WO2011004834A1 - 積層シート及びその製造方法 - Google Patents
積層シート及びその製造方法 Download PDFInfo
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Definitions
- the present invention relates to a laminate sheet that can absorb a liquid component (liquid compound) and to be brought into contact with the skin, and a method for producing the same, and in particular, is impregnated with a liquid component including a cosmetic component and a medicinal component, and is applied to the skin
- the present invention relates to a laminated sheet to be used (liquid-impregnated biological coating sheet) and a method for producing the same.
- a skin care sheet liquid-impregnated biological coating sheet impregnated with a liquid such as cosmetics
- a liquid such as cosmetics
- face masks a wide variety of products because the skin can be easily maintained in a high moist state.
- a sheet material generally, a woven fabric or a non-woven fabric composed of fibers is used, and a non-woven fabric is widely used from the viewpoint of cost.
- a spunlace nonwoven fabric mainly composed of cellulosic fibers represented by highly hydrophilic cotton.
- the spunlace nonwoven fabric made of cellulosic fibers is not sufficient for skin irritation and wearability.
- Patent Document 1 a liquid-impregnated bio-coated sheet such as cosmetics in which ultrafine fibers are arranged on the sheet surface for the purpose of improving the irritation and wearability on the face, An ultrafine fiber layer containing 10% by mass or more of ultrafine fibers having a fineness of 0.5 dtex or less is located on one or both surfaces of the hydrophilic fiber layer containing 50% by mass or more of hydrophilic fibers.
- a skin-coated sheet for impregnating cosmetics has been proposed in which the layers are integrated, and the ultrafine fiber layer is the contact surface with the skin. This document describes that the ratio of the hydrophilic fiber is 10 to 70 parts by mass (preferably 15 to 50 parts by mass) with respect to 100 parts by mass of the covering sheet.
- the skin care sheet cosmetics impregnated sheet
- this document does not describe the fiber diameter distribution of the ultrafine fibers, and the method for forming a nonwoven fabric by splitting the split-type composite fiber provides a nonwoven fabric in which the fibers are uniform and appropriately entangled. This is difficult, and the obtained nonwoven fabric has low adhesion to the skin, is not sufficiently irritating or comfortable to the skin, and for example, a tingling sensation is likely to occur.
- the background of the increasing demand for cosmetic impregnated sheets in recent years is not only intended for the effect of the target component on the skin in various liquids (liquid components) impregnated into the sheet, but the cosmetic impregnated sheet
- the cosmetic impregnated sheet enjoying the comfort of use is also a factor that stimulates the willingness to purchase, and there is value as a favorite product.
- the “feel” when touching the skin is soft, and the cosmetics cover the entire skin as a liquid film, and can be felt for a long time with a “stickiness” that sticks to the skin. It is desired.
- the demand for sheets impregnated with cosmetics typified by face masks has increased in recent years, and accordingly, sheets having higher performance and a good feeling of use have been demanded.
- the cosmetic impregnated sheet is intended to keep the skin in a highly moist state by using cosmetics having various effects during use.
- a liquid retention amount suitable for maintaining is required.
- An object of the present invention is to provide a laminated sheet excellent in the balance between liquid retention and release properties, and excellent in adhesion and fit to the skin in a state impregnated with a liquid component, and a method for producing the same.
- Another object of the present invention is to provide a laminated sheet that is soft when touched to the skin, and that allows a liquid component such as cosmetics to spread throughout the skin and a feeling of adhesion for a long time, and a method for producing the same. There is to do.
- Still another object of the present invention is to provide a laminated sheet capable of suppressing the occurrence of displacement and lifting even when used as a skin care sheet such as a face mask for a long time, and a method for producing the same.
- non-woven fibers having a number average fiber diameter of 10 ⁇ m or less on at least one surface of a liquid retaining layer composed of a non-woven fabric (non-woven fiber aggregate).
- a liquid retaining layer composed of a non-woven fabric
- non-woven fiber aggregate By laminating the adhesion layer composed of an aggregate with a thin or thin film with respect to the liquid retention layer, it is found that the balance between the liquid retention and the release property is excellent, and that the adhesion and fit to the skin can be improved, The present invention has been completed.
- the laminated sheet of the present invention is formed of a nonwoven fiber assembly and is formed on at least one surface of the liquid retaining layer that can absorb the liquid component and is capable of transmitting the liquid component.
- a laminated sheet comprising an adhesion layer for contacting with the skin, wherein the adhesion layer is composed of a non-woven fiber aggregate having a number average fiber diameter of 10 ⁇ m or less, and the adhesion layer and the liquid retaining layer The thickness ratio of the adhesive layer / the liquid retaining layer is 1/4 to 1/100.
- the adhesion layer may be composed of a nonwoven fiber assembly having a standard deviation of fiber diameter of 5 or less.
- the liquid retention layer may be composed of a nonwoven fiber aggregate having a fiber diameter larger than that of the fibers constituting the adhesion layer.
- the liquid retaining layer may include fibers made of a hydrophilic resin, and the adhesion layer may contain fibers made of a thermoplastic resin.
- the liquid retaining layer may contain fibers composed of a hydrophilic resin in a proportion of less than 50% by mass.
- the adhesion layer may be composed of at least one selected from the group consisting of polyester fiber, polyolefin fiber, polyvinyl alcohol fiber and polyurethane fiber.
- the number average fiber diameter of the fibers constituting the liquid retaining layer may be 9 to 32 ⁇ m.
- the number average fiber diameter of the fibers constituting the adhesion layer may be 1 to 8 ⁇ m.
- the liquid retaining layer may have a density of 0.03 to 0.20 g / cm 3 and a porosity of 80% or more.
- the adhesion layer may have a density of 0.05 to 0.35 g / cm 3 and a porosity of 70% or more.
- the adhesion layer may be composed of a melt blown nonwoven fabric.
- the laminated sheet of the present invention may have a 50% elongation stress when wet according to JIS L1913 of about 0.5 to 15 N / 5 cm in at least one direction.
- the laminated sheet of the present invention may be a sheet impregnated with a liquid component.
- the laminated sheet of the present invention may be a skin care sheet (particularly a face mask) in which the liquid component contains a cosmetic.
- the laminated sheet of the present invention may further have another adhesion layer or a non-porous film on the liquid retaining layer.
- the laminated sheet of the present invention is impregnated with 500% by mass of cosmetics based on the mass of the sheet, the frictional force measured according to ASTM-D1984 is 0.6 N or more, and 500% by mass of cosmetics is impregnated.
- the frictional force may be larger than the frictional force impregnated with 900% by mass of the cosmetic material.
- the present invention also includes a method for producing the laminated sheet in which the adhesion layer is formed by a melt blown method and laminated on at least one surface of the liquid retaining layer composed of the nonwoven fiber aggregate.
- the obtained liquid retention layer and the adhesion layer are further entangled by the spunlace method or obtained. You may laminate
- a liquid retention layer is produced by entanglement and wet heat adhesion of hydrophobic fibers and hydrophilic fibers containing an ethylene-vinyl alcohol copolymer by a steam jet method, You may laminate
- the present invention also includes a method of using a laminated sheet in which the adhesive layer is brought into contact with the skin while the laminated sheet is impregnated with a liquid component.
- the term “skin care” is not only meant as a care of skin (skin) with cosmetics or emulsions (so-called skin care), but also as a broad concept that includes other actions that can be associated with the skin.
- the skin care sheet includes, for example, a sheet for cleaning the skin, a sheet for suppressing itching of the skin, a sheet for cooling through the skin, and a sheet for suppressing inflammation through permeation from the skin ( A sheet used in contact with the skin, such as a compress.
- An adhesion layer composed of a nonwoven fiber assembly having a number average fiber diameter of 10 ⁇ m or less is formed thin on the liquid retention layer on at least one surface of the liquid retention layer composed of the nonwoven fiber assembly. Therefore, it is excellent in the balance between the liquid retaining property and the releasing property, and in the state of impregnating the liquid component, it is excellent in the adhesion to the skin and the fit. Further, by uniformly adjusting the fiber diameter of the adhesion layer, the surface becomes flat and smooth, and when the liquid component is impregnated and brought into contact with the skin, the adhesion and fit can be further improved.
- the touch when touching the skin is soft, and a state in which a liquid component such as cosmetics is spread over the entire skin and a feeling of adhesion can be felt for a long time. Furthermore, even if it is used for a long time as a skin care sheet such as a face mask, it is possible to suppress the occurrence of displacement and floating.
- the adhesion layer is composed of melt blown nonwoven nonwoven fabrics, and the distance between the liquid retaining layer and the skin is extremely small, so there is very little irritation when the fibers themselves touch the skin, and they are formed at the interface with the skin.
- the liquid film is extremely strong compared to the existing technology and has achieved sufficient skin adhesion to give the user a sense of security.
- FIG. 1 is a schematic plan view of a sample subjected to an adhesion test.
- FIG. 2 is a schematic plan view showing an outline of a test method for a sample subjected to an adhesion test. It is the schematic side view and schematic perspective view (perspective view seen from the front direction) of the test apparatus used in the adhesion test. It is a graph which shows the relationship between the test force and the displacement of a sample in an adhesive test.
- the laminated sheet of the present invention is formed of a fabric and formed on a liquid retaining layer capable of absorbing a liquid component and at least one surface of the liquid retaining layer, and is capable of transmitting the liquid component (liquid effect component). And an adhesion layer for making contact with the skin. That is, the laminated sheet (liquid-impregnated biological coating sheet) of the present invention is composed of a liquid retaining layer for impregnating a liquid component and an adhesion layer located on the side in direct contact with the skin.
- the liquid retention layer is a cosmetic component or a medicinal component (for example, a moisturizing component, a cleansing component, an antiperspirant component, an aroma component, a whitening component, a blood circulation promoting component, a cooling component, an ultraviolet ray preventing component, and an itching skin. It has the wettability necessary for impregnating liquid components (liquid compounds) including inhibitory components) and voids for retaining liquids, and does not spill during handling during use. For example, it holds until it covers the face), affixes or stands still, and gradually shifts the liquid cosmetic toward the adhesion layer located on the skin side.
- a cosmetic component or a medicinal component for example, a moisturizing component, a cleansing component, an antiperspirant component, an aroma component, a whitening component, a blood circulation promoting component, a cooling component, an ultraviolet ray preventing component, and an itching skin. It has the wettability necessary for impregnating liquid components (liquid compounds) including inhibitory components) and voids for
- the liquid-retaining layer having such characteristics may be usually composed of a woven fabric or a non-woven fabric, but a non-woven fabric (or non-woven fiber aggregate) is preferable from the viewpoint of productivity. Furthermore, it is preferable that the nonwoven fabric which comprises a liquid retention layer contains the fiber comprised with hydrophilic resin, in order to ensure wettability and liquid retention. Fibers made of hydrophilic resin play an important role in taking liquid into the fiber structure when liquid such as cosmetics is added to the sheet, and a large amount of cosmetics once taken into the fiber structure It plays the role of holding the liquid so that it does not spill when handled during use.
- non-woven fabrics are a mixture of fibers composed of hydrophilic resin (hydrophilic fibers) and fibers composed of hydrophobic resins (hydrophobic fibers) because of its excellent balance between liquid retention and release properties.
- the body is particularly preferred.
- the ratio of the hydrophilic fiber is too large, the ability to retain the liquid component of the sheet is increased, and it becomes difficult to release the cosmetic liquid to the skin side during use, or excessive liquid in advance in order to obtain the necessary release amount. Ingredients are required and waste is likely to occur.
- the ratio (mass ratio) between the hydrophilic fiber and the hydrophobic fiber is the role of attracting the liquid component to the inside of the fiber structure, the role of keeping it from dripping when handled, and releasing the liquid component to the skin side.
- hydrophilic fiber / hydrophobic fiber may be about 30/70 to 50/50 (mass ratio).
- the liquid retaining layer may have a plurality of layer structures having different fiber configurations. For example, by increasing the fiber ratio of the hydrophilic fibers in the part close to the skin side, that is, the part close to the adhesion layer, the effect of making the skin side in a high moist state earlier can be expected when used as a cosmetic impregnated sheet. . Specifically, when a laminated sheet having a liquid retention layer in which a layer with an increased fiber ratio of hydrophilic fibers is arranged on the skin side is left on the skin, the liquid component of the hydrophilic fiber is contained in the liquid retention layer. The fiber ratio moves in a high direction, and the skin side can be in a high wet state in a short time.
- the liquid retention layer is, for example, a layer containing 30% by mass or less (for example, 10 to 30% by mass) of hydrophilic fibers located on the surface side and 70% by mass or more (for example, 70%) of hydrophilic fibers located on the adhesion layer side. It may be a two-layer structure composed of layers containing 90 mass%).
- the hydrophilic fiber is not particularly limited as long as it has hydrophilicity, and a synthetic fiber, a natural fiber, a natural plant fiber, an animal protein fiber, etc. are dissolved once and then chemically treated to produce a fiber. Fiber etc. can be selected. Further, the hydrophilic fiber only needs to have at least the surface made of a hydrophilic resin, for example, a resin obtained by hydrophilizing the surface of a hydrophobic resin, or a composite fiber having an inside made of a hydrophobic resin. May be.
- Synthetic fibers include, for example, resins having hydrophilic groups (particularly hydroxyl groups) such as hydroxyl groups, carboxyl groups, and sulfonic acid groups in the molecule, such as polyester resins such as polyvinyl alcohol resins, polyamide resins, and polylactic acid, Examples include synthetic fibers composed of (meth) acrylic copolymers containing (meth) acrylamide units. These synthetic fibers can be used alone or in combination of two or more. Of these synthetic fibers, a hydrophilic resin having a hydroxyl group in the monomer unit is preferable, and a fiber composed of an ethylene-vinyl alcohol copolymer is particularly preferable from the viewpoint of having a hydroxyl group uniformly in the molecule.
- the ethylene unit content (copolymerization ratio) is, for example, about 10 to 60 mol%, preferably about 20 to 55 mol%, and more preferably about 30 to 50 mol%.
- the saponification degree of the vinyl alcohol unit is, for example, about 90 to 99.99 mol%, preferably 95 to 99.98 mol%, more preferably about 96 to 99.97 mol%.
- the viscosity average degree of polymerization is, for example, about 200 to 2500, preferably about 300 to 2000, and more preferably about 400 to 1500.
- a wet heat adhesive resin such as an ethylene-vinyl copolymer
- a bulky and stable liquid retaining layer can be formed by a steam jet method.
- natural fibers examples include cotton or cotton, silk, hemp, silk, and wool. These natural fibers can be used alone or in combination of two or more. Of these, cotton is widely used.
- regenerated fibers include rayon such as viscose rayon, cellulosic fibers such as tencel such as acetate and lyocell, cupra and polynosic. These natural fibers can be used alone or in combination of two or more. Of these, rayon fibers and tencel fibers are widely used.
- a method for imparting hydrophilicity to the fiber surface in a fiber having a surface composed of a hydrophilic resin a method of forming a hydrophilic resin together with the fiber-forming resin and covering at least a part of the fiber surface with the hydrophilic resin It may be.
- a composite fiber formed by a method in which the surface of the fiber is covered with a hydrophilic resin is preferable because the deterioration of the hydrophilic performance is small even when used for a long time.
- a method of forming a hydrophilic resin with a fiber-forming resin is preferable because the manufacturing process is shortened and uniform hydrophilicity can be imparted.
- a fiber in which the entire surface of the fiber is sheathed with a hydrophilic resin that is, a composite fiber having a core-sheath structure in which the sheath portion is composed of a hydrophilic resin is preferable.
- the core-sheath type composite fiber is not particularly limited as long as the sheath part is made of a hydrophilic resin, but the core part retains the fiber shape even when impregnated with a liquid component, and can suppress deterioration of water immersion performance. It is preferably composed of a hydrophobic resin constituting the hydrophobic fiber described later. Furthermore, among the hydrophobic resins, for example, polypropylene resins, polyester resins, polyamide resins, and particularly polyester resins such as polyethylene terephthalate are preferable from the viewpoint of excellent balance of heat resistance and fiber formation.
- the hydrophilic resin in the sheath is preferably a resin constituting a synthetic fiber, particularly a polyvinyl alcohol resin such as an ethylene-vinyl alcohol copolymer, because a bulky and stable nonwoven fabric can be produced.
- cellulosic fibers such as rayon and tencel have absorptivity because water, aqueous solutions, polar solvents, and emulsions that constitute liquid components such as cosmetics penetrate into the fibers. It is particularly preferable in terms of good liquid retention performance.
- ethylene-vinyl alcohol copolymer fibers (especially core-sheath type composite fibers whose sheaths are made of ethylene-vinyl alcohol copolymer) have lower liquid retention performance than cellulosic fibers, but cosmetics etc. It is particularly preferable in that it is familiar with the liquid component and the fiber itself does not absorb the liquid component liquid and can be easily released by pressure or the like. Accordingly, the cellulosic fiber and the ethylene-vinyl alcohol copolymer fiber may be selected according to the viscosity and amount of a liquid component such as cosmetics. You may control. Furthermore, you may mix
- Hydrophobic fiber or non-hydrophilic resin that is not so high in polarity and relatively strong in hydrophobicity
- Hydrophobic fibers work in the direction of maintaining the bulk and stiffness of the liquid retaining layer because the Young's modulus of the fiber itself is hardly lowered even when the liquid retaining layer is in a wet state.
- Such hydrophobic fibers are not particularly limited, but resins having an official moisture content of less than 2.0% in a standard state (20 ° C., 65% RH), such as polyethylene and polypropylene generally used for nonwoven fabrics.
- Polyolefin resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other polyester resins, polyamide resins such as polyamide 6, polyamide 6,6 and polyamide 4,6, and polyurethanes such as polyester polyol type urethane resins Examples thereof include fibers made of resin and polyacrylonitrile resin.
- These hydrophobic fibers can be used alone or in combination of two or more. Of these, polyester fibers are preferred because of their high versatility and excellent mechanical properties.
- the fibers (hydrophilic fibers and hydrophobic fibers) constituting the liquid-retaining layer are further added to conventional additives such as stabilizers (heat stabilizers such as copper compounds, ultraviolet absorbers, light stabilizers, antioxidants, etc.) ), Dispersant, fine particles, colorant, antistatic agent, flame retardant, plasticizer, lubricant, crystallization rate retarder, and the like.
- stabilizers heat stabilizers such as copper compounds, ultraviolet absorbers, light stabilizers, antioxidants, etc.
- Dispersant fine particles, colorant, antistatic agent, flame retardant, plasticizer, lubricant, crystallization rate retarder, and the like.
- additives can be used alone or in combination of two or more.
- These additives may be carried on the surface of the liquid retaining layer or may be contained in the fiber.
- the cross-sectional shape of the fibers (hydrophilic fiber and hydrophobic fiber) constituting the liquid retention layer is not particularly limited, and for example, a round cross section, an irregular cross section (flat shape, elliptical cross section, etc.), a polygonal cross section, a multileaf
- Various cross-sectional shapes such as a shaped cross section (3 to 14 leaf-shaped cross section), a hollow cross section, a V-shaped cross section, a T-shaped cross section, an H-shaped cross section, an I-shaped (dogbone-shaped) cross section, and an array-shaped cross section may be used.
- a round cross section, an elliptical cross section and the like are widely used.
- the fiber length of the fiber constituting the liquid retaining layer is not particularly limited, but may be a short fiber.
- 20 to 70 mm is preferable, and particularly if it is 25 to 60 mm, the card passing property is sufficient. From the viewpoint, it is preferable in that a uniform texture web is easily obtained, and can be adjusted as appropriate according to the application.
- the fiber diameter of the fibers constituting the liquid retention layer is preferably larger than the fibers constituting the adhesion layer from the viewpoint of mechanical properties, and the specific fiber diameter (number average fiber diameter) is liquid retention. 5 ⁇ m or more from the viewpoint of excellent balance between the amount and the release property. For example, from 9 to 32 ⁇ m, preferably from 10 to 25 ⁇ m, more preferably from the viewpoint of the balance between the impregnation properties and retention of liquid components such as lotions. Is about 10 to 20 ⁇ m.
- the basis weight of the nonwoven fabric (nonwoven fiber aggregate) constituting the liquid retaining layer is, for example, 20 to 200 g / m 2 , preferably 25 to 150 g / m 2 , more preferably 30 to 120 g / m 2 (particularly 30 to 100 g). / M 2 ). If this basis weight is too small, it will be difficult to secure a void for the liquid retention formed by the fibers. If the basis weight is too large, the amount of liquid retention increases, and many of the active ingredients remain in the liquid retention layer without reaching the skin, so that the active ingredients are easily wasted.
- the density of the liquid retaining layer depends on the viscosity of the liquid component such as cosmetic to be impregnated, but is, for example, 0.03 to 0.20 g / cm 3 , preferably 0.05 to 0.00. It is about 17 g / cm 3 , more preferably about 0.1 to 0.15 g / cm 3 .
- the density is too low, the liquid holding capacity of the sheet is lowered, and dripping easily occurs during handling during use.
- the density is too high, the amount of liquid retained decreases, and the liquid transfer to the adhesion layer tends to slow down.
- the porosity of the liquid-retaining layer (the porosity in the laminated sheet) is, for example, 80% or more (for example, 80 to 99%), preferably 85% or more, from the viewpoint of ensuring the amount of impregnation of liquid components such as cosmetics. (For example, 85 to 98%), more preferably 90% or more (for example, 90 to 95%).
- the thickness of the liquid retaining layer can be selected from the range of about 100 to 3000 ⁇ m, for example, about 200 to 2000 ⁇ m, preferably about 300 to 1500 ⁇ m, more preferably about 400 to 1200 ⁇ m (particularly about 400 to 1000 ⁇ m).
- the nonwoven fabric or non-woven fiber aggregate constituting the liquid retaining layer can be produced by a conventional method, for example, a spunlace method, a needle punch method, a steam jet method, or the like.
- a spunlace method for example, a spunlace method, a needle punch method, a steam jet method, or the like.
- the span lace method capable of industrially producing at high speed may be used.
- the thermal bond method or the steam jet method particularly, it is possible to achieve uniform adhesion in the thickness direction, and to achieve both high form retention and bulkiness.
- Steam jet method or the like.
- the short fiber for example, a hydrophobic fiber and a hydrophilic fiber may be mixed and opened by carding with a card machine, for example, to create a nonwoven web.
- This non-woven web includes a parallel web arranged in the traveling direction of the card machine according to a blending ratio of fibers constituting the web, a cross web in which parallel webs are cross-laid, a random web arranged randomly, or a parallel web and a random web.
- any of the semi-random webs arranged in the middle of the above may be used, but the entanglement of fibers occurs in the transverse direction, and the elongation in the transverse direction is hindered, so the alongness to the skin tends to decrease during use
- Parallel webs and semi-random webs that can ensure the softness and extensibility of the laminated sheet in the transverse direction are preferred to random webs and cross webs.
- the obtained nonwoven web is subjected to a hydroentanglement process.
- a water flow injected in a columnar shape at high pressure from a nozzle plate in which injection holes having a diameter of 0.05 to 0.20 mm and intervals of about 0.30 to 1.50 mm are arranged in one or two rows is perforated.
- the non-woven web placed on the elastic support member is caused to collide, and the fibers constituting the non-woven web are three-dimensionally entangled and integrated.
- the nonwoven web When the nonwoven web is subjected to three-dimensional entanglement, the nonwoven web is placed on a moving porous support member, for example, a water pressure of 10 to 150 kg / cm 2 ( ⁇ 1 to 15 MPa), preferably 20 to 120 kg / cm.
- a method of performing treatment once or a plurality of times with a water flow of about 2 ( ⁇ 2 to 12 MPa), more preferably about 30 to 100 kg / cm 2 ( ⁇ 3 to 10 MPa) is preferable.
- the injection holes are arranged in a row in a direction perpendicular to the traveling direction of the nonwoven web, and the nozzle plate on which the injection holes are arranged is perpendicular to the traveling direction of the nonwoven web placed on the porous support member.
- the water flow is caused to collide uniformly with the nonwoven fabric web by causing the water flow to swing at the same interval as the spray hole interval.
- the porous support member on which the nonwoven fabric web is placed is not particularly limited as long as the water flow can penetrate the nonwoven fabric web, such as a mesh screen such as a wire mesh or a perforated plate.
- the distance between the spray hole and the nonwoven web can be selected according to the water pressure, and is, for example, about 1 to 10 cm. If it is outside this range, the texture of the nonwoven fabric tends to be disturbed or the three-dimensional entanglement is insufficient.
- a drying process may be performed.
- the drying treatment it is preferable to remove excess moisture from the nonwoven web after treatment, and a known method can be used to remove excess moisture.
- excessive moisture may be removed to some extent using a squeezing device such as a mangle roll, and then the remaining moisture may be removed using a drying device such as a suction band type hot air circulation dryer.
- fibers may be entangled by spraying high-temperature steam (high-pressure steam) onto the obtained nonwoven web to form an adhesion layer.
- high-pressure steam high-temperature steam
- fibers are bonded by using a web containing hydrophilic fibers (wet heat adhesive fibers) having at least a wet heat adhesive resin such as an ethylene-vinyl alcohol copolymer on the surface. Wet heat adhesion may be used. That is, in the steam jet method, when passing the fiber web transported by the belt conveyor through the high-speed high-temperature steam flow ejected from the nozzle of the steam spraying device, the fibers can be entangled with the sprayed high-temperature steam.
- wet heat adhesive fibers When the wet heat adhesive fibers are included, the wet heat adhesive fibers are fused, and the fibers (wet heat adhesive fibers, or the wet heat adhesive fibers and the hydrophobic fibers) are uniformly three-dimensionally bonded in the thickness direction.
- the water vapor injection device may be a combination of two belt conveyors so as to sandwich the fiber web, and each of the belt conveyors may be equipped with a water vapor injection device.
- the endless belt used for the conveyor a net roughly coarser than 90 mesh (for example, a net of about 10 to 60 mesh) is usually used.
- a nozzle for injecting high-temperature steam uses a plate or a die in which predetermined orifices are continuously arranged in one or more rows in the width direction, and the orifices are arranged in the width direction of the fiber web to be supplied. What is necessary is just to arrange.
- the diameter of the orifice is, for example, about 0.05 to 2 mm (particularly 0.1 to 1 mm), and the pitch of the orifice is, for example, about 0.5 to 3 mm (particularly about 1 to 2 mm).
- the pressure of the high temperature steam is, for example, about 0.1 to 2 MPa, preferably about 0.2 to 1.5 MPa, and more preferably about 0.3 to 1 MPa.
- the temperature of the high-temperature steam is, for example, about 70 to 150 ° C., preferably about 80 to 120 ° C., and more preferably about 90 to 110 ° C.
- the processing speed of the high-temperature steam is, for example, 200 m / min or less, preferably 0.1 to 100 m / min, and more preferably about 1 to 50 m / min.
- the adhesion layer Since the adhesion layer that directly contacts the skin with respect to the liquid retention layer for retaining the liquid component described above is a contact surface that supplies the cosmetic from the liquid retention layer to the skin, the cosmetic It is necessary to have a structure that can smoothly supply liquid components such as. Therefore, the adhesion layer is a continuous porous structure capable of supplying a liquid component from the liquid retention layer to the skin.
- the adhesion layer (or dense layer) is a layer located on the surface that directly touches the skin, and feels soft when touched to the skin, and adheres firmly to the skin when applied or left standing. While holding the liquid component supplied from the liquid layer in the pores and fibers between the fibers constituting the adhesion layer, the liquid component is supplied to the skin through the fine holes.
- the adhesion layer is composed of a nonwoven fabric (or non-woven fiber aggregate) having a uniform and extremely fine fiber diameter obtained by a melt blown method or the like, and such an adhesion layer is composed of ultrafine fibers.
- the surface is flat and smooth, so that there is very little irritation even when the fiber touches the skin. Furthermore, it has an excellent role of forming a dense layer of ultrafine fibers or forming a liquid film that spreads uniformly at the contact interface with the skin and adheres to the skin for a long time with this uniform liquid film.
- the non-woven fabric or non-woven fiber aggregate constituting the adhesion layer is not particularly limited as long as it can permeate while appropriately holding a liquid component (liquid effect component), and includes a fiber composed of a thermoplastic resin.
- a thermoplastic resin include polystyrene resin, polyolefin resin, acrylic resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyurethane resin, polyester resin, polyether resin, Examples thereof include polyamide-based resins and thermoplastic elastomers. These thermoplastic resins can be used alone or in combination of two or more. Of these, polyolefin resins, polyvinyl alcohol resins, polyester resins, polyurethane resins, thermoplastic elastomers and the like are preferable.
- polystyrene-based resin examples include polyethylene and polypropylene, but polypropylene-based resins such as polypropylene are particularly preferable because they are inexpensive, easy to form a nonwoven fabric with a low basis weight, and can be stably produced industrially.
- Polypropylene resin is a thin melt-blown non-woven fabric that will be used as an adhesive layer and wound into a roll. After that, it is combined with a liquid-retaining layer with spunlace, etc., so that it has good release properties and high strength even if it has a low weight. This is industrially preferable. Furthermore, the polypropylene resin has little variation in fiber diameter.
- polyvinyl alcohol-based resin examples include polyvinyl alcohol and ethylene-vinyl alcohol copolymer, and ethylene-vinyl alcohol copolymer is preferable from the viewpoint of fiber formation.
- ethylene-vinyl alcohol copolymer the ethylene-vinyl alcohol copolymer exemplified in the liquid retaining layer can be used.
- An ethylene-vinyl alcohol copolymer is excellent in terms of being friendly to the human body because it has little skin irritation and can suppress the occurrence of allergic symptoms. Furthermore, it has high affinity for both aqueous and oily liquid components and can be used for a wide variety of liquid components (aqueous cosmetics, oily emulsions, and the like).
- polyester resin examples include polyalkylene arylates such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
- polyalkylene arylates such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
- poly C 2-4 alkylene arylates such as polyethylene terephthalate and polybutylene terephthalate are preferred for the same industrial reasons as the polypropylene resin.
- a polybutylene terephthalate resin such as polybutylene terephthalate is particularly preferable because it has a soft texture and excellent touch.
- the fiber strength is high and the heat resistance is also high, the structural change hardly occurs due to heating during processing.
- polyurethane-based resin examples include polyester-type urethane-based resins and polyether-type urethane-based resins.
- the polyurethane-based resin can be effectively used, for example, when the adhesion layer is not taken up as a melt-blown nonwoven fabric, and a process that is combined with a liquid retaining layer is adopted at the time of manufacture. Furthermore, since the obtained nonwoven fabric (especially melt blown nonwoven fabric) has stretchability, the polyurethane-based resin can impart stretchability to the composite-integrated laminated sheet.
- the laminated sheet When the laminated sheet is used for a face mask, for example, if it is applied to the skin with tension in an arbitrary direction, the shrinkage of the sheet occurs at the contact portion together with the provision of the active ingredient to the skin, and the force pulling the skin works. This force can also be expected to improve skin wrinkles and looseness.
- the shrinkage of the sheet occurs at the contact portion together with the provision of the active ingredient to the skin, and the force pulling the skin works.
- This force can also be expected to improve skin wrinkles and looseness.
- when used by wrapping around a part where the thickness changes, such as an arm or calf since it has elasticity, it is difficult to shift.
- a feel high adhesion
- polyester-type urethane-based resins are widely used from the viewpoint of stretchability.
- thermoplastic elastomer examples include olefin elastomers, styrene elastomers, polyester elastomers, polyamide elastomers, and the like. These thermoplastic elastomers also have the same advantages as polyurethane resins because they are excellent in shrinkage for the same reason as the urethane resins.
- the fibers constituting the adhesion layer may also contain the same conventional additives as the liquid retaining layer.
- the additives for example, by adding a colorant (colorant) to the resin constituting the melt-blown nonwoven fabric that becomes the adhesion layer, the adhesion layer that is the surface to be attached to the skin can be easily visually identified. It can be colored as you can. It is also possible to manipulate the impression of the product by selecting a color according to the usage scene and the preference of the person.
- the cross-sectional shape of the fibers constituting the adhesion layer may be the same shape as the cross-sectional shape of the fibers constituting the liquid retaining layer, and is usually a round cross section, an elliptic cross section, or the like.
- the fiber diameter of the fibers constituting the adhesion layer is a very fine diameter smaller than the fibers constituting the liquid retention layer from the viewpoint of adhesion to the skin, and the specific fiber diameter (number average fiber diameter) is about 10 ⁇ m or less.
- the specific fiber diameter number average fiber diameter
- 0.1 to 9 ⁇ m preferably 0.5 to 8 ⁇ m (for example, 1 to 8 ⁇ m), more preferably about 1 to 7 ⁇ m (particularly 1.5 to 6 ⁇ m), and particularly preferably 2 It may be about 6 ⁇ m (for example, 2 to 5 ⁇ m).
- the average fiber diameter is too small, the function of transferring a liquid component (liquid effect component) such as cosmetics supplied from the liquid retaining layer to the skin side is deteriorated.
- the average fiber diameter is too large, the liquid film formed at the interface with the skin does not spread uniformly and gives a poor impression when touching the skin.
- the fibers constituting the adhesion layer are ultrafine fibers and have a uniform fiber diameter. That is, the standard deviation of the fiber diameter may be 5 or less, for example, 0 to 5, preferably 0 to 4 (eg 0 to 3), more preferably 0 to 2.5 (especially 0 to 2). For example, it may be about 0.1 to 5, preferably about 0.5 to 3, and more preferably about 1 to 2. Further, the variation rate of the fiber diameter is about 80% or less, for example, 0 to 80%, preferably 0 to 70%, more preferably 0 to 65% (particularly 0 to 60%). It may be about 80%, preferably 10-70%, more preferably about 20-60%. In the present invention, since the fibers constituting the adhesion layer are extremely fine and have a uniform diameter as described above, there is little irritation to the skin and a dense porous structure can be formed.
- the standard deviation of the fiber diameter may be 5 or less, for example, 0 to 5, preferably 0 to 4 (eg 0 to 3), more preferably
- the basis weight of the nonwoven fabric (or non-woven fiber aggregate) constituting the adhesion layer is, for example, 3 to 50 g / m 2 , preferably 4 to 30 g / m 2 , more preferably 4 to 20 g / m 2 (particularly 5 to 10 g). / M 2 ). If the basis weight of the nonwoven fabric (especially meltblown nonwoven fabric) is too small, the fibers on the liquid-retaining layer side will be easily exposed on the surface of the adhesion layer, giving a rough feel when touching the skin, and forming at the interface with the skin The liquid film that spreads out does not spread uniformly, and the adhesion performance deteriorates. When the fabric weight of a nonwoven fabric is too large, the function to transfer liquid effect ingredients, such as cosmetics supplied from a liquid retention layer, to the skin side will fall.
- the density of the adhesion layer (density in the laminated sheet) is, for example, 0.05 to 0.35 g / cm 3 , preferably 0.08 to 0.25 g / cm 3 , more preferably 0.1 to 0.2 g / cm 3 . It is about cm 3 . If the density is too small, the amount of surface fiber on the skin side for forming the adhesion layer is insufficient, and it becomes difficult to form a uniform ultrafine fiber layer on the skin surface. On the other hand, if the density is too high, the function of transferring liquid components such as cosmetics supplied from the liquid retaining layer to the skin side is deteriorated.
- the porosity of the adhesion layer (the porosity in the laminated sheet) is, for example, 70% or more (for example, from the point that liquid effect ingredients such as cosmetics supplied from the liquid retaining layer are uniformly transferred to the skin side in a short time) 70 to 99%), preferably 75% or more (for example, 75 to 95%), more preferably about 80% or more (for example, 80 to 90%).
- the thickness of the melt blown nonwoven fabric used as the adhesion layer can be selected from the range of about 10 to 500 ⁇ m, and is, for example, 30 to 500 ⁇ m, preferably 30 to 200 ⁇ m, more preferably 35 to 150 ⁇ m (particularly 40 to 100 ⁇ m). If the thickness is too small, the amount of fibers for forming the adhesion layer is insufficient, and it becomes difficult to form a uniform ultrafine fiber layer with respect to the skin surface. Conversely, when the thickness is too large, the liquid mobility from the liquid retaining layer to the skin is reduced.
- the nonwoven fabric or non-woven fiber aggregate constituting the adhesion layer is not particularly limited as long as it can form an ultrafine and uniform fiber diameter, and a conventional method can be used, but an ultrafine and uniform fiber diameter can be formed. From the viewpoint, the melt blown method is preferable.
- the melt blown method there can be used a conventional method, a method in which a thermoplastic resin is melt-spun and the obtained fiber is blown off with a high-temperature gas and collected.
- the melt-blown nonwoven fabric used as the adhesive layer is made by extruding (spinning) resin melted and heated from a nozzle having orifices (spinning holes) arranged in a row from a slit provided in the vicinity of the spinning port. High-temperature air heated to a temperature similar to that of the nozzle, finely contacted with the molten resin spun from the orifice, and thinned fiber into a sheet on the collection surface located below the nozzle Is obtained.
- Conventional conditions can be used as manufacturing conditions in the melt blown method.
- the interval between the spinning holes is, for example, about 100 to 4000 holes / m, preferably about 500 to 3000 holes / m, and more preferably about 1000 to 2500 holes / m.
- the single-hole discharge rate is, for example, about 0.01 to 1 g / hole / minute, preferably about 0.05 to 0.5 g / hole / minute, and more preferably about 0.1 to 0.3 g / hole / minute.
- the spinning temperature can be selected according to the type of thermoplastic resin, and is, for example, about 150 to 300 ° C, preferably about 200 to 280 ° C, and more preferably about 220 to 270 ° C.
- the air pressure of the high-temperature air can be selected from the range of about 0.01 to 1 MPa, for example, 0.05 to 0.8 MPa, preferably 0.1 to 0.6 MPa, more preferably about 0.2 to 0.5 MPa. is there.
- the air temperature is, for example, a temperature close to the spinning temperature, for example, a temperature 0 to 50 ° C. higher than the spinning temperature, preferably 3 to 30 ° C. higher than the spinning temperature, more preferably 5 to 20 ° C. higher than the spinning temperature. Is preferred.
- the conveyor speed is, for example, about 1 to 200 m / min, preferably about 5 to 100 m / min, and more preferably about 10 to 80 m / min.
- the basis weight, density, flexibility, and the like of the adhesion layer obtained may be adjusted by appropriately adjusting the air pressure, the conveyor speed, the distance (collecting distance) between the nozzle opening and the conveyor (such as a net conveyor), and the like.
- an adhesion layer is formed on at least one surface of the liquid retaining layer.
- the thickness ratio between the adhesion layer and the liquid retention layer is preferably a thin film with respect to the liquid retention layer.
- the adhesion layer is a continuous porous structure capable of supplying a liquid component from the liquid retaining layer to the skin, but has a structure capable of smoothly supplying a liquid component such as cosmetics.
- a liquid component such as cosmetics
- the thickness ratio of the adhesive layer to the liquid retaining layer is reduced by using a melt-blown nonwoven fabric, which is a thin porous structure, for the adhesive layer that is a layer located on the surface that directly contacts the skin. The distance between the liquid retaining layer and the skin is extremely small.
- the liquid retentive layer can be brought close to the skin, and as a sheet impregnated with a liquid component such as cosmetics, a larger part of the sheet has voids suitable for liquid retention It becomes.
- the basis weight of the laminated sheet of the present invention is, for example, about 23 to 250 g / m 2 , preferably 35 to 150 g / m 2 , more preferably about 40 to 120 g / m 2 .
- the laminated sheet of the present invention is excellent in adhesion to the skin, for example, impregnated with 500% by mass of cosmetic (skin lotion) (“Freshell Essence Lotion AL” manufactured by Kanebo Cosmetics Co., Ltd.) with respect to the sheet mass.
- cosmetic skin lotion
- Freshell Essence Lotion AL manufactured by Kanebo Cosmetics Co., Ltd.
- the frictional force (adhesion) measured in accordance with ASTM-D1984 is 0.6 N or more, for example, 0.6 to 10 N, preferably 0.7 to 5 N, more preferably 0.8 to 5 N. (Especially 1 to 5 N).
- the frictional force impregnated with 900% by mass of cosmetic is 0.3 N or more, for example, 0.3 to 2 N, preferably 0.4 to 1 N, more preferably 0.45 to 0.8 N (particularly 0 .5 to 0.6 N).
- the frictional force impregnated with 500% by mass of cosmetics is larger than the frictional force impregnated with 900% by mass of cosmetics, and the ratio of both is, for example, 500% by mass of frictional force / 900% by mass.
- % Friction force 1.1 / 1 to 10/1, preferably 1.2 / 1 to 9/1, more preferably 1.3 / 1 to 8/1 (especially 1.5 / 1 to 7/1).
- the laminated sheet of the present invention is also excellent in releasing the liquid component that has been retained, and a load of 30 g is applied to a 7.5 cm ⁇ 7.5 cm sized laminated sheet that retains 4.5 g of cosmetics.
- the amount of the cosmetic released is 10% or more (for example, about 10 to 50%, preferably about 20 to 40%).
- the detail of the measuring method of releasability can be measured by the method as described in the below-mentioned Example.
- the laminated sheet of the present invention is excellent in flexibility when wet and is appropriately intertwined so that it can follow the skin such as the face, and has a 50% elongation stress when wet according to JIS L1913. In one direction, for example, it is about 0.5 to 15 N / 5 cm, preferably about 1 to 10 N / 5 cm, and more preferably about 1 to 5 N / 5 cm. If the stress at the time of elongation is too small, it will be too difficult to handle when it is attached to the skin such as the face, and if it is too large, the adhesion to the skin will be reduced. In addition, the measuring method of the stress at the time of 50% expansion
- another layer may be further laminated on the liquid retaining layer (the other surface on which the adhesion layer of the liquid retaining layer is not formed).
- the other layer can be selected according to the application. For example, by forming the adhesion layer on both sides, it is possible to improve the operability of consumers in a face mask or the like.
- the thickness of the adhesion layer as the other layer may be the same thickness as the adhesion layer.
- a non-porous film or sheet may be laminated on the liquid retaining layer.
- a non-porous film When a non-porous film is laminated, when the adhesion layer is brought into contact with the skin, the liquid component of the liquid retention layer is sealed, so that the temperature rises and the pores expand, so that the absorption of the active ingredient is easily promoted.
- a film made of a thermoplastic resin for example, a polyolefin sheet, a polyester sheet, a polyamide sheet, a polyurethane sheet, or the like can be used.
- the thickness of the non-porous film or sheet is, for example, about 3 to 300 ⁇ m, preferably about 5 to 100 ⁇ m, and more preferably about 5 to 50 ⁇ m.
- the laminated sheet of the present invention is also used in applications for absorbing liquid components, for example, surface materials such as napkins and diapers, diaper liners, sheets for absorbing body fluids such as wet tissues (or skin cleaning sheets), etc.
- liquid components for example, surface materials such as napkins and diapers, diaper liners, sheets for absorbing body fluids such as wet tissues (or skin cleaning sheets), etc.
- it can be used, in addition to the adhesion and fit to the skin, it has an excellent balance between liquid retention and release properties, so that a sheet impregnated with a liquid component such as a cosmetic component or a medicinal component is adhered to the skin.
- various skin care sheets such as face masks, makeup removing sheets or cleansing sheets, body washing sheets (sweat wiping sheets, oil removing sheets, etc.), cooling sheets, medicinal or therapeutic sheets (itch prevention sheets, compresses, etc.) It is preferable to use it.
- the sheet for skin care of the present invention may be a sheet used by impregnating these liquid components at the time of use, or a sheet (so-called wet sheet) used by impregnating liquid components in advance.
- liquid components include liquid substances such as solvents and liquid oils, and solutions or dispersions in which the liquid substances contain active ingredients such as cosmetic ingredients or medicinal (efficacy) ingredients (such as cosmetics and emulsions). )
- the solvent may be a lipophilic solvent, but is preferably a hydrophilic solvent from the viewpoint of safety to the human body.
- the hydrophilic solvent include water, lower aliphatic alcohols (eg, C 1-6 alkyl alcohols such as ethanol and isopropanol), alkylene glycols (eg, ethylene glycol, diethylene glycol, propylene glycol, etc.) and the like. .
- These hydrophilic solvents can be used alone or in combination of two or more.
- liquid oil examples include unsaturated higher fatty acids (for example, oleic acid, oleyl alcohol, etc.), animal and vegetable oils (for example, jojoba oil, olive oil, palm oil, camellia oil, macadamian nut oil, avocado oil, corn Oil, sesame oil, wheat germ oil, linseed oil, castor oil, squalane, etc.), mineral oil (eg, liquid paraffin, polybutene, silicone oil, etc.), synthetic oil (eg, synthetic ester oil, synthetic polyether oil, etc.), etc. Is mentioned. These liquid oils can be used alone or in combination of two or more.
- unsaturated higher fatty acids for example, oleic acid, oleyl alcohol, etc.
- animal and vegetable oils for example, jojoba oil, olive oil, palm oil, camellia oil, macadamian nut oil, avocado oil, corn Oil, sesame oil, wheat germ oil, linseed oil, castor oil, squalane, etc.
- liquid oil may be used in combination as an additive (oil) for a hydrophilic solvent such as water or ethanol.
- a hydrophilic solvent such as water or ethanol.
- water, lower alcohols or mixtures thereof are usually used, preferably water and / or ethanol (especially water).
- water / lower alcohol 100/0 to 30/70, preferably 100/0 to 50/50, more preferably 100 / 0 to about 70/30, for example, about 99/1 to about 80/20.
- additives such as moisturizers, emollients, cleansing agents, UV protection agents, surfactants, astringents, enzymes, cooling agents, bactericides or antibacterial agents, emollients, antiseptics, etc.
- examples include oxidants, whitening agents, antiperspirants, rough skin inhibitors, anti-inflammatory agents, skin itching inhibitors, blood circulation promoters, amino acids, cell activators, cooling agents, fragrances, and coloring agents.
- These additives can be used alone or in combination of two or more.
- moisturizers, ultraviolet inhibitors, surfactants, astringents, refreshing agents, enzymes, bactericides or antibacterial agents are commonly used for skin care sheets.
- a moisturizing agent or emollient may be blended in a hydrophilic solvent.
- the humectant or emollient include dipropylene glycol, 1,3-butylene glycol, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sucrose fatty acid ester Glycerin, sodium hyaluronate, polyoxymethylglycoside, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble cellulose ether (methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, etc.).
- the total ratio of the humectant and the emollient is, for example, about 0.1 to 50% by mass, preferably 1 to 30% by mass, and more preferably about 5 to 20% by mass in the solution.
- the ratio of these additives can be appropriately selected depending on the application.
- the ratio of liquid substances such as water and ethanol is usually 30 to 99% by mass, preferably 40 to 95% in the total liquid components including the additives. It is about mass%, more preferably about 50 to 90 mass%.
- the laminated sheet of the present invention is particularly suitable as a sheet to be fixed to the skin such as a face mask or a poultice because it has excellent adhesion to the skin.
- the sheet due to the strong adhesion, the sheet can adhere to minute gaps, such as the base of the nose, even when used for a long time, and the active ingredient of the face mask is effective on the skin. Can penetrate.
- the laminated sheet of the present invention is also suitable for cleansing sheets and skin cleaning sheets. That is, since the laminated sheet of the present invention has a large contact area and can be strongly adhered to the skin, the sheet can be adhered to a minute gap on the face, and makeup (foundation, white powder, lipstick, eye makeup, etc.) Up cosmetics etc. can be removed effectively. Furthermore, since the adhesion layer is formed of uniform ultrafine fibers, the skin irritation is extremely low, and dust in fine pores can be effectively removed.
- the laminated sheet of the present invention when used as a liquid-impregnated biological coating sheet (face mask, cleansing sheet, etc.), the laminated sheet is usually impregnated into the laminated sheet and adhered or contacted to living skin or the like. Used.
- the production method of the laminated sheet of the present invention is not particularly limited as long as the liquid retention layer and the adhesion layer can be integrated (composited).
- the liquid retention layer and the adhesion layer obtained separately by the production method are combined. They may be integrated by bonding or entanglement.
- the entanglement method the spunlace method, needle punch method, steam jet method and the like exemplified in the section of the liquid retaining layer can be used.
- a method for adhering the liquid retaining layer and the adhesive layer a method of directly spraying the adhesive layer onto the obtained liquid retaining layer (direct blown method) or the like can be used.
- the span lace method is widely used from the viewpoint of simplicity.
- the method for producing the laminated sheet of the present invention may be a method for continuously producing the liquid retaining layer and the adhesion layer, and is a method for integrating and integrating the respective nonwoven fabric production lines.
- a method may be employed in which it is later introduced into the other manufacturing process and integrated.
- a meltblown nonwoven fabric used as an adhesion layer is introduced into a spunlace nonwoven fabric production line, and both fibers are entangled and integrated by a water flow such as a spunlace method.
- a method (direct blown method) in which a nonwoven fabric serving as a liquid retaining layer is introduced into a production line and the nonwoven fabric serving as a liquid retaining layer is used as a melt-blown fiber collecting surface may be used.
- the weight was calculated from the weight of the nonwoven fabric (g), the specific gravity of the fiber (g / cm 3 ), and the apparent volume of the nonwoven fabric (cm 3 ) by the following formula.
- the apparent volume of the nonwoven fabric was calculated by multiplying the area obtained by the thickness measurement method as the height of the area of the portion that becomes the surface when the nonwoven fabric is viewed as a sheet.
- Porosity (%) 100 ⁇ [(weight ⁇ 100) / (fiber specific gravity ⁇ apparent volume of nonwoven fabric)] [Average fiber diameter ( ⁇ m)]
- the nonwoven fiber structure of the adhesion layer was observed using a scanning electron microscope.
- the fiber diameters of 100 fibers (50 for Examples 3, 4 and Comparative Example 5) randomly selected from the electron micrographs were measured, and the number average particle diameter and standard deviation were determined. Further, the variation rate was calculated according to the following formula.
- Fluctuation rate (%) standard deviation / number average fiber diameter ⁇ 100] [Adhesion]
- the friction force was measured according to ASTM-D1894 using a precision universal testing machine (“Autograph AGS-D type” manufactured by Shimadzu Corporation). As shown in FIG. 1, the sample 10 was cut into an MD direction of 4.0 cm ⁇ CD direction of 11.0 cm, and in the CD direction, the grip portion 10 a was 1 cm and the grounding portion 10 b was 10 cm. Further, assuming a face mask, this sample was impregnated with cosmetics (“Freschel Essence Lotion AL” manufactured by Kanebo Cosmetics Co., Ltd.) in the following two mass%. As shown in FIG.
- a test was performed in which the grip portion 10 a of the sample 10 was pulled in the direction of the arrow gripped by the clip 12.
- an acrylic plate was fixed on the table 11 for measuring the frictional force, and the sample was placed in the center with the skin side use surface facing down.
- a testing machine equipped with the load cell 15 a load of 10 g / cm 2 was applied to a range of MD 4.0 cm ⁇ CD 10.0 cm (grounding portion 3) for 10 seconds, and then the polyamide yarn 14 via the pulley 13 was applied.
- the peak value of the test force peak value shown in FIG.
- adhesion obtained by horizontally pulling the sample in the CD direction at a speed of 20 mm / min by pulling horizontally was defined as adhesion and measured.
- the adhesion was measured under the following two conditions. (1) 900% by mass was impregnated with respect to the sample mass, and an adhesion value was obtained under conditions simulating the environment immediately after the start of use of the face mask. (2) Impregnation value of 500% by mass with respect to the sample mass was obtained under conditions simulating the environment in the latter half of the use of the face mask.
- the cosmetic is an aqueous cosmetic mainly composed of water and a hydrophilic material.
- ⁇ Evaluation criteria> ⁇ : Good along the skin and feels the same or better than immediately after the start of use. ⁇ : Good along the skin, but the close feeling decreased immediately after the start of use. Along the way, slippage and peeling occurred. In addition, the feeling of adhesion was remarkably reduced compared to immediately after the start of use.
- a filter paper (ADVANTEC FILTER PAPER GLADE2) was cut into 10.0 cm ⁇ 10.0 cm, and five sheets were stacked to measure the weight (filter paper weight A).
- the sample impregnated with the cosmetic was placed on the filter paper, and a 30 g acrylic plate was placed as a load so as to cover the entire surface of the sample. After being left for 1 minute, the sample and the load were removed, and the weight of the filter paper was obtained (filter paper weight B).
- the cosmetic release rate was determined from the weight of the cosmetic transferred from the sample to the filter paper using the following formula.
- Cosmetic release rate (%) (filter paper weight B ⁇ filter paper weight A) ⁇ cosmetic weight C ⁇ 100 [50% elongation stress when wet] It measured based on the method as described in JIS L1913 (general short fiber nonwoven fabric) 6.3.2 (tensile strength and elongation rate test at the time of wetness). Specifically, the sample was placed in water at 20 ° C. ⁇ 2 ° C. until it settled under its own weight, or after being submerged in water for 1 hour or longer, the sample was taken out from the immersion liquid and the stress at 50% elongation was measured immediately. .
- the following raw materials were prepared as raw materials for the laminated sheet.
- a semi-random card web having a basis weight of 60 g / m 2 was prepared by a conventional method. It is placed on a punching drum support having a hole diameter of 0.3 mm and continuously transferred in the longitudinal direction at a speed of 50 m / min. Nonwoven fabric) was produced. In this entanglement process, two nozzles in which orifices having a hole diameter of 0.10 mm are provided at intervals of 0.6 mm along the width direction of the web are used (distance 20 cm between adjacent nozzles).
- the water pressure of the high-pressure water stream injected from the nozzle was set to 3.0 MPa, and the water pressure of the high-pressure water stream injected from the nozzles in the second row was set to 4.0 MPa.
- the previously produced melt blown nonwoven fabric sheet having a basis weight of 5 g / m 2 is unwound from an unwinding device, overlapped with a web, placed on a flat support on a whole having a finer mesh, and continuously transferred and high-pressure water flow Were entangled and subjected to an entanglement treatment to entangle the fibers constituting the two nonwoven fabrics.
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 120 degreeC and obtained the composite nonwoven fabric of 65 g / m ⁇ 2 > of fabric weights.
- the thickness ratio of the obtained nonwoven fabric sheet was 10.6 with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 2.57 ⁇ m, the standard deviation of the fiber diameter distribution is 1.318, and the variation rate is 51.26%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 90.4% for the liquid retaining layer and 86.6% for the adhesion layer.
- Example 2 A composite nonwoven fabric having a basis weight of 45 g / m 2 was obtained in the same manner as in Example 1 except that the basis weight of the semi-random card web was 40 g / m 2 .
- the ratio of the thickness of the obtained nonwoven fabric sheet was 8.7 with respect to the adhesion layer 1.
- the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 2.57 ⁇ m
- the standard deviation of the fiber diameter distribution is 1.318
- the variation rate is 51.26%. there were.
- the porosity of the obtained nonwoven fabric sheet was 93.3% for the liquid retaining layer and 88.6% for the adhesion layer.
- the sheet was impregnated with a cosmetic and the adhesion was measured.
- the adhesion with an impregnation rate of 500% by mass was higher than the adhesion with an impregnation rate of 900% by mass. From this result, it was determined that the adhesion after the start of use was improved.
- MFR polybutylene terephthalate resin
- an entangled fiber web (nonwoven fabric) was produced using 40 parts by mass of rayon fibers and 60 parts by mass of polyester fibers.
- the previously produced melt blown nonwoven fabric sheet having a basis weight of 20 g / m 2 is unwound from an unwinding device, overlapped with a web, placed on a flat support on a whole having a finer mesh, and continuously transferred and high-pressure water flow Were entangled and subjected to an entanglement treatment to entangle the fibers constituting the two nonwoven fabrics.
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 130 degreeC and obtained the composite nonwoven fabric of 80 g / m ⁇ 2 > of fabric weights.
- the ratio of the thickness of the obtained nonwoven fabric sheet was 5.7 with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 5.26 micrometers, the standard deviation of fiber diameter distribution is 1.504, and the variation rate is 28.59%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 90.9% for the liquid retaining layer and 81.2% for the adhesion layer.
- MFR 190 ° C, 2.16 kg
- a semi-random card web having a basis weight of 80 g / m 2 was prepared by a conventional method.
- a fiber web (nonwoven fabric) was produced.
- the previously produced melt blown nonwoven fabric sheet having a basis weight of 20 g / m 2 is unwound from an unwinding device, overlapped with a web, placed on a flat support on a whole having a finer mesh, and continuously transferred and high-pressure water flow Were entangled and subjected to an entanglement treatment to entangle the fibers constituting the two nonwoven fabrics.
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 110 degreeC and obtained the composite nonwoven fabric of 100 g / m ⁇ 2 > of fabric weights.
- the thickness ratio of the obtained nonwoven fabric sheet was the liquid retaining layer 5.2 with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 6.73 micrometers, the standard deviation of fiber diameter distribution is 2.813, and the variation rate is 41.81%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 90.0% for the liquid retaining layer and 85.1% for the adhesion layer.
- Example 5 After uniformly blending using 40 parts by weight of rayon fiber and 60 parts by weight of polyester fiber, a semi-random card web having a basis weight of 60 g / m 2 was prepared by a conventional method. It is placed on a punching drum support having a hole diameter of 0.3 mm and continuously transferred in the longitudinal direction at a speed of 50 m / min. Nonwoven fabric) was produced. In this entanglement process, two nozzles in which orifices having a hole diameter of 0.10 mm are provided at intervals of 0.6 mm along the width direction of the web are used (distance 20 cm between adjacent nozzles).
- the water pressure of the high-pressure water stream injected from the nozzle was set to 3.0 MPa, and the water pressure of the high-pressure water stream injected from the nozzles in the second row was set to 4.0 MPa. Furthermore, it was placed on a flat support on the whole having a fine mesh and continuously transferred, and a high-pressure water stream was jetted to carry out the entanglement treatment, thereby entangling the constituent fibers.
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 110 degreeC and obtained the spunlace nonwoven fabric with a fabric weight of 60 g / m ⁇ 2 >.
- urethane resin Melt viscosity: D ⁇ 65935 constant temperature method: 1.0 ⁇ 10 3 to 5.0 ⁇ 10 3 Pa ⁇ s / 200 ° C.
- spinning temperature is 250 °C
- air temperature 260 °C air pressure 0.4MPa
- single hole discharge amount 0.2g / hole / minute
- 400 spinning holes single line arrangement
- the ratio of the thickness of the obtained nonwoven fabric sheet was 14.2 with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 3.75 micrometers, the standard deviation of fiber diameter distribution is 2.253, and the variation rate is 60.08%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 90.5% for the liquid retaining layer and 86.0% for the adhesion layer.
- Example 6 After uniformly blending using 30 parts by mass of the core-sheath composite fiber and 70 parts by mass of the polyester fiber, a semi-random card web having a basis weight of 100 g / m 2 is prepared by a conventional method, and this card web is 50 mesh, It was transferred to a belt conveyor equipped with a stainless steel endless net having a width of 500 mm.
- the belt conveyor which has the same metal mesh is equipped in the upper part of the metal mesh of this belt conveyor, and it rotated in the same direction at the same speed, and used the belt conveyor which can adjust the space
- the steam web is introduced into the steam jetting device provided in the lower conveyor, and steam treatment is performed by ejecting 0.4 MPa high-temperature steam from the device in the thickness direction of the card web (perpendicularly).
- a molded body steam jet nonwoven fabric having a non-woven fiber structure.
- a nozzle is installed in the lower conveyor so as to spray high-temperature steam toward the web via a conveyor net, and a suction device is installed in the upper conveyor.
- another jetting device which is a combination of the arrangement of the nozzle and the suction device reversed, is installed on the downstream side in the web traveling direction of the jetting device, and steam treatment is performed on both the front and back sides of the web. did.
- steam injection nozzle was 0.3 mm
- steam injection apparatus with which the nozzle was arranged in 1 row at 1 mm pitch along the width direction of the conveyor was used.
- the processing speed was 10 m / min, and the interval (distance) between the upper and lower conveyor belts on the nozzle side and the suction side was 5 mm.
- the nozzles were arranged on the back side of the conveyor belt so as to be almost in contact with the belt.
- melt blown spinning was performed using a urethane resin, and the previously produced steam jet nonwoven fabric was placed on a rotating net conveyor support and collected thereon. As a result, a composite nonwoven fabric having a basis weight of 110 g / m 2 was obtained.
- the thickness ratio of the obtained nonwoven fabric sheet was 26.9 with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 3.89 micrometers, the standard deviation of fiber diameter distribution is 2.482, and the variation rate is 63.79%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 93.5% for the liquid retaining layer and 79.3% for the adhesion layer.
- Example 7 In the same manner as in Example 1, a melt blown nonwoven fabric sheet having a basis weight of 5 g / m 2 was produced using polypropylene resin.
- a semi-random card web having a basis weight of 95 g / m 2 was prepared by a conventional method and entangled in the same manner as in Example 1.
- a fiber web (nonwoven fabric) was produced.
- two nozzles in which orifices having a hole diameter of 0.10 mm are provided at intervals of 0.6 mm along the width direction of the web are used (distance 20 cm between adjacent nozzles).
- the water pressure of the high-pressure water flow injected from the nozzle was 5.0 MPa, and the water pressure of the high-pressure water flow injected from the nozzles in the second row was 6.0 MPa.
- melt blown nonwoven fabric sheet having a basis weight of 5 g / m 2 is unwound from an unwinding device, overlapped with a web, placed on a flat support on a whole having a finer mesh, and continuously transferred and high-pressure water flow Were entangled and subjected to an entanglement treatment to entangle the fibers constituting the two nonwoven fabrics.
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Further dried at 120 ° C., mass per unit area to obtain a composite nonwoven fabric of 100 g / m 2.
- the ratio of the thickness of the obtained nonwoven fabric sheet was 20.3 with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 2.57 ⁇ m, the standard deviation of the fiber diameter distribution is 1.318, and the variation rate is 51.26%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 92.8% for the liquid retaining layer and 88.1% for the adhesion layer.
- Example 8 In the same manner as in Example 1, a melt blown nonwoven fabric sheet having a basis weight of 5 g / m 2 was produced using polypropylene resin.
- a semi-random card web having a basis weight of 40 g / m 2 was prepared by a conventional method. It is placed on a punching drum support having a hole diameter of 0.3 mm and continuously transferred in the longitudinal direction at a speed of 50 m / min. Nonwoven fabric) was produced. In this entanglement process, two nozzles in which orifices having a hole diameter of 0.10 mm are provided at intervals of 0.6 mm along the width direction of the web are used (distance 20 cm between adjacent nozzles).
- the water pressure of the high-pressure water stream injected from the nozzle was set to 3.0 MPa, and the water pressure of the high-pressure water stream injected from the nozzles in the second row was set to 4.0 MPa.
- the previously produced melt blown nonwoven fabric sheet having a basis weight of 5 g / m 2 is unwound from an unwinding device, overlapped with a web, placed on a flat support on a whole having a finer mesh, and continuously transferred and high-pressure water flow Were entangled and subjected to an entanglement treatment to entangle the fibers constituting the two nonwoven fabrics.
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 130 degreeC and obtained the composite nonwoven fabric of 45 g / m ⁇ 2 > of fabric weights.
- the ratio of the thickness of the obtained nonwoven fabric sheet was 1.0 for the liquid retaining layer with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 2.57 ⁇ m, the standard deviation of the fiber diameter distribution is 1.318, and the variation rate is 51.26%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 92.7% for the liquid retaining layer and 87.8% for the adhesion layer.
- a semi-random card web with a basis weight of 60 g / m 2 is prepared by a conventional method, and this card web is formed on a punching drum support having an aperture ratio of 25% and a hole diameter of 0.3 mm. At the same time, it was continuously transferred in the longitudinal direction at a speed of 50 m / min, and at the same time, a high-pressure water flow was jetted from above to carry out the entanglement treatment to produce an entangled fiber web (nonwoven fabric).
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 130 degreeC and obtained the spun lace nonwoven fabric with a fabric weight of 60 g / m ⁇ 2 >. The porosity of the obtained nonwoven fabric sheet was 88.2%.
- Comparative Example 2 After uniform blending using 40 parts by weight of rayon fiber and 60 parts by weight of polyester fiber, the mixture was entangled in the same manner as in Comparative Example 1 for a semi-random card web having a basis weight of 60 g / m 2 produced by a conventional method. And a drying process was performed to obtain a spunlace nonwoven fabric having a basis weight of 60 g / m 2 . The porosity of the obtained nonwoven fabric sheet was 90.4%.
- Comparative Example 3 After the cotton fiber was defibrated to 100 parts by mass, a tangled and dried treatment was performed on a semi-random card web having a basis weight of 60 g / m 2 in the same manner as in Comparative Example 1 to obtain a 60 g / m 2 basis weight. A spunlace nonwoven fabric was obtained. The porosity of the obtained nonwoven fabric sheet was 90.2%.
- a semi-random card web having a basis weight of 32 g / m 2 is prepared by a conventional method, and this card web is formed on a punching drum support having an aperture ratio of 25% and a hole diameter of 0.3 mm. At the same time, it was continuously transferred in the longitudinal direction at a speed of 50 m / min, and at the same time, a high-pressure water flow was jetted from above to carry out the entanglement treatment to produce an entangled fiber web (nonwoven fabric).
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 130 degreeC and obtained the spun lace nonwoven fabric with a fabric weight of 32 g / m ⁇ 2 >.
- semi-random card webs each having a basis weight of 24 g / m 2 were prepared from the two cards by a conventional method.
- the previously produced spunlace nonwoven fabric was laminated while being put, and placed on a punching drum support having an aperture ratio of 25% and a hole diameter of 0.3 mm and longitudinally at a speed of 50 m / min.
- a high-pressure water stream was jetted from above to perform entanglement treatment to produce an entangled laminated fiber web (laminated nonwoven fabric).
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Further, the laminate was dried at 130 ° C. to obtain a laminated spunlace nonwoven fabric having a basis weight of 80 g / m 2 . The porosity of the obtained nonwoven fabric sheet was 86.8%.
- An entangled fiber web (nonwoven fabric) was produced in the same manner as in Example 3 using 40 parts by weight of rayon fibers and 60 parts by weight of polyester fibers.
- the previously produced melt-blown nonwoven fabric sheet with a basis weight of 20 g / m 2 is unwound from an unwinding device, overlapped with a web, and entangled and dried in the same manner as in Example 3 to obtain a composite nonwoven fabric with a basis weight of 80 g / m 2. It was.
- the thickness ratio of the obtained nonwoven fabric sheet was the liquid retaining layer 2.2 with respect to the adhesion layer 1. Moreover, the number average fiber diameter of the adhesion layer comprised by the melt blown nonwoven fabric of the obtained nonwoven fabric sheet is 17.15 micrometers, the standard deviation of fiber diameter distribution is 6.127, and the variation rate is 35.72%. there were. Furthermore, the porosity of the obtained nonwoven fabric sheet was 90.8% for the liquid retaining layer and 92.7% for the adhesion layer.
- a semi-random card web having a basis weight of 60 g / m 2 was prepared by a conventional method. It is placed on a punching drum support having a hole diameter of 0.3 mm and continuously transferred in the longitudinal direction at a speed of 50 / min. Nonwoven fabric) was produced. In this entanglement process, two nozzles in which orifices having a hole diameter of 0.10 mm are provided at intervals of 0.6 mm along the width direction of the web are used (distance 20 cm between adjacent nozzles).
- the water pressure of the high-pressure water stream injected from the nozzle was set to 3.0 MPa, and the water pressure of the high-pressure water stream injected from the nozzles in the second row was set to 4.0 MPa. Furthermore, it was placed on a flat support on the whole having a fine mesh and continuously transferred, and a high-pressure water stream was jetted to carry out the entanglement treatment, thereby entangling the constituent fibers.
- This entanglement treatment was performed using two nozzles in which orifices having a hole diameter of 0.10 mm were provided at intervals of 0.6 mm along the width direction of the web, both under conditions of a water pressure of 5 MPa. . Furthermore, it dried at 130 degreeC and obtained the spun lace nonwoven fabric with a fabric weight of 60 g / m ⁇ 2 >.
- the obtained spunlace nonwoven fabric and a 12 ⁇ m thick polyester film were bonded using an adhesive resin formed by extrusion from a T-die to obtain a composite nonwoven fabric having a basis weight of 91 g / m 2 .
- the thickness ratio of the obtained nonwoven fabric sheet was 13.7 with respect to the film layer 1 as the liquid retaining layer. Moreover, the porosity of the obtained nonwoven fabric sheet was 88.7% in the liquid retaining layer, and 0% in the film layer.
- Comparative Example 7 From the film layer side of the composite nonwoven fabric having a basis weight of 91 g / m 2 obtained in Comparative Example 6, through holes having a diameter of about 900 ⁇ m were made on the entire surface at intervals of 2 cm using a metal needle. The thickness ratio of the obtained nonwoven fabric sheet was 14.2 with respect to the film layer 1. Moreover, the porosity of the obtained nonwoven fabric sheet was 89.0% in the liquid retention layer, and 0.2% in the film layer.
- Comparative Example 8 From the film layer side having a basis weight of 91 g / m 2 obtained in Comparative Example 6, through holes having a diameter of about 900 ⁇ m were made on the entire surface at intervals of 1 cm using a metal needle. The thickness ratio of the obtained nonwoven fabric sheet was 14.4 with respect to the film layer 1. The resulting nonwoven fabric sheet had a porosity of 89.2% for the liquid retaining layer and 0.6% for the film layer.
- the laminated sheet of the present invention absorbs a liquid component and makes contact with the skin, for example, a body fluid absorbing sheet (for example, a surface material such as a napkin or a diaper, a diaper liner, a wet tissue), a skin care sheet (for example, a face). It can be used for masks, makeup removing sheets, cleansing sheets or body washing sheets (sweat wiping sheets, oil removing sheets, cooling sheets, etc.), medicinal sheets (stagnation suppression sheets, poultices, etc.) etc.
- a body fluid absorbing sheet for example, a surface material such as a napkin or a diaper, a diaper liner, a wet tissue
- a skin care sheet for example, a face.
- masks makeup removing sheets, cleansing sheets or body washing sheets (sweat wiping sheets, oil removing sheets, cooling sheets, etc.), medicinal sheets (stagnation suppression sheets, poultices, etc.) etc.
- the laminated sheet of the present invention Because it can adhere to all parts of the human body, including parts that are sensitive to irritation and easily peel off due to gravity or movement even when applied, the entire face, nose, eyes, mouth, neck Masks impregnated with active ingredients such as moisturizing, whitening, etc., cleansing sheets that lift and wipe off makeup, blood circulation promoting ingredients and Skin itch medicated impregnated with suppressing ingredient or therapeutic sheet is particularly useful, such as a cooling sheet for cooling by heat of vaporization is impregnated with a volatile liquid.
- active ingredients such as moisturizing, whitening, etc., cleansing sheets that lift and wipe off makeup, blood circulation promoting ingredients and Skin itch medicated impregnated with suppressing ingredient or therapeutic sheet.
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Abstract
Description
本発明において、保液層とは、美容成分又は薬効(効能)成分(例えば、保湿成分、クレンジング成分、制汗成分、香り成分、美白成分、血行促進成分、冷却成分、紫外線防止成分、皮膚かゆみ抑制成分など)を含む液状成分(液状化合物)を含浸するのに必要な濡れ性と保液するための空隙を有し、使用時の取り扱いにおいても液だれすることなく、体の所定の部位(例えば顔)を覆うまで保持し、貼付あるいは静置すると共に液体化粧料を少しずつ肌側に位置する密着層の方向に移行させる役割を有している。
保液層を構成する不織布又は不織繊維集合体は、慣用の方法、例えば、スパンレース法、ニードルパンチ法、スチームジェット法などにより製造できる。これらの方法のうち、価格面を重視する場合であれば、工業的に高速で生産が可能なスパンレース法を用いてもよい。また、嵩高にすることにより保液性能を高める場合には、サーマルボンド法やスチームジェット法(特に、厚み方向で均一な接着を実現でき、形態保持性と嵩高性とを高度に両立できる点から、スチームジェット法)などを用いてもよい。
前述の液状成分を保液するための保液層に対して、直接肌に触れる面となる密着層は、前記保液層から肌へと化粧料を供給する接触面となることから、化粧料などの液状成分の供給を円滑に行える構造である必要がある。従って、密着層は、保液層から肌へと液状成分の供給が可能な連通した多孔質構造体である。
密着層を構成する不織布又は不織繊維集合体は、極細で均一な繊維径を形成できれば、特に限定されず、慣用の方法を利用できるが、極細でかつ均一な繊維径を有する不織布を形成できる点から、メルトブローン法が好ましい。
本発明の積層シートは、前記保液層の少なくとも一方の面に密着層が形成されている。密着層と保液層との厚み割合は、本発明では、密着層を保液層に対して薄膜とするのが好ましい。
本発明の積層シートの製造方法は、保液層と密着層とを一体化(複合化)できれば、特に限定されず、例えば、前記製造方法で別個に得られた保液層と密着層とを接着や交絡などにより一体化してもよい。交絡方法としては、前記保液層の項で例示されたスパンレース法、ニードルパンチ法、スチームジェット法などを利用できる。保液層と密着層とを接着させる方法としては、得られた保液層に密着層を直接吹き付ける方法(ダイレクトブローン法)などを利用できる。これらのうち、簡便性などの点から、スパンレース法が汎用される。
JISL1906に準じ、温度20℃、湿度65%の標準状態にサンプルを24時間放置後、幅方向1m×長さ方向1mの試料を採取し、天秤を用いて重量(g)を測定する。得られた重量(g)の小数点以下を四捨五入して目付とした。
剃刀(フェザー安全剃刀(株)製「フェザー剃刃S片刃」)を用いて、サンプルを面に垂直にMD方向に切断し、デジタル顕微鏡[(株)キーエンス(KEYENCE)製デジタルマイクロスコープ(DIGITAL MICROSCOPE) VHX-900]にて試料の断面を観察し厚さを計測した。
目付(g/m2)を厚みで除し密度を求めた。
不織布の重量(g)、繊維比重(g/cm3)、不織布の見かけ体積(cm3)から、下式で算出した。なお、不織布の見かけ体積とは、不織布をシートとして見たときの面となる部分の面積に前記厚みの測定法で得られる値を高さとして乗して算出した。
[平均繊維径(μm)]
繊維シートから試験片(縦×横=5cm×5cm)を採取し、試験片の表面における中央部(対角線の交点を中心とする部分)を、走査型電子顕微鏡(SEM)を使用して1000倍の倍率で写真撮影した。得られた写真の中央部(対角線の交点)を中心として写真上に半径30cmの円を描き、その円内から無作為に100本の繊維を選定し、長さ方向の中央部又はそれに近い箇所での繊維径をノギスにより測定し、その平均値を採って平均繊維径(数平均繊維径)とした。なお、測定に当たっては、写真に撮影されている繊維が繊維シートの最表面に位置する繊維であるか、又は内側に位置する繊維であるかを区別せずに、SEM写真に写っている繊維のすべてを対象として平均繊維径を求めた。
走査型電子顕微鏡を用いて密着層の不織繊維構造を観察した。電子顕微鏡写真より無作為に選択した100本(実施例3、4及び比較例5については50本)の繊維径を測定し、数平均粒子径及び標準偏差を求めた。さらに、変動率を下記式に従って算出した。
[密着性]
精密万能試験機((株)島津製作所製「オートグラフAGS-D型」)を用いて、ASTM-D1894に準じて摩擦力を測定した。図1に示すように、サンプル10をMD方向4.0cm×CD方向11.0cmに切り出し、CD方向において、つかみ部分10aを1cm、接地部分10bを10cmとした。さらに、フェイスマスクを想定して、このサンプルに化粧料(カネボウ化粧品(Kanebo)(株)製「フレッシェル エッセンスローションAL」)を下記に示す2種類の質量%で含浸した。図2に示すように、このサンプル10のつかみ部分10aをクリップ12で把持した矢印の方向に引っ張る試験を行った。詳細は、図3に示すように、摩擦力を測定するためのテーブル11上にアクリル板を固定し、肌側使用面を下にして中央にサンプルを載置した。さらに、ロードセル15を備えた試験機を用いて、MD4.0cm×CD10.0cmの範囲(接地部分3)に10g/cm2の荷重を10秒間与えた後、プーリー13を介したポリアミド糸14を水平に引っ張ることにより20mm/minの速度でCD方向にサンプルを水平に引っ張って得られる試験力のピーク値(図4に示すピーク値)を密着性と定義し測定した。なお、密着性は、下記に示す2種類の条件で測定した。
(1)サンプル質量に対し900質量%含浸し、フェィスマスク使用開始直後の環境を模した条件での密着性の値を得た。
(2)サンプル質量に対し500質量%含浸し、フェィスマスク使用後半の環境を模した条件での密着性の値を得た。
サンプルをフェイスマスクの形に切り出し、サンプル質量に対して900質量%の化粧料(カネボウ化粧品(株)製「フレッシェル エッセンスローションAL」)を含浸し上体を起こした姿勢でフェィスマスクとして使用した。5名の被験者により、20分使用後の密着感を以下の基準に従って官能評価した。
〇:肌への沿いが良く、使用開始直後と変わらないか又はそれ以上の密着感を感じた
△:肌への沿いは良いが、使用開始直後に比べ密着感は低下した
×:肌への沿いが悪く、ズレ、剥がれが生じた。また、使用開始直後に比べ密着感は著しく低下した。
サンプルを7.5cm×7.5cmに切り出し、テフロン(登録商標)加工を施した金属板の上で肌側に使用する面を下にして静置した。化粧料(カネボウ化粧品(株)製「フレッシェル エッセンスローションAL」)をサンプル質量に対して900質量%分(化粧料重量C)秤量し、サンプルの肌側に使用する面と異なる面側(保液層側)から全量滴下した。化粧料をスパーテルで拡げ、サンプルに対して概ね均一に化粧料を含浸させた。濾紙(ADVANTEC FILTER PAPER GLADE2)を10.0cm×10.0cmに切り出し5枚重ねて重量を測定した(濾紙重量A)。濾紙を肌に見立て、化粧料を含浸させたサンプルを濾紙の上に静置し、30gのアクリル板を試料の全面を覆う様に荷重として載せた。1分間放置した後、試料と荷重を取り除き、濾紙の重量を求めた(濾紙重量B)。試料から濾紙に移行した化粧料の重量から下式にて化粧料放出率を求めた。
[湿潤時の50%伸長時応力]
JIS L1913(一般短繊維不織布)6.3.2(湿潤時の引張強さ及び伸び率試験)に記載の方法に準拠して測定した。具体的には、サンプルを20℃±2℃の水中に自重で沈降するまで置くか、又は1時間以上水中に沈めておいた後、浸漬液から取り出して速やかに50%伸長時応力を測定した。
[テンセル繊維]:精製セルロース繊維、レンチング社製「リヨセル」、平均繊維径12μm、繊維長38mm
[ポリエステル繊維]:ポリエチレンテレフタレート(PET)繊維、東レ(TORAY)(株)製、平均繊維径12μm、繊維長51mm
[分割繊維]:ポリアミド・ポリエステル層状積層断面分割繊維、クラレ(株)製「WRAMP」平均繊維径17μm、繊維長51mm(分割後の平均繊維径5μm)
[コットン繊維]:コットン繊維、丸三産業(株)製、平均繊維径14μm
[芯鞘複合繊維]:芯部がポリエチレンテレフタレートで構成され、鞘部がエチレン-ビニルアルコール共重合体(EVOH)で構成された芯鞘複合繊維、クラレ(株)製「ソフィスタ」、平均繊維径14μm、繊維長51mm
[ポリプロピレン(PP)樹脂]:MFR(230℃、2.16kg)=1100g/10分
[エチレン-ビニルアルコール共重合樹脂(EVOH)]:MFR(190℃、2.16kg)=12g/10分
[ポリブチレンテレフタレート(PBT)樹脂]:MFR(235℃、2.16kg)=90g
[ポリウレタン樹脂]:溶融粘度D-65935定温法にて1.0×103~5.0×103Pa・s/200℃
[ポリエステルフィルム]:ポリエチレンテレフタレートフィルム、東レ(株)製「ルミラーPX52」、目付16.6g/m2、厚さ12μm
[接着性樹脂]:LDポリエチレン、東ソー(株)製「ペトロセン」
(実施例1)
ポリプロピレン樹脂(MFR=1100g/10分)100質量部を用いて、一般的なメルトブローン製造設備を使用し、紡糸温度260℃、エアー温度270℃、エアー圧力0.4MPa、単孔吐出量0.2g/孔・分、口金における紡糸孔数400個(1列配置)にてメルトブローン紡糸を行い、回転するネットコンベアを支持体として捕集し、目付5g/m2のメルトブローン不織布シートを製造し、巻き取った。
セミランダムカードウェブの目付を40g/m2とする以外は実施例1と同様にして、目付が45g/m2の複合不織布を得た。得られた不織布シートの厚みの比率は、密着層1に対し保液層8.7であった。また、得られた不織布シートのメルトブローン不織布によって構成される密着層の数平均繊維径は2.57μmであり、繊維径分布の標準偏差は、1.318であり、変動率は51.26%であった。さらに、得られた不織布シートの空隙率は、保液層で93.3%、密着層で88.6%であった。
この結果から使用開始後密着性は向上すると判定した。
ポリブチレンテレフタレート樹脂(MFR=90g/10分)100質量部を用いて、一般的なメルトブローン製造設備を使用し、紡糸温度280℃、エアー温度290℃、エアー圧力0.4MPa、単孔吐出量0.3g/孔・分、口金における紡糸孔数400個(1列配置)にてメルトブローン紡糸を行い、回転するネットコンベアを支持体として捕集し、目付20g/m2のメルトブローン不織布シートを製造し、巻き取った。
エチレン-ビニルアルコール共重合樹脂(MFR(190℃、2.16kg)=12g/10分)100質量部に、一般的なメルトブローン製造設備を使用し、紡糸温度250℃、エアー温度260℃、エアー圧力0.4MPa、単孔吐出量0.2g/孔・分、口金における紡糸孔数400個(1列配置)にてメルトブローン紡糸を行い、回転するネットコンベアを支持体として捕集し、20g/m2のメルトブローン不織布シートを製造した。
レーヨン繊維を40質量部、ポリエステル繊維を60質量部の割合で用いて均一に混綿した後、目付60g/m2のセミランダムカードウェブを常法により作製し、このカードウェブを開口率25%、穴径0.3mmのパンチングドラム支持体上に載置して速度50m/分で長手方向に連続的に移送すると同時に、上方から高圧水流を噴射して交絡処理を行って、交絡した繊維ウェブ(不織布)を製造した。この交絡処理に当たっては、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用し(隣接するノズル間の距離20cm)、1列目のノズルから噴射した高圧水流の水圧を3.0MPa、2列目のノズルから噴射した高圧水流の水圧を4.0MPaとして行った。さらに細かい網目を有する全体に平坦な支持体に載置して連続的に移送すると共に高圧水流を噴射して交絡処理を行って、構成する繊維を交絡させた。この交絡処理は、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用して、いずれも高圧水流の水圧5MPaの条件下で行った。さらに110℃で乾燥して、目付けが60g/m2のスパンレース不織布を得た。
芯鞘複合繊維を30質量部、ポリエステル繊維を70質量部の割合で用いて均一に混綿した後、目付100g/m2のセミランダムカードウェブを常法により作製し、このカードウェブを50メッシュ、幅500mmのステンレス製エンドレスネットを装備したベルトコンベアに移送した。尚、このベルトコンベアの金網の上部には同じ金網を有するベルトコンベアが装備されており、それぞれが同じ速度で同方向に回転し、これら両金網の間隔を任意に調整可能なベルトコンベアを使用した。次いで、下側コンベアに備えられた水蒸気噴射装置ヘカードウェブを導入し、この装置から0.4MPaの高温水蒸気をカードウェブの厚み方向に向けて通過するように(垂直に)噴出して水蒸気処理を施し、不織繊維構造を有する成形体(スチームジェット不織布)を得た。この水蒸気噴射装置は、下側のコンベア内に、コンベアネットを介して高温水蒸気をウェブに向かって吹き付けるようにノズルが設置され、上側のコンベアにサクション装置が設置されていた。また、この噴射装置のウェブ進行方向における下流側には、ノズルとサクション装置との配置が逆転した組合せである噴射装置がもう一台設置されており、ウェブの表裏両面に対して蒸気処理を施した。なお、水蒸気噴射ノズルの孔径は0.3mmであり、ノズルがコンベアの幅方向に沿って1mmピッチで1列に並べられた蒸気噴射装置を使用した。加工速度は10m/分であり、ノズル側とサクション側の上下コンベアベルト間の間隔(距離)は5mmとした。ノズルはコンベアベルトの裏側にベルトとほぼ接するように配置した。
実施例1と同様にして、ポリプロピレン樹脂を用いて、目付5g/m2のメルトブローン不織布シートを製造した。
実施例1と同様にして、ポリプロピレン樹脂を用いて、目付5g/m2のメルトブローン不織布シートを製造した。
レーヨン繊維100質量部を均一に解繊した後、目付60g/m2のセミランダムカードウェブを常法により作製し、このカードウェブを開口率25%、穴径0.3mmのパンチングドラム支持体上に載置して速度50m/分で長手方向に連続的に移送すると同時に、上方から高圧水流を噴射して交絡処理を行って、交絡した繊維ウェブ(不織布)を製造した。この交絡処理に当たっては、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用し(隣接するノズル間の距離20cm)、1列目のノズルから噴射した高圧水流の水圧を3.0MPa、2列目のノズルから噴射した高圧水流の水圧を4.0MPaとして行った。さらに細かい網目を有する全体に平坦な支持体に載置して連続的に移送すると共に高圧水流を噴射して交絡処理を行った。この交絡処理は、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用して、いずれも高圧水流の水圧5MPaの条件下で行った。さらに130℃で乾燥して、目付けが60g/m2のスパンレース不織布を得た。得られた不織布シートの空隙率は88.2%であった。
レーヨン繊維を40質量部、ポリエステル繊維を60質量部の割合で用いて均一に混綿した後、常法により作製した目付60g/m2のセミランダムカードウェブに対して比較例1と同様にして交絡及び乾燥処理を行い、目付け60g/m2のスパンレース不織布を得た。得られた不織布シートの空隙率は90.4%であった。
コットン繊維を100質量部に解繊した後、常法により作製した目付60g/m2のセミランダムカードウェブに対して比較例1と同様にして交絡及び乾燥処理を行い、目付60g/m2のスパンレース不織布を得た。得られた不織布シートの空隙率は90.2%であった。
レーヨン繊維を100質量部均一に解繊した後、目付32g/m2のセミランダムカードウェブを常法により作製し、このカードウェブを開口率25%、穴径0.3mmのパンチングドラム支持体上に載置して速度50m/分で長手方向に連続的に移送すると同時に、上方から高圧水流を噴射して交絡処理を行って、交絡した繊維ウェブ(不織布)を製造した。この交絡処理に当たっては、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用し(隣接するノズル間の距離20cm)、1列目のノズルから噴射した高圧水流の水圧を4.0MPa、2列目のノズルから噴射した高圧水流の水圧を5.0MPaとして行った。さらに細かい網目を有する全体に平坦な支持体に載置して連続的に移送すると共に高圧水流を噴射して交絡処理を行った。この交絡処理は、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用して、いずれも高圧水流の水圧5MPaの条件下で行った。さらに130℃で乾燥して、目付けが32g/m2のスパンレース不織布を得た。
ポリブチレンテレフタレート樹脂(MFR=90g)を用いて、エアー圧力を0.4MPaとする以外は実施例3と同様にして、目付20g/m2のメルトブローン不織布シートを製造した。
レーヨン繊維を40質量部、ポリエステル繊維を60質量部の割合で用いて均一に混綿した後、目付60g/m2のセミランダムカードウェブを常法により作製し、このカードウェブを開口率25%、穴径0.3mmのパンチングドラム支持体上に載置して速度50/分で長手方向に連続的に移送すると同時に、上方から高圧水流を噴射して交絡処理を行って、交絡した繊維ウェブ(不織布)を製造した。この交絡処理に当たっては、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用し(隣接するノズル間の距離20cm)、1列目のノズルから噴射した高圧水流の水圧を3.0MPa、2列目のノズルから噴射した高圧水流の水圧を4.0MPaとして行った。さらに細かい網目を有する全体に平坦な支持体に載置して連続的に移送すると共に高圧水流を噴射して交絡処理を行って、構成する繊維を交絡させた。この交絡処理は、穴径0.10mmのオリフィスをウェブの幅方向に沿って0.6mmの間隔で設けてあるノズル2本を使用して、いずれも高圧水流の水圧5MPaの条件下で行った。さらに130℃で乾燥して、目付けが60g/m2のスパンレース不織布を得た。
比較例6で得られた目付91g/m2の複合不織布のフィルム層側から、金属製の針を用い直径約900μmの貫通孔を2cm間隔で全面に施した。得られた不織布シートの厚さの比率はフィルム層1に対し保液層14.2であった。また、得られた不織布シートの空隙率は、保液層で89.0%、フィルム層は0.2%であった。
比較例6で得られた目付91g/m2のフィルム層側から、金属製の針を用い直径約900μmの貫通孔を1cm間隔で全面に施した。得られた不織布シートの厚みの比率は、フィルム層1に対し保液層14.4であった。また、得られた不織布シートの空隙率は、保液層で89.2%、フィルム層は0.6%であった。
11…テーブル(アクリル板)
12…クリップ
13…プーリー
14…ポリアミド糸
15…ロードセル
Claims (19)
- 不織繊維集合体で構成され、かつ液状成分を吸収可能な保液層と、この保液層の少なくとも一方の面に形成され、前記液状成分を透過可能であり、かつ皮膚と接触させるための密着層とで構成された積層シートであって、前記密着層が数平均繊維径10μm以下である不織繊維集合体で構成され、かつ密着層と保液層との厚み割合が、密着層/保液層=1/4~1/100である積層シート。
- 密着層が、繊維径の標準偏差が5以下である不織繊維集合体で構成されている請求項1記載の積層シート。
- 保液層が、密着層を構成する繊維よりも繊維径の大きい不織布繊維集合体で構成されている請求項1記載の積層シート。
- 保液層が親水性樹脂で構成された繊維を含み、かつ密着層が熱可塑性樹脂で構成された繊維を含む請求項1~3のいずれかに記載の積層シート。
- 保液層が、親水性樹脂で構成された繊維を50質量%未満の割合で含み、かつ密着層が、ポリエステル繊維、ポリオレフィン繊維、ポリビニルアルコール系繊維及びポリウレタン繊維からなる群から選択された少なくとも一種で構成されている請求項1~4のいずれかに記載の積層シート。
- 保液層を構成する繊維の数平均繊維径が9~32μmであり、かつ密着層を構成する繊維の数平均繊維径が1~8μmである請求項1~5のいずれかに記載の積層シート。
- 保液層が0.03~0.20g/cm3の密度及び80%以上の空隙率を有し、かつ密着層が0.05~0.35g/cm3の密度及び70%以上の空隙率を有する請求項1~6のいずれかに記載の積層シート。
- 密着層がメルトブローン不織布で構成されている請求項1~7のいずれかに記載の積層シート。
- JIS L1913に準拠した湿潤時の50%伸長時応力が、少なくとも一方向において0.5~15N/5cmである請求項1~8のいずれかに記載の積層シート。
- 液状成分を含浸させた請求項1~9のいずれかに記載の積層シート。
- 液状成分が化粧料を含むスキンケアシートである請求項10記載の積層シート。
- フェイスマスクである請求項11記載の積層シート。
- 保液層の上に、さらに他の密着層を有する請求項1~12のいずれかに記載の積層シート。
- 保液層の上に、さらに非多孔性のフィルムを有する請求項1~12のいずれかに記載の積層シート。
- 化粧料をシート質量に対して500質量%含浸させて、ASTM-D1984に準拠して測定した摩擦力が0.6N以上であり、かつ化粧料を500質量%含浸させた摩擦力が、化粧料を900質量%含浸させた摩擦力よりも大きい請求項1~13のいずれかに記載の積層シート。
- 密着層をメルトブローン法で形成し、不織繊維集合体で構成された保液層の少なくとも一方の面に積層する請求項1記載の積層シートの製造方法。
- 疎水性繊維と親水性繊維とをスパンレース法で交絡させて保液層を製造した後、得られた保液層と密着層とをさらにスパンレース法で交絡させる方法又は得られた保液層に密着層を直接吹き付ける方法で積層する請求項16記載の製造方法。
- 疎水性繊維とエチレン-ビニルアルコール共重合体を含む親水性繊維とをスチームジェット法で交絡及び湿熱接着させて保液層を製造した後、得られた保液層と密着層とをさらにスパンレース法で交絡させる方法又は得られた保液層に密着層を直接吹き付ける方法で積層する請求項16記載の製造方法。
- 請求項1~15のいずれかに記載の積層シートを、液状成分を含浸した状態で、密着層を皮膚に接触させる積層シートの使用方法。
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Also Published As
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JPWO2011004834A1 (ja) | 2012-12-20 |
EP2453047A1 (en) | 2012-05-16 |
JP5562955B2 (ja) | 2014-07-30 |
CN102482818B (zh) | 2015-07-01 |
US9174411B2 (en) | 2015-11-03 |
EP2453047B8 (en) | 2019-11-20 |
TW201106980A (en) | 2011-03-01 |
US20120107387A1 (en) | 2012-05-03 |
EP2453047A4 (en) | 2014-01-01 |
KR101714100B1 (ko) | 2017-03-08 |
KR20120107908A (ko) | 2012-10-04 |
CN102482818A (zh) | 2012-05-30 |
TWI510688B (zh) | 2015-12-01 |
EP2453047B1 (en) | 2019-09-18 |
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