TW202139943A - Fiber and method for preparing the same and artificial ligament/tendon - Google Patents
Fiber and method for preparing the same and artificial ligament/tendon Download PDFInfo
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本揭露關於纖維的組成，更特別關於由纖維編織而成的人工韌帶/肌腱。This disclosure relates to the composition of fibers, and more particularly to artificial ligaments/tendons woven from fibers.
現階段臨床處置手術以自體韌帶/肌腱人工韌帶/肌腱來進行治療。然而取自體組織修補對患者有其不便性與負面影響。以目前市售人工韌帶/肌腱植入修復，長期使用後會產生組織相容性不佳，出現發炎積水腫脹等反應，無法有效促成自體組織再生整合，甚至出現磨損、鬆動及斷裂之情形。因此，無論在臨床或市場，都亟需具組織相容性之人工韌帶/肌腱材料，來強化克服組織再生修復問題。現有技術為了使人造纖維具有良好的生物相容性，通常使用浸潤塗布方式於纖維上塗布上一層具有生物相容性的陶瓷粉體塗層，但此方法無法將具有生物相容性的陶瓷粉體均勻分散於纖維中，其塗布層易出現剝落問題，不但降低生物相容性功用，且剝落碎片更可能引起發炎等副作用。為了將具有生物相容性的陶瓷粉體均勻分散於纖維中，通常加入分散劑降低陶瓷粉體與載體樹脂的界面能，使陶瓷粉體均勻分散於載體樹脂中。然而市售分散劑因分子量小且含有較多活性官能基，不但易遷移至纖維表面產生細胞毒性，且不符合醫療法規規範。換言之，無法在生物相容陶瓷粉體-載體樹脂的複合材料中使用常見的小分子分散劑。At this stage, the clinical treatment operation is based on autologous ligament/tendon artificial ligament/tendon for treatment. However, self-tissue repair has its inconvenience and negative effects on patients. The current commercially available artificial ligament/tendon implants will cause poor histocompatibility, inflammation and swelling after long-term use, which cannot effectively promote the regeneration and integration of autologous tissues, and may even cause wear, looseness and rupture. Therefore, no matter in the clinic or the market, there is an urgent need for tissue-compatible artificial ligament/tendon materials to strengthen and overcome the problem of tissue regeneration and repair. In the prior art, in order to make man-made fibers have good biocompatibility, a layer of ceramic powder coating with biocompatibility is usually coated on the fiber by immersion coating method, but this method cannot remove the ceramic powder with biocompatibility. The body is evenly dispersed in the fiber, and the coating layer is prone to peeling, which not only reduces the biocompatibility function, but also the peeling debris is more likely to cause side effects such as inflammation. In order to uniformly disperse the ceramic powder with biocompatibility in the fiber, a dispersant is usually added to reduce the interface energy between the ceramic powder and the carrier resin, so that the ceramic powder is uniformly dispersed in the carrier resin. However, the commercially available dispersants are not only easy to migrate to the fiber surface to cause cytotoxicity due to their small molecular weight and more active functional groups, but also do not comply with medical regulations. In other words, it is impossible to use common small molecule dispersants in biocompatible ceramic powder-carrier resin composite materials.
綜上所述，目前亟需新的技術將生物相容陶瓷粉體分散於載體樹脂中，再紡絲成纖維並編織成人工韌帶/肌腱，以符臨床或市場需求。In summary, there is an urgent need for a new technology to disperse the biocompatible ceramic powder in the carrier resin, and then spun into fibers and woven into artificial ligaments/tendons to meet clinical or market needs.
本揭露一實施例提供之纖維，包含:0.5至4重量份的生物相容陶瓷粉體區域；以及96至99.5重量份的聚酯區域，其中生物相容陶瓷粉體區域分布於聚酯區域中，至少90%之生物相容陶瓷粉體區域的直徑小於或等於300 nm且大於0 nm，且纖維的生物毒性測試之細胞存活率大於70%。The fiber provided by an embodiment of the present disclosure includes: 0.5 to 4 parts by weight of a biocompatible ceramic powder area; and 96 to 99.5 parts by weight of a polyester area, wherein the biocompatible ceramic powder area is distributed in the polyester area , The diameter of at least 90% of the biocompatible ceramic powder area is less than or equal to 300 nm and greater than 0 nm, and the cell survival rate of the fiber biotoxicity test is greater than 70%.
在一些實施例中，纖維的直徑係2微米至150微米。In some embodiments, the diameter of the fiber ranges from 2 microns to 150 microns.
在一些實施例中，聚酯區域包括聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯或上述之組合，且生物相容陶瓷粉體區域包括羥氧基磷灰石、磷酸三鈣、硫酸鈣或上述之組合。In some embodiments, the polyester region includes polyethylene terephthalate, polybutylene terephthalate, or a combination of the foregoing, and the biocompatible ceramic powder region includes hydroxyapatite, triphosphate Calcium, calcium sulfate or a combination of the above.
在一些實施例中，含生物相容陶瓷粉體區域以及聚酯區域之纖維不需外加分散劑。In some embodiments, the fibers containing the biocompatible ceramic powder region and the polyester region do not require an external dispersant.
本揭露一實施例提供之人工韌帶/肌腱，係由上述纖維編織而成。The artificial ligament/tendon provided by an embodiment of the present disclosure is woven from the above-mentioned fibers.
本揭露一實施例提供纖維的製備方法，包含：混摻生物相容陶瓷粉體與第一聚酯，以形成陶瓷粉體組成物，且生物相容陶瓷粉體與第一聚酯之重量比係10:90至60:40；混摻陶瓷粉體組成物與第二聚酯以形成複合材料，且陶瓷粉體組成物與第二聚酯之重量比係0.5:99.5至4:96；以及紡絲該複合材料以形成纖維；其中第一聚酯之特性黏度(Intrinsic viscosity)係0.35 dL/g至0.55 dL/g，且第二聚酯之特性黏度(Intrinsic viscosity)係0.6 dL/g至0.8 dL/g。An embodiment of the present disclosure provides a method for preparing a fiber, which includes: mixing a biocompatible ceramic powder and a first polyester to form a ceramic powder composition, and the weight ratio of the biocompatible ceramic powder to the first polyester The range is 10:90 to 60:40; the ceramic powder composition and the second polyester are mixed to form a composite material, and the weight ratio of the ceramic powder composition to the second polyester is 0.5:99.5 to 4:96; and The composite material is spun to form fibers; wherein the intrinsic viscosity of the first polyester ranges from 0.35 dL/g to 0.55 dL/g, and the intrinsic viscosity of the second polyester ranges from 0.6 dL/g to 0.8 dL/g.
在一些實施例中，纖維包括：0.5至4重量份的生物相容陶瓷粉體區域；以及96至99.5重量份的聚酯區域，其中生物相容陶瓷粉體區域分布於聚酯區域中，至少90%之生物相容陶瓷粉體區域的直徑小於或等於300 nm且大於0 nm，且纖維的生物毒性測試之細胞存活率大於70%。In some embodiments, the fiber includes: 0.5 to 4 parts by weight of a biocompatible ceramic powder area; and 96 to 99.5 parts by weight of a polyester area, wherein the biocompatible ceramic powder area is distributed in the polyester area, at least The diameter of 90% of the biocompatible ceramic powder area is less than or equal to 300 nm and greater than 0 nm, and the cell survival rate of the fiber biotoxicity test is greater than 70%.
在一些實施例中，纖維的直徑係2微米至150微米。In some embodiments, the diameter of the fiber ranges from 2 microns to 150 microns.
在一些實施例中，第一聚酯與第二聚酯分別包括聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯或上述之組合，且生物相容陶瓷粉體包括羥氧基磷灰石、磷酸三鈣、硫酸鈣或上述之組合。In some embodiments, the first polyester and the second polyester respectively include polyethylene terephthalate, polybutylene terephthalate or a combination of the above, and the biocompatible ceramic powder includes hydroxyoxy Apatite, tricalcium phosphate, calcium sulfate or a combination of the above.
在一些實施例中，含生物相容陶瓷粉體區域以及聚酯區域之纖維不需外加分散劑。In some embodiments, the fibers containing the biocompatible ceramic powder region and the polyester region do not require an external dispersant.
在一些實施例中，第一聚酯之特性黏度與第二聚酯之特性黏度差(∆IV)大於等於0.1 dL/g且小於或等於0.45 dL/g。In some embodiments, the difference (ΔIV) between the intrinsic viscosity of the first polyester and the intrinsic viscosity of the second polyester is greater than or equal to 0.1 dL/g and less than or equal to 0.45 dL/g.
本揭露一實施例提供纖維的製備方法。首先，混摻生物相容陶瓷粉體與第一聚酯，以形成陶瓷粉體組成物。可以理解的是，混摻生物相容陶瓷粉體與第一聚酯的方法可為本技術領域已知的任何合適混摻方法，比如熔融混摻。在一實施例中，生物相容陶瓷粉體包括羥氧基磷灰石、磷酸三鈣、硫酸鈣或上述之組合，且其平均粒徑介於20奈米至100奈米之間，或介於40奈米至80奈米之間。若生物相容陶瓷粉體的粒徑過大，則易於抽絲時產生斷絲或纖維容易斷裂。第一聚酯可為聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯或上述之組合，且其特性黏度(Intrinsic viscosity)係0.35 dL/g至0.55 dL/g，或0.4 dL/g至0.55 dL/g。若第一聚酯的特性黏度過低，則會影響纖維成品機械強度。若第一聚酯的特性黏度過高，則生物相容陶瓷粉體將會團聚而無法有效分散於第一聚酯中，即最終產物中的生物相容陶瓷粉體區域之粒徑過大。在一些實施例中，生物相容陶瓷粉體與第一聚酯之重量比係10:90至60:40，或20:80至60:40。若生物相容陶瓷粉體的用量過低，則陶瓷粉體組成物與纖維之生物相容性可能不足。若生物相容陶瓷粉體的用量過高，則生物相容陶瓷粉體將會團聚而無法有效分散於第一聚酯中，即陶瓷粉體組成物或纖維中的生物相容陶瓷粉體區域之粒徑過大，易於抽絲時產生斷絲或纖維容易斷裂。An embodiment of the present disclosure provides a method for preparing fibers. First, the biocompatible ceramic powder and the first polyester are mixed to form a ceramic powder composition. It is understood that the method of blending the biocompatible ceramic powder and the first polyester may be any suitable blending method known in the art, such as melt blending. In one embodiment, the biocompatible ceramic powder includes hydroxyapatite, tricalcium phosphate, calcium sulfate or a combination of the above, and its average particle size is between 20 nanometers and 100 nanometers, or Between 40nm and 80nm. If the particle size of the biocompatible ceramic powder is too large, it is easy to break the filament or the fiber to break during spinning. The first polyester can be polyethylene terephthalate, polybutylene terephthalate or a combination of the above, and its intrinsic viscosity (Intrinsic viscosity) ranges from 0.35 dL/g to 0.55 dL/g, or 0.4 dL /g to 0.55 dL/g. If the intrinsic viscosity of the first polyester is too low, it will affect the mechanical strength of the finished fiber. If the intrinsic viscosity of the first polyester is too high, the biocompatible ceramic powder will agglomerate and cannot be effectively dispersed in the first polyester, that is, the particle size of the biocompatible ceramic powder region in the final product is too large. In some embodiments, the weight ratio of the biocompatible ceramic powder to the first polyester is 10:90 to 60:40, or 20:80 to 60:40. If the amount of the biocompatible ceramic powder is too low, the biocompatibility between the ceramic powder composition and the fiber may be insufficient. If the amount of biocompatible ceramic powder is too high, the biocompatible ceramic powder will agglomerate and cannot be effectively dispersed in the first polyester, that is, the biocompatible ceramic powder area in the ceramic powder composition or fiber If the particle size is too large, it is easy to break the filament or the fiber is easy to break when spinning.
接著混摻陶瓷粉體組成物與第二聚酯以形成複合材料。可以理解的是，混摻陶瓷粉體組成物與第二聚酯的方法可為本技術領域已知的任何合適混摻方法，比如熔融混摻。在一些實施例中，第二聚酯可為聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、或上述之組合，且其特性黏度(Intrinsic viscosity)係0.6 dL/g至0.8 dL/g，或0.6 dL/g至0.7 dL/g。若第二聚酯的特性黏度過低，則會影響纖維成品機械強度。若第二聚酯的特性黏度過高，則不易進行抽絲。在一些實施例中，第一聚酯之特性黏度與第二聚酯之特性黏度差(∆IV)大於等於0.1 dL/g且小於或等於0.45 dL/g。值得注意的是，第一聚酯與第二聚酯應為相同種類的聚酯，比如均為聚對苯二甲酸乙二酯。若第一聚酯與第二聚酯的種類不同，則陶瓷粉體組成物可能無法有效分散於第二聚酯中。在一些實施例中，陶瓷粉體組成物與第二聚酯之重量比係0.5:99.5至4:96。若陶瓷粉體組成物的用量過低，則陶瓷粉體組成物與纖維之生物相容性可能不足。若陶瓷粉體組成物的用量過高，則易於抽絲時產生斷絲或纖維容易斷裂。Then, the ceramic powder composition and the second polyester are mixed to form a composite material. It is understood that the method of mixing the ceramic powder composition with the second polyester can be any suitable mixing method known in the art, such as melt mixing. In some embodiments, the second polyester may be polyethylene terephthalate, polybutylene terephthalate, or a combination of the above, and its intrinsic viscosity (Intrinsic viscosity) ranges from 0.6 dL/g to 0.8 dL/g, or 0.6 dL/g to 0.7 dL/g. If the intrinsic viscosity of the second polyester is too low, it will affect the mechanical strength of the finished fiber. If the intrinsic viscosity of the second polyester is too high, it is not easy to spin. In some embodiments, the difference (ΔIV) between the intrinsic viscosity of the first polyester and the intrinsic viscosity of the second polyester is greater than or equal to 0.1 dL/g and less than or equal to 0.45 dL/g. It is worth noting that the first polyester and the second polyester should be the same type of polyester, for example, both are polyethylene terephthalate. If the types of the first polyester and the second polyester are different, the ceramic powder composition may not be effectively dispersed in the second polyester. In some embodiments, the weight ratio of the ceramic powder composition to the second polyester is 0.5:99.5 to 4:96. If the amount of the ceramic powder composition is too low, the biocompatibility between the ceramic powder composition and the fiber may be insufficient. If the amount of the ceramic powder composition is too high, filament breakage or fiber breakage is likely to occur during spinning.
值得注意的是，若將第一聚酯、第二聚酯、與生物相容陶瓷粉體一起混摻，則生物相容陶瓷粉體將團聚而無法有效分散。類似地，若先混摻第一聚酯與第二聚酯，再加入生物相容陶瓷粉體進行混摻，則生物相容陶瓷粉體將團聚而無法有效分散。It is worth noting that if the first polyester, the second polyester, and the biocompatible ceramic powder are mixed together, the biocompatible ceramic powder will agglomerate and cannot be effectively dispersed. Similarly, if the first polyester and the second polyester are mixed first, and then the biocompatible ceramic powder is added for mixing, the biocompatible ceramic powder will agglomerate and cannot be effectively dispersed.
接著紡絲複合材料以形成纖維。可以理解的是，紡絲複合材料的方法可為本技術領域已知的任何合適紡絲方法，比如熔體紡絲。在一些實施例中，纖維包括0.5至4重量份的生物相容陶瓷粉體區域；以及96至99.5重量份的聚酯區域。在一些實施例中，纖維包括0.5至3重量份的生物相容陶瓷粉體區域；以及97至99.5重量份的聚酯區域。生物相容陶瓷粉體區域分布於聚酯區域中。可以理解的是，生物相容陶瓷粉體區域來自於複合材料中的生物相容陶瓷粉體，而聚酯區域來自於複合材料中的第一聚酯與第二聚酯。在一些實施例中，生物相容陶瓷粉體區域係生物相容陶瓷粉體聚集之區域，聚酯區域係纖維中排除生物相容陶瓷粉體之區域。至少90%甚至至少95%之生物相容陶瓷粉體區域的直徑小於或等於300 nm且大於0 nm。若生物相容陶瓷粉體區域的直徑過大，則複合材料易堵塞紡嘴/斷絲，且纖維的機械強度較弱。紡絲前的複合材料之生物毒性測試之細胞存活率大於70%，即複合材料不具細胞毒性。紡絲後的纖維的生物毒性測試之細胞存活率大於70%甚至大於100%，即在一些實施例中，纖維不具細胞毒性且可進一步促進細胞生長。The composite material is then spun to form fibers. It is understood that the method of spinning the composite material can be any suitable spinning method known in the art, such as melt spinning. In some embodiments, the fiber includes 0.5 to 4 parts by weight of the biocompatible ceramic powder region; and 96 to 99.5 parts by weight of the polyester region. In some embodiments, the fiber includes 0.5 to 3 parts by weight of the biocompatible ceramic powder region; and 97 to 99.5 parts by weight of the polyester region. The biocompatible ceramic powder area is distributed in the polyester area. It is understandable that the biocompatible ceramic powder area comes from the biocompatible ceramic powder in the composite material, and the polyester area comes from the first polyester and the second polyester in the composite material. In some embodiments, the biocompatible ceramic powder area is the area where the biocompatible ceramic powder gathers, and the polyester area is the area in the fiber where the biocompatible ceramic powder is excluded. At least 90% or even at least 95% of the biocompatible ceramic powder area has a diameter less than or equal to 300 nm and greater than 0 nm. If the diameter of the biocompatible ceramic powder area is too large, the composite material will easily block the spinning nozzle/filament, and the mechanical strength of the fiber will be weak. The cell survival rate of the biotoxicity test of the composite material before spinning is greater than 70%, that is, the composite material is not cytotoxic. The biotoxicity test of the fiber after spinning shows that the cell survival rate is greater than 70% or even greater than 100%, that is, in some embodiments, the fiber is not cytotoxic and can further promote cell growth.
在一些實施例中，纖維的直徑係2微米至150微米或10微米至110微米。在一些實施例中，纖維的直徑係10微米至60微米。在一些實施例中，含生物相容陶瓷粉體區域以及聚酯區域之纖維不需外加分散劑，分散劑例如為分子量小於等於5000且大於0的分散劑，或分子量小於等於3000且大於0的分散劑。這是因為一般常見的分散劑易遷移至纖維表面且具有細胞毒性，不適用於醫療材料如人工韌帶/肌腱。In some embodiments, the diameter of the fiber ranges from 2 microns to 150 microns or from 10 microns to 110 microns. In some embodiments, the diameter of the fiber ranges from 10 microns to 60 microns. In some embodiments, the fibers containing the biocompatible ceramic powder region and the polyester region do not require an external dispersant. The dispersant is, for example, a dispersant with a molecular weight of less than or equal to 5000 and greater than 0, or a molecular weight of less than or equal to 3000 and greater than 0. Dispersant. This is because common dispersants are easy to migrate to the fiber surface and are cytotoxic, and are not suitable for medical materials such as artificial ligaments/tendons.
在一實施例中，上述纖維可編織成人工韌帶/肌腱。可以理解的是，編織纖維的方法可為本技術領域已知的任何合適編織方法。由於本揭露實施例的纖維可促進細胞骨分化，因此比常見的生物相容材料所製成的纖維更適用於人工韌帶/肌腱。經臨床動物實驗驗證，本揭露的纖維在編織成人工韌帶後，經手術植入動物後並無引起肝腎毒性，具有生物相容性。在植入三個月後，週邊軟組織成功長入人工韌帶，形成韌帶化現象。韌帶扣與骨頭間產生間隙，且骨釘與骨頭鑽孔處有癒合現象。此外，本揭露的人工韌帶經手術植入動物後一個月之最大抗拉強度(ultimate tensile strength)高於市售人工韌帶。In one embodiment, the above-mentioned fibers can be woven into artificial ligaments/tendons. It is understood that the method of weaving fibers can be any suitable weaving method known in the art. Since the fibers of the embodiments of the present disclosure can promote cell bone differentiation, they are more suitable for artificial ligaments/tendons than fibers made of common biocompatible materials. It has been verified by clinical animal experiments that the disclosed fiber after being woven into an artificial ligament does not cause liver and kidney toxicity after being surgically implanted in an animal, and has biocompatibility. Three months after implantation, the surrounding soft tissues successfully grew into the artificial ligament, forming a ligamentation phenomenon. There is a gap between the ligament buckle and the bone, and the bone nail and the bone drilled hole are healed. In addition, the ultimate tensile strength of the artificial ligament disclosed in the present disclosure is higher than that of the commercially available artificial ligament one month after being surgically implanted in an animal.
為讓本揭露之上述內容和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下：[ 實施例 ] In order to make the above content and other objectives, features, and advantages of this disclosure more obvious and understandable, the following specifically enumerates the preferred embodiments, coupled with the accompanying drawings, to describe in detail as follows: [ Examples ]
下述實施例的聚酯之特性黏度(IV)根據ASTM D4603進行量測。The intrinsic viscosity (IV) of the polyester in the following examples is measured according to ASTM D4603.
實施例1 取對苯二甲酸二甲酯194.18重量份、乙二醇173.79重量份與鈦酸正丁酯0.01重量份於約200o C下反應約2小時後，再將溫度提高至約260o C，降低壓力至約4torr反應約1小時，再將溫度提高至約270o C，降低壓力至約0.1torr反應至其特性黏度為0.433 dL/g。取上述聚對苯二甲酸乙二酯(PET，其特性黏度為0.433 dL/g)作為第一聚酯，置入真空烘箱後加熱至約120℃並減壓除水。取羥氧基磷灰石(hydroxyapatite)粉體(原始平均粒徑約60nm，購自鈺慶實業)作為生物相容陶瓷粉體。將60重量份的除水後的PET與40重量份的羥氧基磷灰石粉體進料至雙螺桿押出機，以約265℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備陶瓷粉體組成物。以ISO10993-1規範量測陶瓷粉體組成物的細胞毒性(MTT)，其細胞存活率≧70%，即不具細胞毒性。Embodiment 1 After taking the parts by weight of dimethyl terephthalate, 194.18, 173.79 parts by weight of ethylene glycol and 0.01 parts by weight of n-butyl titanate at about 200 o C for about 2 hours the reaction cases, the temperature was increased to about 260 o C, reduce the pressure to about 4torr and react for about 1 hour, then increase the temperature to about 270 o C, reduce the pressure to about 0.1 torr and react until its intrinsic viscosity is 0.433 dL/g. Take the above-mentioned polyethylene terephthalate (PET, with an intrinsic viscosity of 0.433 dL/g) as the first polyester, put it in a vacuum oven, and heat it to about 120° C. and remove water under reduced pressure. Take hydroxyapatite powder (the original average particle size is about 60nm, purchased from Yuqing Industry) as the biocompatible ceramic powder. 60 parts by weight of the dewatered PET and 40 parts by weight of hydroxyapatite powder are fed to a twin-screw extruder, and melt-blended and dispersed at a screw temperature of about 265°C and a rotation speed of 40 rpm to prepare Ceramic powder composition. Measure the cytotoxicity (MTT) of ceramic powder composition according to ISO10993-1 standard, and its cell survival rate is ≧70%, that is, it is not cytotoxic.
實施例2 與實施例1類似，差別在於第一聚酯與羥氧基磷灰石的重量比例由60:40改為40:60。其餘製程與性質量測的方法均與實施例1相同。Example 2 Similar to Example 1, the difference is that the weight ratio of the first polyester to hydroxyapatite is changed from 60:40 to 40:60. The rest of the manufacturing process and the method of quality testing are the same as in Example 1.
實施例3 取對苯二甲酸二甲酯194.18重量份、乙二醇173.79重量份與鈦酸正丁酯0.01重量份於約200o C下反應約2小時後，再將溫度提高至約260o C，降低壓力至約4torr反應約1小時，再將溫度提高至約270o C，降低壓力至約0.1torr反應至其特性黏度為0.502 dL/g。取上述PET (其特性黏度為0.502 dL/g)作為第一聚酯，置入真空烘箱後加熱至120℃並減壓除水。取羥氧基磷灰石粉體(原始平均粒徑60nm)作為生物相容陶瓷粉體。將60重量份的除水後的PET與40重量份的羥氧基磷灰石粉體進料至雙螺桿押出機，以265℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備陶瓷粉體組成物。以ISO10993-1規範量測陶瓷粉體組成物的細胞毒性(MTT)，其細胞存活率≧70%，即不具細胞毒性。After taking the embodiment 3 parts by weight of dimethyl terephthalate, 194.18, 173.79 parts by weight of ethylene glycol and 0.01 parts by weight of n-butyl titanate at about 200 o C for about 2 hours the reaction cases, the temperature was increased to about 260 o C, reduce the pressure to about 4torr and react for about 1 hour, then increase the temperature to about 270 o C, reduce the pressure to about 0.1 torr and react until its intrinsic viscosity is 0.502 dL/g. Take the above-mentioned PET (its intrinsic viscosity is 0.502 dL/g) as the first polyester, put it in a vacuum oven and heat it to 120°C and remove water under reduced pressure. Take hydroxyapatite powder (the original average particle size is 60nm) as the biocompatible ceramic powder. 60 parts by weight of the dewatered PET and 40 parts by weight of hydroxyapatite powder are fed to the twin-screw extruder, and the screw temperature is 265° C. and the rotation speed is 40 rpm for melt mixing and dispersion to prepare ceramics Powder composition. Measure the cytotoxicity (MTT) of ceramic powder composition according to ISO10993-1 standard, and its cell survival rate is ≧70%, that is, it is not cytotoxic.
實施例4 與實施例3類似，差別在於第一聚酯與羥氧基磷灰石的重量比例由60:40改為40:60。其餘製程與性質量測的方法均與實施例3相同。Example 4 Similar to Example 3, the difference is that the weight ratio of the first polyester to the hydroxyapatite is changed from 60:40 to 40:60. The rest of the manufacturing process and the method of quality testing are the same as in Example 3.
實施例5 取市售的PET (購自新光纖維的T-2150T，其特性黏度為0.535 dL/g)作為第一聚酯，置入真空烘箱後加熱至120℃並減壓除水。取羥氧基磷灰石粉體(原始平均粒徑60nm)作為生物相容陶瓷粉體。將60重量份的除水後的PET與40重量份的羥氧基磷灰石粉體進料至雙螺桿押出機，以265℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備陶瓷粉體組成物。以ISO10993-1規範量測陶瓷粉體組成物的細胞毒性(MTT)，其細胞存活率≧70%，即不具細胞毒性。Example 5 Take a commercially available PET (T-2150T purchased from Shinkong Fiber, with an intrinsic viscosity of 0.535 dL/g) as the first polyester, put it in a vacuum oven, and heat it to 120°C and remove water under reduced pressure. Take hydroxyapatite powder (the original average particle size is 60nm) as the biocompatible ceramic powder. 60 parts by weight of the dewatered PET and 40 parts by weight of hydroxyapatite powder are fed to the twin-screw extruder, and the screw temperature is 265°C and the rotation speed is 40 rpm for melt mixing and dispersion to prepare ceramics Powder composition. The cytotoxicity (MTT) of the ceramic powder composition is measured according to the ISO10993-1 standard, and its cell survival rate is ≧70%, that is, it is not cytotoxic.
實施例6 與實施例5類似，差別在於第一聚酯與羥氧基磷灰石的重量比例由60:40改為40:60。其餘製程與性質量測的方法均與實施例5相同。Example 6 Similar to Example 5, the difference is that the weight ratio of the first polyester to hydroxyapatite is changed from 60:40 to 40:60. The rest of the manufacturing process and the method of quality testing are the same as in Example 5.
表1
實施例7 取市售的PET (購自新光纖維的C-0226C，其特性黏度為0.66 dL/g)作為第二聚酯，置入真空烘箱後加熱至120℃並減壓除水。將98.33重量份的除水後的第二聚酯(PET)與1.67重量份的實施例4之陶瓷粉體組成物進料至雙螺桿押出機，以270℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備複合材料。以ASTM D4603量測複合材料的特性黏度。以ISO10993-1規範量測複合材料的細胞毒性(MTT)，其細胞存活率≧70%，即不具細胞毒性。Example 7 Take a commercially available PET (C-0226C purchased from Shinkong Fiber, with an intrinsic viscosity of 0.66 dL/g) as the second polyester, put it in a vacuum oven, and heat it to 120°C and remove water under reduced pressure. 98.33 parts by weight of the dewatered second polyester (PET) and 1.67 parts by weight of the ceramic powder composition of Example 4 were fed to the twin-screw extruder and melted at a screw temperature of 270°C and a rotation speed of 40 rpm Blending and dispersing to prepare composite materials. Measure the intrinsic viscosity of composite materials with ASTM D4603. Measure the cytotoxicity (MTT) of composite materials according to ISO10993-1 standard, and its cell survival rate is ≧70%, that is, it is not cytotoxic.
實施例8 與實施例7類似，差別在於第二聚酯與陶瓷粉體組成物的重量比例由98.33:1.67改為96.67:3.33。其餘製程與性質量測的方法均與實施例7相同。Example 8 Similar to Example 7, the difference is that the weight ratio of the second polyester to the ceramic powder composition is changed from 98.33:1.67 to 96.67:3.33. The rest of the manufacturing process and the method of quality testing are the same as in Example 7.
實施例9 與實施例7類似，差別在於第二聚酯與陶瓷粉體組成物的重量比例由98.3:1.67改為93.34:6.66。其餘製程與性質量測的方法均與實施例7相同。Example 9 Similar to Example 7, the difference is that the weight ratio of the second polyester to the ceramic powder composition is changed from 98.3:1.67 to 93.34:6.66. The rest of the manufacturing process and the method of quality testing are the same as in Example 7.
表2
實施例10 取市售的PET (購自新光纖維的C-0226C，其特性黏度為0.66 dL/g)作為第二聚酯，置入真空烘箱後加熱至120℃並減壓除水。將97.5重量份的除水後的第二聚酯(PET)與2.5重量份的實施例1之陶瓷粉體組成物進料至雙螺桿押出機，以270℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備複合材料。以ASTM D4603量測複合材料的特性黏度。以ISO10993-1規範量測複合材料的細胞毒性(MTT)，其細胞存活率≧70%，即不具細胞毒性。Example 10 Take a commercially available PET (C-0226C purchased from Shinkong Fiber, with an intrinsic viscosity of 0.66 dL/g) as the second polyester, put it in a vacuum oven, and heat it to 120°C and remove water under reduced pressure. 97.5 parts by weight of the dewatered second polyester (PET) and 2.5 parts by weight of the ceramic powder composition of Example 1 were fed to the twin-screw extruder and melted at a screw temperature of 270°C and a rotation speed of 40 rpm Blending and dispersing to prepare composite materials. Measure the intrinsic viscosity of composite materials with ASTM D4603. Measure the cytotoxicity (MTT) of composite materials according to ISO10993-1 standard, and its cell survival rate is ≧70%, that is, it is not cytotoxic.
實施例11 與實施例10類似，差別在於實施例1的陶瓷粉體組成物改為實施例3的陶瓷粉體組成物。其餘製程與性質量測的方法均與實施例10相同。Example 11 Similar to Example 10, the difference is that the ceramic powder composition of Example 1 is changed to the ceramic powder composition of Example 3. The rest of the manufacturing process and the method of quality testing are the same as in Example 10.
實施例12 與實施例10類似，差別在於實施例1的陶瓷粉體組成物改為實施例5的陶瓷粉體組成物。其餘製程與性質量測的方法均與實施例10相同。Example 12 Similar to Example 10, the difference is that the ceramic powder composition of Example 1 is changed to the ceramic powder composition of Example 5. The rest of the manufacturing process and the method of quality testing are the same as in Example 10.
表3
實施例13 取實施例8的複合材料，以熔體紡絲法進行紡絲。將複合材料加入螺桿式擠出機，由旋轉的螺桿送到加熱區，經過擠壓、熔融向前送至計量泵，以紡溫290℃，紡速64 m/min進行紡絲，並於110℃進行延伸以形成纖維，且延伸倍率為3.4%。上述纖維的細度為8.1 den，強度為3.4±0.5 g/den，且伸度為20.6%。以ISO10993-1規範量測纖維的細胞毒性(MTT)，其細胞存活率≧70%，即不具細胞毒性。此外，複合材料製成纖維後的細胞存活率>100%，表示纖維態樣的複合材料可促進細胞生長。Example 13 Take the composite material of Example 8 and spin it by the melt spinning method. The composite material is fed into the screw extruder, sent by the rotating screw to the heating zone, extruded and melted forward to the metering pump, spinning at a spinning temperature of 290°C and a spinning speed of 64 m/min, and spinning at 110 The stretching was performed at ℃ to form fibers, and the stretching ratio was 3.4%. The fineness of the above fiber is 8.1 den, the strength is 3.4±0.5 g/den, and the elongation is 20.6%. Measure the cytotoxicity (MTT) of fiber according to ISO10993-1 standard, and its cell survival rate is ≧70%, that is, it is not cytotoxic. In addition, the cell survival rate after the composite material is made into fibers is >100%, indicating that the fiber-like composite material can promote cell growth.
實施例14 與實施例13類似，差別在於纖維的延伸倍率由3.4%增加至3.8%。其餘製程與性質量測的方法均與實施例14相同。Example 14 Similar to Example 13, the difference is that the elongation ratio of the fiber is increased from 3.4% to 3.8%. The rest of the manufacturing process and the method of quality testing are the same as in Example 14.
表4
由表4可知在一些實施例中，纖維的拉伸強度約介於2.5 g/den至5.5g/den之間。It can be seen from Table 4 that in some embodiments, the tensile strength of the fiber is approximately between 2.5 g/den and 5.5 g/den.
比較例1 與實施例13類似，差別在於採用PET (購自新光纖維的C-0226C)而非複合材料。熔融紡絲形成PET纖維後，以細胞T2B004 P5進行細胞培養貼附與骨分化測試，量測重要分化標誌表現(RUNX2)。然而純PET纖維(無生物相容陶瓷粉體分散其中)無促進細胞骨分化的效果。Comparative example 1 Similar to Example 13, the difference is that PET (C-0226C purchased from Xinguang Fiber) is used instead of a composite material. After melt-spinning to form PET fibers, cell T2B004 P5 was used for cell culture attachment and bone differentiation test to measure the performance of important differentiation markers (RUNX2). However, pure PET fiber (without biocompatible ceramic powder dispersed in it) has no effect on promoting cell bone differentiation.
實施例15 取實施例13的纖維，以細胞T2B004 P5進行細胞培養貼附與骨分化測試，量測重要分化標誌表現(RUNX2)。複合材料的纖維之骨分化快5倍，且細胞貼附性質亦良好。Example 15 Take the fiber of Example 13 and use the cell T2B004 P5 for cell culture attachment and bone differentiation test, and measure the performance of important differentiation markers (RUNX2). The bone differentiation of the fibers of the composite material is 5 times faster, and the cell adhesion properties are also good.
表5
比較例2 取市售的PET (購自新光纖維的C-0226C，其特性黏度為0.66 dL/g)作為聚酯，置入真空烘箱後加熱至120℃並減壓除水。取羥氧基磷灰石粉體(原始平均粒徑60nm)作為生物相容陶瓷粉體。將98重量份的除水後的聚酯與2重量份的羥氧基磷灰石粉體進料至雙螺桿押出機，以270℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備複合材料。將複合材料加入螺桿式擠出機，由旋轉的螺桿送到加熱區，經過擠壓、熔融向前送至計量泵，以紡溫290℃，紡速64 m/min進行紡絲，並於110℃進行延伸以形成纖維。然而複合材料中的陶瓷粉體嚴重團聚且堵塞紡嘴造成斷絲。經掃描電子顯微鏡（Scanning Electron Microscope, SEM）確認比較例1與實施例8的纖維中，生物相容陶瓷粉體區域的直徑分布如下：Comparative example 2 Take a commercially available PET (C-0226C purchased from Shin Kong Fiber, with an intrinsic viscosity of 0.66 dL/g) as polyester, put it in a vacuum oven, and heat it to 120°C and remove water under reduced pressure. Take hydroxyapatite powder (the original average particle size is 60nm) as the biocompatible ceramic powder. 98 parts by weight of the dehydrated polyester and 2 parts by weight of hydroxyapatite powder are fed to the twin-screw extruder, and the screw temperature is 270°C and the rotation speed is 40 rpm for melt mixing and dispersion to prepare Composite materials. The composite material is fed into the screw extruder, sent by the rotating screw to the heating zone, extruded and melted forward to the metering pump, spinning at a spinning temperature of 290°C and a spinning speed of 64 m/min, and spinning at 110 Stretching at °C to form fibers. However, the ceramic powder in the composite material is severely agglomerated and clogging the spinning nozzle, causing filament breakage. Scanning Electron Microscope (SEM) confirms that in the fibers of Comparative Example 1 and Example 8, the diameter distribution of the biocompatible ceramic powder region is as follows:
表6
由表6可知，比較例2未經第一聚酯預分散生物相容陶瓷粉體，直接將生物相容陶瓷粉體分散於第二聚酯中的作法會造成粉體團聚。本揭露先以較低特徵黏度的第一聚酯分散生物相容陶瓷粉體以形成陶瓷粉體組成物，再將陶瓷粉體組成物分散於較高特徵黏度的第二聚酯中，可降低生物相容陶瓷粉體的團聚程度。舉例來說，超過90%甚至超過95%的生物相容陶瓷粉體區域之粒徑小於或等於300 nm。It can be seen from Table 6 that in Comparative Example 2, the method of directly dispersing the biocompatible ceramic powder in the second polyester without pre-dispersing the biocompatible ceramic powder in the first polyester will cause the powder to agglomerate. The present disclosure first disperses the biocompatible ceramic powder with the first polyester with a lower characteristic viscosity to form a ceramic powder composition, and then disperses the ceramic powder composition in the second polyester with a higher characteristic viscosity, which can reduce The degree of agglomeration of the biocompatible ceramic powder. For example, more than 90% or even more than 95% of the biocompatible ceramic powder area has a particle size less than or equal to 300 nm.
比較例3 取市售的PET (購自SABIC的PCG60，其特性黏度為0.60 dL/g)作為第一聚酯，置入真空烘箱後加熱至120℃並減壓除水。取羥氧基磷灰石粉體(原始平均粒徑60nm)作為生物相容陶瓷粉體。將60重量份的除水後的PET與40重量份的羥氧基磷灰石粉體進料至雙螺桿押出機，以265℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備陶瓷粉體組成物。取市售的PET (購自新光纖維的C-0226C，其特性黏度為0.66 dL/g)作為第二聚酯，置入真空烘箱後加熱至120℃並減壓除水，將97.5重量份的除水後的第二聚酯與2.5重量份的上述之陶瓷粉體組成物進料至雙螺桿押出機，以270℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備複合材料。將複合材料加入螺桿式擠出機，由旋轉的螺桿送到加熱區，經過擠壓、熔融向前送至計量泵，以紡溫290℃，紡速64 m/min進行紡絲，並於110℃進行延伸以形成纖維。然而複合材料中的陶瓷粉體嚴重團聚且堵塞紡嘴造成斷絲。Comparative example 3 Take a commercially available PET (PCG60 from SABIC, with an intrinsic viscosity of 0.60 dL/g) as the first polyester, put it in a vacuum oven, and heat it to 120° C. and remove water under reduced pressure. Take hydroxyapatite powder (the original average particle size is 60nm) as the biocompatible ceramic powder. 60 parts by weight of the dewatered PET and 40 parts by weight of hydroxyapatite powder are fed to the twin-screw extruder, and the screw temperature is 265°C and the rotation speed is 40 rpm for melt mixing and dispersion to prepare ceramics Powder composition. Take a commercially available PET (C-0226C purchased from Shinkong Fiber, with an intrinsic viscosity of 0.66 dL/g) as the second polyester, put it in a vacuum oven and heat it to 120°C and remove water under reduced pressure. 97.5 parts by weight The second polyester after water removal and 2.5 parts by weight of the above ceramic powder composition are fed to a twin-screw extruder, and are melt-mixed and dispersed at a screw temperature of 270° C. and a rotation speed of 40 rpm to prepare a composite material. The composite material is fed into the screw extruder, sent by the rotating screw to the heating zone, extruded and melted forward to the metering pump, spinning at a spinning temperature of 290°C and a spinning speed of 64 m/min, and spinning at 110 Stretching at °C to form fibers. However, the ceramic powder in the composite material is severely agglomerated and clogging the spinning nozzle, causing filament breakage.
實施例16 取實施例11之複合材料以熔體紡絲法進行紡絲。將複合材料加入螺桿式擠出機，由旋轉的螺桿送到加熱區，經過擠壓、熔融向前送至計量泵，以紡溫290℃，紡速64 m/min進行紡絲，並於110℃進行延伸以形成纖維，且延伸倍率為3.4%。Example 16 The composite material of Example 11 was spun by the melt spinning method. The composite material is fed into the screw extruder, sent by the rotating screw to the heating zone, extruded and melted forward to the metering pump, spinning at a spinning temperature of 290°C and a spinning speed of 64 m/min, and spinning at 110 The stretching was performed at ℃ to form fibers, and the stretching ratio was 3.4%.
實施例17 取實施例12之複合材料以熔體紡絲法進行紡絲。將複合材料加入螺桿式擠出機，由旋轉的螺桿送到加熱區，經過擠壓、熔融向前送至計量泵，以紡溫290℃，紡速64 m/min進行紡絲，並於110℃進行延伸以形成纖維，且延伸倍率為3.4%。Example 17 The composite material of Example 12 was spun by the melt spinning method. The composite material is fed into the screw extruder, sent by the rotating screw to the heating zone, extruded and melted forward to the metering pump, spinning at a spinning temperature of 290°C and a spinning speed of 64 m/min, and spinning at 110 The stretching was performed at ℃ to form fibers, and the stretching ratio was 3.4%.
表7
由表7可知，比較例3其∆IV小於0.1dL/g，會造成粉體分散不好，堵塞紡嘴造成斷絲。本揭露先以較低特徵黏度的第一聚酯分散生物相容陶瓷粉體以形成陶瓷粉體組成物，再將陶瓷粉體組成物分散於較高特徵黏度的第二聚酯中，且兩聚酯∆IV大於等於0.1可降低生物相容陶瓷粉體的團聚程度。It can be seen from Table 7 that the ΔIV of Comparative Example 3 is less than 0.1 dL/g, which will cause poor powder dispersion, block the spinning nozzle, and cause filament breakage. The present disclosure first disperses the biocompatible ceramic powder with a first polyester with a lower characteristic viscosity to form a ceramic powder composition, and then disperses the ceramic powder composition in a second polyester with a higher characteristic viscosity. Polyester ΔIV greater than or equal to 0.1 can reduce the degree of agglomeration of biocompatible ceramic powder.
比較例4 取1重量份的羥氧基磷灰石粉體(原始平均粒徑60nm)作為生物相容陶瓷粉體、0.67重量份的分散劑A (路博潤 Solplus DP320)、與市售的PET (購自新光纖維的C-0226C，其特性黏度為0.66 dL/g)作為第二聚酯，進料至雙螺桿押出機，以270℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備複合材料。以ISO10993-1規範量測複合材料的細胞毒性(MTT)，其細胞存活率>70%，即具細胞毒性。Comparative example 4 Take 1 part by weight of hydroxyapatite powder (original average particle size 60nm) as biocompatible ceramic powder, 0.67 parts by weight of dispersant A (Lubrizol Solplus DP320), and commercially available PET (purchase C-0226C from Xinguang Fiber, with an intrinsic viscosity of 0.66 dL/g) as the second polyester, was fed to a twin-screw extruder, and melted, mixed and dispersed at a screw temperature of 270°C and a speed of 40rpm to prepare a composite Material. Measure the cytotoxicity (MTT) of composite materials according to ISO10993-1 standards, and the cell survival rate is >70%, which means it is cytotoxic.
比較例5 與比較例4類似，差別在於分散劑A改為分散劑B (畢克化學 BYK P4102)。其餘製程與性質量測的方法均與比較例4相同。Comparative example 5 Similar to Comparative Example 4, the difference is that dispersant A is changed to dispersant B (BYK P4102). The rest of the manufacturing process and the methods of quality testing are the same as those of Comparative Example 4.
比較例6 與比較例4類似，差別在於分散劑A改為分散劑C (畢克化學DISPERPLAST-1018)。其餘製程與性質量測的方法均與比較例4相同。Comparative example 6 Similar to Comparative Example 4, the difference is that dispersant A is changed to dispersant C (BYK DISPERPLAST-1018). The rest of the manufacturing process and the methods of quality testing are the same as those of Comparative Example 4.
表8
由表8可知，採用小分子的分散劑之複合材料具有細胞毒性，而不適用於醫療材料如人工韌帶/肌腱。It can be seen from Table 8 that composite materials using small molecule dispersants are cytotoxic, and are not suitable for medical materials such as artificial ligaments/tendons.
比較例7 將98.98重量份除水後的PET (第一聚酯，購自新光纖維的C-0226C，其特性黏度為0.66 dL/g)與1.02重量份重量份的羥氧基磷灰石粉體(原始平均粒徑60nm，生物相容陶瓷粉體) 進料至雙螺桿押出機，以約265℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備陶瓷粉體組成物。將1.96重量份除水後的PET (第二聚酯，購自新光纖維的T-2150T，其特性黏度為0.535 dL/g) 與98.04重量份的上述之陶瓷粉體組成物進料至雙螺桿押出機，以270℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備複合材料。將複合材料加入螺桿式擠出機，由旋轉的螺桿送到加熱區，經過擠壓、熔融向前送至計量泵，以紡溫290℃，紡速64 m/min進行紡絲，並於110℃進行延伸以形成纖維。然而複合材料中的陶瓷粉體嚴重團聚且堵塞紡嘴造成斷絲。Comparative example 7 98.98 parts by weight of PET (the first polyester, C-0226C purchased from Shin Kong Fiber, with an intrinsic viscosity of 0.66 dL/g) and 1.02 parts by weight of hydroxyapatite powder (original The average particle size is 60nm, the biocompatible ceramic powder) is fed into a twin-screw extruder, and melt-mixed and dispersed at a screw temperature of about 265° C. and a rotation speed of 40 rpm to prepare a ceramic powder composition. 1.96 parts by weight of dewatered PET (the second polyester, T-2150T purchased from Shin Kong Fiber, with an intrinsic viscosity of 0.535 dL/g) and 98.04 parts by weight of the above ceramic powder composition were fed to the twin screw The extruder is melt-mixed and dispersed at a screw temperature of 270°C and a rotation speed of 40 rpm to prepare a composite material. The composite material is fed into the screw extruder, sent by the rotating screw to the heating zone, extruded and melted forward to the metering pump, spinning at a spinning temperature of 290°C and a spinning speed of 64 m/min, and spinning at 110 Stretching at °C to form fibers. However, the ceramic powder in the composite material is severely agglomerated and clogging the spinning nozzle, causing filament breakage.
表9
由表9可知，比較例7其反序添加(先高IV聚酯，後高IV聚酯)，會造成粉體分散不好，堵塞紡嘴造成斷絲。本揭露先以較低特徵黏度的第一聚酯分散生物相容陶瓷粉體以形成陶瓷粉體組成物，再將陶瓷粉體組成物分散於較高特徵黏度的第二聚酯中，可降低生物相容陶瓷粉體的團聚程度。It can be seen from Table 9 that the reverse order addition of Comparative Example 7 (first high IV polyester, then high IV polyester) will cause poor powder dispersion, block the spinning nozzle and cause filament breakage. The present disclosure first disperses the biocompatible ceramic powder with the first polyester with a lower characteristic viscosity to form a ceramic powder composition, and then disperses the ceramic powder composition in the second polyester with a higher characteristic viscosity, which can reduce The degree of agglomeration of the biocompatible ceramic powder.
比較例8 將97.5重量份的除水後PET (購自新光纖維的C-0226C，其特性黏度為0.66 dL/g)與 1.5重量份的除水後PET(購自新光纖維的T-2150T，其特性黏度為0.535 dL/g)，以及1重量份的羥氧基磷灰石粉體(原始平均粒徑60nm)同時進料至雙螺桿押出機，以270℃的螺桿溫度與40rpm的轉速進行熔融混摻分散，以製備複合材料。將複合材料加入螺桿式擠出機，由旋轉的螺桿送到加熱區，經過擠壓、熔融向前送至計量泵，以紡溫290℃，紡速64 m/min進行紡絲，然而複合材料中的陶瓷粉體嚴重團聚且堵塞紡嘴造成斷絲。Comparative example 8 97.5 parts by weight of PET (C-0226C purchased from Xinguang Fiber, with an intrinsic viscosity of 0.66 dL/g) and 1.5 parts by weight of PET (T-2150T purchased from Xinguang Fiber, with an intrinsic viscosity) 0.535 dL/g), and 1 part by weight of hydroxyapatite powder (original average particle size 60nm) were simultaneously fed to the twin-screw extruder, and melted and blended at a screw temperature of 270°C and a rotation speed of 40rpm Disperse to prepare composite materials. The composite material is added to the screw extruder, and the rotating screw is sent to the heating zone, and then sent to the metering pump after extrusion and melting. The spinning temperature is 290℃ and the spinning speed is 64 m/min. However, the composite material The ceramic powder in the powder is severely agglomerated and blocked the spinning nozzle, causing the filament to break.
人工韌帶:臨床動物效能驗證 使用紐西蘭白兔（體重約3公斤）做為試驗動物模式，後肢內側副韌帶（Medial Collateral Ligament, MCL） 進行韌帶重建手術，實驗分為兩組：(1)比較例9：Orthomed市售人工韌帶材料為純PET；(2)實施例18：取實施例8之纖維以平面編織法編織成人工韌帶。手術前以***(舒泰50：若朋20=1：1，0.5 ml/kg)進行麻醉，手術將後肢膝關節打開：沿膝關節前外側及髕骨外側直線作皮膚切口，經切口處打開膝關節滑液囊，兩組人工韌帶分別以手術方式植入於自體MCL (劃一小傷口)旁並與之縫在一起，手術完畢後，將撥開的各層組織及皮膚縫合即完成手術，術後進行動物照護。各組分別進行9個後肢的內側副韌帶重建手術，分別在第1、3、6個月進行後續分析。Artificial ligament: clinical animal efficacy verification Using New Zealand white rabbits (weight about 3 kg) as the experimental animal model, the Medial Collateral Ligament (MCL) of the hind limbs was used for ligament reconstruction surgery. The experiment was divided into two groups: (1) Comparative Example 9: Orthomed commercially available The artificial ligament material is pure PET; (2) Example 18: The fiber of Example 8 is woven into an artificial ligament by a plane weaving method. Before the operation, anesthetize with anesthetics (Shutai 50: Ruopeng 20=1:1, 0.5 ml/kg), and open the knee joint of the hind limbs: make a skin incision along the anterolateral side of the knee joint and the lateral side of the patella, and open through the incision. The synovial sac of the knee joint, two sets of artificial ligaments were surgically implanted next to the autologous MCL (a small wound) and sewn together. After the operation, the various layers of tissue and skin that were removed are sutured to complete the operation. Caring for animals after surgery. Each group underwent 9 hindlimb medial collateral ligament reconstruction surgery, and the follow-up analysis was performed at 1, 3, and 6 months respectively.
人工韌帶經手術植入動物後第0、1、3個月後之血清氨基丙酸轉氨酶(Alanine aminotransferase；ALT)、肌酸酐(creatinine)及血中尿素氮值(Blood urea nitrogen；BUN)，均在正常參考值範圍內(ALT : 22-80 iu/litre、BUN：17 -24 m g/dl、Creatinine: 0.8-1.8 mg/dl)，顯示人工韌帶經手術植入動物後並無引起肝腎毒性，具有生物相容性。Serum Alanine aminotransferase (ALT), creatinine and Blood urea nitrogen (BUN) at 0, 1, and 3 months after artificial ligament implantation into animals were all Within the range of normal reference values (ALT: 22-80 iu/litre, BUN: 17 -24 mg/dl, Creatinine: 0.8-1.8 mg/dl), it shows that artificial ligaments have not caused liver and kidney toxicity after surgical implantation in animals. It is biocompatible.
各組人工韌帶經手術植入動物後一個月及三個月後分別採樣，取下人工韌帶及前後相連的骨骼組織，以肉眼觀察發現：實施例18與比較例9在術後一個月之人工韌帶和骨釘均明顯可見，而在術後三個月之人工韌帶和骨釘均受到軟組織的包覆而無法可見，取下人工韌帶後，亦發現週邊軟組織成功長入人工韌帶，形成韌帶化現象。One month and three months after the artificial ligaments of each group were surgically implanted into the animals, samples were taken respectively. The artificial ligaments and the skeletal tissues connected to each other were taken out. Observed by naked eyes, the artificial ligaments of Example 18 and Comparative Example 9 were artificial Both the ligament and the bone nail are clearly visible, and the artificial ligament and the bone nail are covered by soft tissue and cannot be seen three months after the operation. After the artificial ligament is removed, it is also found that the surrounding soft tissue has successfully grown into the artificial ligament, forming ligamentization Phenomenon.
依據各組人工韌帶經手術植入動物後一個月及三個月後之X光影像顯示，實施例18與比較例9均發現部分人工韌帶有鬆弛現象，韌帶扣與骨頭間產生間隙。術後三個月之X光發現骨釘與骨頭鑽孔處有癒合現象。According to the X-ray images of each group of artificial ligaments one month and three months after being surgically implanted into animals, both Example 18 and Comparative Example 9 found that some artificial ligaments were loose, and there was a gap between the ligament buckle and the bone. Three months after the operation, the X-ray revealed that the bone nail and the bone drilled hole had healed.
各組人工韌帶經手術植入動物後一個月之最大抗拉強度(ultimate tensile strength)，實施例18的平均為約100牛頓(N)，比較例9的平均為約60N。實施例9之纖維促進細胞骨分化表現較純PET好，亦為影響實施例18最大抗拉強度較比較例9好的因素之一。The ultimate tensile strength of the artificial ligaments in each group was approximately 100 Newtons (N) on average in Example 18 and approximately 60N in Comparative Example 9 one month after surgical implantation in animals. The fiber of Example 9 has better performance in promoting cell bone differentiation than pure PET, and it is also one of the factors that affect the maximum tensile strength of Example 18 better than that of Comparative Example 9.
雖然本揭露已以數個較佳實施例揭露如上，然其並非用以限定本揭露，任何所屬技術領域中具有通常知識者，在不脫離本揭露之精神和範圍內，當可作任意之更動與潤飾，因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。Although this disclosure has been disclosed in several preferred embodiments as above, it is not intended to limit the disclosure. Anyone with ordinary knowledge in the relevant technical field can make any changes without departing from the spirit and scope of this disclosure. Therefore, the scope of protection of this disclosure shall be subject to the scope of the attached patent application.
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