganic antibacterial fine particles contained in the antibacterial ethylene-vinyl alcohol copolymer used in the present invention is 0.01 to 10% by weight based on the weight of the ethylene-vinyl alcohol copolymer. It is preferably 0.1 to 5% by weight, more preferably 0.5 to 1.5% by weight. Depending on the ion exchange capacity or adsorption amount of antibacterial metal ions in inorganic fine particles, 90% or more of the ion exchange capacity or metal ion adsorption capacity is an inorganic fine particle that is ion exchanged or adsorbed with antibacterial metal ions (antibacterial Even if the metal fine particles holding inorganic particles) are used, if the amount of the fine particles containing antibacterial metal ions is less than 0.01% by weight, it is difficult to impart sufficient antibacterial performance to the fiber, especially durability. It is difficult to obtain antibacterial performance. On the other hand, if the added amount of the antibacterial metal ion-carrying inorganic fine particles exceeds 10% by weight, the antibacterial performance is sufficient, but aggregation between the inorganic antibacterial fine particles tends to occur in the fiberizing process, and the filter is clogged. This is not preferable because it may occur.

Further, the ethylene content (E: mol%) of the ethylene-vinyl alcohol copolymer used in the present invention and the proportion of inorganic antibacterial fine particles in the ethylene-vinyl alcohol copolymer (W: wt%). And may have the relationship of the following formula.

For example,
1 ≦ (100−E) × W ≦ 90
And preferably
5 ≦ (100−E) × W ≦ 80
It is.

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 therein at least on the outer surface. It may be a fiber made of an antibacterial ethylene-vinyl alcohol copolymer alone or a composite fiber with another thermoplastic polymer.

Other thermoplastic polymers used in the present invention are not particularly limited as long as they can be combined with an antibacterial ethylene-vinyl alcohol copolymer, and a wide variety can be used depending on the purpose of the fiber. For example, other thermoplastic polymers include polyolefin resins, polyester resins, polyamide resins, polyvinyl chloride, polyvinylidene chloride, styrene resins, polyvinyl acetate resins, acrylic resins, polylactic acid resins, Examples thereof include thermoplastic polymers such as polycarbonate resins and thermoplastic elastomers. An ethylene-vinyl alcohol copolymer that does not have antibacterial properties may be used as another thermoplastic polymer.

Of these, polyolefin resins, polyester resins, and polyamide resins are preferably used from the viewpoints of heat resistance, fiber formation, and dimensional stability, and hydrophobic resins such as polyolefin resins and polyester resins are more preferable. Particularly preferred. This point will be described later.

Polyolefin resins are preferably polypropylene, polyethylene and the like, and these polyolefin resins may also contain other copolymerizable units.

Polyester resins include aromatic polyester resins such as poly C _2-4 alkylene arylate resins (polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), especially polyethylene such as PET. A terephthalate resin is preferred. In addition to the ethylene terephthalate unit, the polyethylene terephthalate resin is not limited to other dicarboxylic acids (for example, isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, 4,4′-diphenylcarboxylic acid, bis (carboxyphenyl) ethane. , 5-sodium sulfoisophthalic acid, etc.) and diols (eg, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, Units composed of polyethylene glycol, polytetramethylene glycol, etc.) may be contained in a proportion of 20 mol% or less.

Polyamide resins include polyamide 6, polyamide 6-6, polyamide 6-10, polyamide 10, polyamide 12, polyamide 6-12 and other aliphatic polyamides, and copolymers thereof, aromatic dicarboxylic acids and aliphatic diamines. Semi-aromatic polyamide synthesized from the above is preferred. These polyamide-based resins may also contain other copolymerizable units.

When the antibacterial EVOH-containing fiber of the present invention is a composite fiber, the composite ratio of ethylene-vinyl alcohol copolymer: other thermoplastic polymer is 10:90 to 90:10 by weight ratio. It is desirable. Outside this range, the composite ratio becomes unbalanced, which causes problems such as bending of the released yarn after nozzle discharge and unfavorable spinnability. The composite ratio of ethylene-vinyl alcohol copolymer: other thermoplastic polymer is more preferably 30:70 to 70:30 by weight.

As a composite form in the composite fiber, a sheath core type, a sea-island type, and a lamination are used as long as an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles is contained in at least a part of the outer surface. Arbitrary forms, such as a type | mold and those mixed types, are mentioned. In the case of the sheath core type, any of a two-layer sheath core type and a multilayer sheath core type having three or more layers may be used. In the case of the sea-island type, the shape, number, and dispersion state of the islands can be arbitrarily selected, and part of the islands may be exposed on the fiber surface. Further, 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 in the fiber cross section perpendicular to the fiber length direction. The bonded portions may be parallel, radial, or any other shape.

Among the composite forms described above, the sheath-core type composite fiber is particularly preferable in terms of antibacterial performance because an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles is disposed on the entire fiber surface. Furthermore, in the case of the antibacterial nonwoven sheet of the present invention, if a single fiber of an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles is used, the rigidity decreases due to liquid absorption (absorption of the fluid composition). As a result, it is difficult to maintain the space between the fibers due to the influence of liquid absorption and external force applied at the time of manufacturing, processing, packaging, etc. and its use. It may be difficult to ensure excellent liquid retention and workability. On the other hand, by using a sheath-core type composite fiber and using a hydrophobic resin for the core part, even if the sheath part absorbs liquid, the core part does not absorb liquid and the rigidity does not change. In addition, it is possible to maintain the desired bulkiness, that is, the porosity and to secure the liquid absorbency, maintain the stiffness of the antibacterial nonwoven sheet even in the wet state, and maintain the feel when restrained by the skin. Is possible.

That is, in order to secure a high porosity with the antibacterial nonwoven fabric sheet of the present invention, it is preferable that the antibacterial nonwoven fabric sheet is composed of fibers having high Young's modulus (initial tensile resistance) and high bending elasticity. In particular, in order to ensure high fiber elasticity even when the antibacterial nonwoven sheet is in a liquid-absorbed state during these processing steps, it is preferable that the constituent fibers are made of a highly elastic resin. As the Young's modulus is higher, the porosity when the nonwoven fabric is formed can be maintained, so that the liquid retention can be maintained and the workability can be improved.

In the antibacterial nonwoven sheet of the present invention, when the content of the antibacterial EVOH-containing fiber described later is 40 to 90% by weight, the Young's modulus of the antibacterial EVOH-containing fiber is preferably 25 cN / dtex or more. In particular, the Young's modulus of the antibacterial EVOH-containing fiber is more preferably 25 to 90 cN / dtex, further preferably 30 to 70 cN / 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 obtained antibacterial nonwoven sheet 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 is a single fiber (single-phase fiber) of an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles. However, a sheath-core type composite fiber is preferable because it is easy to achieve both elasticity, liquid retention and liquid release properties.

In the case where the antibacterial EVOH-containing fiber used in the present invention is a sheath-core type composite fiber, the sheath is preferably made of a hydrophilic resin in order to ensure wettability and liquid retention. The sheath composed of a hydrophilic resin is used to incorporate the fluid composition into the antibacterial nonwoven sheet when a fluid composition containing cosmetics (beauty liquid) is added to the antibacterial nonwoven sheet. It plays an important role and also holds a large amount of cosmetics once taken into the antibacterial nonwoven sheet so as not to drip when handled during use.

Resins with a higher Young's modulus than ethylene-vinyl alcohol copolymers and excellent spinnability in combination with ethylene-vinyl alcohol copolymers include polyolefin resins and polyester resins. Polyester resin is optimal in that the shrinkage of the antibacterial nonwoven sheet is high and the workability is good.

In order to maintain the porosity of the antibacterial non-woven sheet, the liquid retention amount is high, the non-woven fabric is stiff and the workability when wet is good, the sheath-core type composite fiber is preferable, and the diameter of the core part Is preferably 5 to 15 μm. More preferably, the core has a diameter of 8 to 12 μm. As described above, a hydrophobic resin, particularly a polyester resin is preferably used for the core. When the diameter of the core is less than 5 μm, the stiffness of the fiber is lowered, resulting in a problem that the density of the nonwoven fabric is increased and the impregnation amount of the fluid composition is likely to be lowered. Furthermore, the stiffness of the nonwoven fabric is also lowered, and the spreadability and the wearability in the state impregnated with the fluid composition may be lowered. On the other hand, when the diameter of the core exceeds 15 μm, the stiffness of the fiber becomes too strong, so that the liquid-containing sheet (described later) used by impregnating a fluid composition containing cosmetics, particularly used to cover the face. In some cases, along the face may decrease, and the density of the nonwoven fabric decreases due to the strong stiffness of the fibers, so the distance between the fibers in the nonwoven fabric becomes too long to hold the cosmetics between the fibers, and unnecessary liquid is released. It becomes easy to do.

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 an irregular shape. In the case of an irregular cross section, for example, a flat shape, an oval shape, a triangle shape, a quadrilateral shape, a pentagon shape, a hexagon shape, a heptagon shape, an octagon shape, and other polygonal shapes, T shapes, H shapes, V shapes, dog bones (I shapes) Shape) can be any shape such as a multi-leaf shape such as a 3 to 8 leaf shape, or a hollow cross-sectional shape thereof.

The fineness of the antibacterial EVOH-containing fiber used in the present invention can be selected from the range of 0.01 to 100 dtex, for example, preferably 0.5 to 30 dtex, more preferably 1.0 to 10 dtex, depending on the application. When the fineness of the antibacterial EVOH-containing fiber is less than 0.01 dtex, the inorganic antibacterial fine particles easily fall off from the fiber. When the fineness of the antibacterial EVOH-containing fiber exceeds 100 dtex, the antibacterial present in the resin Since the performance of the agent is not fully exhibited and the stiffness of the fiber is too strong, the liquid-containing sheet, particularly the face mask, used to impregnate a fluid composition containing cosmetics, especially used to cover the face In the case of (described later), the conformity to the face may be reduced, and the density of the nonwoven fabric is reduced due to the strong stiffness of the fibers, so the distance between the fibers in the nonwoven fabric becomes too long and the cosmetic cannot be held between the fibers. Since it becomes easy to discharge | release a liquid, it is not preferable.

The antibacterial EVOH-containing fiber used in the present invention or the fiber product using the fiber is further added with conventional additives such as stabilizers (heat stabilizers such as copper compounds, ultraviolet absorbers, light stabilizers, antioxidants). Agent), fine particles, colorant, fluorescent brightener, antistatic agent, flame retardant, deodorant, plasticizer, lubricant, crystallization rate retarder, and the like. These additives can be used alone or in combination of two or more. These additives may be contained in the fiber or may be supported on the surface of the fiber assembly.

The production method of the antibacterial EVOH-containing fiber used in the present invention is not particularly limited. For example, when the composite fiber is composed of two components with a hydrophobic resin, each resin is melted in a separate extruder. It can be obtained by kneading and subsequently guiding both the resins to a spinning head, discharging them from the same spinning nozzle, and taking them off by a take-up roller.

In addition, the antibacterial EVOH-containing fiber used in the present invention is usually drawn and used, and the drawing method is a step of drawing between hot rolls when the fiber discharged from the nozzle during spinning is taken up by a take-up roller. Alternatively, a two-step method may be employed in which the film is drawn once and then hot-drawn at a low speed in a water bath or a hot stove.

The aforementioned antibacterial EVOH-containing fiber is excellent in touch and hydrophilicity. However, for example, when an antibacterial EVOH-containing fiber is used to make an antibacterial nonwoven sheet, the impregnation property when impregnated with an aqueous fluid composition is excellent, but the fiber itself has low water absorption. In addition, the liquid absorption speed is slow, and it is difficult to retain the retained aqueous fluid composition in the sheet space. Therefore, when the aqueous fluid composition is impregnated and used, it takes time to absorb the liquid and the workability efficiency is lowered, or a part of the aqueous fluid composition is unnecessarily released from the inside of the sheet and flows down. Therefore, the antibacterial nonwoven sheet of the present invention does not use 100% of the antibacterial EVOH-containing fiber, and the antibacterial EVOH-containing fiber is used in combination with a solvent-spun cellulose-based fiber and entangled with each other. is important.

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

When the content of the antibacterial EVOH-containing fiber is less than 30% by weight, the unique squeaky feeling of the cellulosic fiber is particularly strong when wet, and the smoothness of the obtained antibacterial nonwoven sheet is reduced. In addition, when the content of the antibacterial EVOH-containing fiber is less than 30% by weight, the ratio of incorporating the fluid composition into the fiber increases, and effective use on the skin is hindered. On the other hand, when the content of the antibacterial EVOH-containing fiber exceeds 90% by weight, the impregnation power, particularly the impregnation speed, is lowered, and the fluid composition holding power is lowered, and the fluid composition is unnecessarily released from the inside of the sheet. It is not preferable because it will flow down and become useless.

Solvent-spun cellulosic fibers used in the present invention are different from so-called regenerated cellulosic fibers, such as conventional viscose rayon and copper ammonia rayon, in which cellulose is once chemically converted to a cellulose derivative and then returned to cellulose again. It means a fiber (purified cellulose fiber) in which cellulose is precipitated from a solution obtained by simply dissolving it in a solvent without chemically changing the cellulose.

A preferred example of the solvent-spun cellulose fiber used in the present invention was produced by a method of further stretching a fiber obtained by subjecting a spinning stock solution in which cellulose is dissolved in amine oxide to dry and wet spinning in water to precipitate cellulose. A cellulosic fiber is mentioned. A typical example of such a fiber is lyocell, which is sold under the trade name “Tencel” (registered trademark) by the Austrian Lenzing company. Such a fiber is very preferable because it has a round or oval cross-sectional shape unlike a regenerated cellulosic fiber used for general purposes, and therefore has a low risk of damaging the skin when used by other people. Furthermore, since the fiber strength of viscose rayon fiber decreases under wet conditions, the sheet obtained by mixing this fiber will be deformed and work in a wet state impregnated with a fluid composition containing chemicals. Sex is reduced. For example, when it is used as a liquid-containing sheet (described later) comprising a fiber and a flowable composition containing a cosmetic, the wearability is inferior. On the other hand, the antibacterial nonwoven sheet of the present invention is very preferable because it hardly deteriorates even under wet conditions, and does not change in form and has excellent wearability.

Usually, the solvent-spun cellulose fiber is often beaten by a beater, refiner, high-speed disaggregator, etc. to fibrillate the fiber, but in the present invention, fine fibers adhere to the face due to fiber fibrillation. In order to prevent this, it is desirable to use solvent-spun cellulosic fibers that are not substantially fibrillated.

The single fiber fineness of the solvent-spun cellulose-based fiber is not particularly limited, but it is preferably 1 to 3 dtex, since the softness when touching the skin is often preferred. It is preferably 1 to 2 dtex, more preferably 1.3 to 1.7 dtex. When the single fiber fineness exceeds 3 dtex, the touch to the skin may be deteriorated, or the liquid absorbability and liquid retention of the fluid composition containing the cosmetic may be inferior. On the other hand, if it is less than 1 dtex, the density of the nonwoven fabric increases and the inter-fiber voids decrease, which is not preferable because the amount of impregnation of the fluid composition decreases.

Furthermore, the polarity of the entire antibacterial nonwoven sheet can be adjusted by the mixing ratio of the antibacterial EVOH-containing fiber and the solvent-spun cellulosic fiber and the resin polarity of the antibacterial ethylene-vinyl alcohol copolymer. Although the amount of impregnation of the object and the touch can be determined, by adjusting the thickness of each fiber, the touch can be adjusted without affecting the amount of impregnation of the fluid composition. That is, when solvent-spun cellulose-based fibers are thickened, the number of cellulose-based fibers decreases and the surface area decreases with the same basis weight, and the hydrophilicity of the resulting antibacterial nonwoven fabric sheet decreases. On the contrary, when the cellulose fiber is thinned, the hydrophilicity of the antibacterial nonwoven sheet increases. Moreover, about the touch, it becomes rough by similarly making this cellulose fiber thick.

For example, when the mixing ratio of the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber is 60:40, the ethylene component of the antibacterial ethylene-vinyl alcohol copolymer is 50 mol%, and the saponification degree is 98%, Antibacterial EVOH content for solvent-spun cellulosic fibers for use in liquid-containing sheets (especially face masks) (described later) in which an antibacterial non-woven sheet used by coating and the like and a fluid composition containing cosmetics are integrated The ratio of fiber thickness is preferably in the range of 0.3 to 3.0, and more preferably in the range of 0.3 to 2.0.

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 cellulosic fiber is too long, uniform entanglement between the fibers becomes difficult. In particular, if the entanglement between the two fibers is insufficient, the uniformity of the antibacterial nonwoven sheet is insufficient. Thus, not only the touch is deteriorated, but also the problem that the efficiency of liquid absorption and release of the fluid composition is reduced is not preferable. In addition, if the fiber length of the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber is too short, not only is the fiber coming out of the antibacterial nonwoven sheet easily generated, but also flexibility and stretchability are lowered, which is not preferable. From this point of view, the fiber length of the antibacterial EVOH-containing fiber and solvent-spun cellulose fiber used in the present invention is preferably 5 to 60 mm, and more preferably 10 to 50 mm. The ratio of the fiber length of the solvent-spun cellulose fiber and 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 EVOH-containing fiber and the solvent-spun cellulosic fiber are uniformly blended to form a web, which can be entangled by hydroentanglement to obtain the desired antibacterial nonwoven sheet. It can be formed by a direct method such as a spun bond method or a melt blow method, a dry method such as a card method or an airlaid method using staple fibers, or a wet method. Among these, the dry method is most suitable as the method for producing the antibacterial nonwoven sheet of the present invention, since it is easier to mix the fibers and secure the space for impregnating the fluid composition. As the staple fiber web in this case, a random web, a semi-random web, a parallel web, a cross wrap web, or the like is preferably used. In forming the web, it is preferable that the antibacterial EVOH-containing fiber and the solvent-spun cellulosic fiber are mixed with the above-described mixing ratio.

In the antibacterial nonwoven fabric sheet of the present invention, it is preferable that the surface has irregularities, and as described above, the constituent webs are entangled by subjecting the obtained web to hydroentanglement and irregularities are formed on the surface. Can be made. The irregularities are formed on the surface of the antibacterial nonwoven sheet by carrying out the production under predetermined conditions at the time of hydroentanglement. As a result, not only the voids in the nonwoven fabric but also the fluid composition can be held in the recesses on the surface of the antibacterial nonwoven sheet. It becomes possible to hold a fee. Further, at this time, the entire fiber absorbs water from the water flow, and a part of the solvent-spun cellulose-based fiber that is easy to move by the force of the water flow extends in the water flow direction, that is, in the height direction of the convex portion, and at the same time has hydrophilicity and lipophilicity. When the antibacterial EVOH-containing fiber shown is a sheath-core type composite fiber with a hydrophobic resin, it is difficult to move in the height direction of the convex part because of the hydrophobicity and rigidity of the core part, so most of the fibers are It becomes the form extended in the nonwoven fabric surface direction. Since these fibers are basically in a state of being mixed with each other, the antibacterial nonwoven sheet of the present invention has both hydrophilicity and lipophilicity. Both can hold. In addition, the fluid composition held here does not enter the tissue of the nonwoven fabric, and therefore, the liquid-containing sheet in which the antibacterial nonwoven fabric sheet of the present invention and the fluid composition containing cosmetics are integrated is The presence of cosmetics on the surface of the antibacterial nonwoven sheet makes it very easy to migrate to the skin, and expresses a very good migration to the skin. Even when the cosmetic is uneven on the surface of the antibacterial nonwoven sheet, the fiber itself has both hydrophilic and oleophilic properties, so that the cosmetic does not flow down.

The above-mentioned unevenness is preferably continuous in a certain direction at a pitch of 0.04 to 0.5 mm, while the height difference between the recesses and the protrusions is in the range of 0.1 to 0.4 mm. If the height difference is less than 0.1 mm, the surface of the nonwoven fabric becomes too smooth, and the fluid composition cannot be held using the surface irregularities, so that the impregnation property is lowered, which is not preferable. Further, since the entire surface comes into contact with the skin, a feeling of stuffiness or stickiness is generated at the time of wearing, which is not preferable. If the height difference exceeds 0.4 mm, the portion that holds the fluid composition becomes large, so that the amount of liquid retention is improved, but the ratio of solvent-spun cellulose-based fibers tends to be high near the convex tip, Since the liquid absorption behavior at this portion depends on the properties of the solvent-spun cellulose-based fiber, the liquid retention amount is improved while the liquid discharge property is likely to be lowered. Furthermore, the smoothness of the surface is hindered, the touch is lowered, and the feeling of wearing is lowered, which is not preferable. On the other hand, when the pitch is less than 0.04 mm, the recesses become too narrow, and the fluid composition containing cosmetics cannot enter, making it difficult to effectively use the surface irregularities and holding the fluid composition, which is not preferable. Furthermore, when the pitch exceeds 0.5 mm, it becomes difficult to hold the fluid composition that has entered the concave portion because the inter-fiber distance of the portion constituting the convex portion is too wide.

The irregularities on the surface of the nonwoven fabric described above can be processed for a sheet in which fibers are entangled with each other in advance by hydroentanglement. The pre-treated hydroentanglement is a nozzle in which a web is arranged on a metal perforated plate or a woven structure support and nozzles having a nozzle diameter of 0.08 to 0.2 mm and a pitch of 0.4 to 1 mm are arranged in one to three rows A preferred method is one or a plurality of times of treatment from a plate with a water flow of 1 to 6 MPa, more preferably 2 to 4 MPa.

The irregularities on the surface of the nonwoven fabric described above are preferably formed by water flow treatment on the fiber woven structure in at least the final treatment of the water flow entanglement treatment. As the support for the woven structure, the warp and the weft are each preferably made of monofilaments having a wire diameter of 0.01 to 1 mm, more preferably 0.02 to 0.5 mm, and the thickness of the woven structure is 0.1 to 1 mm. It is preferable to use one. When the diameter of the monofilament exceeds 1 mm, the fiber moves to the periphery where the warp is present on the weft, and a hole is formed in the surface of the nonwoven fabric, resulting in poor surface smoothness. Further, from a nozzle provided with orifices having a hole diameter of 0.05 to 0.3 mm, more preferably 0.08 to 0.2 mm from above the woven structure at intervals of 0.4 to 1 mm, a water pressure of 6 to 15 MPa, more preferably A columnar water flow of 8 to 10 MPa may be jetted onto the web that has been entangled to some extent in the previous stage.

By such hydroentanglement treatment, an antibacterial nonwoven fabric sheet having irregularities suitable for holding the fluid composition on the surface can be obtained.

As will be described later, the antibacterial nonwoven sheet of the present invention is suitably used by integrating with water to form a water-containing sheet or by integrating with a fluid composition containing cosmetics to form a liquid-containing sheet. be able to. When the antibacterial nonwoven sheet of the present invention is used as a liquid-containing sheet, the copolymer composition of the ethylene-vinyl alcohol copolymer used in the present invention is adjusted according to the polarity of the fluid composition containing the cosmetic. The impregnating property of the fluid composition can be improved.

That is, when using the lipophilic fluid composition, it is preferable to use a copolymer having a high ethylene composition. When using the hydrophilic fluid composition, it is preferable to use a copolymer having a low ethylene composition. . Similarly, the hydrophilicity can be adjusted by the degree of saponification. Furthermore, not only the degree of saponification but also the affinity with various fluids can be adjusted by the type of unsaponified ester and the functional group modification of the hydroxyl group.

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

Although the actual impregnation property varies depending on the viscosity of the fluid composition, the copolymer composition of the ethylene-vinyl alcohol copolymer and / or the solvent spinning is considered in consideration of the balance with the touch and the liquid retaining property. It can adjust by the ratio of a cellulosic fiber.

The antibacterial EVOH-containing fiber and solvent-spun cellulose fiber having such properties are uniformly mixed to form a single layer, and the porosity is 80 to 95% so as to have a predetermined inter-fiber gap. By making the hydroentangled non-woven fabric into a lightweight, total hydrophilic and oleophilic balanced in a high dimension, it is easy to absorb both oily and aqueous components to the same extent and to release easily. It becomes possible.

The antibacterial nonwoven sheet of the present invention can be along a surface having a complicated shape due to this flexibility, particularly in a wet state, and this is at the time of 50% wet extension in at least one direction of the nonwoven fabric. It is correlated with stress, and this value is preferably 500 g / 50 mm or less. More preferably, it is 400 g / 50 mm or less, More preferably, it is 300 g / 50 mm or less. When this value exceeds 500 g / 50 mm, it becomes difficult for the base material to follow the unevenness of the face, and it becomes difficult to replenish cosmetics to the entire face. On the other hand, when the stress at the time of 50% wet extension is less than 100 g / 50 mm in, for example, a nonwoven sheet that is not entangled or insufficiently entangled, the processability at the time of nonwoven fabric production is Since troubles such as failure and poor handling may occur, it is not suitable for the antibacterial nonwoven sheet of the present invention.

The basis weight suitable for the antibacterial nonwoven fabric sheet of the present invention is preferably in the range of 30 to 100 g / m ² from the viewpoint of adhesion to the skin and liquid absorption, and particularly preferably in the range of 40 to 70 g / m ² . When the basis weight is less than 30 g / m ² , the absolute fiber amount is decreased, and the amount of the fluid composition that can be absorbed and held between the fibers is extremely decreased. On the other hand, when the amount exceeds 100 g / m ² , the amount of fibers becomes too large, and the thickness of the antibacterial nonwoven fabric sheet becomes too thick.

The apparent density of the antibacterial nonwoven sheet of the present invention is not particularly limited, but is preferably 0.03 to 0.20 g / cm ³ , more preferably 0.05 to 0.17 g / cm ³ , and still more preferably. Is 0.06 to 0.15 g / cm ³ , particularly preferably 0.08 to 0.12 g / cm ³ . If the apparent density is too low, the liquid holding capacity of the antibacterial nonwoven fabric sheet is low, and dripping easily occurs during handling during use. On the other hand, when the apparent density of the antibacterial nonwoven fabric sheet is too high, the liquid retention amount decreases.

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

In addition, the antibacterial nonwoven sheet of the present invention needs to ensure the desired liquid absorbency as well as the liquid release property at the same time. That is, the antibacterial nonwoven sheet of the present invention uses both fibers having hydrophilicity and lipophilicity as constituent fibers, so that liquids having both properties are absorbed and adsorbed. Of these, the lipophilic component is mainly held by the antibacterial EVOH-containing fiber part, and the hydrophilic component is partly held by the antibacterial EVOH-containing fiber and the majority is held by the solvent-spun cellulosic fiber. it can. These liquids are retained on the fiber surface, and those that cannot be retained directly on the fiber surface because of the amount exceeding this amount are the same type of fibers (antibacterial EVOH-containing fibers or solvent-spun cellulose fibers). By filling and holding in the enclosed fiber voids, it becomes possible to secure a liquid amount that is equal to or greater than the adsorption amount of the nonwoven fabric constituting fibers. Therefore, for the sake of convenience, the void ratio is used in order to clarify the existence of the void filled with the liquid described here. The antibacterial nonwoven sheet of the present invention preferably has a porosity of 80 to 95%. More preferably, it is 85 to 93%. When the porosity exceeds 95%, the distance between fibers is too wide, and the fluid composition cannot be held by the hydrophilic portion of the fibers, which is not preferable. On the other hand, if it is less than 80%, the distance between the fibers is too small, and the fluid composition cannot enter the nonwoven fabric, so that the amount of liquid absorption is reduced.

<Liquid sheet, face mask>
The present invention has excellent antiseptic and antibacterial properties without containing parabens, is soft and soft, and is impregnated with a fluid composition containing cosmetics such as a cosmetic liquid, and is pressed with a finger. The present invention also provides a liquid-containing sheet and a face mask in which the flowable composition returns quickly. In other words, the present inventors can absorb a fluid composition by entanglement of antibacterial EVOH-containing fibers containing a specific antibacterial ethylene-vinyl alcohol copolymer as a component with solvent-spun cellulose fibers. In a liquid-containing sheet in which an antibacterial nonwoven sheet is formed and the antibacterial nonwoven sheet and the flowable composition are integrated, flow including cosmetics such as cosmetic liquids is controlled by controlling the recovery to compression in the thickness direction. It has also been found that the fluid composition can be quickly returned even if it is pushed with a finger in a state impregnated with the fluid composition.

In the liquid-containing sheet of the present invention, the fluid composition may be water (in this case, referred to as “water-containing sheet”), or may contain a cosmetic. When a fluid composition containing a cosmetic is used, it can be suitably used for a skin care sheet, and particularly preferably used for a face mask. That is, the antibacterial nonwoven sheet of the present invention is used for absorbing and using a fluid composition, for example, a surface material such as a napkin or a diaper, a diaper liner, a sheet for absorbing a body fluid such as a wet tissue (or a skin cleanser). Sheet, etc.), but it has an excellent balance between liquid retention and release and can be easily adhered to the skin. Applications in which a sheet (liquid-containing sheet) impregnated with an antibacterial non-woven fabric is in close contact with the skin, for example, face mask, makeup removing sheet or cleansing sheet, body washing sheet (sweat wipe sheet, oil removing sheet, etc.), cooling sheet , Preferably used for various skin care sheets such as medicinal or therapeutic sheets (itch prevention sheets, compresses etc.) For even faster return of the flowable composition, particularly preferably used in a face mask.

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 (so-called wet sheet) used by impregnating the fluid composition in advance. Good.

There is no restriction | limiting in particular in a fluid composition in the use which impregnates a fluid composition in the antibacterial nonwoven fabric sheet of this invention. Examples thereof include aqueous fluid compositions such as water, aqueous solutions, and aqueous emulsions, organic solvents, solutions using these as a medium, and mixtures thereof. Moreover, the fluid composition which melt | dissolved and / or disperse | distributed various solid, liquid, gas which melt | dissolves well in these fluid compositions is also used suitably. An antibacterial nonwoven fabric sheet having excellent functionality can be obtained by a flowable composition in which various active ingredients are dissolved and / or dispersed. The flowable composition also includes a solution or dispersion (cosmetics, milky lotion, cosmetic liquid, etc.) containing active ingredients such as cosmetic ingredients or medicinal (efficacy) ingredients. Of these, hydrophilic fluid compositions including aqueous fluid compositions and fluid compositions containing polar organic solvents are advantageous from the viewpoint of impregnation, and also advantageous from the viewpoint of safety to the human body. It is. In particular, an aqueous fluid composition is most advantageous from the viewpoint of liquid retention. Examples of the polar organic solvent include various organic solvents having a polar functional group. Examples of the polar functional group include a hydroxyl group, an aldehyde group, a carboxyl group, an alkoxycarbonyl group, an ether group, a carbonyl group, an amino group, a nitro group, and a thio hydroxyl group. , Etc. Examples of these hydrophilic fluid compositions include water, lower aliphatic alcohols (eg, C _1-6 alkyl alcohols such as ethanol and isopropanol), and alkylene glycols (eg, ethylene glycol, diethylene glycol, propylene glycol and the like). ) And the like. Unsaturated higher fatty acids (eg, oleic acid, oleyl alcohol, etc.), animal and vegetable oils (eg, jojoba oil, olive oil, palm oil, camellia oil, macadamian nut oil, avocado oil, corn oil, sesame oil, wheat Germ oil, linseed oil, castor oil, squalane, etc.), mineral oil (eg, liquid paraffin, polybutene, silicone oil, etc.), synthetic oil (eg, synthetic ester oil, synthetic polyether oil, etc.) are also suitably used. .

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

Flowable compositions include conventional additives such as humectants or emollients (eg, dipropylene glycol, 1,3-butylene glycol, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymers, polyoxypropylenes). Ethylene sorbitan fatty acid ester, polyoxyethylene sucrose fatty acid ester, glycerin, sodium hyaluronate, polyoxymethyl glycoside, polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose ether (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl Methylcellulose, etc.), UV protection agents, surfactants, astringents, enzymes, cooling agents, bactericides or antibacterial agents, emollients ( For example, salicylic acid or derivatives thereof, lactic acid, urea etc., antioxidants (eg tocopherol or derivatives thereof, polyphenols such as anthocyanins), whitening agents (eg ascorbic acid or derivatives thereof, cysteine, placenta extract, arbutin, Kojic acid, lucinol, ellagic acid, chamomile extract, etc.), antiperspirants (eg, astringents such as aluminum compounds, zinc compounds, tannins), rough skin prevention agents (eg, glycyrrhizinate, vitamins, etc.) Inflammatory agents (eg, allantoin, guaiazulene, glycyrrhizic acid or its salt, glycyrrhetinic acid or its salt, ε-aminocaproic acid, tranexamic acid, ibuprofen, indomethacin, etc.), blood circulation promoter (eg, peony, rosemary, clove) ), Vitamins (eg, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, vitamin K, etc.), amino acids (eg, tryptophan, cysteine, etc.), cell activators (eg, riboflavin, pyridoxine, nicotinic acid) Pantothenic acid, α-tocopherol, or derivatives thereof, plant extracts such as Yukinosita extract, etc.), fragrances (for example, synthetic fragrances, essential oils, essential oil components, etc.), etc. Two or more types can be used in combination.

Among these additives, for skin care sheets, for example, moisturizers, ultraviolet absorbers, surfactants, cooling agents, enzymes, astringents, bactericides, or antibacterial agents are generally used. In particular, in a face mask (face pack), for example, a humectant or an emollient may be blended in a hydrophilic solvent. The total proportion of the humectant and the emollient is, for example, 0.1 to 50% by weight, preferably 1 to 30% by weight, more preferably 5 to 20% by weight in the solution.

The proportion of these additives can be appropriately selected depending on the application. For example, the proportion of water or ethanol is usually 30 to 99% by weight, preferably 40 to 95% in the total fluid composition containing the additive. % By weight, more preferably 50 to 90% by weight.

The amount of impregnation 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 depending on the purpose of the user. For example, the fluid containing the water-containing sheet or cosmetic provided by the present invention In the liquid-containing sheet in which the functional composition and the antibacterial nonwoven sheet are integrated, 200 to 1000% by weight with respect to the weight of the substrate is preferable from the viewpoints of cost and performance.

In the liquid-containing sheet of the present invention comprising the antibacterial nonwoven sheet and the flowable composition containing the cosmetic, the antibacterial nonwoven sheet has a high liquid-absorbing performance capable of holding a sufficient amount of the cosmetic. It is necessary to be. In the present invention, this is expressed by using the liquid absorption speed and the liquid retention rate.

First, the antibacterial nonwoven sheet suitable for the liquid-containing sheet of the present invention needs to have excellent liquid absorption performance, and the preferable liquid absorption speed is 5 seconds or less. More preferably, it is 3 seconds or less, More preferably, it is 2 seconds or less, Most preferably, it is 1.5 seconds or less. When the liquid absorption speed exceeds 5 seconds, the fluid composition containing the cosmetic is difficult to impregnate, and in particular, when the fluid composition containing the individual cosmetic is impregnated in each household, the fluid composition is used. May flow down on the surface, and as a result, the antibacterial nonwoven sheet is not impregnated with the cosmetic material, which is wasteful. As a fluid composition containing cosmetics, an oil fluid composition generally has a high viscosity, and an aqueous fluid composition tends to have a low viscosity. If the viscosity is low, the liquid absorption rate tends to increase. In the former, the preferred liquid absorption speed is 5 seconds or less, while in the latter, it is 3 seconds or less.

An antibacterial nonwoven fabric sheet suitable for a liquid-containing sheet using a flowable composition containing cosmetics needs to be able to supply a sufficient amount of cosmetics to the skin. For this reason, it is necessary that the liquid retention ratio, which is the ratio of the liquid retention amount to the nonwoven fabric basis weight, which is an index of the liquid retention amount of the fluid composition containing cosmetics to the antibacterial nonwoven sheet, is higher, and is preferable. The liquid ratio is 900% or more, more preferably 1000% or more. In order to impregnate a flowable composition containing a desired amount of cosmetics with an antibacterial nonwoven sheet having a low liquid retention rate, it is necessary to prepare various antibacterial nonwoven sheets with different basis weights and compositions according to the amount of impregnation. Although it occurs, the antibacterial nonwoven sheet of the present invention can cope with various amounts of impregnation with one kind.

In addition, when the liquid-containing sheet of the present invention is applied to the face, the flowable composition containing cosmetics flows along the face in the nonwoven fabric, and finally does not cause troubles such as dripping from the chin and soiling the clothes. It is also important. In the present invention, this performance is expressed as a liquid dripping rate, and this value is preferably 3.5% or less. More preferably, it is 3% or less, More preferably, it is 2.5% or less.

And it is extremely important that the flowable composition containing the cosmetic material impregnated in a large amount in the antibacterial nonwoven fabric sheet and held so as not to dripping by the method as described above efficiently migrates to the skin. . In the present invention, this is expressed as a release rate, and this value is desirably 95% or more. If the release rate is less than 95%, an effective cosmetic is incorporated into the fiber and cannot be effectively used on the skin. It is preferable that the ratio of the fluid composition containing the cosmetic retained and retained by the antibacterial nonwoven sheet is 95% or more.

In particular, the liquid-containing sheet of the present invention does not necessarily have a high basis weight by balancing at a high level in the impregnation property of the flowable composition containing cosmetics, that is, the liquid absorption speed and the liquid retention amount, the liquid dripping rate, and the release rate. Without securing, it is possible to realize a liquid-containing sheet that has excellent wet fit and can supply a sufficient amount of cosmetics to the skin.

The antibacterial nonwoven sheet of the present invention is usually used by impregnating the fluid composition, but it may be used by impregnating the fluid composition at the time of use, or may be impregnated with the fluid composition in advance. Also good. In the former case, there is a merit that the user can make a liquid-containing sheet impregnated by selecting his / her favorite cosmetic for use of the liquid-containing sheet containing the cosmetic, for example. Moreover, the product package can be simplified by being supplied in a dry state.

When used for the liquid-containing sheet described above, the antibacterial nonwoven sheet is a cosmetic component or a medicinal (efficacy) component (for example, a moisturizing component, a cleansing component, an antiperspirant component, a scent component, a whitening component, a blood circulation promoting component, a cooling component, an ultraviolet ray) It has a wettability necessary for impregnating a fluid composition containing an absorbent component, a skin itch suppressing component, etc.) and a gap for retaining the liquid, and it is prescribed for the body without dripping even during handling. It is preferable to hold until it covers the part (for example, the face), stick or leave it, and to have the role of shifting the cosmetic gradually to the skin side. The antibacterial nonwoven sheet is excellent in liquid retention and has a proper stiffness or elasticity, and when impregnated with the fluid composition, the reversion to compression and the return of the fluid composition are fast. When the antibacterial nonwoven sheet is formed with high elastic fibers having a specific Young's modulus, the fluid composition is excellent in returnability and the thickness is quickly recovered. Can be recovered in a short time.

With regard to the above-described decompression with respect to compression, specifically, when the flowable composition is impregnated with 900% by weight with respect to its own weight and a load of 260 g / cm ² is applied for 1 minute and removed, the decompression with respect to compression in the thickness direction does not occur. It is preferably 35% or more (for example, 35 to 100%) in 5 minutes, more preferably 50 to 99% (for example, 60 to 95%), still more preferably 65 to 90% (particularly 70 to 85%). It is. If the repositioning is less than 35%, the fluid composition such as a cosmetic liquid cannot sufficiently return to the pressing portion. In addition, the said rearrangement can be measured by the method as described in the Example mentioned later in detail.

Regarding the return of the fluid composition described above, specifically, when the fluid composition is impregnated with 900% by weight with respect to its own weight, and a load of 620 g is applied to a circular portion having a diameter of 1.2 cm and removed for 1 minute. The return rate of the serum after 5 minutes may be 45% or more, for example, 50 to 99%, preferably 60 to 98% (for example, 65 to 95%), more preferably 70 to 92% ( Especially 80 to 90%). If the return rate is too low, the fluid composition after pressing is insufficient, and the face mask cannot sufficiently penetrate the cosmetic liquid into the skin. The return rate can be measured in detail by the method described in the examples described later.

When used in the liquid-containing sheet of the present invention, the antibacterial nonwoven sheet is excellent in flexibility when wet and is appropriately intertwined so that it can follow the skin such as the face, and is wet according to JIS L 1913. The stress at 30% elongation at the time (wet stress at 30% elongation) is preferably 0.5 to 10 N / 5 cm, more preferably 1 to 8 N / 5 cm, still more preferably 1.5 to 5 N / in at least one direction. 5 cm, particularly preferably 2 to 4 N / 5 cm. If the stress at 30% wet extension is too small, it will be too difficult to handle when it is attached to the skin such as the face, and if it is too large, the adhesion to the skin will decrease. The stress at 30% elongation can be measured in detail by the method described in Examples described later.

When the fluid composition contains water, the water-containing sheet of the present invention can be provided with a function by containing at least one of the fluid composition and the active ingredient in addition to water. These fluid compositions and active ingredients do not need to be water-soluble, but those having a high affinity with water can improve the homogeneity of the water-containing sheet and increase the fluid composition and active ingredients that add functions. It is easy to impregnate the antibacterial nonwoven sheet at a concentration. In addition, it is advantageous in terms of production efficiency as well as improving the homogeneity of the water-containing sheet to be integrated with the antibacterial nonwoven sheet together with water in the state of an aqueous solution, dispersion or emulsion. In particular, aqueous solutions, aqueous dispersions, and aqueous emulsions have a high affinity with the solvent-spun cellulose-based fibers of the antibacterial nonwoven sheet of the present invention, and can be integrated at a high concentration with the antibacterial nonwoven sheet, so that a high function can be obtained. It is even more advantageous in terms of homogeneity and production efficiency.

The fluid composition containing the cosmetic used for the liquid-containing sheet of the present invention is in the state of, for example, a solution, a dispersion, or an emulsion. Further, for example, it contains at least one of water and the above fluid composition. The cosmetic includes at least one substance having a 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 no fluidity. When the cosmetic itself has fluidity, the cosmetic composition alone may be integrated with the antibacterial nonwoven sheet as a fluid composition, but the fluidity composition is usually mixed with other liquids to increase fluidity. As well as improving the production efficiency when integrating, the release characteristics are also improved. Since the liquid mixed with cosmetics has high affinity with cosmetics, it can be integrated with the antibacterial nonwoven sheet at a high concentration, so that a high function can be obtained, and the fluid composition containing cosmetics and the antibacterial nonwoven sheet can be combined. This is even more advantageous in terms of the homogeneity and production efficiency of the integrated liquid-containing sheet. There is no restriction | limiting in particular as a function of the cosmetics to be used, The cosmetics which have various functions normally known can be used 1 type or in mixture.

As described above, the present invention also provides a face mask using a liquid-containing sheet in which a fluid composition containing a cosmetic and an antibacterial nonwoven sheet are integrated. Although the sheet | seat produced by fuse | melting a heat-adhesive component like the patent document 1 mentioned above improves the shrinkage | contraction at the time of wetness, the whole sheet | seat becomes hard and the along property to skin falls. Furthermore, since the surface of the sheet is mainly composed of hydrophilic fibers, it will take in the chemical solution impregnated in the fibers, and it will not be able to be sufficiently wiped off to the object to be wiped. In the case of a sheet to be coated, there arises a problem that an active ingredient such as a cosmetic liquid cannot be sufficiently released. Moreover, although the nonwoven fabric sheet disclosed in Patent Document 2 described above is excellent in flexibility and liquid retention, the sheet has low stiffness (rigidity), and when pressed with a finger to bring the face mask into close contact with the face, the thickness is reduced. Recovery and recovery of cosmetic liquid (cosmetics) is slow. For this reason, it is difficult to efficiently spread the cosmetic liquid over the entire face. In particular, in the face mask, although it is necessary to press and touch the place where the cosmetic liquid is desired to be replenished or where the close contact is difficult, the face mask adheres to the target part in the conventional face mask. The serum was not supplied enough. In addition, in order to improve the conformity of the face mask to the skin (face), face masks with a layer formed of ultrafine fibers on the skin contact side and face masks with a three-dimensional structure have been developed. ing. However, even with these face masks, the conformity to the skin is not sufficient, and the current situation is that the action of pressing and adhering the pasted face mask once with a finger is repeated. Therefore, by repeating the action of pressing against the skin, the cosmetic liquid stored in the pressed part is pushed out each time, resulting in an insufficient state of the cosmetic liquid.

According to the present invention, a face mask in which such a conventional problem is solved is also provided. That is, the antibacterial nonwoven sheet of the present invention, as described above, uses a specific antibacterial fiber and solvent-spun cellulose fiber to form a nonwoven fabric that can absorb the fluid composition, and the thickness of the antibacterial nonwoven sheet. Since the reversion to compression in the direction is controlled, the antibacterial property is excellent, and even when pressed with a finger in a state impregnated with a liquid component such as a cosmetic liquid, the fluid composition quickly returns. Moreover, even if it pushes with a finger | toe in the state impregnated with the fluid composition, thickness recovery is quick. Therefore, for example, when it is used as a face mask, it is possible to efficiently replenish the cosmetic liquid to a desired site. Furthermore, by using a sheath-core type composite fiber having a sheath part formed of an ethylene-vinyl alcohol copolymer, flexibility, liquid retention, and form stability can be improved.

The antibacterial nonwoven sheet of the present invention is particularly suitable as a liquid-containing sheet that is fixed not only to a face mask but also to a skin such as a poultice because it has excellent adhesion to the skin. For example, since the liquid-containing sheet of the present invention can easily correct a floating part without being in close contact, the liquid-containing sheet can be in close contact with fine gaps such as the base of the nose, and the active ingredient of the liquid-containing sheet is effectively applied to the skin. Can penetrate.

The liquid-containing sheet of the present invention is also suitable for cleansing sheets, skin cleaning sheets, and the like. As described above, since the liquid-containing sheet of the present invention can adhere the sheet to minute gaps on the face, makeup (makeup cosmetics such as foundation, white 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 liquid-impregnated biofilm sheet, it is usually used by impregnating the liquid-containing sheet with a fluid composition and sticking or contacting the skin of a living body. Therefore, it is important to be antibacterial. The liquid-containing sheet of the present invention may be laminated with other layers. For example, in order to promote absorption of active ingredients, a non-porous film or sheet may be laminated on the side not in contact with the skin. Good.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, each physical property value in a present Example was measured with the following method.

[Spinnability]
In the spinning process in fiber production, when the spun yarn is cooled and solidified and then taken up on a bobbin via a take-up roller, the case where the yarn can be taken out without being broken is defined as “a: good spinnability”. The spinnability was evaluated as “b: poor spinnability” when the yarn was cut and could not be taken up, and when yarn breakage occurred at the single yarn level and fluff was generated.

[Fineness]
Evaluation was made according to JIS L 1015 “Testing method for chemical fiber staples (8.5.1)”.

[Strength]
Evaluation was performed according to JIS L 1015 “Testing method for chemical fiber staples (8.7.1)”.

[Elongation]
Evaluation was performed according to JIS L 1015 “Testing method for chemical fiber staples (8.7.1)”.

[Young's modulus]
Examples 7 to 11 and Comparative Examples 9 to 17 were evaluated according to JIS L 1015 “Testing method for chemical fiber staples (8.11)”.

[Antimicrobial]
150 g of the antibacterial nonwoven fabric sheet obtained in Examples or Comparative Examples was put into a bucket containing 20 liters of water at a temperature of 60 ° C., scoured for 30 minutes, rinsed for 30 minutes, dehydrated and dried. The scoured non-woven sheet was tested for antibacterial properties in accordance with JIS L 1902 “Antimicrobial test method and antibacterial effect of textile products”. In addition, Staphylococcus aureus and Klebsiella pneumoniae were used as test bacteria (bacterial solution concentration 1 / 20NB, fungus liquid drop amount 0.2ml), cotton cloth was used as an unprocessed sample, and the bactericidal activity value was calculated from the following formula. . In addition, when a bactericidal activity value is 0 or more, it is recognized that there exists a bactericidal effect.

-Bacteriostatic activity value: a value representing the difference in the number of viable bacteria before and after the action time as a logarithm. Bacteriostatic activity value = Log (A / B)
A = Number of bacteria dispersed and recovered immediately after inoculation of unprocessed specimen B = Number of bacteria dispersed and recovered after 18 hours of incubation of processed specimen [Thickness]
The thickness of the antibacterial nonwoven fabric sheet obtained in Examples or Comparative Examples was measured according to JIS L 1096 “Fabric and Knitted Fabric Test Method (8.5)”. The thickness meter was measured using a Digimatic indicator manufactured by Mitutoyo Corporation at a measuring point of 1 inch (diameter) and a load of 12 g / cm ² .

[Unit weight]
The basis weight of the antibacterial nonwoven fabric sheet obtained in the examples or comparative examples was measured according to JIS P 8124 “Paper and paperboard basis weight measurement method”.

[Porosity]
The porosity (%) of the antibacterial nonwoven fabric sheet obtained in Examples or Comparative Examples is calculated from the following formula based on the nonwoven fabric basis weight (g / m ² ), fiber specific gravity (g / cm ³ ), and nonwoven fabric thickness (cm). Calculated with

Porosity (%) = 100 − {(nonwoven fabric basis weight / fiber ratio / nonwoven fabric thickness) / 100}
[touch]
The touch when the antibacterial nonwoven fabric sheet obtained in Examples or Comparative Examples was touched was subjected to sensory evaluation by five subjects according to the following criteria.
<Evaluation criteria>
X: The touch is good. Y: The touch is not good. Z: The touch is not good. [Liquid absorption speed]
The liquid absorption rate of the antibacterial nonwoven fabric sheet obtained in Examples or Comparative Examples was measured according to JIS L 1907 “Fabricity Water Absorption Test Method (7.1.1 (Drip Method))”. A drop of liquid was dropped from 1 cm above the non-woven fabric in a state of gripping the surroundings with a burette, and the time until no special light reflection of the droplets on the surface was measured. The following tests I and II were carried out with the liquid to be dropped.

Test I: Ion-exchanged water Test II: Nisshin Oillio Group Co., Ltd. Edible oil blend [Retention rate]
The liquid retention of the antibacterial nonwoven fabric sheet obtained in Examples or Comparative Examples was measured in accordance with JIS L 1907 “Fabricity Water Absorption Test Method (7.2 (Water Absorption Rate Method))”. A test piece is cut into a 5 cm square and the weight C (g) is measured. The test piece was immersed in a flowable composition containing cosmetics (Asan Roller Lotion manufactured by Asan Co., Ltd.) for 30 seconds. Thereafter, the test piece was taken out from the liquid with one side, and the weight D (g) after 10 seconds and the weight E (g) after 1 minute were measured.

The liquid retention rate F (%) is calculated by the following formula.
Liquid retention ratio F (%) = {(EC) / 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 whose liquid retention rate was measured was sandwiched between filter papers (corrected filter paper No. 2) cut into a 10 cm square and weighed to about 2.5 g, and a 2 kg weight was placed from above, and left for 1 minute. After 1 minute, a sample is taken out and the increased weight H (g) of the filter paper weight is measured.

The release rate G (%) of the fluid composition containing the cosmetic composition was calculated by the following formula.
G (%) = {H / (EC)} × 100
[Relocation]
The original repeat positions of the antibacterial nonwoven fabric sheets of Examples 7 to 11 and Comparative Examples 9 to 17 were measured as follows. A sample cut in 5 cm in the MD direction and 5 cm in the CD direction is prepared, and impregnated with 900% of a cosmetic liquid (“Freschel Essence Lotion NA” manufactured by Kanebo Cosmetics Co., Ltd.) with respect to the sample weight, as shown in FIG. The sample 3 was spread on an acrylic plate (measuring table) 4 and allowed to stand, and the initial thickness was measured with a laser displacement meter 1. Next, a load 2 of 260 g / cm ² was placed in the center of the original fabric (nonwoven fabric) for 60 seconds, and the displacement from immediately after removing the load until 300 seconds was measured. When the thickness of the original fabric before measurement was I, the thickness immediately after removing the load was J, and the thickness after removing the load was 300 K, the original repeat position (%) was determined according to the following formula.

Original repeat position (%) = [(I−K) / (I−J)] × 100
[Liquid return]
The liquid return of the antibacterial nonwoven fabric sheets of Examples 7 to 11 and Comparative Examples 9 to 17 to the original fabric was measured as follows. A sample cut in MD direction 5 cm × CD direction 5 cm was prepared, and impregnated with 900% beauty liquid (“Freschel Essence Lotion NA” manufactured by Kanebo Cosmetics Co., Ltd.) with respect to the sample weight, as shown in FIG. The sample 3 was spread on an acrylic plate (measuring table) 14 and allowed to stand, and a 620 g load 12 was placed on a circular central portion having a diameter of 1.2 cm for 60 seconds, and the serum immediately after the load was removed. The width of the part where there was no was measured. Furthermore, the width | variety of the part which does not have a cosmetic liquid 300 seconds after removing a load was measured. When the width of the part without the cosmetic liquid immediately after removing the load is L, and the width of the part without the cosmetic liquid 300 seconds after removing the load is M, the liquid return (%) to the original fabric is expressed according to the following formula. Asked.

Liquid return to original fabric (%) = [(LM) / L] × 100
[Uneven height difference]
The difference in height between the concave and convex portions on the surface of the antibacterial nonwoven fabric sheet obtained in the examples or comparative examples is the difference in height between the concave and convex portions observed by cross-section of the nonwoven fabric using a microscope KEYENCE VH-6300. The difference was calculated by measuring three points and averaging.

[Wet 50% elongation stress]
The stress at the time of 50% wet extension of the antibacterial nonwoven fabric sheets of Examples 1 to 6 and Comparative Examples 1 to 8 was measured using Shimadzu Autograph AGS-50D, sample width 50 mm, measurement length 100 mm, measurement speed 200 mm / When the tensile test is performed at min, the strength value when the elongation reaches 50% is indicated.

[Wet 30% elongation stress]
The stress at 30% wet elongation of the antibacterial nonwoven fabric sheets of Examples 7 to 11 and Comparative Examples 9 to 17 was measured according to JIS L 1913 “General nonwoven fabric test method (6.3.2 (Tensile strength and elongation test when wet). )) ”Was measured according to the method described. Specifically, the sample was placed in water at 20 ° C. ± 2 ° C. until it settled under its own weight, or after being submerged in water for 1 hour or longer, the sample was taken out from the immersion liquid and the stress at 30% elongation was measured immediately. .

(Reference Example 1: Single fiber)
(1) Silver-based inorganic antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average) in which 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% is supported by silver ions on an inorganic ion exchanger 1 part by weight of a particle size of 2.5 μm and a substantially cubic shape) was blended and spun by a melt extruder at a spinning temperature of 240 ° C. The spun yarn was cooled and solidified, and then taken up on a bobbin via a take-up roller.

(2) Next, this crimped yarn is heat-drawn at a draw temperature of 80 ° C. at a draw ratio of 2 times, and after applying an oil agent in an oil agent bath, a crimp applying device such as a stuffer-type crimp applying device is used. The crimping process was performed. Following the crimping treatment, the fiber was dried with hot air at 100 ° C. and then cut to 51 mm to obtain an antibacterial EVOH-containing fiber (1.7 dtex, 51 mm long, circular cross section). Both spinnability and stretchability were good, the strength was 2.4 cN / dtex, and the elongation was 33%. The evaluation results are shown in Table 1.

(Reference Example 2: Composite fiber)
(1) Silver-based inorganic antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average) in which 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% is supported by silver ions on an inorganic ion exchanger Using a composite spinning apparatus composed of a melt extruder with a copolymer blended with 1 part by weight of a particle size of 2.5 μm and a substantially cubic shape) as a sheath part and a thermoplastic polymer composed of polyethylene terephthalate as a core part, Spinning was carried out with a round cross-section die bonded to a sheath core mold at a spinning temperature of 280 ° C. and a sheath core weight ratio of 50:50. The spun yarn was cooled and solidified, and then wound on a bobbin via a take-up roller.

(2) Next, this crimped yarn is heat-drawn at a draw temperature of 80 ° C. at a draw ratio of 2 times, and after applying an oil agent in an oil agent bath, a crimp applying device such as a stuffer-type crimp applying device is used. The crimping process was performed. Following the crimping treatment, the fiber was dried with hot air at 100 ° C. and then cut to 51 mm to obtain an antibacterial EVOH-containing fiber (3.4 dtex, 51 mm length, sheath core weight ratio 50:50, circular cross section , Core diameter 12.5 μm). Both spinnability and stretchability were good, the strength was 2.9 cN / dtex, and the elongation was 27%.

(Reference Example 3: Composite fiber)
(1) The anti-bacterial properties shown in Table 1 below are obtained by heat-drawing the weft yarn of Reference Example 2 at a drawing temperature of 80 ° C. at a draw ratio of 2 and applying an oil agent in an oil bath and cutting it to 10 mm. EVOH-containing fibers were obtained (3.4 dtex, 10 mm length, sheath core weight ratio 50:50, circular cross section, core diameter 12.5 μm). Both spinnability and stretchability were good, the strength was 2.9 cN / dtex, and the elongation was 27%.

(Reference Example 4: Single fiber)
Silver-based inorganic antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average particle size 2) in which 99% by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 85 mol% is supported by silver ions on an inorganic ion exchanger. 0.5 μm, approximately cubic shape) 1 part by weight was blended, and yarns were produced in the same manner as in Reference Example 1 to obtain antibacterial EVOH-containing fibers (1.7 dtex, 51 mm long, circular cross section). Both spinnability and stretchability were good, the strength was 3.1 cN / dtex, and the elongation was 38%.

(Reference Example 5: Composite fiber)
The yarn was produced in the same manner as in Reference Example 2 except that the resin discharge rate, take-up speed, and draw ratio were adjusted so that the fineness was 5.5 dtex to obtain antibacterial EVOH-containing fibers (3.4 dtex, 51 mm length, (Sheath core weight ratio 50:50, circular cross section, core diameter 16.0 μm). Both spinnability and stretchability were good, the strength was 2.9 cN / dtex, and the elongation was 36%.

(Reference Example 6: Composite fiber)
(1) Using a composite spinning device consisting of a melt extruder with a ethylene polymer 44 mol% ethylene-vinyl alcohol copolymer as a sheath and a thermoplastic polymer made of polyethylene terephthalate as a core, The spinneret was spun at a spinning temperature of 280 ° C. and a sheath core weight ratio of 50:50. The spun yarn was cooled and solidified, and then wound on a bobbin via a take-up roller.

(2) Next, this crimped yarn is heat-drawn at a draw temperature of 80 ° C. at a draw ratio of 2 times, and after applying an oil agent in an oil agent bath, a crimp applying device such as a stuffer-type crimp applying device is used. The crimping process was performed. Subsequent to crimping treatment, the fiber was dried with hot air at 100 ° C. and then cut to 51 mm to obtain EVOH-containing fiber (3.4 dtex, 51 mm length, sheath core weight ratio 50:50, circular cross section, core Part diameter 12.5 μm). Both spinnability and stretchability were good, the strength was 3.6 cN / dtex, and the elongation was 38%.

[Example 1]
A card web having a weight per unit area of about 60 g / m ² was prepared by mixing 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 1 and 30% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length) manufactured by Lenzing. .

Next, a water flow was sprayed on the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 92%. The results of each evaluation are shown in Table 1.

This sheet had sufficient liquid retention and release properties and good touch.
[Example 2]
A card web having a weight per unit area of about 60 g / m ² was prepared by mixing 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 2 and 30% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length). .

Next, a water flow was sprayed on the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 1. This sheet had sufficient liquid retention and release properties and good touch.

[Example 3]
70% by weight of the antibacterial EVOH-containing fiber of Reference Example 3 and 30% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 12 mm length) manufactured by Lenzing, dispersed in water, and a basis weight of about 60 g by a wet method. A wet nonwoven fabric of / m ² was produced.

Next, a water stream was sprayed on the wet nonwoven fabric, and an entanglement treatment was performed to obtain a water-entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 90%. The results of each evaluation are shown in Table 1. This sheet had sufficient liquid retention and release properties and good touch.

[Example 4]
A card web having a weight per unit area of about 60 g / m ² was prepared by mixing 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 5 and 30% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length) manufactured by Lenzing. .

Next, a water flow was sprayed on the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 97%. The results of each evaluation are shown in Table 1. This sheet had sufficient liquid retention and release properties and good touch.

[Example 5]
A water stream was sprayed onto the card web obtained in Example 2 and entangled to give a water-entangled nonwoven fabric with a basis weight of 60 g / m ² to obtain the antibacterial nonwoven sheet of the present invention. In the water entanglement treatment, a nozzle in which orifices having a diameter of 0.15 mm were provided at intervals of 0.6 mm in the web width direction was entangled by jetting water pressure of 8 MPa in two steps on the front and back sides. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 99%. The results of each evaluation are shown in Table 1. While this sheet had sufficient liquid retention and release properties, the touch was slightly inferior.

[Example 6]
The same procedure as in Example 1 was conducted except that 10% by weight of the antibacterial EVOH-containing fiber obtained in Reference Example 2 and 90% by weight of solvent-spun cellulose-based fiber were mixed to produce a card web having a basis weight of 60 g / m ^2. An antibacterial nonwoven sheet was obtained. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 88%. The results of each evaluation are shown in Table 1. This sheet had a good touch although it was slightly inferior in liquid retention and release properties.

[Comparative Example 1]
An attempt was made to produce yarn in the same manner as in Reference Example 2, except that silver-based inorganic antibacterial fine particles (manufactured by Sinanen Zeomic Co., Ltd., average particle size: 0.008 μm, approximately cubic shape) in which silver ions are supported on an inorganic ion exchanger However, stable spinning could not be performed due to poor spinnability.

[Comparative Example 2]
Although we tried to produce yarn in the same manner as in Reference Example 2 except that silver-based inorganic antibacterial fine particles (Sinanen Zeomic Co., Ltd., average particle size 25 μm, approximately cubic shape) in which silver ions were supported on an inorganic ion exchanger were blended. Stable yarn could not be produced due to poor spinnability.

[Comparative Example 3]
Silver-based inorganic antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average particle diameter of 2), in which 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 8 mol% is supported by silver ions on an inorganic ion exchanger. .5 μm, approximately cubic shape) 1 part by weight was blended and an attempt was made to produce yarn in the same manner as in Reference Example 1. However, stable spinning could not be achieved due to poor spinnability.

[Comparative Example 4]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 4 and 30% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length) manufactured by Lenzing. .

Subsequently, a water flow was sprayed on this card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 93%. The results of each evaluation are shown in Table 2. Although this sheet had a good touch, it was inferior in liquid retention and release properties and was difficult to use because of its low water absorption rate.

[Comparative Example 5]
An antibacterial nonwoven fabric sheet was obtained in the same manner as in Example 1 except that a card web having a basis weight of 60 g / m ² was prepared using 100% by weight of the antibacterial EVOH-containing fiber obtained in Reference Example 2. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 96%. The results of each evaluation are shown in Table 2. Although this sheet had excellent liquid retention and release properties, it was difficult to use because of its low water absorption rate, and the touch was somewhat inferior.

[Comparative Example 6]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 2 and 30% by weight of the cotton fiber manufactured by Marusan Co., Ltd.

Subsequently, a water flow was sprayed on this card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 94%. The results of each evaluation are shown in Table 2. This sheet was not satisfactory in terms of liquid retention, release, flexibility, and fit to the skin.

[Comparative Example 7]
The wet nonwoven fabric obtained in Example 3 was used as an antibacterial nonwoven fabric sheet without any hydroentanglement treatment. The results of each evaluation are shown in Table 2. The non-woven fabric sheet had a porosity of 78%, and although it had a good touch at first, it was inferior in liquid retention and release properties and was not satisfactory in handling.

[Comparative Example 8]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 50% by weight of the EVOH-containing fiber of Reference Example 6 and 50% by weight of solvent-spun cellulose-based fiber (Lyocell, 1.7 dtex, 38 mm length) manufactured by Lenzing.

Next, a water flow was sprayed onto the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain a nonwoven fabric sheet. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 2. This sheet had sufficient liquid retention and release properties and a good touch, but was extremely inferior in antibacterial properties.

(Reference Example 7: Single fiber)
(1) Silver antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average particle diameter) in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% 2.5 parts by weight (approximately 2.5 μm, approximately cubic shape) was blended and spun in a melt extruder at a spinning temperature of 240 ° C. The spun yarn was cooled and solidified, and then taken up on a bobbin via a take-up roller.

(2) Next, this crimped yarn is heat-drawn at a drawing temperature of 80 ° C. at a draw ratio of 2.4 times, and after applying an oil agent in an oil bath, a crimp applying device such as a stuffer-type crimp applying device. The crimp process was performed using. Subsequent to the crimping treatment, the fiber was dried with hot air at 100 ° C. and then cut into an arbitrary cut length to obtain an antibacterial EVOH-containing fiber (1.4 dtex, circular cross section). Both spinnability and stretchability were good, the strength was 3.1 cN / dtex, the elongation was 26%, and the Young's modulus was 30.8 cN / dtex.

(Reference Example 8: Composite fiber)
(1) Silver antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average particle diameter) in which silver ions are supported on an inorganic ion exchanger in 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% A round cross section using a compound spinning apparatus consisting of a melt extruder with a copolymer blended with 1 part by weight as a sheath and a thermoplastic polymer composed of polyethylene terephthalate as a core. The spinneret was spun at a spinning temperature of 280 ° C. and a sheath core weight ratio of 50:50. The spun yarn was cooled and solidified, and then wound on a bobbin via a take-up roller.

(2) Next, this crimped yarn is heat-drawn at a drawing temperature of 80 ° C. at a draw ratio of 2.6 times, and after applying an oil agent in an oil bath, a crimp applying device such as a stuffer-type crimp applying device. The crimp process was performed using. Following the crimping treatment, the fiber was dried with hot air at 100 ° C., and then cut into an arbitrary cut length to obtain the antibacterial EVOH-containing fiber shown in Table 3 below (1.7 dtex, sheath core weight ratio) 50:50, circular cross section, core diameter 8.9 μm). Both spinnability and stretchability were good, the strength was 3.6 cN / dtex, the elongation was 31%, and the Young's modulus was 33.9 cN / dtex.

(Reference Example 9: Composite fiber)
(1) The anti-bacterial property shown in Table 3 below is obtained by heat-drawing the weft yarn of Reference Example 8 at a drawing temperature of 80 ° C. at a draw ratio of 2 and applying an oil agent in an oil bath and cutting it to 10 mm. An EVOH-containing fiber was obtained (1.7 dtex, 10 mm length, sheath core weight ratio 50:50, circular cross section, core diameter 8.9 μm). Both spinnability and stretchability were good, the strength was 3.6 cN / dtex, the elongation was 31%, and the Young's modulus was 33.9 cN / dtex.

(Reference Example 10: Single fiber)
Silver-based inorganic antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average particle size 2) in which 99% by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 85 mol% is supported by silver ions on an inorganic ion exchanger. 0.5 μm, approximately cubic shape) 1 part by weight was blended, and yarns were produced in the same manner as in Reference Example 7 to obtain antibacterial EVOH-containing fibers (1.4 dtex, 51 mm length, circular cross section). Both spinnability and stretchability were good, the strength was 3.7 cN / dtex, the elongation was 24%, and the Young's modulus was 35.1 cN / dtex.

(Reference Example 11: Composite fiber)
The yarn was produced in the same manner as in Reference Example 8 except that the resin discharge amount, take-up speed, and draw ratio were adjusted so that the fineness was 5.5 dtex, and antibacterial EVOH-containing fibers were obtained (5.5 dtex, 51 mm length, (Sheath core weight ratio 50:50, circular cross section, core diameter 16.0 μm). Both spinnability and stretchability were good, the strength was 2.7 cN / dtex, the elongation was 36%, and the Young's modulus was 28.7 cN / dtex.

(Reference Example 12: Composite fiber)
(1) Using a composite spinning device consisting of a melt extruder with a ethylene polymer 44 mol% ethylene-vinyl alcohol copolymer as a sheath and a thermoplastic polymer made of polyethylene terephthalate as a core, The spinneret was spun at a spinning temperature of 280 ° C. and a sheath core weight ratio of 50:50. The spun yarn was cooled and solidified, and then wound on a bobbin via a take-up roller.

(2) Next, this crimped yarn is heat-drawn at a draw temperature of 80 ° C. at a draw ratio of 2 times, and after applying an oil agent in an oil agent bath, a crimp applying device such as a stuffer-type crimp applying device is used. The crimping process was performed. Subsequent to crimping treatment, the fiber was dried with hot air at 100 ° C. and then cut to 51 mm to obtain EVOH-containing fiber (3.4 dtex, 51 mm length, sheath core weight ratio 50:50, circular cross section, core Part diameter 12.5 μm). Both spinnability and stretchability were good, the strength was 3.6 cN / dtex, the elongation was 38%, and the Young's modulus was 38.5 cN / dtex.

[Example 7]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 7 and 50% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length). .

Next, a water flow was sprayed on the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 90%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the original fabric, and good touch.

[Example 8]
A card web having a basis weight of about 60 g / m ² was prepared by blending 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 50% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length). .

Next, a water flow was sprayed on the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 92%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the original fabric, and good touch.

[Example 9]
50% by weight of the antibacterial EVOH-containing fiber of Reference Example 9 and 50% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 12 mm length) manufactured by Lenzing, dispersed in water, and a basis weight of about 60 g by a wet method. A wet nonwoven fabric of / m ² was produced.

Next, a water stream was sprayed on the wet nonwoven fabric, and an entanglement treatment was performed to obtain a water-entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 86%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the original fabric, and good touch.

[Example 10]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 11 and 50% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length). .

Next, a water flow was sprayed on the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 94%. The results of each evaluation are shown in Table 3. This sheet had sufficient liquid retention, liquid return to the original fabric, and good touch.

[Example 11]
The card web obtained in Example 8 was sprayed with a water flow and entangled to obtain a water-entangled nonwoven fabric with a basis weight of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In the water entanglement treatment, a nozzle in which orifices having a diameter of 0.15 mm were provided at intervals of 0.6 mm in the web width direction was entangled by jetting water pressure of 8 MPa in two steps on the front and back sides. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 98%. The results of each evaluation are shown in Table 3. While this sheet had sufficient liquid retention and liquid return to the original fabric, the result was slightly inferior to the touch.

[Comparative Example 9]
An attempt was made to produce yarn in the same manner as in Reference Example 8, except that silver inorganic antibacterial fine particles (manufactured by Sinanen Zeomic Co., Ltd., average particle size 0.008 μm, substantially cubic shape) in which silver ions were supported on an inorganic ion exchanger were blended However, stable spinning could not be performed due to poor spinnability.

[Comparative Example 10]
Although we tried to produce yarn in the same manner as in Reference Example 8, except that silver-based inorganic antibacterial fine particles (manufactured by Sinanen Zeomic Co., Ltd., average particle size 25 μm, approximately cubic shape) in which silver ions were supported on an inorganic ion exchanger were blended Stable yarn could not be produced due to poor spinnability.

[Comparative Example 11]
Silver-based inorganic antibacterial fine particles (“AV10D” manufactured by Sinanen Zeomic Co., Ltd., average particle diameter of 2), in which 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 8 mol% is supported by silver ions on an inorganic ion exchanger. .5 μm, approximately cubic shape) 1 part by weight was blended, and an attempt was made to produce a yarn in the same manner as in Reference Example 7. However, the yarn could not be produced stably due to poor spinnability.

[Comparative Example 12]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 10 and 50% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length). .

Next, a water flow was sprayed onto the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of about 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Further, the porosity of the obtained liquid retaining sheet was 91%. The results of each evaluation are shown in Table 4.

Although this sheet had a good touch, liquid retention and liquid return to the original fabric were not sufficient.

[Comparative Example 13]
An antibacterial nonwoven fabric sheet was obtained in the same manner as in Example 7 except that a card web having a weight per unit area of 60 g / m ² was prepared from the antibacterial EVOH-containing fiber obtained in Reference Example 8. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 96%. The results of each evaluation are shown in Table 4.

This sheet was not satisfactory for liquid return to the original fabric, and further, it was difficult to use because of its low water absorption rate, and the touch was poor.

[Comparative Example 14]
A card web having a basis weight of about 60 g / m ² is prepared by blending 35% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 65% by weight of solvent-spun cellulose fiber (Lyose manufactured by Lenzing Co., Ltd., 1.7 dtex, 38 mm length). did.

Subsequently, a water flow was sprayed on this card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 4.

This sheet was not satisfactory in terms of liquid retention, liquid absorption speed, and liquid return to the original fabric.

[Comparative Example 15]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 30% by weight of the cotton fiber manufactured by Marusan Co., Ltd.

Next, a water flow was sprayed on the card web, and an entanglement treatment was performed to obtain a water entangled nonwoven fabric having a basis weight of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet of the present invention. In the hydroentanglement process, a nozzle having 0.1 mm diameter orifices provided at intervals of 0.6 mm in the width direction of the web was used, and water pressure of 6 MPa was jetted in two steps on the front and back sides to be entangled. Moreover, the porosity of the obtained antibacterial nonwoven fabric sheet was 93%. The results of each evaluation are shown in Table 4.

This sheet was not satisfactory in terms of liquid retention, flexibility, and fit to the skin.

[Comparative Example 16]
The wet nonwoven fabric obtained in Example 9 was used as an antibacterial nonwoven fabric sheet without any hydroentanglement treatment. The porosity of this antibacterial nonwoven fabric sheet was 74%, and although it had a good touch at first, it was inferior to the stress when stretched by 30% when wet, and was not satisfactory in handleability.

[Comparative Example 17]
A card web having a basis weight of about 60 g / m ² was prepared by mixing 50% by weight of the EVOH-containing fiber of Reference Example 12 and 50% by weight of solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm length) manufactured by Lenzing.

The sheet had sufficient liquid retention and release properties and good touch, but was inferior in antibacterial properties.

The antibacterial nonwoven sheet of the present invention absorbs a liquid component and makes contact with the skin, for example, a body fluid absorbing sheet (for example, a surface material such as a napkin or a diaper, a diaper liner, a wet tissue), a skin care sheet (for example, , Face masks, makeup removing sheets, cleansing sheets or body washing sheets (sweat wiping sheets, oil removing sheets, cooling sheets, etc.), medicinal sheets (stagnation suppression sheets, compresses, etc.), etc. The non-woven fabric sheet is impregnated with a liquid component such as cosmetic liquid (cosmetics), and even when pressed with a finger, the liquid component quickly returns, so the entire face, nose, eyes, mouth, neck, etc. are moisturized, whitened, etc. It is useful for face masks impregnated with these active ingredients and having antibacterial properties.

1 Laser displacement meter, 2,5 ... Load, 3,6 ... Sample, 4,7 ... Measurement table.

Claims

An antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles dispersed therein is present on at least a part of the fiber surface, and the average particle diameter of the inorganic antibacterial fine particles is 0.01 to 20 μm. The antibacterial ethylene-vinyl alcohol copolymer has an ethylene content of 10 to 70 mol% and a solvent-spun cellulose fiber entangled with each other. Antibacterial nonwoven sheet.
2. The antibacterial nonwoven fabric sheet according to claim 1, wherein the antibacterial fibers and the solvent-spun cellulosic fibers have a fiber length of 5 to 60 mm and are entangled with each other.
The antibacterial fiber is a sheath-core type composite fiber, and the sheath part contains an antibacterial ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles having an average particle diameter of 0.01 to 20 μm dispersed therein. 3. The antibacterial nonwoven fabric sheet according to claim 1, wherein the antibacterial nonwoven fabric sheet is a polymer and the core portion is made of a hydrophobic resin and has a diameter of 5 to 15 μm.
The antibacterial nonwoven sheet according to any one of claims 1 to 3, wherein a surface of the antibacterial nonwoven sheet has irregularities.
The antibacterial nonwoven sheet according to any one of claims 1 to 4, wherein the antibacterial fiber is contained in an amount of 30 to 90% by weight.
The antibacterial nonwoven fabric sheet according to claim 5, wherein the antibacterial fiber is contained in an amount of 40 to 90% by weight, and the Young's modulus of the antibacterial fiber is 25 cN / dtex or more.
A liquid-containing sheet in which the antibacterial nonwoven fabric sheet according to any one of claims 1 to 6 and the fluid composition are integrated.
The liquid-containing sheet according to claim 7, wherein the flowable composition contains water.
The liquid-containing sheet according to claim 7, wherein the fluid composition contains a cosmetic.
The liquid-containing sheet according to claim 9, which is a skin care sheet.
When the flowable composition is impregnated with 900% by weight with respect to its own weight and the load of 260 g / cm 2 is applied for 1 minute and removed, the repositioning to compression in the thickness direction is 35% or more in 5 minutes. The liquid-containing sheet according to claim 9 or 10, wherein the liquid-containing sheet is characterized.
A face mask using the liquid-containing sheet according to any one of claims 9 to 11.