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CN105818492B - A kind of bioactivity phosphate base continuous glass fibre composite material for weaving and application thereof - Google Patents

A kind of bioactivity phosphate base continuous glass fibre composite material for weaving and application thereof Download PDF

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Publication number
CN105818492B
CN105818492B CN201610188723.8A CN201610188723A CN105818492B CN 105818492 B CN105818492 B CN 105818492B CN 201610188723 A CN201610188723 A CN 201610188723A CN 105818492 B CN105818492 B CN 105818492B
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glass fibre
bioactivity
continuous glass
phosphate base
weaving
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CN105818492A (en
Inventor
祖群
克里斯·路德
刘劲松
刘晓玲
张焱
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Nanjing Fiberglass Research and Design Institute Co Ltd
University of Nottingham
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Sinoma Science and Technology Co Ltd
University of Nottingham
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    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/067—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of fibres or filaments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/026—Ceramic or ceramic-like structures, e.g. glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04—Macromolecular materials
    • A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • 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
    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
    • 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
    • B32B5/08—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 the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • 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
    • B32B2250/20—All layers being fibrous or filamentary
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Textile Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Woven Fabrics (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Materials For Medical Uses (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a kind of bioactivity phosphate base continuous glass fibre composite material for weaving and application thereof, bioactivity phosphate base continuous glass fibre composite material for weaving, its composition includes bioactivity phosphate base continuous glass fibre fabric and biocompatible polymer, or include blend fabric and biocompatible polymer, wherein, blend fabric is the blend fabric of biological reactive phosphate base continuous glass fibre and acid fiber by polylactic.The mechanical property of bioactivity phosphate base continuous glass fibre composite material for weaving of the present invention reaches the level of skeleton, mechanical performance matches with bone tissue, there are excellent biocompatibility, degradability and absorbability simultaneously, can be matched in excellence or beauty with natural bone, and processing characteristics is good.

Description

A kind of bioactivity phosphate base continuous glass fibre composite material for weaving and application thereof
Technical field
The present invention relates to a kind of bioactivity phosphate base continuous glass fibre composite material for weaving and application thereof, belong to raw Thing field of medical materials.
Background technology
The bone renovating material effect of clinical practice has three kinds：It is fixed in self-bone grafting, osteoacusis and bone.Bone induction material is direct Inducing mesenchymal cell differentiation is osteogenic cell, Gegenbaur's cell, and then forms the performance of bone tissue, such as autologous bone, people's tooth；Bone passes The property led material is to provide support for the formation of blood vessel and disconnected symphysis, and such as tricalcium phosphate, hydroxyapatite, PLA are artificial Polymeric material；Metal and nonmetallic two classes material are fixed with bone, it is such as direct with metal hone lamella using more for metal material Knochenbruch is connected or is fixed up by face in or beyond knochenbruch.Bone internal fixation material needs to use when being many fracture patient operations Operating equipment, fixing metal material in the traditional bone clinically applied at present mainly has stainless steel, pure titanium or titanium alloy etc., this A little is all permanent implanted material (can not biodegradable, nonabsorable), metal material be chronically implanted people know from experience cause deteriorate, mistake Quick, stress is blocked and causes osteoporosis, postoperative possible second fracture, and need carried out after patient's union it is secondary Operation is taken out, and considerably increases pain and the financial burden of patient.In recent years, bone inside-fixture made of existing absorbable material For clinic, compared with metal inside-fixture, most attraction is exactly the absorbable interior fixed dress with biodegradability Put, secondary take out is not required to after fracture fixation and healing is carried out and is performed the operation.The conventional absorbable material of orthopaedics is divided into macromolecule at present Material, inorganic material and composite three major types.
The material formed by two or more different absorbable material optimum organization is referred to as absorbable composite. Absorbable composite be broadly divided into compound between the compound, high polymer material between high polymer material and inorganic material and It is compound between high polymer material or inorganic material and bioactive substance.Single polymers have it not as bone internal fixation material Foot, does not have osteoconductive, the speed of Bone Defect Repari defect is very slow, for the bony defect of human body, it is difficult to reaches complete reparation first； Secondly, the mechanical property of materials is also insufficient as the bone fracture internal fixation material of bearing position.
In the late two decades, composition for repairing bone is more and more in clinical research and application, such as：Inorganic and organic composite Mixed with polymers such as material, hydroxyapatite, 45S5 bio-vitrics, phosphate glass and PLA etc..It is fixed in this kind of bone The existing clinical practice of composite, but the relatively low situation of intensity and modulus is still suffered from, generally also it is only used for non-weight bearing area Internal fixation of fracture, osteotomy, joint fusion etc..And it is exactly to adopt further to improve one of approach of composite materials property With continuous lod polymer, bearing position application can be used as, i.e. material initial mechanical performance should exceed or approach Compact bone, i.e. 100~200MPa of tensile strength, compressive strength reach 150MPa, and bending strength reaches 250MPa, and bending modulus reaches To 25GPa, fracture toughness is in 8MPa/m1/2.Reinforcing fiber has organic or inorganic fiber of carbon fiber, biological absorbable etc..Carbon is fine Dimension enhancing polymer initial strength and modulus are higher, but one side price is high, on the other hand itself and polymer interface poor compatibility, Mechanical property decay is fast in vivo, and carbon fiber can not degradable absorption, the particle after it degrades is dispersed in group Around knitting, body may be caused to damage.Organic fiber strengthens polymer, though improving the strength of materials, modulus, which is improved, to be had Limit.Existing inorganic silicate glass fiber reinforced polymer report, manufactured composite have preferable mechanical property, but silicon Hydrochlorate bioactivity glass degradation time is longer, it is necessary to time of 1 to 2 years, SiO2It can not convert in vivo and body bone tissue Similar material, its metabolic mechanism are also not very clear.
Bioactivity phosphate glass has excellent solubility property in aqueous solution, and rate of dissolution can be from a few hours Change to several weeks, it is that glass has bioactivity basic to dissolve the monovalence of release or divalent ion.With good degradation property Phosphate-based glass turns into Bone Defect Repari new bio glass material, is more and more studied and applied in recent years.
Bioactivity phosphate glass can occur series reaction at interface, be formed in the presence of tissue liquid One layer of hydroxyapatite similar to skeleton inorganic salts, it can reach and combined closely to meet with human body hard tissue or soft tissue Different clinical requirements.Since the 1970s comes out, phosphate-based glass has been applied to the neck such as plastic surgery, dentistry Domain, such as it is used for pocket defect, the inserts of gum and the devitrified glass of corona for filling bone.And phosphate-based glass conduct Bone Defect Repari medicine equipment, such as bone internal fixation material, in addition to good degradability, in degradation process, group can be promoted Knit the growth of cell, it is often more important that, as internal fixation material should also have with bone tissue similar in mechanical property.But with Body bone tissue is compared, and the bending modulus of phosphatized spheroidal fossils reaches 200GPa, far above the rigidity (7~40GPa) of people's bone, Mechanical performance mismatches with bone tissue, limits its application in load-bearing Bone Defect Repari field to a certain extent.
In addition, the degradable high polymer material such as PLA (PLA), PGA and polycaprolactone for developing in recent years, is obtained Relevant authentication was obtained, for a series of clinical practices, such as interior fixed hone lamella, screw, holdfast, treats four limbs non-weight bearing bone bone Folding, hand and foot's Fracture of bone and joint, cancellous bone fracture of head of femur, cranium jaw are fixed, vertebral fracture, children's femoral fracture etc..But by It is less than normal person's cortex bone in its mechanical property, can only be used to the repair of fractured bones of non-weight bearing area cancellous bone.
There are some researches show fiber is such as made in some phosphate glasses, and tensile strength can reach or more than human Cortex's bone Level, the defects of fragility of block phosphate glass is big, fracture toughness and mechanical strength are relatively low can be overcome.It is well known that Using continuous glass fibre processing yarn fabric enhancing composite, the designability of composite has been can further improve, it is such as excellent Change 0 °/90 ° direction fiber contents, adjustment fabric laying direction, different fiber hybrids, different fabric construction layings, etc. so that The anisotropy of composite can reach sets requirement, while also cause composite to have good drilling, screw thread processed etc. Using processing characteristics.However, phosphate glass fibre is compared with the silicate glass fiber of existing industrial applications at present, in fibre Very big deficiency also be present in terms of dimension shaping and textile process.Although existing document report bioactivity phosphate base glass fibre Making, but due to phosphate glass fibre forming technology poor performance, while poor chemical stability, make its fibre forming property bad, no Has spinnability.The single continuous fiber for being only for research obtained by present, although also giving higher intensity (900- 1400MPa) and modulus (40-65GPa) data.It is well known that the performance of glass fiber single filament, it is impossible to represent continuous glass fibers Tie up the performance of yarn.Because monofilament is by processing abrasion, and with the contact with moisture time in air is short, suffered chemical erosion Action time is also short, therefore the filament properties of experimental determination are higher by 30~40% than the continuous fiber yarn after processing.It is and single Root fiber can not carry out textile process, it is difficult to industrial applications, it is impossible to it is excellent to play the mechanical performances such as continuous glass fibre intensity Gesture, the performance that enhancing polymer composites performance and normal person's cortex bone are made of monofilament are also variant.
The content of the invention
To solve Bone Defect Repari bioactive composite material mechanics and processing characteristics is bad, absorbable and compatibility is not strong etc. Problem, a kind of bioactivity phosphate base continuous glass fibre composite material for weaving of offer of the invention and application thereof.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
A kind of bioactivity phosphate base continuous glass fibre composite material for weaving, its composition include bioactivity phosphate Base continuous glass fibre fabric and biocompatible polymer, or comprising blend fabric and biocompatible polymer, wherein, mix Yarn fabric is the blend fabric of biological reactive phosphate base continuous glass fibre and acid fiber by polylactic.
The application is compound by high molecular polymers such as phosphate glass fibre and polylactic acid fibers, and fiber reinforcement is made Composite, the premium properties of the original component of each material can be not only kept, can also obtained not available for single component material Performance.
The mechanical property of application gained composite reaches the level of skeleton, while has excellent bio-compatible Property, degradability, can match in excellence or beauty, and processing characteristics is good with natural bone.
In order to be further ensured that the performances such as the mechanical property of gained composite and biocompatibility, the application is using many Bioactivity phosphate base continuous glass fibre precursor is drawn in the porous bushing that 50 holes are let slip a remark, its filament diameter is at 5~25 μm Between controllable, preferably 7~17 μm, more preferably 9~13 μm, road textile process after progress.
The application bioactivity phosphate base continuous glass fibre feature is fibrous mechanical property height, and single fiber stretching is strong Spend for 700~1500MPa, 50~65GPa of stretch modulus；The tensile strength of manufactured yarn is not less than 0.25N/tex.Fiber connects Continuous property is good, the textile process such as is easy to doff, twists thread, and fibre chemistry stability is good, places do not lump or efflorescence in atmosphere.
The twisting of bioactivity phosphate base continuous glass fibre is made into phosphate glass fibre a twist yarn, glass in yarn Fiber can include a kind of component or two kinds of component phosphate glass fibres, also can by a kind of component phosphate-based glass fiber with Acid fiber by polylactic blending is into textile strand, and the ratio of two kinds of fiber contents is the demand according to composite board amount containing yarn in scribbled To design and produce, preferable phosphate base continuous glass fibre is 0.15~1.5 with acid fiber by polylactic scribbled volume ratio.
Phosphate base continuous glass fibre fabric or blend fabric can use known loom to be made into flat woven thing, wrap The Textile Machineries such as rapier loom, fly-shuttle loom, inkle loom are included, institutional framework can be plain weave, twill, satin weave, leno, basket Deng can also use three dimensional knitting machine, weave 3-D solid structure fabric.
The volume content (Vf) of phosphate base continuous glass fibre is controlled between 10% to 65% in composite board.It is compound Material shaping uses hot-press method, sheet or tabular fabric is coated with mould, thermoplastic fibre, powder or sheet material are applied in advance It is added in fabric, then carries out hot pressing, the composite being pressed into, composite can be further processed into hone lamella, bone Fixed bone renovating material in nail etc. is absorbable.
In order to further improve the biocompatibility of the mouldability of fiber and products obtained therefrom, bioactivity, degradability and power Learn performance, it is preferable that the component of the phosphate base continuous glass fibre used in bioactivity phosphate base continuous glass fibre fabric Including：P2O5：35~55%, CaO：10~40%, MgO：10~30%, B2O3：2~20%, Na2O：0~24%, K2O：0~ 5%, Fe2O3：1~10%, MxOy：0~15%, the MxOyIt is Ag2O、CuO2、Ga2O3Deng the percentage is Mole percent Than.
The application glass ingredient designs fibre forming, degraded, bioactivity and the fibre for needing comprehensive consideration phosphate-based glass The changing factors such as mechanical property are tieed up, phosphate-based glass composition and content are adjusted by creative research so as to be applied to Strengthen the continuous phosphate-based glass fiber prescription of polymer composites.
P in phosphate-based glass2O5As Network former, glass body structure is formed during melt supercooled, substantially Unit is phosphorus oxygen tetrahedron [PO4], there is the oxygen with double bond in each phosphorus oxygen tetrahedron, a tetrahedral drift angle is broken Split and deform, glassy structure is the chain structure that the closing linkwork being interleaved with each other by many is formed.P in composition2O5Contain Measure low, be not easy to form glassy state；Improve P2O5Content, help to reduce glass smelting temperature and recrystallization temperature, this is advantageous to glass Fibre forming, but too high P2O5Content so that glass degradation rate increases, and chemical stability reduces, and is unfavorable for rear road weaving and adds Work.Currently preferred P2O5Content is 35~55mol%.
In polynary phosphate glass, Na is introduced2O can improve glass melting performance, reduce recrystallization temperature, and suitable The Na of amount2O contributes to aggregation network, improves the chemical stability of glass, but excessive introducing, increases in phosphate glass Non-bridging oxygen quantity between [PO4] tetrahedron, the glass mechanical property for making to have reduces, while accelerates the dissolving of glass, reduces glass Glass bioactivity.Currently preferred Na2O content is 0~24mol%.K+Ion electric-field intensity is less than Na+, suspension, which acts on, compares Na+Height, a small amount of introduce helps to reduce devitrification of glass trend, but high level can destroy the mechanical property of glass, while increases glass Glass rate of dissolution so that glass does not have bioactivity.Currently preferred K2O content is 0~5mol%.
CaO plays an important role to phosphate glass glass degradation rate and bioactivity, Ca+Ion belongs to network outer body Ion, network structure, filling and network space are not involved in, there is accumulation effect to network structure, improving CaO content contributes to glass The tight ness rating of network structure, the mechanical property and chemical stability of glass are improved, reduce glass biodissolution and cytotoxicity.CaO Too high levels are too low, can all cause devitrification of glass to aggravate and homogeneous glass can not be made.CaO content of the present invention be 10~ 40mol%.Mg+And network-modifying ion, ionic radius are less than Ca+Ion, MgO, which substitutes CaO, can improve the consistency of network, Increase fiber forming temperature, help to widen the shaping window of glass fibre, improve phosphate glass fibre forming technology performance. As MgO substitutes the increase of CaO amounts, glass biodissolution rate reduces, and the glass bioactivity not influenceed.It is currently preferred Content of MgO is 10~30mol%.
B is added in phosphate glass2O3Also the network structure intensity of glass can be improved, it is durable to improve glass fibre chemistry Property and mechanical stability, make drawing glass fiber strand have it is certain can the process-cycle, be advantageous to glass fabric Weaving, meanwhile, introduce appropriate B2O3Phosphate glass also there is good bioactivity, appropriate B2O3Help to suppress Crystallization, but too high B2O3Introducing will destroy network structure, accelerate devitrification of glass, glass fibre forming technology degradation, this hair Bright preferable B2O3Content is 0~20mol%.
Fe is introduced in phosphate glass2O3Glass biodissolution can be reduced so that the degradation rate of phosphate-based glass is controllable. With Fe2O3The increase of content, phosphate glass rate of dissolution are reduced, biocompatibility had no adverse effect, but content is unsuitable It is too high, currently preferred Fe2O3Content is 1~10mol%.
Present invention additionally comprises Ag is adulterated in phosphate glass2O、CuO、Ga2O3Deng the introducing of these oxides, in phosphoric acid Being discharged into salt glass degradation process in surrounding tissue has antibacterial action.
In order to be further ensured that the mechanical property of products obtained therefrom and biocompatibility, the continuous glass of bioactivity phosphate base Yarn used in fabric is that the bioactivity phosphate base continuous glass fibre of one or two kinds of components has twist yarn or non-twist thick Yarn, yarn used in blend fabric are bioactivity phosphate base continuous glass fibre and acid fiber by polylactic mixed yarn.
In order to meet various demands, the fabric in thing reactive phosphate base continuous glass fibre composite material for weaving is net The shape of shape, planar cloth or solid (can be cylinder etc.), the institutional framework of fabric is leno, basket, plain weave, twill, satin weave Or 3 D multi-directional.
In order to further improve the quality of products obtained therefrom, bioactivity phosphate base continuous glass fibre composite material for weaving In fabric using weaving fiber size for reinforcemeent, coating quality dosage (quality of size relative to coating size after fiber Quality) be 0.4~1.5%.
As the further preferred scheme of the application, weaving fiber size for reinforcemeent includes：Soluble polyurethane, polypropylene Yogurt liquid, polycarbonate emulsion, polydactyl acid emulsion, phosphino- polyacrylic acid (PPA), glyceride, monoglyceride or sorbierite In fatty acid ester any one or it is two or more.It so can further lift the quality of products obtained therefrom.
In order to be further ensured that the mechanical property of products obtained therefrom, processing characteristics, the absorbable performance such as row and biocompatibility, It is preferred that biocompatible polymer is polylactide (PLA), polylactic acid powder, PLLA (PLLA), poly- DL- third are handed over Ester (PDLLA), PGA (PGA), polyurethane (PU), makrolon (PC), polyvinyl alcohol (PVA), PLLA and second Lactide copolymers, poly- DL- lactides and PLLA copolymer, PLLA and trimethylene carbonate copolymer, One or more kinds of mixtures arbitrarily matched in caprolactone or glycolide copolymer.
In order to be further ensured that mechanical property, biocompatibility and the absorbability of gained composite, it is preferable that biology is living Acid phosphate base continuous glass fibre fabric accounts for the 10~65% of composite volume.
In order to be further ensured that the performance of products obtained therefrom, bioactivity phosphate base continuous glass fibre fabric is entered Row surface treatment (it is be complete in fabric knitting, with biocompatible polymer it is compound before be surface-treated), surface conditioning agent Quality dosage for 0.3~1.5% the quality of fabric after processing (quality of surface conditioning agent relative to), surface conditioning agent includes What one or more arbitrarily matched in titanate coupling agent, phosphate coupling agent, polydactyl acid or dibutylphosphoric acid ester is mixed Compound.
The application composite has controllable biodegradable performance, and the time degraded in simulated body fluid in vitro can pass through Phosphate base continuous glass fibre component, fiber aftertreatment technology, phosphate base continuous glass fibre and polymer fiber it is mixed The methods of spinning ratio, is adjusted.The content of phosphate base continuous glass fibre is higher in blend fabric, and degradation time is shorter.
In order to be further ensured that composite obtained by the application and the matching of people's cortex bone, the application bioactivity phosphoric acid The curved Qu Qiangdu of alkali continuous glass fibre composite material for weaving is 200~300MPa, and bending modulus is 12~30GPa.
The application bioactivity phosphate base continuous glass fibre composite material for weaving, have well in degradation process Mechanical property, impregnated 7 weeks in phosphate buffer (PBS), strength retention ratio is more than 50%.
Above-mentioned bioactivity phosphate base continuous glass fibre composite material for weaving can be used for manufacturing medical device.
Above-mentioned medical device is preferably implant.Implant is preferably bone renovating material fixed in adsorbable bone. Bone renovating material is preferably hone lamella or nail.
The NM technology of the present invention is with reference to prior art.
The mechanical property of bioactivity phosphate base continuous glass fibre composite material for weaving of the present invention reaches skeleton Level, mechanical performance matches with bone tissue, while has excellent biocompatibility, degradability and absorbability, Neng Gouyu Natural bone matches in excellence or beauty, and processing characteristics is good.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention Content is not limited solely to the following examples.
The specific preparation method of the application phosphate base continuous glass fibre composite material for weaving is as follows：
(1) prepared by batch
Raw material components are mixed according to formula, MgO, Na in formula2O, K2O, Fe2O3, CaO etc. has the phosphoric acid of respective substance Salt introduces, B2O3By H3BO3Introduce, remaining P is by P2O5Introduce.
(2) batch is handled
Due to P2O5The moisture absorption, while substantial amounts of heat is released, after batch weighs up, treat that the batch moisture absorption is anti-in fume hood It should finish, the secondary water that quality dosage is Glass Batch Quality 2% can be sprayed before water absorption reaction starts.
(3) glass smelting
The fusing energy of frit is using heat radiation and electric smelting heating means, phosphate glass liquid hot(test)-spot temperature control in kiln At 1250 DEG C~1300 DEG C, phosphate glass fusing and the requirement of homogenizing are met.
(4) glass melting kiln
Glass furnace is made up of high temperature resistant refractory material, such as dense zircon block, or liner platinum-rhodium alloy, its refractory material Thickness matches with the furnace design life-span；Meanwhile on furnace construction, using liner platinum-rhodium alloy smelting furnace and bottom floater guide block path Hierarchical design so that phosphate glass flows into bottom again after being first completely melt in smelting furnace, avoids charging from producing temperature of glass liquid It is raw to influence.
(5) wire drawing
Melt the glass metal clarified and enter more than 50 holes porous platinum-rhodium alloy bushings, drawing process coating weaving increases Strong type size (match somebody with somebody by water soluble chitosan polymer (Nantong is emerging into biological factory, carboxymethyl chitosan) and dibutylphosphoric acid ester The aqueous solution of system, wherein water soluble chitosan polymer content 4wt%, dibutylphosphoric acid ester 0.5wt%), coating quality dosage is 0.8%.
(6) spin
Textile yarn is made in phosphate glass fibre twisting, also can be degradable by phosphate-based glass fiber and PLA etc. Polymer fiber blending.
(7) fabric knitting
Using the Textile Machinery such as rapier loom or fly-shuttle loom, inkle loom, according to fabric texture, certain surface weight is made into With the phosphate base continuous glass fibre or mixed fiber fabric of thread count.
(8) fabric surface treatments
Dried after cleaning fabric using deionized water, the fabric after cleaning is put into processing agent solution and impregnated, after dipping Drying.
(9) composite manufactures
Composite material for weaving laying has three kinds of methods：Polylactic acid powder (Shenzhen City Guanghua Weiye Industry Co., Ltd) is scattered In fabric laying, fabric replace laying, blend fabric laying with polylactic acid film or fabric, the polymer such as PLA will be contained Fabric insert hot pressing carried out in mould, hot pressing temperature control is at 190 DEG C to 220 DEG C, and hot pressing duration was at 15 to 40 minutes, pressure The content (Vf) of the phosphate glass fibre in 2 to 4 MPas, composite board is controlled to control between 10% to 65%.
Embodiment 1
Glass formula, 48P2O5-12B2O3-20MgO-14CaO-1Na2O-5Fe2O3。
According to step 1 to 6, the continuous glass glass fiber list twist yarn of phosphate base (a diameter of 10- of glass fiber single filament is made 12 μm), the line density of yarn is 16.5tex, is that 16tex acid fiber by polylactic yarn is pooled capital blending with line density, phosphorus in scribbled The volume ratio of silicate glass fiber and acid fiber by polylactic is 1：4, phosphate glass fibre is made and pools capital with acid fiber by polylactic blending There is twist yarn, blending is had into twist yarn warping, warp thread coiled hair is made.According to step 7 rapier loom, weaved by plain weave technique into thickness The phosphate glass and acid fiber by polylactic blending ribbon for 0.32mm are spent, ribbon is through 5 close 12/cm, filling density/cm.According to step Rapid 8 are surface-treated, and clean blending ribbon, in surface coating surface inorganic agent, inorganic agent each component mass ratio is：Metatitanic acid Ester coupling agent：Dibutylphosphoric acid ester：Ethanol=1:1:100, the quality dosage of surface conditioning agent is the 1.9% (weight of surface conditioning agent Measure the weight relative to textile tapes after processing).Composite board manufacture is carried out according to step 9, the ribbon after processing is unidirectional Laying (blend fabric laying), the number of plies are 8 layers, are put into mould and carry out hot pressing.Hot pressing condition is 180 DEG C, 4MPa, hot pressing time For 20 minutes, composite plate is made.
Composite (20%Vf, i.e. thing reactive phosphate base the continuous glass fibre volume content of Woven glass cloth enhancing For 20%), initial flexural strength and modulus are respectively 250MPa and 12GPa.In phosphate buffer (0.15Mol/L PH 7.2) after being degraded 28 days in, its bending strength remains to maintain more than the 50% of initial strength.
(GB/T16886 is pressed in the biocompatibility test to fabric《The part of BiologicalEvaluationofMedicalDevice the 5th： Vitro cytotoxicity test》Test method), osteosarcoma cell can successfully be attached to fabric surface, and along fiber side Cover to growth and finally whole fabric.By the blue experiment of ALMA and DNA detections, (GB/T16886 is pressed relative to control group 《The part of BiologicalEvaluationofMedicalDevice the 5th：Vitro cytotoxicity test》Defined control group), the osteosarcoma in experimental group is thin Born of the same parents show higher cytoactive and DNA quantity.In addition, the composite of fabric enhancing is similarly shown good Biocompatibility, by cultivating osteosarcoma cell in composite cross-sections (including fiber and PLA base material), it is found that its is right Osteocyte has good affinity, and promotes cell division growth.
Embodiment 2
Glass formula, 48P2O5-12B2O3-20MgO-14CaO-0.5Na2O-0.5K2O3-5Fe2O3.
According to step 1 to 6, the continuous glass glass fiber list twist yarn of phosphate base (a diameter of 13 μ of glass fiber single filament is made M), the line density of yarn is 16.5tex, is that 16tex acid fiber by polylactic yarn is pooled capital blending with line density, phosphate in scribbled The volume ratio of glass fibre and acid fiber by polylactic is 1：3, phosphate glass fibre and acid fiber by polylactic blending plying, which is made, sth. made by twisting Yarn, blending there is into twist yarn warping, warp thread coiled hair is made.According to step 7 rapier loom, it is into thickness by the weaving of plain weave technique 0.32mm phosphate glass and acid fiber by polylactic blend fabric.Composite board manufacture, blend fabric are carried out according to step 9 It is put into after laying in mould and carries out hot pressing.Hot pressing condition is 180 DEG C, 4MPa, and hot pressing time is 20 minutes, and composite plate is made.
Composite (25%Vf, i.e. thing reactive phosphate base the continuous glass fibre volume content of Woven glass cloth enhancing For 25%), initial flexural strength and modulus are respectively 260MPa and 12GPa.In phosphate buffer (0.15Mol/L PH 7.2) after being degraded 28 days in, its bending strength remains to maintain more than the 50% of initial strength.
The experimental result of biocompatibility is the same as embodiment 1.
Embodiment 3
Glass ingredient is same as Example 2, and the volume ratio of phosphate glass fibre and acid fiber by polylactic is in scribbled 1：1.5, it is fine into the phosphate glass that thickness is 0.32mm and PLA by the weaving of plain weave technique according to step 7 rapier loom Tie up blend fabric.Composite board manufacture is carried out according to step 9, blend fabric, which is put into after laying in mould, carries out hot pressing. Hot pressing condition is 180 DEG C, 4MPa, and hot pressing time is 20 minutes, and composite plate is made.
Composite (40%Vf, i.e. thing reactive phosphate base the continuous glass fibre volume content of Woven glass cloth enhancing For 25%), initial flexural strength and modulus are respectively 280MPa and 14GPa.In phosphate buffer (0.15Mol/L PH 7.2) after being degraded 28 days in, its bending strength remains to maintain more than the 50% of initial strength.
The experimental result of biocompatibility is the same as embodiment 1.

Claims (12)

  1. A kind of 1. bioactivity phosphate base continuous glass fibre composite material for weaving, it is characterised in that：It is formed comprising biology Reactive phosphate base continuous glass fibre fabric and biocompatible polymer, or polymerize comprising blend fabric and biocompatibility Thing, wherein, blend fabric is the blend fabric of biological reactive phosphate base continuous glass fibre and acid fiber by polylactic；
    The component of bioactivity phosphate base continuous glass fibre includes：P2O5：35~55%, CaO：10~40%, MgO：10~ 30%, B2O3：2~20%, Na2O：0~24%, K2O：0~5%, Fe2O3：1~10%, MxOy：0~15%, the MxOyIt is Ag2O、CuO2Or Ga2O3, the percentage is molar percentage.
  2. 2. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1, it is characterised in that：It is raw The single fiber diameter of thing reactive phosphate base continuous glass fibre is 7~17 μm.
  3. 3. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1 or 2, its feature exist In：Yarn used in bioactivity phosphate base continuous glass fibre fabric is the bioactivity phosphoric acid of one or more kinds of components Alkali continuous glass fibre has twist yarn or roving, and yarn used in blend fabric is the continuous glass fibers of bioactivity phosphate base Dimension and acid fiber by polylactic mixed yarn；Fabric in bioactivity phosphate base continuous glass fibre composite material for weaving for it is netted, The shape of planar cloth or solid, the institutional framework of fabric is leno, basket, plain weave, twill, satin weave or 3 D multi-directional.
  4. 4. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1 or 2, its feature exist In：Fabric in bioactivity phosphate base continuous glass fibre composite material for weaving is using weaving fiber size for reinforcemeent, coating Quality dosage is 0.4~1.5%.
  5. 5. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 4, it is characterised in that：Spin Knitting fiber size for reinforcemeent includes：Soluble polyurethane, polyacrylate emulsion, polycarbonate emulsion, polydactyl acid emulsion, phosphine The mixture of one or both of based polyacrylic acid, glyceride, monoglyceride or Span any of the above proportioning.
  6. 6. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1 or 2, its feature exist In：Bioactivity phosphate base continuous glass fibre accounts for the 10~65% of composite volume.
  7. 7. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1 or 2, its feature exist In：The volume ratio of bioactivity phosphate base continuous glass fibre and acid fiber by polylactic is 0.15~1.5 in blend fabric.
  8. 8. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1 or 2, its feature exist In：Biocompatible polymer is polylactide, PLLA, poly- DL- lactides, PGA, polyurethane, poly- carbonic acid Ester, polyvinyl alcohol, PLLA and glycolide copolymer, poly- DL- lactides and PLLA copolymer, poly- L- third Lactide is appointed with one or more kinds of in trimethylene carbonate copolymer, polylactic acid powder, caprolactone or glycolide copolymer The mixture for proportioning of anticipating.
  9. 9. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1 or 2, its feature exist In：Bioactivity phosphate base continuous glass fibre fabric is surface-treated, surface conditioning agent quality dosage be 0.3~ 1.5%, surface conditioning agent include it is a kind of in titanate coupling agent, phosphate coupling agent, polydactyl acid or dibutylphosphoric acid ester or The two or more mixtures arbitrarily matched.
  10. 10. bioactivity phosphate base continuous glass fibre composite material for weaving as claimed in claim 1 or 2, its feature exist In：The bending strength of bioactivity phosphate base continuous glass fibre composite material for weaving is 200~300MPa, and bending modulus is 12~30GPa；Bioactivity phosphate base continuous glass fibre composite material for weaving impregnates 7 weeks in phosphate buffer PBS, Strength retention ratio is more than 50%.
  11. 11. bioactivity phosphate base continuous glass fibre composite material for weaving described in claim 1 to 10 any one Purposes, it is characterised in that：For manufacturing medical device.
  12. 12. purposes as claimed in claim 11, it is characterised in that：Medical device is implant.
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