WO2020029785A1 - 预混合的硅酸锶基生物学水凝性粘固粉糊剂组合物及其制备方法和应用 - Google Patents

预混合的硅酸锶基生物学水凝性粘固粉糊剂组合物及其制备方法和应用 Download PDF

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WO2020029785A1
WO2020029785A1 PCT/CN2019/097075 CN2019097075W WO2020029785A1 WO 2020029785 A1 WO2020029785 A1 WO 2020029785A1 CN 2019097075 W CN2019097075 W CN 2019097075W WO 2020029785 A1 WO2020029785 A1 WO 2020029785A1
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paste composition
cement powder
powder paste
strontium silicate
mixed
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PCT/CN2019/097075
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English (en)
French (fr)
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吴秉民
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北京赛濡特口腔医疗器械有限公司
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Priority to JP2021531162A priority Critical patent/JP7483708B2/ja
Priority to EP19847130.2A priority patent/EP3834855A4/en
Priority to US17/266,102 priority patent/US20210290495A1/en
Publication of WO2020029785A1 publication Critical patent/WO2020029785A1/zh

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    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/50—Preparations specially adapted for dental root treatment
    • A61K6/54—Filling; Sealing
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/838—Phosphorus compounds, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/853—Silicates
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52—Hydrogels or hydrocolloids
    • 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
    • A61L2400/06—Flowable or injectable implant compositions
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses

Definitions

  • the present invention relates to a hydraulically setting cement paste for biomedical use, and more particularly to a biologically hydraulically premixed strontium silicate based cement for orthopedic, dental and orthopedic applications. Powder paste composition and preparation method and application thereof.
  • the invention belongs to the technical field of medicine.
  • strontium silicate and calcium silicate can be hydrated when mixed with water, and solidify and harden by precipitating colloidal strontium silicate and calcium silicate hydrate (Sr-SH, CSH), and ordinary Portland cement (OPC).
  • silicate-based biocement materials have good applications in the field of biomedicine, especially can be used as dental filling materials in clinical dentistry, and have been widely used.
  • the ideal dental filling material must have good biocompatibility, antibacterial and clinical performance.
  • biological activity is used as a basis for measuring the binding properties of materials and dental bodies. Therefore, bio-cement materials have also attracted more and more attention from dentists and researchers.
  • MTA mineral trioxide aggregates
  • Mahmoud Torabinejad first disclosed a method for repairing dental cavities with MTA materials in 1998 (US Patent No. 5,769,638).
  • the main components of this MTA material are tricalcium silicate and dicalcium silicate, which are similar to Portland cement and can be used in root canal filling materials, but the deployment is more cumbersome and wasteful.
  • the Chinese patent application application number CN200880011743.1 entitled "Premixed biologically hydraulic cementitious powder paste composition and its application” discloses a premixed cementitious powder that can be used for medical or dental purposes.
  • this patent pre-mixes tricalcium silicate, dicalcium silicate and organic solvents, which is convenient for doctors to use, but the coagulation time is too long, and it takes 72 hours to coagulate. Excessive coagulation time not only causes patient waiting time Prolonged and more complicated surgery.
  • the Chinese patent application entitled "Injectable high-efficiency suspension-stable calcium phosphate bone cement and its preparation method and application” discloses an injectable calcium phosphate bone cement material system. Silica and its modified products to improve the suspension stability of calcium phosphate cement premixed system. The disadvantage is that the calcium phosphate bone cement has insufficient strength and is easily broken.
  • Strontium is an indispensable trace element in the human body. It is a normal component of human bones and teeth. The normal concentration of strontium in human bones is 360ppm. 99.0% of strontium in the body is present in bones and teeth. Strontium functions on the human body Mainly related to the formation of bones. Studies have shown that strontium can regulate the differentiation of MSCS (bone marrow mesenchymal stem cells) into osteoblasts and promote the synthesis and precipitation of bone matrix proteins.
  • MSCS bone marrow mesenchymal stem cells
  • strontium can promote osteoblast differentiation and osteogenesis; strontium can also replace calcified tissue bone
  • strontium silicate hydrate (Sr-SH) composite hydroxyapatite composition has a better biocompatibility and promotes osteogenesis and bone strength compared with calcium silicate hydrate (CSH). effect.
  • the purpose of the present invention is to provide a pre-mixed strontium silicate-based biological hydrosetting cement powder paste composition with short coagulation time, high biological activity and good clinical operation performance, and a preparation method and application thereof.
  • the present invention adopts the following technical means:
  • the pre-mixed strontium silicate-based cement powder paste composition of the present invention includes:
  • the solid component (a) accounts for 60% of the total mass of the cement powder paste composition- 92%
  • the liquid component (b) accounts for 8-40% of the total mass of the cement powder composition.
  • the strontium silicate-based cement powder paste composition further includes: component (c): at least one radiation blocking material.
  • the radiation blocking material is selected from at least one of zirconia, bismuth oxide, and tantalum oxide.
  • the solid components (a) and (c) account for the total mass of the cement powder paste composition 60% -92%, and the liquid component (b) accounts for 8% -40% of the total mass of the cement powder paste composition.
  • the solid component (a) accounts for 20% to 82% of the total mass of the cement powder paste composition
  • the solid component (c ) Accounts for 10% to 40% of the total mass of the cement powder paste composition
  • the liquid component (b) accounts for 8% to 40% of the total mass of the cement powder paste composition.
  • the strontium silicate-based adhesive is based on components (a) and (b) or components (a), (b), and (c).
  • the solid powder paste composition further includes: component (d): at least one calcium phosphate compound.
  • the calcium phosphate compound is selected from at least one of tricalcium phosphate, tetracalcium phosphate, calcium dihydrogen phosphate, and hydroxyapatite.
  • the solid components (a), (c), and (d) account for the cement powder paste combination 60% -92% of the total mass of the material, and the liquid component (b) accounts for 8% -40% of the total mass of the cement powder composition.
  • the solid component (a) accounts for 10% to 42% of the total mass of the cement powder paste composition
  • the solid component (c) accounts for 10% to 40% of the total mass of the cement powder paste composition
  • the solid component (d) accounts for 10% to 40% of the total mass of the cement powder paste composition
  • the liquid component (b) accounts for 8% to 40% of the total mass of the cement powder paste composition.
  • the pre-mixed strontium silicate-based cement powder paste composition provided by the present invention can be prepared according to the following steps:
  • the mixed paste is transferred to a medical syringe equipped with an injection hose needle, and a suspension stable premixed strontium silicate-based cement powder paste can be obtained.
  • the present invention also proposes the use of the pre-mixed strontium silicate-based cement powder paste composition for preparing orthopedic or dental filling materials.
  • the pre-mixed strontium silicate-based biologically-hydratable cementitious powder paste of the present invention has strontium silicate as the main phase and at least one water-miscible non-aqueous solvent, preferably, it may further include at least one A kind of calcium phosphate and at least one radiation blocking material to prepare a bio-hydraulic cement paste with excellent injectability.
  • the material remains fluid under sealed conditions, fills bones or teeth, and comes into contact with physiological fluids, hydrating, solidifying and hardening.
  • the present invention utilizes the excellent biocompatibility and biological activity of the strontium silicate-based biological hydrosetting cement powder paste, and prepares it into a strontium silicate-based biological hydraulic gel cement powder paste.
  • the paste can be used. For medical purposes, it can be used as a filling material in the fields of pulp capping, root canal therapy, dental restoration and other fields.
  • the pre-mixed strontium silicate-based cement powder paste of the present invention has a short setting time, is convenient for doctors to operate, and the reaction temperature is not obvious;
  • the pre-mixed strontium silicate-based cement powder paste of the present invention has the following advantages:
  • Strontium silicate is more biocompatible than calcium silicate, and combined with calcium phosphate salt, it is easy to form hydroxyapatite that promotes bone formation;
  • the strontium silicate hydration products are mostly dense small pompom-like microstructures, and the needle-like hydration products are finer, have better cross-linking degree, and have a denser structure.
  • the material has better strength and toughness and good biocompatibility; moreover, by adjusting the ratio of calcium phosphate and strontium silicate, to meet different requirements; such as adjusting to 30- 40MPa is used as a root canal filling material, which has lower strength than calcium silicate paste and can be well used for retreatment; if it is adjusted, it can be used for repair.
  • Strontium is an indispensable trace element in the human body. Strontium can promote the differentiation and osteogenesis of osteoblasts; Strontium can also replace a small amount of calcium in calcified tissue bones and dental hydroxyapatite crystals. Strontium silicate It can replenish strontium and reduce tooth lattice defects, thereby improving tooth bone strength.
  • Example 1 is a pre-mixed strontium silicate-based cement powder paste material obtained in Example 1;
  • Example 2 is a photograph of the strontium silicate-based cement powder paste obtained in Example 1 after water coagulation;
  • Example 3 is a microscope photograph of the material obtained after water coagulation in Example 1;
  • Example 4 is an XRD elemental analysis diagram of the hydrocoagulated material obtained in Example 1;
  • Constant temperature and humidity box It can maintain an environment with a temperature of 37 °C ⁇ 1 °C and a relative humidity of not less than 95%.
  • Penetration meter a flat end face indenter with a mass of 100 g ⁇ 0.5 g and a diameter of 2 mm ⁇ 0.1 mm.
  • the tip of the indenter is a cylinder with a length of at least 5 mm.
  • the end face of the indenter should be a horizontal plane and a long The shafts are at right angles.
  • Metal block The minimum size is 8mm ⁇ 20mm ⁇ 10mm. Place it in a constant temperature and humidity box at 37 °C ⁇ 1 °C for at least 1h before use.
  • Flat glass about 1mm thick, for example: glass slide.
  • the stainless steel mold Place the stainless steel mold on a flat glass sheet, and fill the stainless steel mold with the prepared root canal filling paste (that is, the suspension and stable pre-mixed strontium silicate-based cement powder paste prepared in the embodiment), and the material is flush with the upper end of the mold; After the reconciliation is completed, place the above components on a metal block in a constant temperature and humidity box.
  • the prepared root canal filling paste that is, the suspension and stable pre-mixed strontium silicate-based cement powder paste prepared in the embodiment
  • Component (a) 55% strontium silicate
  • Component (b) polyethylene glycol 22%
  • Component (c) 23% of zirconia.
  • step (1) (2) Put components (a), (c), and (b) of step (1) into a glass container in sequence, and mechanically mix with a stainless steel stirring rod, and fully blend for 10 minutes;
  • the mixed paste is transferred to a medical syringe equipped with an injection hose needle, and a suspension-stabilized pre-mixed strontium silicate-based cement powder paste can be obtained.
  • the material is kept fluid in a sealed condition, and the extruded sample is placed in a constant temperature and humidity box at 37 ° C and a humidity of 95% or above (or filled with teeth to contact with physiological body fluids), hydrated, solidified and hardened. Setting time: 13 hours.
  • FIG. 1 is a premixed strontium silicate-based cement powder paste material obtained in Example 1;
  • FIG. 2 is a photograph of the strontium silicate-based cement powder paste obtained in Example 1 after water coagulation;
  • FIG. 3 is this Example 1 obtains a micrograph of the material after water coagulation;
  • FIG. 3 shows that the needle-like structure on the small velvety structure of the strontium silicate hydration product Sr-SH is fine and dense, staggered with each other, and glued together. Forms a dense, high-strength microstructure, very similar to the hydroxyapatite small pomp structure, and has good mechanical properties.
  • FIG. 4 is an XRD elemental analysis diagram of the hydrocoagulated material obtained in Example 1.
  • FIG. 4 is an XRD elemental analysis diagram of the hydrocoagulated material obtained in Example 1.
  • strontium silicate hydrate is mainly composed of Sr, Si, and O elements (note: the H element is in an electron microscope) Not shown in XRD analysis), strontium has a good effect on strengthening teeth and bones.
  • the pre-mixed strontium silicate-based cement powder paste material obtained in Example 1 was placed in a 37 ° C, 95% constant temperature and humidity box for a hydration test, and the materials were placed in 0.5, 1, 2, 3, and 5 , 8, 12, 24, 48 hours, take out and measure with an infrared thermometer, the temperature is 37.0 °C, 36.8 °C, 37.1 °C, 36.9 °C, 37.0 °C, 37.0 °C, 36.6 °C, 37.1 °C, 37.0 °C, the temperature is basically No change, which proves that the pre-mixed strontium silicate-based cement powder paste material prepared in Example 1 has the effect of not significantly increasing the reaction temperature.
  • Component (a) 18% tristrontium silicate
  • Component (b) polyethylene glycol 27%
  • Component (c) 30% of tantalum oxide
  • Component (d) anhydrous calcium dihydrogen phosphate 16%, tetracalcium phosphate 9%.
  • step (1) Put components (a), (c), (d), and (b) of step (1) in a glass container in sequence, and mechanically mix with a stainless steel stirring rod, and fully blend for 10 minutes;
  • the mixed paste is transferred to a medical syringe equipped with an injection hose needle, and a suspension-stabilized pre-mixed strontium silicate-based cement powder paste 2 can be obtained.
  • the material is kept fluid in a sealed condition, and the extruded sample is placed in a constant temperature and humidity box at 37 ° C and a humidity of 95% or above (or filled with teeth to contact with physiological body fluids), hydrated, solidified and hardened. Setting time: 13 hours.
  • the pre-mixed strontium silicate-based cement powder paste material obtained in this Example 2 was placed in a 37 ° C, 95% constant temperature and humidity box for a hydration test, and the materials were placed in 0.5, 1, 2, 3, and 5 Take out at 8, 8, 12, 24, 48 hours and measure with an infrared thermometer.
  • the temperature is basically unchanged in the range of 36-38 ° C, which proves that the pre-mixed strontium silicate-based cement powder paste material prepared in Example 2 has The effect of increasing the reaction temperature is not obvious.
  • Component (c) Bismuth trioxide 32%.
  • step (1) Put components (a), (c), (d), and (b) of step (1) in a glass container in sequence, and mechanically mix with a stainless steel stirring rod, and fully blend for 10 minutes;
  • the mixed paste is transferred to a medical syringe equipped with an injection hose needle, and a suspension-stable pre-mixed strontium silicate-based cement powder paste 3 can be obtained.
  • the material is kept fluid in a sealed condition, and the extruded sample is placed in a constant temperature and humidity box at 37 ° C and a humidity of 95% or above (or filled with teeth to touch physiological body fluids), hydrated, solidified and hardened, and the coagulation time: 18 hours.
  • the pre-mixed strontium silicate-based cement powder paste material obtained in Example 3 was placed in a 37 ° C, 95% constant temperature and humidity box for a hydration test, and the materials were placed in 0.5, 1, 2, 3, and 5 Take out at 8, 8, 12, 24, 48 hours, and measure with an infrared thermometer.
  • the temperature is basically unchanged in the range of 36-38 ° C, which proves that the pre-mixed strontium silicate-based cement powder paste material prepared in Example 3 has The effect of increasing the reaction temperature is not obvious.
  • Component (b) 35% polyethylene glycol
  • step (1) Put components (a) and (b) of step (1) into a glass container in sequence, and mechanically mix with a stainless steel stirring rod, and fully blend for 10 minutes;
  • the mixed paste is transferred to a medical syringe equipped with an injection hose needle, and a suspension-stable pre-mixed strontium silicate-based cement powder paste 4 can be obtained.
  • the material is kept fluid under sealed conditions, and the extruded sample is placed in a constant temperature and humidity box at 37 ° C and a humidity of 95% or above (or filled with teeth to contact with physiological body fluids), hydrated, solidified and hardened. Setting time: 12 hours.
  • the pre-mixed strontium silicate-based cement powder paste material obtained in Example 4 was placed in a 37 ° C, 95% constant temperature and humidity box for a hydration test, and the materials were placed in 0.5, 1, 2, 3, and 5 Take out at 8, 8, 12, 24, and 48 hours and measure with an infrared thermometer. The temperature is basically unchanged at about 37 ° C, which proves that the reaction temperature of the pre-mixed strontium silicate-based cement powder prepared in Example 4 does not increase significantly. .

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Abstract

一种预混合硅酸锶基水凝性粘固粉糊剂组合物及其制备方法和应用。预混合的硅酸锶基水凝性粘固粉糊剂以硅酸锶为主相，与至少一种与水可混溶的非水相溶剂，还包括至少一种磷酸钙化合物以及至少一种阻射材料，制备得到具有优异可注射性能的生物学水凝性粘固粉糊剂。硅酸锶基水凝性粘固粉糊剂在密封条件下保持流体，接触到生理体液后水化凝固硬化。硅酸锶基材料具有优良的生物相容性和生物活性，制备得到的预混合硅酸锶基粘固粉糊剂能够用于医学和牙科用途，包括盖髓术、根管治疗术、牙科修复术等。

Description

预混合的硅酸锶基生物学水凝性粘固粉糊剂组合物及其制备方法和应用 技术领域
本发明涉及用于生物医学用途的水凝性粘固粉糊剂，更具体而言，涉及用于骨科、牙科和矫形外科用途的具有生物学水凝性的预混合的硅酸锶基粘固粉糊剂组合物及其制备方法和应用。本发明属于医药技术领域。
背景技术
众所周知，硅酸锶、硅酸钙与水混合时可以水合，并通过沉淀胶状的硅酸锶、硅酸钙水合物(Sr-S-H、C-S-H)而凝固和硬化，与普通的波特兰水泥(OPC)相似。
这些硅酸盐系生物水泥材料在生物医学领域具有良好的用途，尤其可作为牙科充填材料在牙科临床上使用，已获得广泛的应用。理想的牙科充填材料必须具有良好的生物相容性、抗菌性和临床操作性能。除此之外，生物活性作为衡量材料与牙本体结合性能的依据，因此，生物水泥材料也受到越来越多的牙科医生及研究者的重视。
目前牙科充填材料中应用最多的硅酸钙类材料是三氧矿化物材料(Mineral Trioxide Aggregate，MTA)。Mahmoud Torabinejad在1998年首先公开了用MTA材料对牙洞进行修复的方法(美国专利，5,769,638)。该MTA材料主要成分为硅酸三钙和硅酸二钙，和波特兰水泥类似，可用于根管填充材料中，但调配比较麻烦，还造成浪费。发明名称为“预混合的生物学水凝性粘固粉糊剂组合物及其应用”的中国专利申请(申请号CN200880011743.1)公开了一种可用于医学或牙科用途的预混合粘固粉糊剂，该专利将硅酸三钙、硅酸二钙和有机溶剂预混合，方便了医生使用，但凝结时间过长，有的需要72小时才能凝固，过长的凝结时间不但导致病人等待时间延长，而且使手术过程更加复杂。
发明名称为“可注射高效悬浮稳定的磷酸钙骨水泥及其制备方法与应用”的中国专利申请(申请号CN200910197934.8)公开了一种可注射磷酸钙骨水泥材料体系，该专利通过添加气相二氧化硅及其改性产品来提高磷酸钙骨水泥预混体系的悬浮稳定性。不足之处在于磷酸钙骨水泥强度不足，容易破碎。
因此，进一步研发凝结时间短、生物活性高、抗压强度足够、临床操作性能好的的预混合的生物学水凝性粘固粉糊剂具有非常重要的意义。
锶是人体不可缺少的一种微量元素，它是人体骨骼和牙齿的正常组成部分，锶在人骨骼中的正常浓度是360ppm，体内99.0％的锶存在于骨骼和牙齿中，锶对人体的功能主要是与骨骼的形成密切相关。研究表明：锶可调节MSCS(骨髓间质干细胞)向成骨细 胞分化，并促进骨基质蛋白的合成和沉淀，因此锶对成骨细胞分化和骨生成具有促进作用；锶还可取代钙化组织骨骼和牙齿羟基磷灰石晶体中少量的钙，少量锶元素的置换，可减少晶格缺陷，使原子间的排列更加紧密，起到一定强化作用，从而改善牙齿骨质强度；硅酸锶水合物(Sr-S-H)复合羟基磷灰石组合物在起到填充密封作用的同时，与硅酸钙水合物(C-S-H)相比，具有更好的生物相容性和促进成骨、提高骨强度的作用。
发明内容
本发明的目的在于提供凝结时间短、生物活性高、临床操作性能好的预混合的硅酸锶基生物学水凝性粘固粉糊剂组合物及其制备方法和应用。
为了达到上述目的，本发明采用了以下技术手段：
本发明的预混合的硅酸锶基粘固粉糊剂组合物，所述的预混合硅酸锶基粘固粉糊剂组合物包括：
组分(a)：至少一种硅酸锶化合物，其中所述硅酸锶化合物优选选自：硅酸锶、硅酸三锶、硅酸二锶以及它们的混合物；和
组分(b)：至少一种基本无水的液体载体，其与所述的至少一种硅酸锶化合物混合，所述基本无水的液体载体优选选自：乙二醇、丙二醇、聚乙二醇、液态甘油、乙醇、硅油、丁香油、动物油、植物油、有机酸以及它们的混合物。
根据本发明的具体实施方案，优选的，所述的预混合的硅酸锶基粘固粉糊剂组合物中，固体组分(a)占粘固粉糊剂组合物总质量的60％-92％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
根据本发明的具体实施方案，优选的，所述的硅酸锶基粘固粉糊剂组合物还包括：组分(c)：至少一种阻射材料。
根据本发明的具体实施方案，优选的，所述的阻射材料选自氧化锆、氧化铋、氧化钽中的至少一种。
根据本发明的具体实施方案，优选的，所述的预混合的硅酸锶基粘固粉糊剂组合物中，固体组分(a)，(c)占粘固粉糊剂组合物总质量的60％-92％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。进一步优选的，所述的预混合硅酸锶基粘固粉糊剂组合物中，固体组分(a)占粘固粉糊剂组合物总质量的20％-82％，固体组分(c)占粘固粉糊剂组合物总质量的10％-40％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
根据本发明的具体实施方案，优选的，在组分(a)和(b)的基础上或者组分(a)、(b)和(c)的基础上，所述的硅酸锶基粘固粉糊剂组合物还包括：组分(d)：至少一种磷酸钙化合 物。
根据本发明的具体实施方案，优选的，所述的磷酸钙化合物选自磷酸三钙、磷酸四钙、磷酸二氢钙、羟基磷灰石中的至少一种。
根据本发明的具体实施方案，优选的，所述的预混合硅酸锶基粘固粉糊剂组合物中，固体组分(a)，(c)以及(d)占粘固粉糊剂组合物总质量的60％-92％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。进一步优选的，固体组分(a)占粘固粉糊剂组合物总质量的10％-42％，固体组分(c)占粘固粉糊剂组合物总质量的10％-40％，固体组分(d)占粘固粉糊剂组合物总质量的10％-40％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
本发明提供的预混合的硅酸锶基粘固粉糊剂组合物可以是按照以下步骤制备的：
将各个组分依次放入玻璃容器中，用不锈钢搅拌棒进行机械混合，充分调和；
之后将混合糊剂转移至配有注射软管针头的医用注射器中，即可得到悬浮稳定的预混合硅酸锶基粘固粉糊剂。
进一步的，本发明还提出了所述的预混合的硅酸锶基粘固粉糊剂组合物在制备用于骨科或牙科充填材料中的用途。
本发明的预混合的硅酸锶基生物学水凝性粘固粉糊剂以硅酸锶为主相、至少一种与水可混溶的非水相溶剂，优选的，还可包括至少一种磷酸钙、至少一种阻射材料，制备出具有优异可注射性能的生物学水凝性粘固粉糊剂。该材料在密封条件下保持流体，填充到骨骼或牙齿中接触到生理体液后，水化凝固硬化。本发明利用硅酸锶基生物学水凝性粘固粉糊剂优良的生物相容性、生物活性，将其制备成硅酸锶基生物学水凝性粘固粉糊剂，该糊剂可用于医学用途，尤其可作为充填材料用于盖髓术、根管治疗术、牙科修复术等领域。
相较于现有技术，本发明的优点在于：
(1)相较于磷酸钙水泥，本发明的预混合硅酸锶基粘固粉糊剂凝固时间短、便于医生操作、反应升温不明显；
(2)相较于预混合硅酸钙牙科充填材料，本发明的预混合硅酸锶基粘固粉糊剂具有以下优点：
(A)凝固快；
(B)硅酸锶比硅酸钙生物相容性好，与磷酸钙盐合用，易形成促进成骨的羟基磷灰石；
(C)提高骨强度，例如从图3可以看出，硅酸锶水化产物多为致密的小绒球样显微 组织，针状水化产物更细小，相互交联度好，结构更加致密，而且与羟基磷灰石绒球状结构相似，因而，材料强度及韧性更好、生物相容性好；而且，通过调节磷酸钙和硅酸锶的比例，满足不同的要求；如调至30-40MPa用于根管充填材料，比硅酸钙糊剂强度低，可以很好的用于再治疗；如调硬，可以用于修补。
(D)锶是人体不可缺少的一种微量元素，锶对成骨细胞分化和骨生成具有促进作用；锶还可取代钙化组织骨骼和牙齿羟基磷灰石晶体中少量的钙，使用硅酸锶可补充锶元素、减少牙齿晶格缺陷，从而改善牙齿骨质强度。
附图说明
图1为实施例1得到的预混合硅酸锶基粘固粉糊剂材料；
图2为实施例1得到的硅酸锶基粘固粉糊剂水凝固后的照片；
图3为实施例1得到水凝固后的材料的显微镜照片；
图4为实施例1得到的水凝后材料的XRD元素分析图；
具体实施方式
下面结合具体实施例来进一步描述本发明，本发明的优点和特点将会随着描述而更为清楚。但实施例仅是范例性的，并不对本发明的范围构成任何限制。本领域技术人员应该理解的是，在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换，但这些修改和替换均落入本发明的保护范围内。
凝固时间的测试方法
1、器具
1.1、恒温恒湿箱：能维持温度37℃±1℃，相对湿度不低于95％的环境。
1.2、针入度计：具有质量为100g±0.5g、直径为2mm±0.1mm的平坦端面压头，压头尖部为长度至少为5mm的圆柱，压头的端面应是一水平面，与长轴成直角。
1.3、模具：不锈钢环形模具，模具型腔内径d＝10mm，高h＝2mm。
1.4、金属块：最小尺寸8mm×20mm×10mm，使用前放置于37℃±1℃的恒温恒湿箱中至少1h。
1.5、平玻璃片：厚约1mm，例如：载玻片。
2、试样制备
将不锈钢模具放置在平玻璃片上，将调和好的根管填充糊剂(即实施例制备的悬浮稳定的预混合硅酸锶基粘固粉糊剂)充满不锈钢模具，材料与模具上端齐平；调和结束后，将上述组件放于恒温恒湿箱中的金属块上。
3、步骤
固化8小时后，每经过1小时取出试样轻轻的将针入度计的压头垂直放于根管填充糊剂的水平面上，抬起压头并擦拭干净，重复上述操作直到肉眼观察不到压痕出现；从调和结束后开始计时，直到压痕不再出现的时间记录为凝固时间。
4、结果：不出现压痕时记录凝固时间。
实施例1 悬浮稳定的预混合硅酸锶基粘固粉糊剂的制备
(1)按照以下重量百分比称取各原料：
组分(a)：硅酸三锶55％；
组分(b)：聚乙二醇22％；
组分(c)：氧化锆23％。
(2)将步骤(1)的组分(a)、(c)、(b)依次放入玻璃容器中，用不锈钢搅拌棒进行机械混合，充分调和10min；
(3)之后将混合糊剂转移至配有注射软管针头的医用注射器中，即可得到悬浮稳定的预混合硅酸锶基粘固粉糊剂。
该材料在密封条件下保持流体，挤出制样放在37℃、95％以上湿度恒温恒湿箱中(或填充到牙齿接触到生理体液)，水化凝固硬化，凝固时间：13小时。
图1为本实施例1得到的预混合硅酸锶基粘固粉糊剂材料；图2为本实施例1得到的硅酸锶基粘固粉糊剂水凝固后的照片；图3为本实施例1得到水凝固后的材料的显微镜照片；该图3显示：该硅酸锶水化产物Sr-S-H小绒球状结构上的针状组织又细又密、相互交错，胶连在一起，形成致密、高强韧度的显微组织结构，极似羟基磷灰石小绒球结构，力学性能好。图4为本实施例1得到的水凝后材料的XRD元素分析图，该图4显示该硅酸锶水合物(Sr-S-H)主要由Sr、Si、O元素构成(备注：H元素在电镜XRD分析中显示不出来)，锶元素对强化牙齿和骨骼有好作用。
将本实施例1得到的预混合硅酸锶基粘固粉糊剂材料置于37℃、95％恒温恒湿箱中进行水化试验，材料放入在第0.5、1、2、3、5、8、12、24、48小时取出，用红外测温计测量，温度分别是37.0℃、36.8℃、37.1℃、36.9℃、37.0℃、37.0℃、36.6℃、37.1℃、37.0℃，温度基本不变，证明本实施例1制备的预混合硅酸锶基粘固粉糊剂材料具有反应升温不明显的效果。
实施例2悬浮稳定的预混合硅酸锶基粘固粉糊剂的制备
(1)按照以下重量百分比称取各原料：
组分(a)：硅酸三锶18％；
组分(b)：聚乙二醇27％；
组分(c)：氧化钽30％；
组分(d)：无水磷酸二氢钙16％，磷酸四钙9％。
(2)将步骤(1)的组分(a)、(c)、(d)、(b)依次放入玻璃容器中，用不锈钢搅拌棒进行机械混合，充分调和10min；
(3)之后将混合糊剂转移至配有注射软管针头的医用注射器中，即可得到悬浮稳定的预混合硅酸锶基粘固粉糊剂2。
该材料在密封条件下保持流体，挤出制样放在37℃、95％以上湿度恒温恒湿箱中(或填充到牙齿接触到生理体液)，水化凝固硬化，凝固时间：13小时。
将本实施例2得到的预混合硅酸锶基粘固粉糊剂材料置于37℃、95％恒温恒湿箱中进行水化试验，材料放入在第0.5、1、2、3、5、8、12、24、48小时取出，用红外测温计测量，温度在36-38℃范围内基本不变，证明本实施例2制备的预混合硅酸锶基粘固粉糊剂材料具有反应升温不明显的效果。
实施例3悬浮稳定的预混合硅酸锶基粘固粉糊剂的制备
(1)按照以下重量百分比称取各原料：
组分(a)：硅酸三锶12％，硅酸二锶7％；
组分(b)：甘油29％；
组分(c)：三氧化二铋32％。
组分(d)：磷酸二氢钙20％；
(2)将步骤(1)的组分(a)、(c)、(d)、(b)依次放入玻璃容器中，用不锈钢搅拌棒进行机械混合，充分调和10min；
(3)之后将混合糊剂转移至配有注射软管针头的医用注射器中，即可得到悬浮稳定的预混合硅酸锶基粘固粉糊剂3。
该材料在密封条件下保持流体，挤出制样放在37℃、95％以上湿度恒温恒湿箱中(或填充到牙齿接触到生理体液)，水化凝固硬化，凝固时间：18小时。
将本实施例3得到的预混合硅酸锶基粘固粉糊剂材料置于37℃、95％恒温恒湿箱中进行水化试验，材料放入在第0.5、1、2、3、5、8、12、24、48小时取出，用红外测温计测量，温度在36-38℃范围内基本不变，证明本实施例3制备的预混合硅酸锶基粘固 粉糊剂材料具有反应升温不明显的效果。
实施例4悬浮稳定的预混合硅酸锶基粘固粉糊剂的制备
(1)按照以下重量百分比称取各原料：
组分(a)：硅酸三锶65％；
组分(b)：聚乙二醇35％；
(2)将步骤(1)的组分(a)、(b)依次放入玻璃容器中，用不锈钢搅拌棒进行机械混合，充分调和10min；
(3)之后将混合糊剂转移至配有注射软管针头的医用注射器中，即可得到悬浮稳定的预混合硅酸锶基粘固粉糊剂4。
该材料在密封条件下保持流体，挤出制样放在37℃、95％以上湿度恒温恒湿箱中(或填充到牙齿接触到生理体液)，水化凝固硬化，凝固时间：12小时。
将本实施例4得到的预混合硅酸锶基粘固粉糊剂材料置于37℃、95％恒温恒湿箱中进行水化试验，材料放入在第0.5、1、2、3、5、8、12、24、48小时取出，用红外测温计测量，温度在37℃左右基本不变，证明本实施例4制备的预混合硅酸锶基粘固粉糊剂材料反应升温不明显。

Claims (17)

  1. 预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合硅酸锶基粘固粉糊剂组合物包括：
    组分(a)：至少一种硅酸锶化合物；和
    组分(b)：至少一种基本无水的液体载体，其与所述的至少一种硅酸锶化合物混合。
  2. 如权利要求1所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合的硅酸锶基粘固粉糊剂组合物中，固体组分(a)占粘固粉糊剂组合物总质量的60％-92％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
  3. 如权利要求1所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述硅酸锶化合物选自：硅酸锶、硅酸三锶、硅酸二锶以及它们的混合物。
  4. 如权利要求1所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述基本无水的液体载体选自：乙二醇、丙二醇、聚乙二醇、液态甘油、乙醇、硅油、丁香油、动物油、植物油、有机酸以及它们的混合物。
  5. 如权利要求1所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的硅酸锶基粘固粉糊剂组合物还包括：
    组分(c)：至少一种阻射材料。
  6. 如权利要求5所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的阻射材料选自氧化锆、氧化铋、氧化钽中的至少一种。
  7. 如权利要求5所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合的硅酸锶基粘固粉糊剂组合物中，固体组分(a)，(c)占粘固粉糊剂组合物总质量的60％-92％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
  8. 如权利要求7所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合硅酸锶基粘固粉糊剂组合物中，固体组分(a)占粘固粉糊剂组合物总质量的20％-82％，固体组分(c)占粘固粉糊剂组合物总质量的10％-40％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
  9. 如权利要求1所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的硅酸锶基粘固粉糊剂组合物还包括：
    组分(d)：至少一种磷酸钙化合物。
  10. 如权利要求9所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的磷酸钙化合物选自磷酸三钙、磷酸四钙、磷酸二氢钙、羟基磷灰石中的至少一种。
  11. 如权利要求9所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合硅酸锶基粘固粉糊剂组合物中，固体组分(a)以及(d)占粘固粉糊剂组合物总质量的60％-92％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
  12. 如权利要求11所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合硅酸锶基粘固粉糊剂组合物中，固体组分(a)占粘固粉糊剂组合物总质量的10％-42％，固体组分(d)占粘固粉糊剂组合物总质量的10％-40％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
  13. 如权利要求5所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的硅酸锶基粘固粉糊剂组合物还包括：
    组分(d)：至少一种磷酸钙化合物。
  14. 如权利要求13所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的磷酸钙化合物选自磷酸三钙、磷酸四钙、磷酸二氢钙、羟基磷灰石中的至少一种。
  15. 如权利要求13所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合硅酸锶基粘固粉糊剂组合物中，固体组分(a)，(c)以及(d)占粘固粉糊剂组合物总质量的60％-92％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
  16. 如权利要求15所述的预混合的硅酸锶基粘固粉糊剂组合物，其特征在于，所述的预混合硅酸锶基粘固粉糊剂组合物中，固体组分(a)占粘固粉糊剂组合物总质量的10％-42％，固体组分(c)占粘固粉糊剂组合物总质量的10％-40％，固体组分(d)占粘固粉糊剂组合物总质量的10％-40％，液体组分(b)占粘固粉糊剂组合物总质量的8％-40％。
  17. 权利要求1所述的预混合的硅酸锶基粘固粉糊剂组合物在制备用于骨科或牙科充填材料中的用途。
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