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

Abstract

The invention discloses a biologically active phosphate-based continuous glass fiber textile composite material and its application. The biologically active phosphate-based continuous glass fiber textile composite material comprises a biologically active phosphate-based continuous glass fiber fabric and biocompatible The polymer may comprise a blended fabric and a biocompatible polymer, wherein the blended fabric is a blended fabric of bioactive phosphate-based continuous glass fiber and polylactic acid fiber. The mechanical properties of the biologically active phosphate-based continuous glass fiber textile composite material of the present invention reach the level of human bones, the mechanical properties match with bone tissue, and at the same time have excellent biocompatibility, degradability and absorbability, which can be comparable to natural bones , and good processing performance.

Description

A kind of bioactive phosphate-based continuous glass fiber textile composite material and its application

technical field

The invention relates to a bioactive phosphate-based continuous glass fiber textile composite material and its application, belonging to the field of biomedical materials.

Background technique

There are three types of bone repair materials in clinical application: osteoinduction, osteoconduction and bone internal fixation. Osteoinductive materials directly induce mesenchymal cells to differentiate into osteoprogenitor cells and osteoblasts, and then form bone tissue, such as autologous bone and human teeth; osteoconductive materials provide scaffolds for the formation of blood vessels and the healing of broken bones. Such as tricalcium phosphate, hydroxyapatite, polylactic acid and other artificial polymer materials; metal and non-metal materials are used for bone fixation, and metal materials are more widely used, such as using metal bone plates to fix the bone directly inside or outside the broken bone. To connect or fix broken bones. Internal bone fixation materials are the surgical equipment that many fracture patients need to use during surgery. The traditional internal bone fixation metal materials currently used in clinical practice mainly include stainless steel, pure titanium or titanium alloys, etc. These are permanent implant materials (not Biodegradable, non-absorbable), long-term implantation of metal materials into the human body will cause erosion, allergies, and osteoporosis due to stress shielding, and may fracture again after surgery, and a second surgery is required to remove the patient after the fracture heals, which greatly increases pain and financial burden to patients. In recent years, bone internal fixators made of absorbable materials have been used clinically. Compared with metal internal fixators, the most attractive is the biodegradable absorbable internal fixation device, which is used in fracture fixation and healing. There is no need for secondary removal surgery. At present, the commonly used absorbable materials in orthopedics are divided into three categories: polymer materials, inorganic materials and composite materials.

The optimal combination of two or more different absorbable materials is called absorbable composite material. Absorbable composite materials are mainly divided into composites between polymer materials, composites between polymer materials and inorganic materials, and composites between polymer materials or inorganic materials and bioactive substances. A single polymer has its shortcomings as a bone internal fixation material. First, it does not have osteoconductivity, and the speed of bone repair defect is very slow. It is difficult to achieve complete repair of bone defects in the human body; second, the mechanical properties of the material are not enough to be used as a load-bearing part. materials for internal fixation of fractures.

In the past two decades, there have been more and more clinical researches and applications of composite materials for bone repair, such as: inorganic and organic composite materials, hydroxyapatite, 45S5 bioglass, phosphate glass mixed with polymers such as polylactic acid, etc. This type of bone internal fixation composite material has been used clinically, but its strength and modulus are still low, and it can usually only be used for fracture internal fixation, osteotomy, arthrodesis, etc. in non-load-bearing parts. One of the ways to further improve the mechanical properties of composite materials is to use continuous fiber reinforced polymers so that they can be used as load-bearing parts, that is, the initial mechanical properties of the material should exceed or approach compact bone, that is, the tensile strength is 100-200 MPa, and the compression strength is 100-200 MPa. The strength reaches 150MPa, the flexural strength reaches 250MPa, the flexural modulus reaches 25GPa, and the fracture toughness is 8MPa/m ^1/2 . Reinforcing fibers include carbon fibers, bioabsorbable organic or inorganic fibers, and the like. The initial strength and modulus of carbon fiber reinforced polymer are high, but on the one hand, the price is high, on the other hand, its compatibility with the polymer interface is poor, and the mechanical properties decay quickly in the body, and carbon fiber cannot be completely degraded and absorbed. Particles of the particles spread around tissues and may cause damage to the organism. Organic fiber-reinforced polymers improve the strength of the material, but the modulus is limited. Inorganic silicate glass fiber-reinforced polymers have been reported, and the composite materials made have good mechanical properties, but the degradation time of silicate bioactive glass is long, which takes 1 to 2 years, and _SiO2 cannot Transformation of substances similar to human bone tissue, the metabolic mechanism is not very clear.

Bioactive phosphate glass has excellent solubility properties in aqueous solutions, and the dissolution rate can vary from hours to weeks. The monovalent or divalent ions released by dissolution are the basis for the glass to have biological activity. Phosphate-based glass with good degradation performance has become a new type of bioglass material for bone repair, and has been more and more researched and applied in recent years.

Under the action of human tissue fluid, bioactive phosphate glass can undergo a series of reactions at the interface to form a layer of hydroxyapatite similar to the inorganic salt of human bone, which can be closely combined with human hard or soft tissues to meet different clinical needs. Require. Since its introduction in the 1970s, phosphate-based glasses have been used in orthopedics, dentistry, and other fields, such as glass-ceramics for filling cavity defects in bones, filling materials for gums, and crowns. As a medical device for bone repair, such as bone internal fixation material, phosphate-based glass not only has good degradability, but also can promote the growth of tissue cells during the degradation process. More importantly, as an internal fixation material, it should also have Mechanical properties similar to those of bone tissue. However, compared with human bone tissue, the flexural modulus of phosphate glass-ceramics reaches 200GPa, which is much higher than the stiffness of human bone (7-40GPa). Applications in the field of bone repair.

In addition, degradable polymer materials such as polylactic acid (PLA), polyglycolide, and polycaprolactone developed in recent years have obtained relevant certifications and are used in a series of clinical applications, such as internal fixation bone plates, screws, and anchors Treatment of non-weight-bearing bone fractures of limbs, bone and joint fractures of hands and feet, femoral head fractures of cancellous bone, craniomandibular fixation, vertebral fractures, femur fractures in children, etc. However, because its mechanical properties are lower than those of normal human cortical bone, it can only be used for fracture repair of cancellous bone in non-weight-bearing parts.

Studies have shown that if some phosphate glass is made into fibers, the tensile strength can reach or exceed the level of human cortical bone, which can overcome the defects of high brittleness, low fracture toughness and low mechanical strength of bulk phosphate glass. As we all know, the use of continuous glass fibers to process textile-reinforced composite materials can further improve the designability of composite materials, such as optimizing the fiber content in the 0°/90° direction, adjusting the direction of fabric layup, mixing different fibers, and laying up different fabric structures. , etc., so that the anisotropy of the composite material can meet the set requirements, and it also makes the composite material have good processing properties such as drilling and threading. However, compared with the existing industrially applied silicate glass fibers, phosphate glass fibers still have great deficiencies in fiber forming and textile processing. Although the production of bioactive phosphate-based glass fibers has been reported in the literature, due to the poor forming process performance and poor chemical stability of phosphate glass fibers, it has poor fiber-forming properties and no spinnability. What is currently obtained is only a single continuous fiber for research, although higher strength (900-1400MPa) and modulus (40-65GPa) data are also given. As we all know, the performance of glass fiber monofilament cannot represent the performance of continuous glass fiber yarn. Since the monofilament has not been processed and worn, and the contact time with the moisture in the air is short, and the chemical attack time is also short, the performance of the monofilament measured in the laboratory is 30-40% higher than that of the processed continuous fiber yarn. Moreover, a single fiber cannot be processed for textile processing, which is difficult for industrial application, and cannot give full play to the advantages of mechanical properties such as the strength of continuous glass fibers. The performance of reinforced polymer composites made of monofilaments is still different from that of normal human cortical bone.

Contents of the invention

In order to solve the problems of poor mechanical and processing properties, poor absorbability and poor compatibility of bioactive composite materials for bone repair, the present invention provides a bioactive phosphate-based continuous glass fiber textile composite material and its application.

In order to solve the problems of the technologies described above, the technical scheme adopted in the present invention is as follows:

A bioactive phosphate-based continuous glass fiber textile composite material, which consists of a bioactive phosphate-based continuous glass fiber fabric and a biocompatible polymer, or a blended fabric and a biocompatible polymer, wherein the blended fabric It is a blended fabric of bioactive phosphate-based continuous glass fibers and polylactic acid fibers.

This application combines phosphate glass fiber with polymers such as polylactic acid fiber PLA to make fiber-reinforced composite materials, which can not only maintain the excellent performance of the original components of each material, but also obtain the advantages that single-component materials do not have. performance.

The mechanical properties of the composite material obtained through the application have reached the level of human bones, and at the same time, it has excellent biocompatibility and degradability, comparable to natural bones, and has good processing performance.

In order to further ensure the mechanical properties and biocompatibility of the obtained composite material, the application adopts a porous bushing plate with no less than 50 holes to draw a bioactive phosphate-based continuous glass fiber precursor, and its single filament diameter is between 5 and 5. It is controllable between 25 μm, preferably 7-17 μm, more preferably 9-13 μm, for subsequent textile processing.

The bioactive phosphate-based continuous glass fiber of this application is characterized by high fiber mechanical properties, the tensile strength of a single fiber is 700-1500MPa, and the tensile modulus is 50-65GPa; the tensile strength of the yarn made is not less than 0.25N /tex. The fiber has good continuity, which is convenient for textile processing such as winding and twisting. The fiber has good chemical stability and will not agglomerate or pulverize when placed in the air.

The bioactive phosphate-based continuous glass fiber is twisted to make phosphate glass fiber twisted yarn. The glass fiber in the yarn can contain one component or two components of phosphate glass fiber, or one component of phosphoric acid Salt-based glass fibers and polylactic acid fibers are blended into textile yarns. The ratio of the two types of fiber content in the blended yarns is designed and produced according to the requirements of the yarn content of the composite sheet. The preferred blend of phosphate-based continuous glass fibers and polylactic acid fibers The yarn volume ratio is 0.15-1.5.

Phosphate-based continuous glass fiber fabrics or blended fabrics can be woven into plane woven fabrics using known looms, including rapier looms, shuttle looms, ribbon looms and other textile machinery equipment, and the organizational structure can be plain weave, twill weave, satin weave, etc. Pattern, leno, mat pattern, etc., can also use three-dimensional knitting machine to weave three-dimensional three-dimensional structure fabric.

The volume content (Vf) of the phosphate-based continuous glass fiber in the composite sheet is controlled between 10% and 65%. Composite material molding adopts hot pressing method, sheet or plate fabric is laid in the mold, thermoplastic fiber, powder or sheet is pre-applied in the fiber fabric, and then hot pressed to form a composite material, the composite material can be further It can be processed into bone plates, bone nails and other absorbable internal fixation bone repair materials.

In order to further improve the formability of the fiber and the biocompatibility, bioactivity, degradability and mechanical properties of the resulting product, preferably, the components of the phosphate-based continuous glass fiber used in the bioactive phosphate-based continuous glass fiber fabric include: P ₂ O ₅ : 35-55%, CaO: 10-40%, MgO: 10-30%, B ₂ O ₃ : 2-20%, Na ₂ O: 0-24%, K ₂ O: 0-5% , Fe ₂ O ₃ : 1-10%, M _x O _y : 0-15%, said M _x O _y is Ag ₂ O, CuO ₂ , Ga ₂ O ₃ , etc., said percentages are mole percentages.

The design of glass components in this application needs to comprehensively consider the changing factors such as fiber formation, degradation, biological activity and fiber mechanical properties of phosphate-based glass. Through creative research and adjustment of the composition and content of phosphate-based glass, a material suitable for reinforced polymer composites is obtained. continuous phosphate-based glass fiber formulation.

In the phosphate-based glass, P ₂ O ₅ is used as a network former to form the main structure of the glass during the quenching process of the melt. The basic unit is the phosphorus-oxygen tetrahedron [PO4], and each phosphorus-oxygen tetrahedron has an oxygen with a double bond. , to break and deform one of the corners of the tetrahedron, and the glassy structure is a chain structure composed of many interwoven closed chains. Low P ₂ O ₅ content in the composition makes it difficult to form a glass state; increasing the P ₂ O ₅ content helps to reduce the glass melting temperature and crystallization temperature, which is conducive to the formation of glass fibers, but too high P ₂ O ₅ The content will increase the degradation rate of glass and reduce the chemical stability, which is not conducive to the subsequent textile processing. The preferred content of P ₂ O ₅ in the present invention is 35-55 mol%.

In multi-component phosphate glass, the introduction of Na ₂ O can improve the glass melting process performance, reduce the crystallization temperature, and an appropriate amount of Na ₂ O helps to aggregate the network and improve the chemical stability of the glass, but too much introduction, Increase the number of non-bridging oxygen between [PO4] tetrahedrons in phosphate glass, reduce the mechanical properties of some glasses, accelerate the dissolution of the glass, and reduce the biological activity of the glass. The preferred Na ₂ O content in the present invention is 0-24 mol%. The electric field strength of K ⁺ ions is lower than that of Na ⁺ , and the network breaking effect is higher than that of Na ⁺ . A small amount of introduction can help reduce the glass crystallization tendency, but a higher content will destroy the mechanical properties of the glass, and increase the dissolution rate of the glass, so that the glass does not Biologically active. The preferred K ₂ O content in the present invention is 0-5 mol%.

CaO plays an important role in the degradation rate and biological activity of phosphate glass glass. Ca ⁺ ions belong to the extracellular ions of the network, do not participate in the network structure, fill the gaps with the network, and have an accumulation effect on the network structure. Increasing the CaO content contributes to the glass network. The tightness of the structure improves the mechanical properties and chemical stability of the glass, and reduces the solubility and cytotoxicity of the glass. If the CaO content is too high or too low, the crystallization of the glass will be aggravated and homogeneous glass cannot be made. The content of CaO in the present invention is 10-40 mol%. Mg ⁺ is also an ion outside the network, and its ionic radius is smaller than that of Ca ⁺ ions. Substituting MgO for CaO can increase the density of the network, increase the fiber forming temperature, help to broaden the forming window of glass fiber, and improve the performance of phosphate glass fiber forming process. As the amount of MgO substituted for CaO increased, the dissolution rate of the glass decreased without affecting the biological activity of the glass. The preferred MgO content in the present invention is 10-30 mol%.

Adding B ₂ O ₃ to phosphate glass can also increase the strength of the network structure of the glass, improve the chemical durability and mechanical stability of the glass fiber, and make the drawn glass fiber strands have a certain processable period, which is beneficial to the glass fiber fabric. At the same time, the phosphate glass with an appropriate amount of B ₂ O ₃ also has good biological activity, and an appropriate amount of B ₂ O ₃ helps to inhibit devitrification, but the introduction of too high B ₂ O ₃ will destroy the network structure, Glass crystallization is accelerated, and the glass fiber forming process performance is deteriorated. The preferred B ₂ O ₃ content in the present invention is 0-20 mol%.

The introduction of Fe ₂ O ₃ into phosphate glass can reduce the glass solubility and make the degradation rate of phosphate-based glass controllable. With the increase of Fe ₂ O ₃ content, the dissolution rate of phosphate glass decreases, which has no negative impact on biocompatibility, but the content should not be too high. The preferred content of Fe ₂ O ₃ in the present invention is 1-10 mol%.

The present invention also includes doping Ag ₂ O, CuO, Ga ₂ O ₃ etc. in the phosphate glass. The introduction of these oxides will be released into the surrounding tissues during the degradation process of the phosphate glass to have antibacterial effect.

In order to further ensure the mechanical properties and biocompatibility of the obtained product, the yarn used in the bioactive phosphate-based continuous glass fiber fabric is one or two components of bioactive phosphate-based continuous glass fiber with twisted yarn or roving , the yarn used in the blended fabric is a blended yarn of bioactive phosphate-based continuous glass fiber and polylactic acid fiber.

In order to meet various needs, the fabric in the material-active phosphate-based continuous glass fiber textile composite material is in the shape of mesh, flat cloth or three-dimensional (can be a cylinder, etc.), and the fabric structure is leno, mat, plain weave , twill, satin or three-dimensional multi-directional.

In order to further improve the quality of the resulting product, the fabric in the bioactive phosphate-based continuous glass fiber textile composite material uses a textile-enhanced sizing, and the coating mass dosage (the quality of the sizing relative to the quality of the fiber after coating the sizing) is 0.4~1.5%.

As a further preferred solution of the present application, the textile-enhanced sizing agent includes: water-soluble polyurethane, polyacrylic acid emulsion, polycarbonate emulsion, modified polylactic acid emulsion, phosphine-based polyacrylic acid (PPA), glyceride, glyceride or Any one or two or more of sorbitol fatty acid esters. This can further enhance the quality of the resulting product.

In order to further ensure performances such as mechanical properties, processability, absorbability and biocompatibility of the product obtained, preferably, the biocompatible polymer is polylactide (PLA), polylactic acid powder, poly-L-lactide (PLLA), poly-DL-lactide (PDLLA), polyglycolide (PGA), polyurethane (PU), polycarbonate (PC), polyvinyl alcohol (PVA), poly-L-lactide and Glycolide copolymer, poly-DL-lactide and poly-L-lactide copolymer, poly-L-lactide and trimethylene carbonate copolymer, caprolactone or glycolide copolymer A mixture of one or more than two in any proportion.

In order to further ensure the mechanical properties, biocompatibility and absorbability of the obtained composite material, preferably, the bioactive phosphate-based continuous glass fiber fabric accounts for 10-65% of the volume of the composite material.

In order to further ensure the performance of the resulting product, the bioactive phosphate-based continuous glass fiber fabric is surface-treated (it is surface-treated before the fabric is woven and compounded with a biocompatible polymer), and the quality consumption of the surface treatment agent is 0.3 to 1.5% (the quality of the surface treatment agent relative to the quality of the treated fabric), the surface treatment agent includes one or both of titanate coupling agent, phosphate coupling agent, modified polylactic acid or dibutyl phosphate A mixture of any of the above.

The composite material of this application has controllable biodegradability, and the degradation time in the simulated body fluid in vitro can be determined by the phosphate-based continuous glass fiber component, fiber post-treatment process, blending ratio of phosphate-based continuous glass fiber and polymer fiber, etc. method to adjust. The higher the content of phosphate-based continuous glass fibers in the blend, the shorter the degradation time.

In order to further ensure the compatibility of the composite material obtained in this application with human cortical bone, the bioactive phosphate-based continuous glass fiber textile composite material of this application has a flexural strength of 200-300 MPa and a flexural modulus of 12-30 GPa.

The bioactive phosphate-based continuous glass fiber textile composite material of the present application has good mechanical properties during the degradation process, and the strength retention rate is above 50% after being immersed in phosphate buffer saline (PBS) for 7 weeks.

The bioactive phosphate-based continuous glass fiber textile composites described above can be used in the manufacture of medical device devices.

The aforementioned medical device is preferably an implant. The implant is preferably an absorbable bone repair material for internal fixation of bone. The bone repair material is preferably a bone plate or a bone nail.

The technologies not mentioned in the present invention refer to the prior art.

The mechanical properties of the biologically active phosphate-based continuous glass fiber textile composite material of the present invention reach the level of human bones, the mechanical properties match with bone tissue, and at the same time have excellent biocompatibility, degradability and absorbability, which can be comparable to natural bones , and good processing performance.

detailed description

In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

The specific preparation method of the phosphate-based continuous glass fiber textile composite material of the present application is as follows:

(1) Batch preparation

Mix the raw material components according to the formula. In the formula, MgO, Na ₂ O, K ₂ O, Fe ₂ O ₃ , CaO, etc. are introduced by phosphates of corresponding substances, B ₂ O ₃ is introduced by H ₃ BO ₃ , and the rest of P is introduced by P ₂ O ₅ introduced.

(2) batch material processing

Because P ₂ O ₅ absorbs moisture and releases a large amount of heat at the same time, after the batch is weighed, wait for the moisture absorption reaction of the batch to be completed in the fume hood. time water.

(3) Glass melting

The melting energy of the glass frit adopts thermal radiation and electric melting heating method, and the hot spot temperature of the phosphate glass liquid in the kiln is controlled at 1250 ℃ ~ 1300 ℃, which meets the requirements of phosphate glass melting and homogenization.

(4) Glass melting furnace

The glass melting furnace is made of high-temperature-resistant refractory materials, such as dense zirconium bricks, etc., or lined with platinum-rhodium alloy. The thickness of the refractory material matches the design life of the furnace; The layered design of the passageway between the furnace and the bottom blocking brick allows the phosphate glass to be completely melted in the furnace before flowing into the bottom layer, so as to avoid the influence of the addition of materials on the temperature of the glass liquid.

(5) drawing

The melted and clarified glass liquid enters the porous platinum-rhodium alloy drawing bushing with more than 50 holes, and the textile-enhanced wetting agent (water-soluble chitosan polymer (Nantong Xingcheng Biological Products Factory, hydroxymethyl chitosan) is coated during the drawing process The aqueous solution prepared with dibutyl phosphate, wherein the water-soluble chitosan polymer content is 4wt%, dibutyl phosphate is 0.5wt%), and the coating mass consumption is 0.8%.

(6) Spinning

Phosphate-based glass fibers are twisted to make textile yarns, and phosphate-based glass fibers can also be blended with degradable polymer fibers such as PLA.

(7) Fabric Weaving

Using rapier looms or shuttle looms, ribbon looms and other textile machinery equipment, according to the fabric structure design, weave phosphate-based continuous glass fiber or blended fiber fabrics with specific surface weight and warp and weft density.

(8) Fabric surface treatment

The fabric is washed with deionized water and then dried, and the washed fabric is soaked in a treatment agent solution, and then dried after soaking.

(9) Composite material manufacturing

There are three methods for laying up textile composite materials: polylactic acid powder (Shenzhen Guanghua Weiye Industrial Co., Ltd.) is dispersed in the fabric laying, fabrics and polylactic acid films or fabrics are alternately laid, and blended fabrics are laid. The fabric of the object is put into a mold for hot pressing, the hot pressing temperature is controlled at 190°C to 220°C, the hot pressing time is 15 to 40 minutes, and the pressure is controlled at 2 to 4 MPa. The content of phosphate glass fiber in the composite sheet ( Vf) is controlled between 10% and 65%.

Example 1

Glass formulation, 48P ₂ O ₅ -12B ₂ O ₃ -20MgO-14CaO-1Na ₂ O-5Fe ₂ O ₃ .

According to steps 1 to 6, phosphate-based continuous glass fiber single-twisted yarn (glass fiber monofilament diameter is 10-12 μm) is made, the linear density of the yarn is 16.5tex, and the linear density is 16tex The polylactic acid fiber yarn is plied and blended , the volume ratio of phosphate glass fiber and polylactic acid fiber in the blended yarn is 1:4, and the blended twisted yarn made of phosphate glass fiber and polylactic acid fiber is made, and the blended twisted yarn is warped to make a warp disc head. According to step 7, use a rapier loom to weave a phosphate glass and polylactic acid fiber blended belt with a thickness of 0.32mm according to the plain weave process, with a warp density of 12 pieces/cm and a weft density of 5 pieces/cm. Perform surface treatment according to step 8, clean the blended textile belt, and apply a surface treatment agent on the surface. The mass ratio of each component of the treatment agent is: titanate coupling agent: dibutyl phosphate: ethanol = 1:1:100, surface treatment The mass consumption of the agent is 1.9% (the weight of the surface treatment agent is relative to the weight of the treated textile belt). According to step 9, the composite material plate is manufactured, and the treated webbing is unidirectionally laminated (blend fabric laminate), the number of layers is 8 layers, and it is put into a mold for hot pressing. The hot-pressing conditions are 180° C., 4 MPa, and the hot-pressing time is 20 minutes to make a composite board.

The composite material reinforced by glass fiber fabric (20% Vf, that is, the volume content of active phosphate-based continuous glass fiber is 20%), the initial bending strength and modulus are 250MPa and 12GPa, respectively. After 28 days of degradation in phosphate buffer (0.15Mol/L pH7.2), its bending strength can still maintain more than 50% of its initial strength.

In the biocompatibility test of fiber fabrics (according to the test method of GB/T16886 "Biological Evaluation of Medical Devices Part 5: In Vitro Cytotoxicity Test"), osteosarcoma cells can be successfully attached to the surface of fiber fabrics, and along the The fibers grow in one direction and eventually cover the entire fabric. Through alamar blue test and DNA detection, compared with the control group (the control group specified in GB/T16886 "Biological Evaluation of Medical Devices Part 5: In Vitro Cytotoxicity Test"), the osteosarcoma cells in the experimental group showed higher Cell viability and DNA quantity. In addition, fabric-reinforced composites also exhibit good biocompatibility. By culturing osteosarcoma cells in the cross-section of the composite (including fibers and polylactic acid substrates), it was found that it has a good affinity for bone cells. , and promote cell division and growth.

Example 2

Glass formula, 48P2O5-12B2O3-20MgO-14CaO-0.5Na2O-0.5K2O3-5Fe2O3.

According to steps 1 to 6, make phosphate-based continuous glass fiber single-twisted yarn (glass fiber monofilament diameter is 13 μm), the linear density of the yarn is 16.5tex, and the linear density is 16tex polylactic acid fiber yarn ply blending, blending The volume ratio of phosphate glass fiber and polylactic acid fiber in the yarn is 1:3, and the phosphate glass fiber and polylactic acid fiber are blended and twisted yarn, and the blended twisted yarn is warped to make a warp head. According to step 7, use a rapier loom to weave a phosphate glass and polylactic acid fiber blended fabric with a thickness of 0.32 mm according to the plain weave process. According to step 9, the composite material plate is manufactured, and the blended fabric is put into a mold after being laminated for hot pressing. The hot-pressing conditions are 180° C., 4 MPa, and the hot-pressing time is 20 minutes to make a composite board.

The composite material reinforced by glass fiber fabric (25% Vf, that is, the volume content of active phosphate-based continuous glass fiber is 25%), the initial bending strength and modulus are 260MPa and 12GPa, respectively. After 28 days of degradation in phosphate buffer (0.15Mol/L pH7.2), its bending strength can still maintain more than 50% of its initial strength.

The experimental results of biocompatibility are the same as in Example 1.

Example 3

The glass composition is the same as in Example 2. The volume ratio of phosphate glass fiber to polylactic acid fiber in the blended yarn is 1:1.5. According to step 7, use a rapier loom to weave phosphate glass with a thickness of 0.32mm according to the plain weave process. Blended fabric with polylactic acid fiber. According to step 9, the composite material plate is manufactured, and the blended fabric is put into a mold after being laminated for hot pressing. The hot-pressing conditions are 180° C., 4 MPa, and the hot-pressing time is 20 minutes to make a composite board.

The composite material reinforced by glass fiber fabric (40% Vf, that is, the volume content of active phosphate-based continuous glass fiber is 25%), the initial bending strength and modulus are 280MPa and 14GPa, respectively. After 28 days of degradation in phosphate buffer (0.15Mol/L pH7.2), its bending strength can still maintain more than 50% of its initial strength.

The experimental results of biocompatibility are the same as in Example 1.

Claims (12)

1. A bioactive phosphate-based continuous glass fiber textile composite material, characterized in that: its composition comprises a bioactive phosphate-based continuous glass fiber fabric and a biocompatible polymer, or comprises a blended fabric and a biocompatible polymer fabric, wherein the blended fabric is a blended fabric of bioactive phosphate-based continuous glass fiber and polylactic acid fiber; The components of the bioactive phosphate-based continuous glass fiber include: P ₂ O ₅ : 35-55%, CaO: 10-40%, MgO: 10-30%, B ₂ O ₃ : 2-20%, Na ₂ O : 0~24%, K ₂ O: 0~5%, Fe ₂ O ₃ : 1~10%, M _x O _y : 0~15%, said M _x O _y is Ag ₂ O, CuO ₂ or Ga ₂ O ₃ , the stated percentages are mole percentages. 2. The bioactive phosphate-based continuous glass fiber textile composite material according to claim 1, characterized in that: the single fiber diameter of the bioactive phosphate-based continuous glass fiber is 7-17 μm. 3. The bioactive phosphate-based continuous glass fiber textile composite material as claimed in claim 1 or 2, characterized in that: the yarns used in the bioactive phosphate-based continuous glass fiber fabric are biological materials of one or more components. The active phosphate-based continuous glass fiber has twisted yarn or roving, and the yarn used in the blended fabric is a blended yarn of bioactive phosphate-based continuous glass fiber and polylactic acid fiber; the bioactive phosphate-based continuous glass fiber textile composite material The fabric is in the shape of mesh, flat cloth or three-dimensional, and the structure of the fabric is leno, mat weave, plain weave, twill weave, satin weave or three-dimensional multi-directional. 4. The bioactive phosphate-based continuous glass fiber textile composite material as claimed in claim 1 or 2, characterized in that: the fabric in the bioactive phosphate-based continuous glass fiber textile composite material adopts a textile-enhanced sizing, coated The mass dosage is 0.4-1.5%. 5. The bioactive phosphate-based continuous glass fiber textile composite material as claimed in claim 4, wherein: the textile-enhanced sizing agent comprises: water-soluble polyurethane, polyacrylic acid emulsion, polycarbonate emulsion, modified polylactic acid Emulsion, phosphine-based polyacrylic acid, glyceride, glyceride or sorbitol fatty acid ester, or a mixture of two or more in any proportion. 6. The bioactive phosphate-based continuous glass fiber textile composite material according to claim 1 or 2, characterized in that: the bioactive phosphate-based continuous glass fiber accounts for 10-65% of the volume of the composite material. 7. The bioactive phosphate-based continuous glass fiber textile composite material according to claim 1 or 2, wherein the volume ratio of the bioactive phosphate-based continuous glass fiber to the polylactic acid fiber in the blended fabric is 0.15-1.5. 8. The bioactive phosphate-based continuous glass fiber textile composite material as claimed in claim 1 or 2, wherein the biocompatible polymer is polylactide, poly-L-lactide, poly-DL- Lactide, polyglycolide, polyurethane, polycarbonate, polyvinyl alcohol, poly-L-lactide and glycolide copolymer, poly-DL-lactide and poly-L-lactide copolymer , Poly-L-lactide and trimethylene carbonate copolymer, polylactic acid powder, caprolactone or glycolide copolymer, or a mixture of two or more in any ratio. 9. The bioactive phosphate-based continuous glass fiber textile composite material according to claim 1 or 2, characterized in that: the bioactive phosphate-based continuous glass fiber fabric is surface treated, and the mass dosage of the surface treatment agent is 0.3 to 1.5 %, the surface treatment agent includes titanate coupling agent, phosphate coupling agent, modified polylactic acid or dibutyl phosphate, or a mixture of two or more in any proportion. 10. The bioactive phosphate-based continuous glass fiber textile composite material as claimed in claim 1 or 2, characterized in that: the bioactive phosphate-based continuous glass fiber textile composite material has a flexural strength of 200-300 MPa and a flexural modulus of 12-30GPa; the bioactive phosphate-based continuous glass fiber textile composite material is immersed in phosphate buffer saline PBS for 7 weeks, and the strength retention rate is above 50%. 11. The use of the biologically active phosphate-based continuous glass fiber textile composite material according to any one of claims 1 to 10, characterized in that it is used for manufacturing medical devices. 12. The use according to claim 11, characterized in that the medical device is an implant.