TWI508747B - Dental filling resin - Google Patents
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Description
本發明係關於一種樹脂,且特別是有關於一種牙科填補樹脂。 This invention relates to a resin, and more particularly to a dental filling resin.
近年來,臨床牙科在牙本質黏著系統以及複合樹脂的研發及應用廣受關注。原因在於複合樹脂較先前汞齊合金材料美觀、使用方便而且沒有毒性以及環境污染等問題,因此複合樹脂逐漸取代汞齊而成為齲齒窩洞填補的主流材料。然而現今複合樹脂材料仍有其應用上的問題存在,例如目前已知的齲齒窩洞填補材料,在其光固化後會有聚合收縮的情況發生,這將導致牙齒齒質與樹脂填補物之間產生微小的縫隙,此即稱為填補物的邊緣性滲漏,此外,比起汞齊合金材料,複合樹脂材料更容易聚集細菌貼附於其上而形成生物膜。上述現象均易導致牙齒與複合樹脂填補物介面之間,產生齲齒的病灶以及臨床上所稱的繼發性齲齒。 In recent years, clinical dentistry has received much attention in the development and application of dentin adhesion systems and composite resins. The reason is that the composite resin is more aesthetically pleasing than the previous amalgam alloy material, easy to use, and has no toxicity and environmental pollution. Therefore, the composite resin gradually replaces the amalgam and becomes the mainstream material for filling the cavity. However, today's composite resin materials still have problems in their application. For example, the currently known dentate cavity filling material will have a polymerization shrinkage after photocuring, which will result in the generation of tooth dentition and resin filling. The tiny gap, which is called the edge leakage of the filler, is more likely to form a biofilm than the amalgam alloy material, and the composite resin material is more likely to accumulate on the bacteria. All of the above phenomena are likely to cause lesions between the teeth and the composite resin filling interface, and the clinically known secondary dental caries.
本發明提供一種牙科填補樹脂,以多壓克力官能基之單體進行聚合,能有效減低聚合收縮量,避免牙齒齒質與樹脂填補物之間產生縫隙所造成的繼發性齲齒問題。此外,尚具有改質後的抗菌單體進一步提供更穩定的抑菌功效,使 齲齒窩洞更不易產生二次蛀牙的疑慮。 The invention provides a dental filling resin, which is polymerized by a monomer with multiple acryl functional groups, can effectively reduce the amount of polymerization shrinkage, and avoid the secondary caries problem caused by the gap between the tooth tooth and the resin filler. In addition, the modified antibacterial monomer further provides a more stable antibacterial effect, so that The caries cavity is less likely to cause secondary caries.
本發明之一態樣係提出一種牙科填補樹脂,包含至少一樹脂單元、至少一填充單元以及至少一抗菌單元。樹脂單元,其結構如式I所示:
在本發明之一實施方式中,上述第一取代基包含具有上述壓克力官能基之第一單元;以及兩端各具有一醯胺鍵(-CONH-)之第二單元,其中,第二單元兩端之醯胺鍵係分別與第一單元、樹脂單元之主幹(backbone)連接。 In one embodiment of the invention, the first substituent comprises a first unit having the acryl functional group; and a second unit having a guanamine bond (-CONH-) at each end, wherein the second unit The indole bond at both ends of the unit is connected to the backbone of the first unit and the resin unit, respectively.
在本發明之一實施方式中,上述第一取代基如式III所示:。 In one embodiment of the invention, the first substituent is as shown in Formula III: .
在本發明之一實施方式中,上述第一取代基如式IV所示:
在本發明之一實施方式中,上述第一取代基如式V 所示:。 In one embodiment of the invention, the first substituent is as shown in Formula V: .
在本發明之一實施方式中,上述填充單元係具有第二取代基之二氧化矽粉體。 In one embodiment of the invention, the filling unit is a cerium oxide powder having a second substituent.
在本發明之一實施方式中,上述第二取代基如式VI所示:
在本發明之一實施方式中,上述抗菌單元係至少一改質後表沒食子兒茶素沒食子酸酯單元,改質後表沒食子兒茶素沒食子酸酯單元為表沒食子兒茶素沒食子酸酯之至少一羥基被第三取代基取代。 In one embodiment of the present invention, the antibacterial unit is at least one modified epigallocatechin gallate unit, and the epigallocatechin gallate unit is modified after the modification. At least one hydroxyl group of gallocatechin gallate is substituted with a third substituent.
在本發明之一實施方式中,上述第三取代基與上述第一取代基相同。 In one embodiment of the invention, the third substituent is the same as the first substituent.
在本發明之一實施方式中,樹脂單元之重量份係20~40,填充單元之重量份係60~80,抗菌單元之重量份係0.01~0.02。 In one embodiment of the present invention, the resin unit has a weight fraction of 20 to 40, the filling unit has a weight fraction of 60 to 80, and the antimicrobial unit has a weight fraction of 0.01 to 0.02.
本發明之另一態樣係提出一種牙科填補樹脂的製造方法,包含提供至少一樹脂單元,其結構如式I所示:
在本發明之一實施方式中,進一步包含添加光起始劑並照光,使第一、第二以及第三取代基之壓克力官能基彼此交聯共聚。 In an embodiment of the present invention, further comprising adding a photoinitiator and illuminating, the acrylic functional groups of the first, second and third substituents are cross-linked and copolymerized with each other.
為了使本揭示內容的敘述更加詳盡與完備,下文針對了本發明的實施態樣與具體實施例提出了說明性的描述;但這並非實施或運用本發明具體實施例的唯一形式。以下所揭露的各實施例,在有益的情形下可相互組合或取代,也可在一實施例中附加其他的實施例,而無須進一步的記載或說明。在以下描述中,將詳細敘述許多特定細節以使讀者能夠充分理解以下的實施例。然而,可在無此等特定細節之情況下實踐本發明之實施例。 The description of the embodiments of the present invention is intended to be illustrative and not restrictive. The embodiments disclosed herein may be combined or substituted with each other in an advantageous manner, and other embodiments may be added to an embodiment without further description or description. In the following description, numerous specific details are set forth However, embodiments of the invention may be practiced without these specific details.
本發明之牙科填補樹脂,包含樹脂單元、填充單元以及抗菌單元。樹脂單元的結構如下式I所示:
(I),n為0~0.07,R1為具有壓克力官能基之第一取代基。式I所示係一種環氧丙烯酸酯(epoxy acrylate,EA)衍生物,括號旁之係數n表示括號內之分子結構出現的比率,舉例言之,在本發明之一實施方式中,n為0.07即代表100個樹脂單元中,有7個樹脂單元之結構如下所示:
在本發明另一實施方式中,第一取代基如式IV所
示:,製作的方式例如可以是將六亞甲基二異氰酸鹽(1,6-diisocyanatohexane,HDI),與甲基丙烯酸-2-羥基乙酯(2-hydroxyethyl
methacrylate,HEMA)先進行如下列方程式所示之反應,生成二聚物(II):
在本發明又一實施方式中,第一取代基如式V所示:
,製作的方式例如可以是將2,4-二異氰酸甲苯(toluene 2,4-diisocynate,TDI)與甲基丙烯酸-2-羥基乙酯(2-hydroxyethyl
methacrylate,HEMA)先進行如下列方程式所示之反應,生成二聚物(III):
值得注意的是,本發明各實施方式中的樹脂單元(即環氧丙烯酸酯之衍生物)是藉由環氧丙烯酸酯導入以上所例示具有壓克力官能基的各第一取代基,而形成多壓克力官能基之單體。據此,本發明各實施方式中的樹脂單元具有較純粹環氧丙烯酸酯更高的官能度(即密度更高的壓克力官能基),這在後續其與填充單元、抗菌單元聚合時,藉由高度交聯聚合而減低聚合收縮應變量(polymerization shrinkage)。詳言之,純粹之環氧丙烯酸酯樹脂照光聚合時,由於原本分子間的凡得瓦力被共價鍵所取代,因此產生聚合收縮,而聚合初期材料仍為可流動態,內部應力可藉由材料的流動而釋出,然而當材料達凝膠點時即轉為不可流動態,此時聚合收縮應力會導致材料微裂或與牙本質產生裂縫。當樹脂反應較完全時,由於有較多的壓克力官能基參與聚合反應,使得收縮量增大,然而若是由多官能度的樹脂單體形成交聯網狀結構,由於分子體積增大,造成自由體積減少,將使得聚合收縮量減低。如此便避免了牙齒齒質與樹脂填補物之間產生微小的縫隙,造成聚集細菌從而導致牙齒與複合樹 脂填補物介面之間產生臨床上所稱之繼發性齲齒等問題。 It is to be noted that the resin unit (i.e., the derivative of epoxy acrylate) in each embodiment of the present invention is formed by introducing an epoxy acrylate into each of the first substituents having an acrylic functional group as exemplified above. A monomer with multiple acryl functional groups. Accordingly, the resin unit in each embodiment of the present invention has a higher functionality than the pure epoxy acrylate (ie, a higher density acrylic functional group), which is subsequently polymerized with the filling unit and the antimicrobial unit. The polymerization shrinkage is reduced by highly cross-linked polymerization. In detail, when the pure epoxy acrylate resin is photopolymerized, since the original intrinsic van der Waals force is replaced by a covalent bond, polymerization shrinkage occurs, and the material in the initial stage of polymerization is still flowable, and the internal stress can be borrowed. It is released by the flow of the material, but when the material reaches the gel point, it turns into a non-flowable dynamic state, at which time the polymerization shrinkage stress causes the material to crack or crack with the dentin. When the resin reacts more completely, the amount of shrinkage increases due to more acrylic functional groups participating in the polymerization reaction. However, if the polyfunctional resin monomer forms a crosslinked network structure, the molecular volume increases. The reduction in free volume will result in a reduction in the amount of polymerization shrinkage. This avoids the formation of tiny gaps between the tooth dentine and the resin filler, causing the accumulation of bacteria and the formation of the teeth and the compound tree. There is a clinical problem called secondary caries between the fat filling interface.
本發明之牙科填補樹脂中,填充單元具有第二取代基,第二取代基亦具有壓克力官能基。填充單元係扮演無機填料之角色並發揮提升整體牙科填補樹脂之機械強度的功效。在本發明之一實施方式中,填充單元係具有第二取代基之二氧化矽(SiO2)粉體。第二取代基之結構可如下式VI所示之甲基丙烯酸酯基三甲氧基矽(3-(trimethoxy silyl)propyl methacrylate,MSMA):
本發明之牙科填補樹脂中,抗菌單元具有至少一第三取代基,第三取代基具有壓克力官能基。抗菌單元可由葡萄糖酸氯己定(chlorhexidine gluconate)或是沒食子兒茶素沒食子酸酯(epigallocatechin gallate,EGCG)等具有抗菌功效的材料加以改質而成,以進一步抑制整體牙科填補樹脂上的細菌,從而避免前述牙齒齒質與樹脂填補物之間微小的縫隙產生臨床上所稱之繼發性齲齒等問題。在本發明之一實施方式中,抗菌單元係改質後表沒食子兒茶素沒食子酸酯單元,改質後表沒食子兒茶素沒食子酸酯單元為以下所示之表
沒食子兒茶素沒食子酸酯(EGCG):
在本發明另一實施方式中,第三取代基如式IV所示:,製作的方式例如可以是將六亞甲基二異氰酸鹽(1,6-diisocyanatohexane,HDI),與甲基丙烯酸-2-羥基乙酯(2-hydroxyethyl methacrylate,HEMA)先進行如下列方程式所示之反應,生成二聚物(II):
在本發明又一實施方式中,第三取代基如式V所示:
,製作的方式例如可以是將2,4-二異氰酸甲苯(toluene 2,4-diisocynate,TDI)與甲基丙烯酸-2-羥基乙酯(2-hydroxyethyl methacrylate,HEMA)先進行如下列方程式所示之反應,生成二聚物(III):
而二聚物(III)再以其一端之異氰酸(-NCO)與沒食子兒茶素沒食子酸酯(EGCG)中的羥基(-OH)反應形成醯胺鍵(-CONH-),從而如式V所示之第三取代基接枝於沒食子兒茶素沒食子酸酯(EGCG),即形成改質後表沒食子兒茶素單元。綜合上述,第三取代基與第一取代基可為相同或不同之結構,值得注意的是,抗菌單元之第三取代基亦具有壓克力官能基,以供其與樹脂單元之第一取代基、填充單元之第二取代基所帶有的壓克力官能基交聯共聚。此外更值得注意的是,未改質的沒食子兒茶素沒食子酸酯(EGCG)因為具有8個羥基(-OH),雖具有活性極高之良好抗菌效果,但在接觸到空氣後也極易氧化變質,本實施例中將未改質的沒食子兒茶素沒食子酸酯(EGCG)作了前述第三取代基之改質後,可 有效提高其穩定性,並具有延長抗菌效果之特殊功效。 The dimer (III) is further reacted with an isocyanate (-NCO) at one end to form a guanamine bond with a hydroxyl group (-OH) in gallic catechin gallate (EGCG) (-CONH- Thus, the third substituent as shown in Formula V is grafted to gallocatechin gallate (EGCG) to form a modified epigallocatechin unit. In summary, the third substituent and the first substituent may be the same or different structures, and it is noted that the third substituent of the antibacterial unit also has an acrylic functional group for the first substitution with the resin unit. The acrylic functional group carried by the second substituent of the base unit is crosslinked and copolymerized. In addition, it is more noteworthy that the unmodified gallocatechin gallate (EGCG) has 8 hydroxyl groups (-OH), although it has a very high activity and good antibacterial effect, but it is in contact with air. Afterwards, it is also highly susceptible to oxidative deterioration. In this embodiment, the unmodified catechin gallate (EGCG) is modified by the third substituent. It effectively improves its stability and has the special effect of prolonging the antibacterial effect.
在本發明各實施方式之牙科填補樹脂中,樹脂單元之第一取代基、填充單元之第二取代基以及抗菌單元之第三取代基三者彼此交聯共聚。製造方法係將如上所述之樹脂單元、填充單元以及抗菌單元充分混合後,使樹脂單元之第一取代基、填充單元之第二取代基以及抗菌單元之第三取代基三者彼此交聯共聚。明確言之,如上所述之樹脂單元、填充單元以及抗菌單元因為均具有壓克力官能基之有機結構,因此僅需挑選適當溶劑、溫度或攪拌條件,即可將三者在適當比例下均勻混合分散。在本發明之一實施方式的牙科填補樹脂中,樹脂單元之重量份係20~40,填充單元之重量份係60~80,改質後表沒食子兒茶素單元之重量份係0.01~0.02。混合後,又因上述之樹脂單元、填充單元以及抗菌單元因為均具有壓克力官能基,故僅需施予光或熱等反應條件,便可使均勻混合分散之樹脂單元、填充單元以及抗菌單元各自之壓克力官能基發生聚合反應,使三者形成具有低聚合收縮量、良好機械強度以及兼具抗菌功效之牙科填補樹脂。在本發明之一實施方式中,在混合樹脂單元、填充單元以及抗菌單元的步驟中,進一步包含添加光起始劑並照光,使該第一、第二以及第三取代基之壓克力官能基彼此交聯共聚。光起始劑例如可以是三級胺化合物,包括對-(N,N-二甲基氨基)苯乙烯(p-(N,N-dimethylamino)styrene)、對-(N,N-二甲基氨基)甲基丙烯酸芐酯(p-(N,N-dimethylamino)benzyl methacrylate)、甲基丙烯酸二甲基胺基乙酯(2-(dimethylamino)ethyl methacrylate,DMAEMA)和對二甲胺基苯甲酸乙酯(Ethyl 4-dimethylaminobenzoate, EDMAB),但不以此為限。照光波段例如可以是400~520nm,但亦不以此為限,可視臨床上牙科填補可操作之條件作適度調整。此外,亦可視臨床個案之牙科填補需求,以其他的牙洞填補或黏著材料搭配本發明之牙科填補樹脂,以一併施加或分段施加的手法應用於臨床個案上。 In the dental filling resin according to each embodiment of the present invention, the first substituent of the resin unit, the second substituent of the filling unit, and the third substituent of the antibacterial unit are cross-linked and copolymerized with each other. In the manufacturing method, after the resin unit, the filling unit, and the antibacterial unit as described above are sufficiently mixed, the first substituent of the resin unit, the second substituent of the filling unit, and the third substituent of the antibacterial unit are cross-linked and copolymerized with each other. . Specifically, since the resin unit, the filling unit, and the antibacterial unit as described above all have an organic structure of an acrylic functional group, it is only necessary to select an appropriate solvent, temperature or stirring condition to uniformly homogenize the three at an appropriate ratio. Mixed dispersion. In the dental filling resin according to one embodiment of the present invention, the weight fraction of the resin unit is 20-40, and the weight fraction of the filling unit is 60-80, and the weight fraction of the epigallocatechin unit after the modification is 0.01~ 0.02. After mixing, since the resin unit, the filling unit, and the antibacterial unit all have an acrylic functional group, it is only necessary to apply a reaction condition such as light or heat to uniformly mix and disperse the resin unit, the filling unit, and the antibacterial unit. The acrylic functional groups are polymerized to form a dental filling resin having a low polymerization shrinkage, good mechanical strength, and an antibacterial effect. In an embodiment of the present invention, in the step of mixing the resin unit, the filling unit, and the antibacterial unit, further comprising adding a photoinitiator and illuminating the acrylic functional groups of the first, second, and third substituents The groups are crosslinked and copolymerized with each other. The photoinitiator may, for example, be a tertiary amine compound, including p-(N,N-dimethylamino)styrene (p-(N,N-dimethylamino)styrene), p-(N,N-dimethyl P-(N,N-dimethylamino)benzyl methacrylate, 2-(dimethylamino)ethyl methacrylate (DMAEMA) and p-dimethylaminobenzoic acid Ethyl 4-dimethylaminobenzoate, EDMAB), but not limited to this. The illumination band can be, for example, 400 to 520 nm, but it is not limited thereto, and can be appropriately adjusted according to the conditions in which the clinical dental filling can be operated. In addition, the dental filling material of the present invention may be combined with other dental cavity filling or adhesive materials according to the dental filling requirements of the clinical case, and applied in a clinical case by a method of applying or segmenting together.
最後要強調的是,本發明所揭示之牙科填補樹脂具有低聚合收縮量、良好機械強度以及抗菌功效。以多壓克力官能基之單體進行聚合,能有效減低聚合收縮量,避免牙齒齒質與樹脂填補物之間產生縫隙所造成的繼發性齲齒問題。此外尚具有改質後的抗菌單體提供更穩定的抑菌功效,使齲齒窩洞更不易產生二次蛀牙的疑慮。 Finally, it is emphasized that the dental filling resin disclosed in the present invention has low polymerization shrinkage, good mechanical strength, and antibacterial efficacy. Polymerization with a monomer having multiple acryl functional groups can effectively reduce the amount of polymerization shrinkage and avoid the secondary caries problem caused by the gap between the tooth tooth and the resin filler. In addition, the modified antibacterial monomer provides a more stable antibacterial effect, making the caries cavity more difficult to cause secondary caries.
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.
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TW201503902A TW201503902A (en) | 2015-02-01 |
TWI508747B true TWI508747B (en) | 2015-11-21 |
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TW102127448A TWI508747B (en) | 2013-07-31 | 2013-07-31 | Dental filling resin |
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TW (1) | TWI508747B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4387240A (en) * | 1978-06-02 | 1983-06-07 | Minnesota Mining And Manufacturing Company | Oligomeric methacryl substituted alkylsiloxanes |
TW200842134A (en) * | 2007-04-23 | 2008-11-01 | Univ Nat Taiwan | Modified epoxy acrylic-based resin, producing method and use thereof |
-
2013
- 2013-07-31 TW TW102127448A patent/TWI508747B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4387240A (en) * | 1978-06-02 | 1983-06-07 | Minnesota Mining And Manufacturing Company | Oligomeric methacryl substituted alkylsiloxanes |
TW200842134A (en) * | 2007-04-23 | 2008-11-01 | Univ Nat Taiwan | Modified epoxy acrylic-based resin, producing method and use thereof |
Non-Patent Citations (2)
Title |
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Kim, O. and Shim, W.J.," Studies on the Preparation and Dental Properties of Antibacterial Polymeric Dental Restorative Composites Containing Alkylated Ammonium Chloride Derivatives", Journal of Polymer Research, 2001, Vol.8, No.1, P.49-57 * |
Saito, K., et al.," Antibacterial Activity and Bond Strength to Enamel of Catechin-Incorporated 4-META/MMA-TBB Resin as an Orthodontic Adhesive Resin", Journal of Hard Tissue Biology, 2011, Vol.20, No.3, P.203-210. * |
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