TWI614228B - 陶瓷表面改質方法 - Google Patents
陶瓷表面改質方法 Download PDFInfo
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- TWI614228B TWI614228B TW105139211A TW105139211A TWI614228B TW I614228 B TWI614228 B TW I614228B TW 105139211 A TW105139211 A TW 105139211A TW 105139211 A TW105139211 A TW 105139211A TW I614228 B TWI614228 B TW I614228B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title description 6
- 238000004381 surface treatment Methods 0.000 title description 2
- 239000000758 substrate Substances 0.000 claims abstract description 36
- -1 silane compound Chemical class 0.000 claims abstract description 33
- 230000003385 bacteriostatic effect Effects 0.000 claims abstract description 31
- 238000002715 modification method Methods 0.000 claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 30
- 238000012986 modification Methods 0.000 claims abstract description 28
- 230000004048 modification Effects 0.000 claims abstract description 28
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 15
- 230000001681 protective effect Effects 0.000 claims abstract description 15
- 238000006482 condensation reaction Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 7
- JCSVHJQZTMYYFL-UHFFFAOYSA-N triethyl(methyl)silane Chemical compound CC[Si](C)(CC)CC JCSVHJQZTMYYFL-UHFFFAOYSA-N 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001580 bacterial effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims 2
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 10
- 230000003373 anti-fouling effect Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000004053 dental implant Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011253 protective coating Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 206010061218 Inflammation Diseases 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 210000002421 cell wall Anatomy 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000004054 inflammatory process Effects 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 208000025157 Oral disease Diseases 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 208000030194 mouth disease Diseases 0.000 description 2
- 208000028169 periodontal disease Diseases 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 208000017667 Chronic Disease Diseases 0.000 description 1
- 208000002064 Dental Plaque Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035965 Postoperative Complications Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000007505 plaque formation Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
- C04B41/4535—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied as a solution, emulsion, dispersion or suspension
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- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
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- A61K6/00—Preparations for dentistry
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- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
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Abstract
一種陶瓷表面改質方法，包括以下步驟。將抑菌離子與含有矽烷化合物的溶膠凝膠溶液混合，以形成改質溶液。之後，將陶瓷基材置入改質溶液中，以進行改質鍵結反應，使改質溶液中的抑菌離子得以透過矽烷化合物接枝於陶瓷基材的表面。接著，對經改質鍵結反應的陶瓷基材進行燒結縮合反應，以在陶瓷基材的表面上形成保護膜，保護膜係以疏水層貼附於陶瓷基材的表面，且於所述疏水層上散布有抑菌離子。
Description
本發明是有關於一種陶瓷表面改質方法，且特別是有關於一種兼具口腔美觀與防汙抑菌的陶瓷表面改質方法。
目前市面上大多以陶瓷氧化鋯作為假牙與植牙贋復體的材料，氧化鋯除了具有精密陶瓷應有的高強度、硬度、耐高溫、耐酸鹼腐蝕及高化學穩定性等條件外，還具有比一般陶瓷高的堅韌性與相當好的生物相容性，故廣泛應用於人體醫學上。
在習知技術中，陶瓷膺復體成型後大多僅表面拋光處理，提供表面光澤使陶瓷具美觀及光滑性，令膺復體不易殘留食物，多著重於口腔美觀取向。然而，上述處理方法並無法防止細菌附著，因此，容易造成假牙或贋復體表面附著牙菌斑而引發牙周病或齲齒的困擾。
基於上述，發展出一種能夠兼具口腔美觀與防汙抑菌之功效的陶瓷表面改質方法，藉由表面處理技術改善牙周病比例攀升所造成牙齒周圍發炎的各項疾病，為目前所需研究的重要課題。
本發明提供一種陶瓷表面改質方法，能夠於陶瓷贋復體表面形成兼具疏水、防汙、透光與抑菌性的防護鍍膜。
本發明的陶瓷表面改質方法包括以下步驟。將抑菌離子與含有矽烷化合物的溶膠凝膠溶液混合，以形成改質溶液。之後，將陶瓷基材置入改質溶液中，以進行改質鍵結反應，使改質溶液中的抑菌離子得以透過矽烷化合物接枝於陶瓷基材的表面。接著，對經改質鍵結反應的陶瓷基材進行燒結縮合反應，以在陶瓷基材的表面上形成保護膜，保護膜係以疏水層貼附於陶瓷基材的表面，且於疏水層上散布有抑菌離子。
在本發明的一實施例中，矽烷化合物包括選自由四乙氧基矽烷（TEOS）、3-胺基丙基三乙氧基矽烷（APTES）、3-甲基丙烯醯氧基丙基三甲氧基矽烷（MPTMS）、甲基三乙基矽烷（MTES）、甲基三甲氧基矽烷（MTMS）、甲基三乙氧基矽烷（MTEOS）及六甲基二矽氨烷（HMDS）所組成的族群中的至少兩者以上。
在本發明的一實施例中，陶瓷基材的材料包括氧化鋯。
在本發明的一實施例中，陶瓷基材包括假牙或植牙贋復體。
在本發明的一實施例中，保護膜的厚度為10 nm至200 nm。
在本發明的一實施例中，抑菌離子包括銀離子、金離子、銅離子、鈦離子或鉑離子。
在本發明的一實施例中，改質溶液中所含有抑菌離子及矽烷化合物的重量百分比分別為5%至30%，且抑菌離子與矽烷化合物的莫耳濃度比為1：4。
在本發明的一實施例中，將抑菌離子與溶膠凝膠溶液混合是在40℃至100℃的溫度下進行，轉速為500 rpm至2000 rpm。
在本發明的一實施例中，改質溶液的pH值為2.0至4.0。
在本發明的一實施例中，改質鍵結反應的反應時間為60分鐘至180分鐘。
在本發明的一實施例中，燒結縮合反應是在300℃至500℃的溫度下進行20分鐘至60分鐘。
基於上述，本發明提供一種陶瓷表面改質方法，以化學性溶膠-凝膠技術對陶瓷進行表面改質，採用矽烷化合物搭載抑菌離子於陶瓷氧化鋯表面形成保護膜，再以高溫縮合形成緻密防護，使陶瓷贋復體表面形成兼具疏水、防汙、透光與抑菌性之防護鍍膜。如此一來，可作為牙科假牙與贋復體的表面防汙抑菌釉料，降低口腔牙菌斑與食物沾附而誘發口腔發炎與各種口腔慢性疾病的可能性。
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例作詳細說明如下。
本發明提出一種陶瓷表面改質方法，包括以下步驟。首先，將抑菌離子與含有矽烷化合物的溶膠凝膠溶液（sol-gel solution）混合，以形成改質溶液。之後，將陶瓷基材置入改質溶液中，以進行改質鍵結反應，使改質溶液中的抑菌離子得以透過矽烷化合物接枝於陶瓷基材的表面。接著，對經改質鍵結反應的陶瓷基材進行燒結縮合反應，以在陶瓷基材的表面上形成保護膜，保護膜係以疏水層貼附於陶瓷基材的表面，且於疏水層上散布有抑菌離子。
在進行本發明的陶瓷表面改質方法之前，可先進行陶瓷表面的清潔前處理製程，以去除陶瓷表面殘留的雜質或殘料。陶瓷表面的清潔前處理製程可包括依序以超純水（ultra-pure water）與丙酮對陶瓷表面震洗5分鐘，並重複此步驟一次。
以下將針對本發明的陶瓷表面改質方法中的各細節進行詳細說明。
＜ 形成改質溶液 ＞
在本發明的陶瓷表面改質方法中，將具有抑菌性的金屬離子與含有矽烷化合物的溶膠凝膠溶液混合，以形成pH值例如是2.0至4.0的酸性改質溶液。更詳細而言，改質溶液中所含有抑菌離子及矽烷化合物的重量百分比分別例如是5%至30%，且其餘由水及溶劑所組成，所述溶劑可以是酒精，但並不以此為限。抑菌離子與矽烷化合物的莫耳濃度比較佳為1:4。在本實施例中，抑菌離子與溶膠凝膠溶液混合例如是在40℃至100℃的溫度下進行約1.5小時至2小時，轉速例如是500 rpm至2000 rpm。
在本實施例中，具有抑菌性的金屬離子可包括銀離子、金離子、銅離子、鈦離子或鉑離子。然而，本發明並不以此為限，亦可使用其他具有抑菌作用的金屬離子。由於細菌的細胞壁多為帶負電電荷，因此，當帶正電荷的金屬離子與細菌接觸時，能夠在正、負離子量不平衡的情況下產生拉力，進而導致細菌的細胞壁被拉破而產生破洞，無法合成細胞壁而影響繁殖，使口腔菌無法於假牙或贋復體表面生長與繁殖，藉此產生抑菌效果。
在本實施例中，矽烷化合物可包括選自由四乙氧基矽烷（tetraethyl orthosilicate，TEOS）、3-胺基丙基三乙氧基矽烷（3-Triethoxysilylpropylamine，APTES）、3-甲基丙烯醯氧基丙基三甲氧基矽烷（(3-Mercaptopropyl)trimethoxysilane，MPTMS）、甲基三乙基矽烷（Methyltriethoxysilane，MTES）、甲基三甲氧基矽烷（Methyltrimethoxysilane，MTMS）、甲基三乙氧基矽烷（Methyltriethoxysilane，MTEOS）及六甲基二矽氨烷（Hexamethyldisilazane，HMDS）所組成的族群中的至少兩者以上。其中，本實施例係選擇四乙氧基矽烷與甲基三乙基矽烷混合成熔膠凝膠容易，且較佳莫耳濃度比為1：1。然而，本發明並不以此為限，亦可使用其他能夠製備溶膠凝膠溶液的矽烷化合物。
＜ 改質鍵結反應 ＞
在本發明的陶瓷表面改質方法中，於形成改質溶液之後，將陶瓷基材置入改質溶液中，以進行改質鍵結反應。在本實施例中，陶瓷基材的材料可包括氧化鋯，其例如是假牙或植牙贋復體。陶瓷基材的表面通常會生成氧化物，致使陶瓷基材上的氧與改質溶液中矽烷化合物所帶有的矽形成離子價結，並同時使抑菌離子透過矽烷化合物接枝於陶瓷基材表面。更詳細而言，改質鍵結反應的反應時間例如是60分鐘至180分鐘。
＜ 燒結縮合反應 ＞
在本發明的陶瓷表面改質方法中，在進行改質鍵結反應之後，對陶瓷基材進行燒結縮合反應，以在陶瓷基材的表面上形成厚度例如是10 nm至200 nm的保護膜，其中保護膜係以疏水層貼附於陶瓷基材的表面，且於疏水層上散布有抑菌離子，待溫度降至常溫後即可存放。在本實施例中，燒結縮合反應例如是在300℃至500℃的溫度下進行20分鐘至60分鐘。
本發明提出一種陶瓷表面改質方法，採用矽烷化合物搭配抑菌金屬離子以化學性溶膠-凝膠技術進行陶瓷表面改質，其中藉由溶膠-凝膠輔助陶瓷基材表面與抑菌離子鍵結，再以高溫縮合反應形成緻密防護層。改質溶液中的矽烷化合物可於陶瓷表面形成具有疏水性的防汙保護層，其表面接觸角為90∘以上，以減少食物沾黏附著與口腔牙菌斑形成。同時，改質溶液中的金屬離子具有抑菌作用，可使口腔陶瓷假牙或贋復體具有表面抑菌性，因此，可減少因口腔清潔不當而引起的口腔疾病、發炎與感染等風險，達到兼具口腔植牙贋復之美觀性，且不影響贋復體外觀形貌與透光性，以確保加值陶瓷假牙或贋復體表面改質釉料鍍膜製程的品質。
以下，藉由實驗例來詳細說明上述實施例所提出的陶瓷表面改質方法。然而，下述實驗例並非用以限制本發明。
實驗例
為了證明本發明的陶瓷表面改質方法能夠於陶瓷表面形成具有疏水性的防汙保護層，以下特別作此實驗例。
必須說明的是，由於陶瓷表面改質方法已於上文中詳細地描述，因此，下文中有關陶瓷表面的改質，為求方便說明故省略製備細節之敘述。
陶瓷基材疏水性評估
針對經本發明的改質方法進行表面改質的實例1以及未經表面改質的比較例，量測其表面接觸角以評估疏水性，並將量測結果列於表1中。由於表面接觸角的測量方法為本領域習知技術，故在此不予贅述。
實例1的陶瓷表面改質方法如下：將銀(Ag)離子與含有TEOS及MTES的溶膠凝膠溶液在70℃的溫度下以1:4的混合比例混合，轉速為300 rpm，以形成pH值為3的改質溶液。之後，將陶瓷基材置入改質溶液中，以進行改質鍵結反應，改質鍵結反應的反應時間為120分鐘。接著，對陶瓷基材在400℃的溫度下進行120分鐘的燒結縮合反應，以在陶瓷基材的表面上形成100 nm的保護膜。
表 1<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td><b>實例</b><b>1</b></td><td><b>比較例</b></td></tr><tr><td> 表面接觸角 </td><td> 120∘ </td><td> 60∘ </td></tr></TBODY></TABLE>
如上方表1所示，經本發明的改質方法進行表面改質的實例1表面接觸角為120∘，而未經表面改質的比較例之表面接觸角為60∘。當表面接觸角為90∘以上時，可推知具有良好的疏水特性，因此，可得知未經表面改質的比較例呈現親水特性。相較之下，經本發明的改質方法進行表面改質的實例1可在表面形成具有良好疏水特性的保護鍍膜，且鍍膜厚度為100 nm，如此一來，可在不影響原先陶瓷外型形貌的前提下，達到減少食物殘留與牙菌斑附著的表面型態。
綜上所述，本發明提供一種陶瓷表面改質方法，以化學性溶膠-凝膠技術對陶瓷進行表面改質，採用矽烷化合物搭載抑菌離子於陶瓷氧化鋯表面形成保護膜，再以高溫縮合形成緻密防護，使陶瓷贋復體表面形成兼具疏水、防汙、透光與抑菌性之防護鍍膜。如此一來，達到兼具口腔美觀與防汙抑菌之功效，因此，使贋復牙體技術不僅能夠達到口腔美觀與牙體光澤度，更能輔助患者口腔植牙贋復體表面清潔，同時兼顧防汙抑菌之作用，進而有效降低國人口腔疾病的罹患率，並改善口腔發炎情況或患者術後併發症之衍生問題。
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。
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Claims (10)
- 一種陶瓷表面改質方法，包括：將抑菌離子與含有矽烷化合物的溶膠凝膠溶液混合，以形成改質溶液；將陶瓷基材置入所述改質溶液中，以進行改質鍵結反應，使所述改質溶液中的所述抑菌離子得以透過所述矽烷化合物接枝於所述陶瓷基材的表面；以及對經所述改質鍵結反應的所述陶瓷基材進行燒結縮合反應，以在所述陶瓷基材的表面上形成保護膜，所述保護膜係以疏水層鍵結於所述陶瓷基材的表面，且於所述疏水層上散布有所述抑菌離子。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述矽烷化合物包括選自由四乙氧基矽烷(TEOS)、3-胺基丙基三乙氧基矽烷(APTES)、3-甲基丙烯醯氧基丙基三甲氧基矽烷(MPTMS)、甲基三乙基矽烷(MTES)、甲基三甲氧基矽烷(MTMS)、甲基三乙氧基矽烷(MTEOS)及六甲基二矽氨烷(HMDS)所組成的族群中的至少兩者以上。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述陶瓷基材的材料包括氧化鋯。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述保護膜的厚度為10nm至200nm。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述抑菌離子包括銀離子、金離子、銅離子、鈦離子或鉑離子。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述改質溶液中所含有所述抑菌離子及所述矽烷化合物的重量百分比分別為5%至30%，且所述抑菌離子與所述矽烷化合物的莫耳濃度比為1：4。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中將所述抑菌離子與所述溶膠凝膠溶液混合是在40℃至100℃的溫度下進行，轉速為500rpm至2000rpm。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述改質溶液的pH值為2.0至4.0。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述改質鍵結反應的反應時間為60分鐘至180分鐘。
- 如申請專利範圍第1項所述的陶瓷表面改質方法，其中所述燒結縮合反應是在300℃至500℃的溫度下進行20分鐘至60分鐘。
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