TWI632890B - Antibacterial non-woven sheet, liquid-containing sheet and mask - Google Patents

Abstract

The antibacterial nonwoven fabric sheet of the present invention is an antibacterial ethylene-vinyl alcohol copolymer contained in a state where inorganic antibacterial fine particles are dispersed inside at least a part of a fiber surface, and the average particle diameter of the inorganic antibacterial fine particles is 0.01 to 20 μm, and the antibacterial ethylene-vinyl alcohol copolymer with an ethylene content of 10 to 70 mol%, antibacterial fibers and solvent-spun cellulose fibers are interwoven with each other. It does not contain parabens, etc. It also has excellent antiseptic and antibacterial properties. It is soft and has a good feel. It has good impregnation and liquid retention when impregnated with various fluid compositions. It can also be highly efficient by pressure. An antibacterial non-woven fabric sheet which releases the fluid composition and has low toughness or shrinkage due to impregnation of the fluid composition, and has excellent form stability.

Description

Antibacterial non-woven sheet, liquid-containing sheet and mask

The present invention relates to an antibacterial non-woven fabric that is a base material for making the liquid composition effective for the absorption and absorption of the skin. The liquid composition is for cleaning, wiping, or moisturizing the skin including excreta, sebum, cosmetics, and the like. Cosmetic composition for functional and cosmetic purposes. In addition, the present invention relates to a liquid-containing sheet impregnated with a fluid composition containing a cosmetic ingredient, a medicinal ingredient, and the like, and integrated with an antibacterial nonwoven fabric sheet, and in particular, an antibacterial mask applied to the skin.

Conventionally, among water-containing sheets such as wet tissue, disposable wet wipes, and sheet-like cosmetics covering the skin, which integrate water or a water-based fluid composition with a non-woven sheet, there have been proposals: Non-woven fabrics of hydrophilic fibers such as rhenium or fibrous fabrics composed of blended fibers of hydrophilic fibers and heat-adhesive composite fibers are treated with high-pressure water flow, or various non-woven fabrics having improved functional properties. However, hydrophilic fibers such as osmium have problems such as the occurrence of wrinkles due to the decrease in the toughness of the fibers or the shrinkage of the fibers when wet, leading to a decrease in form stability that impairs workability or liquid retention. Or water is absorbed into the fiber Problems such as the effect of the inability to use water effectively. In order to improve the above-mentioned problems, a composite wet sheet is proposed, which is composed of two parts of heat-bonded non-woven fabric, which are composed of hydrophobic synthetic short fibers containing 50% by weight or more, and the constituent fibers are joined by a local heat-pressing portion. A fiber fabric made of hydrophilic short fibers containing 40% by weight or more is laminated and entangled (for example, refer to Japanese Patent Application Laid-Open No. 2001-336053 (Patent Document 1)).

However, in a sheet produced by fusing a heat-adhesive component like Patent Document 1, although the shrinkage when wet is improved, the entire sheet is hardened and the fit to the skin is reduced. Furthermore, since the surface of the sheet uses hydrophilic fibers as the main fibers, the impregnated chemical solution is absorbed into the fibers and cannot be sufficiently released to the object to be wiped. In addition, as market demand expands, functions for absorbing various liquid compositions are further required.

In order to solve these problems, for example, in Japanese Patent Application Laid-Open No. 2008-261067 (Patent Document 2), a non-woven sheet is proposed, which is a solvent-spun cellulose-based fiber having a fiber length of 30 to 60 mm and a sheath core. The non-woven sheet composed of interlaced composite fibers is a water-containing sheet with good touch and excellent liquid retention and release properties and morphological stability. The sheath-core composite fiber is composed of a sheath portion and a core portion. The sheath portion is an ethylene-vinyl alcohol copolymer, and the core portion is made of a hydrophobic resin and has a diameter of 5 to 15 μm.

In recent years, antibacterial properties have been required for these nonwoven fabric sheets. In particular, preservatives such as parabens and antibacterials have been used in many cases. Agent. However, due to concerns about the endocrine disrupting effect in butyl paraben, the level of the possibility of temporary irritation in parabens as a whole, etc., the use of parabens should be limited. In addition, there may be skin problems such as rough skin and inflammation when attached to the skin. Therefore, it is desirable to prevent corrosion without parabens (without using parabens), Antibacterial.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-336053

[Patent Document 2] Japanese Patent Laid-Open No. 2008-261067

That is, the problem to be solved by the present invention is to provide an antibacterial nonwoven fabric sheet which has excellent anticorrosion and antibacterial properties even without parabens, etc., is soft and has a good touch, and is impregnated with various fluidity. The composition has good impregnation and liquid-retaining properties, so that the fluid composition can be efficiently released by pressure and the like, and the toughness is reduced or the shrinkage is reduced due to the impregnation of the fluid composition, and the morphology is stable. Excellent. In addition, the present invention provides a liquid-containing sheet having a good touch and a liquid composition containing water and the like, which is excellent in liquid-retaining property, release property, and form stability.

The inventors have diligently studied in view of the above problems and completed the present invention.

That is, the first invention is an antibacterial nonwoven fabric sheet characterized in that at least a part of a fiber surface has an antibacterial ethylene-vinyl alcohol copolymer contained in a state in which inorganic antibacterial microparticles are dispersed therein, and the inorganic antibacterial microparticles The antibacterial fiber and the solvent-spun cellulose-based fiber system having an average particle diameter of 0.01 to 20 μm and the ethylene content of the antibacterial ethylene-vinyl alcohol-based copolymer of 10 to 70 mol% are interlaced with each other.

The second invention is the antibacterial nonwoven fabric sheet according to the first invention, wherein the fiber length of the antibacterial fiber and the solvent-spun cellulose fiber is 5 to 60 mm, and these are interlaced with each other.

The third invention is the antibacterial nonwoven fabric sheet according to the first invention and / or the second invention, wherein the antibacterial fiber is a sheath-core type composite fiber, and the sheath is an inorganic antibacterial with an average particle diameter of 0.01 to 20 μm dispersed inside. An antibacterial ethylene-vinyl alcohol-based copolymer contained in the state of fine particles, and the core is made of a hydrophobic resin and has a diameter of 5 to 15 μm.

The fourth invention is the antibacterial nonwoven fabric sheet according to the first to third inventions, wherein the surface of the antibacterial nonwoven fabric sheet has unevenness.

The fifth invention is the antibacterial nonwoven fabric sheet according to the first to fourth inventions, and comprises 30 to 90% by weight of the aforementioned antibacterial fibers.

The sixth invention is a thin antibacterial nonwoven fabric as in the fifth invention. The sheet contains 40 to 90% by weight of the antibacterial fiber, and the Young's ratio of the antibacterial fiber is 25 cN / dtex or more.

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

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

A ninth invention is the liquid-containing sheet according to the seventh invention, wherein the fluid composition contains a cosmetic.

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

The eleventh invention is the liquid-containing sheet according to the ninth or tenth invention, which is impregnated with 900% by weight of a fluid composition with respect to its own weight and removed after a load of 260g / cm ² is loaded for one minute. The response to compression in the thickness direction is 35% or more for 5 minutes.

The twelfth invention is a facial mask using the liquid-containing sheet according to the ninth invention to the eleventh invention.

By the above-mentioned means, the present invention provides an antibacterial nonwoven fabric sheet which is a base material which is effective in adsorbing and absorbing the fluid composition to the skin, and provides a liquid-containing sheet and a mask including the antibacterial nonwoven fabric sheet. This flowable composition is a cosmetic material which contains skin excretion, sebum, cosmetics, etc., wipes, wipes, or has moisturizing and beauty functions.

The antibacterial ethylene-vinyl alcohol copolymer fibers and the solvent-spun cellulose fibers containing at least a part of the surface of the first invention-based fiber in a state in which the inorganic antibacterial fine particles are dispersed therein are not only hydrophilic, but also The two fibers are interlaced to form a non-woven sheet, so they are soft and have a good touch. In addition, both the fiber on which at least a part of the fiber surface has an antibacterial ethylene-vinyl alcohol copolymer and the solvent-spun cellulose-based fiber-based fluid composition have high impregnation properties, and can rapidly impregnate a fluid composition such as water.

In addition, the antibacterial ethylene-vinyl alcohol-based copolymer has a hydrophobic portion, and by adjusting the ethylene content of the antibacterial ethylene-vinyl alcohol-based copolymer, or adjusting at least a part of the fiber surface, the fiber and the solvent-spun fiber of the antibacterial ethylene-vinyl alcohol copolymer are present. The content of plain fibers can be impregnated with various fluid compositions.

Furthermore, the hydrophilic fluidity composition of the solvent-spun cellulose-based fiber-based water or aqueous solution, a polar solvent, such emulsions, etc. is high in liquid retention. On the other hand, a fiber system having an antibacterial ethylene-vinyl alcohol copolymer having at least a part of the fiber surface has a low liquid-retaining property. Therefore, the fluid composition near the fiber in which the antibacterial ethylene-vinyl alcohol copolymer is present in at least a part of the fiber surface is easily leaked to the outside by pressure or the like. Furthermore, the antibacterial ethylene-vinyl alcohol-based copolymer fibers are present in at least a part of the surface of the fibers from which the flowable composition has been released. The fibers are highly impregnated and further absorb the flowable composition from the solvent-spun cellulose fibers. The fluid composition will continuously leak to the outside at an appropriate rate. The antibacterial nonwoven fabric sheet of the present invention is made by at least part of the fiber surface The fibers of the bacterial ethylene-vinyl alcohol copolymer and the solvent-spun cellulose fiber are interlaced with each other, and the fluid composition can be moved quickly. Thereby, since the release property of the impregnated fluid composition is improved, the fluid composition can be used efficiently.

The antibacterial ethylene-vinyl alcohol copolymer exists in a state in which inorganic antibacterial microparticles having a specific particle diameter are dispersed therein, and the physical antibacterial particles caused by abrasion and the like can prevent the inorganic antibacterial microparticles from passing through the fiber. And / or the shedding of the non-woven sheet, and the antibacterial performance is continuously exhibited.

In the second invention, the fiber length of the antibacterial ethylene-vinyl alcohol-based copolymer and the solvent-spun cellulose-based fiber is 5 to 60 mm at least in part on the surface of the fiber, so that the rigidity and moderate softness of the nonwoven fabric can be ensured. It is flexible and flexible, and can realize soft touch and comfort to the skin. In addition, particularly in the production by fiber interlacing under dry conditions, a bulky nonwoven sheet having excellent impregnation and excellent cushioning properties of the fluid composition can be obtained.

The third invention is a sheath-core type composite fiber in which an antibacterial ethylene-vinyl alcohol copolymer is a sheath portion and a hydrophobic resin is a core portion, and the diameter of the core portion is set to 5 to 15 μm. Antibacterial non-woven sheet that reduces shrinkage caused by impregnation, does not easily become wrinkles, and does not impair liquid retention or workability. In addition, since the skin can feel the core's toughness during use, it has a soft touch, and improves adhesion to the skin, for example, in applications such as base materials for which the adhesion to the skin is important.

The fourth invention is to make the surface of the antibacterial nonwoven fabric sheet It has unevenness, and when it is in close contact with the skin, an air layer is formed between the skin and the skin, so it is not easy to get hot. In addition, since the surface of the antibacterial nonwoven fabric sheet has unevenness, the surface area is increased, and thus the adhesion to the skin is improved. The wet composition is impregnated with the fluid composition and released under pressure, the disposable wet wipes, the liquid-containing sheet using the fluid composition containing the cosmetic is used to hold the fluid composition in the recess, and Smoothing the convex parts that are easy to contact with the skin, while releasing the good fluid composition, the touch is better. In addition, the liquid-retaining effect of the fluid composition is enhanced by the recessed portion, and the fluid composition having a wide polarity can be maintained without adjusting the overall polarity by the copolymerization ratio of the antibacterial ethylene-vinyl alcohol copolymer.

The fifth invention is because the antibacterial nonwoven sheet of the present invention contains 30 to 90% by weight of the aforementioned antibacterial fibers, and contains 70 to 10% by weight of a solvent-spun cellulose fiber to improve the feel and flow in impregnation. In the case of using a sexual composition, a fluid composition having impregnation, release, and hydrophilic properties is excellent in liquid retention, and it may become stable in shape due to shrinkage or reduction in toughness of the fiber without impregnation. Antibacterial nonwoven sheet with excellent balance.

The sixth invention is that since the antibacterial nonwoven sheet of the present invention contains 40 to 90% by weight of antibacterial fibers, and the Young's rate of the antibacterial fibers is 25 cN / dtex or more, it can have antibacterial properties and be soft, It has a good touch, and is quickly impregnated with a fluid composition containing a cosmetic such as a cosmetic liquid, and becomes an antibacterial non-woven sheet with moderate toughness and elasticity.

The seventh invention relates the antibacterial nonwoven fabric sheet of the present invention to The fluid composition becomes an integrated liquid-containing sheet. Therefore, the fluid composition has good touch, and the fluid composition has excellent liquid retention, release properties, and form stability. It is suitable for wet tissues, disposable wipes, skin care sheets, Masks and other uses.

The eighth invention is a liquid-containing sheet (a water-containing sheet) containing water, which has a good feel, and is excellent in liquid retention, release property, and form stability, and is suitable for the above-mentioned applications.

According to the ninth invention, the liquid composition containing the liquid-containing sheet of the cosmetic material has a good feel and excellent release property and morphological stability of the cosmetic material. Therefore, the fluid composition can be easily and perfectly adhered to the skin.

The tenth invention is a mask which is excellent in impregnation and liquid retention of a fluid composition containing a cosmetic by using the liquid-containing sheet described above.

According to the eleventh invention, when the cosmetic liquid (cosmetic material) impregnated with 900% by weight relative to its own weight is removed at a load of 260 g / cm ² for 1 minute, the recovery of compression in the thickness direction is 5 minutes35 % Or more, it can be a liquid-containing sheet capable of sufficiently retaining the returned cosmetic liquid of the pressing portion.

The twelfth invention is a mask that can sufficiently penetrate the skin with a cosmetic liquid (cosmetic) by using the liquid-containing sheet described above.

1‧‧‧laser displacement gauge

2,5‧‧‧Load

3, 6‧‧‧ samples

4, 7‧‧‧ measuring station

[Fig. 1] It is a schematic diagram for explaining a method for measuring a raw material roll recovery in the examples.

[Fig. 2] A schematic diagram for explaining a measurement method of liquid return to a raw material roll in the example.

<Antibacterial nonwoven sheet>

The antibacterial nonwoven fabric sheet of the present invention is a fiber in which an antibacterial ethylene-vinyl alcohol copolymer is present in at least a part of the fiber surface (hereinafter, sometimes referred to as "antibacterial EVOH-containing fiber" or simply "antibacterial" "Fiber") and a solvent-spun cellulose fiber are mutually intertwined, and the above-mentioned fibers that have been uniformly mixed are non-woven by a water flow method, etc., to realize a soft and bulky fiber interlaced body.

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

The proportion of antibacterial ethylene-vinyl alcohol copolymer-based ethylene units (copolymerization ratio) used in the present invention is 10 to 70 mol%, and the remainder is a vinyl alcohol unit alone, or a combination of vinyl alcohol and other vinyl-based monomer units Constituted by repeating units. The proportion of the ethylene unit is preferably 20 to 55 mol%, and more preferably 30 to 50 mol%. In addition, when a vinyl alcohol unit is used in combination with other vinyl-based monomer units, the proportion of vinyl alcohol units is not particularly limited, but it is usually more than other vinyl-based monomer units. In terms of mole ratios, vinyl alcohol units are preferred (vinyl alcohol Unit): (Other vinyl monomer units) = 55:45 to 99.9: 0.1, more preferably 70:30 to 99.9: 0.1, and particularly preferably 80:20 to 99.9: 0.1.

If the proportion of ethylene units in the ethylene-vinyl alcohol copolymer is less than 10 mol%, the linearity during fiberization becomes poor, and single yarn breaks and yarn breaks increase during spinning. , And those who lack flexibility. Furthermore, the problem of morphological change caused by swelling in low-temperature (20-60 ° C) water also occurs.

On the other hand, if the proportion of ethylene units exceeds 70 mol%, since the proportion of vinyl alcohol units, that is, the proportion of hydroxyl groups will inevitably decrease, the hygroscopicity will decrease, and the effect of the inorganic fine particles held inside the copolymer will not be sufficiently obtained. So bad.

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

In addition, although the number average molecular weight of the ethylene-vinyl alcohol copolymer is not particularly limited, it is preferably 5,000 to 25,000, and more preferably 8,000 to 20,000. Here, the number average molecular weight is a value measured by a GPC method.

This ethylene-vinyl alcohol-based polymer is sold under the trade name "EVAL" made by Kuraray Co., Ltd. and "SoarnoL" made by Japan Synthetic Chemical Industry Co., Ltd., and is easily available. this In addition, an ethylene / vinyl acetate copolymer can also be produced from a commercially available ethylene and vinyl acetate by radical polymerization or the like and saponified for use.

The type of the inorganic antibacterial microparticles used in the present invention is not particularly limited, and an inorganic system which can generate volatilization, decomposition, deterioration, etc. by heating during melt spinning of the fiber, and which does not reduce the antibacterial effect in a short time, can be used. Any of antibacterial particles.

Examples of the inorganic antibacterial microparticles include inorganic antibacterial microparticles containing titanium ions, copper ions, zinc ions, tin ions, and other metal ions having an antibacterial effect in an inorganic carrier, and titanium dioxide inorganic antibacterial microparticles. , And one or more 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 antibacterial metal ions and can suppress the deterioration of the fiber. For example, it is preferable to use an inorganic carrier with such an inorganic carrier. Lattice of inorganic support. The inclusion lattice refers to an inorganic powder having the inclusion lattice in a gap to which atoms or molecules enter, and has a property of enclosing a molecule in a part having a structure of a minute layered or cage-like cavity.

Examples of the inorganic carrier having an inclusion lattice include zeolites, layered phosphates (zirconium phosphate, titanium phosphate, calcium phosphate, etc.), layered clay minerals, transition metal sulfides, graphite, transition metal oxides, and layered Oxygen salt and so on. These inorganic carriers can be used alone or in combination of two or more kinds.

Among them, zeolite and zirconium phosphate having high ion exchange energy are particularly preferable. Among the above-mentioned inorganic antibacterial fine particles, in the present invention, Inorganic antibacterial fine particles having silver ions held in the aforementioned inorganic carrier are particularly suitable for use.

The average particle diameter of the inorganic antibacterial fine particles contained in the ethylene-vinyl alcohol copolymer used in the present invention is 0.01 to 20 μm, preferably 0.1 to 10 μm, and more preferably 0.3 to 6 μm. If the average particle size of the inorganic antibacterial fine particles is larger than 20 μm, yarn breakage and filter clogging are likely to occur during spinning, and the inorganic antibacterial fine particles are liable to fall off from the fibers. In addition, in order to obtain more In the case of fine fibers, it is necessary to make the inorganic antibacterial fine particles smaller than the fiber diameter, and it is desirable that the ratio of the inorganic antibacterial fine particles / fiber diameter is 0.8 or less. On the other hand, when the average particle size of the inorganic antibacterial fine particles is less than 0.01 μm, aggregation and the like between the inorganic fine particles are likely to occur during kneading, and it is not easy to disperse uniformly in the ethylene-vinyl alcohol copolymer.

The addition amount of the inorganic antibacterial fine particles contained in the antibacterial ethylene-vinyl alcohol copolymer used in the present invention is preferably set to 0.01 to 10% by weight based on the weight of the ethylene-vinyl alcohol copolymer. It is more preferably 0.1 to 5% by weight, and particularly preferably 0.5 to 1.5% by weight. Although it also depends on the ion exchange capacity or adsorption capacity of the antibacterial metal ions in the inorganic fine particles, more than 90% of the ion exchange capacity or metal adsorption energy is the inorganic fine particles that have been subjected to antibacterial metal ion exchange or adsorption ( In the case of inorganic fine particles holding antibacterial metal ions), if the amount of inorganic fine particles holding antibacterial metal ions is less than 0.01% by weight, it is difficult to impart sufficient antibacterial properties to the fiber, and it is particularly difficult to obtain durable antibacterial properties. . On the other hand, if the inorganic nature of antibacterial metal ions is maintained, When the amount of the microparticles added exceeds 10% by weight, the antibacterial performance is sufficient. However, in the fibrillation step, aggregation between inorganic antibacterial fine particles is likely to occur, and there is a concern that a filter clogging may occur, and the like is not preferable.

In addition, the ratio of the ethylene content (E: mole%) of the ethylene-vinyl alcohol copolymer used in the present invention to the inorganic antibacterial fine particles in the ethylene-vinyl alcohol copolymer (W: weight%), It can have the relationship of the formula shown below.

For example, 1 ≦ (100-E) × W ≦ 90

It is preferably 5 ≦ (100-E) × W ≦ 80.

The antibacterial EVOH-containing fiber of the present invention is not particularly limited as long as at least the outer surface has an antibacterial ethylene-vinyl alcohol copolymer contained in a state in which inorganic antibacterial fine particles are dispersed therein, and the antibacterial ethylene-ethylene The fiber composed of the alcohol-based copolymer alone may be a composite fiber with other thermoplastic polymers.

The other thermoplastic polymer system used in the present invention is not particularly limited as long as it can be compounded with an antibacterial ethylene-vinyl alcohol copolymer, and a wide variety can be used depending on the purpose of the fiber. Examples of other thermoplastic polymers include polyolefin resins, polyester resins, polyamide resins, polyvinyl chloride, polyvinylidene chloride, styrene resins, polyvinyl acetate resins, Thermoplastic polymers such as acrylic resins, polylactic acid resins, polycarbonate resins, and thermoplastic elastomers. In addition, an ethylene-vinyl alcohol copolymer having no antibacterial property may be used as another Thermoplastic polymer.

Among the above, from the viewpoints of heat resistance, fiber formation properties, and dimensional stability, polyolefin resins, polyester resins, and polyamide resins are particularly preferred, and polyolefin resins and polyester resins are more preferred. Resin's hydrophobic resin is particularly good. This point will be described later.

Polyolefin-based resins are preferably polypropylene, polyethylene, or the like, and these polyolefin-based resins may contain other units capable of polymerizing.

Polyester resins are aromatic polyester resins (polyethylene terephthalate (PET), polytrimethylene terephthalate, etc.) such as poly C _2-4 alkylene alylate resin. Polybutylene terephthalate, polyethylene naphthalate, etc.), especially polyethylene terephthalate resins such as PET. Polyethylene terephthalate-based resins may contain other dicarboxylic acids (for example, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, phthalic acid, 4,4'-diphenylcarboxylic acid, bis (carboxyphenyl) ethane, sodium 5-sulfonic acid isophthalate, etc.) or glycol (e.g., diethylene glycol Alcohol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, polyethylene glycol, polytetramethylene Diol, etc.).

In the polyamide resin, aliphatic polyamides such as polyamide 6, polyamide 6-6, polyamide 6-10, polyamide 10, polyamide 12, and polyamide 6-12 are preferred. Amines and copolymers thereof, semi-aromatic polyfluorene amines synthesized from aromatic dicarboxylic acids and aliphatic diamines, and the like. Polyamide resins It may contain other units which can be copolymerized.

In the case where the antibacterial EVOH-containing fiber of the present invention is a composite fiber, the composite ratio of ethylene-vinyl alcohol-based copolymer: other thermoplastic polymers is preferably 10 to 90: 90 to 10 in terms of weight ratio. If it is outside this range, problems such as bending of the discharge line after the nozzle is discharged due to the imbalance of the compounding ratio may be caused, resulting in poor spinnability, which is not preferable. Ethylene-vinyl alcohol copolymer: The composite ratio of other thermoplastic polymers is more preferably 30 to 70: 70 to 30 in terms of weight ratio.

In terms of the composite form of the composite fiber, as long as at least a part of the outer surface has an ethylene-ethylene copolymer containing inorganic antibacterial fine particles inside the fiber, a sheath-core type, a sea-island type, a lamination type, or a mixture thereof may be listed. Type and other arbitrary forms. In the case of the sheath-core type, it may be any of a two-layer sheath-core type and a multilayer sheath-core type having three or more layers. In addition, in the case of a sea-island type, the shape, number, and dispersion state of the islands can be arbitrarily selected, and a part of the islands may be exposed on the fiber surface. Furthermore, in the case of the bonding type, it can be in any state in the fiber cross section at right angles to the longitudinal direction of the fiber, the bonding surface is linear, arc-shaped, or any other random curve. A plurality of bonding portions may be made parallel or radial, and may have other arbitrary shapes.

In the aforementioned composite form, in particular, the sheath-core type composite fiber is an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles arranged on the entire surface of the fiber, and therefore it is suitable from the viewpoint of antibacterial performance. Furthermore, when the antibacterial nonwoven fabric sheet of the present invention is produced, a separate ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles is used. Fibers are liable to become soft due to the decrease in rigidity due to liquid absorption (absorption of fluid composition). In the steps of manufacturing, processing, packaging and the like, and the use of fibers, due to liquid absorption or external forces applied at the time, etc. Due to the effect of compression, it is difficult to maintain the space between the fibers, and as a result, it may become difficult to ensure excellent liquid retention or workability. In contrast, because the sheath-core type composite fiber is made and a hydrophobic resin is used in the core portion, even if the sheath portion absorbs liquid, the core portion does not absorb liquid and does not cause a change in rigidity. Therefore, even in these processing steps, It also maintains the desired volume, that is, the porosity, ensures liquid absorption, maintains the toughness of the antibacterial nonwoven sheet even in a wet state, and maintains the feeling when pressed against the skin.

That is, in order to ensure a high porosity in the antibacterial nonwoven fabric sheet of the present invention, it is preferable to constitute the antibacterial nonwoven fabric sheet with fibers having a high Young's ratio (initial tensile strength) and high bending elasticity. Next, even in the case where the antibacterial nonwoven fabric sheet is in a state after liquid absorption in these processing steps, in order to ensure high fiber elasticity, it is preferable that the composed fiber is made of a highly elastic resin. The higher the Young's rate, the more the void ratio after the non-woven fabric can be maintained, so that the liquid retaining property can be maintained and the workability can be improved.

In the antibacterial nonwoven fabric sheet of the present invention, when the content ratio of the antibacterial EVOH-containing fiber described later is 40 to 90% by weight, the Young's ratio of the antibacterial EVOH-containing fiber is preferably 25 cN / dtex or more. In particular, the Young's rate of fibers containing antibacterial EVOH is more preferably 25 to 90 cN / dtex, even more preferably 30 to 70 cN / dtex, and particularly preferably 35 to 60 cN / dtex. If the Young's rate of the fiber containing antibacterial EVOH is too low, The toughness and elasticity of the obtained antibacterial nonwoven fabric sheet can be improved by methods. The structure of the antibacterial EVOH-containing fiber is not particularly limited as long as it has the aforementioned Young's ratio. Although it may be a single fiber (single-phase fiber) of an ethylene-vinyl alcohol copolymer containing inorganic antibacterial fine particles, it is easy to combine From the viewpoints of elasticity, liquid retaining property, and liquid releasing property, sheath-core type composite fibers are preferred.

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 or liquid retention. When a sheath portion made of a hydrophilic resin is attached to the antibacterial nonwoven fabric sheet and a fluid composition containing cosmetics (cosmetic liquid) is added, it plays an important role in absorbing the fluid composition into the antibacterial nonwoven sheet interior. It also plays the role of avoiding the dripping of a large amount of cosmetic materials once absorbed in the antibacterial nonwoven sheet during the operation.

Examples of the resin having excellent spinnability in a combination of a resin having a higher Young's rate than the ethylene-vinyl alcohol copolymer and the ethylene-vinyl alcohol copolymer include polyolefin resins and polyester resins. From the viewpoint that the Young's rate is higher, shrinkage of the antibacterial nonwoven fabric sheet can be suppressed, and workability is also good, polyester resins are most suitable.

In order to maintain the porosity of the antibacterial non-woven sheet and maintain a high liquid volume, it exhibits toughness in the non-woven fabric and improves the workability when wet. Sheath-core composite fibers are preferred, and the core diameter is preferably 5 ~ 15 μm. The diameter of the core portion is more preferably 8 to 12 μm. As the core, a hydrophobic resin as described above is used, and a polyester resin is particularly preferred. If the diameter of the core portion is less than 5 μm, the toughness of the fiber is reduced, and as a result, it is easy to occur. The problem that the density of the non-woven fabric is increased and the impregnation amount of the fluid composition is reduced is not good. Furthermore, there are cases where the toughness of the non-woven fabric is lowered, and in particular, the expandability and the mountability are lowered in a state of being impregnated with the fluid composition. On the other hand, since the toughness of the fiber becomes too strong when the diameter of the core exceeds 15 μm, the liquid-containing sheet used for covering the face with impregnated fluid-containing composition (described later) is particularly used. In some cases, the fit to the face may be reduced, and further, due to the strong toughness of the fiber, the density of the non-woven fabric may be reduced, and the distance between the fibers in the non-woven fabric may be too far, which may cause the cosmetic material to fail to be held between the fibers and become Easy to release liquid unnecessarily.

In addition, 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 a profiled profile, for example, it can be a flat, oval, triangular, quadrangular, pentagonal, hexagonal, heptagonal, or octagonal polygon, T-shaped, H-shaped, V-shaped, or dog bone (I (Letter shape), 3 to 8 leaf shapes, and many other shapes, such as hollow cross-sectional shapes.

The fineness of the antibacterial EVOH-containing fiber used in the present invention can be selected according to the application, for example, it is selected from the range of 0.01 to 100 dtex, preferably 0.5 to 30 dtex, and more preferably 0.1 to 10 dtex. When the fineness of the fiber containing antibacterial EVOH is less than 0.01 dtex, it is easy to cause the inorganic antibacterial fine particles to fall off from the fiber. In addition, when the fineness of the fiber containing antibacterial EVOH exceeds 100 dtex, it cannot be fully utilized. In addition to the performance of the antibacterial agent inside the resin, the toughness of the fiber will become too strong. Therefore, it is particularly useful for liquid-containing sheets that are used to cover the face with impregnated fluid-containing compositions, especially facial masks ( Rear There are cases in which the fit to the face is reduced, and the strength of the fibers reduces the density of the non-woven fabric, which causes the distance between the fibers in the non-woven fabric to become too far, resulting in a cosmetic that cannot be held between the fibers. It becomes easy to release a liquid unnecessarily and is not good.

The antibacterial EVOH-containing fiber used in the present invention, or a fiber product using the fiber, may further contain conventional additives such as a stabilizer (a heat stabilizer of a copper compound, an ultraviolet absorber, a light stabilizer, Antioxidants, etc.), fine particles, colorants, fluorescent whitening agents, antistatic agents, flame retardants, deodorants, plasticizers, lubricants, crystallization rate delaying agents, and the like. These additives may be used alone or in combination of two or more kinds. These additives may also be contained in the fibers and may be supported on the surface of the fiber assembly.

Although the manufacturing method of the antibacterial EVOH-containing fiber used in the present invention is not particularly limited, for example, in the case of a composite fiber composed of two components with a hydrophobic resin, each resin may be separately extruded separately. Melt-kneading is performed, the two resins are introduced into a spinning head, and then the resin is ejected from the same spinning nozzle, and is obtained by a pulling roller.

In addition, although the antibacterial EVOH-containing fiber used in the present invention is usually stretched and used, the stretching method can be used to stretch between the heat rollers when the fiber discharged from the nozzle is pulled by a pull roller during spinning. For the one-stage method, a two-stage method with low-speed heat extension in a water bath or a hot blast stove after one-time drawing can also be adopted.

The aforementioned antibacterial EVOH-containing fibers are tactile and hydrophilic Excellent sex. However, for example, in the case of using an antibacterial EVOH-containing fiber to make an antibacterial nonwoven fabric sheet, although the impregnation property when impregnated with a water-based fluid composition is excellent, the fiber itself has low water absorption and therefore absorbs water. The liquid speed is slow, and it is also difficult to hold the liquid-retaining aqueous fluid composition in the sheet space. Therefore, in the case where the water-based fluid composition is impregnated and used, it takes time to absorb the liquid and the workability efficiency is reduced. In addition, a part of the water-based fluid composition is unnecessarily released from the inside of the sheet, flows out, and is wasted. The antibacterial non-woven sheet of the invention does not use 100% of antibacterial EVOH-containing fibers, and it is important to use solvent-spun cellulose fibers and antibacterial EVOH-containing fibers together and intersect each other.

In the antibacterial non-woven fabric sheet of the present invention, it is preferred that the antibacterial EVOH-containing fiber is contained in an amount of 30 to 90% by weight, and more preferably 40 to 90% by weight. The lower limit value of the content rate of the fiber containing antibacterial EVOH is more preferably 50% by weight or more, particularly preferably 60% by weight or more, and the upper limit value of the content rate of the fiber containing antibacterial EVOH is even more preferably 80% by weight. Hereinafter, it is still more preferably 75% by weight or less, and particularly preferably 70% by weight or less. The solvent-spun cellulose fiber preferably contains 10 to 70% by weight, and more preferably 10 to 60% by weight. The lower limit value of the content ratio of the solvent-spun cellulose fiber is more preferably 20% by weight or more, still more preferably 25% by weight or more, particularly preferably 30% by weight or more. The upper limit of the ratio is more preferably 50% by weight or less, and particularly preferably 40% by weight or less.

If the content of antibacterial EVOH fiber is less than 30% Amount%, especially when wet, the unique dry feeling of the cellulose-based fiber is enhanced, and the smoothness of the obtained antibacterial nonwoven fabric sheet is reduced. In addition, if the content of the antibacterial EVOH-containing fiber is less than 30% by weight, the rate of absorption of the fluid composition into the fiber increases, which prevents effective use of the skin. On the other hand, if the content of the antibacterial EVOH-containing fiber exceeds 90% by weight, the impregnation force, especially the impregnation speed, is reduced, and the holding power of the fluid composition is reduced, making the fluid composition unnecessary from the inside of the sheet. Release, waste and waste are not good.

The solvent-spun cellulose-based fiber used in the present invention means that it is different from the so-called cellulose slime, copper ammonium tincture, etc., which temporarily converts cellulose into a cellulose derivative and then returns to cellulose. Regenerated cellulose fibers are fibers (purified cellulose fibers) obtained by precipitating cellulose only from a solution obtained by dissolving it in a solvent without changing the chemical properties of the cellulose.

As a preferable example of the solvent-spun cellulose fiber used in the present invention, a spinning dope obtained by dissolving cellulose in an amine oxide is subjected to dry-wet spinning in water to precipitate cellulose. A cellulose fiber produced by a method in which the obtained fiber is further extended. A typical example of such a fiber is cellulose fiber (Lyocell), which is sold under the trade name of "TENCEL" by Lenzing, Austria. Such fibers are different from widely used regenerated cellulose fibers in that they have a round or elliptical cross-sectional shape, so they have a low risk of damaging the skin during use and are therefore very good. In addition, the strength of the slime fiber is reduced under wet conditions, so the sheet obtained by mixing the fibers is impregnated. When it contains a fluid composition such as a chemical solution, it deforms in a wet state, which reduces workability. In addition, for example, when used as a liquid-containing sheet (to be described later) composed of a fiber and a fluid-containing composition including a cosmetic as a whole, the wearability is poor. On the other hand, the antibacterial non-woven fabric sheet of the present invention has almost no decrease in strength even under wet conditions, and therefore has no morphological change and is excellent in wearability.

Generally, the solvent-spun cellulose fiber is fibrillated in many forms by being beaten by a beater, a refiner, a high-speed pulverizer, and the like, but in the present invention, it is preferable to prevent fiber fibrillation. Thin fibers are adhered to the face, and the cellulose-based fibers are spun using a solvent that is not substantially fibrillated.

Although the single fiber fineness of the solvent-spun cellulose-based fiber is not particularly limited, it is most preferable that the feeling when contacting the skin is a soft one. Therefore, it is preferably 1 to 3 dtex, and more preferably 1 to 2 dtex. , And more preferably 1.3 ~ 1.7dtex. When the single-fiber fineness exceeds 3 dtex, the touch to the skin may be deteriorated, or the liquid absorbing composition or the liquid retaining property of the fluid composition containing the cosmetic may be deteriorated. On the other hand, if it is less than 1 dtex, the density of the nonwoven fabric becomes high, and the inter-fiber voids are reduced. Therefore, the impregnated amount of the fluid composition is reduced, which is unfavorable.

Furthermore, the polarity of the entire antibacterial nonwoven fabric sheet can be determined by adjusting the mixing ratio of the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber, or the resin polarity of the antibacterial ethylene-vinyl alcohol copolymer. The impregnated amount and feel of the fluid composition, but by adjusting the thickness of each fiber, the impregnated amount of the fluid composition is not affected, and Ability to adjust touch. That is, if the solvent-spun cellulose-based fiber is made thick, the number of the cellulose-based fiber is reduced and the surface area is also reduced in the same unit weight, so that the hydrophilicity of the antibacterial nonwoven sheet produced is made hydrophilic. Sex decreased. Conversely, if the cellulose-based fibers are modified, the hydrophilicity of the antibacterial nonwoven fabric sheet increases. In addition, the same applies to the tactile system as the cellulose-based fiber becomes thicker.

For example, when the mixing ratio of the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber is 60:40, and the ethylene content of the antibacterial ethylene-vinyl alcohol copolymer is 50 mol% and the saponification degree is 98%, For the use of a liquid-containing sheet (particularly a mask) (described later) in which an antibacterial nonwoven fabric sheet used for covering a face and a fluid composition containing a cosmetic material are integrated, an antibacterial EVOH-containing fiber is spun with a solvent The thickness of the cellulose fiber 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 a range of 5 to 60 mm. If the fibers of the antibacterial EVOH-containing and solvent-spun cellulose fibers are too long, uniform interlacing of the fibers becomes difficult, especially when the interlacing of the two fibers is insufficient. Insufficient, not only the feeling of touch is deteriorated, but also the problem of lowering the efficiency of absorbing and releasing the liquid composition is caused, which is not good. In addition, if the fiber length of the fiber containing the antibacterial EVOH and the solvent-spun cellulose-based fiber is too short, not only the fiber is easily pulled out from the antibacterial nonwoven sheet, but also the flexibility and stretchability are reduced, which is not good. From this point of view, the antibacterial The fiber length of the EVOH fiber and the solvent-spun cellulose fiber is preferably 5 to 60 mm, and more preferably 10 to 50 mm. In addition, 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, although an antibacterial EVOH-containing fiber and a solvent-spun cellulose fiber can be uniformly mixed with cotton and then woven, and the water can be entangled to form an antibacterial nonwoven sheet, However, as for the fabric formation system, a dry method such as a spinning method or a melt-blown method, a carding method using cotton fibers, and an air-laying method can be used. Method, or using a wet method. Among them, the method for producing an antibacterial nonwoven fabric sheet of the present invention is most preferably a dry method from the viewpoint that it is easier to perform mixing of fibers and securing a space impregnated with a fluid composition. In this case, the aspect of the cotton-like fiber fabric is preferably a random fabric, a semi-random fabric, a parallel fabric, a cross-lapping fabric, or the like. When forming the woven fabric, it is preferable that the antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber are mixed with cotton at the aforementioned mixing ratio.

In the antibacterial nonwoven fabric sheet of the present invention, it is preferable that the surface has irregularities, and the resulting fabric may be subjected to a water stream complexing treatment as described above to interlace the constituent fibers and cause irregularities on the surface. This unevenness is produced on the surface of the antibacterial nonwoven fabric sheet by manufacturing under specific conditions when water flow is complexed. Thereby, not only the voids in the nonwoven fabric, but also the recessed portions on the surface of the antibacterial nonwoven fabric sheet can maintain the fluid composition. Therefore, it is not necessary to thicken the antibacterial nonwoven fabric sheet. Can hold a large amount of cosmetics on the surface. Furthermore, at this time, a part of the solvent-spun cellulose-based fiber that the entire fiber absorbs water from the water stream and is easily moved by the force of the water stream will extend in the direction of the water stream, that is, the height of the convex portion, and display at the same time. Antibacterial EVOH-containing fibers that are hydrophilic and lipophilic, especially in the case of sheath-core type composite fibers with hydrophobic resins, due to the hydrophobicity and rigidity of the core portion, it is difficult to move toward the height of the convex portion, so that Most of the fibers have a shape extending toward the nonwoven surface. Since these fiber systems are basically mixed with each other, the antibacterial nonwoven fabric sheet of the present invention has both hydrophilicity and lipophilicity. Therefore, both the hydrophilicity and the lipophilic fluidity composition can be maintained in this uneven shape. In addition, the fluid composition held here does not enter the non-woven fabric. Therefore, the liquid-containing sheet that integrates the antibacterial non-woven fabric sheet of the present invention and the fluid composition containing a cosmetic material is made by applying the cosmetic material. It is present on the surface of the antibacterial non-woven sheet and is very easy to transfer to the skin, and exhibits extremely good transferability to the skin. In addition, even in a case where the cosmetics are located on the uneven surface of the antibacterial nonwoven fabric sheet, since the fiber itself has both hydrophilic and lipophilic properties, the phenomenon of falling of the cosmetics does not occur.

The unevenness described above is preferably such that the difference in height between the concave portion and the convex portion is in a range of 0.1 to 0.4 mm and is continuous in a certain direction at a pitch of 0.04 to 0.5 mm. When the height difference is less than 0.1 mm, the surface of the nonwoven fabric is too smooth, and the surface unevenness cannot be used to maintain the fluid composition. Therefore, the impregnation property is lowered, which is not good. Furthermore, since the entire face is brought into contact with the skin, it is not good to have a feeling of swelter or stickiness during use. In addition, the height difference exceeds At 0.4 mm, the portion holding the fluidity composition will increase, so the liquid retention will increase, but the ratio of solvent spinning cellulose fibers near the front end of the convex portion will easily increase, and the liquid absorption behavior in this portion Depending on the properties of the solvent-spun cellulose fiber, the possibility of increasing the liquid holding capacity but lowering the liquid repellency is increased. Furthermore, the smoothness of the surface is impeded, which reduces the tactile sensation and reduces the feeling of use. In addition, if the pitch is less than 0.04 mm, the recessed portion becomes too narrow to prevent the flowable composition containing cosmetics from entering, and it becomes difficult to effectively use the surface irregularities to maintain the flowable composition, which is not good. Furthermore, when the pitch exceeds 0.5 mm, the inter-fiber distance of the portion constituting the convex portion becomes too wide and it becomes difficult to maintain the fluid composition entering the concave portion, which is not preferable.

The above-mentioned unevenness on the surface of the non-woven fabric can be processed for a sheet in which the fabric is entangled with fibers by water flow entanglement in advance. The pre-processed water stream complexing system can be appropriately exemplified: nozzle nozzle plates having a nozzle diameter of 0.08 to 0.2 mm and a pitch of 0.4 to 1 mm are arranged in a 1 to 3 row on a porous metal plate or a support of a fabric structure, A method of treating the fabric once or multiple times under a water flow of 1 to 6 MPa, preferably 2 to 4 MPa.

The unevenness on the surface of the non-woven fabric is preferably formed by water flow treatment on the fabric structure of the fiber in at least the final treatment of the water flow complexation treatment. As for the support of the fabric structure, it is more preferable to use the warp and weft yarns with a diameter of 0.01 ~ 1mm, more preferably a monofilament of 0.02 ~ 0.5mm, and the thickness of the fabric structure is 0.1 ~ 1mm . If the diameter of the monofilament exceeds 1 mm, the In the part above the yarn, the fibers will move around, resulting in openings on the surface of the non-woven fabric and poor surface smoothness. Furthermore, from the nozzles with orifices of 0.05 to 0.3 mm, more preferably 0.08 to 0.2 mm, provided at intervals of 0.4 to 1 mm, water pressure can be sprayed from the top of the fabric structure to the fabric that has been entangled to the extent that it is a previous stage. 6 ~ 15MPa, more preferably 8 ~ 10MPa columnar water flow.

By such a water stream complexing treatment, an antibacterial nonwoven fabric sheet having an uneven surface suitable for holding the fluid composition can be obtained.

The antibacterial nonwoven fabric sheet of the present invention can be suitably used by forming an aqueous sheet by integrating with water as described later, or by forming a liquid-containing sheet by integrating with a fluid composition containing cosmetics. When the antibacterial nonwoven fabric sheet of the present invention is used as a liquid-containing sheet, the copolymerization composition of the ethylene-vinyl alcohol-based copolymer used in the present invention can be improved by adjusting the polarity of the fluid composition containing the aforementioned cosmetic material to adjust the polarity of the copolymer. Impregnability of the fluid composition.

That is, in the case of using the aforementioned lipophilic fluid composition, a copolymer having a high composition of ethylene is preferably used, and in the case of using the aforementioned hydrophilic fluid composition, a copolymer having a low composition is preferably used. Copolymer. Similarly, hydrophilicity can be adjusted even by the degree of saponification. Furthermore, depending on the type of the unsaponified ester or the functional group modification of the hydroxyl group, not only the degree of saponification, but also the affinity with various fluids can be adjusted.

In addition, the impregnability can be improved by adjusting the ratio of the solvent-spun cellulose fiber. That is, in the case of using a lipophilic fluid composition, it is preferable to reduce the ratio of the solvent-spun cellulose fiber, and in the case of using a hydrophilic fluid composition, it is preferable to increase the solvent spinning. Proportion of silk cellulose fibers.

Although the actual impregnation varies depending on the viscosity of the fluid composition, etc., it may also take into consideration the balance with the feel, liquid retention, etc., and the copolymer composition of the ethylene-vinyl alcohol copolymer and / or the solvent may be used. The proportion of the spun cellulose fiber is adjusted.

The antibacterial EVOH-containing fiber and the solvent-spun cellulose-based fiber having such properties are uniformly mixed with cotton to form a single layer, and a specific inter-fiber void is desired so that the void ratio becomes 80 to 95%. The non-woven fabric is complexed by the water flow formed by this method, thereby being able to be a lightweight, woven fabric that absorbs and releases both oily components and water-based components to the same degree and easily achieves a high-dimensional balance of overall hydrophilicity and lipophilicity.

Although the antibacterial non-woven sheet of the present invention can adhere to a surface having a complicated shape by its softness, especially when it is in a wet state, this is the same as when the non-woven fabric is 50% stretched in at least one direction of wetness. For stress, this value is preferably 500g / 50mm or less. It is more preferably 400 g / 50 mm or less, and even more preferably 300 g / 50 mm or less. If the value exceeds 500 g / 50 mm or less, it is difficult for the substrate to adhere to the unevenness of the face, and it becomes difficult to supply cosmetics to the entire face, which is not good. On the other hand, for example, in a non-staggered state or a non-staggered state of a non-woven fabric sheet, when the stress at 50% wet stretching is less than 100 g / 50 mm, the step quality at the time of non-woven fabric production may be poor. , Or the problem that the operability is deteriorated, it is not suitable for the antibacterial nonwoven fabric sheet of the present invention.

The weight per unit area of the antibacterial nonwoven fabric sheet suitable for the present invention is preferably in the range of 30 to 100 g / m ² in terms of adhesion to the skin or liquid absorption, and particularly in the range of 40 to 70 g / m ² . The range is better. When the weight per unit area is less than 30 g / m ² , the absolute fiber amount becomes small, and the amount of the fluid composition that can absorb and hold liquid between the fibers becomes extremely small, which is not preferable. In addition, when it exceeds 100 g / m ² , the amount of the system fibers becomes too large, the thickness of the antibacterial nonwoven fabric sheet becomes too thick, and the adhesion is reduced, which is not good.

Although the apparent density of the antibacterial nonwoven fabric sheet of the present invention is not particularly limited, it is preferably 0.03 to 0.20 g / cm ³ , more preferably 0.05 to 0.17 g / cm ³ , and still more preferably 0.06 to 0.15 g / cm ³ Especially preferred is 0.08 ~ 0.12g / cm ³ . If the apparent density is too low, the liquid-retaining ability of the antibacterial nonwoven fabric sheet will be lowered, and dripping will easily occur during handling during use. On the other hand, if the apparent density of the antibacterial nonwoven fabric sheet is too high, the liquid holding capacity will decrease.

Although the thickness of the antibacterial nonwoven fabric sheet of the present invention is not particularly limited, it 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, and particularly preferably 500. ~ 1000μm.

In addition, the antibacterial nonwoven fabric sheet of the present invention needs to ensure both the liquid-absorbent property and the liquid-repellent property for the purpose. That is, although the antibacterial nonwoven fabric sheet of the present invention uses fibers having both hydrophilicity and lipophilicity as constituent fibers, it absorbs and adsorbs liquids having both properties and holds them. However, among these liquids, The oily component is mainly retained in the fiber portion containing the antibacterial EVOH, while the hydrophilic component is partially retained in the fiber containing the antibacterial EVOH and is mostly retained in the solvent-spun cellulose fiber. In addition, these liquids are held on the fiber surface and become more than this. If the amount cannot be directly maintained on the fiber surface, it can be ensured by filling and maintaining the fiber gap formed by the same type of fibers (fibers containing antibacterial EVOH or solvent-spun cellulose fibers). The non-woven fabric constitutes a liquid amount greater than the adsorption amount of the fibers. Therefore, in order to facilitate the explanation, the existence of the voids filled with the liquid held here is clarified, and the porosity is used. The porosity of the antibacterial nonwoven fabric sheet of the present invention is preferably 80 to 95%. More preferably, it is 85 to 93%. When the porosity exceeds 95%, the distance between the fibers becomes too wide, and the fluid composition cannot be maintained by the hydrophilic portion of the fiber, which is not good. In addition, when the distance is less than 80%, the distance between the fibers is too narrow, and the fluid composition does not enter the nonwoven fabric, so that the amount of liquid absorption is reduced, which is not good.

<Liquid-containing sheet, mask>

The present invention also provides excellent antiseptic and antibacterial properties even without parabens, is soft and has a good feel, and is used in a state of being impregnated with a fluid composition containing a cosmetic liquid or the like. Liquid-containing sheets and masks that return the fluid composition quickly by pressing with a finger. That is, the present inventors also found that by controlling the recovery of the compression in the thickness direction in the liquid-containing sheet, in the state of impregnating the fluid composition containing a cosmetic liquid or the like, even if the finger is pressed, The liquid composition can be quickly returned. The liquid-containing sheet is made of a specific antibacterial ethylene-vinyl alcohol copolymer as a component, and the antibacterial EVOH-containing fiber and the solvent-spun cellulose fiber are interlaced with each other to form An antibacterial nonwoven fabric sheet that absorbs the fluid composition, and the antibacterial nonwoven sheet is composed with the fluidity Integration of things.

In the liquid-containing sheet of the present invention, the fluid composition may be water (in this case, referred to as a "water-containing sheet"), or may include a cosmetic. When a fluid composition containing a cosmetic is used, it can be suitably used for skin care sheets, especially for a facial mask. That is, although the antibacterial nonwoven fabric sheet of the present invention can be used for the purpose of absorbing a fluid composition, for example, liquids such as a surface material of a napkin or a diaper, a diaper liner (Napkin Liners), or a wet tissue, etc. It is used for a sheet (or a sheet for skin cleaning), etc., but because the balance of liquid retention and release properties is excellent, and it can be easily adhered to the skin, the antibacterial nonwoven fabric sheet of the present invention described above is preferably used. Use of a sheet (liquid-containing sheet) impregnated with a fluid composition containing a cosmetic ingredient or a medicinal ingredient to adhere to the skin, for example, a mask, a makeup remover sheet or a cleansing sheet, a body wash sheet (a sweat wipe sheet, an oil absorption sheet) Flakes, etc.), cooling flakes, medicinal or therapeutic flakes (antipruritic flakes, wet cloths, etc.) are used in various skin care flakes. Since the return of the fluid composition is rapid even with finger pressure, it is particularly preferred Use in a mask.

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

In the use for impregnating the antibacterial nonwoven fabric sheet of the present invention with a fluid composition, the fluid composition is not particularly limited. Examples thereof include aqueous fluid compositions such as water, aqueous solutions, and aqueous emulsions, organic solvents or solutions using these as a medium, and mixtures thereof. In addition, a fluid composition that dissolves and / or disperses various solids, liquids, gases, etc. that are well dissolved or dispersed in these fluid compositions is also suitable for use. An antibacterial nonwoven fabric sheet having excellent functionality can be produced by dissolving and / or dispersing a fluid composition in which various active ingredients are dissolved. In addition, the fluid composition also includes a solution or dispersion (cosmetics, lotion, cosmetic liquid, etc.) containing an active ingredient such as a cosmetic ingredient or a medicinal (potency) ingredient. Among them, a hydrophilic fluid composition including an aqueous fluid composition or a polar organic solvent-containing fluid composition is advantageous from the viewpoint of impregnation, and from the viewpoint of safety to the human body and the like. Words are also beneficial. 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 thiohydroxy group. Examples of such hydrophilic fluid composition include: water, lower aliphatic alcohols (e.g., C _1-6 alkanols such as ethanol and isopropanol), alkanediols (e.g., ethylene glycol , Diethylene glycol, propylene glycol, etc.). In addition, unsaturated higher fatty acids (for example, oleic acid, oleyl alcohol, etc.), animal and plant oils (for example, jojoba oil, olive oil, coconut oil, camellia oil, Australian walnut oil, avocado oil, Corn oil, sesame oil, wheat germ oil, linseed oil, castor oil, squalane, etc.), mineral oils (e.g., flowing paraffin, polybutene, silicone oil, etc.), synthetic oils (e.g., synthetic ester oils) , Synthetic polyether oil, etc.) are also suitable for use.

These fluid compositions can be used alone or in combination of two or more. For example, it can be combined with a hydrophilic solvent such as water or ethanol. The liquid oil is used as an additive (oil content). Among these fluid compositions, water, a lower alcohol, or a mixture thereof may be generally used, preferably water and / or ethanol, and more preferably only water. For example, in the case of using water and a lower alcohol (especially ethanol) in combination, the ratio of the two is water / lower alcohol = 100/0 ~ 30/70, preferably 100/0 ~ 50/50, more preferably It is 100/0 ~ 70/30, and particularly preferred is 99/1 ~ 80/20.

Examples of commonly used additives in the fluid composition include: humectants or lubricants (for example, dipropylene glycol, 1,3-butanediol, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer). , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sucrose fatty acid ester, glycerin, sodium hyaluronate, polyoxymethyl glycoside, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose Ethers (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, etc.), UV inhibitors, surfactants, astringents, enzymes , Cooling agents, bactericides or antibacterial agents, skin softeners (for example, salicylic acid or its derivatives, lactic acid, urea, etc.), antioxidants (for example, tocopherol or its derivatives, anthocyanins, etc.) Phenols, etc.), whitening agents (e.g., ascorbic acid or derivatives thereof, oxidized cysteine, placenta, arbutin, gallic acid, rucinol, Turkish tannic acid, chamomile extract, etc.), Antiperspirants (e.g. aluminum compounds, zinc compounds, tannic acid Astringent, etc.), skin roughness preventives (for example, glycyrrhizin, vitamins, etc.), anti-inflammatory agents (for example, allantoin, guaiazulene, glycyrrhizin or its salt, glycyrrhizin or Its salts, ε-aminocaproic acid, Tauranic acid, Ibuprofen, Indomethacin Indomethacin, etc.), blood circulation promoters (for example, peony, rosemary, cloves, etc.), vitamins (for example, vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, vitamin K, etc.), amines Acid (e.g., tryptophan, oxidized cysteine, etc.), cell activating agent (e.g., riboflavin, pyridoxine, nicotinic acid, pantothenic acid, α-tocopherol, or derivatives thereof, tiger Botanical extracts, such as plant extracts, etc.), fragrances (for example, synthetic fragrances, essential oils, essential oil components, etc.) and the like. These additives may be used alone or in combination of two or more kinds.

Among these additives, for skin care sheet, for example, humectants, ultraviolet absorbers, surfactants, cooling agents, enzymes, astringents, bactericides, or antibacterial agents can be widely used. In particular, in a face pack, for example, a humectant or a lubricant may be blended in a hydrophilic solvent. The total ratio of the humectant and the lubricant is, for example, 0.1 to 50% by weight in the solvent, preferably 1 to 30% by weight, and more preferably 5 to 20% by weight.

The proportion of the aforementioned additives may be appropriately selected according to the application. For example, the proportion of water or ethanol is usually 30 to 99% by weight, preferably 40 to 95% by weight, and more preferably in a fully fluid composition containing the additive. It is 50 to 90% by weight.

The impregnation amount of the fluid composition to be used is not particularly limited as long as a specific effect can be obtained, and may be appropriately selected according to the purpose of the user. For example, the water-containing sheet provided by the present invention or makeup The liquid-containing sheet in which the fluid composition of the material is integrated with the antibacterial nonwoven sheet is 200 to 1000% by weight based on the weight of the base material. It is better in terms of cost and performance.

In addition, in the liquid-containing sheet of the present invention composed of an antibacterial non-woven fabric sheet and a fluid composition containing a cosmetic, the antibacterial non-woven fabric sheet must have a high liquid absorption property capable of maintaining a sufficient amount of the cosmetic. In the present invention, this is expressed using the liquid absorption speed and the liquid retention rate.

First, the antibacterial nonwoven fabric sheet suitable for the liquid-containing sheet of the present invention must have excellent liquid-absorbing performance, and the liquid-absorbing speed is preferably 5 seconds or less. It is more preferably 3 seconds or less, even more preferably 2 seconds or less, and particularly preferably 1.5 seconds or less. If the liquid absorption speed exceeds 5 seconds, it is not easy to impregnate the fluid composition containing cosmetics, especially when the fluid composition is impregnated and used in personal cosmetics contained in various households. There is a possibility that the surface may flow down, and as a result, the antibacterial nonwoven fabric sheet cannot be impregnated with a cosmetic material, which is not good because it is wasteful. In terms of fluid compositions containing cosmetics, oily fluid compositions tend to have high viscosity, and water-based fluid compositions tend to have low viscosity, while liquid viscosity tends to increase when the viscosity is low. Therefore, the better liquid absorption speed of the former is less than 5 seconds, and the latter is less than 3 seconds.

The antibacterial non-woven fabric sheet suitable for the liquid-containing sheet containing the fluid composition containing the cosmetic material must be able to supply a sufficient amount of the cosmetic material to the skin in a larger amount. Therefore, the liquid retention rate as a ratio of the liquid retention amount to the weight of the non-woven fabric must be higher. The preferred liquid retention rate is 900% or more, and more preferably 1000% or more. This liquid retention rate is for fluidity including cosmetics. An indicator of the liquid holding capacity of the antibacterial nonwoven sheet of the composition. Antibacterial non-woven fabric sheet with a low liquid retention rate is contained for the purpose of impregnation It is necessary to prepare various antibacterial nonwoven fabric sheets whose weight or composition is changed in accordance with the impregnated amount of the fluid composition of the cosmetic. However, the antibacterial nonwoven fabric sheet of the present invention can correspond to various impregnation amounts with one type.

In addition, when the liquid-containing sheet of the present invention is attached to the face, it is also possible to avoid problems such as flowing of a composition containing cosmetics flowing down the face in a non-woven fabric and dripping from the chin to stain clothes. important. In the present invention, the performance is expressed by the drip rate, and the value is preferably 3.5% or less. It is more preferably 3% or less, and even more preferably 2.5% or less.

Next, by the method as stated above, it is extremely important to efficiently transfer the fluid composition containing the cosmetic material impregnated into the antibacterial non-woven sheet in a large amount and kept in a manner to prevent dripping to the skin. In the present invention, this is expressed as a release rate, and this value is preferably 95% or more. If the release rate is less than 95%, effective cosmetics cannot be absorbed into the fibers and used effectively on the skin. The ratio of the fluid composition containing the cosmetic material held and held by the antibacterial nonwoven fabric sheet to be released is preferably 95% or more.

In particular, the liquid-containing sheet of the present invention is based on the impregnation of the fluid composition containing the cosmetic, that is, the liquid absorption rate and the liquid retention amount, and thus the drip rate, and the release rate is balanced in a high-dimensional manner. It is not necessary to ensure a high basis weight to achieve excellent comfort when wet, and further, it is possible to supply a sufficient liquid to the liquid-containing sheet of the skin.

Although the antibacterial nonwoven fabric sheet of the present invention is usually used by impregnating the fluid composition, it can be used by impregnating these fluid compositions during use, or the fluid composition can be impregnated in advance. In the former case This has the advantage that the user can make and impregnate his or her favorite cosmetics in applications such as liquid-containing flakes containing cosmetics. In addition, the product can be supplied in a dry state, and packaging of the product can be simplified.

In the case of using the above liquid-containing sheet, the antibacterial non-woven fabric sheet preferably has the wettability necessary for impregnating the fluid composition and the space for retaining the liquid, and will not drip during the operation during use, and The fluid composition contains a cosmetic ingredient or a medicinal ingredient (effect), and holds, attaches, or rests until it covers a specific part of the body (for example, the face) and has the function of transferring cosmetics to the skin side in small amounts. (For example, a moisturizing component, a cleansing component, an antiperspirant component, an aromatic component, a whitening component, a blood circulation promoting component, a cooling component, an ultraviolet absorbing component, a skin antipruritic component, etc.). The antibacterial non-woven sheet is excellent in liquid retention and has moderate toughness or elasticity. After impregnating the fluid composition, the compression recovery and the return of the fluid composition are rapid. In particular, if there is a specific Young's as described above, The antibacterial nonwoven sheet is formed by high elastic fibers with a high rate, the flowability of the fluid composition is excellent, and the thickness is quickly restored, so it can be restored to the same liquid-retaining state as the uncompressed part in a short time.

Regarding the above-mentioned response to compression, specifically, when the fluid composition is impregnated with 900% by weight of its own weight and removed at a load of 260 g / cm ² for 1 minute, the response to compression in the thickness direction is removed. It is preferably 35% or more (for example, 35 to 100%), more preferably 50 to 99% (for example, 60 to 95%), and even more preferably 65 to 90% (especially 70 to 85%) for 5 minutes. If the recovery is less than 35%, the fluid composition such as a cosmetic liquid cannot be sufficiently returned to the pressing portion. It should be noted that the response can be measured in detail by a method described in Examples described later.

Regarding the return of the above-mentioned flowable composition, specifically, when 900% by weight of the flowable composition was impregnated with its own weight and a load of 620g in a circular shape with a diameter of 1.2cm was partially loaded for 1 minute, it was removed for 5 minutes. The return rate of the subsequent beauty liquid can be more than 45%, such as 50 to 99%, preferably 60 to 98% (for example, 65 to 95%), and more preferably 70 to 92% (especially 80 to 90%). . If the return rate is too low, the fluid composition after the pressing is insufficient, and the cosmetic liquid cannot be sufficiently penetrated into the skin. The return rate can be measured in detail by a method described in Examples described later.

In the case of the liquid-containing sheet used in the present invention, the antibacterial non-woven sheet is excellent in softness even when wet, and is appropriately complexed so as to follow the skin of the face and the like, and when wet according to JIS L 1913 The stress at 30% elongation (stress at 30% wet) is preferably 0.5 to 10N / 5cm, more preferably 1 to 8N / 5cm, even more preferably 1.5 to 5N / 5cm, and particularly preferably 2 in at least one direction. ~ 4N / 5cm. If the stress is too small when wet at 30% elongation, it will be stretched too much when worn on the skin of the face and the like, and if it is too large, the adhesion to the skin will be reduced. The stress at the 30% elongation can be measured in detail by a method described in Examples described later.

In the case where the fluid composition contains water, the water-containing sheet of the present invention can be added with functions other than water, for example, by including at least one of the above-mentioned fluid composition or active ingredient. Although these liquidity The composition or active ingredient does not need to be water-soluble, but those with a high affinity for water can improve the homogeneity of the water-containing flakes, and it is easy to impregnate the fluid composition or active ingredient with additional functions with antibacterial properties at a high concentration Non-woven sheet. In addition, those who are integrated with the antibacterial nonwoven fabric sheet in the state of an aqueous solution, a dispersion, and an emulsion together with water improve the homogeneity of the water-containing sheet and the production efficiency is also advantageous. In particular, the aqueous solution, the aqueous dispersion, and the aqueous emulsion are highly compatible with the solvent-spun cellulose fibers of the antibacterial nonwoven sheet of the present invention, and the antibacterial nonwoven sheet can be integrated at a high concentration to obtain a high function. It is more advantageous in terms of homogeneity and production efficiency of the water-containing flakes.

The fluid-containing composition containing a cosmetic used in the liquid-containing sheet of the present invention is, for example, in a state of a solution, a dispersion, an emulsion, or the like. Moreover, for example, it contains at least 1 type of water or the said fluid composition. The cosmetic material includes at least one kind of cosmetic material functioning in a case where the cosmetic material itself has fluidity, and the cosmetic material has a form such as a solid and has substantially no fluidity. When the cosmetic material itself has fluidity, although the cosmetic material can be integrated with the antibacterial nonwoven sheet only as a fluid composition, it is usually mixed with other liquids to improve fluidity and improve integration of the fluid composition. Time production efficiency and improve release. The liquid system mixed with the cosmetic has high affinity with the cosmetic, and the antibacterial nonwoven sheet can be integrated at a high concentration to obtain a high function. The fluid composition containing the cosmetic and the antibacterial nonwoven sheet are integrated. The water-containing flakes are more advantageous in terms of homogeneity and production efficiency. There are no particular restrictions on the functions of the cosmetics used, and makeup with various functions commonly known can be used. 1 kind of raw materials or mixed and used.

As described above, the present invention also provides a mask using a liquid-containing sheet in which a fluid-containing composition containing a cosmetic material and an antibacterial nonwoven fabric sheet are integrated. Although a sheet produced by fusing a heat-adhesive component like the above-mentioned Patent Document 1 has improved shrinkage when wet, the entire sheet becomes hard and the adhesion to the skin is reduced. In addition, since the surface of the sheet uses hydrophilic fibers as the main fiber, the impregnated liquid medicine is absorbed into the fibers and cannot be sufficiently released to the object to be wiped. In addition, for example, it covers the skin with a mask In the case of flakes, etc., there is a problem that an effective ingredient such as a cosmetic liquid cannot be sufficiently released. In addition, although the non-woven sheet disclosed in the above-mentioned Patent Document 2 is excellent in softness and liquid retention, the sheet has low toughness (rigidity). When a finger is pressed to make the mask adhere to the face, the thickness is restored and beauty is achieved. Liquid (cosmetic) returns slowly. Therefore, it is difficult to apply the beauty liquid to the entire face efficiently. In particular, in a facial mask, whether or not it is necessary to press the finger to make up the part to be replenished with cosmetic liquid or the part that is difficult to be adhered, in the conventional facial mask, although the facial mask is adhered to the intended part, the supply of the cosmetic liquid is not Full state. In addition, in order to improve the fit of the mask to the skin (face), a mask having a layer made of ultrafine fibers on the side in contact with the skin, or a mask having a three-dimensional structure has also been developed. However, even these masks have insufficient adhesion to the skin. At present, it is necessary to repeat the operation of pressing the attached mask with a finger once. Therefore, by repeating the action of pressing on the skin, the beauty solution that is accumulated in the part that is being pressed each time is squeezed out, and the insufficient state of the beauty liquid is promoted. fruit.

The present invention also provides a mask that solves such a conventional problem. That is, the antibacterial nonwoven fabric sheet of the present invention is formed by spinning the cellulose-based fiber using a specific antibacterial fiber and a solvent as described above to form a nonwoven fabric capable of absorbing a fluid composition, and controlling the antibacterial nonwoven sheet. The compression recovery in the thickness direction is excellent in antibacterial properties, and even when the liquid composition such as a cosmetic liquid is impregnated with a finger, the fluid composition returns quickly. Moreover, even if it is pressed with a finger while the fluid composition is impregnated, the thickness recovers quickly. Therefore, for example, when it is used as a facial mask, the beauty liquid can be efficiently replenished to a desired part. Further, by using a sheath-core type composite fiber having a sheath portion formed of an ethylene-vinyl alcohol-based copolymer, flexibility, liquid retention, and morphological stability can be improved.

Moreover, since the antibacterial nonwoven fabric sheet of the present invention is excellent in adhesion to the skin, it is not only a mask, but is particularly suitable as a liquid-containing sheet fixed to the skin such as a wet cloth. For example, the liquid-containing sheet of the present invention can easily correct the non-adhesive and floating part, and can be adhered to the fine gaps such as the root of the nose, so that the effective ingredients of the liquid-containing sheet can be effectively penetrated into the skin.

In addition, the liquid-containing sheet of the present invention is also suitable for a cleansing sheet or a skin-washing sheet. As described above, since the liquid-containing sheet of the present invention can adhere to the sheet even in the fine gaps of the face, it can effectively remove cosmetics (makeup cosmetics such as base makeup, powder, lipstick, eye makeup, etc.). In this way, the liquid-containing sheet of the present invention is used as a liquid-impregnated organism. When a film sheet is used, the liquid-containing sheet is usually impregnated with a fluid composition, and is used by being attached to or in contact with the skin of a living body. Therefore, antibacterial properties are important. In addition, the liquid-containing sheet of the present invention may be laminated with other layers. For example, a non-porous film or sheet may be laminated on a side not in contact with the skin in order to promote absorption of an active ingredient.

[Example]

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

"Spinnability"

In the spinning step of fiber manufacturing, after the spun yarn is cooled and solidified, when it is drawn to the take-up tube via a drawing roller, it can be taken without cutting the yarn as "a: The spinnability was good, and the case where the yarn was cut so that it could not be pulled, and the case where the yarn was cut to the extent that the fluff was generated, was regarded as "b: poor spinnability", and the spinnability was evaluated.

〔Fineness〕

Evaluation was performed in accordance with JIS L 1015 "Test method for chemical fiber cotton-like fibers (8.5.1)".

〔strength〕

According to JIS L 1015 "Test method for chemical fiber cotton fiber" (8.7.1) ".

[Extensibility]

Evaluation was performed in accordance with JIS L 1015 "Test method for chemical fiber cotton-like fibers (8.7.1)".

[Young's rate]

Examples 7 to 11 and comparative examples 9 to 17 were evaluated in accordance with JIS L 1015 "Test method for chemical fiber cotton-like fibers (8.11)".

〔Antibacterial property〕

150 g of the antibacterial nonwoven fabric sheet obtained in the example or the comparative example was put into a 20-liter bucket filled with water at a temperature of 60 ° C., and after 30 minutes of scouring treatment, it was rinsed for 30 minutes, and then dehydrated and dried. The refined non-woven sheet was tested for antibacterial property in accordance with JIS L 1902 "Test method and antibacterial effect of antibacterial properties of fiber products". In addition, the test bacteria used Staphylococcus aureus and Pneumococcus (the concentration of the bacterial solution was 1/20 NB, and the amount of drip of the bacterial solution was 0.2 ml). A cotton cloth was used in the non-process inspection system, and the bactericidal activity value was calculated from the following formula. A bactericidal activity value of 0 or more is considered to have a bacteriostatic effect.

‧Static bacterial activity value: logarithmic value showing the difference in the number of germs before and after the action time

Static bacteria activity value = Log (A / B)

A = Number of bacteria recovered after inoculation of unprocessed specimens

B = Number of bacteria dispersed and recovered after 18 hours of culture of processed specimens

〔thickness〕

The thickness of the antibacterial nonwoven fabric sheet obtained in the examples or comparative examples was measured in accordance with JIS L 1096 "Testing method for cloths and knitted fabrics (8.5)". The thickness gauge was measured using a digital indicator made by Mitutoyo Corporation with a 1-inch (diameter) probe and a load of 12 g / cm ³ .

[Unit weight]

The weight per unit area of the antibacterial nonwoven fabric sheet obtained in the examples or comparative examples was measured in accordance with JIS P 8124 "Method for Measuring Paper and Paperboard Weighing".

[Voidage]

The porosity (%) of the antibacterial nonwoven fabric sheet obtained in the examples or comparative examples was calculated from the nonwoven fabric weight (g / cm ² ), the fiber specific gravity (g / cm ³ ), and the nonwoven fabric thickness (cm), and was calculated by the following formula.

Void ratio (%) = 100-{(non-woven weighing / fiber ratio / non-woven thickness) / 100}

〔Touch feeling〕

Functional evaluation was performed by 5 subjects based on the following criteria The touch when the antibacterial nonwoven fabric sheet obtained by the Example or the comparative example was touched.

<Evaluation Criteria>

X: Good touch

Y: slightly worse

Z: Poor touch

〔Aspiration speed〕

The liquid absorption speed of the antibacterial nonwoven fabric sheet obtained in the Example or the comparative example was measured based on JIS L 1907 "Test method for water absorption of a fiber product (7.1.1 (driving method)"). While holding the surroundings, measure the time until a drop of liquid is dropped from the surface of the non-woven fabric with a measuring tube 1 cm above the non-woven fabric until the liquid droplets on the surface have no special light reflection. The following tests I and II were performed with the dripped liquid.

Test I: Ion-exchanged water

Test II: edible blending oil manufactured by Nissin Olivier Group Co., Ltd.

〔Liquid retention rate〕

The liquid retention rate of the antibacterial nonwoven fabric sheet obtained in the Example or the comparative example was measured based on JIS L 1907 "Test method for water absorption of fiber products (7.2 (water absorption method))." Cut the test piece into 5cm To measure the weight C (g). This test piece was immersed in a fluid composition (Laura lotion, manufactured by Eisan Co., Ltd.) for 30 seconds. Then, the weight D (g) after 10 seconds was taken out of the liquid while holding the test piece, and the weight (g) after 1 minute was measured.

The liquid holding rate F (%) was calculated by the following formula.

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

[Release rate]

The release rates of the antibacterial nonwoven fabric sheets of Examples 1 to 6 and Comparative Examples 1 to 8 were measured in the following manner. The sample for measuring the liquid retention rate was sandwiched between about 2.5 g of filter paper (corrected filter paper No. 2) cut into 10 cm squares, and a 2 kg scale was placed from above and left for 1 minute. After 1 minute, the sample was taken out to determine the increase in weight H (g) of the weight of the filter paper.

The release rate G (%) of the fluid composition containing the cosmetic composition is calculated by the following formula.

G (%) = (H / (E-C)) × 100

〔Reply〕

The raw material roll recovery of the antibacterial nonwoven fabric sheets of Examples 7 to 11 and Comparative Examples 9 to 17 were measured in the following manner. Prepare a sample cut into 5 cm in the MD direction and 5 cm in the CD direction, and impregnate 900% of the cosmetic liquid ("Freshel Essence Lotion NA" manufactured by Kanebo Cosmetics Co., Ltd.) with respect to the weight of the sample. As shown in Figure 1, sample 3 Open and stand on an acrylic plate (measurement table) 4 and measure the initial thickness with a laser displacement gauge 1. Next, a load of 260 g / cm ^{2 was} placed on the center of the raw material roll (non-woven fabric) for 60 seconds, and the displacement from the removal of the load to 300 seconds was measured. When the thickness of the raw material roll before measurement is set to I, the thickness after the load is removed is set to J, and the thickness after 300 seconds of the removed load is set to K, the raw material roll recovery (% ).

Raw material roll response (%) = [(I-K) / (I-J)] × 100

[Liquid Return]

The return of the antibacterial nonwoven fabric sheet to the raw material roll of Examples 7 to 11 and Comparative Examples 9 to 17 was measured in the following manner. Prepare a sample cut into 5 cm in the MD direction and 5 cm in the CD direction, and impregnate 900% of the cosmetic liquid ("Freshel Essence Lotion NA" by Kanebo Cosmetics Co., Ltd.) with respect to the weight of the sample. As shown in Figure 2, sample 3 Open and rest on the acrylic plate (measurement table) 14 and place a load of 620 g at the center of a circular shape with a diameter of 1.2 cm for 12 60 seconds, and measure the width of the part without the cosmetic liquid after removing the load. Furthermore, the width | variety of the part which does not have a cosmetics liquid after 300 seconds of load removal was measured. When the width of the part without beauty liquid after removing the load is set to L, and the width of the part without beauty liquid after removing the load for 300 seconds is set to M, the liquid return to the raw material roll is calculated according to the following formula (% ).

Return toward the liquid of the raw material roll (%) = [(L-M) / L] × 100

[Uneven height difference]

Antibacterial nonwoven fabric sheets obtained in Examples or Comparative Examples The height difference between the recessed part and the raised part on the surface is measured with a microscope VH-6300 manufactured by KEYENCE Corporation to observe the cross section of the nonwoven fabric. The height difference between the three adjacent recessed parts and the raised part is measured and averaged.

[Stress at 50% Wet Elongation]

The stress at the time of 50% elongation of the antibacterial non-woven sheet of Examples 1 to 6 and Comparative Examples 1 to 8 was measured using Shimazu Corporation's auto-stereoscopic mapping device AGS-50D. The test towel was 50 mm, the measurement length was 100 mm, and the measurement speed was 200 mm. When the tensile test is performed, it is expressed by the strength value at the point when the elongation reaches 50%.

[Stress when wet 30% elongation]

The stress at the time of 30% wet elongation of the antibacterial nonwoven fabric sheets of Examples 7-11 and Comparative Examples 9-17 is based on JIS L 1913 "General nonwoven test method (6.3.2 (tensile strength and elongation test when wet)) ". Specifically, the sample was left in water at 20 ° C. ± 2 ° C. until it was precipitated by its own weight, or was immersed in water for more than 1 hour, and then it was taken out of the immersion solution to rapidly measure the stress at 30% elongation.

(Reference example 1: Individual fiber)

(1) Into 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 44 mol%, silver-based inorganic antibacterial fine particles (manufactured by SINANEN ZEOMIC Corporation) incorporated with silver ions and supported by an inorganic ion exchanger "AV10D", an average particle diameter of 2.5 m, and a slightly cubic shape) 1 part by weight, and a spinning twist was performed at a spinning temperature of 240 ° C using a melt extruder. After the back-twisted yarn is cooled and solidified, it is drawn to the winding tube through a drawing roller.

(2) Next, the coiled wire is thermally stretched at an elongation temperature of 80 ° C. and an elongation ratio of 2 times. After applying the oil agent in an oil bath, the coiled yarn is crimped by a crimping device such as a staff type crimping device. deal with. After the crimping treatment, the fibers were dried with hot air at 100 ° C, and then cut into 51 mm to obtain antibacterial EVOH-containing fibers (1.7 dtex, 51 mm long, circular cross section). It is good in terms of spinnability and elongation, with a strength of 2.4 cN / dtex and an elongation of 33%. The evaluation results are shown in Table 1.

(Reference Example 2: Composite fiber)

(1) Into 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 44 mol%, silver-based inorganic antibacterial microparticles ("AV10D" manufactured by SINANEN ZEOMIC Corporation) with silver ions supported by an inorganic ion exchanger are blended. , Average particle diameter 2.5 μm, slightly cubic) 1 part by weight of a copolymer as a sheath portion, a thermoplastic polymer composed of polyethylene terephthalate as a core portion, and a composite composed of a melt extruder is used The spinning device uses a circular cross-section nozzle to perform a backhand twist at a spinning temperature of 280 ° C and a sheath-core weight ratio of 50:50. After the back-twisted yarn is cooled and solidified, it is taken up by a take-up tube through a take-up roller.

(2) Next, this coil was taken up at an elongation temperature of 80 ° C, Hot drawing is performed at a draw ratio of 2 times, and after the oil agent is applied in the oil bath, a crimping process is performed using a crimping device such as a staff type crimping device. After the crimping treatment, the fiber was dried with hot air at 100 ° C, and then cut into 51 mm to obtain an antibacterial EVOH-containing fiber (3.4 dtex, 51 mm long, sheath-core weight ratio 50:50, circular cross-section, core (12.5 μm in diameter). It is good in terms of spinnability and elongation, with a strength of 2.9 cN / dtex and an elongation of 27%.

(Reference Example 3: Composite fiber)

(1) The coiled wire of Reference Example 2 was heat-drawn at an elongation temperature of 80 ° C. and an elongation ratio of 2 times. After applying the oil agent in the oil bath, it was cut into 10 mm to obtain the antimicrobial-containing agent shown in Table 1 below. EVOH fiber (3.4 dtex, 10 mm long, sheath-to-core weight ratio 50:50, circular cross section, core diameter 12.5 μm). It is good in terms of spinnability and elongation, with a strength of 2.9 cN / dtex and an elongation of 27%.

(Reference example 4: Individual fiber)

In 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 85 mol%, silver-based inorganic antibacterial microparticles ("AV10D" manufactured by SINANEN ZEOMIC Co., Ltd., with an average particle diameter) mixed with silver ions supported by an inorganic ion exchanger 2.5 μm, slightly cube-shaped) 1 part by weight, and silk reeling was performed in the same manner as in Reference Example 1 to obtain an antibacterial EVOH-containing fiber (1.7 dtex, 51 mm long, circular cross section). Good spinnability and elongation, strength is 3.1cN / dtex, Elongation is 38%.

(Reference Example 5: Composite fiber)

Except that the resin discharge amount, pull speed, and draw ratio were adjusted so that the fineness was 5.5 dtex, reeling was performed in the same manner as in Reference Example 2 to obtain antibacterial EVOH-containing fibers (3.4 dtex, 51 mm long, sheath-to-core weight ratio 50:50, circular cross section, core diameter 16.0 μm). It is good in terms of spinnability and elongation, with a strength of 2.9 cN / dtex and an elongation of 36%.

(Reference Example 6: Composite fiber)

(1) An ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% is used as a sheath portion, a thermoplastic polymer composed of polyethylene terephthalate is used as a core portion, and a melt extruder is used. The composite spinning device uses a circular cross-section nozzle to perform a backhand twist at a spinning temperature of 280 ° C and a sheath-to-core weight ratio of 50:50. After the back-twisted yarn is cooled and solidified, it is taken up by a take-up tube through a take-up roller.

(2) Next, the coiled wire is thermally stretched at an elongation temperature of 80 ° C. and an elongation ratio of 2 times. After applying the oil agent in an oil bath, the coiled yarn is crimped by a crimping device such as a staff type crimping device. deal with. After the crimping treatment, the fibers were dried with hot air at 100 ° C, and then cut into 51 mm to obtain EVOH-containing fibers (3.4 dtex, 51 mm length, sheath-to-core weight ratio 50:50, circular cross section, core 12.5 μm in diameter). Good spinnability and extensibility, strength is 3.6cN / dtex, Elongation is 38%.

[Example 1]

A unit weight of about 60 g was prepared by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 1 and 30% by weight of a solvent-spun cellulose fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing). / m ² carded cotton fabric.

Next, a jet of water was sprayed onto the carded cotton fabric, and a complexing treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 92%. The results of each evaluation are shown in Table 1.

This sheet has sufficient liquid retention and release properties, and has a good touch.

[Example 2]

Fabricated by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 2 and 30% by weight of a solvent-spun cellulose fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing) with a unit weight of about 60g / m ² carded cotton fabric.

Next, a jet of water was sprayed onto the carded cotton fabric, and a complexing treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 95%. The results of each evaluation are shown in Table 1. This sheet has sufficient liquid retention and release properties, and has a good touch.

[Example 3]

The antibacterial EVOH-containing fiber of Reference Example 3 was 70% by weight, and the solvent-spun cellulose fiber (Lyocell, 1.7dtex, 12 mm long) manufactured by Lenzing was 30% by weight, and dispersed in water. The wet method produces a wet nonwoven fabric having a weight per unit area of about 60 g / m ² .

Then, a water stream is sprayed on the wet nonwoven fabric, and a complexing treatment is performed to prepare a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 90%. The results of each evaluation are shown in Table 1. This sheet has sufficient liquid retention and release properties, and has a good touch.

[Example 4]

A unit weight of about 60 g was produced by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 5 and 30% by weight of a solvent-spun cellulose-based fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing). / m ² carded cotton fabric.

Next, a jet of water was sprayed onto the carded cotton fabric, and a complexing treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 97%. The results of each evaluation are shown in Table 1. This sheet has sufficient liquid retention and release properties, and has a good touch.

[Example 5]

A stream of water was sprayed on the carded cotton fabric obtained in Example 2 and subjected to a complexing treatment to form a stream of non-woven fabric with a weight per unit area of 60 g / m ² to obtain the antibacterial non-woven sheet of the present invention. In addition, the water flow complexing process uses nozzles provided with orifices of 0.15 mm in diameter at 0.6 mm intervals in the width direction of the fabric, and sprays 8 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 99%. The results of each evaluation are shown in Table 1. As a result, the sheet had sufficient liquid-retaining property and release property, and on the other hand, the touch was slightly worse.

[Example 6]

10% by weight of the antibacterial EVOH-containing fibers obtained in Reference Example 2 and 90% by weight of the solvent-spun cellulose-based fibers were mixed with cotton to prepare a carded fabric with a basis weight of 60 g / m ² . Other than that, an antibacterial nonwoven fabric sheet was obtained in the same manner as in Example 1. The void ratio of the obtained antibacterial nonwoven fabric sheet was 88%. The results of each evaluation are shown in Table 1. Although this sheet is slightly inferior in liquid retention and release properties, it has a good touch.

[Comparative Example 1]

A silver-based inorganic antibacterial fine particle (manufactured by SINANEN ZEOMIC Co., Ltd., with an average particle diameter of 0.008 μm and a substantially cubic shape) was incorporated in the inorganic ion exchanger to support silver ions, except that it was performed in the same manner as in Reference Example 2. Reeling, but because of poor spinning properties, reeling cannot be performed stably.

[Comparative Example 2]

The silver-based inorganic antibacterial microparticles (made by SINANEN ZEOMIC, with an average particle diameter of 25 μm and a substantially cubic shape) doped with silver ions supported by the inorganic ion exchanger were mixed in the same manner as in Reference Example 2 漅Silk, but reeling cannot be performed stably due to poor spinnability.

[Comparative Example 3]

In 99 parts by weight of an ethylene-vinyl alcohol copolymer having an ethylene content of 8 mol%, silver mixed with silver ions supported by an inorganic ion exchanger is mixed. Based on 1 part by weight of inorganic antibacterial fine particles ("AV10D" manufactured by SINANEN ZEOMIC, average particle diameter 2.5 μm, slightly cubic shape). Although reeling was performed in the same manner as in Reference Example 1, it was unstable due to poor spinning properties. Ground reeling.

[Comparative Example 4]

A unit weight of about 60 g was produced by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 4 and 30% by weight of a solvent-spun cellulose fiber (Lyocell, 1.7 dtex, 38 mm long manufactured by Lenzing). / m ² carded cotton fabric.

Then, a water stream was sprayed onto the carded fabric, and a complex treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 93%. The evaluation results are shown in Table 2. Although this sheet has a good feel, it is difficult to use because it has poor liquid retention and release properties and a slow water absorption rate.

[Comparative Example 5]

A carded fabric having a basis weight of 60 g / m ^{2 was} produced using 100% by weight of the antibacterial EVOH-containing fiber obtained in Reference Example 2, and an antibacterial non-woven sheet was obtained in the same manner as in Example 1. The void ratio of the obtained antibacterial nonwoven fabric sheet was 96%. The evaluation results are shown in Table 2. Although this sheet has excellent liquid-retaining property and release property, it is difficult to use because of its slow water absorption rate, and the touch is also slightly poor.

[Comparative Example 6]

A carded fabric having a basis weight of about 60 g / m ^{2 was} produced by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 2 and 30% by weight of cotton fibers manufactured by Maruzan Co., Ltd.

Then, a water stream was sprayed onto the carded fabric, and a complex treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 94%. The evaluation results are shown in Table 2. This sheet is not satisfactory for liquid retention, release, softness, and comfort to the skin.

[Comparative Example 7]

The wet-type non-woven fabric obtained in Example 3 was directly made into an antibacterial non-woven fabric sheet without performing a water stream complexing treatment. The evaluation results are shown in Table 2. The non-woven fabric sheet had a porosity of 78%, and although it had a fairly good feel, it had poor liquid retention and release properties, and was not satisfactory in handling properties.

[Comparative Example 8]

A unit weight of about 60 g / m is produced by blending 50% by weight of EVOH-containing fiber of Reference Example 6 and 50% by weight of solvent-spun cellulose-based fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing). ² carded cotton fabric.

Next, a jet of water was sprayed onto the carded cotton fabric, and a non-woven fabric was entangled with a stream of water having a basis weight of 60 g / m ² by applying a complexing treatment to obtain a non-woven sheet. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained nonwoven fabric sheet was 95%. The evaluation results are shown in Table 2. Although the sheet has sufficient liquid-retaining property, release property, and good touch, the antibacterial property is obviously inferior.

(Reference Example 7: Individual fibers)

(1) Into 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 44 mol%, silver-based antibacterial microparticles ("AV10D" manufactured by SINANEN ZEOMIC Co., Ltd., average particle) are incorporated in an inorganic ion exchanger to support silver ions. Diameter 2.5 μm, slightly cubic) 1 part by weight, and back-twisted using a melt extruder at a spinning temperature of 240 ° C. After the back-twisted yarn is cooled and solidified, it is drawn to the winding tube through a drawing roller.

(2) Next, the coiled wire is thermally stretched at an elongation temperature of 80 ° C. and an elongation ratio of 2.4 times. After applying the oil agent in an oil bath, the coil is wound using a crimping device such as a staff type crimping device. deal with. Following the crimping treatment, the fibers were dried with hot air at 100 ° C., and then cut into arbitrary cut lengths to obtain antibacterial EVOH-containing fibers (1.4 dtex, circular cross section). It is good in terms of spinnability and elongation, the strength is 3.1 cN / dtex, the elongation is 26%, and the Young's rate is 30.8 cN / dtex.

(Reference Example 8: Composite fiber)

(1) Into 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 44 mol%, a silver-based antibacterial fine particle ("AV10D" manufactured by SINANEN ZEOMIC Corporation, which is supported by an inorganic ion exchanger) (Particle diameter 2.5 μm, almost cubic) 1 part by weight of a copolymer as a sheath portion, a thermoplastic polymer composed of polyethylene terephthalate as a core portion, and a composite spinning composed of a melt extruder The device uses a circular cross-section nozzle to perform a backhand twist at a spinning temperature of 280 ° C and a sheath-core weight ratio of 50:50. Backhand twisted After the yarn is cooled and solidified, it is taken up by the take-up roller through a take-up roller.

(2) Next, the coiled wire is thermally stretched at an elongation temperature of 80 ° C. and an elongation ratio of 2.6 times. After applying the oil agent in the oil bath, the coiled yarn is crimped by a crimping device such as a staff type crimping device. deal with. Following the crimping treatment, the fibers were dried with hot air at 100 ° C, and then cut to arbitrary cut lengths to obtain antibacterial EVOH-containing fibers (1.7 dtex, sheath-to-core weight ratio 50) shown in Table 3 below: 50, circular cross-section, core diameter 8.9 μm). It is good in terms of spinnability and elongation, the strength is 3.6cN / dtex, the elongation is 31%, and the Young's rate is 33.9cN / dtex.

(Reference Example 9: Composite fiber)

(1) The coiled wire of Reference Example 8 was heat-drawn at an elongation temperature of 80 ° C. and an elongation ratio of 2 times. After applying the oil agent in the oil bath, it was cut into 10 mm to obtain the antibacterial-containing bacteria shown in Table 3 below. EVOH fiber (1.7 dtex, 10 mm long, sheath-to-core weight ratio 50:50, circular cross section, core diameter 8.9 μm). It is good in terms of spinnability and elongation, the strength is 3.6cN / dtex, the elongation is 31%, and the Young's rate is 33.9cN / dtex.

(Reference Example 10: Individual fibers)

In 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 85 mol%, silver-based inorganic antibacterial microparticles ("AV10D" manufactured by SINANEN ZEOMIC Co., Ltd., with an average particle diameter) mixed with silver ions supported by an inorganic ion exchanger 2.5 μm, slightly cube-shaped) 1 part by weight, silk reeling was performed in the same manner as in Reference Example 7 to obtain resistance-containing Bacterial EVOH fiber (1.4dtex, 51mm long, circular cross section). It is good in terms of spinnability and elongation, the strength is 3.7cN / dtex, the elongation is 24%, and the Young's rate is 35.1cN / dtex.

(Reference Example 11: Composite fiber)

Except that the resin discharge amount, pull speed, and draw ratio were adjusted so that the fineness became 5.5 dtex, reeling was performed in the same manner as in Reference Example 8 to obtain an antibacterial EVOH-containing fiber (5.5 dtex, 51 mm length). (Sheath core weight ratio 50:50, circular cross section, core diameter 16.0 μm). It is good in terms of spinnability and elongation, the strength is 2.7cN / dtex, the elongation is 36%, and the Young's rate is 28.7cN / dtex.

(Reference Example 12: Composite fiber)

(1) An ethylene-vinyl alcohol copolymer having an ethylene content of 44 mol% is used as a sheath portion, a thermoplastic polymer composed of polyethylene terephthalate is used as a core portion, and a melt extruder is used. The composite spinning device uses a circular cross-section nozzle to perform a backhand twist at a spinning temperature of 280 ° C and a sheath-to-core weight ratio of 50:50. After the back-twisted yarn is cooled and solidified, it is taken up by a take-up tube through a take-up roller.

(2) Next, the coiled wire is thermally stretched at an elongation temperature of 80 ° C. and an elongation ratio of 2 times. After applying the oil agent in an oil bath, the coiled yarn is crimped by a crimping device such as a staff type crimping device. deal with. Following the crimping treatment, the fibers were dried with hot air at 100 ° C, and then cut to 51 mm to obtain EVOH-containing fibers (3.4 dtex, 51 mm long, Sheath core weight ratio 50:50, circular cross section, core diameter 12.5 μm). It is good in terms of spinnability and elongation, the strength is 3.6cN / dtex, the elongation is 38%, and the Young's rate is 38.5cN / dtex.

[Example 7]

A unit weight of about 60 g was produced by blending cotton with 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 7 and 50% by weight of a solvent-spun cellulose fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing) / m ² carded cotton fabric.

Next, a jet of water was sprayed onto the carded cotton fabric, and a complexing treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 90%. The results of each evaluation are shown in Table 3. This sheet has sufficient liquid retention, returns liquid to the raw roll, and has a good touch.

[Example 8]

A unit weight of about 60 g was produced by blending cotton with 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 50% by weight of a solvent-spun cellulose fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing). / m ² carded cotton fabric.

Next, a jet of water was sprayed onto the carded cotton fabric, and a complexing treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 92%. The results of each evaluation are shown in Table 3. This sheet has sufficient liquid retention, returns liquid to the raw roll, and has a good touch.

[Example 9]

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

Then, a water stream is sprayed on the wet nonwoven fabric, and a complexing treatment is performed to prepare a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 86%. The results of each evaluation are shown in Table 3. This sheet has sufficient liquid retention, returns liquid to the raw roll, and has a good touch.

[Example 10]

A unit weight of about 60 g was produced by blending cotton with 50% by weight of the antibacterial EVOH-containing fiber of Reference Example 11 and 50% by weight of a solvent-spun cellulose fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing). / m ² carded cotton fabric.

Next, a jet of water was sprayed onto the carded cotton fabric, and a complexing treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 94%. The results of each evaluation are shown in Table 3. This sheet has sufficient liquid retention, returns liquid to the raw roll, and has a good touch.

[Example 11]

A water stream was sprayed onto the carded cotton fabric obtained in Example 8 and subjected to a complexing treatment to form a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing process uses nozzles provided with orifices of 0.15 mm in diameter at 0.6 mm intervals in the width direction of the fabric, and sprays 8 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 98%. The results of each evaluation are shown in Table 3. As a result, the sheet had sufficient liquid-retaining property and returned to the raw material roll, and on the other hand, the touch was slightly worse.

[Comparative Example 9]

A silver-based inorganic antibacterial fine particle (manufactured by SINANEN ZEOMIC Co., Ltd., with an average particle diameter of 0.008 μm and a substantially cubic shape) mixed with an inorganic ion exchanger supported with silver ions was carried out in the same manner as in Reference Example 8 Reeling, but because of poor spinning properties, reeling cannot be performed stably.

[Comparative Example 10]

The silver-based inorganic antibacterial microparticles (made by SINANEN ZEOMIC, with an average particle diameter of 25 μm and a substantially cubic shape) doped with silver ions supported by the inorganic ion exchanger were mixed in the same manner as in Reference Example 8 Silk, but reeling cannot be performed stably due to poor spinnability.

[Comparative Example 11]

In 99 parts by weight of an ethylene-vinyl alcohol-based copolymer having an ethylene content of 8 mol%, silver-based inorganic antibacterial microparticles ("AV10D" manufactured by SINANEN ZEOMIC Co., Ltd., with an average particle diameter) incorporated in the inorganic ion exchanger and supporting silver ions are blended. 2.5 μm, slightly cubic) 1 part by weight. Although the reeling was performed in the same manner as in Reference Example 7, the reeling could not be performed stably due to poor spinnability.

[Comparative Example 12]

Fabricated by blending 50% by weight of antibacterial EVOH-containing fiber of Reference Example 10 and 50% by weight of solvent-spun cellulose-based fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing) with a unit weight of about 60g / m ² carded cotton fabric.

Then, a jet of water was sprayed on the carded cotton fabric, and a complex treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of about 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The porosity of the obtained liquid-retaining sheet was 91%. The evaluation results are shown in Table 4.

Although the sheet has a good touch, the liquid-retaining property or the liquid return to the raw roll is insufficient.

[Comparative Example 13]

An antibacterial non-woven fabric sheet was obtained in the same manner as in Example 7 except that a carded fabric having a basis weight of 60 g / m ^{2 was} produced from 100% by weight of the antibacterial EVOH-containing fiber obtained in Reference Example 8. The void ratio of the obtained antibacterial nonwoven fabric sheet was 96%. The evaluation results are shown in Table 4.

This sheet does not satisfy the liquid return of the raw material roll, and it is difficult to use due to the slow water absorption speed, and the touch is slightly worse.

[Comparative Example 14]

Fabricated by blending 35% by weight of antibacterial EVOH-containing fiber of Reference Example 8 and 65% by weight of solvent-spun cellulose-based fibers (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing) with a unit weight of about 60g / m ² carded cotton fabric.

Then, a water stream was sprayed onto the carded fabric, and a complex treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 95%. The evaluation results are shown in Table 4.

The sheet cannot sufficiently satisfy the points of liquid retention, liquid absorption speed, and liquid return to the raw material roll.

[Comparative Example 15]

A carded fabric having a basis weight of about 60 g / m ^{2 was} produced by blending 70% by weight of the antibacterial EVOH-containing fiber of Reference Example 8 and 30% by weight of cotton fiber manufactured by Maruzan Co., Ltd.

Next, a jet of water was sprayed onto the carded cotton fabric, and a complexing treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain the antibacterial nonwoven fabric sheet of the present invention. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 93%. The evaluation results are shown in Table 4.

This sheet system cannot satisfy various points of liquid retention, release property, softness, and comfort to the skin.

[Comparative Example 16]

The wet-type non-woven fabric obtained in Example 9 was directly made into an antibacterial non-woven fabric sheet without performing a water flow complexing treatment. The antibacterial nonwoven sheet had a porosity of 74%, and although it had a fairly good feel, it had poor stress at the time of 30% when wet, and was not satisfactory in handling properties.

[Comparative Example 17]

A unit weight of about 60 g / m is produced by blending 50% by weight of EVOH-containing fiber of Reference Example 12 and 50% by weight of solvent-spun cellulose-based fiber (Lyocell, 1.7dtex, 38mm long manufactured by Lenzing) ² carded cotton fabric.

Then, a water stream was sprayed onto the carded fabric, and a complex treatment was performed to produce a water stream complex nonwoven fabric having a weight per unit area of 60 g / m ² to obtain an antibacterial nonwoven fabric sheet. In addition, the water flow complexing treatment uses nozzles provided with orifices having a diameter of 0.1 mm at intervals of 0.6 mm in the width direction of the fabric, and sprays 6 MPa of water pressure on each of the front and back sections to stagger them. The void ratio of the obtained antibacterial nonwoven fabric sheet was 95%. The evaluation results are shown in Table 4.

Although the sheet has sufficient liquid-retaining property, release property, and good touch, the antibacterial property is obviously inferior.

[Industrial availability]

The antibacterial nonwoven fabric sheet of the present invention can be used for absorbing liquid components and contacting the skin, for example, body fluid absorption sheets (for example, surface materials such as napkins, diapers, diaper pads, wet tissues, etc.), and skin care. Sheets (for example, a mask, a makeup remover sheet, a cleansing sheet, or a body cleansing sheet (sweat wipe sheet, oil absorbing sheet, cooling sheet, etc.)), a medicinal sheet (antipruritic sheet, wet cloth, etc.), and the like. In particular, the antibacterial nonwoven fabric sheet of the present invention is in a state of being impregnated with a liquid component such as a cosmetic liquid (cosmetics), and the liquid component returns quickly even if it is pressed with a finger, and therefore, it can be used for the entire face, nose, and eyes , Moisturizing, whitening and other effective ingredients impregnated in the corners of the mouth, neck, etc., and has an antibacterial mask.

Claims (12)

An antibacterial non-woven sheet characterized in that at least a part of a fiber surface has an antibacterial ethylene-vinyl alcohol copolymer contained in a state in which inorganic antibacterial microparticles are dispersed therein, and the inorganic antibacterial microparticle system retains silver ions on zeolite Or inorganic antibacterial microparticles in zirconium phosphate, the average particle diameter of the inorganic antibacterial microparticles is 0.3 to 20 μm, and the antibacterial ethylene-vinyl alcohol copolymer has an ethylene content of 10 to 70 mol%. Interlaced with solvent-spun cellulose fibers. For example, the antibacterial non-woven fabric sheet of claim 1, wherein the fiber length of the aforementioned antibacterial fiber and the solvent-spun cellulose-based fiber is 5 to 60 mm, and these are interlaced with each other. The antibacterial non-woven sheet according to claim 1, wherein the antibacterial fiber is a sheath-core composite fiber, and the sheath is an antibacterial ethylene contained in a state in which inorganic antibacterial fine particles having an average particle diameter of 0.3 to 20 μm are dispersed in the sheath- A vinyl alcohol-based copolymer, and the core is made of a hydrophobic resin and has a diameter of 5 to 15 μm. The antibacterial nonwoven fabric sheet according to claim 1, wherein the surface of the antibacterial nonwoven fabric sheet has unevenness. The antibacterial nonwoven fabric sheet according to claim 1, which contains 30 to 90% by weight of the aforementioned antibacterial fibers. For example, the antibacterial non-woven fabric sheet of claim 5, which contains 40 to 90% by weight of the aforementioned antibacterial fibers, and the Young's rate of the aforementioned antibacterial fibers is 25 cN / dtex or more. A liquid-containing sheet in which the antibacterial non-woven 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 fluid composition contains water. The liquid-containing sheet according to claim 7, wherein the fluid composition comprises a cosmetic. The liquid-containing sheet according to claim 9, which is a skin care sheet. For example, if the liquid-containing sheet of claim 9 is impregnated with 900% by weight of the aforementioned fluid composition with respect to its own weight and is removed at a load of 260 g / cm ² after 1 minute of load, the compression in the thickness direction is restored. It is more than 35% for 5 minutes. A facial mask using a liquid-containing sheet as claimed in claim 9.