CN101087631B - Method and material for protecting skin - Google Patents

Method and material for protecting skin Download PDF

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Publication number
CN101087631B
CN101087631B CN2005800448021A CN200580044802A CN101087631B CN 101087631 B CN101087631 B CN 101087631B CN 2005800448021 A CN2005800448021 A CN 2005800448021A CN 200580044802 A CN200580044802 A CN 200580044802A CN 101087631 B CN101087631 B CN 101087631B
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application
ion
fiber
copper
insoluble
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CN101087631A (en
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J·加贝
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Cupron Corp
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Cupron Corp
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Priority claimed from IL17185205A external-priority patent/IL171852A/en
Priority claimed from PCT/IL2005/001171 external-priority patent/WO2006051529A1/en
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Abstract

The invention provides a skin cosmetology method of defending, reducing, and eliminating furrow, which includes coating material containing water-fast copper compound on the skin, wherein, the compound releases Cu<+> ion, Cu<++> ion, or the two ions when connects to fluid.

Description

Skin protection is with method and material
Invention field
The present invention relates to be used to reduce, prevent or remove wrinkle and the beauty method of more level and smooth and more strong skin surface is provided, and relate to the material that has mixed the water-insoluble copper compound and reducing to, preventing and removing wrinkle and the application in the more level and smooth and more strong skin surface is provided.
More particularly; The present invention relates to the beauty method that is used to prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided; Comprise pending body surface used the material that has mixed the water-insoluble copper compound that described chemical compound discharges Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
The invention still further relates to and when contacting with fluid, discharge Cu +Ion, Cu ++The water-insoluble copper compound of ion or its combination at preparation contact body surface so that prevention, reduce and remove wrinkle and the material of more level and smooth and more strong skin surface is provided, such as the application in cast film, silk or the sheath.Described sheath or cast film have novel monolithic layer, and this layer has except that moisture performance or micropore.
In addition; The present invention relates to have the application that the particulate thin polymer film of microcosmic water-insoluble of the ionic oxide formation copper of powder type is used for preventing, reduce and remove wrinkle and the material of more level and smooth and more strong skin surface is provided in preparation; Directly be embedded with the said granule that part exposes and give prominence to from its surface in the said thin polymer film, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
Similarly, the present invention relates to mix release Cu when contacting with fluid +Ion, Cu ++The application that the fiber of the water-insoluble copper compound of ion or its combination is used for preventing, reduce and remove wrinkle and the material of more level and smooth and more strong skin surface is provided in preparation.
As stated, in the preferred embodiment of the invention, described fiber be have the said chemical compound that mixes wherein and said chemical compound from its surface outstanding polymer fiber.
Be described below, in other preferred embodiment of the present invention, applied described copper compound on the described fiber.
In other preferred embodiment of the present invention; Described material is made up of component of polymer; Described component of polymer is selected from polyamide, polyester, acrylic acid and gathers olefin(e); Can also comprise that described material is the form of fiber, yarn or sheet such as polypropylene, polyurethanes, polyolefin, polyethylene and other hydrophilic and this type of hydrophobic polymer material.
Describe with reference to embodiment and accompanying drawing as hereinafter, unexpectedly found at present and can discharge Cu when the contacting with fluid having mixed +Ion, Cu ++The material of the water-insoluble copper compound of ion or its combination is used to produce the contact body surface so that prevention, reduce and remove wrinkle and fabric, thin film, silk or the sheath of the cosmetic applications of more level and smooth and more strong skin surface are provided.
More particularly, found unexpectedly that at present material of the present invention can effectively prevent, reduces and remove wrinkle and more level and smooth and more strong skin surface is provided.
On market, can buy the cream that is used for local application, it comprises that the organic copper peptide is as its composition.Therefore yet as what recognize, designing described cream is to penetrate skin and system according to the copper key in the organic copper peptide, and described product is not instructed or pointed out those skilled in the art can be with discharging Cu when the contacting with fluid +Ion, Cu ++The material of the water-insoluble copper compound of ion or its combination is used to produce the contact body surface so that prevention, reduce and remove wrinkle and fabric, thin film, silk or the sheath of the cosmetic applications of more level and smooth and more strong skin surface are provided.
Background of invention
In WO 98/06508 and WO 98/06509, instructed to have directly or the different aspect of the fabric of the metal wholly or in part of its fiber of strong bonded or metal oxide coating, wherein metal and metallic oxide comprise that copper combines with described fiber.
More particularly; The method that comprises the following steps is provided: the fabric that plating (a) is provided in WO 98/06509; The fabric of this plating comprises: (i) comprise the fabric of fiber, described fiber is selected from natural fiber, synthetic cellulose fibres, regenerated fiber, acrylic fiber, polyolefine fiber, polyurethane fibre, vinyl fiber and admixture thereof; The coating that (ii) comprises the material that is selected from metal and metallic oxide, the fabric of plating are characterised in that coating directly combines with fiber; (b) fabric with plating mixes goods.
In context of the present invention, term " fabric " comprising: no matter fiber is natural (for example Cotton Gossypii, silk thread, Pilus Caprae seu Ovis and linen), still is by the synthetic threads of those fibre spinnings; With knitting, braiding of processing and non-braided fabric by those yarns.Scope of the present invention comprises all natural fibers and all synthetic fibers that is used for fabric applications, and including, but are not limited to synthetic cellulose fibres (is regenerated celulose fibre, such as artificial silk; And cellulose derivative fibres, such as typel); Azlon; Acrylic fiber; Polyolefine fiber; Polyurethane fibre; And vinyl fiber, but do not comprise nylon and polyester fiber and admixture thereof.
Present invention resides in the application of product of technological improvement of the metallide of the plastics that are used for containing metal, the printed circuit board (PCB) that particularly is made of plastics.For example, referring to Encyclopediaof Polymer Science and Engineering (Jacqueline I.Kroschwitz, editor), Wiley and Sons, 1987, vol.IX, pp 580-598.As the application in fabric, this method comprised for two steps.The first step is through making catalytic precious metal nucleation site be deposited in activated textile on the fabric.This step is through at first immersing fabric low-oxidation-state Reducing agent cationic solution and then this fabric is immersed precious metal cation solution, preferred Pd++ cationic solution, most preferably acid PdCl 2Carry out in the solution.Low-oxidation-state cation is reduced into noble metal self with precious metal cation, is oxidized to higher oxidation state simultaneously.Preferred Reducing agent cation is a soluble cation under initial low-oxidation-state and final high oxidation state, and for example, Sn++ is oxidized to Sn++++, or Ti+++ is oxidized to Ti++++.
Second step was reduction, and promptly closely near activatory fabric reducing metal cation, it reduces by precious metal catalyst.The cationic Reducing agent that is used to reduce is generally molecular species, for example, with regard to Cu++, is formaldehyde.Because Reducing agent is oxidized, so metal cation is called " oxidant cations " in this article.The fabric of consequent plating is characterised in that its coat of metal directly combines with fabric fibre.
In WO 98/06508, describe and asked for protection a kind of composition of matter, comprising:
(a) comprise the fabric of fiber, described fiber is selected from natural fiber, synthetic cellulose fibres, azlon, acrylic fiber, polyolefine fiber, polyurethane fibre, vinyl fiber and admixture thereof; With
(b) comprise the coating of the material that is selected from metal and metallic oxide;
This composition of matter is characterised in that described coating directly combines with described fiber.
This open source literature is also asked for protection a kind of composition of matter, comprising:
(a) comprise the fabric of fiber, described fiber is selected from natural fiber, synthetic cellulose fibres, azlon, acrylic fiber, polyolefine fiber, polyurethane fibre, vinyl fiber and admixture thereof; With
(b) a plurality of nucleation site, described nucleation site comprises at least a noble metal separately;
This composition of matter is characterised in that the reduction of at least a metal cation kind of catalysis, makes into reductive metal, plates described reductive metal for thus described fiber.
In addition, instruct and asked for protection the method that is used to produce said product in this open source literature.
The method for optimizing of fabric that is used for preparing the plating of this open source literature comprises the following steps:
A) select a kind of fabric; Its form is selected from yarn and fabric; Described fabric comprises fiber, and described fiber is selected from natural fiber, synthetic cellulose fibres, azlon, acrylic fiber, polyolefine fiber, polyurethane fibre, vinyl fiber and admixture thereof;
B) described fabric immersion is contained at least a solution with Reducing agent cation type of at least two kinds of positive oxidation state, described at least a cation type is the low form at least two kinds of positive oxidation state;
C) described fabric is immersed the solution that contains at least a precious metal cation kind, produce activatory fabric thus; With
D) at least a oxidant cations kind of reduction in the medium of the said activatory fabric of contact produces the fabric of plating thus.
Yet; This open source literature is limited to fiber and the fabric according to the coating that is used for application described herein of method preparation as herein described; But, do not instruct in this open source literature or point out the fiber of this type coating and fabric can prepare the material that is used to prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided effectively.
Similarly; In this open source literature the instruction or the prompting cation copper is mixed in the polymer slurries of hydrophobic polymer; Have with production and to be encapsulated in the said polymer and from the thin film of the microscopic particles of wherein outstanding cation copper and the probability of fiber, the present invention finds that unexpectedly they can also be used to the material for preparing prevention, reduces and remove wrinkle and more level and smooth and more strong skin surface are provided effectively.
According to the description among the USSN 10/240993; Discovery is added in the polymer slurries to be formed through the Cu++ with the little percentage ratio of water-insoluble copper oxide particle form; Resulting polymers has antimicrobial property, and the content of document instruction is introduced this paper as a reference.
In addition; This article is found unexpectedly and has been described through the copper oxide with particle form and joins in the polymer slurries such as polyethylene, polypropylene, polyesters and similar hydrophobicity or this base polymer of hydrophilic polymer material, can have the antimicrobial of extensive use and fiber, yarn or the sheet of ntiviral characteristic by extrusion molding.The application that new antimicrobial of in to said description, describing and antiviral polymeric material are paid close attention to is: its application in the carpet backing layer; Even can be used for hospital facility, because can not producing mycete, abnormal smells from the patient and can make, it is not deposited in any virally inactivated on it; As the application of the composition of molded non-knitting product, maybe can see through air such as the air filter in hospital or the aircraft and maybe can see through liquid and can be used for filtering the fluid of circulation and make antibacterial that said fluid finds and virally inactivated face shield; Form continuous, open and flat, texture or tensile form are arranged, it can be used for clothes product, such as stocking, socks, shirt or any clothes product that can mix hydrophobic polymer fiber or yarn; Form short use subsequently, or can with other fiber, such as the staple fiber of Cotton Gossypii fusion, the yarn of fusion can be used to produce various braidings or knit product then, such as socks, sheet etc.; With the application of this type with the polymeric material of two composition form of yarns productions; Wherein core is that a kind of chemical compound and the sheath around core are the polymer that contains the insoluble shape copper oxide particle of water; Thereby produce the yarn of numerous intended application, it is staple fiber continuous, open and flat, that texture, stretchable form or conduct weak point are arranged.The instance that use said back one can be the application of polyethylene core in forming yarn with the polymer jacket that has mixed said water-insoluble copper oxide particle; Described yarn has the enhanced anti-drag that is cut or tears; Also have antimicrobial and ntiviral characteristic simultaneously and have multiple application, be included in Application in Food Industry.
Described material is described as being processed by any synthetic polymer, and this polymer allows cationic, oxidized copper granule is introduced its liquid slurry state.The instance of some material is that polyamide-based (nylon), polyester, acrylic acid and polyene belong to hydro carbons, such as polyethylene and polypropylene.When cupric oxide powder is ground to form fine powder; For example size is at the 1-10 micron and with a small amount of introducing slurry; For example; As acceptable when being used for masterbatch that production extruded fibers and thin film implement and accounting for the amount of polymer weight 0.25-10%, find subsequently to show antimicrobial and ntiviral characteristic by the product of this slurry production.
Be different from for example at the fiber described in WO98/06508 and the WO 98/06509; Wherein the fiber outside is coated; In described product, polymer has the microcosmic water-insoluble granule of the cationic oxidation copper that is encapsulated in wherein, and the center is divided described granule to expose and be outstanding from its surface.Verified these granules from the outstanding exposure of polymer material membrane have activity, as the training centre confirmation through test and this description described in the said description, because they are relevant with the present invention, so be introduced into this paper as a reference.
Yet, do not instruct in the described US description yet or point out polymeric material as herein described can be effective to preparation prevention, reduce and remove wrinkle and more level and smooth and more strong skin surface is provided and is exemplary material with this paper.
Generally speaking, the product in the said description with can be used for product of the present invention and produce as follows:
1. by polymer manufacture slurry arbitrarily, primary raw material preferably from polyamide, gather olefin(e), polyurethanes and polyester.Can also use in the said material more than one combination, as long as they have the compatibility and maybe can be adjusted into the compatibility.Polymer raw material is generally the form of pearl and in fact can be single composition, two composition or multicomponent.These pearls are heated to preferably under about 120-180 ℃ temperature, melt.
2. at hot mix stages, before extrusion molding, the water-insoluble powder of cationic oxidation copper is joined in the described slurry and it is fully distributed in the slurry of whole heating.Granular size is preferably at the 1-10 micron, and but, when thin film or fiber thickness can hold larger particles, described size can be bigger.
3. push liquid slurry through forming circle or being called the hole on a series of metal plates of other required form of spinning head with pressure then.When pushing slurry when the approximating pore, they form ultimate fibre, if or they are contacted with each other, their formation thin film or sheaths so.Use cold air upwards to push hot liquid fiber or thin film, form the fiber or the circular piece of continuous series.Upwards push the speed controlling fiber of slurry or the thickness of sheet according to the size in hole with through the hole with by thin cooling blast.
The antimicrobial compositions that comprises particles of inorganic material has been described in WO 94/15463; Described particles of inorganic material has first coating that antimicrobial property is provided and second coating that defencive function is provided; Wherein said first coating can be the chemical compound of silver or copper or silver, copper and zinc, and preferably contains the chemical compound of silver oxide and copper oxide (II).Yet; This patent is based on complicated with expensive method; This method comprises with the second protective finish plating compositions; Described second protective finish is selected from silicon dioxide, silicate, borosilicate, aluminium silicate salt, aluminium oxide, aluminum phosphate or its mixture, and in fact all claim all relates to and have continuous coated compositions, wraps said coating and draws together silicon dioxide, aqueous alumina and dioctyl azelate.
On the contrary, The present invention be more particularly directed to have the application of the particulate thin polymer film of microcosmic water-insoluble of the cationic oxidation copper of powder type, described particle release is encapsulated in Cu wherein ++, the center is divided described granule to expose and is outstanding from its surface, and this characteristic is instruction in said open source literature, also prompting, and the present invention has following advantage: confirmed the release Cu that exposes ++Outstanding water-insoluble granule from polymeric material can be effective to prevention, reduce and remove wrinkle and more level and smooth and more strong skin surface is provided.
A kind of bactericidal composition has been described in EP 427858; It is characterized in that having applied on the fine inorganic particles antibacterial metal and/or antisepsis metallic compound, and this patent is instructed not also or point out the particulate polymer of microcosmic water-insoluble of the cationic oxidation copper that has mixed powder type can discharge the Cu that is encapsulated in wherein ++, the center is divided described granule to expose and is outstanding from its surface.
Use and ion Cu have been described in DE 4403016 ++The antibacterial of opposite copper and Fungicidal composition, and this patent is not instructed or point out the particulate polymer of microcosmic water-insoluble of the cationic oxidation copper that has mixed powder type can discharge the Cu that is encapsulated in wherein ++, the center is divided described granule to expose and is outstanding from its surface.
In JP-01 046465, described the ionic condom of release antibacterial that uses metal, described metal is selected from copper, silver, hydrargyrum and alloy thereof, and these metals have antibacterial and kill and wound the effect of sperm, and wherein said metal is micronization copper preferably.As known, although also mentioned mantoquita, such as copper chloride, copper sulfate and copper nitrate, they are water soluble salt, can dissolve and decompose the polymer of introducing them.Similarly, although mentioned Red copper oxide, Cu especially ++Ionic species, and therefore the release Cu of exposure is not instructed or pointed out to described patent ++The outstanding and verified application that is effective to prevent, reduce and remove wrinkle and the material of more level and smooth and more strong skin surface is provided from polymeric material.
In JP-01 246204, described a kind of antimicrobial molded products, wherein the mixture of powdery copper compound and organopolysiloxane is dispensed into thermoplastic molded goods so that prepare cloth, socks etc.This patent mentions especially and has instructed and can not metal ion self introduced polymer molecule and need comprise organopolysiloxane that it also can provide the connection approach that copper ion is released into fiber surface.Therefore, as cognoscible, described copper compound can be sealed, but the release Cu of exposure is not instructed or pointed out to this patent ++The application of outstanding water-insoluble copper oxide particle from polymeric material.
The fiber that is preferred for producing underwear with good resistance fungus and health effect has been described in JP-03 113011; Wherein said synthetic fibers contain copper or copper compound and germanium or its combination of compounds; But; The germanium of the existence that this patent instruction and requirement expose therein and the major part of copper compound are preferably metallic copper, are monovalence Cu +The Hydro-Giene (Water Science). of chemical compound and water solublity mantoquita.Therefore, the release Cu of exposure is not instructed or pointed out to this patent ++The application of outstanding water-insoluble copper oxide particle from polymeric material.
In EP 116865, describe and asked for protection the polymer product that contains zeolite granular, wherein at least part kept at least a have the metal ion of antibacterial attribute and thus this patent do not instruct or point out the release Cu of exposure ++Water-insoluble copper oxide particle self and in the application that does not have in the presence of the zeolite, described granule is outstanding and verified from polymeric material can be used for prevention effectively, reduce and remove wrinkle and more level and smooth and more strong skin surface is provided.
Describe and asked for protection the polymer that contains amorphism silicic acid alumina particles among the EP 253653; The amorphism silicic acid aluminum solid particle that described granule includes organic polymer and amorphism silicic acid aluminum solid particle or handles with coating reagent, in the said amorphism silicic acid aluminum solid particle some maintains the metal ion with bactericidal action at least.Therefore, the release Cu of exposure is not instructed or pointed out to this patent ++Water-insoluble copper oxide particle self and in the application that does not have in the presence of the amorphism silicic acid alumina particles, the release Cu of exposure ++The water-insoluble copper oxide particle outstandingly and verified from polymeric material be effective to prevention, reduce and remove wrinkle and more level and smooth and more strong skin surface is provided.
Therefore, there is not one piece to instruct or pointed out release Cu when contacting with fluid in the said open source literature +Ion, Cu ++The application of the water-insoluble copper compound of ion or its combination in preparation fabric or cast film, silk or sheath, described fabric or cast film, silk or sheath contact body surface are so that prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface is provided.
Summary of the invention
Therefore, relate in the preferred aspect of the present invention having mixed when contacting with fluid and discharge Cu +Ion, Cu ++The application that the fiber of the water-insoluble copper compound of ion or its combination is used for preventing, reduce and remove wrinkle and the material of more level and smooth and more strong skin surface is provided in preparation.
In the preferred embodiment of the present invention aspect this, described material is made up of textile material or substrate, and described textile material or substrate have mixed with the cation type fibre treated of copper and mixed and discharged Cu when the contacting with fluid +Ion, Cu ++The water-insoluble copper compound of ion or its combination.
It should be noted that described fiber or substrate can be processed by hydrophilic or hydrophobic polymer material.
In said preferred embodiment aspect first of the present invention, described fiber be have wherein mixed said chemical compound and said chemical compound from its surface outstanding polymer fiber.
In the present invention's other preferred embodiment aspect this, applied described copper compound on the described fiber.
Second preferred aspect of the present invention relates to the application that the particulate thin polymer film of microcosmic water-insoluble of the ionic oxide formation copper with powder type is used for preventing, reduce and remove wrinkle and the material of more level and smooth and more strong skin surface is provided in preparation; Directly be embedded with the said granule that part exposes and give prominence to from its surface in the said thin polymer film, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
The 3rd preferred aspect of the present invention relates to has mixed release Cu when contacting with fluid +Ion, Cu ++The application of the clothes product of the wearing that the fiber of the water-insoluble copper compound of ion or its combination is used in preparation to prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided.
In addition, aspect this 3rd of the present invention in, described fiber be preferably have wherein mixed said chemical compound and said chemical compound from its surface outstanding polymer fiber, or applied described copper compound on the described fiber.
The particulate thin polymer film of microcosmic water-insoluble that the 4th aspect of the present invention relates to the ionic oxide formation copper with powder type is used for the application that is worn over the removable tubular overwrap on the user cervical region that prevents, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided in preparation; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
The 5th aspect of the present invention relates to has mixed release Cu when contacting with fluid +Ion, Cu ++The fiber of the water-insoluble copper compound of ion or its combination is used for the application that is worn over the removable tubular overwrap on the user cervical region that prevents, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided in preparation.
In addition, aspect this 5th of the present invention in, described fiber be preferably have wherein mixed said chemical compound and said chemical compound from its surface outstanding polymer fiber, or applied described copper compound on the described fiber.
The 6th preferred aspect of the present invention relates to has mixed release Cu when contacting with fluid +Ion, Cu ++The application that the fiber of the water-insoluble copper compound of ion or its combination is used for preventing, reduce and remove wrinkle and the fabric of more level and smooth and more strong skin surface is provided in preparation.
Preferred described fabric can be used for pillowcase, covering, sheet or trend towards any textile that crumpled body surface can contact.
The 7th preferred aspect of the present invention relates to has mixed release Cu when contacting with fluid +Ion, Cu ++The application that the fiber of the water-insoluble copper compound of ion or its combination is used for preventing, reduce and remove wrinkle and the socks of more level and smooth and more strong skin surface are provided in preparation.
The 8th preferred aspect of the present invention relates to has mixed release Cu when contacting with fluid +Ion, Cu ++The application of the towelling material that the fiber of the water-insoluble copper compound of ion or its combination is used in preparation preventing, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided.
Similarly; In the preferred embodiment of the invention; Described fiber can be for being worn over cervical region scarf on every side and the removable tubular overwrap form that is worn over the user cervical region, and they are used for preventing, reduce and remove wrinkle and more level and smooth and more strong skin surface is provided.
In the extra embodiment preferred of the present invention, described fiber can be the form of part facial film at least.
Because exist, so described fiber can also be the form of gloves of dressing with the beauty treatment mode, so that prevention, reduce and remove the lip-deep wrinkle of hand and more level and smooth and more strong skin surface is provided on the hand surface to its hands responsive people of outward appearance that corrugates.
In addition, of the present invention aspect these in, described fiber be preferably have wherein mixed said chemical compound and said chemical compound from its surface outstanding polymer fiber, or applied described copper compound on the described fiber.
The present invention provides the beauty method that is used to prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided in one aspect of the method; Comprise the polymeric material that constitutes by component of polymer using on it; Described component of polymer is selected from polyamide, polyester, acrylic acid and gathers olefin(e); Described material is the form of fiber, yarn, sheath, silk or sheet, and has the microcosmic water-insoluble granule of the ionic oxide formation copper of powder type, and described granule directly is embedded in the polymeric material; The center is divided described granule to expose and is outstanding from its surface, and these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
In first group of embodiment preferred of the present invention, described material discharges Cu when the contacting with fluid for having to have mixed +Ion, Cu ++The fabric of the fiber of the water-insoluble copper compound of ion or its combination.
In second group of embodiment preferred of the present invention; Described material is the particulate thin polymer film of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
In the 3rd group of embodiment preferred of the present invention; Described material is the particulate polymer fiber of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
In the 4th group of embodiment preferred of the present invention; Described material is the particulate polymer filament of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
In the 5th group of embodiment preferred of the present invention; Described material is the particulate polymer jacket of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
In the 6th group of embodiment preferred of the present invention; Described material is the particulate thin polymer film of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination, wherein said thin film has the ability through the infiltration dispersing liquid.
In the 7th group of embodiment preferred of the present invention; Described material is the particulate thin polymer film of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination spreads all over the micropore that runs through so that excessive liquid is discharged on the wherein said thin film.
As stated, based on the beat all discovery of the present invention, promptly mixed release Cu when contacting with fluid +Ion, Cu ++The beauty method that the material of the water-insoluble copper compound of ion or its combination can be used to prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided can prepare this very many goods of the cosmetic applications of ideal effect.
Can be used for polymeric material of the present invention through the following step production: the preparation polymer slurries, described polymer is selected from polyamide, polyester, acrylic acid and gathers olefin(e) and composition thereof; Introduce mainly the powder that becomes by water-insoluble cationic oxidation copper group and make it be dispersed in the said slurry and then the described slurry of extrusion molding wherein discharge Cu so that form polymeric material +Ion, Cu ++The water-insoluble copper oxide particle of ion or its combination is encapsulated in wherein; The center is divided described granule to expose and is outstanding from its surface, make this polymeric material form fiber, yarn or sheet then in case process be suitable for contacting have skin ulcer, scratch, burn and dermopathic body surface and treat and their fabric of healing.
At US 6; 124; Describe and asked for protection clothes product in 221 with antibiotic, antifungal and anti-yeast character; The fabric that comprises at least one block of plating; This fabric comprises fiber, and described fiber is selected from natural fiber, synthetic cellulose fibres, azlon, acrylic fiber, polyolefine fiber, polyurethane fibre, vinyl fiber and admixture thereof, and has the oxidant cations kind coating of at least a copper that comprises antibiotic, antifungal and anti-yeast effective dose.
In described description, having described described clothes product can effectively anti-tinea pedis (TineaPedis), white candida mycoderma (Candida Albicans), thrush (Thrush) and the antibacterial that causes the foot abnormal smells from the patient; Be selected from brevibacterium (brevubacterium), acinetobacter (acinetobacter), Micrococcus (micrococCus) and combination thereof; Yet; Described patent is not instructed or is pointed out the plan application of this type clothes product or can effectively treat wound, such as skin ulcer, cold sore, skin openings, ulcer, infringement, scratch, burn and dermatosis.
The textile of in WO 01/81671, having described the fiber of the cationic form that has mixed copper coated also can effectively make the antibiotic resistance strain inactivation of antibacterial, and the cation type of described copper preferably comprises Cu ++Ion; Yet; In addition in this description; Described and be used to handle hospital environment so that through making excretory this bacterioid inactivation of infected patient come the textile of prevention infection diffusion, and in this description not instruction or prompting can effectively treat wound by the clothes product that this type textile constitutes, such as skin ulcer, cold sore, skin openings, ulcer, infringement, scratch, burn and dermatosis.
Describe and asked for protection release Cu among the WO 01/74166 ++The application of ionic granule in the preparation polymeric material; Described polymeric material has release and is encapsulated in microscopic particles wherein; The center is divided described granule to expose and is outstanding from its surface; Described polymeric material effectively suppresses HIV-1 propagation; Yet this open source literature is limited to the application of this base polymer material of instruction in preparation condom and possible glove, and its inventor do not recognize at that time and this open source literature in instruction or prompting the present invention do not provide the design that can be effective to prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided yet.
The air filter or the water filter of the copper metal, copper oxide, chloride, carbonate and the sulfate that comprise anti-poisonous steam and gas and antibacterium and virus in US 5848592, US 5492882, FR 2764518, GB 1382820 and US 5217626, have been disclosed separately.With regard to GB1382820, disclosed the pneumatic filter that has mixed active carbon and/or one or more HMW metallic oxides or multiple oxide, so that go down to posterity with physics mode blocking-up and prevention of bacterial.With regard to US 5215626, disclosed and mixed permanganate compounds, silver compound and water-soluble copper compound, such as the water strainer of the mixture of copper chloride or copper sulfate.
Yet none instruction or prompting have been mixed and when contacting with fluid, have been discharged Cu in the described list of references +Ion, Cu ++The fiber of the water-insoluble copper compound of ion or its combination preparation contact body surface for use in prevention, reduce and remove wrinkle and the application in the fabric of more level and smooth and more strong skin surface is provided.
DATABASE WPI Section Ch, Week 199031 Derwent PublicationsLtd .London, GB; Class B04, An 1990-234808 XP002247181 & JP02 161954 and DATABASE WPI Section Ch, Week 198821 DerwentPublications Ltd .London, GB; Class A88; An 1988-145060XP002247182 & JP 63 1088007 relates to the hollow porous fibre; And especially disclosed among the JP631088007 with the bonded cuprammonium treatment of cellulose body fluid; Yet, both not instructions in the described list of references, also release Cu when contacting with fluid has not been mixed in prompting +Ion, Cu ++The fiber of the water-insoluble copper compound of ion or its combination preparation contact body surface for use in prevention, reduce and remove wrinkle and the application in the fabric of more level and smooth and more strong skin surface is provided.
As stated, instruct and asked for protection antimicrobial and antiviral polymeric material among the WO 01/74166, it has release and is encapsulated in Cu wherein ++Ion and the microscopic particles of giving prominence to from its surface, but do not instruct or point out method of the present invention in the document.Similarly; WO01/81671 instruction and the method for having asked for protection opposing and having prevented nosocomial infection; Comprise the textile that health care facilities is provided the fiber of the cationic form that has mixed copper coated; Wherein said textile can effectively make the antibiotic resistance strain inactivation of antibacterial, but release Cu when contacting with fluid has not been mixed in instruction or prompting yet in the document +Ion, Cu ++The fiber of the water-insoluble copper compound of ion or its combination preparation contact body surface for use in prevention, reduce and remove wrinkle and the application in the fabric of more level and smooth and more strong skin surface is provided.
Therefore, none instruction or pointed out theme of the present invention in the above-mentioned open source literature.
In the method for the invention; The cation type of copper must the contact liq medium so that can make atomic dispersion go into medium; No matter said medium is as the acting perspire of the carrier of said atomic dispersion, still joins in fiber or the fabric so that promote the liquid or the surfactant of ion-transfer to handled skin surface.
Has the Cu of being selected from order to form the beauty treatment material that the present invention is used to prevent, reduce and remove wrinkle and more level and smooth and more strong skin surface are provided, can preferably to adopt +And Cu ++The fiber of ionic ion copper, and they are included in the substrate.In a kind of knitting substrate, said fiber can be with any other fiber fusion and by knitting or be woven into substrate.In the non-knitting structure, fiber can be blended into thin layer.Both of these case this, can preferably multilamellar be placed another layer top so that form pad.
According to the similar mode and combines hereinafter described moderate modification preparation to be used for the ion copper of the inventive method described in the description formerly of above-mentioned reference, and through on the substrate or the acquisition of the redox reaction in liquid separately.This production method is the plastics electroless plating coating that conduct is used to contain metal, the improvement of the technology of the printed circuit board (PCB) that particularly is made of plastics.For example, referring to Encyclopedia of Polymer Science and Engineering (Jacqueline I.Kroschwitz, editor), Wiley and Sons, 1987, vol.IX, pp 580-598.As the application in fiber or fabric or film, this method comprised for two steps.The first step is through making catalytic precious metal nucleation site be deposited in activation substrate on the substrate surface.This step is through at first immersing substrate low-oxidation-state Reducing agent cationic solution and then this substrate is immersed precious metal cation solution, preferred Pd++ cationic solution, most preferably acid PdCl 2Carry out in the solution.Low-oxidation-state cation is reduced into noble metal self with precious metal cation, is oxidized to higher oxidation state simultaneously.Preferred Reducing agent cation is a soluble cation under initial low-oxidation-state and final high oxidation state, and for example, Sn++ is oxidized to Sn++++, or Ti+++ is oxidized to Ti++++.
In second step, close to coming the reducing metal cation with activatory substrate, it reduces by precious metal catalyst.The cationic Reducing agent that is used to reduce is generally molecular species, for example, with regard to Cu++, is formaldehyde.Because Reducing agent is oxidized, so metal cation is called " oxidant cations " in this article.The substrate of consequent plating is characterised in that its coat of metal directly combines with substrate.
Based on said method, the person trained in a certain field who knows this area can also be according to its color identification oxidant state.When substrate being swum in the copper solution so that reduce as stated, on every side of substrate, obtained various colors.The upside of substrate is glossiness bright copper (red/Huang) color, and this is the characteristic of elemental copper-Cu.The downside of fabric is a black, and this is the characteristic of CuO.Any substrate that is positioned at top substrate below also above that side show degree of blackness.
In said method, this method is changed so that with the different cation types of copper but not elemental copper or copper oxide (CuO-black) plated fiber cellulose fiber or substrate.
The form of this electroless plating coating process is included on the surface for preparing on fabric or the substrate from such as copper sulfate or this type of the copper nitrate copper solution cationic form of native copper also.Must be at first the fiber of treating coating or substrate be immersed in the solution that contains at least a Reducing agent cation type with at least two kinds of positive oxidation state, immerse at least a cation type then in the solution than low state at least two kinds of positive oxidation state.Then fiber or substrate immersion are contained in the solution of at least a precious metal cation kind, produce activatory surface thus.
Make at least a oxidant cations kind in the fiber contact medium then, the surface of described medium contact activation.Add Reducing agent then and copper is reduced to himself on the fiber surface from solution.Owing to there is not following change, so the fiber or the substrate that use this scheme to produce show the elemental copper coating on fiber, under the fiber that described fiber is arranged in fiber or substrate crowd's top and black is positioned at and be dispersed throughout fiber or substrate crowd.
As stated, in order to obtain to be effective to prevent, to reduce and remove wrinkle and more level and smooth and more strong skin surface is provided, must obtain the cation type of copper.The active compound of copper must contain Cu (I) or Cu (II) kind or they both.On cellulose, necessary Using P d+ is so that for example make all fibres have equisaturation simultaneously through immersion and extruding in order to ensure these kinds.If big groups of fibers is immersed Pd++ solution, the first batch of fiber that contacts this solution so can partially absorb more Pd++ solution than other of groups of fibers, and this can disturb cation copper deposition.In addition, washing the fibre between first process of Sn++ that must be in comprising water and second process of Pd++.The residual Sn++ solution that is retained between the fiber can cause Pd++ directly to be reduced into the solution between the fiber, and only can go back the Pd++ on the fibril at random, thereby influences the deposition of copper once more.Although these 2 seem maybe be very small, they have direct influence to coating.
In addition, the change of administration system that is used for the copper solution of said process is absolutely necessary.The ill effect of reduction process is to generate hydrogen on the fiber.This hydrogen occurs as the bubble on the fiber surface.The formation of hydrogen is Pd++ results of interaction on copper solution and the fiber surface.If not when forming at once through known method own, such as extruding from fiber surface except that dehydrogenation, the fiber of ingress of air will coated elemental copper so.These just are positioned at the copper oxide that the subsurface fiber of elemental copper can become black.Yet,, will all obtain required cation type in the groups of fibers so if when the bubble formation of hydrogen, remove it at once.Required color is a brown, and this color or cupric oxide with the copper metal is different.The extra indication of cation type is that fiber is non-conductive.
This method has produced Cu (I) and Cu (II) the kind ingredient as the copper oxide chemical compound.What the analysis of the residual cupric oxide powder that forms through this method was confirmed to form from the teeth outwards is the copper oxide chemical compound of 70%Cu (I) and 30%Cu (II).Verified these chemical compounds are very effective to treatment skin ulcer, scratch and burn.The activity of copper has been utilized the redox reaction of cation type and water and when contact with water, can between Cu (II) and Cu (I), have been changed.Cu (I) is more effective to HIV than Cu (II), and Cu (II) is more stable than Cu (I).
In being equivalent to the U.S. Patent application US 10/339886 of PCT/IL03/00230, to have described and asked for protection and be used to make the virally inactivated device that comprises filtering material, described device has wherein mixed and has been selected from Cu +And Cu ++The ion copper of ion and combination thereof, also that the document is relevant instruction is introduced this paper as a reference.
In this description, described and used the cellulose fibre coating that on said fiber surface, forms the copper solution of copper oxide, wherein method therefor has produced Cu (I) and Cu (II) the kind ingredient as the copper oxide molecule.Then described fiber is mixed filter, find that it can effectively make the HIV-1 inactivation.
Although do not understand the mechanism of hydrophilic polymer material of the present invention as yet fully; But according to the result who obtains; Think when making this polymeric material contacting with fluid water-bearing media; Described medium can leach the cation type of copper in the said polymer, and described in PCT/IL03/00230, antiviral activity has utilized the redox reaction of this cation type and water and when contact with water, can between Cu (II) and Cu (I), change.Cu (I) is more effective than Cu (II), and Cu (II) is more stable than Cu (I).Cu (II) compound oxidation is must be more than Cu (I) chemical compound more slow and can increase shelf life of product.
As stated, discovery of the present invention is to have mixed and when contacting with fluid, discharges Cu +Ion, Cu ++The material of the water-insoluble copper compound of ion or its combination unexpectedly effectively prevents, reduces and remove wrinkle and more level and smooth and more strong skin surface is provided, thereby can produce all new line products of the present invention.
Where no matter keep it in mind the fabric body contact, described product all can be strengthened better skin appearance, is the description of some product and final application scheme thereof below:
By the polymer of handling or cellulose yarn are thread can daytime or night and any the same socks knitting of dressing of other socks, it can make foot seem more fresh and alive.
2. the reduced wrinkle that can in sleep, dress and the knitted glove that improves the hand skin flexibility.
3. facial film that improves facial skin and the eye cover that can in sleep, wear.
4. the nightwear of processing by knitting or knit goods that improves whole skin that can dress at night.
By cellulose or polymer fiber process can daytime or wear night improve the knitting of skin of neck outward appearance or braiding scarf.
6. can place on the specific pockmark to improve the elastic bandage of skin texture on this pockmark.
7. no matter the braiding or the knitted underwear of can be by day or dressing night and can improve the skin texture of the health specific region that it contacts be underwears, underwear, or medicated bra.
8. bed linen and nightwear: they are by Cotton Gossypii/polyester or the textile form processed based on the fabric of Cotton Gossypii; Wherein the yarn of certain percentage (can between 3%-10%, change) is a cellulose processed, or wherein yarn fibers is the polymer of silk or staple fiber form.Goods can be knitting, such as plasticity wadding or socks, maybe can be knit goods, such as head covering or other clothes product.
9. cervical region is used sheath: they are preferably processed by new respirable polymer, and described polymer can use the water-insoluble cationic oxidation copper of introducing pressing method to produce these polymer through their wickings and dispersion moisture.
Although in conjunction with some preferred embodiment and the following example and illustrate and describe the present invention, make and more completely to understand and to understand its aspect, and do not mean that and limit the invention to these specific embodiments.On the contrary, as what can comprise in the scope of the invention like the claim definition of awaiting the reply, should comprise all selections, modification and equivalent technical solutions.Therefore; The following example that comprises preferred embodiment is used to explain enforcement of the present invention; Specific embodiments shown in should understanding only as an example and purpose be to explain discussion to the preferred embodiment of the invention, and provide their reason to be to think that it is the most useful and be used to understand the description to goods operating procedure and the principle of the invention and design aspect.
Description of drawings:
Accompanying drawing 1a and accompanying drawing 1b are for using the photo of the foot part of patient heel of getting before and after the socks of the present invention in like hereinafter embodiment 3;
Accompanying drawing 2a and accompanying drawing 2b are the photo at two handss of described in hereinafter embodiment 3, dressing the volunteer who gets a pair of gloves of the present invention front and back;
Accompanying drawing 3 can be breathed the electron micrograph of thin film for polypropylene; Described thin film prepares through the following step: the water-insoluble copper oxide with 1% is introduced masterbatch; After this cast film; Thereby form the particulate thin film of microcosmic water-insoluble of ionic oxide formation copper, wherein directly be embedded with the said granule that part exposes and give prominence to from its surface with powder type; And on its electron micrograph, be shown as white point;
Accompanying drawing 4 is the electron micrograph of polyester fiber; Described fiber prepares through the following step: the water-insoluble copper oxide with 1% is introduced masterbatch; After this extruded fibers; Thereby form the particulate fiber of microcosmic water-insoluble of ionic oxide formation copper, wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, and on its electron micrograph, be shown as white point with powder type.
Accompanying drawing 5 is the sketch map of following up a case by regular visits in 9 days of relevant erythema.
Accompanying drawing 6 is the sketch map of following up a case by regular visits in 36 days of relevant erythema.
Accompanying drawing 7 is the sketch map of treatment in relevant ichthyotic 9 days.
Accompanying drawing 8 is relevant ichthyotic sketch map of following up a case by regular visits in 36 days.
Accompanying drawing 9 is the sketch map of following up a case by regular visits in 9 days of relevant be full of cracks.
Accompanying drawing 10 is the sketch map of following up a case by regular visits in 39 days of relevant be full of cracks.
Accompanying drawing 11 for the use listed according to the pillowcase of the present invention's preparation table to the observed result of women's wrinkle.
Embodiment 1 is by cellulose processed fiber production fabric
First.Select cellulose fibre to be used for required final application.In fiber, can use such as Tencel or acetas or viscose or this fibrid of raw cotton.Must be noted that fiber is necessary for based on cellulosic, initial binding fiber because coating uses OH from the teeth outwards.The fibre length of selecting is for the final function of using and be the common knowledge in the industry (promptly with regard to combing Cotton Gossypii etc., with long staple fiber and the fiber mixing with equal length).
Second.Make fiber through various chemical methodes as described herein:
1. the fiber that is prepared in the thin pad deposits to guarantee correct cation type.
2. will fill up and immerse stannum dichloride and hydrochloric acid solution.This pad dipping short period is absorbed so that guarantee fully.
3. dummy block and remove nearly all liquid and use water washing then is so that guarantee to remove all solution of tin.
4. then pad is placed the extremely dilute solution of palladium chloride and hydrochloric acid.Although can other slaine be used for this method, find that palladium is the most effective.
5. after from palladium chloride, taking out, washing and dummy block are to guarantee to remove all external liquid once more.At this moment, this spacer changes into cervine color.
6. use copper sulfate, Polyethylene Glycol and EDTA to prepare the copper-bath of chelating.Through sodium hydroxide being added to the pH of control solution in this solution.In copper-bath, add Reducing agent.Although can use many Reducing agents, formaldehyde is elected to be preferred chemical compound.
7. pad is put into this solution and make its experience can reach the technology of absorption in 7 minutes.In the coating process, must push or pat this pad downwards.
Then with this pad of water washing so that remove excessive dust and make its drying.
9. when this method finishes, have for fiber coating and described fiber with the ionic species of copper and mixed dark-coloured dark-brown.
10. with fiber and other fiber (identical untreated or other fiber) fusion, so that end-product only contains the fiber of the copper oxide coating of aequum.In some situation, other fiber of 1% admixture/99% is required, and in other situation, preparation as many as 30% fibre treated/70% other fiber or combination arbitrarily.Can carry out this process according to being the known several kinds of modes of the technical staff who knows yarn fabric yarn field.
11. make blended fiber through all normal textile processes, promptly with regard to the opening textile product: carded, sliver, weaving.
12. it is in case obtained yarn, just can be knitting or weave it according to required final application.
13. fabric can be used as or can be colored or print use subsequently, but can not bleached, because this can cause copper self from cellulosic substrate, to separate.
14. yarn fabric is easy to be converted to required product subsequently.
Embodiment 2: the polymeric material by handling prepares fabric or thin film:
Embodiment 2a: the preparation of fiber
A1. the selective polymer material is used for required final application.Such as this fibrids such as polyester, polypropylene, polyethylene, nylon 66 is operable fiber.Fiber can form thread form or short staple fiber form.
A2. use with the identical host material of required yarn that adds cupric oxide powder and prepare masterbatch.With regard to the final application of most of fabric, masterbatch can have the cupric oxide powder of the 20%-25% concentration that is included in wherein.Can join in the polymer of treating extrusion molding this masterbatch and dilution, so that only about 1% or 2% material is present in the finished product yarn.A certain amount of this copper appears on the polymeric fiber surface and can in electron microscope image, observe.
A3. be filamentary fibers like fruit fiber, so can be knitting or be woven into textile with it.
A4. behave like fruit fiber and make short fiber, so can with its with other fiber just serving as that the mode of the above-mentioned coated fiber of mixing is mixed and deferred to identical production process then.
In case A5. yarn forms, just can be with it knitting or be woven into textile, this product be deferred to normal and acceptable system and is carried out the conversion of finished product.
Embodiment 2b: the preparation of thin film or sheath
B1. select to be used for the polymeric material of required final application.Such as this fibrids such as polyester, polypropylene, polyethylene, nylon 66, nylon 6 is operable fiber.Described polymeric material can form thin film or sheath.
B2. use with the required polymer phase that adds cupric oxide powder host material together and prepare masterbatch.With regard to the final application of major part, masterbatch can have the cupric oxide powder that accounts for 1-3% concentration therein.Can this masterbatch be joined in the polymer of treating extrusion molding.A certain amount of this copper appears on thin polymer film or the jacket surface and can in electron microscope image, observe.
The preparation of embodiment 2C-fiber
Amount to the polyamide pair-component cpd of 500 grams through two kinds of beading chemical substances preparations of heating in each comfortable 160 ℃ of independent bath down.
Then two kinds of independent compositions are mixed with each other and it was stirred 15 minutes, become evenly up to the color of this mixture.
Once more blended chemicals branch is gone into independent two jars.In a jar, add 25 gram CuO and Cu 2The mixture of O powder obtains 1% mixture.In second jar, add the CuO and the Cu of 6.25 grams 2The O mixture obtains 0.25% mixture.In two kinds of situation, keep 160 ℃ temperature.Stir these chemical compounds, even up to their color change.
Make two kinds of mixture through being with foraminous spinning head, described hole can produce the fiber that diameter is the 50-70 micron.Be lower than 20 microns granule owing to the cupric oxide powder that will discharge Cu++ grinds to form, block so observe the hole of spinning head.The fiber of extrusion molding is carried out air cooling and centers on the cone spinning.
The gained nylon fiber that has wherein mixed the copper oxide that discharges Cu++ can use in many application of the present invention, comprises binder, and diabetes are used socks, suffers from glove or the socks of eczema or psoriatic patient or its hands or sufficient usefulness etc.
As what it will be appreciated by those skilled in the art that; The conventional method and the difference between this method of producing any synthetic fibers have been in raw material, to add the cupric oxide powder that discharges Cu++; And, can exchange this base polymer of use such as polyester, nylon and polypropylene to many application of the present invention.
Embodiment 3: the regeneration of sufficient heel area:
With regard to accompanying drawing 1a and 1b, can observe the sufficient heel of volunteer front and back and the photo of plantar region, wherein in accompanying drawing 1a, can observe described zone and corrugate and patch.Polyester socks of the present invention were dressed 6 days, and these polyester socks have 1% and mix the Cu of its toes bottom and sufficient heel area +And Cu ++The fiber of insoluble copper oxide chemical compound.When the said time limit finishes, obtain like observed another photo in accompanying drawing 1b, and as viewed, skin is more strong, soft, patch is less, and does not almost have wrinkle, but on the black-and-white photograph of accompanying drawing, be not easy to observe.
Embodiment 4: the minimizing of dorsal surface wrinkle:
With regard to accompanying drawing 2a, can be observed the photo of volunteer's two handss.Described volunteer only wears cotton system glove of the present invention subsequently on its left hand, continue the time limit and about every night 10 hours at 3 nights.Described glove are processed by 97% Cotton Gossypii and are comprised 3% cellulose fibre of the present invention, have applied Cu on the wherein said fiber +And Cu ++Insoluble copper oxide chemical compound.Shown in accompanying drawing 2b, only after 3 days, the left hand of user is the more level and smooth and obvious much less of wrinkle just.
Embodiment 5: clinical trial:
The Board Certified Neurologist Dr.Michael S.Smith that request has master's degree uses experimental statistics analysis use to mix release Cu +And Cu ++The socks of one fritter textile of ionic water-insoluble copper compound are to various brothers' diseases, the i.e. effectiveness of erythema, ichthyosis, be full of cracks, abnormal smells from the patient and edema.Notice and write down other indication, such as pruritus and burn, herpes and drain, but these do not belong to cosmetic problem.
Studied one group of patient; And result and brothers doctor are compared patient's with the socks treatment of the present invention of not using of similar disease experience.
The result:
Think that following result all has statistical significance, promptly have reliable medical evidence to show to use socks treatment of the present invention during follow-up investigation effectively because all results' confidence interval does not comprise 0 and all results' p-value＜0.001.
Demographic:
In all 56 patients, 17 is the women, and 39 is the male.The mean age of this group is 58 years old, and standard deviation is 16 years old (scope 21-85 year).21 (21) is diabetes, and 21 ages surpass 65 years old, and subsequently 24 are carried out following up a case by regular visits to more than 1 time.
Variable:
7 kinds of measured values have been studied: erythema, burn and pruritus, edema, ichthyosis, herpes, be full of cracks, drain and abnormal smells from the patient.Only ichthyosis is present among all 56 patients, wherein has erythema (referring to table) in 51.Edema (6), abnormal smells from the patient (5) and drain (3) are least common variable." long term follow-up meant used the socks post-evaluation once more than.The used order grade that has three kinds of levels: exist, improve and disappear.Thinking moves forward along this grade (from " existences " to " improvements " or the past two kinds of situation to " ") positive sign that disappears, thinks oppositely mobile (from " improvement " to " the negative sign of existence ").Disappear if recognize when a patient goes to a doctor after dressing socks first, should can be " identical " long term follow-up by scoring at the most by individuality so.Therefore, can think that " identical " is equal to " keeping improving ".Average length of time in the long-term stage is defined as the time between the date of following up a case by regular visits to for the first time when relevant this patient is estimated for the last time.Only there is the patient of particular problem in statistics when this research begins subsequently.Exhausted situation about not having is not exist the patient of particular problem a kind of situation to occur.In the situation of edema, abnormal smells from the patient and drain, sample size is too small and can't draw any conclusion, but, still the result is tabulated.
Embodiment 5A: erythema (51 patients)
A1. in the average 9 days time limit, all 51 patients improve; 22 (42%) disappear fully (4-28 days).95% confidence interval of disappearing is (0.29,0.58).Although this result means the percentage ratio (parameter) that we do not understand whole colony and disappear fully, we are very confident to think that it belongs in the interval of 29%-58%.Do not having general no patient's improvement under other treatment situation if we understand in advance in this time range, the result who obtains so has meaning very much; Promptly be not occurrent.
This experimental result is shown in Fig. 5.
A2. (22 patients) studies for a long period of time:
19 (86%) has been kept its improvement or has been disappeared, 95% C1 (0.65,0 97).3 patients (14%) do not keep improvement or return to " existence ", 95% C1 (0.03,0.34).Follow up a case by regular visits to average during be 36 days.Diabetics and surpass 65 years old patient improvement is all arranged in early days or for a long time.
This experimental result is shown in Fig. 6.
Embodiment 5B: ichthyosis (56 patients):
There are 55 (55) to improve (98%) in the B1.56 position, 5 disappear (9%), and 1 rest on identical.95% confidence interval of identical improvement is (0.90,1.00); Disappear and be (0.03,0.20).As far as effect, the p-value is all very meaningful.
This experimental result is shown in Fig. 7.
B2. (24 patients) studies for a long period of time:
21 (88%) has kept improving or disappearing, and 3 are recovered when average 34 days following up a case by regular visits to.95% confidence interval is (0.68,0.97), wherein p-value＜0.001.In addition, diabetics and middle-older patient all have improvement.
This experimental result is shown in Fig. 8.
Attention: follow up a case by regular visits to figure and have identical yardstick with the above-mentioned figure that helps comparison.
Embodiment 5C: be full of cracks (37 patients):
C1. all 37 patients improve; 15 (40%) disappear fully, and wherein average follow-up period is 10 days, 95% C1 (0.25,0.58).This is very significant.Shown in result such as the accompanying drawing 9.
C2. (17 patients) studies for a long period of time:
In average 39 days follow-up period, all 17 patients improve; 6 (35%) disappear fully, 95% C1 (0.14,0.62).Diabetics and middle-older patient are total to be improved.Shown in result such as the accompanying drawing 10.
Embodiment 5D: edema (6), drain (3) and abnormal smells from the patient (5):
3 patients with edema improve; 1 disappears.All 3 patients with drain improve; 2 disappear.Have among 5 patients of abnormal smells from the patient 3 improvement are arranged, wherein 2 disappear.Data have been summarized in the relevant table.In addition, word " deterioration " mean patient from " disappear " or " improvement " be back to " existence ".
Discuss:
The purpose of this research is to observe to be suffered from the socks whether sick patient of various brothers only have a fiber bale of the present invention through wearing and just can improve.A problem in the above-mentioned disease of treatment is to obtain and use the compliance of this treatment (special-purpose socks).Relevant issues are at suitable administering therapeutic (special-purpose socks) on the plantar surfaces of toe and between toe.
1. with regard to the purpose of these embodiment, the analysis of the data that provide is inferred as follows:
A. the patient is the rational representational sample of the patient colony of these diseases of existence.Still there is not the information of receiving with this deduction contradiction.There are male, women, old people, youngster, diabetics and ND.
B. the patient is independently of one another; Promptly being selected from one by one, body influences selecting another individual nothing.
C. the definition that improves and disappear is constant as far as every patient.
D. known sample size and suitably analyzing.
E. can the result be defined as and be divided into two.
The existence of these deductions can use binomial probability to distribute.
2. the matched group that does not have report; Yet the information of receiving thinks that brothers doctor thinks that any patient is only disappeared or improved through the socks of dressing customization is impossible in this search time scope.Owing to obtained this category information,, promptly existed medical evidence to think and use fiber bale treatment of the present invention effective in this follows up a case by regular visits to the time limit so think that all The above results have statistical significance.
Importantly understand the vocabulary that is used to describe this research:
-colony: the group that relevant hope is learned.In this case, colony is all patients with above-mentioned pedopathy.
-sample: the inferior group of colony.
-random sample: the Asia group of selection, wherein each member in the colony has the selection probability of definite non-zero.
-parameter, the DATA REASONING value of colony.
-statistics: the DATA REASONING value of sample.
-p-value: the concrete sample statistics that we can obtain is learned probability (or an above extremum), and condition is that invalid inferring (unaltered inferring) is correct.Study in the whole process at this, the p-value less than 0.001 mean obtain separately these results at random probability in 1000 less than 1.Generally speaking, think have 1 to be " cut-off point in 20.Minitab software can't be calculated to 4 decimal digits with the p-value, obtain thus here numerous in addition less.
The confidence interval contains the seemingly reasonable value of the certain limit that is useful on parameter.We are called the confidence interval with it, although because unknown, parameter exists really, and the interval is contained or do not contain this parameter.It is not a probability problem.With regard to this research, if inferring in the time bar that uses conventional therapy research, we do not have the patient to improve, as long as the interval does not contain 0, the result just has meaning so, is 0 because do not have like reasonable value in the parameter.Improve if infer some other ratio, think that so any interval that does not contain occurrence has meaning.In this research, owing to obtained above-mentioned information, so All Ranges has all reached statistical significance.
Cycle of inference: we take a sample from colony, obtain result's (statistics) and use this value to infer about some situation as the parameter of colony's ingredient.
Importantly recognize all members that can identify hardly in the colony, its DATA REASONING value, parameter are still unknown thus.With regard to this research,, be used to represent the similar colony ratio that also can improve so ratio is improved the sample results of (or disappearing) because we can not learn all members in the colony.If sample is selected suitably, estimated value has value so.Certainly, we must recognize that other samples can produce other result, thus, as stated, have the seemingly reasonable value that sample has of can thinking of certain limit, and our sample are one of those possible values.
Conclusion:
Owing to compared the medical history contrast, use with having mixed as discharging Cu according to the present invention +And Cu ++The patient of the socks of the fritter textile of ionic water-insoluble copper compound exists in scenario and significantly improves or disappear:
Erythema
Be full of cracks
Ichthyosis
Abnormal smells from the patient
In addition; (in 51 19) be diabetes or the patient above 65 years old (10 diabetes and above 65 years old) because nearly 40% in the group; So this research as far as all above-mentioned situation of the people that suffers from diabetes improve or disappear aspect have statistical significance, comprise the middle and elderly diabetic patient.
As known, erythema is characterised in that the skin rubefaction that causes because of blood capillary swelling and hyperemia and is generally inflammation or the sign of infection, and is that beauty treatment is paid close attention to thus.
Ichthyosis is a cosmetic problem when its psoriasis with microorganism property is relevant, cosmetic problem that the product that it can the application of the invention improves and yes.
Edema for observable swelling on some position in vivo and modal be to occur in foot and shank, wherein also relate to peripheral edema.Swelling is that excess fluid is accumulated in spatial result in the outside tissue of subcutaneous blood vessel, and uses method of the present invention and product can promote its alleviation.
Be full of cracks is common cracking on the skin, and wherein it is connected with mucosa, produces crack appearance skin ulcer or ulcer, and this also is can be according to the cosmetic problem of the present invention's processing.
Abnormal smells from the patient is the main cosmetic problem that can use product of the present invention and method processing.
Embodiment 6: pillowcase is studied the effect of facial wrinkles:
Ten seven (17) women of regular use skin treatment product are given to discharge Cu when the contacting with fluid by having mixed +Ion, Cu ++The pillowcase that the fabric of the fiber of ion or its combination constitutes, and request is before test using every night when finishing according to the 1st week after the pillowcase sleep of the present invention's preparation, is taken pictures to them when the 4th week finished when the 2nd week finished and in addition.When the 8th week finished, the request candidate was made a phone call and is notified the receiver the relevant information of improving or worsening that on the skin overall appearance, whether exists.The request candidate does not use any ight oil or white, washes one's face and only get into sleep in night.The purpose of estimating is only to observe the effect of pillowcase to the foot of the bird on the face, fine wrinkle and microgroove.Observational technique is taken pictures at the night of nature for using the 3.4psi digital camera.
The indication candidate is facial when sleep to keep in touch with the pillowcase side.The person washs pillowcase once weekly at all situations.The indication candidate washes one's face with their normally used identical soap before sleeping, but does not use any oil or freshener.
The age of all candidates is all in 45-60 year.There is not 1 candidate to make medicament.Having 2 people in the known candidate at least is the smoker.
With regard to the purpose of this test, the request dermatologist observes whether there is any possible side effect.Do not observe side effect and confirmed the biocompatibility test that carries out in advance.Ask 1 group of 10 different women to use following value to estimate photo:
1. " A " on the subordinate list is labeled as not have and improves.
2. " B " on the subordinate list is labeled as slight improvement.
3. " C " on the subordinate list is labeled as improvement.
4. " D " on the subordinate list is labeled as remarkable improvement.
The name of 17 candidates can obtain in independent file and on the relevant with it figure as accompanying drawing 11, be expressed as numeral 1～17.In independent file, obtain 10 judgement persons' name.
Shown in accompanying drawing 11; As can be independently observed results of judgement person record from these, the analysis that face is carried out in time shows that bird foot wrinkle, the minimizing of microgroove and the piebald shape hyperpigmentation in some situation totally significantly improve (liver spots).In all situations, skin appearance and texture totally improve.
The obvious the present invention of those skilled in the art is not limited to the particular content of above-mentioned exemplary embodiments; And can be with other concrete form embodiment of the present invention under the situation that does not break away from spirit of the present invention; And need think that embodiment of the present invention and embodiment are exemplary in all respects thus and not play the qualification effect; Benchmark is with reference to the claim that awaits the reply, but not foregoing description, and belong to claim equivalents and scope change and include therein thus.

Claims (28)

1. when contacting with fluid, discharge Cu +Ion, Cu ++The water-insoluble copper compound of ion or its combination at preparation contact body surface so that reduce and remove the application in the material of wrinkle.
2. the particulate polymeric material of microcosmic water-insoluble that has the ionic oxide formation copper of powder type is used for reducing and removes wrinkle and the application of the material of more level and smooth and more strong skin surface is provided in preparation; Described granule directly is embedded in the polymeric material; The center is divided described granule to expose and is outstanding from its surface, and these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
3. claim 1 or 2 application, wherein said material is the fabric with the fiber that has mixed the water-insoluble copper compound.
4. the application of claim 2; Wherein said material is the particulate thin polymer film of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
5. the application of claim 2; Wherein said material is the particulate polymer fiber of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
6. the application of claim 1; Wherein said material is the particulate polymer filament of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
7. the application of claim 1; Wherein said material is the particulate polymer jacket of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination.
8. claim 1 or 2 application are wherein mixed pillowcase with described material.
9. claim 1 or 2 application are wherein mixed sheet with described material.
10. claim 1 or 2 application, wherein said material mixes part facial film at least.
11. the application of claim 1 or 2 is wherein mixed scarf with described material.
12. the application of claim 1 or 2 is wherein mixed the tubular overwrap that removably is arranged in the user cervical region with described material.
13. the application of claim 1 or 2 wherein is incorporated in the elongation panel that adheres to that scalable centers on the user body part that is used for that has disposed interlock on its opposite end with described material.
14. the application of claim 1 or 2; The polymeric material of wherein said material for constituting by component of polymer; Described component of polymer is selected from polyamide, polyester, acrylic acid and gathers olefin(e), and described material is the form of fiber, yarn, sheath, silk or sheet.
15. the application of claim 1 or 2, wherein said material are fabric or cast film, silk or sheath.
16. the application of claim 1 or 2, wherein said material is used to prepare pillowcase.
17. the application of claim 14 has applied said copper compound on the wherein said fiber.
18. the application of claim 1 or 2, wherein said material is used to prepare nightwear.
19. the application of claim 1 or 2, wherein said material is used to prepare glove.
20. the application of claim 1 or 2, wherein said material is used to prepare sheath.
21. the application of claim 1 or 2, wherein said material are used to prepare part facial film at least.
22. the application of claim 14, wherein said fiber are used to be prepared in the elongation panel that adheres to that scalable centers on the user body part that is used for that has disposed interlock on its opposite end.
23. the application of claim 1 or 2, wherein said material is used to prepare socks.
24. the application of claim 1 or 2, wherein said material is used to prepare the towelling material.
25. the application of claim 1; Wherein said material is the particulate thin polymer film of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination, wherein said thin film has the ability through the infiltration dispersing liquid.
26. the application of claim 1 or 2; Wherein said material is the particulate thin polymer film of microcosmic water-insoluble with ionic oxide formation copper of powder type; Wherein directly be embedded with the said granule that part exposes and give prominence to from its surface, these granules discharge Cu when contacting with fluid +Ion, Cu ++Ion or its combination spreads all over the micropore that runs through so that excessive liquid is discharged on the wherein said thin film.
27. the application of claim 1 or 2, wherein said material are hydrophilic polymer material.
28. the application of claim 1 or 2, wherein said material are hydrophobic polymer material.
CN2005800448021A 2004-11-09 2005-11-09 Method and material for protecting skin Active CN101087631B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
IL165,118 2004-11-09
IL16511804A IL165118A0 (en) 2004-11-09 2004-11-09 Methods and materials for skin care
IL171,852 2005-11-09
IL17185205A IL171852A (en) 2005-11-09 2005-11-09 Cosmetic methods and materials for skin care
PCT/IL2005/001171 WO2006051529A1 (en) 2004-11-09 2005-11-09 Methods and materials for skin care

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CN101087631A CN101087631A (en) 2007-12-12
CN101087631B true CN101087631B (en) 2012-04-25

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ZA (1) ZA200703711B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2624806B1 (en) * 2010-10-04 2017-06-21 Cupron Inc. Cosmetic skin care compositions comprising insoluble copper oxide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
US 2004/105894 A1,权利要求12，实施例7.

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CN101087631A (en) 2007-12-12
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