CN101680117A - Production and use of laminated nanofibrous structures - Google Patents

Production and use of laminated nanofibrous structures Download PDF

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Publication number
CN101680117A
CN101680117A CN200880016104.4A CN200880016104A CN101680117A CN 101680117 A CN101680117 A CN 101680117A CN 200880016104 A CN200880016104 A CN 200880016104A CN 101680117 A CN101680117 A CN 101680117A
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CN
China
Prior art keywords
outlet
receiving plane
fiber
distance
nanofibrous structures
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Granted
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CN200880016104.4A
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Chinese (zh)
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CN101680117B (en
Inventor
P·韦斯特布鲁克
T·范坎普
S·德弗利茨
K·德克莱克
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Universiteit Gent
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Universiteit Gent
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Priority claimed from EP20070009995 external-priority patent/EP1967617A1/en
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Publication of CN101680117B publication Critical patent/CN101680117B/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D7/00—Collecting the newly-spun products
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00—Other non-woven fabrics
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

An electrospinning device is described for producing fibrous porous structures. The device is adapted for providing a predetermined distance profile for the distance between outlets of the electrospinning device and the receiving surface. The latter may be obtained by geometrically adapting the electrospinning device or by moving the outlets with respect to the receiving surface during growth of the fibrous structure. A fibrous structure obtained by the described electrospinning device is also described which comprises fibres, wherein the diameter of the fibres has a predetermined profile along a dimension of the electrospun fibrous structure. Furthermore application of the laminated structure for wound dressing and teeth bleaching is discussed.

Description

The production of laminated nanofibrous structures and purposes
TECHNICAL FIELD OF THE INVENTION
The present invention relates to fibre structure, make the method and apparatus of this fibre structure.Particularly, the present invention relates to method and system, products obtained therefrom (such as nanofibrous structures) and their purposes of static weaving (electrospin) fibre structure.The invention still further relates to art of wound dressings.More specifically, the present invention relates near the method and system of the amount of liquid of control surface, for example in art of wound dressings.The invention still further relates to the dental applications field.More specifically, the application relates to method, product and the system in whitening teeth field.
Background of invention
Nanofibrous structures is used for the multiple application in clothes, filtration, medical science and national defence field.High porosity according to nanofibrous structures can be used for absorbing, fixes and comprises chemicals, solvent, solution, melt and liquid mutually, and nanofibrous structures receives great concern.In many preferred high fields that absorb, the about 5mL.cm of preferred acquisition -2Absorptive capacity.In identical field, preferred big nanofibrous structures.For the absorbent properties that guarantees total is identical, thickness is useful to make total have clocklike.And the application need of nanofibrous structures aspect filtration has high contamination capacity, the multi-level strong construction of filtering, hanging down cutoff and limited pressure drop.Nanostructured can use the static Weaving device to produce.Show a kind of basic equipment among Fig. 1, it is made up of high voltage source 1 and analgesia pump (anaesthesia pump) 2, this pump comprises a syringe 3, this syringe contains polymer solution 4, this pump transports this polymer solution at the tip of metal needle 5, described metal needle is arranged in spinning head 6, and described spinning head 6 comprises that one is gone up conductive plate 7 and a lower conducting plate 8.Between upper plate and lower plate, apply electric field, cause the polymer solution of needle tip to extrude towards the surface of the element of below.The electric field that produces makes polymer solution overcome the cohesive force that polymer solution is kept together.Electric field is that polymer solution droplets sprays, and forms the fiber of nano-scale, finally is collected on the plate of below to the result of cohesive force adjustment.The stock size of the structure of deposition is that diameter is about arc surface of 10 to 15cm.Therefore, when using the single injector system, can not obtain the high surface area of many application needs with economically feasible method.
In US 2002/0175449, the equipment and the method that are used for static textile polymer fiber are disclosed.This method comprises by regulating the electric-field intensity at the most advanced and sophisticated place of electric charge control spinning head on the change electric field electrode, so that the fiber of controlled diameter is provided.By changing electrostatic potential, change the injection stream acceleration, cause changing the diameter of the nanofiber of shaping.This electrostatic potential changes and changes injection stream stability, and therefore, the corresponding variation can be used for stablizing new injection stream in the combination electrode.Distance between two adjacent spinning heads can change so that optimize electric field, that is, the electric field of single spinning head can not influenced each other.
A concrete application of nanofibrous structures is the wound dressing device.Wound dressing can be applied to multiple wound type, such as otch, tear, fray, stab, perforating wound, burn.
Originally synthetic wound dressing uses dressing of gauze base or paste bandage (such as zinc thickener bandage) to make.Modern wound dressing design often comprises important properties, preserves moisture and antibacterial functions such as having to preserve moisture with moisture absorbing or have.Under the situation of burn, the wound fluid of handling the wound generation is a subject matter especially.Being often used in the technology of handling this class wound is that wound is kept dry, and cures better because this can help to reduce to infect and help.Yet an investigation discloses, and for special wound, it is more favourable making wound fluid remain on wound circumference.Reason is to have been found that to have important molecule and the co-factor that relates in the Wound healing process in the diffusate.
Several wound dressing designs are disclosed and can buy from the market.A kind of wound dressing of specific category is to use the material of static weaving.US 4,878, and 908 disclose a kind of example of wound dressing design, and it has the textiles liner, there is the material cushion that is covered with the static weaving on adhesive surface, the absorbent material pad at the edge.Yet still there is improved space in this wound dressing design.
In one aspect, the present invention relates to the dental bleaching field.For dental bleaching, two main kinds of known attractive in appearanceization application are application of implementing in the dentistry clinic and the application that (for example in consumer family or in any suitable place) implements beyond the dentistry clinic.In these schemes some need repeatedly be visited the dentistry clinic.
Some schemes about the application that can implement outside the dentistry clinic relate to the use carriage, and this carriage is made into mouth and the tooth that is fit to the user, and but they are made in the dentistry clinic can use at home.Because cost, this class device may need usually to reuse and must be very firm so that allow repetitive operation, clean, add and fill, install, remove etc.
People provide lower cost solution, wherein adopt single system that size is fit to all users of planting.Because these systems often can not mate with tooth is perfect, so often increase the consumption of bleaching agent.On the other hand, this type systematic also has the problem that bleaching agent leaks into gum and randomly swallowed.
The US2005/0196352A1 of P﹠G discloses a kind of method of bleaching tooth, and wherein, this method comprises to a plurality of adjacent teeth and applies the dental bleaching delivery system.This dental bleaching delivery system comprises strip material and has the dental bleaching composition of peroxide active component.This method comprises that the first with strip material is applied on the front of tooth, around the second portion of the folding strip material of the incisxal edge of a plurality of adjacent teeth, the second portion of folding strip material with the incisxal edge that covers adjacent teeth so that apply this second portion to the lingual surface of tooth.
Summary of the invention
An object of the present invention is to provide the inventive arrangement or the method for producd fibers (for example nanofiber) structure.An advantage of embodiments of the present invention is, the method and apparatus that can obtain to comprise the fibre structure of fiber and produce this fibre structure, and wherein, the diameter of described fiber changes along with the dimension of static textile fabric structure, for example reduces.An advantage of embodiments of the present invention is, the method and system that produces the nanofibrous structures with robust construction is provided, and so-called robust construction seldom or not decomposes in promptly using, the nanofibrous structures of distortion or layering.An advantage of embodiments of the present invention is that the method and system that produces firm, porous and/or reproducible nanofibrous structures is provided.And an advantage of embodiments of the present invention is, fibre structure with good liquid absorption capacity and their production method are provided.Another advantage of embodiments of the present invention is, fibre structure with good control releasability and filtering property and their production method are provided.An advantage of embodiments of the present invention is to provide fibre structure with economically feasible method.An advantage of embodiments of the present invention is, can obtain to have the fibre structure of the combination of two or more above-mentioned advantages.An advantage of embodiments of the present invention is to make layer structure.An advantage of embodiments of the present invention is, adopts to move different nozzles relative to receiver and can obtain good overlapping.
Can realize above purpose by method and apparatus of the present invention.
The present invention relates to the static Weaving device of producd fibers structure, described static Weaving device comprises the outlet of one group of output solution or melt, acceptance is from the receiving plane of the output of described one group of outlet, wherein, described receiving plane is designed to move along the first direction parallel with described receiving plane, described vertical production of moving responsible described fibre structure, between described one group of outlet and described receiving plane, produce the voltage source of electrical potential difference, be characterised in that in the tool, described static Weaving device is designed so that in the production process of described fibre structure, there is the outlet of equipment in the static fabrication processes and accepts the curvilinear motion that the distance basis between the face is scheduled to, so that obtain the fiber thickness profile of predetermined fibre structure outside.This variation according to predetermined curve can obtain by predetermined distance Curve, this distance be outlet with receiving plane between the edge are distances perpendicular to the direction of receiving plane, for different outlets along described first direction.Should predetermined distance Curve can be distance Curve that increases or the distance Curve that reduces.Should predetermined distance Curve can be dull distance Curve that increases or the dull distance Curve that reduces.An advantage of embodiments of the present invention is, the equipment that allows to produce the fibre structure that comprises fiber is provided, wherein, the diameter of described fiber is along the dimension (dimension) of described static textile fabric structure and reduce, and, in the arbitrary portion vertical with described dimension, the localized variation of fibre diameter is lower than predetermined level, for example is lower than 10%.In embodiments of the present invention, the diameter of described fiber reduces along a dimension dullness of described static textile fabric structure.In other embodiment of the present invention, the diameter of fiber is according to the dimension variation of predetermined fibre diameter curve along static textile fabric structure.For example, the diameter of described fiber along a dimension of described static textile fabric structure monotonously, reduce continuously.
In embodiments of the present invention, described one group of outlet comprises the subgroup outlet, each outlet of described subgroup outlet is by forming with the equidistant outlet of described receiving plane, and the distance between each subgroup and the receiving plane changes according to vertical growing direction of predetermined distance Curve along fibre structure.An advantage of embodiments of the present invention is, can produce the layer structure that comprises two or more adjacent layers, wherein, each layer with two adjacent layers be by fibrous, and the average diameter of this fiber is less than the average diameter of the fiber of an one adjacent layer, greater than the average diameter of the fiber of its another adjacent layer.
In embodiments of the present invention, outlet group can be included at a certain angle with respect in the receiving plane plane inclined.This is favourable, because it allows to produce the fibre structure that comprises fiber, wherein, the diameter of described fiber reduces continuously along a dimension of fibre structure.
According to the embodiment of the present invention, the variable in distance of nozzle and receiver appears in the static fabrication processes, before the variable in distance in the randomly described process and this process and/or variable in distance afterwards combined.
In embodiments of the present invention, the distance of 1cm is at least separated at least two of described outlet group adjacent outlets mutually.An advantage of embodiments of the present invention is that the equipment that can produce the fibre structure with high porosity is provided.At least two adjacent outlets of described outlet group separate the distance of 1cm at least.Particularly advantageously, two adjacent outlets separate distance, the highly beneficial ground of 4cm at least, and two adjacent outlets separate the distance of 8cm at least.Two outlets of described outlet group can be separated from each other the distance of 1cm at least separately, advantageously separate at least 4cm, more advantageously separate the distance of 6cm at least.In other words, the distance that has at least an outlet (for example nozzle) to leave another nearest outlet is 1cm at least, 4cm at least advantageously, more advantageously 6cm at least.Great majority or all described outlets can separate the distance of 1cm at least with other outlet, advantageously separate at least 4cm, more advantageously separate the distance of 6cm at least.An advantage of embodiments of the present invention is to provide and can produce equipment firm, that have the fibre structure of high porosity and fibers straight.As an optional feature, outlet (for example pin) is arranged in triangular arrangement or multiple arrangement.
In embodiments of the present invention, the distance between the outlet can be designed to obtain to comprise at least 50% basically not with the fibre structure of the crosslinked fiber of adjacent fiber.An advantage of embodiments of the present invention is that the equipment that can produce the fibre structure that only has low-level cross filament is provided.
In embodiments of the present invention, the distance between the outlet can be designed to can obtain to comprise the fibre structure of at least 50% fibers straight.
Described equipment can comprise control device, is used for changing significantly in the static fabrication processes diameter of the fiber that produces.
In embodiments of the present invention, the device of diameter that is used for changing the fiber of generation can be or to change the control device of the distance between described first plane and the described receiving plane in addition in the production process of fibre structure.As an optional feature, the lower part is designed to and can vertically mutually moves with top.
In embodiments of the present invention, equipment can be designed to produce a plurality of fibers, and wherein, at least 50% fiber has 3 to 2000nm average diameter in described a plurality of fibers.
In embodiments of the present invention, equipment can be designed to use polymer solution or the melt that comprises at least a following material: polyamide, polystyrene, polycaprolactone, polyacrylonitrile, poly(ethylene oxide), PLA, polyacrylic acid, polyesteramide, polyvinyl alcohol, polyimides, polyurethane, PVP, polyethylene vinyl acetate ester-vinyl alcohol, collagen, cellulose, shitosan, methacrylate, silk or metal.
The invention still further relates to the method for producd fibers structure, said method comprising the steps of: one group of outlet that is used to export solution or melt is provided, the receiving plane of acceptance from the output of described outlet group is provided, described receiving plane is moved at the first direction parallel with described receiving plane, between described outlet group and described receiving plane, apply electrical potential difference, move and apply in the electrical potential difference process described, provide solution or melt to described outlet, wherein, providing to outlet in the process of solution or melt, outlet and the distance of accepting between the face change according to predetermined curve, so that obtain predetermined fiber thickness profile.The existence of this predetermined curve be by along the direction of fibre structure longitudinal growth, outlet along and receiving plane between caused that in variation perhaps actual the relatively moving of organizing relative receiving plane by outlet causes perpendicular to the distance on the direction of receiving plane.Should predetermined distance Curve can be the distance Curve that increases or reduce, for example dull increasing be stuck with paste the dull distance Curve that reduces.At least two adjacent outlets of described two or more outlets can separate the distance of 1cm at least, advantageously separate at least 4cm, more advantageously separate the distance of 6cm at least.Two outlets of described outlet group can separate the distance of 1cm at least separately with another outlet, advantageously separate at least 4cm, more advantageously separate the distance of 6cm at least.
Can be randomly reach variable in distance between outlet and the receiving plane by in the production process of fibre structure, adjusting distance between described adjacent outlet and the described receiving plane.
This distance can be adjusted by relatively moving between described outlet group and the described receiving plane is provided.
As a favourable optional feature, this method can also comprise along being parallel to described receiving plane and moving the outlet and/or the described receiving plane of at least one described outlet group perpendicular to the direction of described first direction mutually.
Method can be designed to produce a plurality of fibers, and wherein, at least 50% of described a plurality of fibers have 3 to 2000nm average diameter.
Method can be designed to use polymer solution or the melt that comprises at least a following material: polyamide, polystyrene, polycaprolactone, polyacrylonitrile, poly(ethylene oxide), PLA, polyacrylic acid, polyesteramide, polyvinyl alcohol, polyimides, polyurethane, PVP, polyethylene vinyl acetate ester-vinyl alcohol, collagen, cellulose, shitosan, methacrylate, silk or metal.
As an optional feature, can between outlet group and receiving plane, apply the electrical potential difference of 100V to 200000V.
As another optional feature, the polymer solution of each outlet or the pump rate of melt can be 0.01 to 500ml.h -1
As an optional feature, solution or melt can contain other compound, such as antibiotic, medicinal, hydrophobic/hydrophilic, etch-proof, catalysis, oxidation/compound reduction and other character.
The invention still further relates to the static textile fabric structure that use is produced according to the method for the embodiment of the invention described above.
The invention still further relates to the static textile fabric structure that comprises fiber, wherein, the diameter of described fiber is according to predetermined fibre diameter curve, along a dimension variation of described static textile fabric structure, and wherein, described fibre diameter any perpendicular to the variation on the direction of described dimension less than 10%.
In embodiments of the present invention, structure comprises at least 50% fibers straight, wherein, at least 50% fibers straight by 50% or be included on the 5 μ m distances more be the fibrous of straight part basically.
Static textile fabric structure can comprise at least 50% basically not with the crosslinked fiber of adjacent fiber.
The fibre structure of static weaving can comprise at least 50% random orientation fiber.
The fibre structure of static weaving can have at least 60% porosity.
Its fiber 50% or have 3 to 2000nm more, preferably be equal to or greater than 10nm, preferably be equal to or less than the average diameter of 700nm.
The invention still further relates to the fibre structure of the static weaving that comprises two or more layers, wherein, each described layer is different from average diameter fibrous of the fiber of adjacent layer by average diameter.
In embodiments of the present invention, fibre structure comprises two or more adjacent layers, and wherein, each layer with two adjacent layers is by fibrous, this fiber has the average diameter of preliminary dimension, and this diameter can be greater than or less than the average diameter of the fiber of its adjacent layer.In some embodiments, the average diameter of fiber can be less than the average diameter of the fiber of an one adjacent layer and greater than the average diameter of the fiber of its another adjacent layer.For example, diameter can be used as the function of the degree of depth and reduces, and increases as the function of the degree of depth, reduces earlier afterwards to increase as the function of the degree of depth, increases earlier as the function of the degree of depth afterwards to reduce etc.
Another purpose of embodiments of the present invention provides near the good devices or the method for the liquid (for example diffusate) the control wound.An advantage of embodiments of the present invention is, amount that can controlling liquid and flowing.An advantage of embodiments of the present invention is to absorb controlled quatity, the optional liquid measure of oozing out in a large number.An advantage of embodiments of the present invention is, the contact surface by the wound dressing device can reach the transfer that good control fluid left and/or arrived wound.This transfer can surpass the zone to the contact surface that is different from wound or wound dressing.An advantage of embodiments of the present invention is that the control that can reach fluid discharges, and for example reaches the control release of fluid in a side opposite with the contact-making surface of wound dressing device.An advantage of embodiment is, when using the embodiment of ad hoc structure, but the wound fluid can be absorbed and remains on wound circumference, even is discharged in the wound again.An advantage of embodiments of the present invention is that the wound dressing device can be controlled the amount of the diffusate that leaves wound, so that there is the diffusate of controlled quatity near wound.
Realize above purpose by the method and apparatus of embodiments of the present invention.
The present invention relates to be used to control near the wound dressing device of the fluid of wound, this wound dressing device comprises the nanofibrous structures that comprises a plurality of fibers, wherein, described nanofibrous structures comprises the contact surface that contacts wound, the fibre diameter of nanofibrous structures changes on the direction perpendicular to contact surface, so as control from wound absorption fluids and/or release fluids to wound.An advantage of embodiments of the present invention is to reach the effect that controlling liquid absorbs.An advantage of embodiments of the present invention is to realize a large amount of liquid-absorbent.An advantage of embodiment is, can absorb the liquid of controlled quatity, can discharge absorbed liquid at the opposite side of dressing or absorbed liquid is discharged back wound.
The wound dressing device can comprise in the centre position perpendicular to the direction of contact-making surface and has following character fiber, promptly the diameter of the fiber in this centre position less than the diameter of the fiber on the contact-making surface and less than with the contact-making surface opposed surface on the diameter of fiber.An advantage is can obtain to absorb liquid and/or discharge the predetermined curve of liquid to wound from wound.
Surface from contact-making surface to the nanofibrous structures opposite with contact-making surface, the diameter of fiber can reduce.An advantage of embodiments of the present invention is can set up from contact-making surface to another surperficial hydrodynamic and shift.An advantage of embodiments of the present invention is that wound (can be regarded as the liquid release surface) can keep dry basically.As an alternative or additional means, the liquid of controlled quatity can remain near wound or the wound, and this may be favourable to healing process.An advantage of embodiments of the present invention is, with the contact-making surface opposite surfaces on can obtain the most effective evaporation properties because the there has the highest specific area.Therefore, opposite with contact-making surface one side can be used as the liquid emission surface.As an alternative or additional means, can also realize that returning control to wound discharges.
The diameter of fiber can also be followed another kind of relation, such as beginning to reduce from contact-making surface, reaches minimum at the center of structure, begins to increase to the nanofibrous structures surface opposite with contact-making surface from this center always.Adopt this class formation to extract fluid and release of fluid is returned wound from wound.This causes the fluid balance in the wound, a kind of situation that helps the Wound healing process that is described as recently.
Nanofibrous structures can be to comprise the two-layer at least laminar nano fibre structure with nanofiber of different-diameter.
The wound dressing device can comprise the intermediate layer of at least one nanofiber, and between other nanofiber layer of wound dressing device, thus, this at least one intermediate layer can comprise the nanofiber of diameter less than the diameter of the fiber in other layer.
Nanofibrous structures can be the static weaving.An advantage of embodiments of the present invention is, can make the wound dressing device in mode efficiently.
Nanofibrous structures can have 65 to 99%, preferred 70 to 98,75 to 95% mean porosities more preferably.An advantage of embodiments of the present invention is to obtain high absorptive capacity.Liquid absorption capacity can be 1 to 25g/1g polymer, advantageously 10 to 25g/1g polymer.
And nanofibrous structures can comprise the compound that forms gel.An advantage of embodiments of the present invention is, the absorptive capacity of wound dressing device even can be increased to the liquid-absorbent of maximum 70g/1g polymer.
The coating that the compound of formation gel can be used as on the single nanofiber provides.The compound that forms gel can be by being provided in nanofiber in the wound dressing device by the static weaving.
Nanofibrous structures can comprise the part of at least one aperture less than 150nm, so that as stopping the barrier of bacterium.An advantage of embodiments of the present invention is, because the hole dimension in the nanofibrous structures is basically less than the stock size of bacterium, so can obtain the wound bacterial barriers.
Nanofiber layer can comprise liquid transportation barrier at least a portion nanofiber layer of contact-making surface one side, this liquid transportation barrier prevents that liquid side direction on contact-making surface from flowing.Lateral flow means flowing of any direction in the contact-making surface plane.An advantage of embodiments of the present invention is that the cross infection between the adjacent wound can reduce, because can reduce, slow down even prevent liquid flowing from a wound to another wound.Liquid transportation barrier can be designed to contact-making surface with nanofibrous structures and be distributed in a plurality of little, independent, nanofiber districts of separating, so that prevent near the liquid flow between the adjacent area contact-making surface.Liquid transportation barrier can comprise the nanofiber and/or the coherent nanofiber of fusing.Liquid transportation barrier can be on perpendicular to the direction of contact-making surface the extension degree of depth only.An advantage of embodiments of the present invention is, at first, can reach and suppress the effect that diffusate flows to adjacent wound area, secondly, can help effective evaporation providing the part of moisture content to sprawl with the contact-making surface opposition side, the 3rd, diffusate is remained in the nanofibrous structures discharge back in the wound with after being used for, process is needed if this is Wound healing.
Nanofiber layer can also comprise liquid transportation barrier, is used for making liquid to remain on nanofibrous structures so that be discharged in the wound later on.
And nanofibrous structures can comprise the nanofiber that contains pasteurization material, and described nanofiber is arranged near the position the wound dressing device contact-making surface.The nanofiber that contains pasteurization material can be soluble after nanofibrous structures absorbs liquid, produces the sterilization and the antimicrobial and/or bactericidal property of equipment.An advantage of embodiments of the present invention is that antibiotic and/or bactericidal property may reside in the wound dressing device, does not need to use independent product to produce antibiotic and/or bactericidal property.
The nanofiber that comprises pasteurization material can comprise
Figure G2008800161044D00101
Nanofiber.
Figure G2008800161044D00102
Fiber can obtain by the static PVP-I solution of weaving.
The wound dressing device can absorb 1 to 25g liquid/1g nanofibrous structures, and wherein density of liquid is 1kg/L.
The wound dressing device can have 3 to 25 times, preferred 4 to 25 times, more preferably 5 to 25 times to the liquid absorption capacity of own wt, and wherein density of liquid is about 1kg/L.
Equipment can be suitable for burn wound dressing or big wound dressing, and nanofibrous structures has at least 30cm * 30cm, preferred 40cm * 40cm, the contact-making surface of 50cm * 50cm more preferably.Perhaps, equipment can be fit to very little wound, has less than 2cm * 2cm or even less than the size of 5mm * 5mm.Nanofibrous structures can have the thickness of 50 μ m to 5000 μ m.
The wound dressing device can cut into Any shape by hand or with the machine that uses machinery, heat or induced with laser cutting.
Nanofibrous structures can be installed on the substrate with bond property, so that adhere on the skin of wound circumference.
At least 30%, advantageously at least 50% nanofiber of nanofibrous structures can have 3 to 2000nm average diameter.
Nanofibrous structures can comprise at least 50% fibers straight, and wherein, these fibers have part straight basically on the distance of 5 μ m at least.
Nanofibrous structures can comprise the fiber of at least 50% random orientation.
The invention still further relates to and use aforesaid wound dressing device to be used for the wound wrapping.
And, the present invention relates to be used for the method for wound wrapping, this method comprises the nanofibrous structures that obtains to have the contact-making surface that is used to contact wound, wherein, the diameter of fiber on perpendicular to the direction of contact surface according to predetermined curvilinear motion, by contact wound location nanofibrous structures, make described nanofibrous structures be in predetermined direction.
An advantage of embodiments of the present invention is, can be by the wound dressing device, promptly by nanofibrous structures transportation oxygen.This helps to improve Wound healing.
Another object of the present invention provides good method and the system that is used for whitening teeth, is also referred to as dental bleaching.An advantage of embodiments of the present invention is that method and system can be sent dental bleaching agent part or its component exactly.An advantage of embodiments of the present invention is that the method and system that allows small leaks or do not leak into periodontal mouth zone is provided.An advantage of embodiments of the present invention is can provide to canine tooth and send dental bleaching agent part or its component.An advantage of embodiments of the present invention is, provides and/or to be fixed on system on user's tooth with the equipment stable position.An advantage of embodiments of the present invention is, provide the component of bleaching agent part still less or still less the specific nature of bleaching agent part be used for equipment is fixed on (component that does not for example need the fixing teeth bleaching agent part) method and system on the tooth.An advantage of embodiments of the present invention is, provides to use low viscosity dental bleaching agent, more effectively method for whitening and system.
An advantage of embodiments of the present invention is that the equipment that provides the good fit while can cover canine tooth can be provided.An advantage of embodiments of the present invention is, can be with smooth and/or mode whitening teeth uniformly.An advantage of embodiments of the present invention is, can with accurately and basically uniformly mode brighten row's front tooth, comprise canine tooth.An advantage of embodiments of the present invention is also can cover canine cusp and therefore can brighten canine cusp.An advantage of embodiments of the present invention is can realize transporting the brightener for tooth part well by equipment.Therefore, an advantage of embodiments of the present invention is, can avoid the broken line in the fibre structure, but still obtain good coupling, can keep the collapsed shape on the tooth in the equipment use.Can avoid suppressing the transportation of dental bleaching agent part or its component owing to the existence of broken line.An advantage of embodiments of the present invention is the possibility that the fibre structure in the equipment provides the well-formed to mate.
An advantage of embodiments of the present invention is that the fibre structure of equipment can allow the water infiltration, therefore helps the absorption of brightener for tooth part.
An advantage of embodiments of the present invention is that fibre structure can have the fibre diameter that changes as the function of the degree of depth in the fibre structure, so that the release profiles of control dental bleaching agent part.
An advantage of embodiments of the present invention is that the method and system of permission is provided.
Can realize above purpose by method and apparatus of the present invention.
The present invention relates to be used for the dental whitening systems of whitening teeth, this dental whitening systems comprises dental whitening part nanofibrous structures and that comprise bleaching agent.An advantage of embodiments of the present invention is that method and system can be sent dental bleaching agent part or its component exactly.An advantage of embodiments of the present invention is that the method and system that allows small leaks or do not leak into periodontal mouth zone is provided.Use an advantage of nanofibrous structures to be, system can adapt to tooth and keep matched well with tooth.
Dental whitening part can have 10 centipoise to 1000 centipoises, advantageously 10 centipoise to 400 centipoises, the viscosity of 10 centipoise to 199 centipoises more advantageously.An advantage of embodiments of the present invention is, can provide the dental whitening part can have method and system than low viscosity (because absorption of fluids and releasing properties of nanofibrous structures).An advantage of embodiments of the present invention is, the low viscosity gel can be used for dental whitening to be used, wherein, this gel since nanofibrous structures can be retained in the system.An advantage of embodiments of the present invention is, limit, reduce or even avoided from structure, spilling, for example drain to the gums of mouth or the risk on the palate.
The dental whitening part can be a tooth whitening gel, and wherein, tooth whitening gel can also comprise the material that forms gel.An advantage of embodiments of the present invention is the generation of using gel to reduce or prevent to leak.This can increase user's comfort level.For example, this can cause the stimulation that reduces around teeth part mouth.
The concentration that forms the material of gel can be lower than 0.1 weight % of dental whitening part, for example is lower than 0.09 weight % of dental whitening part.
The material that forms gel can comprise carboxymethyl cellulose, carboxy-propyl cellulose, natural gum, poloxamer or carboxyl polyethylene.An advantage of embodiments of the present invention is can use the material of the formation gel of low concentration, because the viscosity of bleaching agent part is because the existence of nanofibrous structures can be lower.
The nanofibrous structures of system can be designed to mate row's front tooth.An advantage of embodiments of the present invention is that nanofibrous structures can be designed so that it can be compressed on one group of tooth.
The nanofibrous structures of system can be designed to mate front tooth and canine tooth, comprises the tip of canine tooth.Front tooth is four front teeth on mouth top or four front teeth of mouth bottom.An advantage of embodiments of the present invention is, can also bleach the canine tooth adjacent with front tooth, because these canine teeth often have more yellow, bleach these canine teeth simultaneously and will cause the color of canine tooth and front tooth more even, so that between canine tooth and front tooth, produce little contrast.
Nanofibrous structures can be compressed to the thickness of 100nm to 10mm.An advantage of embodiments of the present invention is, by use can with the compressible nanofibrous structures of tooth coupling, can accomplish to be fit to front tooth and canine tooth.An advantage of embodiments of the present invention is, equipment or at least its fibre structure can be extruded on the tooth so that by this equipment of extruding or its fibre structure at least, equipment or at least its fibre structure take the shape of tooth.
Nanofibrous structures can have 1 μ m to 5000 μ m, the thickness of 1 μ m to 2000 μ m advantageously.
The structure of nanofibrous structures can be designed to the adhesive effect of energy inducible system at dental surface.An advantage of embodiments of the present invention is that for having adhesive effect at dental surface, we do not propose other component or character requirement to the dental whitening part.
Nanofibrous structures can have 65 to 99%, preferred 70 to 98,75 to 95% mean porosities more preferably.An advantage of embodiments of the present invention is that the designed porosity of nanofibrous structures becomes can produce this class adhesive effect.
System can be designed so that to be fixed on the front side of tooth, the dorsal part that the use second portion is fixed on tooth with first.
The porosity of nanofibrous structures can change on its cross section, is suitable for the controlled transportation of bleaching agent to tooth.
The porosity of nanofibrous structures can have predetermined change curve on its cross section, be suitable for the predetermined release profiles of bleaching agent to tooth.An advantage of embodiments of the present invention is, can provide the control of bleaching agent to discharge, and helps to obtain in processing procedure effect of uniform.
The porosity of nanofibrous structures can increase from a side a to side that will contact dental surface of contact substrate layer.
Nanofibrous structures can be to comprise the two-layer at least laminar nano fibre structure with nanofiber of different-diameter.
Dental whitening systems can comprise that substrate layer, this substrate layer of being used to support nanofibrous structures are that water is impermeable and water-fast basically.An advantage of embodiments of the present invention is that substrate can make system mate tooth better.An advantage of embodiments of the present invention is, substrate can provide and prevent that bleaching agent part from leaking into the barrier on gum district for example and/or the tongue.
Nanofibrous structures comprises and contains the fiber that pH sets agent.An advantage of embodiments of the present invention is that before using or before preparation is for the system that uses, setting agent to small part pH can keep separating with bleaching agent.This is favourable, because it can in use increase the efficient of bleaching agent or it can increase the life of product of system.Another advantage of embodiments of the present invention is that pH setting agent can be included in the nanofibrous structures, avoids needing to store separately other component before using.
The brightener for tooth part can comprise pH and set agent.
PH sets agent can comprise any in NaOH, hydrogen chloride, sodium phosphate, sodium bicarbonate, sodium stannate, citric acid or the natrium citricum or their combination.
It can be 0.1 weight % to 10 weight % that pH in the part sets agent content.
The concentration of bleaching agent can be 0.1 to 25 weight % of dental whitening part, advantageously 0.5 to 10 weight %, 1 to the 7 weight % of dental whitening part more advantageously of dental whitening part.
Bleaching agent can comprise peroxide or produce any in the compound of peroxide or their combination.Peroxide can be for example hydrogen peroxide or calper calcium peroxide.The compound that produces peroxide can be a percarbonate, such as carbamide peroxide, perborate or peroxy acid.Advantageously spendable bleaching agent is hydrogen peroxide or carbamide peroxide or their mixture.An advantage of hydrogen peroxide is that it has high efficiency.
The dental whitening part can also comprise filling compound.
Filling compound can comprise one or more in glycerine, D-sorbite, polyethylene glycol or the propylene glycol.
Nanofibrous structures at least 30%, preferred at least 50% nanofiber can have 3 to 2000nm average diameter.
Nanofibrous structures can comprise at least 50% fibers straight, and wherein, these fibers have part straight basically on the distance of at least 5 μ m.
Nanofibrous structures can comprise the fiber of at least 50% random orientation.
Nanofibrous structures can be the nanofibrous structures of static weaving.
5 to 14 days the time interim frequency with 1 day 2 times in 2 to 30 minutes to the tooth application system after, can be obtained up to few 1 and the dental whitening benefit (based on the vita color standards) of maximum 14 colourities.An advantage of embodiments of the present invention is that good whitening effect is provided.
Dental whitening systems can be to make nanofibrous structures and dental bleaching partly keep the kit that separates in the storage process that is designed to before use.
This kit can also comprise the pallet that is used for when bringing into use dental whitening systems nanofibrous structures being immersed in the dental bleaching part.
Nanofibrous structures can comprise the fiber of being made by polyamide, and this polyamide uses the mixture of formic acid and acetate, weaves by static and make.The ratio of formic acid and acetate can be 90/10 to 10/90 (weight %), preferred 30/70 to 70/30 (weight %), 40/60 to 60/40 (weight %) more preferably.It can be 50/50 weight percent.
The invention still further relates to aforesaid dental whitening systems and be used for dental bleaching.
The invention still further relates to nanofibrous structures, this nanofibrous structures is designed to the dental whitening field.
Nanofibrous structures can be designed to mate row's front tooth.
The nanofibrous structures of system can be designed to mate front tooth and canine tooth, comprises the tip of canine tooth.
Nanofibrous structures can be compressed to the thickness of 100nm to 5mm.
Nanofibrous structures can have 1 μ m to 5000 μ m, the thickness of 1 μ m to 2000 μ m advantageously.
The structure of nanofibrous structures can be designed to the adhesive effect of energy generation system at dental surface.
Nanofibrous structures can have 65 to 99%, preferred 70 to 98,75 to 95% mean porosities more preferably.
System can be designed so that to be fixed on the front side of tooth, the dorsal part that the use second portion is fixed on tooth with first.
The porosity of nanofibrous structures can change on its cross section, is suitable for the controlled transportation of bleaching agent to tooth.
The porosity of nanofibrous structures can have predetermined change curve on its cross section, be suitable for the predetermined release profiles of bleaching agent to tooth.
The porosity of nanofibrous structures can increase from a side a to side that will contact dental surface of contact substrate layer.
Nanofibrous structures can be to comprise the two-layer at least laminar nano fibre structure with nanofiber of different-diameter.
Dental whitening systems can comprise that substrate layer, this substrate layer of being used to support nanofibrous structures are that water is impermeable and water-fast basically.
Nanofibrous structures can comprise and contain the fiber that pH sets agent.
PH sets agent can comprise any in NaOH, hydrogen chloride, sodium phosphate, sodium bicarbonate, sodium stannate, citric acid or the natrium citricum or their combination.
PH in the part sets 0.1 weight % to the 10 weight % that agent can be a part.
Nanofibrous structures can comprise the fiber of being made by polyamide, and this polyamide uses the mixture of formic acid and acetate, weaves by static and make.The ratio of formic acid and acetate can be 90/10 to 10/90 (weight %), preferred 30/70 to 70/30 (weight %), 40/60 to 60/40 (weight %) more preferably.It can be 50/50 weight percent.
The invention still further relates to aforesaid nanofibrous structures and be used for dental bleaching.
The invention still further relates to method for whitening, this method comprises nanofibrous structures is immersed in the dental whitening part, with preset time the nanofibrous structures of dipping is applied to tooth, removes nanofibrous structures afterwards.Dental whitening partly may reside in the original container, and this container can seal.The dental whitening part can be packaging together with nanofibrous structures.They can be packaged in the container, and the dental whitening part will be dumped into this container.This class packing can seal with plastic film or hardboard.In order to flood nanofibrous structures, can make nanofibrous structures be arranged in container, nanofibrous structures is facing to the dental whitening part.
This method can also be included in the process of described dipping nanofibrous structures provides described pH regulator agent and the initial of described bleaching agent to contact.
This method can also be included in before the described dipping nanofibrous structures, provides the dental whitening part in the container that is fit to the dipping nanofibrous structures.
The invention still further relates to the method for producing nanofibrous structures, this method comprises the mixture static weaving nanofiber that uses formic acid and acetate.The ratio of formic acid and acetate can be 90/10 to 10/90 (weight %), preferred 30/70 to 70/30 (weight %), 40/60 to 60/40 (weight %) more preferably.It can be 50/50 weight percent.
In appended independence and dependent claims, narrated of the present invention concrete and preferably aspect.Feature from dependent claims can make up with the feature of suitable and independent claims that not only clearly narrate in the claims and the feature of other dependent claims.
Though the equipment in this field improve constantly, change and progress,, believe the present novel basically improvement of notion representative, comprise breaking away from previous way, cause providing more effective, stable and the equipment of this class character reliably.
Instruction of the present invention can be designed for the improved method and apparatus of the fibre structure of producing the character with raising.
From following specific descriptions, in conjunction with the accompanying drawings, above and other character of the present invention, feature and advantage will become very clear, accompanying drawing illustrates design of the present invention by way of example.This explanation only is to provide for example, does not limit the scope of the invention.The reference diagram of below quoting refers to accompanying drawing.
Brief Description Of Drawings
Fig. 1 is the schematic side view of prior art static Weaving device.
Fig. 2 is the perspective diagram of the static Weaving device of an embodiment of the invention.
Fig. 3 is the perspective diagram of the static Weaving device of another embodiment of the invention.
Fig. 4 is the perspective diagram of the static Weaving device of another embodiment of the invention.
Fig. 5 is the floor map of the location of the outlet used in the static Weaving device of embodiments of the present invention.
Fig. 6 is the floor map of the location of the outlet used in the static Weaving device of other embodiment of the present invention.
Fig. 7 shows an example of the obtainable laminar nano fibre structure of the method and system that uses embodiments of the present invention.
Fig. 8 shows an example of the nanofibrous structures with layer structure, and layered structure comprises that average diameter is the layer of 500nm, and this nanofibrous structures can use the method for an embodiment of the invention to obtain.
Fig. 9 illustrates another layer of the nanofibrous structures example of Fig. 8, and this layer has the average diameter of 300nm.
Figure 10 shows in the example of Fig. 8 the relation of distance between the nanofiber diameter and outlet and receiving plane, and it can be used for an embodiment of the invention.
Figure 11 illustrates an example of the nanofibrous structures with layer structure, and it is the 285nm fiber that a side of layered structure comprises average diameter, and this nanofibrous structures can use the method for an embodiment of the invention to obtain.
Figure 12 illustrates the opposite side of the nanofibrous structures example of Fig. 8, and this side has the average diameter of 180nm.
Figure 13 shows the curve of distance between outlet and the receiving plane and is used for the average nanofiber diameter of variable concentrations that this can be used for an embodiment of the invention on the one hand.
Figure 14 illustrates the fibre structure of each subgrade with different static weaving method preparations with Figure 16, wherein, hierarchy obtains after applying mechanical force, and Figure 15 illustrates the fibre structure according to an embodiment of the invention preparation, shows no layering after applying mechanical force.
Figure 17 is used in the schematic diagram of z direction continually varying fibre diameter according to the equipment of an embodiment of the invention production wound dressing device.
The wound dressing schematic representation of apparatus that Figure 18 is to use the equipment described in Figure 17 to obtain.
Figure 19 is according to an embodiment of the invention, is used to produce the schematic diagram of the alternate device of the wound dressing device with layer structure, and layered structure has the fibre diameter that changes on the z direction.
The wound dressing schematic representation of apparatus that Figure 20 is to use the equipment described in Figure 19 to obtain.
Figure 21 is a kind of wound dressing schematic representation of apparatus according to an embodiment of the invention, and this wound dressing device has the fluid transport barrier that is present on the nanofibrous structures full depth, is used for preventing that fluid from shifting in wound dressing device side direction.
Figure 22 is a kind of wound dressing schematic representation of apparatus according to an embodiment of the invention, and this wound dressing device has the fluid transport barrier that only is used on the nanofibrous structures segment thickness, is used for preventing that fluid from shifting in wound dressing device side direction.
Figure 23 is a kind of wound dressing schematic representation of apparatus, and this wound dressing device has littler fibre diameter in the centre position, and it can use the equipment described in Figure 17 to obtain.
Figure 24 is a kind of stratiform wound dressing schematic representation of apparatus, and this wound dressing device has littler fibre diameter in the centre position, and it can use the equipment described in Figure 19 to obtain.
Figure 25 shows the sketch map example that can be used for the nanofibrous structures of dental whitening systems according to an embodiment of the invention.
The specific descriptions of illustrated embodiment
We will illustrate the present invention with reference to concrete embodiment and some accompanying drawing, but the present invention is not subjected to their restriction, and will be only limited by the claims.Described accompanying drawing only is schematically and is nonrestrictive.In the accompanying drawings, some size of component may be exaggerated, and for purposes of illustration, do not draw in proportion.Size and relative size with relative of the present invention actual dwindle not corresponding.
And, illustrate and claims in the term first, second, third, etc. be used for temporarily, spatially, key element like graduation ground or other any way region class, be not that declaration order is necessary.Should be appreciated that so the term that uses is interchangeable under suitable situation, working of an invention mode as herein described can be different from as herein described or shown in other operation in tandem.
Should be noted that the term that uses in claims " comprises " should not be interpreted as being confined to hereinafter listed meaning, and it does not get rid of other element or step.Therefore, the existence or the adding of one or more further features, integral body, step or element or their group are not still got rid of in the existence that it should be interpreted as specifying described feature, integral body, step or be called element.Therefore, term " equipment that comprises device A and B " should be not limited to the equipment only be made up of element A and B.It means that about the present invention, unique relevant equipment component is A and B.
" embodiment " or " a kind of embodiment " that run through this explanation refers to be included at least one embodiment of the present invention about the described concrete feature of this embodiment, structure or character.Therefore, in this explanation the term of a plurality of positions " in one embodiment " or " in one embodiment " be not must be all (but can) refer to identical embodiment.And concrete feature, structure or character in one or more embodiment can make up in any suitable manner, and this is that those of ordinary skill in the art will understand from the disclosure.
Similarly, should be appreciated that various features of the present invention accumulates in single embodiment, figure or their description sometimes in explanation illustrative embodiments of the present invention, so that simplify the disclosure and help to understand one or more various inventive aspects.Yet this method of the present disclosure should not be construed as the such purpose of reflection, i.e. claimed invention need be than the more feature of clear narration in each claim.Yet claims reflected as following, and the aspect of invention is to be less than all features of single above disclosed embodiment.Therefore, during the claims after specifying clearly were included in view of the above and specify, each claim existed as independently embodiment of the present invention.
And, though more described herein embodiments comprise some is not the further feature that comprises in other embodiment, but the combination of features of different embodiments is intended to fall within the scope of the invention, and form different embodiments, this can be understood by those skilled in the art.For example, in following claims, can in any combination, use any claimed embodiment.
In explanation provided herein, many concrete details have been narrated.Yet, should be appreciated that implementing embodiments of the present invention can not have these details.In other cases, well-known method, structure and technology show no longer in detail, so that can not obscure understanding of this description.
It only is in order to help to understand the present invention that following term is provided.
Unless provide in addition, term " increase " is construed as the development of describing this parameter Chao Genggao value when being used for parameter, and described development randomly comprises plateau, has definite value in the described parameter of this state.
Unless provide in addition, term " reduces " to be construed as when being used for parameter describes this parameter towards the more development of low value, and described development randomly comprises plateau, has definite value in the described parameter of this state.
Unless provide in addition, term " increases " development that is construed as this parameter of description Chao Genggao value when being used for parameter continuously or monotonously, and described development does not comprise plateau, has definite value in the described parameter of described plateau.Unless provide in addition, term " reduces " to be construed as when being used for parameter continuously or monotonously describes this parameter towards the more development of low value, and described development does not comprise plateau, has definite value in the described parameter of described plateau.
Now, by describing several embodiments of the present invention in detail the present invention is described.Very clear, can be according to those skilled in the art's knowledge, do not break away from technology of the present invention and instruct and dispose other embodiment of the present invention, the present invention only is subjected to the restriction of the term of appended claims
Aspect first, the present invention relates to be used for the static Weaving device of producd fibers structure (such as nanofibrous structures).In an embodiment aspect first, the static Weaving device comprises the one group of outlet that is used to export solution or melt.Static Weaving device of the present invention is a multiinjector equipment, comprises that promptly two or more are used to export the equipment of the outlet of solution or melt (for example three or more outlets).These outlets are designed to export material, for example will be used for the solution or the melt material of producd fibers.For example, outlet can be nozzle, pin (such as metal needle), aperture or analog.In embodiments of the present invention, two or more outlets, for example three or more outlets are separated from each other 1cm at least, for example the distance of 4cm at least.For example, outlet can separate 1 to 100cm distance.By making outlet separate 1cm or farther, 4cm or farther advantageously, with respect to the fiber of gained under the less at interval situation, the fibre structure of gained of the present invention is firmer usually, porous and comprise more straight fiber more.Therefore distance evaporating solvent well causes the gained fibre structure to have high porosity between bigger outlet (for example pin).Be not bound by theory, this effect may be due in the moment of these fiber collectings a kind of fibre forming more completely process.Advantageously, the distance between two or more outlets is 4cm, more advantageously 6cm or bigger, 8cm at least more advantageously at least.Maximum spacing is arbitrarily, for example can be depending on someone and wishes the porosity that reaches.
For spacing between bigger outlet, the fiber that constitutes fibre structure may obtain 5 μ m or longer, 10 μ m or longer or even 20 μ m or longer straight line portion.Simultaneously or except this straight line portion, the most of fibers (promptly 50% or more) that constitute fibre structure are tending towards becoming no crosslinked, and are promptly not crosslinked with adjacent fiber.For example, most fiber does not have crosslinked with adjacent fiber basically at contact point.According to the embodiment of the present invention, acquisition comprises no crosslinked, the therefore fibre structure of interconnected fiber not, that is, wherein most of fibers, for example at least 50%, advantageously at least 70%, more advantageously at least 90% even more advantageously 95% fiber keeps independent.Therefore, no crosslinked can be less than 1 crosslinked/1mm fibre length, advantageously less than 1 crosslinked/5mm fibre length, more advantageously less than 1 crosslinked/1cm fibre length, more advantageously less than 1 crosslinked/5cm fibre length even more advantageously no crosslinked on whole fibre length.This effect is obvious especially for separating 4cm or farther outlet.Thus, the crosslinked covalent bond that can be defined as another polymer chain of polymer chain connecting a fiber and adjacent fiber.Weak physics interacts, and interacts or hydrogen bond does not belong to the scope of crosslinked definition such as Van der Waals force.
When 3 of uses or more a plurality of outlet, outlet (for example pin) advantageously is arranged to the triangle sets (see figure 5), between each outlet is that 1cm, maximum are 100cm apart from minimum, and more advantageously minimum is that 4cm, maximum are 100cm, and more advantageously minimum is that 6cm, maximum are 100cm.In embodiments of the present invention, use volatilization easily and/or easy Ionized solvent, the location of pin can be transformed into as shown in Figure 6.In Fig. 6, observe with identical shown in Fig. 5 the single location of pin, but for per two hand-manipulating of needle, remove the third line.In this case, single pin can not centered on by other pin in all sides simultaneously.This can make solvent easily form district's evaporation from fiber.The purpose of the pin arrangement shown in Fig. 6 is when using volatility or ionizing solvent, to avoid facilitating discharge.The sum of outlet is not limit maximum.For example, used outlet sum can be for example 3 to 20000 in the layout, for example 5 to 20000.Advantageously, the outlet of using in the layout (for example pin) sum is at least 3 to 500 (see figure 5)s.Different rows can be parallel such as the outlet of adjacent lines, but be subjected to displacement mutually with respect to outlet.This can assess about the mean direction that relatively moves of receiving plane.The layout of outlet can be so that outlet be arranged in leg-of-mutton outlet group.For example, different row can produce staggered outlet layout.Layout can be so that two adjacent row go out the flexuose outlet layout of interruption-forming.
Static Weaving device of the present invention also comprises receiving plane.Receiving plane can randomly apply with perforated or imperforated layer, for example, and polymers/plastics layer perforation or imperforated.Receiving plane can be the planar section on bigger surface, and not necessarily its all part all is flat.For example, receiving plane can be a part that comprises the bigger band of the part of wriggling.Liquid surface can be contained in this surface, and fiber laydown is on this liquid surface.Receiving plane is designed to accept from one group of two or more outlet, the outputs of three or more outlets advantageously.Receiving plane can be metallic plate, paper tinsel, fabric construction, liquid surface etc.Receiving plane can be taked any spatial orientation.For example, it can be a level, and the outlet group is positioned at the top of receiving plane, and perhaps receiving plane is above the outlet group.In these cases, outlet respectively down or up.For example, outlet (for example pin) is positioned at lower plane, and solution or melt (for example polymer solution or melt) ejecta moves to the equipment top.Dash receiver can also vertical orientation.It also is possible (for example being 45 ° or any other angle with level) certainly that dash receiver is taked other direction.The set of outlet (on the one hand) and receiving plane (on the other hand) is also referred to as spinning head.In receiving plane and the outlet group at least one is designed to be movably, promptly provides one or more relative motions between receiving plane and outlet group.In embodiments of the present invention, the direction of outlet group can be designed to move, can be parallel with receiving plane or vertical with receiving plane.The motion of outlet can also be to be parallel to receiving plane and perpendicular to the combination of the motion of receiving plane.In embodiments of the present invention, advantageously reciprocating motion of the motion of outlet, for example motion between two fixing points.This reciprocating motion is preferably parallel with receiving plane and perpendicular to the travel direction that is used for the fibre structure longitudinal growth.The motion of receiving plane can be parallel with described receiving plane, vertical with described receiving plane or the two combination.Advantageously, in embodiments of the present invention, receiving plane can move continuously in the direction parallel with described receiving plane.Advantageously, equipment is designed so that outlet group and receiving plane do relative motion, and this relative motion is for example to be parallel to the first direction of receiving plane and also to be parallel to receiving plane but to be different from the combination of relative motion of the second direction of first direction.For example, receiving plane can be designed to first direction angled, such as randomly doing relative motion being substantially perpendicular on the direction of described first direction.Described first and second directions are can be mutually vertical and be parallel to described receiving plane.Advantageously, outlet group and receiving plane can move relative to each other, so that the outlet group is by the first direction that is parallel to receiving plane (y direction for example, see Fig. 2) motion, for example reciprocally motion between two inversion points, receiving plane is pressed second direction (for example the x direction is seen Fig. 2), the still motion continuously in the plane of described receiving plane perpendicular to first direction.Such reciprocating motion of outlet is favourable, because it can make the output of outlet overlapping at receiving plane when different outlet receives the output of outlet.The output of an outlet can be called the fiber umbrella (fibre umbrellas) on the receiving plane when face that is received received.The fiber umbrella is owing to their electric charge has the tendency of very high mutual repulsion, if this kind layout is used fixed system, if promptly there is not at least a reciprocal relative motion between receiving plane and outlet group, the fiber umbrella can be easily not overlapping so.Can select the amount that does relatively reciprocating motion, make the output of adjacent outlet overlap at least.And, in this way, promptly use reciprocating motion can increase the width of gained fibre structure.The outlet group is advantageously with 0.1cm.s -1To 100cm.s -1Average speed, the direction that vertically increases along fibre structure do relatively reciprocating motion with respect to receiving plane.Other relative motion, preferred parallel outlet and continuous relative motion between the receiving plane on a direction of receiving plane can be produced bigger fibre structure surface area continuously.Aspect this, receiving plane advantageously can 10cm.h -1To 100cm.h -1Speed motion.
Static Weaving device of the present invention also comprise be adapted at exporting and receiving plane between apply the voltage source of electrical potential difference.Voltage source can be the high direct voltage voltage source, and it can apply at (promptly between outlet and the receiving plane) on the spinning head and be selected from 100 to 200000V electrical potential difference.For example, outlet (for example pin) can be in contact with one another by conduction (for example metal) plate or supporting structure electricity.In other embodiments, the semiconductive or non-conductive first material face (for example dull and stereotyped) or supporting structure can be used in combination with the device (such as metal wire) that is used to be electrically connected all outlet ports (for example pin).Voltage source can be with the conductive structure that comprises outlet or the device (for example metal wire) that is used to be electrically connected all outlet ports (for example pin) link to each other.The preferred ground connection of receiving plane.Randomly, it can earth-free (floating) use, but the preferred safety measure that is fit to that adopts.Perhaps, can also use second direct voltage source that receiving plane is set in a certain electromotive force.
Of the present invention one preferred embodiment in, voltage source can programme controlledly maybe can be set.The voltage that applies can be used as outlet (tip) to the function of receiver (receiving plane) distance and is regulated or control.This can manually or automatically operate.Can carry out optimization to the voltage that applies so that obtain steady state operation.
And system can be designed to accept the information about the polymer solution relevant parameter, and these polymer solution relevant parameters can influence the steady state operation of system, so that obtain to have the fiber of relatively-stationary fibre diameter.For example, the static textile department for example can be designed for accepting as the data input or by measuring the information that obtains, these information about the solvent of the concentration of the polymer that will be utilized, charge density, use or in the viscosity any one, they combination or they are whole.
The static Weaving device of embodiments of the present invention can also comprise at least one container, and being used to hold will be from the solution or the melt of described outlet static weaving.This container can contain polymer solution or melt.Perhaps, container can be in the outside of static Weaving device.
The static Weaving device of embodiments of the present invention advantageously also comprises the device that is used for providing to outlet solution or melt.Being used for providing the device of solution or melt to outlet can be any device known to those skilled in the art.Be used for providing the example of the device of solution or melt to include but not limited to pump or syringe etc. and conveyer (such as pipe) to outlet.
For example, can provide solution or melt (for example polymer solution or melt) to each outlet (for example pin) by single assembly (such as single peristaltic pump).In some embodiments, can use multichannel device (such as multi-channel peristaltic pump), wherein, each passage gives an independent outlet reinforced.Can also use a plurality of multichannel devices (for example pump), depend on that needs add the quantity of the outlet of polymer solution or melt.In other embodiments, analgesia pump can be used for giving outlet (for example pin) reinforced by syringe, and this syringe has been filled polymer solution or melt and has been positioned at analgesia pump.Perhaps, can use from the solution of center tank or melt and give outlet reinforced, this center tank remains under predetermined, for example constant pressure with pressure valve and/or compressed air.In some embodiments, a large amount of outlets (for example pin) can be passed through a source, and for example peristaltic pump or analgesia pump come feed.The solution of each outlet (for example pin) for example injection speed of polymer solution or melt can be 0.01 to 500ml.h -1
Can be used for solution of the present invention or melt is known any solution or the melt that is fit to form by the static weaving fiber of those skilled in the art.This solution or melt can derive from polymer.Suitable polymers includes but not limited to polyamide, polystyrene, polycaprolactone, polyacrylonitrile, poly(ethylene oxide), PLA, polyacrylic acid, polyesteramide, polyvinyl alcohol, polyimides, polyurethane, PVP, collagen, polyethylene vinyl acetate ester-vinyl alcohol, cellulose and Related product, shitosan, methacrylate, silk or their combination.Solution or melt can also comprise metallic particles or as the metal of the dissolving of metal ion, so that can form metallic fiber.
As an optional feature, solution or melt can contain other compound, such as antibiotic, medicinal, hydrophobic/hydrophilic, etch-proof, catalysis, oxidation/compound reduction and other character.
Static Weaving device of the present invention can also randomly comprise element on every side, promptly centers on the element of other element of static Weaving device.For example, element can form around the shell of spinning head and prevent the spinning head instability on every side, such as air agitation and/or allow solvent to recover.Advantageously, avoid in spinning head, taking place air agitation, because it can cause the unstable of melt or solution ejecta and the instability of the fiber umbrella that produced by these ejectas on receiving plane.For example, element can be made up of so that form shell the plate of interconnected non-conducting material on every side.
Static Weaving device of the present invention can also comprise temperature control equipment/system that one or more is optional.These temperature control equipments can be added into the static Weaving device, so that for example obtain higher reproducibility in fiber production.The fluctuation of temperature is influential to the evaporation rate of solvent, and is therefore, also influential to the porosity of the final size of fiber and structure.Therefore, temperature control finally is favourable.By using temperature controlled container (for example liquid bath, such as oil bath or water-bath), solution in the container or melt can be controlled temperature systems.Can also be in solution operating temperature control from the transportation that the pipe of container through adding cover extremely exports, the described pipe that adds cover directly or indirectly links to each other with cooling/heating systems (all temperature controlled containers as described).By use will heat/gas of cooling brings the device of spinning head into, can carry out temperature to spinning head and control.For example, can comprise can be in the temperature control system of the scope inner control temperature of 280-1500K for static Weaving device of the present invention.
The static Weaving device of embodiments of the present invention can be designed to can be at steady state operation.This can reach by artificial or self-regulating process parameter.Owing to changing jet expansion, can for example determine with experimental technique such as voltage to be applied, humidity or flow velocity to the variation of receiver apart from the technological parameter of the static weaving that produces.In principle, when change between jet expansion and the receiver apart from the time to optimize the voltage that applies be bigger advantage.Yet other parameter also can be regulated such as the flow velocity of starting material.Therefore, the static Weaving device can be designed to change other technological parameter, such as the flow velocity and/or the humidity of the material for the treatment of the static weaving.In order to regulate the flow velocity of the material for the treatment of the static weaving, for example, the static Weaving device can assemble controllable pump, is used to change the speed to the export supply material, and perhaps it can be reequiped with having the outlet with variable outlet opening degree that can set.In order to regulate humidity, the static Weaving device can assemble the system that is used for controlled humidity, such as drying device and/or humidifier.The adjusting of technological parameter can be according to predetermined rule, according to computation model, carry out based on the T﹠E experiment or with any other suitable manner.For example, can be optimized up to reaching stable state by regulating parameter.Stable state can be defined as the situation that taylor cone " Taylor cone " is constant and weaving is implemented in a continuous manner.Can detect this stable state from optics, for example with the naked eye or with optical detector observe, the adjustment of parameter can be carried out in mode artificial or automatic and/or automation.Wherein, taylor cone is the shape of drop of distortion, and it is by being present in the most advanced and sophisticated place of outlet, forming when applying high voltage that the drop of the suspension of taper causes.
Static Weaving device of the present invention is designed to be able in the production process of fibre structure in outlet (5, Fig. 1) and receiving plane (8, provide predetermined distance Curve Fig. 1), so that cause along the predetermined fibre diameter curve on the dimension of the fibre structure of static weaving.Can on the thickness dimension of the fibre structure that static is weaved, obtain predetermined fibre diameter curve.This can obtain to comprise the static textile structural of fiber, and wherein, the diameter of the fiber on the direction of the fibre structure of static weaving has predetermined curve.This can be favourable, because it can control some character of the fibre structure of static weaving on this direction.Predetermined distance Curve can still the invention is not restricted to this by making the distance between outlet (5) and the receiving plane (8) reduce or increase to obtain (outlet is along described first direction for difference) on the direction perpendicular to receiving plane.In one embodiment, Yu Ding distance Curve can by dullness reduce or increase export (5) and receiving plane (8) between distance obtain.This feature allows to obtain to comprise the static textile structural of fiber, and wherein, the diameter of described fiber reduces along a dimension of described static textile fabric structure, and for example dullness reduces.This can realize by the mode that substitutes multiple but that do not repel mutually, will be explained below.By the outlet group is moved relative to the other side with receiving plane, wherein at least one parts moves (seeing the first following embodiment that shows with reference to figure 2) along the direction perpendicular to receiving plane, or by outlet being placed the top of receiving plane according to a randomly fixing preset distance curve, can realize providing predetermined distance Curve between outlet (5) and the receiving plane (8) along vertical growing direction of fibre structure, for example (monotonously) reduce or increase distance.This also causes receiving plane different with the distance of first group of outlet and second group of outlet.For example in the fiber thickness curve that reduces or increase, outlet can be located by this way, and outlet farther on vertical growing direction of fibre structure is from receiving plane nearlyer (this will show with reference to figure 3 and 4).One significantly substitutes is to make outlet be positioned the top of receiving plane by this way, and outlet farther on vertical growing direction of fibre structure is also farther from receiving plane.As showing,, can accomplish this point by making the receiving plane and the distance of single outlet have difference and having difference by the distance between the different subgroups that make receiving plane and outlet.
Perhaps, receiving plane can move so that change distance or be in certain angle, so that obtain predetermined distance Curve, and for example that increase or that reduce monotonously outlet and the distance between the receiving plane.
First embodiment that preset distance curve (for example reduce or increase distance) between outlet and the receiving plane is provided be in fiber production process relatively receiving plane vertically move (preferably continuously) and put in order and organize and export (or vertically move receiving plane relative to the outlet group).In this embodiment, the receiving plane of the fibre structure that supporting increases exposes to the open air in longer period again or repeatedly is exposed to outlet again, so that make up fibre structure at the thickness direction of fibre structure with different fibre diameters according to predetermined curve.Therefore, this fibre structure only exposes to the open air or takes place in the long enough time and just can obtain after the exposing to the open air again of enough number of times.If the use endless belt can easily be realized exposing to the open air again.Otherwise, can adopt the reciprocating motion of receiving plane at directions X, so that produce big fibre structure, tackle the limited size of static textile department simultaneously.If the vertically opposite motion of receiving plane and outlet group is discontinuous, will produce the fibre structure of layering, wherein, each layer subsequently is fibrous by average diameter different with preceding one deck (for example less than preceding one decks).If this motion is continuous, the average diameter of the fiber of Chan Shenging reduces (or increasing) continuously along a size (for example thickness) of fibre structure so.Can limit the variation of the fibre diameter of any part vertical, for example be lower than 10% with described dimension.In system, wherein fibre structure relative receiving plane in the outlet moving process vertically moves, and depends on the speed of motion perpendicular to the vary in diameter in the part of thickness dimension.The motion of receiving plane is slow more, and given lip-deep variation will be more little.
Some cause that the example of fiber thickness curve is perpendicular to (for example along the z direction) described receiving plane and moves the outlet group, towards the outlet group or away from outlet group (for example along the z direction) mobile receiving plane (perhaps comprise simultaneously towards with situation) vertically away from the outlet group, towards or move outlet group or receiving plane away from the other side.Distance between outlet and the receiving plane can be advantageously 1 to 100cm, more advantageously change in the 4cm to 100cm.First embodiment can make fiber diameter fluctuate as the function of the thickness of gained fibre structure.Because fibre structure is by making it and be exposed to the static textile department for a long time or forming by it is exposed to the open air again, so this system causes batch process.
In Fig. 2, follow geometrical axis x, y and z to show the example of the static Weaving device of first embodiment, first embodiment provides predetermined distance Curve, for example randomly dull reduce or increase export and receiving plane between distance.The Z axle is a vertical axis, and x and y axle are defined as two orthogonal trunnion axis.This equipment comprises high voltage source 1 and pump 2 (for example peristaltic pump, analgesia pump or remain on container constant pressure under with compressed air).Equipment also comprises the upper element 7 with one group of outlet 5 (are pins at this), and this element 7 is with the mode horizontal positioned on plane.Equipment also comprises and is designed to the receiving plane 8 (endless belt) that moves repeatedly in X-direction.Equipment comprises that also the device 11 that is used for transmitting/provide to outlet solution or melt makes outlet group 5 relative receiving planes 8 make the device 10 of relative motion (doing dull vertical motion, reciprocating in the Y direction in the Z direction at this) with being used to.Be wrapped in element 9 (is transparent at this) on every side around this equipment.Equipment also comprises vacuum extractor 15 and desolvates so that remove.This vacuum extractor can link to each other with chimney or solvent regeneration system.In the example of Fig. 2, high voltage source 1 is the dc source that can apply 100 to 200.000V electrical potential differences on spinning head, and described spinning head is made up of two elements that are arranged parallel to each other 7 and 8.Upper element 7 is the plates that comprise some holes, has metal needle 5 to be arranged in the hole.These pins electrically contact mutually by metallic plate 7.In another equipment, semiconductive or nonconducting upper plate 7 can be used in combination with (for example metal) line of the conduction that is connected all pins 5.When upper plate conducted electricity, high voltage source 1 was connected with upper plate 7, perhaps linked to each other with the line that is connected all pins 5.Lower plate 8 is metallic plate, paper tinsel or fabric construction, and it randomly can be coated with polymers/plastics layer perforation or imperforated.This plate earthing.Randomly, it can earth-free (floating) use, but this can cause unsafe situation.In another embodiment, upper plate and lower plate are reversed, and therefore, pin is arranged in lower plate and the polymer ejecta sprays to its upper side.
The equipment of describing among Fig. 2 can be operated by the following method: set the voltage between outlet 5 and the receiving plane 8.By being used for providing the effect of the device 2 of solution or melt, treat that the liquid of static weaving or melt are transported to outlet 5 through transfer device 11 (is a flexible pipe at this) from receiver to outlet.In order to cause distance Curve between outlet and receiving plane in the static textile operation, the telecontrol equipment 10 by operation is used to make the motion of outlet group or makes the receiving plane motion obtains relative motion by outlet (is upper plate at this) is moved in the Z direction.This just motion realizes along the predetermined curve of the variation in fiber diameter of the thickness of gained fibre structure (for example mat).Distance between outlet and the receiving plane preferably can change in 1 to 100cm.The specification that the actual boundary value of using is depended on the product that to obtain.Simultaneously, endless belt 8 is fibre structures that accumulation forms.In this way, when receiving plane with a parallel direction of described receiving plane on during relative described outlet campaign, can realize the distance Curve of being scheduled to, for example randomly dull reduce or increase export and receiving plane between distance.Simultaneously, comprise that the upper plate 7 of outlet is reciprocating between two inversion points in the Y direction, so that guarantee that solution or melt output (being also referred to as the nanofiber umbrella) are well overlapping.Those parachute kits have the tendency of mutual repulsion, and when lacking the reciprocating motion of Y direction, this is unfavorable for the overlapping of them.Therefore, this reciprocating motion is particularly preferred.And the reciprocating motion of use Y direction can increase the width of fibre structure.The motion of receiving plane 8 can be produced big nanofibrous structures surface area.
The equipment of Fig. 2 can be produced such fibre structure, and wherein, fibre diameter changes according to predetermined curve, and for example along the thickness monotone variation of gained fibre structure, but the present invention is not limited only to this.For example, the predetermined curve of fibre diameter can also be, and is bigger at the surface diameter of fibre structure, littler at the surface diameter of fibre structure, perhaps any curve that other needs.The vary in diameter of gained can be continuous or discontinuous.If discontinuous, the fibre structure of generation looks like layering.First embodiment is not suitable for continuous producd fibers structure.Ensuing two embodiments advantageously can be produced fibre structure of the present invention continuously, and this often than batch production more preferably.
Provide the outlet and receiving plane between the preset distance curve (for example randomly dullness reduce or increase apart from) second embodiment arrange a plurality of outlet groups along the direction of vertical production of described fibre structure, its middle outlet group according to predetermined curve according to vertical producd fibers structural configuration.For example, along described vertically, the distance of each outlet group and receiving plane less than next outlet group and receiving plane apart from (see figure 3), this sees and causes curve that reduce or increase, for example the monotone increasing little curve that adds deduct.The specific examples of the curve that increases or reduce substitute obviously that yes arranges a plurality of outlet groups along vertical growing direction of described fibre structure, wherein, along described direction, the distance of each outlet group and receiving plane is greater than the distance of next outlet group and receiving plane.The advantage of these two selections is, they can produce big nanofibrous structures surface area continuously, and the embodiment of Fig. 2 only can the batch production fibre structure.
In Fig. 3, follow geometrical axis x, y and z to show the example of the static Weaving device of second embodiment, second embodiment provides predetermined distance Curve, for example randomly dull reduce or increase export and receiving plane between distance.The Z axle is a vertical axis, and x and y axle are defined as two orthogonal trunnion axis.This equipment is made up of two outlet groups, and each outlet group connects high voltage source 1 and pump 2 (being hidden in the chest) herein, and two groups of outlets are with the planar fashion horizontal positioned.Equipment also comprises and is designed to the receiving plane 8 (endless belt) that moves along X-direction below two groups of outlets.System also comprises the device 11 that is used for transmitting/providing to outlet solution or melt.Be used to make the device 10 of 5 groups of relative receiving plane 8 motions of outlet optional, but can provide in addition at this.Distance between the receiving plane that this device 10 can be used to regulate each group outlet and will produce the special fiber structure.The static Weaving device of Fig. 3 is particularly suitable for continuous production, particularly the fibre structure of continuous production layering.In other words, the quantity that has the layer of different fibre diameters in the layer structure has determined the quantity of required element (outlet group), and this is (Fig. 3 has shown the equipment that comprises two elements) in principle without limits.And, use a series of interconnective elements to help to increase the output of this laminar nano fibre structure certainly.
During operation, the equipment of describing among Fig. 3 can be operated by the following method: set the voltage respectively export between 5 groups and the receiving plane 8.By being used for providing the effect of the device 2 of solution or melt, treat that the liquid of static weaving or melt are transported to from receiver through transfer device 11 (is a flexible pipe at this) respectively to export 5 groups to outlet.Receiving plane is collected the fibre structure that forms from described receiving plane simultaneously in the directions X continuous motion.When directions X advanced, receiving plane was exposed to the output of outlet, for example monotone variation or near monotone variation.Simultaneously, outlet is in the reciprocating motion of Y direction, so that make the output of outlet overlapping well on receiving plane.
The 3rd embodiment is arranged to outlet outlet is included in respect in the out-of-level plane of receiving plane, and the 3rd embodiment provides predetermined distance Curve, such as outlet that reduces or increase and the distance Curve between the receiving plane.Though the equipment of second embodiment provides predetermined distance Curve, such as reduce or increase export and receiving plane between apart from (see figure 3), still, the fibre structure of acquisition is layering, and at the interface two-layer, the diameter of fiber changes in discontinuous mode.In the 3rd embodiment, this embodiment provides predetermined distance Curve, such as reduce or increase export and receiving plane between distance, can obtain such fibre structure, wherein, variation at a dimension interior diameter of fibre structure is milder, for example, can obtain on the thickness of the fibre structure that produces vary in diameter continuously.In an example, the outlet group arranges that by this way outlet is included in respect in the out-of-level plane of receiving plane, so that make the angle of 5 to 50 ° of the relative receiving plane of outlet group (upper plate that for example comprises the outlet group) (usually relative horizontal direction) inclinations.This causes increasing continuously or reduces the direction along x, and promptly the direction that vertically increases along fibre structure exports the distance between (for example needle tip) and the receiving plane (for each hand-manipulating of needle).Although can there be described angle, preferred, the direction of each outlet the invention is not restricted to this perpendicular to receiving plane.Provide the example of the 3rd embodiment of predetermined outlet and the distance Curve between the receiving plane to be schematically illustrated among Fig. 4.Use this equipment, nanofibrous structures that can continuously production stratiform, this nanofibrous structures shows the level and smooth average nanometer diameter curve (Fig. 7) as the function of the degree of depth, and for the device of Fig. 3, between individual layer, at the interface, can only make the discontinuous variation of nanofiber diameter.
In Fig. 4, follow geometrical axis x, y and z to show the example of the static Weaving device of the 3rd embodiment, the 3rd embodiment provides predetermined outlet and the distance Curve between the receiving plane.The Z axle is a vertical axis, and x and y axle are defined as two orthogonal trunnion axis.This equipment is made up of for 7 groups two plane exits, and each outlet group connects high voltage source 1 and pump 2 (being hidden in the chest) herein, in this example, and two groups of relative and receiving plane 8 inclination placements of outlet.Should be noted that the distance Curve that to implement to substitute.Receiving plane 8 is designed to move along X-direction below two groups of outlets.System also comprises the device 11 that is used for transmitting/providing to outlet solution or melt.Be used to make the device 10 of 5 groups of relative receiving plane 8 motions of outlet optional, but can provide in addition at this.This device 10 can be used to regulate the gradient of 7 groups of plane exits, so that make the distance between each outlet group and the receiving plane produce different variations.This adjusting can realize using identical equipment to produce different special fiber structures.
During operation, the equipment of describing among Fig. 4 can be operated by the following method: set the voltage respectively export between 5 groups and the receiving plane 8.By being used for providing the effect of the device 2 of solution or melt, treat that the liquid of static weaving or melt are transported to from container through transfer device 11 (is a flexible pipe at this) respectively to export 5 groups to outlet.Receiving plane is collected the fibre structure that forms simultaneously in the directions X continuous motion.When directions X advanced, receiving plane is exposed to the output of the exit position with different distance, and was for example more and more approaching.Simultaneously, outlet is in the reciprocating motion of Y direction, so that make the output of outlet overlapping well on receiving plane.
In some embodiments, static Weaving device of the present invention comprises the telecontrol equipment that is used to make outlet group and/or the motion of described receiving plane, such as, but not limited to one or more motor and one or more drive unit (such as power transmission shaft).Telecontrol equipment can be designed to cause aforesaid one or more relative motion.
Equipment can comprise and is used to control the described telecontrol equipment and the therefore controller of the motion of controlling fiber structure production process middle outlet and receiving plane, perhaps be used for setting the controller of the distance and/or the gradient of each outlet group, so that in the production process of fibre structure, obtain variable in distance according to the target fibers structure.This controller specifically can be designed to control the static textile department so that in the production process of fibre structure, for example obtains the variable in distance of outlet and receiving plane in single static fabrication processes.Do not need to suspend the static fabrication processes and/or need in the interval of the nanofiber of deposition different-diameter, not postpone morely, just can implement this point.The deposition different-diameter nanofiber between delay can less than 60 seconds, advantageously less than 10 seconds, more advantageously less than 1 second.In a favourable embodiment, between the operation of the nanofiber that deposits different-diameter, there is not delay.Controller can be produced in the hardware and in the software.It can be designed to implement control, calibrate or adjust step, and this step is used for as using aforesaid system to implement static weaving method can implementing.The controller that the invention still further relates to so and so on.Controller can comprise treating apparatus and can be exclusively used in the task of implementing the aforesaid static textile department of control especially.
An advantage of embodiments of the present invention is, use aforesaid static textile department, can in weaving experimentation, operate static the variable in distance between outlet (tip) and the receiver (receiving plane), so that between the nano-fiber material of deposition different-diameter on the receiving plane, do not have basically or not delay generation.The advantage that causes thus is to obtain firm nanofibrous structures, but do not have during normal use maybe to take place the risk of disintegration when applying moderate force.
An advantage of embodiments of the present invention is that this type of static textile department provides the nanofibrous structures with good reproducibility and good mechanical strength.
Aspect second, the present invention relates to the method for producd fibers structure.This method comprises the outlet group that is provided for exporting solution or melt, be provided for accepting receiving plane from the output of described outlet group, make described receiving plane to the first direction motion that is parallel to described receiving plane, between described outlet group and described receiving plane, apply electrical potential difference (being voltage), in described motion with apply in the electrical potential difference process and provide solution or melt to outlet.According to the embodiment of the present invention, provide in the process of solution or melt to outlet, exist the outlet of equipment and the distance between the receiving plane to change, so that all obtaining predetermined fiber thickness curve in the fibre structure according to predetermined curve described.Predetermined curve can be the curve that randomly reduces along described first direction dullness.Because the geometry of system (for example Fig. 3 and 4 embodiment) or, can obtain this curve because the actual relative motion of relative receiving plane is organized in outlet.About existing further feature according to the section port of the equipment at least of predetermined curve and the variable in distance between the receiving plane described in first aspect.
An advantage of embodiments of the present invention is, owing in deposition process, there is the variation between outlet and the receiving plane, can obtain the good interaction between the different nanofibers, though be not chemical action, so that the structure that good bonding and acquisition has good mechanical strength takes place between the nanometer.Owing to might in single static weaving part, make structure,, can not cause for example crosslinked fiber simultaneously so the bonding meeting between the different fiber is enough good so that make up firm structure.More specifically, by still have at preceding one deck some wet in one deck fiber under (for example fluid content can be 2% 6% or for example 2% to 5%) deposition, different fibers is easy to bond slightly mutually, thus, it is a kind of weak interaction that bonding interacts, and it is crosslinked not to be that chemical interaction does not take place yet.This method advantageously can be implemented with the system described in first aspect.
Electrical potential difference can be selected in 100 to 200000V.Movement step can by be used to make described outlet group and/or described receiving plane further the drive unit of motion operate so that fiberfill structure well.Therefore, further motion takes place at least one in receiving plane and the outlet group.The further motion of outlet can be reciprocating motion, for example the motion between two fixing points.Advantageously, receiving plane further continuous motion on a direction parallel with described receiving plane.Advantageously, the outlet group is done further reciprocating motion on the first direction parallel with receiving plane, and receiving plane is parallel with receiving plane but be different from and do further motion on the second direction of described first direction.For example, receiving plane can be angled with first direction, does further motion such as randomly being substantially perpendicular to described first direction.Described first and second directions are can be mutually vertical and be parallel to described first plane and described receiving plane.Advantageously, outlet group and receiving plane can further move relative to each other, so that the outlet group is moved between two inversion points along y direction (seeing for example Fig. 2, Fig. 3 or Fig. 4), receiving plane is pressed perpendicular to the still further motion continuously of the direction (for example x direction among Fig. 2, Fig. 3 or Fig. 4) in the plane of described receiving plane of y direction.The outlet group can be with 0.1cm.s -1To 100cm.s -1Average speed further move.Receiving plane can be with 10cm.h -1To 100cm.h -1Speed motion.
Solution or melt can be kept in the container, and this container can be temperature control, but not necessarily must be temperature controlled.Provide solution or the melt can be by being used for providing the drive unit of solution or melt to operate to outlet.This device (such as pump) is delivered to outlet through delivery apparatus with solution or melt, and this delivery apparatus can be temperature control, but not necessarily must be temperature controlled.When being positioned at the exit, solution or melt form drop, can pull out filament and under the effect of electrical potential difference from this drop, this filament directive receiving plane.Therefore, receiving plane is as collection surface.It is normally conical and form so-called umbrella, the i.e. zone that is capped on the receiving plane to leave the shape of ejecta of the solution of outlet or melt.
An advantage of embodiments of the present invention is, in static weaving experiment, there are the outlet of system and the variable in distance between the receiving plane, because this can obtain the nanofibrous structures of vary in diameter, the laminar nano fibre structure that for example has subgrade, described subgrade has the nanofiber of different-diameter, still has mechanically firm nanofiber micro-structural simultaneously.
According to an embodiment of this aspect, the method for static weaving also comprises the variation in view of jet expansion and receiver distance, the weave variation of other parameter of realization static.Other parameter that can change can be the voltage, the humidity that for example apply, be provided to the melt of nozzle or the flow velocity of solution.Therefore, solution or melt parameter can be considered or can also change.This type of parameter can be concentration, charge density, solvent for use and/or the viscosity of for example used polymer.This type of adjustment or optimization can be carried out with experimental technique.In principle, when change between jet expansion and the receiver apart from the time to optimize the voltage that applies be bigger advantage.The variation of one or more parameter can be according to predetermined rule, according to the model that calculates, carry out based on the T﹠E experiment or with any other suitable manner.For example, can be optimized up to reaching stable state by regulating parameter.Stable state can be defined as the point that taylor cone " Taylor cone " is constant and weaving is implemented in a continuous manner.Can detect this stable state from optics, for example with the naked eye or use optical detector, the adjustment of parameter can with artificial or automatically and/or the mode of automation carry out.
An advantage of embodiments of the present invention is, uses this control of process parameters, adjusting and/or optimization, can obtain not have the fibre structure of bead, changes the diameter of fiber in the structure simultaneously in the identical static weaving time.An advantage of embodiments of the present invention is, considers the parameter of above identification, can produce to have nanofiber under limit, for example do not have the pearl fiber or only has the scope of the fiber of limited amount pearl.An advantage is, can obtain big processing range, and wherein, the risk that has the risk of a large amount of pearls or no longer produce nanofiber on nanofiber is reduced or even avoids.The big processing range that acquisition is operated under limit causes producing with reproducible mode of height and continuous mode the possibility of nanofiber.
Aspect the 3rd, the present invention relates to fibre structure.Compare with the nanofibrous structures of the prior art of common description, first embodiment of fibre structure of the present invention shows a plurality of advantages and innovation aspect.These features obtain by the characteristic of the static Weaving device of used first aspect of the present invention.Fibre structure of the present invention shows the dimension of the diameter of its single fiber along fibre structure, for example variation on the thickness of fibre structure.In one embodiment, the present invention relates to comprise the static textile fabric structure of fiber, wherein, the diameter of described fiber is according to predetermined curvilinear motion.For example reduce or dullness reduces, and wherein, the variation of fibre diameter can be less than 10% in perpendicular to any part of described dimension along a dimension of described static textile fabric structure.Predetermined curve for example can also be, in the centre position of the depth direction of fibre structure, the diameter minimum of fiber.In one embodiment, static textile fabric structure of the present invention is a layer structure of being made up of nanofiber layer, and each layer subsequently is by average diameter fibrous less than the fibre diameter of preceding one deck.Therefore, the average diameter of fiber changes according to predetermined curve, and for example dullness reduces or dull increasing on static textile fabric thickness of structure.
Static textile fabric structure of the present invention can cut into any required shape according to the needs of the application of imagination.Surface area can be at 5mm 2To 10mm 2The interior variation, thickness changes in 100nm to 30cm, and the diameter of single fiber changes in 3nm to 5 μ m.In one embodiment, static textile fabric structure of the present invention is porous.Static textile fabric structure optimization has at least 60% porosity.The aperture can change between 30nm to 8 μ m.
As a favourable feature, static textile fabric structure of the present invention can comprise great majority, and promptly 50% or more fibers straights.In one embodiment, compound forms pulvinulus.The linearity of fiber can for example be inferred from graphical analysis.Preferably, it is straight being included in most of fibers in the fibre structure (promptly 50% or more), promptly has part straight basically on 5 μ m distances (promptly 50% or more) by great majority and forms.Basically straight must be understood that, the main shaft of fiber, promptly along the axle of machine direction less than 45 °, for example less than 30 ° or for example less than 5 ° angle in change, the scope that changes of taking measurement of an angle is 10 microns a distance.This angle is the maximum angle that can measure between the tangent line at two some places of main shaft on the fibre length of being considered.Linear standard deviation on the distance of being considered can be no more than 5%.
As a favourable feature, fibre structure of the present invention can comprise seldom or do not have crosslinked, for example micrometer fibers or nanofibrous structures, the most of fibers that wherein comprise (promptly 50% or more) are essentially no crosslinked.Fibre structure is a static textile fabric structure, and it is the structure of making by the static weaving.They advantageously do not take place crosslinked with adjacent fiber.Therefore, crosslinked meaning occurs in two connections between the fiber, is not only the contact of two fibers.This is that spacing between outlet is at least 1cm, advantageously is at least the result of 4cm.Be not bound by theory, believe that this effect is owing to the easier evaporation of solvent in the fiber forming process, therefore evaporation more quickly.Believe that for exit separation the solvent evaporation accounts for the too many time in the fiber forming process less than 1cm.This causes the fusion of adjacent fiber and therefore and crosslinked.If fibre structure is made by melt, problem may be not eliminate the fuel factor that takes place when outlet is leaned on too closely mutually fully.Then, fibre forming is incomplete, may have the middle phase between a kind of melt and the solid, makes to form crosslinked fiber.Other favorable characteristics of gained fibre structure is, they have at least 65%, 65 to 99% porosity advantageously.
Should be noted that crosslinked between the fiber do not comprise the mechanical strength that causes the fiber bonding and cause gained in the structure of the present invention weak interaction non-chemically.Therefore, this interaction causes the mechanical strength in the front of nanofibrous structures of the present invention, avoids the negative effect that is caused by crosslinked simultaneously.
In embodiment, the invention still further relates to the wherein unified fibre structure of thickness of fiber, the standard deviation of thickness is no more than 80%, advantageously 50%, more advantageously 20% in the promptly whole fibre structure.
The invention still further relates to and comprise fibre structures a plurality of or all above character of determining.As optional feature, fibre structure of the present invention can be made into the fiber that comprises great majority (promptly 50% or more) random orientation, promptly is not in the specific direction (for example, non-alignment).Last effect helps the porosity that obtains to improve.In the embodiment of a direction continuous motion, can be 10cm.h by the speed of for example selective reception face at receiving plane -1To 100cm.h -1Obtain this effect.
As an optional feature, the diameter of the most of fibers that comprise in the fibre structure of the present invention (promptly 50% or more fiber) is 3nm or bigger, 10nm or bigger advantageously.As an optional feature, the diameter of the most of fibers that comprise in the fibre structure of the present invention (promptly 50% or more) is 2000nm or littler, advantageously 800nm or littler, 700nm or littler more advantageously.When fiber had 800nm or littler average diameter, they were called as nanofiber, and the fibre structure of making thus is called nanofibrous structures.As an optional feature, the diameter of the most of fibers that comprise in the fibre structure of the present invention (promptly 50% or more) is 3 to 2000nm, advantageously 10 to 2000nm, advantageously 3 to 800nm, more advantageously 10 to 700nm.Fiber can have such diameter, wherein, the variation in local, unplanned on the whole length less than diameter dimension 100%, more advantageously on whole length less than 50% of diameter dimension.Diameter deviation in the part, unplanned greater than average diameter 200% the time, fiber is not called fiber or is called as beading fiber (beaded fibre).
As seeing from example, fibre diameter depends on the distance between outlet and the receiving plane.Relation curve between fibre diameter and the distance can be that polymer and solvent are specific.Therefore, after having studied polymer solution or melt, can determine curve, because it is that polymer and solvent are specific.It can pass through T﹠E, experimental result, theoretical model and wait to determine.As another optional feature, the fibre structure of gained has 15 to 10000cm width.
In the embodiment aspect the 3rd of the present invention, the fibre-forming polymer structure has at least 65% porosity, and width is 15 to 10000cm.
Be applied to the fibre structure that the method for second aspect of the equipment of first aspect can obtain to have outstanding character, noticeable character is the variation of fibre diameter on a dimension of fibre structure.
In some embodiments aspect the 3rd, obtain layering, i.e. the fibre structure of multilayer.Advantageously, for each is to adjacent layer in the fibre structure, fiber diameter is different.This can be by using different outlet group and the distances between the receiving plane to realize (seeing for example Fig. 3) to each layer.The corresponding body that the fibre structure of institute's score layer is compared their non-layered has multiple advantage.At first, the layer with little fibre diameter with have how many big fibers layer combinations improve the bulk strength of fibre structure.The second, as the function of using, can optimize the absorption/releasing properties of fibre structure, in single production stage, finally can obtain multitask and multi-functional, such as in single sandwich construction, carrying out multilevel filtration by the structure of using layering.
Should be appreciated that, though herein at equipment of the present invention discussed preferred embodiment, concrete structure and layout and material, but, under situation about not departing from the scope of the present invention with spirit, can also do the variation or the modification of various forms and details.For example, can in described method, add within the scope of the invention or the deletion step.Though we have described the present invention about production method, static Weaving device and gained fibre structure, but, the invention still further relates to the controller that is used to control the relative distance between outlet and the receiving plane, so that in fibre structure, produce different character between the different layer.
Shuo Ming mode has been discussed a plurality of embodiment by way of example.The mode of embodiment 1-3 by example illustrates the vary in diameter on the degree of depth of the nanofibrous structures of making in single static weaving experiment.Embodiment 4 and two examples of 5 explanations have wherein illustrated the limit that is used for static weaving different materials.Embodiment 7,9,11 and 13 explanation static weaving experiments, wherein, use the method for an embodiment of the invention to obtain firm nanofibrous structures, and embodiment 6,8,10 and 12 describes relatively static weaving experiment, wherein, (separating on the time) obtains the different subgrades in the nanofibrous structures in different static weaving experiments.The advantage of these embodiment and comparative example explanation embodiments of the present invention.Embodiment 14 explanation with about the described similar result of embodiment 4-13, but the material difference.Its explanation static weaving techniques of embodiments of the present invention and system applies are extensively and seriously be not subjected to the restriction of static textile material.
Embodiment 1
By polyesteramide (PEA) (the about 20.000g.mol of molecular weight from the synthetic acquisition of aliphatic acid -1) be dissolved in the chloroform so that obtain the solution of 25%PEA.Use a plurality of multi-channel peristaltic pumps, export 15ml.h with each -1Flow velocity this solution pump is delivered to one group of 24 outlet.In spinning head, on outlet and receiving plane, apply about 1000V.cm -1Electric field so that can implement the static weaving of polymer solution.Outlet designs with triangular layout, totally 4 goes 6 outlets of every row.Temperature is controlled at 298K.Exit face is in the position that relative receiving plane is 10 ° of angles, and the motion vertical of exit face is in the motion of receiving plane.The speed of receiving plane is 40cm.h -1, and the speed of exit face is 1cm.s -1Weave after 2 hours, obtain the thick nanofibrous structures of 300 μ m, length is that about 1.5m, width are 80cm.Average nanofiber diameter is changed to the 300nm (Fig. 9) of opposite side with change in depth from the 500nm (Fig. 8) of structure one side.Side with maximum gauge is corresponding to deriving from the fiber that is in the nearest outlet of relative receiving plane, and minimum diameter (at the opposite side of nanofibrous structures) derives from and the outlet farthest of receiving plane distance.Figure 10 shows the relation of the distance between nanofiber diameter and outlet and the receiving plane.
Embodiment 2
Polyamide 6/6 (PA66) (the about 20.000g.mol of molecular weight -1) be dissolved in the formic acid so that obtain the solution of 14%PA66.Use a plurality of multi-channel peristaltic pumps, export 2ml.h with each -1Flow velocity this solution pump is delivered to two groups of outlets, every group of 24 outlets.In spinning head, on outlet and receiving plane, apply about 3.500V.cm -1Electric field so that can implement the static weaving of polymer solution.Outlet designs with triangular layout, totally 4 goes 6 outlets of every row.Use two spinning heads, each is operated with different outlets and the distance between the receiving plane.Temperature is controlled at 298K.First exit face and receiving plane leave the distance of 4cm, and second exit face and receiving plane leave the distance of 6cm.The speed of receiving plane is 60cm.h -1, and the speed of exit face is 1cm.s -1Weave after 2 hours, obtain the thick nanofibrous structures of 100 μ m, length is that about 1.2m, width are 80cm.In a step, average nanofiber diameter is changed to the 180nm (Figure 12) of opposite side with change in depth from the 285nm (Figure 11) of structure one side.Side with maximum gauge is corresponding to the fiber that derives from the exit face that leaves receiving plane 4cm, and minimum diameter (at the opposite side of nanofibrous structures) derives from and the exit face of receiving plane at a distance of 6cm.
Figure 13 shows the distance between outlet and the receiving plane and the curved line relation of average nanofiber diameter, and it is to use as described in example 1 above processing unit (plant) to obtain.PA66 at variable concentrations has drawn this figure.
Embodiment 3
(molecular weight is about 30,000g.mol for cellulose acetate (CA) -1) be dissolved in acetone/dimethylacetylamide (2: 1) so that obtain the solution of 14%CA.Use a plurality of multi-channel peristaltic pumps, export 10ml.h with each -1Flow velocity this solution pump is delivered to two groups of outlets, every group of 24 outlets.In spinning head, on outlet and receiving plane, apply about 850V.cm -1Electric field so that can implement the static weaving of polymer solution.Outlet designs with triangular layout, totally 4 goes 6 outlets of every row.Use two spinning heads, each is operated with different outlets and the distance between the receiving plane.Temperature is controlled at 298K.First exit face and receiving plane leave the distance of 20cm, and second exit face and receiving plane leave the distance of 15cm.The speed of receiving plane is 60cm.h -1, and the speed of exit face is 1cm.s -1Weave after 2 hours, obtain the thick nanofibrous structures of about 200 μ m, length is that about 1.2m, width are 80cm.Average nanofiber diameter is changed to the 450nm of opposite side with change in depth from the 470nm of structure one side.Side with maximum gauge is corresponding to the fiber that derives from the exit face that leaves receiving plane 15cm, and minimum diameter (at the opposite side of nanofibrous structures) derives from and the exit face of receiving plane at a distance of 20cm.
Embodiment 4
Polyamide 6/6 (PA66) are dissolved in the formic acid so that obtain the solution of 14%PA66.Use a plurality of multi-channel peristaltic pumps that solution pump is delivered to one group of pin.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Use following operational parameter value, promptly the tip obtains a kind of steady state operation to distance, the flow velocity of receiver and the voltage that applies, and produces the fiber that does not contain pearl or have the pearl that reduces or reduce as far as possible.
Most advanced and sophisticated to the receiver distance Flow velocity The voltage that applies
??6cm ??2mL?h-1 ??20kV
??7cm ??2mL?h-1 ??23kV
??8cm ??2mL?h-1 ??26kV
??9cm ??2mL?h-1 ??28,5kV
??6cm ??1mL?h-1 ??16,5kV
??6cm ??3mL?h-1 ??22kV
??6cm ??4mL?h-1 ??24kV
??6cm ??5mL?h-1 ??26,5kV
Most advanced and sophisticated to receiver distance, flow velocity and the combination of the voltage that applies cause good limit.This condition is by obtaining at fixing tip to receiver distance and the voltage that fixing flow velocity manual adjustment applies.
Embodiment 5
In embodiment 5, described with embodiment 4 in similarly the experiment.By being dissolved in the chloroform so that obtain the solution of 24%PEA from the synthetic polyesteramide that obtains of aliphatic acid.Use a plurality of multi-channel peristaltic pumps that solution pump is delivered to one group of pin.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Use following operational parameter value, promptly most advanced and sophisticated to receiver distance (being presented in first row), flow velocity (being presented in first row) and the voltage (representing) that applies with kV, given tip is to receiver distance and flow velocity, obtain a kind of steady state operation, produce the fiber that does not contain pearl or have the pearl that reduces or reduce as far as possible.
Figure G2008800161044D00391
Tip shown in the table to the combination of distance, the flow velocity of receiver and the voltage that applies causes good limit.This condition is by obtaining at fixing tip to receiver distance and the voltage that fixing flow velocity manual adjustment applies.
Embodiment 6
Polyamide 6/6 (PA66) are dissolved in the formic acid so that obtain the solution of 14%PA66.Use a plurality of multi-channel peristaltic pumps, with each pin 5ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 4500V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 6cm.
Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.After 10 minutes, at the identical condition deposit second layer.Repeat 6 times so that obtain 7 layers layer structure.Therefore, these layers are to make in different static weaving experiments, and these experiments separate in time.When this layer structure was applied mechanicals efforts, it demonstrated weak intensity because the bonding force between the single layer a little less than.This point is described in Figure 14, shows after applying mechanical force, and these 7 layers layering takes place.
Embodiment 7
Polyamide 6/6 (PA66) are dissolved in the formic acid so that obtain the solution of 14%PA66.Use a plurality of multi-channel peristaltic pumps, with each pin 5ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 4500V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 6cm.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.Immediately at the identical condition deposit second layer.According to an embodiment of the invention, repeat 10 times so that obtain 11 layers layer structure.When this layer structure was applied mechanicals efforts, it demonstrates was a bonding nanofiber pulvinulus that intensity is big, wherein detected less than single layer.This point is described in Figure 15, shows that layering does not take place this structure.
Comparing embodiment 6 and 7 shows that the nanofibrous structures that uses embodiments of the present invention to obtain has the advantage that intensity is good, structure is good.
Embodiment 8
Polyamide 6/6 (PA66) are dissolved in the formic acid so that obtain the solution of 14%PA66.Use a plurality of multi-channel peristaltic pumps, with each pin 2ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 3,500V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 6cm.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.After 10 minutes, with 2ml.h -1The speed deposition second layer, apply 3300V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 7cm.After 10 minutes, deposit one deck under the following conditions again: each pin 2ml.h -1Speed, apply 3500V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 6cm.At last, deposit the 4th, the 5th and layer 6 under the following conditions, each 10 minutes blanking times: each pin 2ml.h -1Speed, apply 3,300V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 7cm.Therefore, these layers are to make in different static weaving experiments, separate in time.When this layer structure was applied mechanicals efforts, it demonstrated weak intensity because the bonding force between the single layer a little less than.This point is described in Figure 16, shows this structure generation layering once more.
Embodiment 9
Polyamide 6/6 (PA66) are dissolved in the formic acid so that obtain the solution of 14%PA66.Use a plurality of multi-channel peristaltic pumps, with each pin 2ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 3,500V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 6cm.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.With 2ml.h -1Speed deposit the second layer immediately, apply 3300V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 7cm.Deposit the 3rd layer subsequently under the following conditions: each pin 2ml.h -1Speed, apply 3500V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 6cm.At last, deposit the 4th, the 5th and layer 6 under the following conditions at once: each pin 2ml.h -1Speed, apply 3,300V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 7cm.Therefore, this nanofibrous structures obtains in single static weaving experiment basically, wherein, according to the embodiment of the present invention, causes between the static weaving deposition of different subgrades of nanofiber of different-diameter life period delay hardly.When this layer structure was applied mechanicals efforts, it demonstrates was a bonding nanofiber seat that intensity is big, wherein detected less than single layer.Acquisition is similar to the result shown in Figure 15.
Comparing embodiment 8 and 9 shows that once more the nanofibrous structures that uses embodiments of the present invention to obtain has the advantage that intensity is good, structure is good.And from different chemical compositions as can be seen, these results do not rely on the chemical composition of employed material basically.
Embodiment 10
Polyesteramide is dissolved in the chloroform so that obtain the solution of 24%PEA.Use a plurality of multi-channel peristaltic pumps, with each pin 12ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 750V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 25cm.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.After 10 minutes, at the identical condition deposit second layer.Repeat 10 times so that obtain 11 layers layer structure.Therefore, these layers are to make in different static weaving experiments, separate in time.When this layer structure was applied mechanicals efforts, it demonstrated weak intensity because the bonding force between the single layer a little less than.
Embodiment 11
By being dissolved in the chloroform so that obtain the solution of 24%PEA from the synthetic polyesteramide that obtains of aliphatic acid.Use a plurality of multi-channel peristaltic pumps, with each pin 12ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 750V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 25cm.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.Immediately at the identical condition deposit second layer.According to an embodiment of the invention, repeat 10 times so that obtain 11 layers layer structure.When this layer structure was applied mechanicals efforts, it demonstrates was a bonding nanofiber seat that intensity is big, wherein detected less than single layer.
Comparing embodiment 10 and 11 shows that for dissimilar static weaving solution, the nanofibrous structures that uses embodiments of the present invention to obtain has the advantage that intensity is good, structure is good equally.Determine also that thus the method and system of embodiments of the present invention produces good structure, is independent of used material basically.
Embodiment 12
By being dissolved in the chloroform so that obtain the solution of 24%PEA from the synthetic polyesteramide that obtains of aliphatic acid.Use a plurality of multi-channel peristaltic pumps, with each pin 12ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 750V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 25cm.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.After 10 minutes, with 12ml.h -1The speed deposition second layer, apply 1,400V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 10cm.After 10 minutes, deposit one deck under the following conditions again: each pin 12ml.h -1Speed, apply 750V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 25cm.At last, deposit the 4th layer under the following conditions: each pin 12ml.h -1Speed, apply 1,400V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 10cm.Therefore, these layers are to make in different static weaving experiments, separate in time.When this layer structure was applied mechanism, it demonstrated weak intensity because the bonding force between the single layer a little less than.
Embodiment 13
By being dissolved in the chloroform so that obtain the solution of 24%PEA from the synthetic polyesteramide that obtains of aliphatic acid.Use a plurality of multi-channel peristaltic pumps, with each pin 12ml.h -1Flow velocity this solution pump is delivered to one group of pin, apply 750V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 25cm.Temperature is controlled at 298K.The position of these pins is left 6cm mutually.Obtain the ground floor nanofiber.With 12ml.h -1Speed deposit the second layer immediately, apply 1,400V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 10cm.Deposit the 3rd layer subsequently under the following conditions: each pin 12ml.h -1Speed, apply 750V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 25cm.At last, deposit the 4th layer immediately under the following conditions: each pin 12ml.h -1Speed, apply 1,400V.cm -1Electromotive force, most advanced and sophisticated distance to receiving plane is 10cm.Therefore, this nanofibrous structures obtains in single static weaving experiment basically, and wherein, according to the embodiment of the present invention, causing between the static weaving deposition of different subgrades of nanofiber of different-diameter hardly, application time postpones.When this layer structure was applied mechanism, it demonstrates was a bonding nanofiber seat that intensity is big, wherein detected less than single layer.
Comparing embodiment 12 and 13 shows that once more the nanofibrous structures that uses embodiments of the present invention to obtain has the advantage that intensity is good, structure is good.
Embodiment 14
In order to illustrate when the system that uses embodiments of the present invention and/or when using the method for embodiments of the present invention, the advantage of gained is independent of used static weaving solution basically, uses following polymer to repeat above experiment.Polystyrene, polycaprolactone, polyacrylonitrile, poly(ethylene oxide), PLA, polyacrylic acid, polyesteramide, polyvinyl alcohol, polyimides, polyurethane, PVP, collagen, cellulose and Related product, shitosan, methacrylate, silk, the nanofiber that contains metal, polythene-ethenol copolymer and polyethylene vinyl acetate ester copolymer.Can see similar result and advantage.
According to another aspect, the present invention relates to be used to control the fluid of at least one wound circumference, for example the wound dressing device of wound fluid.The control fluid can comprise that control is present in the amount of the fluid of wound circumference.The fluid of control wound circumference can comprise the effluent of the fluid of controlling wound circumference.The control fluid can comprise the fluid of absorption from least one wound.This wound dressing device can be particularly suitable for the wound dressing of burn wound, but the invention is not restricted to this.The wound dressing device comprises the nanofibrous structures that contains multiple fiber.Nanofibrous structures can use any method described in the application's the others to make.Nanofibrous structures can be identical or similar with the application's embodiment or any nanofibrous structures described in the aspect.Nanofibrous structures can comprise the contact-making surface that is used to contact wound.The diameter of the fiber of nanofibrous structures changes on the direction perpendicular to contact-making surface, so as control from the wound absorption fluids and/or with release of fluid to wound.This variation can be the difference of the fibre diameter between the different layers in the sandwich construction and/or the more continuous variation of fibre diameter.Variation can be the variation of the density of the variation of variation, fibre density of porosity and/or fiber.Aspect concrete, the variation of the diameter of porosity, fiber or the density of fiber can be according to predetermined change curve, so that the wound dressing device provides predetermined diffusate to absorb and/or release profiles.Curve can be like this, and there is fast Absorption in the contact side between wound and wound dressing device, can shift fast from this side to opposition side so that wound is dry basically.Another kind of curve can be, the contact side between wound and wound dressing exists and absorbs, and is transferred in the dressing to a degree of depth, if the release of fluid of wound slows down, fluid at first is absorbed so, and the fluid that is stored in the dressing can discharge back wound.The wound dressing device can for example have and have bigger fibre diameter at wound contact-making surface place, the fibre diameter in the centre position of wound dressing device is littler, become big curve once more at the opposing face diameter.Curve can be so, and the wound dressing device comprises a middle part storage partly, and it can return release of fluid in the wound in the latter half, so that for example prevent the wound too dry.
Nanofibrous structures is the structure of a porous advantageously.Structure can have at least 65% porosity, for example mean porosities.Porosity, for example mean porosities can be in 65 to 99%, advantageously 70 to 98, more advantageously 75 to 95% scope.Nanofibrous structures can for example can absorb 1-25 water, solution, compound or the gel doubly that is equivalent to himself weight.It can for example have 3 to 25 times, advantageously 4 to 25 times, more advantageously 5 to 25 times to the liquid absorption capacity of own wt, and wherein density of liquid is about 1kg/L.An advantage of embodiments of the present invention is based on the high porosity of structure, can obtain high absorptive capacity fully.In concrete embodiment of the present invention, nanofibrous structures can also comprise the active liquid absorption and/or gel forms compound, is used for further increasing liquid absorption capacity.This active liquid absorbs and/or gel forms compound and can cause 1-70 doubly to the liquid absorption capacity of himself weight.This active liquid absorption and/or gel formation compound for example can be used as coating and are applied on the single fiber, and still, gel forms compound and can also add on the nanofibrous structures by different modes.For example, active water absorbs and/or an example of gel formation compound can be a polyacrylic acid, but the invention is not restricted to this.
The aperture can change between 30nm to 8 μ m.According to certain embodiments of the present invention, can select the aperture of at least one part of nanofibrous structures less than 150nm, for example less than 125nm or less than 100nm.Bacterium has the size greater than 150nm usually.Therefore, when in a single day this structure is used on the surface of pending and/or protection, just form good bacterial barriers, prevent pending surperficial infected.
Nanofibrous structures can comprise nanofiber, so that the nanofiber of at least 30%, advantageously at least 50% nanofibrous structures has 3 to 2000nm average diameter.Be deposited on nano fabrics structure on the substrate can have 1 μ m to 5000 μ m, advantageously 1 μ m to 2000 μ m, advantageously 10 μ m to 2000nm, advantageously 3 to 800nm, 10 to 700nm average thickness more advantageously.The diameter of the most of fibers that comprise in the fibre structure of the present invention (promptly 50% or more fiber) can be 3nm or bigger, 10m or bigger advantageously.As an optional feature, the diameter of the most of fibers that comprise in the fibre structure of the present invention (promptly 50% or more) is 2000nm or littler, advantageously 800nm or littler, 700nm or littler more advantageously.For the application, have the above-mentioned diameter that is proposed or the fiber that is in a kind of diameter range will be called as nanofiber, corresponding structure can be called nanofibrous structures.In embodiment, the invention still further relates to the wherein unified fibre structure of thickness of fiber, the standard deviation of thickness is no more than 80%, advantageously 50%, more advantageously 20% in the promptly whole fibre structure.Fibre diameter depends on the distance between outlet and the receiving plane.Relation curve between fibre diameter and the distance can be specific for polymer and solvent.Therefore, after having studied polymer solution or melt, can determine curve, because this is specific for polymer and solvent.Can pass through T﹠E, experimental result, theoretical model waits to determine.Single nanofiber can have the length of 10 μ m to 50m.
Nanofibrous structures can comprise at least 50% fibers straight, and wherein, the distance that these fibers have at least 5 μ m is straight basically part.The linearity of fiber can for example be inferred from graphical analysis.Preferably, it is straight being included in most of fibers in the fibre structure (promptly 50% or more), is promptly had in the straight basically part of 5 μ m distance (promptly 50% or more) by great majority and forms.Basically straight must be understood that, the main shaft of fiber, promptly along the axle of machine direction less than 45 °, for example less than 30 ° or for example less than 5 ° angle in change, the scope that changes of taking measurement of an angle is 10 microns a distance.This angle is the angle of the maximum that measures between the tangent line at two some places of main shaft on the fibre length of being considered.Linear standard deviation on the distance of being considered can be no more than 5%.
As a favourable feature, fibre structure of the present invention can comprise seldom crosslinked or do not have crosslinked, for example micrometer fibers or nanofibrous structures, the most of fibers that wherein comprise (promptly 50% or more) are essentially no crosslinked.They advantageously do not take place crosslinked with adjacent fiber.Therefore, crosslinked meaning occurs in two connections between the fiber, is not only the contact of two fibers.This is that spacing between outlet is at least 1cm, for example is at least the result of 4cm.Be not bound by theory, believe that this effect is owing to the easier evaporation of solvent in the fiber forming process, therefore evaporation more quickly.Believe that the solvent evaporation accounts for the too many time in the fiber forming process for breaking in the exit separation of 1cm.This causes the fusion of adjacent fiber and therefore and crosslinked.If fibre structure is made by melt, problem may be not eliminate the fuel factor that takes place when outlet is leaned on too closely mutually fully.Then, fibre forming is incomplete, may have the middle phase between a kind of melt and the solid, makes to form crosslinked fiber.
Nanofibrous structures can comprise the fiber of at least 50% random orientation.In one embodiment, compound forms pulvinulus.
Advantageously, can obtain nanofibrous structures by static a kind of material of weaving.The fiber of feature shown in having can obtain by the static textile technology that uses the multiinjector system.Nozzle can the be separated by spacing of 1cm at least, the spacing of 4cm at least advantageously.
On a large scale material can be used to produce nanofibrous structures, and the polymer from following polymer class is wherein arranged: polyamide, polystyrene, polycaprolactone, polyacrylonitrile, poly(ethylene oxide), PLA, polyacrylic acid, polyesteramide, polyvinyl alcohol, polyimides, polyurethane, collagen, cellulose and Related product, shitosan, methacrylate, silk, polyethylene vinyl acetate ester copolymer, polythene-ethenol copolymer, polyvinyl butyrate and contain the nanofiber of metal.
The wound dressing device can have any suitable shape.They can be made into square or rectangle, but can also cut into alternative shape according to the needs of contemplated application.Surface area can be at 5mm 2To 10m 2Between change.The wound dressing device can be suitable for burn wound dressing or big wound dressing, and nanofibrous structures has at least 30cm * 30cm, advantageously 40cm * 40cm, the contact-making surface of 50cm * 50cm more advantageously.But dressing also can be used for minor cut or wound, and nanofiber has at least 2mm * 2mm or 5mm * 5mm, the contact-making surface of 20mm * 20mm more advantageously.The wound dressing device can cut into Any shape by hand or with the machine that uses machinery, heat or induced with laser cutting.The thickness of equipment records on the direction perpendicular to contact-making surface usually, can be 100nm to 30cm, for example 50 μ m to 5000 μ m.
The nanofibrous structures of wound dressing device can be fixed on the substrate.Substrate can be far longer than nanofibrous structures, and can have bond properties at the edge (for example by glue is provided) so that the wound dressing device is adhered on the skin of wound circumference.Perhaps or in addition, this bond property directly can also be given the edge of nanofibrous structures, no matter be had or not substrate to exist.
Shuo Ming mode the invention is not restricted to this by way of example, and we will discuss a plurality of concrete embodiments, and the optional feature and advantage of embodiments of the present invention are described.
In first concrete embodiment, aforesaid wound dressing device is discussed.In these wound dressing devices, the function that the diameter of nanofiber can be used as the degree of depth of nanofibrous structures changes in a controlled manner.By change crossing over the nanofibrous structures degree of depth, promptly, can reach the absorption of good, controlled liquid and/or (biology) reactive compound perpendicular to the diameter of the nanofiber of the direction of the contact-making surface of wound dressing device.The fiber of whole nanofibrous structures can be made by identical materials, perhaps can be made from a variety of materials.Advantageously, can obtain nanofibrous structures by static a kind of material of weaving.The fiber of feature shown in having can obtain by the static textile technology that uses the multiinjector system.Nozzle can be separated by at least 1cm, the spacing of 4cm or 6cm at least for example.And, in order to control diameter, can adjust the distance between nozzle and the receiving plane.Shuo Ming mode the invention is not restricted to this by way of example, and we have described the static weaving method that multiple production has the wound dressing device of different-diameter.In the equipment of first kind of use static weaving method production wound dressing device, the distance between the receiving plane of the nozzle of static Weaving device and static Weaving device can change in process, and this causes the diameter variation of single nanofiber.Figure 17 more specifically shows this point.Figure 17 display part static Weaving device 100, it comprises one group of nozzle 102 and receiving plane 104.Between nozzle 102 and receiving plane 104, for example applied voltage by the voltage source (not shown).Nozzle location can be displaced sideways in all directions relatively, and this can make the different fibers of generation suitably overlapping.And system is designed to provide the variable in distance between jet expansion and the receiving plane.Figure 17 also shows the spraying area 106 of taper, and wherein material is injected.Receiving plane 104 can be the some of surface of moving or the surface of moving.In second kind of device, by producing the layer of layer structure, wherein each layer apart from production, obtains the variation of nanofiber diameter with constant nozzle-receiving plane.Figure 19 more specifically schematically shows this point.Figure 19 illustrates the equipment among a kind of Figure 17 of being similar to, wherein, the variation of the distance in the static Weaving device 200 between nozzle sets 102 and the receiving plane 104 is not that the motion by jet expansion 102 provides, but by providing a plurality of different jet expansion group 202a, 202b, the 202c different with the distance of receiving plane 104 to provide.The variation of other parameter of the static weaving that causes owing to jet expansion to the variation of receiver distance can for example be determined with experimental technique such as voltage to be applied.Yet, in principle, when change between jet expansion and the receiver apart from the time to optimize the voltage that applies be bigger advantage, but also can adjust other parameter, such as the flow velocity of starting material.This can be according to predetermined rule, according to the model that calculates, carry out based on the T﹠E experiment or with any other suitable manner.For example, can be optimized up to reaching stable state by regulating parameter.Stable state can be defined as taylor cone " Taylor cone " the constant and point of enforcement in a continuous manner of weaving.Taylor cone is the common triangle that drips and obtain when vertical polymer solution is brought into electric field when.Can detect this stable state from optics, for example with the naked eye or use optical detector, the adjustment of parameter can with artificial or automatically and/or the mode of automation carry out.According to the example of present embodiment, can obtain such nanofibrous structures, the nanofiber of its medium-small diameter (for example 3nm to 1.5 μ m) is in a side, and the nanofiber of larger diameter (for example 50nm to 5 μ m) is at opposite side, for example contact side.Very clear, follow first kind of device, can obtain the continuous or quasi-continuous variation of nanofiber diameter as the function of the degree of depth, a kind of wound dressing device 150 of correspondence is presented among Figure 18, and for second kind of device, to obtain several discontinuous steps in vary in diameter, a kind of wound dressing device 250 of correspondence is presented among Figure 20.In favourable embodiment, the fibre diameter in the nanofibrous structures reduces from contact side to its opposition side of wound dressing device.
An advantage of embodiments of the present invention is can obtain the small-bore, because the high-specific surface area of nanofibrous structures can make absorbed liquid evaporation in the structure.Very clear, will obtain the most effective evaporation properties in equipment one side of the nanofiber that has minimum diameter, because can obtain the highest specific area and liquid is maximum to this surperficial transmission speed in that side.
Another advantage of embodiments of the present invention is, the wound dressing device not only can absorb a large amount of liquid or make fluid evaporator at opposite side at contact side, and at the absorbed liquid of a side (contact side or contact-making surface) of the wound dressing device wound of sepage (for example from) by effectively to the opposite side transportation of structure, condition is to utilize the wound dressing device with suitable manner, the location that is the wound dressing device makes the nanofiber with maximum gauge be present on the contact-making surface, and the nanofiber with minimum diameter is present in an opposite side.This means that on the cross section of equipment, the diameter of nanofiber discharges side from the liquid-absorbent side to liquid direction reduces.
Another advantage of embodiments of the present invention is, owing to might during single static weaving, make the wound dressing device of static weaving, so the bonding meeting between the different fibers is enough good so that make up firm structure, and can not cause for example crosslinked fiber.More specifically, layer by deposition in front is (for example comprising 2% to 6% moisture content) deposition one deck fiber down when still some is wet, and different fibers is easy to bond slightly mutually, thus, this bonding is a kind of weak interaction, is not that chemical interaction neither be crosslinked.An advantage of embodiments of the present invention is that can obtain does not have the pearl fibre structure, changes the diameter of fiber in the wound dressing device simultaneously in the identical static weaving time.For example, this can be by the different parameters during the control static weaving, change nozzle-receiver distance simultaneously and obtain.
An advantage of embodiments of the present invention is, the wound dressing device is provided, it can absorb the liquid from a surface (for example sepage wound) effectively, and based on absorb liquid effectively, on the cross section of equipment fluid transfer and discharge liquid effectively by evaporation effectively at the opposite side of equipment, set up the dynamic removal mechanisms at work of liquid.And the individual advantage of embodiment is that when the fluid forming process finished, the fluid of Xi Shouing can discharge back wound before.Because the support of these three advantages, the liquid of equipment are removed character and can be had and keep the liquid release surface almost dry or make the actual amount of the fluid that is present in wound surface keep the possibility of stable state.In other favourable embodiment, equipment is suitable to be used to prevent the wound bone dry.Two examples of this wound dressing device are presented among Figure 23 and Figure 24, illustrate to be designed to from wound absorption liquid, storaging liquid and stage afterwards it be discharged back the wound dressing device of wound.Figure 22 shows corresponding wound dressing device 400, and wherein diameter changes continuously, and this can obtain with the system shown in Figure 17, and Figure 24 shows layer structure 450, and it can obtain with the system shown in Figure 19.These two kinds of structures perpendicular to the diameter of the fiber in the centre position of the direction of contact-making surface less than the diameter of the fiber of contact-making surface and less than diameter near the fiber on the contact-making surface opposed surface.In the equipment of Figure 24, provide intermediate layer with this fiber.This embodiment has such advantage, can control near the Fluid Volume of wound, so that wound can not become dry, this wound for some type is favourable.
In second concrete embodiment, nanofibrous structures also is designed for preventing or reducing the risk of the mutual infection of handling with identical dressing owing to being linked to each other by the wound dressing device of wound on every side.If infected at the previous wound of application device, this shortcoming can take place.By using aforesaid nanofibrous structures, the top of nanofibrous structures at least wherein, promptly the part in the face of wound forms pattern, and the present invention can solve such problem.An example of this figuratum structure 300 is presented among Figure 21, though the invention is not restricted to this.Dissimilar patterns can be provided.
At least can make the top of nanofibrous structures form pattern, so that the one side of the contact wound of wound dressing device is separated into a plurality of littler districts.The size in these districts can be all identical or different.The size in preferred single zone can be 5cm * 5cm, preferred 2cm * 2cm, 1cm * 1cm more preferably.The pattern of nanofibrous structures or its part can obtain in any suitable manner, such as by handling with heat according to pattern to be formed.For example, the figuratum structure of heating can be used for producing the pattern of nanofibrous structures or its part.Because heating, pattern is burnt in the layer, because nanofiber is with local melting and be bonded together.Very clear, in these parts, structure loses its nanofiber character.At these boundaries, liquid therefore easily a district from pattern be transferred to adjacent district, therefore cause reducing or prevent that the infected wound liquid in a wound district from contacting with another wound district.In other words, form horizontal barrier so that prevent the effluent of wound liquid.Laterally another advantage of barrier is to prevent that the wound fluid from transferring near the wound the healthy skin, and described wound advantageously should keep dry.Should be noted that the viewpoint that horizontal barrier is provided can also be used for such nanofibrous structures in nanofibrous structures, wherein,, promptly do not have the variation of fibre diameter perpendicular to the direction of the contact-making surface of nanofibrous structures at the depth direction of nanofibrous structures.
In the nanofibrous structures of this specific embodiment, liquid that can not arrives another district from a district of pattern, and therefore, more close mutually Qu Buhui is moistening because of a liquid source of release.For example, this means that burn wound can not infected by the burn wound around handling with identical device, because diffusate can not transfer to the peripheral region for burn wound.
Figuratum layer (contact) with pending surface and as first embodiment described common layer combination may be useful.Then, be eliminated and be given common layer by figuratum layer wound moisture content, there, moisture content is more easily propagated and is evaporated.The latter is in conjunction with the advantage of the big moisture content absorptive capacity of advantage that prevents cross pollution between the wound and common layer and good evaporation (so that moisture content can easily leave nanofibrous structures).Flowed back to patterned layer from the liquid that can not that has patterned layer to transfer to the pattern-free district, this is because nanofiber diameter changes, and diameter reduces along cross section from liquid-absorbent side (contacting with patterned layer is arranged) to the side that discharges liquid by evaporation.
Perhaps, use middle pattern-free district fluid storage can had the pattern area that has of patterned layer, and therefore can select liquid is discharged back wound (if desired) so that the actual liquid that the wound surface place is existed is kept stable state with bigger fibre diameter.Example according to the wound dressing device 350 of this design is presented among Figure 22.
Liquid barrier can also be used for preventing that liquid from removing too much from the wound dressing device.Use this pattern can promote the fluid storage that wound is discharged in dressing, to prepare against the possibility that discharges back later in the wound.This can keep the stable state of wound surface place real fluid, finds that by the investigation about burn wound in Europe this helps Wound healing process and dynamics.
In the 3rd concrete embodiment, the nanofibrous structures described in the embodiment more than any one is disclosed, wherein, in nanofibrous structures, also added character antibiotic and/or sterilization.By doing like this, nanofibrous structures advantageously can provide antibiotic and/or bactericidal action, if pending surface is infected before application structure, this is with particularly useful.Because the aperture in the nanofibrous structures may be less, so bacterium can be retained in the wound, owing to the aperture reason, bacterium can not be absorbed.According to the embodiment of the present invention, by the nanofiber layer that comprises antibiotic and/or bactericidal property is provided, can provide antibiotic and/or bactericidal property.This layer can be by being coated with nanofiber or obtaining by the weave fiber of this material of static with antibiotic and/or Fungicidal substance.The nanofiber layer that comprises this material advantageously can be positioned at the liquid-absorbent side, and therefore, this layer can directly contact pending surface.Therefore, this layer can comprise the nanofiber of the reactive compound with antibiotic and/or bactericidal property, for example contains I 2PVP (PVP).When being applied to the surface, fiber can be dissolved in the liquid of surface release, the compound of the imagination of this meeting activation energy killing bacteria.One preferred embodiment in, can add the nanofiber that has antibiotic and/or antibacterial character more than one deck, so that can prolong antibiotic and/or bactericidal effect.The latter can obtain by a fact, and this layer that is positioned at away from wound can cause antibiotic and/or bactericidal property in the slower moment.
In yet another aspect, the present invention relates to be used for the purposes of the nanofibrous structures described in the embodiments of the present invention that wound dressing uses.This purposes has benefited from as above about described one or more the different feature and advantage of the equipment of first aspect.
In yet another aspect, the present invention relates to the method for wound wrapping, this method comprises the nanofibrous structures that obtains to have the contact-making surface that is used to contact wound, wherein, the diameter of fiber on perpendicular to the direction of contact surface according to predetermined curvilinear motion.This method also comprises by wound is contacted along predetermined direction with nanofibrous structures, thereby nanofibrous structures is set.Can there be other method step, shows one of the wound dressing device described in first aspect of the present invention, the function of a plurality of or whole features.
According to another aspect, the present invention relates to be used for the dental whitening systems of whitening teeth.The system that is used for whitening teeth comprises two parts.First part comprises a nanofibrous structures.Second part comprises the dental whitening part that contains bleaching agent.Nanofibrous structures can be used for keeping the dental whitening part when using the system of bleaching teeth.In other words, nanofibrous structures in use can be as the carrier of dental whitening part.Nanofibrous structures can offer a plurality of teeth and be used for dental whitening, is also referred to as dental bleaching.The structure of nanofibrous structures can be designed so that it can suitably absorb, keeps and discharge the dental whitening part, and the viscosity of this dental whitening part is 10 centipoise to 1000 centipoises, advantageously 10 centipoise to 400 centipoises, 10 centipoise to 199 centipoises more advantageously.Nanofibrous structures can use any method described in the application's the others to make.Nanofibrous structures can be identical or similar with the application's embodiment or any nanofibrous structures described in the aspect.
Nanofibrous structures can be subjected to the support of substrate layer, but the invention is not restricted to this.Optional substrate layer can be any material that proof can be used for the oral cavity.For example, it can be the material that can adapt to teeth patterning, such as aluminium foil, because it is applicable to the deposition of nanofiber in the static weaving method and can keeping its shape after the tooth bending.Yet nanofibrous structures self also can be designed to a fixed structure, and it can keep its shape when being provided on the tooth with box lunch.
Nanofibrous structures can be designed to mate a plurality of teeth, for example row's front tooth.Nanofibrous structures can be based on the long-pending adhesive effect of undertaking this layer and dental surface of its high contact surface.Nanofibrous structures can be designed to a fixed structure, makes device have adhesive effect to tooth.Pending tooth can comprise front tooth.Advantageously, structure can be designed for handling simultaneously front tooth and canine tooth.In a favourable embodiment, structure can be designed for covering the tip of canine tooth, for example in conjunction with covering front tooth.Nanofibrous structures can be designed so that to be fixed on the front side of tooth, the dorsal part that the use second portion is fixed on tooth with first.Figure among Figure 25 refers to the exemplary first by the system that is formed by the optional substrate of nanofibrous structures (for example a kind of nanofibrous structures) covering.In the side of first of device, the excision triangle is so that first that can bending apparatus, and makes remaining part meet the zone at the tooth dorsal part.The Zone Full of the first of device is covered on the front surface of tooth.Originally, the first of equipment is flat, and it limpens and preferably meets the shape of tooth in the time of on being applied to tooth.Because nanofiber layer is a highly porous property, compressible and fluffy structure, therefore can ideally wrap up around the shape of each single tooth, finally can obtain to make it on tooth, to fit and make triangle cooperate the feature of dorsal part, finally ideally meet teeth patterning.
Device have 0.5 to 15.0cm, more preferably 2 to 10cm, optimally 4 to 8cm length and 0.3 to 5.0cm, more preferably 0.5 to 4cm, 1 to 3cm width optimally.At the length side of first of device, excision triangle fragment in case can be on tooth the first of easily crooked and adaptation arrangement.The first of these triangle fragment penetrating devices, the degree of depth is 0.1 to 2.0cm, more preferably 0.3 to 1.5cm, optimally 0.5 to 1cm, leg length is 0.13 to 2.5cm, more preferably 0.4 to 2.0cm, optimally 0.7 to 1.3cm.In an alternative embodiment, rectangular edge is rounded to avoid lip-syncing to damage.Other suitable device shape can also be provided.
Nanofibrous structures can comprise nanofiber, so that the nanofiber of at least 30%, advantageously at least 50% nanofibrous structures has 3 to 2000nm average diameter.Be deposited on nano fabrics structure on the substrate and can have 1 μ m to 5000 μ m, the average thickness of 1 μ m to 2000 μ m advantageously, advantageously 10 to 2000nm, advantageously 3 to 800nm, 10 to 700nm diameter more advantageously.The diameter of the most of fibers that comprise in the fibre structure of the present invention (promptly 50% or more fiber) can be 3nm or bigger, 10m or bigger advantageously.As an optional feature, the diameter of the most of fibers that comprise in the fibre structure of the present invention (promptly 50% or more) is 2000nm or littler, advantageously 800nm or littler, 700nm or littler more advantageously.For the application, have the diameter of above-mentioned suggestion or the fiber that is in the described diameter range will be called as nanofiber, corresponding structure can be called nanofibrous structures.In embodiment, the invention still further relates to the wherein unified fibre structure of thickness of fiber, the standard deviation of thickness is no more than 80%, advantageously 50%, more advantageously 20% in the promptly whole fibre structure.Fibre diameter depends on the distance between outlet and the receiving plane.Relation curve between fibre diameter and the distance can be specific for polymer and solvent.Therefore, after having studied polymer solution or melt, can determine curve, because it is specific for polymer and solvent.It can pass through T﹠E, experimental result, theoretical model and wait to determine.Single nanofiber can have the length of 10 μ m to 50m.
Fibrous material can be any suitable material, such as polyamide, polystyrene, polycaprolactone, polyacrylonitrile, poly(ethylene oxide), PLA, polyacrylic acid, polyesteramide, polyvinyl alcohol, polyimides, polyurethane, collagen, cellulose and Related product, shitosan, methacrylate, silk, polyethylene vinyl acetate ester copolymer, polythene-ethenol copolymer, polyvinyl butyrate with contain the nanofiber of metal.Nanofibrous structures can also comprise the fiber that contains the pH regulator material, and this will further specify in this application.Can also be in nanofibrous structures other component of introducing device, for example by the concrete nanofiber of weaving.Nanofibrous structures can comprise the fiber of being made by polyamide, and this polyamide uses the mixture of formic acid and acetate, weaves by static and make.The ratio of formic acid and acetate can be 90/10 to 10/90 (weight %), preferred 30/70 to 70/30 (weight %), 40/60 to 60/40 (weight %) more preferably.It can be 50/50 weight percent advantageously.An advantage of about 50/50 weight percent percentage is to realize stable state production and high flow rate continuously.
This structure can have at least 65% porosity, for example mean porosities.Porosity, for example mean porosities can be in 65 to 99%, advantageously 70 to 98, more advantageously 75 to 95% scope.The aperture can change between 30nm to 8 μ m.Nanofibrous structures can for example can absorb and be equivalent to himself weight 3-12 water, solution, compound or gel doubly.
Nanofibrous structures can comprise at least 50% fibers straight, and wherein, it is straight basically part on 5 μ m distances at least that these fibers have.The linearity of fiber can for example be inferred from graphical analysis.Preferably, it is straight being included in most of fibers in the fibre structure (promptly 50% or more), promptly has part straight basically on the distance of 5 μ m (promptly 50% or more) by great majority and forms.Basically straight must be understood that, the main shaft of fiber, promptly along the axle of machine direction less than 45 °, for example less than 30 ° or for example less than 5 ° angle in change, the scope that changes of taking measurement of an angle is 10 microns a distance.This angle is the angle of the maximum that measures between the tangent line at two some places of main shaft on the fibre length of being considered.Linear standard deviation on the distance of being considered can be no more than 5%.
As a favourable feature, fibre structure of the present invention can comprise seldom crosslinked or do not have crosslinked, for example micrometer fibers or nanofibrous structures, the most of fibers that wherein comprise (promptly 50% or more) are essentially no crosslinked.Thus, the no crosslinked covalent bond that can be defined as another polymer chain that does not have polymer chain connecting a fiber and adjacent fiber.Distance between the three or more individual outlets can also be designed to obtain the essentially no any chemically combined fibre structure of at least 50% fiber.They advantageously do not take place crosslinked with adjacent fiber.Therefore, crosslinked meaning occurs in two connections between the fiber, is not only the contact of two fibers.This is that spacing between outlet is at least the result of 1cm.Be not bound by theory, believe that this effect is owing to the easier evaporation of solvent in the fiber forming process, therefore evaporation more quickly.Believe that for exit separation the solvent evaporation accounts for the too many time in the fiber forming process less than 1cm.This causes the fusion of adjacent fiber and therefore and crosslinked.If fibre structure is made by melt, problem may be not eliminate the fuel factor that takes place when outlet is leaned on too closely mutually fully.Then, fibre forming is incomplete, may have the middle phase between a kind of melt and the solid, makes to form crosslinked fiber.More weak physics interacts, and interacts or hydrogen bond does not belong to the scope of crosslinked definition such as Van der Waals.
Nanofibrous structures can comprise the fiber of at least 50% random orientation.In one embodiment, compound forms pulvinulus.
Advantageously, can obtain nanofibrous structures by static a kind of material of weaving.The fiber of feature shown in having can obtain by the static textile technology that uses the multiinjector system.Nozzle can be separated by at least 1cm, the spacing of 4cm at least for example.And, in order to control diameter, can adjust the distance between nozzle and the receiving plane.In the static fabrication processes, change the variation that distance can realize fibre diameter in the nanofibrous structures.The variation of other parameter of the static weaving that causes owing to the variation that is exported to the receiver distance can for example be determined with experimental technique such as voltage to be applied.
In concrete embodiment of the present invention, nanofibrous structures can on one or more dimension, have variation porosity, fibre diameter or the density of fiber, such as depth direction at nanofibrous structures, be on the cross section of nanofibrous structures and/or surface direction, promptly along in the plane on the surface of the nanofibrous structures that is applicable to the contact tooth these variations taking place.The variation of the diameter of porosity, fiber or the density of fiber can be according to predetermined change curve, so that the dental whitening part or the predetermined release profiles of its bleaching agent more specifically are provided.This variation can obtain according to the feature of the method described in the others, and the gained nanofibrous structures can have, some or all of feature of the nanofibrous structures described in the application's the embodiment of others.
In an example, the porosity of nanofibrous structures can increase from a side a to side that will contact dental surface of contact substrate layer.Can obtain the variation of the density of the diameter of porosity continuous or stepwise, fiber or fiber.In an example, comprise two-layer at least laminar nano fibre structure by use with nanofiber of different-diameter, can obtain this variation.
Therefore, provide predetermined density, porosity or diametral curve that predetermined dental bleaching agent rate of release can be provided, this is for providing according to predetermined curve, and for example the unified predetermined curve of bleaching agent release is advantageously.Other curve can also be provided.For example, discharge most of (for example about 40% to 50%) bleaching agent, and remainder can release in the ensuing period of longer time (for example subsequently 9 minutes) at initial period (for example preceding 4 minutes).In one aspect, the invention still further relates to the nanofibrous structures described in the embodiments of the present invention that are designed to the dental whitening field.Also be applied to this aspect of the present invention with the identical feature and advantage described in these embodiments about nanofibrous structures.
As implied above, dental whitening partly comprises bleaching agent, and it is the active component of bleaching teeth or a plurality of teeth or comprises the reagent that this component maybe can discharge or produce this component.Bleaching agent is sometimes referred to as bleaching compounds, can be peroxide, such as product, calper calcium peroxide or its combination of hydrogen peroxide or generation hydrogen peroxide.Bleaching agent can also be the compound that produces peroxide, such as the combination of carbamide peroxide, perborate, percarbonate, oxyacid and/or these chemical reagent.For example, operable bleaching concentration of component, for example concentration of hydrogen peroxide can be 1 to 25 weight % of 0.1 to 35 weight % of dental whitening part, preferred dental whitening part, 3 to 16 weight % of dental whitening part more preferably.Can adopt the concentration (for example hydrogen peroxide) of bleaching agent by this way, active component, for example the concentration of hydrogen peroxide can be 0.1 to 35 weight %, preferred 1 to 25 weight %, 3 to 16 weight % more preferably.
The dental whitening part can comprise filling compound.Filling compound can comprise one or more in glycerine, D-sorbite, polyethylene glycol or the propylene glycol.
The dental bleaching structure can also comprise the pH regulator compound, and it is a kind of regular national technical standard buffer solution.For example, it can be following any material or their combination, NaOH, hydrogen chloride, sodium phosphate, sodium bicarbonate, sodium stannate, citric acid or natrium citricum, but bright being not limited thereto of we.It can be 0.1 weight % to 10 weight % that pH in the dental bleaching part sets agent.In some embodiments, can directly in the dental bleaching part, provide the pH regulator agent.Because the activity of bleaching agent, stability and decomposition depend on that usually it is present in the pH of dental bleaching part wherein, so, can add the pH regulator agent so that have best bleaching agent activity.Yet, in dental bleaching part, provide immediately the pH regulator agent needing to cause in the storage process bleaching agent almost in non-activity and the use bleaching agent have aspect these two of enough activity this mutually.Yet, the pot-life of this compromise restriction dental bleaching product, or to I haven't seen you for ages the most effective time limit of restriction system.
Country is preferred embodiment of the present invention, can send pH regulator agent and bleaching agent separately.For the storage of bleaching agent, select bleaching agent to be stored in the pH of dental bleaching part wherein, make to have low decomposition rate, pH partly is about 5 such as dental bleaching, so that bleaching agent is in very stable status.When preparing to use or behind use and the pH regulator agent composition, because the effect of pH regulator agent, the pH of dental bleaching part can reach 7.5-8.0.For example, when brightener for tooth was had the nanofibrous structures absorption of pH regulator agent, this thing happens in meeting.Under this pH, but the relatively poor bleaching activity of bleach stability is stronger.Therefore, use during bleaching about 7.5 pH, use when storing that to be starkly lower than 6 pH be favourable.
A concrete scheme that overcomes storage problem is provided in one embodiment, and wherein, the pH regulator agent is as the powder on the substrate on the nanofibrous structures or that carry nanofiber (if existence).As an alternative or additional form, bleaching agent can be provided for nanofibrous structures respectively or support its substrate.In a preferred embodiment, in the fiber of nanofibrous structures, provide the pH regulator agent.For example, the latter can be by to the solution that is used to make nanofibrous structures, and the pH regulator material that for example adds appropriate amount in the static weaving solution is realized.The advantage of doing like this is that the different operation that the restriction user need implement can limit and reduce in use or the needs of the different component that stores respectively before preparing.
The dental whitening part can be a gel.It can comprise the material that forms gel.The concentration that forms the material of gel can be lower than 0.1 weight % of dental whitening part, for example is lower than 0.09 weight % of dental whitening part.The material that forms gel can comprise any in carboxymethyl cellulose, carboxy-propyl cellulose, natural gum, poloxamer or the carboxyl polyethylene or their combination.An advantage of embodiments of the present invention is the generation of using gel to reduce or prevent to leak.The latter can increase user's comfort level.For example, this can cause the stimulation of minimizing to around teeth part mouth.
Dental whitening part can comprise taste products so that produce good taste when carrying out dental bleaching.The example of this taste products can be spearmint/peppermint for example.
An advantage of embodiments of the present invention is that the viscosity of brightener for tooth part can be lower.Viscosity can be 10 centipoise to 1000 centipoises, advantageously 10 centipoise to 400 centipoises, 10 centipoise to 199 centipoises more advantageously.An advantage of embodiments of the present invention is, can provide the dental whitening part can have method and system than low viscosity (because absorption of fluids and releasing properties of nanofibrous structures).An advantage of embodiments of the present invention is, limit, reduce or even avoided from structure, exposing, for example leak into the gums of mouth or the risk on the palate.Perhaps, do not use gel, and be to use the aqueous solution and the aqueous solution is fixed in the nanofibrous structures.And low viscosity causes the bleaching compounds in the gel to have higher activity, so bleaching agent can more effectively be discharged in the tooth.
Dental whitening systems can comprise gum or palate protection component, such as the chemical constituent of protection gum or palate protection component (as
Figure G2008800161044D00571
), but the invention is not restricted to this.
According to an embodiment of the invention, dental whitening systems can be to make nanofibrous structures and dental bleaching partly keep the kit that separates in the storage process that is designed to before use.When the pH regulator agent is provided in nanofibrous structures, or when separating with dental bleaching agent at least, the latter causes and might bleach under the pH that optimizes, and makes bleaching agent produce high efficiency.Dental whitening systems can be packed into and be steeped in the shape cover, and this bubble shape cover itself can be used as the immersion dish, is used for nanofibrous structures is immersed in the dental whitening part.
Therefore, this equipment can be used as two parts and is delivered in user's hand, and the nanofibrous structures that wherein contains the pH regulator agent is a part, and dental whitening partly is another part.
In yet another aspect, the present invention relates to be used to implement the method for dental bleaching.The method of embodiments of the present invention can comprise uses nanofibrous structures and the dental whitening part of implementing dental bleaching.This method can be implemented in any suitable place, and the selection such as by the consumer promptly is not limited to for example can also use at home in the dentistry clinic.The advantage of this method is, it provides dental bleaching, and this produces aesthetic.This method can use the system for bleaching tooth described in any embodiment of first aspect of the present invention to implement, but the invention is not restricted to this.The dental whitening part can be packaged in the entire package with nanofibrous structures, but the dental whitening part advantageously with does not directly contact with nanofibrous structures in storage process.Nanofibrous structures and/or dental whitening part can be packed in the container, wherein will be dumped into the dental whitening part.This class packing can seal with plastic film or hardboard.Dental whitening partly may reside in the original container, and this container can seal.This method can be included in before the described dipping nanofibrous structures, provides the dental whitening part in the container that is fit to the dipping nanofibrous structures.
According to the embodiment of the present invention, this method comprises nanofibrous structures is immersed in the dental bleaching part.In order to flood nanofibrous structures, nanofibrous structures is put in the container, nanofibrous structures is facing to described dental whitening part.This method can also be included in the process of described dipping nanofibrous structures provides described pH regulator agent and the initial of described bleaching agent to contact.
According to the embodiment of the present invention, this method comprises that also the nanofibrous structures that will soak is applied to preset time of tooth and removes nanofibrous structures afterwards.Use the nanofibrous structures that soaked and to comprise that the shape that makes nanofibrous structures is fit to the shape of tooth.By using nanofibrous structures, the shape of structure can adapt to the shape of tooth rightly.Nanofibrous structures can have such structure, and feasible bond property by structure (for example because the surface area of the fiber of the nanofibrous structures that can contact with tooth) can be fixed on the tooth.Using nanofibrous structures can comprise around tooth extruding nanofibrous structures.Using the nanofibrous structures that soaked can comprise nanofibrous structures is applied on front tooth and the adjacent canine tooth so that cover the tip of canine tooth.The advantage of doing like this is, can obtain uniform bleaching, can bleach a plurality of teeth simultaneously thus, such as front tooth and canine tooth.In some embodiments of the present invention, nanofibrous structures can be designed to, apply the nanofibrous structures that soaked after, can dental whitening partly be discharged in the tooth by controlled way (for example controlled flow velocity).For example, this point can realize by the nanofibrous structures that uses used fiber to have different-diameter, porosity or density.And the method for embodiments of the present invention can comprise the step of the function of one or more component that one or more shows the dental whitening systems described in first aspect.
Shuo Ming mode below illustrates the exemplary method according to an embodiment of the invention, but the invention is not restricted to this by way of example.Thus, we illustrate a kind of method for whitening, and this method is utilized the dental whitening systems described in first aspect.This dental whitening systems comprises nanofibrous structures, and in the present example, it is deposited on the substrate; With a dental whitening part, in the present example, it is the tooth whitening gel in plastics or glass container.The amount of tooth whitening gel is 1 to 2ml.In the present example, these two kinds of components are stored in the plastic blister shape cover that seals with plastic film or cardboard.According to this exemplary method, this bubble shape cover can be opened, and can therefrom take nanofibrous structures and dental whitening part away.Then, these plastics or glass container can be opened, and dental whitening partly can be poured in the described bubble shape cover, and these goods can be used as plate and operate.Then nanofibrous structures (being deposited on the substrate in the present example) is placed bubble shape cover.By nanofibrous structures partly being provided to dental whitening, keeping substrate (if existence), will advantageously operate the latter simultaneously towards away from the dental whitening part.Therefore, the dental whitening part is absorbed by nanofibrous structures.This process was finished in 2-5 minute.In the process that absorbs the dental whitening part, preferred dental bleaching agent contacts for the first time with the pH regulator agent, because the pH regulator agent can be present in the nanofibrous structures at the very start, perhaps can and begin to offer nanofibrous structures before the immersion with dental bleaching part separate storage.In immersion process, dental bleaching agent can also mix with the pH regulator agent, and this will cause pH to increase to about 7-9.Then, can from bubble shape cover, take out the nanofibrous structures that soaked, by light pressure system is positioned on the front tooth then.This location can comprise covering front tooth and canine tooth, comprises their tip.The location can comprise folded part, and for example gable climbs over tooth and they are fixed on the tooth dorsal part.This fixing can enforcement by light pressure is provided wherein obtains adhesive effect by nanofibrous structures, do not need to add adhesive.Make the nanofibrous structures that is deposited on the substrate on tooth, keep one section preset time.After the processing, remove the nanofibrous structures that is deposited on the substrate and water rinse tooth or brush teeth with hand.
In yet another aspect, the invention still further relates to the dental whitening systems or the purposes of nanofibrous structures in the dental whitening field of any embodiment of above-mentioned aspect.The advantage of described system and/or structure and feature can cause the favourable purposes of this system and/or structure.
Shuo Ming mode by way of example below show the example of a plurality of first specific embodiment, but embodiments of the present invention is not limited thereto.
Embodiment 15
Equipment comprises that (1) is deposited on the nanofibrous structures on the substrate, its size is 7cm * 2cm, (2) be filled in tooth whitening gel (1ml) or the solution in plastics or the glass container and comprise (1) and (2) and with the bubble shape cover of plastic film or hardboard sealing.Open bubble shape cover, take out component 1 and 2.Open plastics or glass container, gel is poured in the bubble shape cover.The nanofibrous structures that is deposited on the substrate is placed in the bubble shape cover, makes nanofibrous structures towards gel (downwards).Gel is absorbed by nanofibrous structures.This process was finished in 2-5 minute.In the absorption process of gel or solution, it can also mix with the pH regulator agent in being present in nanofibrous structures, and this will cause pH to increase to 8 approximately.From bubble shape cover, take out the nanofibrous structures that is deposited on the substrate, complete element is placed on the front tooth by light pressure.Then, folding gable climbs over tooth, is fixed in the dorsal part of tooth.Because nanofibrous structures, they have viscosity inherently.The time that the nanofibrous structures that contains gel that is deposited on the substrate was kept on tooth 10 minutes.After the processing, remove the nanofibrous structures that is deposited on the substrate and water rinse tooth and/or brush teeth with hand.This process repeated twice in one day, continued for example 7 days.
4 testers use aforesaid device according to above-mentioned program.All testers have when beginning corresponding to
Figure G2008800161044D00591
A on the color standard 3Color of teeth.After 7 days processing, the VITA colourity of all teeth is brought up to A 1Colourity, this is visually than A 3Want Bai Deduo.After 6 months, still keep A 1Value.
Embodiment 16
The tooth whitening gel that can be used for embodiments of the present invention (for example the above embodiments 15) can be contain D-sorbite 26, glycerine 25, hydrogen peroxide (35% solution) 20, carboxymethyl cellulose 0.10,
Figure G2008800161044D00601
2.50, citric acid 0.04, natrium citricum 0.5, tender leaf/peppermint 0.10 and water is so that obtain the tooth whitening gel of 100m/m%.It is 6% that said composition causes the concentration of hydrogen peroxide.Therefore, can use the embodiment of aspect of the present invention and/or the device described in the embodiment and program to use this gel.
Embodiment 17
The tooth whitening gel that can be used for embodiments of the present invention (for example the above embodiments 15) can be contain D-sorbite 21, glycerine 20, hydrogen peroxide (35% solution) 40, carboxymethyl cellulose 0.10,
Figure G2008800161044D00602
3.50, citric acid 0.04, natrium citricum 0.5, tender leaf/peppermint 0.10 and water is so that obtain the tooth whitening gel of 100m/m%.It is 12% that said composition causes the concentration of hydrogen peroxide.Therefore, can use the embodiment of aspect of the present invention and/or the device described in the embodiment and program to use this gel.
Embodiment 18
The tooth whitening gel that can be used for embodiments of the present invention (for example the above embodiments 15) can be contain D-sorbite 21, glycerine 20, hydrogen peroxide (35% solution) 50, carboxymethyl cellulose 0.10, 3.50, citric acid 0.04, natrium citricum 0.5, tender leaf/peppermint 0.10 and water is so that obtain the tooth whitening gel of 100m/m%.It is 15% that said composition causes the concentration of hydrogen peroxide.Therefore, can use the embodiment of aspect of the present invention and/or the device described in the embodiment and program to use this gel.
Embodiment 19
The tooth whitening gel that can be used for embodiments of the present invention (for example the above embodiments 15) can be contain D-sorbite 14.5, glycerine 13.9, hydrogen peroxide (35% solution) 66.7, carboxymethyl cellulose 0.10,
Figure G2008800161044D00604
2.50, citric acid 0.04, natrium citricum 0.5, tender leaf/peppermint 0.10 and water is so that obtain the tooth whitening gel of 100m/m%.It is 20% that said composition causes the concentration of hydrogen peroxide.Therefore, can use the embodiment of aspect of the present invention and/or the device described in the embodiment and program to use this gel.
Embodiment 20
The tooth whitening gel that can be used for embodiments of the present invention (for example the above embodiments 15) can be contain D-sorbite 6, glycerine 6, hydrogen peroxide (35% solution) 83.3, carboxymethyl cellulose 0.10,
Figure G2008800161044D00605
2.50, citric acid 0.04, natrium citricum 0.5, tender leaf/peppermint 0.10 and water is so that obtain the tooth whitening gel of 100m/m%.It is 25% that said composition causes the concentration of hydrogen peroxide.Therefore, can use the embodiment of aspect of the present invention and/or the device described in the embodiment and program to use this gel.
Embodiment 21
Embodiment described in the above embodiment 15 to 20 for example can be used in combination with the nanofibrous structures that comprises the fiber that polyamide makes, and wherein, described nanofiber makes by using formic acid and acetate 50/50% to carry out the static weaving as solvent.

Claims (25)

1. electrospinning device that is used for the electrospun fibers structure, described electrospinning device comprises:
-one group of outlet (5) that is used to export solution or melt,
-be used for the receiving plane (8) of acceptance from the output of described outlet (5) group, wherein, described receiving plane (8) is designed to and can moves up in the first party parallel with described receiving plane (8), by the described mobile vertical production that is used for described fibre structure,
-be used between described outlet group and described receiving plane producing the voltage source (1) of electrical potential difference,
It is characterized in that described electrospinning device is designed to following form: in the electrostatic spinning process, the outlet of described equipment and the distance between the receiving plane change according to predetermined curve, thereby obtain predetermined fiber thickness curve in whole fibre structure.
2. electrospinning device as claimed in claim 1, it is characterized in that, described electrospinning device is designed to following form: for different described outlets, along described first direction, provide between described outlet (5) and the receiving plane (8) at preset distance curve, thereby cause the variation of distance perpendicular to the distance on the direction of receiving plane (8).
3. electrospinning device as claimed in claim 1 or 2 is characterized in that, described preset distance curve is the distance Curve that reduces or increase.
4. electrospinning device as claimed in claim 3 is characterized in that, described distance Curve is the distance Curve of increase that dullness reduces or dull.
5. as the described electrospinning device of above any one claim, it is characterized in that, described outlet (5) group comprises at least two outlets (5) subgroup, wherein, each described subgroup is by forming with the equidistant outlet of described receiving plane (8) (5), wherein, the distance between each subgroup and the receiving plane (8) can be set according to the described preset distance curve along described first direction.
6. as the described electrospinning device of above any one claim, it is characterized in that described outlet group is included in respect to receiving plane with in a kind of angle plane inclined.
7. as the described electrospinning device of above any one claim, it is characterized in that the distance of 1cm is at least separated at least two adjacent outlets (5) of described outlet (5) group mutually.
8. as the described electrospinning device of above any one claim, it is characterized in that, the distance between the outlet (5) in each described outlet (5) group be designed to obtain to comprise at least 50% basically not with the fibre structure of the crosslinked fiber of adjacent fiber.
9. as the described electrospinning device of above any one claim, it is characterized in that, described outlet (5) group be designed to can with the parallel and vertical direction of described receiving plane (8) with described first direction on move back and forth.
10. as the described electrospinning device of above any one claim, it is characterized in that, described equipment comprises the control device (10) that is used to change distance between described outlet and the receiving plane, so that change the diameter of the fiber of being produced in the described electrostatic spinning process of described fibre structure.
11. the method for a producd fibers structure said method comprising the steps of:
-be provided for exporting outlet (5) group of solution or melt,
-be provided for accepting receiving plane (8) from the output of described outlet (5) group,
-make described receiving plane (8) move up in the first party parallel with described receiving plane (8),
-between described outlet (5) group and described receiving plane (8), apply electrical potential difference,
-move and apply in the electrical potential difference process described, provide solution or melt to described outlet (5),
It is characterized in that provide in the process of solution or melt to outlet described, the distance between described outlet (5) and the receiving plane changes according to predetermined curve, with the fiber thickness curve that obtains to be scheduled to.
12. method as claimed in claim 11, it is characterized in that, for different outlets, by along described first direction, provide between described outlet (5) and the receiving plane (8) at preset distance curve, obtain described variable in distance perpendicular to the distance on the direction of receiving plane (8).
13., it is characterized in that described preset distance curve is the distance Curve that reduces or increase as claim 11 or 12 described methods.
14. method as claimed in claim 13 is characterized in that, described distance Curve is the distance Curve of increase that dullness reduces or dull.
15. as any described method in the claim 11 to 14, this method also is included in and is parallel on described receiving plane (8) and the direction perpendicular to described first direction, reciprocally moves in described outlet (5) group and/or the described receiving plane (8) at least one.
16. as any described method in the claim 11 to 15, it is characterized in that, obtaining described variable in distance perpendicular to relatively moving on the direction of receiving plane by the outlet receipts face that connects is provided.
17. electrospun fibers structure that comprises fiber, it is characterized in that, the diameter of described fiber is according to predetermined curve, along a dimension variation of described electrospun fibers structure, and in any part perpendicular to described dimension, the variation of described fibre diameter is less than 10%.
18. electrospun fibers structure as claimed in claim 17 is characterized in that, the diameter of described fiber is according to predetermined curve, along a dimension variation of described electrospun fibers structure.
19. as claim 17 or 18 described electrospun fibers structures, it is characterized in that structure comprises at least 50% fibers straight, wherein, at least 50% fibers straight is by 50% or have the fibrous of part straight basically on 5 μ m distances more.
20. as any described electrospun fibers structure in the claim 17 to 19, it is characterized in that, comprise at least 50% basically not with the crosslinked fiber of adjacent fiber.
21. as any described electrospun fibers structure in the claim 17 to 20, it is characterized in that, comprise the fiber of at least 50% random orientation.
22., it is characterized in that having at least 65% porosity as any described electrospun fibers structure in the claim 17 to 21.
23. as any described electrospun fibers structure in the claim 17 to 22, it is characterized in that, wherein 50% or more fiber have 3 to 2000nm average diameter.
24. as any described electrospun fibers structure in the claim 17 to 23, described fibre structure comprises two or more adjacent layers, wherein, each layer with two adjacent layers is by having the fibrous of following character: the average diameter of this fiber is less than the average diameter of the fiber of an one adjacent layer, greater than the average diameter of the fiber of its another adjacent layer.
25. a controller is used to be controlled to be the electrospinning device middle outlet (5) of claim 1 to 10 and the distance between the receiving plane (8) provides the preset distance curve.
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PCT/EP2008/052835 WO2008110538A2 (en) 2007-03-09 2008-03-10 Nanofibrous structures and their use in dental applications
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