CN102753503B - 改进骨粘固剂在陶瓷基材上的粘附的表面调整 - Google Patents
改进骨粘固剂在陶瓷基材上的粘附的表面调整 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 239000000919 ceramic Substances 0.000 title claims abstract description 28
- 239000002639 bone cement Substances 0.000 title claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims description 36
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 34
- 239000002318 adhesion promoter Substances 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005046 Chlorosilane Substances 0.000 claims description 3
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 3
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 3
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 9
- 239000007943 implant Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009455 aseptic packaging Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- -1 glycidyl ester Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种陶瓷基材,其表面被改性以改进骨粘固剂的粘附。
Description
本发明涉及一种陶瓷基材,其表面被改性以改进骨粘固剂的粘附。
例如可用作植入物的陶瓷基材的表面改性的目的是改进基于聚甲基丙烯酸甲酯(PMMA)的市售骨粘固剂的粘附,以得到基材材料和粘固剂之间的高结合强度。在EP1202702B1中公开了一种方法,在该方法中通过植入物上三层的涂层体系可改进骨粘固剂在植入物上的粘附。该三层体系由(i)硅酸盐层(SiO2)、(ii)硅烷粘附促进剂和(iii)保护性的聚合物覆盖层组成。该SiO2-层的施加是必需的,以确保该硅烷粘附促进剂在预调整过的表面上的结合。
本发明的目的在于,提供一种比现有技术简化的表面调整方法,以改进骨粘固剂在例如可用作植入物的陶瓷基材上的粘附。
本发明的目的通过具有独立权利要求的特征的基材得以实现。优选方案示于从属权利要求中。
令人意外地发现,在其表面上具有足够羟基基团(OH-基团)的陶瓷基材可用相应选择的和合适的硅烷粘附促进剂直接改性,这类陶瓷基材例如包括氧化铝陶瓷、氧化锆陶瓷和由氧化锆与氧化铝的不同组成形成的混合陶瓷。根据本发明可不用预先施加SiO2-层。本发明的合适的硅烷粘附促进剂是某些硅烷,优选是甲氧基硅烷类、乙氧基硅烷类和/或氯硅烷类。在这里,这些硅烷与基材表面的OH-基团反应,其中在硅烷与基材之间形成共价键。
不同硅烷粘附促进剂的有效连接可通过测定水的接触角和通过测定基材表面上的硅含量来证实。
此外,为改进粘固剂的粘附,使用无菌硅烷粘附促进剂是有利的,其一方面与基材表面的OH-基团反应,并且另一方面具有至少一个可与骨粘固剂的单体成分(甲基丙烯酸甲酯)反应的反应性基团。对此,含反应性丙烯酸酯基团或甲基丙烯酸酯基团的无菌硅烷粘附促进剂已证实是本发明所优选的。
经合适的和无菌的硅烷粘附促进剂预调整过的表面可在施加该无菌的硅烷粘附促进剂后直接与市售的骨粘固剂接触,由此由于该无菌的硅烷粘附促进剂的丙烯酸酯/根基团或甲基丙烯酸酯/根基团与骨粘固剂的单体成分之间的化学反应形成共价键,该共价键确保了基材与粘固剂之间的牢固结合。令人意外的是,这种结合也可在潮湿条件下如在水性介质中形成。
此外,根据本发明可在经合适的硅烷粘附促进剂预调整过的基材表面上施加聚合物覆盖层,所述覆盖层在完全聚合后实现对基材表面的保护功能。基于甲基丙烯酸甲酯、聚甲基丙烯酸甲酯、BisGMA(双酚A-二甲基丙烯酸缩水甘油酯)、TEGDMA(三甘醇二甲基丙烯酸酯)、苯酚树脂和/或这些成分的混合物的覆盖层已证实是本发明所优选的。覆盖层中所含的反应性双键与硅烷粘附促进剂的双键反应,以致该硅烷粘附促进剂不再会受物理和化学的污染。
接着,经硅烷粘附促进剂和聚合物保护层预处理过的基材可借助于适当的方法进行灭菌和无菌包装。这类无菌的和经包装的基材是防污染的,并且可经数月的贮存和运输而无质量损坏。通过在经硅烷粘附促进剂和聚合物覆盖层预处理过的基材表面上施加骨粘固剂以活化该聚合物覆盖层,这导致该聚合物覆盖层掺合进骨粘固剂的聚合物网状组织中。这时在骨粘固剂和基材材料之间形成牢固粘附的,甚至在水性介质中也稳定的接合。
因此,本发明涉及一种陶瓷基材,其中
·所述基材的表面经硅烷粘附促进剂改性。
一种根据本发明的陶瓷基材是特别优选的,其中
·所述基材在其表面具有含羟基基团(OH-基团);
·所述基材是氧化铝陶瓷、氧化锆陶瓷或由氧化锆和氧化铝的不同组成形成的混合陶瓷;
·所述硅烷粘附促进剂是与该基材表面上的OH-基团形成共价键的硅烷;
·所述硅烷粘附促进剂选自无菌硅烷粘附促进剂;
·所述硅烷粘附促进剂选自甲氧基硅烷、乙氧基硅烷和/或氯硅烷;
·所述无菌硅烷粘附促进剂一方面与基材表面的OH-基团反应,并且另一方面具有可与骨粘固剂的单体成分反应的至少一个反应性基团;
·所述无菌硅烷粘附促进剂具有反应性丙烯酸酯/根基团或甲基丙烯酸酯/根基团。
此外,本发明涉及一种陶瓷基材,其中
·该经硅烷粘附促进剂预调整过的基材表面另外具有聚合物覆盖层,该覆盖层在完全聚合后实现对基材表面的保护功能;
特别优选的是一种根据本发明的具有聚合物覆盖层的陶瓷基材,其中
·所述覆盖层基于甲基丙烯酸甲酯、聚甲基丙烯酸甲酯、BisGMA、TEGDMA、苯酚树脂和/或这些成分的混合物。
Claims (7)
1.陶瓷基材,其特征在于,所述基材的表面用硅烷粘附促进剂改性,其中所述用硅烷粘附促进剂预调整过的基材表面另外具有聚合物覆盖层,该覆盖层经完全聚合后实现对基材表面的保护功能,
其中,所述硅烷粘附促进剂选自无菌硅烷粘附促进剂,和所述无菌硅烷粘附促进剂一方面与基材表面的OH-基团反应,并且另一方面具有至少一个可与骨粘固剂的单体成分反应的反应性基团。
2.根据权利要求1的陶瓷基材,其特征在于,所述基材在其表面上具有羟基基团(OH-基团)。
3.根据权利要求1或2的陶瓷基材,其特征在于,所述基材是氧化铝陶瓷、氧化锆陶瓷或由氧化锆和氧化铝的不同组成形成的混合陶瓷。
4.根据权利要求1或2的陶瓷基材,其特征在于,所述硅烷粘附促进剂是与所述基材表面的OH-基团形成共价键的硅烷。
5.根据权利要求1或2的陶瓷基材,其特征在于,所述硅烷粘附促进剂选自甲氧基硅烷、乙氧基硅烷和/或氯硅烷。
6.根据权利要求1或2的陶瓷基材,其特征在于,所述无菌硅烷粘附促进剂具有反应性丙烯酸酯/根基团或甲基丙烯酸酯/根基团。
7.根据权利要求1的陶瓷基材,其特征在于,所述覆盖层基于甲基丙烯酸甲酯、聚甲基丙烯酸甲酯、BisGMA、TEGDMA、苯酚树脂和/或这些成分的混合物。
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PCT/EP2010/070000 WO2011083024A1 (de) | 2009-12-17 | 2010-12-16 | Oberflächenkonditionierung zur verbesserung der knochenzementadhäsion an keramischen substraten |
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US10014177B2 (en) | 2012-12-13 | 2018-07-03 | Corning Incorporated | Methods for processing electronic devices |
EP2932496A4 (en) * | 2012-12-13 | 2016-11-02 | Corning Inc | GLASS AND METHOD FOR PRODUCING GLASS ARTICLES |
US10086584B2 (en) | 2012-12-13 | 2018-10-02 | Corning Incorporated | Glass articles and methods for controlled bonding of glass sheets with carriers |
TWI617437B (zh) | 2012-12-13 | 2018-03-11 | 康寧公司 | 促進控制薄片與載體間接合之處理 |
US9340443B2 (en) | 2012-12-13 | 2016-05-17 | Corning Incorporated | Bulk annealing of glass sheets |
US10510576B2 (en) | 2013-10-14 | 2019-12-17 | Corning Incorporated | Carrier-bonding methods and articles for semiconductor and interposer processing |
CN106132688B (zh) | 2014-01-27 | 2020-07-14 | 康宁股份有限公司 | 用于薄片与载体的受控粘结的制品和方法 |
JP2017518954A (ja) | 2014-04-09 | 2017-07-13 | コーニング インコーポレイテッド | デバイスで改質された基体物品、およびそれを製造する方法 |
CN107635769B (zh) | 2015-05-19 | 2020-09-15 | 康宁股份有限公司 | 使片材与载体粘结的制品和方法 |
CN107810168A (zh) | 2015-06-26 | 2018-03-16 | 康宁股份有限公司 | 包含板材和载体的方法和制品 |
TW202216444A (zh) | 2016-08-30 | 2022-05-01 | 美商康寧公司 | 用於片材接合的矽氧烷電漿聚合物 |
TWI821867B (zh) | 2016-08-31 | 2023-11-11 | 美商康寧公司 | 具以可控制式黏結的薄片之製品及製作其之方法 |
WO2019036710A1 (en) | 2017-08-18 | 2019-02-21 | Corning Incorporated | TEMPORARY BINDING USING POLYCATIONIC POLYMERS |
US11331692B2 (en) | 2017-12-15 | 2022-05-17 | Corning Incorporated | Methods for treating a substrate and method for making articles comprising bonded sheets |
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US4826430A (en) * | 1984-04-23 | 1989-05-02 | Johnson & Johnson Consumer Products, Inc. | Adhesive primer for alumina brackets |
NZ223704A (en) * | 1987-03-13 | 1990-02-26 | Johnson & Johnson Dental Prod | Silica-containing adhesive primer for coating alumina articles and methods of use in orthodontics |
JP3260817B2 (ja) * | 1992-05-08 | 2002-02-25 | 京セラ株式会社 | 補綴具とその製造方法 |
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US20120258320A1 (en) | 2012-10-11 |
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EP2513014A1 (de) | 2012-10-24 |
JP2013514105A (ja) | 2013-04-25 |
RU2593841C2 (ru) | 2016-08-10 |
AU2010340894A1 (en) | 2012-08-02 |
CA2784967A1 (en) | 2011-07-14 |
RU2012129863A (ru) | 2014-01-27 |
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KR20120105030A (ko) | 2012-09-24 |
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