WO2021042325A1 - 临时假牙材料的组合物 - Google Patents

临时假牙材料的组合物 Download PDF

Info

Publication number
WO2021042325A1
WO2021042325A1 PCT/CN2019/104523 CN2019104523W WO2021042325A1 WO 2021042325 A1 WO2021042325 A1 WO 2021042325A1 CN 2019104523 W CN2019104523 W CN 2019104523W WO 2021042325 A1 WO2021042325 A1 WO 2021042325A1
Authority
WO
WIPO (PCT)
Prior art keywords
plasticizer
powder
liquid
composition
temporary
Prior art date
Application number
PCT/CN2019/104523
Other languages
English (en)
French (fr)
Inventor
方旭伟
林元敏
林孟淳
Original Assignee
台北科技大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 台北科技大学 filed Critical 台北科技大学
Priority to PCT/CN2019/104523 priority Critical patent/WO2021042325A1/zh
Publication of WO2021042325A1 publication Critical patent/WO2021042325A1/zh

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C13/00—Dental prostheses; Making same
    • A61C13/08—Artificial teeth; Making same
    • A61C13/087—Artificial resin teeth
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry

Definitions

  • the present invention relates to a temporary denture material composition; in particular, it relates to a temporary denture material composition using citric acid ester as a plasticizer.
  • Temporary dentures are dentures that can be worn for about 1 week to 3 months.
  • the main users are patients who have undergone root canal treatment, periodontal disease, or implant prosthesis, or those who wear dentures. Maintain the function of the teeth. According to statistics, as many as 75.3% of the population over the age of 65 have toothlessness. With the trend of aging society, the demand for temporary dentures is bound to increase day by day.
  • the plasticizer in the temporary denture material is the key material for its performance.
  • the most widely used denture plasticizers are phthalate compounds, such as Dibutyl Phthalate (DBP).
  • DBP Dibutyl Phthalate
  • the present invention provides a composition of temporary denture material, including: a powder and a liquid; wherein the powder includes: polymethyl methacrylate (PMMA) And an initiator; the liquid agent includes: methyl methacrylate, a catalyst, and a plasticizer; wherein, the plasticizer is a citrate compound.
  • PMMA polymethyl methacrylate
  • the plasticizer is a citrate compound.
  • the plasticizer is triethyl citrate or acetyl tributyl citrate.
  • the initiator is benzoyl peroxide (BPO).
  • the catalyst is N,N-dimethyl-p-toluidine (DMPT).
  • the ratio of the powder to the liquid is 3:1 to 1:1 (W/V).
  • the powder includes: 60-90% polymethyl methacrylate (PMMA), 0-5% benzoyl peroxide (BPO), 0-1% pigment, 0-1% opaque agent, 0-20% plasticizer, and mixed with inorganic particles to 100%.
  • PMMA polymethyl methacrylate
  • BPO benzoyl peroxide
  • the liquid agent includes: 1-5% catalyst, 0-20% crosslinking agent, 0-20% plasticizer, 0-0.1% inhibitor, 5-10% % Organic solvent, 5-10% ultraviolet (UV) absorber, and mixed with methyl methacrylate (MMA) to 100%.
  • the proportion of the plasticizer is between 2-10%.
  • the present invention provides a method for preparing temporary dentures, including:
  • a methyl methacrylate, a catalyst, and a plasticizer Provide a methyl methacrylate, a catalyst, and a plasticizer, and mix the methyl methacrylate, the catalyst, and the plasticizer to form a liquid agent;
  • the mixture is placed at room temperature, and after the mixture is hardened, a temporary denture is obtained.
  • the powder and the liquid are mixed and placed at 20°C-25°C to form a temporary denture.
  • Figure 1 is the test result of the highest polymerization temperature of the temporary denture material composition of the present invention.
  • Figure 2 shows the curing time test of the temporary denture material composition of the present invention.
  • Figure 3 is the cytotoxicity test result of the temporary denture material composition of the present invention. After co-cultivation of fibroblast L929 and the temporary denture material composition extract, the cells after (A) 24 hours and (B) 72 hours were recorded respectively Survival rate.
  • Fig. 4 shows the results of the flexural strength test of the temporary denture of the present invention.
  • Fig. 5 is the results of the toughness test of the temporary denture of the present invention.
  • Fig. 6 is the surface hardness test result of the temporary denture of the present invention.
  • initiator in this specification refers to a substance that cracks and forms free radical ions when heated, which causes the monomers in the liquid to polymerize, including but not limited to benzoyl peroxide (BPO) or Diisobutylazonitrile.
  • hardening or “curing” in this specification refers to a reaction in which the physical properties of a compound, such as viscosity or hardness, change over time due to a chemical reaction between the components.
  • plasticizer in this specification refers to a substance that does not directly participate in the polymerization reaction but will be uniformly distributed inside the resin after polymerization to interfere with the interaction and bonding between polymer molecules. It is more pure than without plasticizers. The polymer is soft to resist internal stress caused by chewing. Possible plasticizers include, but are not limited to, triethyl citrate (TEC) or acetyl tributyl citrate (ATBC).
  • TEC triethyl citrate
  • ATBC acetyl tributyl citrate
  • crosslinking agent used in this specification refers to the ability to produce bonding between linear molecules so that multiple linear molecules are bonded and cross-linked to form a network structure, and to promote or regulate the formation of covalent bonds or ionic bonds between polymer molecular chains.
  • the substances include but are not limited to ethylene dimethacrylate (EGDMA).
  • catalyst in this specification refers to a substance that accelerates the decomposition of the initiator at room temperature to increase the speed of monomer polymerization, including but not limited to N,N-dimethyl-p-toluidine (N,N-dimethyl- p-toluidine (DMPT)), dihydroxyethyl-p-toluidine (N,N-dihydroxyethyl-para-toluidine), or sulfonic acid.
  • N,N-dimethyl-p-toluidine N,N-dimethyl- p-toluidine (DMPT)
  • dihydroxyethyl-p-toluidine N,N-dihydroxyethyl-para-toluidine
  • sulfonic acid sulfonic acid
  • inhibitor in this specification refers to a substance that maintains the shelf life of the material and reduces the early occurrence of the polymerization reaction, such as hydroquinone.
  • organic solvent in this specification refers to a substance that uniformly mixes the components of the liquid, such as methanol, ethanol, or propanol.
  • UV absorber used in this manual is a substance that can filter out harmful ultraviolet light to delay product aging, including but not limited to ethyl 2-cyano-3,3-diphenyl acrylate (Ethyl 2 -cyano-3,3 diphenylacrylate).
  • opaque agent in this specification is used to make the color of temporary dentures similar to the color of existing teeth; for example, titanium dioxide.
  • organic particles in this specification includes but is not limited to silicon carbide or aluminum oxide.
  • pigment in this specification refers to a substance added to adjust the color similar to the patient's existing teeth, such as iron oxide.
  • the present invention provides a temporary denture material composition, which has high hardness, high toughness, high bending strength, and excellent biocompatibility.
  • the present invention uses citrate ester compounds instead of phthalate esters as plasticizers in the temporary denture material composition. Therefore, the prepared temporary denture has excellent flexural strength and biocompatibility, and conforms to international standards.
  • the present invention provides a composition of temporary denture material, including: a powder and a liquid;
  • the powder includes: polymethyl methacrylate (PMMA) and an initiator;
  • the liquid includes: methyl methacrylate, a catalyst, and a plasticizer;
  • the plasticizer is a citrate compound.
  • the citrate compound is triethyl citrate (TEC) or acetyl tributyl citrate (ATBC).
  • the feature of the temporary denture material composition of the present invention is that it does not include phthalate compounds.
  • the pigment is iron oxide; the opaque agent is titanium dioxide; the plasticizer is citrate esters or phthalate esters; and the inorganic particles are silicon carbide or alumina particles.
  • the powder includes: 60-90% PMMA, 0-2% BPO, 0-1% pigment, 0-1% opaque agent, 0-20% plasticizer Agent, and blending of inorganic particles to 100%.
  • the powder includes 99% PMMA and 1% BPO.
  • the liquid agent includes: methyl methacrylate (MMA) and N,N-dimethyl-p-toluidine (DMPT) as a catalyst.
  • the liquid may further include: a cross-linking agent, such as ethylene glycol dimethacrylate (EGDMA); a plasticizer, such as DBP, triethyl citrate (triethyl citrate (TEC)), acetyl tributyl citrate (ATBC); inhibitors, such as hydroquinone; organic solvents, such as methanol; and UV absorbers, such as 2-cyano-3,3 -Ethyl 2-cyano-3,3 diphenylacrylate.
  • a cross-linking agent such as ethylene glycol dimethacrylate (EGDMA)
  • a plasticizer such as DBP, triethyl citrate (triethyl citrate (TEC)), acetyl tributyl citrate (ATBC)
  • inhibitors such as hydroquinone
  • organic solvents such
  • the liquid agent further includes: 1-5% catalyst, 0-20% crosslinking agent, 0-20% plasticizer, 0-0.1% inhibitor, and 5-10% organic solvent , 5-10% UV absorber, and mixed with MMA to 100%.
  • the liquid agent includes: 1% DMPT, 5% methanol, 1% 2-cyano-3,3-diphenyl ethyl acrylate, crosslinking agent, plasticizer Agent, and blended with MMA to 100%.
  • the liquid agent further includes: 0-15% of TEC or ATBC as a plasticizer.
  • the plasticizer is 0-15% TEC or ATBC; preferably 2%-10%, more preferably 2%-5%.
  • the crosslinking agent is 0-20% EGDMA.
  • the liquid agent includes: methyl methacrylate (MMA), a catalyst, and a plasticizer.
  • the catalyst is N,N-dimethyl-p-toluidine (DMPT).
  • the liquid agent includes: 1-5% catalyst, 0-20% cross-linking agent, 0-20% plasticizer, 0-0.1% inhibitor, 5-5% 10% organic solvent, 5-10% UV absorber, and blended methyl methacrylate monomer (MMA) to 100%.
  • the liquid agent includes: 1% DMPT, 5% methanol, 1% 2-cyano-3,3-diphenyl acrylate, 0-10% Coupling agents (e.g. EGDMA), 0-10% plasticizers (e.g. TEC or ATBC), and incorporation of MMA to 100%.
  • Coupling agents e.g. EGDMA
  • plasticizers e.g. TEC or ATBC
  • the ratio of the powder to the liquid is between 3:1 and 1:1 (weight:volume (W/V)). In a more preferred embodiment, the ratio of the powder to the liquid is 2:1 (W/V).
  • the present invention provides a method for preparing temporary dentures, including:
  • a methyl methacrylate, a catalyst, and a plasticizer Provide a methyl methacrylate, a catalyst, and a plasticizer, and mix the methyl methacrylate, the catalyst, and the plasticizer to form a liquid agent;
  • the mixture is placed at room temperature, and after the mixture is hardened, a temporary denture is obtained.
  • the powder and the liquid are mixed and placed at 20°C to 25°C and wait for the formation of temporary dentures.
  • the curing time of the mixture is 100-500 seconds after mixing, preferably 180-250 seconds.
  • a powder is prepared, including: 99% polymethyl methacrylate (PMMA) as a polymer and 1% benzoyl peroxide (BPO) as an initiator.
  • PMMA polymethyl methacrylate
  • BPO benzoyl peroxide
  • a liquid which includes: 1% DMPT, 5% methanol, 1% 2-cyano-3,3-diphenyl ethyl acrylate, crosslinking agent, plasticizer, and blending Add MMA to 100%; wherein the crosslinking agent is 0-20% EGDMA, and the plasticizer is 0-15% TEC or ATBC.
  • the ratio of the powder to the liquid is 3:1 to 1:1 (weight:volume (W/V)), for example, 2:1 (W/V).
  • W/V weight:volume
  • After mixing the powder and the liquid stir and place at room temperature, about 20°C-25°C, and pass the following periods: mixing period (20-45 seconds after mixing), polymerization period (50-100 seconds), The appearance period (90-140 seconds), and the hardening period (180-250 seconds), and then temporary dentures are formed.
  • Figure 1 reveals the test results of the highest polymerization temperature of the temporary denture material composition. It can be seen from Figure 1 that if temporary dentures are prepared at room temperature (22 ⁇ 1°C), the types of plasticizers (DBP, TEC, ATBC) have no significant effect on the polymerization temperature of denture materials, and the maximum polymerization temperature is about 60- Between 70°C.
  • FIG. 2 Curing time test of temporary denture material composition. It can be seen from Figure 2 that if a temporary denture is prepared at room temperature, the curing time may be different due to the addition of plasticizers. In particular, citrate plasticizers significantly increase the curing time, and the curing time mostly falls between 200-300 Between seconds.
  • fibroblasts (L929) were seeded in 96-well plates with a cell density of 1 ⁇ 104 cells/100 ⁇ l MEM medium in each plate, and cultured for 1 day.
  • the serum-free culture medium is configured as MTT ((3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide)) reagent, and the ratio of culture medium to MTT solution is 1 mg/ml. Add 50 ⁇ l of MTT reagent to each well plate and put it into the incubator.
  • Figure 3 respectively discloses the cell survival rates after the co-cultivation of fibroblast L929 and the temporary denture material composition extract (A) 24 hours and (B) 72 hours respectively. It can be observed that the cytotoxicity of ATBC added with different plasticizers is less than that of the plasticizers DBP and TEC and has a higher survival rate, but the cytotoxicity caused by TEC is not significantly improved compared to DBP (statistical method: single factor independent Analysis of variance (One-way ANOVA)).
  • ATBC as a plasticizer causes lower toxicity to cells.
  • F is the force to withstand the maximum load (N); b is the average width of the test piece (mm); h is the average thickness of the test piece (mm); l is the distance between the two lower fulcrums (mm).
  • a universal testing machine is used to conduct a bending strength test to analyze the effects of adding DBP, TEC, and ATBC on the bending strength of the temporary denture sample.
  • adding ATBC as a plasticizer can increase the flexural strength of temporary dentures and is better than DBP and TEC.
  • the addition amount is preferably 0-5%, but not more than 10%.
  • the toughness of temporary dentures is the integral area under the curve of stress (Y-axis) and strain (X-axis), and the unit is Also MPa.
  • FIG. 5 The results of the toughness test are shown in Figure 5.
  • a universal testing machine is used to conduct a toughness test to analyze the effect of adding DBP, TEC, and ATBC on the bending strength of the temporary denture sample.
  • adding ATBC or TEC as a plasticizer can increase the toughness of temporary dentures, which is better than DBP, and TEC is better than ATBC.
  • the addition amount is preferably 0-5%, but not more than 10% .
  • Tables 1-3 respectively disclose the quantitative results of the three-point bending test of ATBC (Table 1), TEC (Table 2), and DBP (Table 3).
  • the temporary denture material is filled into a stainless steel mold (diameter 15mm, thickness 1mm). After the temporary denture is completely cured, the sample is immersed in ultrapure water and placed in an oven at 37°C. Take it out after 24 hours, and place the sample to be tested on a micro hardness tester (HMV-2series), and use a diamond indenter to apply a load of 4.903N to the sample for 10 seconds. Finally, the average length of the diagonal indentation on the surface of the sample is measured to calculate the surface hardness of the temporary denture. The calculation formula is:
  • d is the length of the indentation
  • F is the load
  • g is the gravitational constant
  • the results of the hardness test are shown in Figure 6.
  • This experiment uses a micro hardness tester to measure the surface hardness of temporary dentures, and compares the effects of adding DBP, TEC, or ATBC as plasticizers on the surface hardness of temporary dentures.
  • the DBP plasticizer at a low ratio helps increase the surface hardness, and the overall p value is 0.0001. According to the literature, this is an anti-plasticization effect; while the TEC and ATBC plasticizers also show significant effects on the samples. Influence, the p-values are 0.0148 and 0.0055, respectively.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dentistry (AREA)
  • Dental Preparations (AREA)

Abstract

一种临时假牙材料的组合物，包括：一粉剂和一液剂；其中，该粉剂包括：聚甲基丙烯酸甲酯和一起始剂；该液剂包括：甲基丙烯酸甲酯、一催化剂、和一增塑剂；其中，该增塑剂是一柠檬酸酯类化合物。该临时假牙材料组合物具有高硬度、高韧性、高抗弯强度、以及优良的生物兼容性。

Description

临时假牙材料的组合物 技术领域
本发明关于一种临时假牙材料的组合物；特定而言，关于一种使用柠檬酸酯作为增塑剂的临时假牙材料组合物。
背景技术
临时假牙是一种用于佩戴的假牙，可使用时间约为1周至3个月，主要使用者为接受根管治疗、牙周病、或植体赝复的患者或佩戴假牙者，可适当地维持牙齿咬合的功能。根据统计，年龄在65岁以上者，高达75.3％的人口有缺牙的情形，随着高龄化社会趋势，临时假牙需求势必与日俱增。
临时假牙材料中的增塑剂是其性能优劣的关键材料。其中最广为使用的假牙增塑剂为邻苯二甲酸酯类的化合物，如邻苯二甲酸二丁酯(Dibutyl Phthalate(DBP))。但由于DBP其具有生物毒性，可能造成甲状腺素和生长激素的破坏、影响生殖器官发育、且难以为环境所分解，因此多国(包括中国台湾)国家已禁用或限制其仅能低浓度添加，例如使用量不可高于0.1％。
因此，有必要研发一种不含邻苯二甲酸酯类化合物的临时假牙材料，并同时兼具良好塑化功效以及生物兼容性，减少临时假牙对于人体的伤害。
发明内容
为解决前述问题并达成发明的目的，本发明提供一种临时假牙材料的组合物，包括：一粉剂和一液剂；其中，该粉剂包括：聚甲基丙烯酸甲酯(Poly methyl methacrylate，PMMA)和一起始剂；该液剂包括：甲基丙烯酸甲酯、一催化剂、和一增塑剂；其中，该增塑剂是一柠檬酸酯类化合物。
于本发明的一实施例中，该增塑剂是柠檬酸三乙酯或乙酰基柠檬酸三丁酯。
于本发明的一实施例中，该起始剂是过氧化苯甲酰(BPO)。
于本发明的一实施例中，该催化剂是N,N-二甲基对甲苯胺(N,N-dimethyl-p-toluidine，DMPT)。
于本发明的一实施例中，该粉剂和该液剂的比例介于3:1至1:1(W/V)。
于本发明的一实施例中，该粉剂包括：60-90％的聚甲基丙烯酸甲酯粉末(Poly methyl methacrylate，PMMA)、0-5％的过氧化苯甲酰(Benzoyl Peroxide，BPO)、0-1％的色素、0-1％的不透明剂、0-20％的增塑剂、以及掺入无机粒子至100％。
于本发明的一实施例中，该液剂包括：1-5％的催化剂、0-20％的交联剂、0-20％的增塑剂、0-0.1％的抑制剂、5-10％的有机溶剂、5-10％的紫外线(UV)吸收剂、以及掺入甲基丙烯酸甲酯单体(methyl methacrylate，MMA)至100％。
于本发明的一实施例中，该增塑剂的比例介于2-10％。
另一方面，本发明提供一种制备临时假牙的方法，包括：
提供一聚甲基丙烯酸甲酯和一起始剂，混合该聚甲基丙烯酸甲酯和该起始剂，形成一粉剂；
提供一甲基丙烯酸甲酯、一催化剂、和一增塑剂，混合该甲基丙烯酸甲酯、该催化剂、和该增塑剂，形成一液剂；
混合该粉剂和该液剂，获得一混合物；以及
将该混合物放置于室温，待该混合物硬化后，而得一临时假牙。
于本发明的一实施例中，该粉剂和该液剂混合后放置于20℃-25℃待形成临时假牙。
应了解先前的一般描述及以下的详述两者皆仅为示例性及解释性的且并不限制本发明。
附图说明
本发明先前的概述以及以下详述在配合随附附图阅读时得以更佳地被了解。为说明本发明，在附图中显示目前较佳的实施例。
在附图中：
图1为本发明的临时假牙材料组合物最高聚合温度测试结果。
图2为本发明的临时假牙材料组合物的固化时间测试。
图3为本发明的临时假牙材料组合物的细胞毒性试验结果，纤维母细胞L929和临时假牙材料组合物萃取液共同培养后分别记录(A)第24小时和(B)第72小时后的细胞存活率。
图4是本发明的临时假牙的抗弯强度试验结果。
图5是本发明的临时假牙的韧性试验结果。
图6是本发明的临时假牙的表面硬度试验结果。
具体实施方式
本发明的技术特征，包含特定特征，揭示于申请专利范围，针对本发明的技术特征，较佳的理解兹配合说明书、依据本发明原理的实施例、和附图将本发明详细说明如下。
本发明说明书及权利要求范围中所述的所有技术性及科学用语，除非另有所定义，皆为本发明所属技术领域普通技术人员可知晓之定义。其中单数用语“一”、“一个”、“该”、或其近似用语，除非另有说明，皆可指涉多于一个对象。本说明书使用之“或”、“以及”、“和”，除非另有说明，皆指涉“或/和”。此外，用语“包含”、“包括”皆非有所限制之开放式连接词。前述定义仅说明用语定义之指涉而不应解释为对发明目标之限制。除非另有说明，本发明所用的材料皆为市售易于取得。
于本说明书，若无特别说明，百分比的符号(％)均指涉重量百分比(W/W)。
本说明书用语“起始剂”是指涉受热时裂解并形成自由基离子、使液剂内的单体产生聚合反应之一物质，包括但不限于过氧化苯甲酰(benzoyl peroxide，BPO)或双异丁酯偶氮基晴(diisobutylazonitrile)。
本说明书用语“硬化”或“固化”是指涉由于各成分之间产生化学反应，使一组合物之物理性质，例如黏性或硬度，随时间经过而改变之反应。
本说明书用语“增塑剂”是指涉不直接参与聚合反应但聚合后会均匀分布在树脂的内部，以干扰聚合物分子间的互相作用和键结之一物质，较无塑化剂之纯聚体为软，藉此以抵抗因咀嚼所产生的内应力， 可能之增塑剂包括但不限于柠檬酸三乙酯(TEC)或乙酰基柠檬酸三丁酯(ATBC)。
本说明书用语“交联剂”是指涉能在线型分子间产生接合从而使多个线型分子相互键合交联成网络结构，以及促进或调节聚合物分子链间共价键或离子键形成之物质，包括但不限于双甲基丙烯酸伸乙酯(EGDMA)。
本说明书用语“催化剂”是指使其在室温下加速起始剂的分解进而增加单体聚合的速度之一物质，包括但不限于N,N-二甲基对甲苯胺(N,N-dimethyl-p-toluidine(DMPT))、二羟乙基-p-甲苯胺(N,N-dihydroxyethyl-para-toluidine)、或磺酸。
本说明书用语“抑制剂”是指涉维持材料的保存年限及降低聚合反应的提早发生之一物质，例如氢醌(Hydroquinone)。
本说明书用语“有机溶剂”是指涉使液剂成分混和均匀之一物质，例如甲醇、乙醇、或丙醇。
本说明书用语“紫外线(UV)吸收剂”是能够过滤掉有害的紫外光以推迟产品老化的速度之物质，包括但不限于2-氰基-3,3-二苯基丙烯酸乙酯(Ethyl 2-cyano-3,3 diphenylacrylate)。
本说明书用语“不透明剂”是用于使临时假牙的颜色和既有牙齿颜色相似；例如二氧化钛。
本说明书用语“无机粒子”包括但不限于碳化硅或氧化铝。
本说明书用语“色素”是指调整为和患者既有牙齿相似的颜色所加入之一物质，例如氧化铁。
本发明提供一种临时假牙材料组合物，具有高硬度、高韧性、高抗弯强度、以及优良的生物兼容性。
本发明为克服先前技术的缺点，以柠檬酸酯类化合物取代邻苯二甲酸酯类作为临时假牙材料组合物中的增塑剂。因此制得之临时假牙具有优异的抗弯强度以及生物兼容性，并符合国际规范标准。
本发明提供一种临时假牙材料的组合物，包括：一粉剂和一液剂；
其中，该粉剂包括：聚甲基丙烯酸甲酯(PMMA)和一起始剂；该液剂包括：甲基丙烯酸甲酯、一催化剂、和一增塑剂；
其中，该增塑剂是一柠檬酸酯类化合物。
于本发明的一特定实施例，该柠檬酸酯类化合物是柠檬酸三乙酯(triethyl Citrate(TEC))或乙酰基柠檬酸三丁酯(acetyl tributyl citrate(ATBC))。
于本发明的临时假牙材料组合物之特征在不包括邻苯二甲酸酯类化合物。
根据本发明的一实施例，该色素为氧化铁；不透明剂为二氧化钛；增塑剂为柠檬酸酯类、邻苯二甲酸酯类；以及无机粒子为碳化硅或氧化铝粒子。
根据本发明的一较佳实施例，该粉剂包括：60-90％的PMMA、0-2％的BPO、0-1％的色素、0-1％的不透明剂、0-20％的增塑剂、以及掺入无机粒子至100％。
根据本发明的一更佳实施例，该粉剂包括：99％的PMMA和1％的BPO。
根据本发明，该液剂包括：甲基丙烯酸甲酯(MMA)以及作为催化剂的N,N-二甲基对甲苯胺(N,N-dimethyl-p-toluidine(DMPT))。于一特定实施例，该液剂尚可包括：交联剂，例如双甲基丙烯酸伸乙酯(ethylene glycol dimethacrylate(EGDMA))；增塑剂，例如DBP、柠檬酸三乙酯(triethyl Citrate(TEC))、乙酰基柠檬酸三丁酯(acetyl tributyl citrate(ATBC))；抑制剂，例如氢醌(Hydroquinone)；有机溶剂，例如甲醇；以及UV吸收剂，例如2-氰基-3,3-二苯基丙烯酸乙酯(Ethyl 2-cyano-3,3 diphenylacrylate)。
根据本发明，该液剂尚包括：1-5％的催化剂、0-20％的交联剂、0-20％的增塑剂、0-0.1％的抑制剂、5-10％的有机溶剂、5-10％的UV吸收剂、以及掺入MMA至100％。
根据本发明的一更佳实施例，该液剂包括：1％的DMPT、5％的甲醇、1％的2-氰基-3,3-二苯基丙烯酸乙酯、交联剂、增塑剂、以及掺入MMA至100％。
根据本发明，该液剂尚包括：0-15％的TEC或ATBC为增塑剂。
于本发明的一实施例中，该增塑剂是0-15％的TEC或ATBC；较佳为2％-10％，更佳为2％-5％。
于本发明的一较佳实施例中，该交联剂是0-20％的EGDMA。
根据本发明，该液剂包括：甲基丙烯酸甲酯(MMA)、一催化剂、和一增塑剂。
于本发明的一较佳实施例，该催化剂是N,N-二甲基对甲苯胺(DMPT)。
于本发明的一较佳实施例，该液剂包括：1-5％的催化剂、0-20％的交联剂、0-20％的增塑剂、0-0.1％的抑制剂、5-10％的有机溶剂、5-10％的UV吸收剂、以及掺入甲基丙烯酸甲酯单体(MMA)至100％。
于本发明的一更佳实施例，该液剂包括：1％的DMPT、5％的甲醇、1％的2-氰基-3,3-二苯基丙烯酸乙酯、0-10％的交联剂(例如EGDMA)、0-10％的增塑剂(例如TEC或ATBC)、以及掺入MMA至100％。
于一较佳实施例，该粉剂和该液剂之比例介于3:1至1:1(重量：体积(W/V))。于一更佳实施例，该粉剂和该液剂之比例是2:1(W/V)。
另一方面，本发明提供一种制备临时假牙的方法，包括：
提供一聚甲基丙烯酸甲酯和一起始剂，混合该聚甲基丙烯酸甲酯和该起始剂，形成一粉剂；
提供一甲基丙烯酸甲酯、一催化剂、和一增塑剂，混合该甲基丙烯酸甲酯、该催化剂、和该增塑剂，形成一液剂；
混合该粉剂和该液剂，获得一混合物；以及
将该混合物放置于室温，待该混合物硬化后，而得一临时假牙。
于一较佳实施例，该粉剂和该液剂混合后放置于20℃～25℃并等待形成临时假牙。
于一较佳实施例，该混合物的硬化时间是混合后100-500秒，较佳为180-250秒。
实施例1临时假牙的制备方法
首先制备一粉剂，包括：99％做为聚合物的聚甲基丙烯酸甲酯(PMMA)以及1％作为起始剂的过氧化苯甲酰(benzoyl peroxide(BPO))。
然后制备一液剂，该液剂包括：1％的DMPT、5％的甲醇、1％的2-氰基-3,3-二苯基丙烯酸乙酯、交联剂、增塑剂、以及掺入MMA至100％；其中该交联剂是0-20％的EGDMA，该增塑剂是0-15％的TEC或ATBC。
该粉剂和该液剂之比例介于3:1至1:1(重量：体积(W/V))，例如 2:1(W/V)。将该粉剂和该液剂混合后搅拌后放置于室温，约20℃-25℃，并经过以下期间：混合期(混合后第20-45秒)、聚合期(第50-100秒)、团状期(第90-140秒)、以及硬化期(第180-250秒)，而后形成临时假牙。
图1揭示临时假牙材料组合物最高聚合温度测试结果。可自图1得知，若于室温(22±1℃)制备临时假牙，增塑剂种类(DBP、TEC、ATBC)对于假牙材料聚合温度并无显着影响，最高聚合温度大约落于60-70℃之间。
图2临时假牙材料组合物的固化时间测试。可由图2得知，若于室温制备临时假牙，其固化时间可能因为加入增塑剂而有所差异，特别是柠檬酸酯类增塑剂明显增加固化时间，其固化时间大多落于200-300秒之间。
实施例2添加增塑剂的临时假牙的细胞毒性试验
首先，取2克(g)之该粉剂和该液剂之混合物，硬化后浸泡于10ml MEM培养液中24小时，维持在温度37℃，得到该混合物之萃取液，萃取比例为0.2g/ml。
另，将纤维母细胞(L929)接种于96孔盘，每个孔盘中细胞密度为1×104细胞/100μl MEM培养基，培养1日。
而后移除细胞培养基，再加入过滤后含10％胎牛血清(Fetal Bovine Serum，FBS)之材料萃取液及控制组无萃取材料之培养液，培养24-72小时。再将培养液移除，并以磷酸盐缓冲生理盐水(PBS)清洗后移除PBS。以不含血清之培养液配置为MTT((3-(4,5-Dimethylthiazol-2-yl)-2,5-Diphenyltetrazolium Bromide))反应试剂，培养液与MTT溶液比例为1mg/ml。于各孔盘加入50μl MTT试剂并放入培养箱，2小时后去除MTT试剂，并加入100μl抗冻剂(DMSO)，使用回转式震荡器摇晃96孔盘30分钟。待反应完成，以ELISA读取机测量波长570奈米(nm)之吸光值。控制组则为市售暂时牙冠及牙桥树脂材料，包括ALIKE TM和Tempron TM，并比较传统增塑剂(DBP)制备之假牙之细胞毒性。
结果揭示于图3。图3分别披露纤维母细胞L929和临时假牙材料组合物萃取液共同培养后分别记录(A)第24小时和(B)第72小时后之细胞存活率。可以观察到添加不同增塑剂ATBC之细胞毒性皆小于增塑 剂DBP及TEC而有较高之存活率，但TEC造成之细胞毒性相较于DBP并无显着改善(统计方法：单因子独立变异数分析(One-way ANOVA))。
故可得知，使用ATBC作为增塑剂对于细胞造成较低的毒性。
实施例3添加增塑剂的临时假牙材料的三点弯曲试验
首先将临时假牙材料填入不锈钢模具(长度25厘米(mm)、宽度2mm、高度2mm)，待临时假牙完全固化后，将假牙浸泡于超纯水中并放在37℃烘箱内放置24小时，取出后将待测样品置于万能试验机(Shimadzu autograph，AGS-500G)，万能试验机之传感器下降速率为每分钟1mm，以进行抗弯强度测试，再以公式计算弯曲强度(flexural strength)。计算公式为：
Figure PCTCN2019104523-appb-000001
其中，F为承受最大荷重的力(N)；b为试片平均宽度(mm)；h为试片平均厚度(mm)；l为两个下支点的间距(mm)。
抗弯强度测试结果揭示于图4，表1另揭示。本实施例使用万能试验机进行弯曲强度试验，分析添加DBP、TEC、及ATBC对临时假牙样品抗弯强度之影响。依据图4可得知，添加ATBC作为增塑剂可增加临时假牙之抗弯强度，且优于DBP和TEC，添加量则以0-5％为佳，但不宜超过10％。
此外，临时假牙之韧性则为应力(Y轴)与应变(X轴)作曲线下积分面积，单位是
Figure PCTCN2019104523-appb-000002
亦为MPa。
韧性测试结果揭示于图5。本实施例使用万能试验机进行韧性试验，分析添加DBP、TEC、及ATBC对临时假牙样品抗弯强度之影响。依据图5可得知，添加ATBC或TEC作为增塑剂可增加临时假牙之韧性，且优于DBP，且TEC又优于ATBC，添加量则以0-5％为佳，但不宜超过10％。
此外，表1-3分别披露ATBC(表1)、TEC(表2)、以及DBP(表3)之三点弯曲试验之量化结果。
表1
Figure PCTCN2019104523-appb-000003
表2
Figure PCTCN2019104523-appb-000004
表3
Figure PCTCN2019104523-appb-000005
实施例4临时假牙的硬度试验
首先，将临时假牙材料填入不锈钢模具中(直径15mm、厚度1mm)，待临时假牙完全固化后，将样本浸泡于超纯水并置于37℃烘箱内。待24小时后取出，并将待测样品置于微小硬度计(HMV-2series)，以及使用金刚石压头施加于样品的荷重为4.903N，持续10秒钟。最后量测样品表面对角线压痕的平均长度，以计算出临时假牙的表面硬度。计算公式为：
Figure PCTCN2019104523-appb-000006
其中，d表示压痕长度，F则为荷重，g为重力常数。
硬度试验结果揭示于图6。此实验使用微小硬度计以量测临时假牙表面硬度，比较添加DBP、TEC、或ATBC作为增塑剂对临时假牙表面硬度的影响。在低比例下的DBP增塑剂，有助于表面硬度的增加，整体p值为0.0001，根据文献，此为抗塑化效果；而TEC及ATBC增塑剂也表现出对于样品有显着的影响，其p值分别是0.0148及0.0055。
于本说明书实施例揭示的内容，本发明所属领域普通技术人员可明显得知前述实施例仅为例示而非限制；本发明所属技术领域普通技 术人员可通过诸多变换、替换而实施，并不与本发明的技术特征有所差异。依据说明书实施例，本发明可有多种变换仍无碍于实施。本说明书提供的权利要求界定本发明的范围，该范围涵盖前述方法与结构及与其相等的发明。

Claims (10)

  1. 一种临时假牙材料的组合物，包括：一粉剂和一液剂；
    其中，该粉剂包括：聚甲基丙烯酸甲酯(PMMA)和一起始剂；该液剂包括：甲基丙烯酸甲酯、一催化剂、和一增塑剂；
    其中，该增塑剂是一柠檬酸酯类化合物。
  2. 如权利要求1所述的组合物，其中该增塑剂是柠檬酸三乙酯或乙酰基柠檬酸三丁酯。
  3. 如权利要求1所述的组合物，其中该起始剂是过氧化苯甲酰(BPO)。
  4. 如权利要求1所述的组合物，其中该催化剂是N,N-二甲基对甲苯胺(DMPT)。
  5. 如权利要求1所述的组合物，其中该粉剂和该液剂的比例介于3:1至1:1(W/V)。
  6. 如权利要求1所述的组合物，其中该粉剂包括：60-90％的聚甲基丙烯酸甲酯(PMMA)、0-5％的过氧化苯甲酰(BPO)、0-1％的色素、0-1％的不透明剂、0-20％的增塑剂、以及掺入无机粒子至100％。
  7. 如权利要求1所述的组合物，其中该液剂包括：1-5％的催化剂、0-20％的交联剂、0-20％的增塑剂、0-0.1％的抑制剂、5-10％的有机溶剂、5-10％的UV吸收剂、以及掺入甲基丙烯酸甲酯单体(MMA)至100％。
  8. 如权利要求7所述的组合物，其中该增塑剂的比例介于2-10％。
  9. 一种制备临时假牙的方法，包括：
    提供一聚甲基丙烯酸甲酯和一起始剂，混合该聚甲基丙烯酸甲酯和该起始剂，形成一粉剂；
    提供一甲基丙烯酸甲酯、一催化剂、和一增塑剂，混合该甲基丙烯酸甲酯、该催化剂、和该增塑剂，形成一液剂；
    混合该粉剂和该液剂，获得一混合物；以及
    将该混合物放置于室温，待该混合物硬化后，而得一临时假牙。
  10. 如权利要求9所述的方法，其中该粉剂和该液剂混合后放置于20℃-25℃并等待形成临时假牙。
PCT/CN2019/104523 2019-09-05 2019-09-05 临时假牙材料的组合物 WO2021042325A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/104523 WO2021042325A1 (zh) 2019-09-05 2019-09-05 临时假牙材料的组合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/104523 WO2021042325A1 (zh) 2019-09-05 2019-09-05 临时假牙材料的组合物

Publications (1)

Publication Number Publication Date
WO2021042325A1 true WO2021042325A1 (zh) 2021-03-11

Family

ID=74852691

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/104523 WO2021042325A1 (zh) 2019-09-05 2019-09-05 临时假牙材料的组合物

Country Status (1)

Country Link
WO (1) WO2021042325A1 (zh)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0825855B2 (ja) * 1993-04-20 1996-03-13 亀水化学工業株式会社 機能印象材
JP2002119523A (ja) * 2000-10-17 2002-04-23 Kamemizu Kagaku Kogyo Kk 義歯床用軟質裏装材及び該裏装材を用いた義歯床の裏装方法
US20060134012A1 (en) * 2002-12-16 2006-06-22 Symington John M Temporary pharmacologically-inactive dental coating for the in situ protection of dental therapeutic agents from saliva and abrasion from chewing
TW200631598A (en) * 2004-11-12 2006-09-16 Combe Inc Denture liner, denture liner kit and method for making a denture liner
CN102811694A (zh) * 2010-01-20 2012-12-05 国立大学法人冈山大学 医疗用树脂组合物及其制造方法以及医疗用试剂盒
CN105358119A (zh) * 2013-07-08 2016-02-24 3M创新有限公司 包含凝聚和聚集的纳米粒子的混合物的可硬化牙科组合物、组件套盒及其用途
CN105722494A (zh) * 2013-07-30 2016-06-29 登士柏国际公司 抗冲改性的义齿基托组合物
CN106535949A (zh) * 2014-07-01 2017-03-22 贺利氏古萨有限公司 可自聚合的假体材料以及具有改进的颜色稳定性的聚合的、断裂韧性的假体材料
CN109562025A (zh) * 2016-07-20 2019-04-02 株式会社德山齿科 粉液型义齿基托用内装材料

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0825855B2 (ja) * 1993-04-20 1996-03-13 亀水化学工業株式会社 機能印象材
JP2002119523A (ja) * 2000-10-17 2002-04-23 Kamemizu Kagaku Kogyo Kk 義歯床用軟質裏装材及び該裏装材を用いた義歯床の裏装方法
US20060134012A1 (en) * 2002-12-16 2006-06-22 Symington John M Temporary pharmacologically-inactive dental coating for the in situ protection of dental therapeutic agents from saliva and abrasion from chewing
TW200631598A (en) * 2004-11-12 2006-09-16 Combe Inc Denture liner, denture liner kit and method for making a denture liner
CN102811694A (zh) * 2010-01-20 2012-12-05 国立大学法人冈山大学 医疗用树脂组合物及其制造方法以及医疗用试剂盒
CN105358119A (zh) * 2013-07-08 2016-02-24 3M创新有限公司 包含凝聚和聚集的纳米粒子的混合物的可硬化牙科组合物、组件套盒及其用途
CN105722494A (zh) * 2013-07-30 2016-06-29 登士柏国际公司 抗冲改性的义齿基托组合物
CN106535949A (zh) * 2014-07-01 2017-03-22 贺利氏古萨有限公司 可自聚合的假体材料以及具有改进的颜色稳定性的聚合的、断裂韧性的假体材料
CN109562025A (zh) * 2016-07-20 2019-04-02 株式会社德山齿科 粉液型义齿基托用内装材料

Similar Documents

Publication Publication Date Title
Han et al. Evaluation of physical properties and surface degradation of self-adhesive resin cements
Shawkat et al. Oxygen inhibition and incremental layer bond strengths of resin composites
US9682018B2 (en) Denture tooth and material
CN102643500A (zh) 有机-无机纳米复合树脂及其制备方法
US20120296005A1 (en) Medical resin composition, manufacturing process therefor and medical kit
CN111297698B (zh) 齿科粘结剂、其制备方法及应用
JP2007126417A (ja) 歯科用硬化性組成物
Cândea Ciurea et al. Evaluation of the biocompatibility of resin composite‐based dental materials with gingival mesenchymal stromal cells
WO2022087464A1 (en) Polymerizable composition for dental tooth and material 3d printing
Chay et al. Effects of surface treatment and aging on the bond strength of orthodontic brackets to provisional materials
Jerri Evaluate polymer degree of conversion of bulk-fill composite restoration
TWI743552B (zh) 臨時假牙材料之組合物
WO2021042325A1 (zh) 临时假牙材料的组合物
GB2347679A (en) Resin material for denture base
WO2017073664A1 (ja) 硬化性組成物、歯科用硬化性組成物および歯科用有機無機複合粒子
Katayama et al. A study on the characteristics of resin composites for provisional restorations
US20090036612A1 (en) Material for Producing Plastic Molded Parts that can be Used in the Field of Dentistry
CN112535640A (zh) 临时假牙材料的组合物
JPH09249514A (ja) 歯科用レジン強化型セメント用前処理剤
JP6821165B2 (ja) 義歯床、マウスピース及びそれらの製造方法
JPH01186807A (ja) 歯科用複合材料
JP3481070B2 (ja) 軟質リベース材装着用キット
Pithon et al. Evaluation of cytotoxicity and degree of conversion of orthodontic adhesives over different time periods
KR102668433B1 (ko) 고강도 및 고심미성의 치아 수복용 강화 복합소재 및 그 제조방법
CN115844736B (zh) 基于热释电原理的粘接剂组合物及其用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19944131

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19944131

Country of ref document: EP

Kind code of ref document: A1