TWI724984B - Oral care composition - Google Patents
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本發明係關於一種口腔護理組合物，特別是關於一種包含有二氧化矽核殼顆粒的口腔護理組合物。 The present invention relates to an oral care composition, in particular to an oral care composition containing silica core-shell particles.
二氧化矽(SiO2)顆粒通常係以煅燒二氧化矽或沉澱二氧化矽的形式，用作為口腔護理組成物中的研磨劑及/或增稠劑。使用二氧化矽的利益之一為其低成本。然而，二氧化矽除了其研磨及/或增稠效應外，利用有限。因此，口腔護理組成物中必須添加其他的活性劑，以提供所欲的效用(例如，加入抗菌劑用以提供抗-細菌效用，加入齒石控制劑作為齒石控制)。需要添加其他的活性劑不僅造成該口腔護理組成將無法符合在使用其他活性劑所可能引起的規律負荷之可能性，亦增加了該口腔護理組成物將無法讓組成物的使用者滿意之可能性(例如，使用者對界面活性劑月桂基硫酸鈉(SLS)敏感，使用者厭惡鋅化合物的味道，鹹味及目前齒石-控制劑之結晶化問題等)。再者，可能造成進一步的問題。例如，使用抗菌劑常見的問題為細菌對試劑產生抗藥性。 Silica (SiO 2 ) particles are usually in the form of calcined or precipitated silica and are used as abrasives and/or thickeners in oral care compositions. One of the benefits of using silicon dioxide is its low cost. However, apart from its grinding and/or thickening effects, silicon dioxide has limited use. Therefore, other active agents must be added to the oral care composition to provide the desired effects (for example, antibacterial agents are added to provide anti-bacterial effects, and tartar control agents are added for tartar control). The need to add other active agents not only causes the possibility that the oral care composition will not meet the regular load that may be caused by the use of other active agents, but also increases the possibility that the oral care composition will not satisfy the users of the composition (For example, users are sensitive to the surfactant sodium lauryl sulfate (SLS), users hate the taste of zinc compounds, salty taste, and current tartar-control agent crystallization problems, etc.). Furthermore, it may cause further problems. For example, a common problem with the use of antibacterial agents is that bacteria develop resistance to the agent.
已知核-殼結構的膠體顆粒已有數十年。最有名的實施例為光-衍射貴蛋白石，其係在自然環境中於數千年中緩慢形成的。其核-殼結構係在1960年代以電子顯微鏡所發現。從那時候起，已製造出各種合成的核-殼膠體顆粒。然而，此等核-殼物質之合成通常為複雜的，需要多步驟的塗覆方法(參見Kalele等人，“Nanoshell particles：synthesis,properties and applications”,current science,vol. 91,no.8,2006年10月25日)。因此，雖然知道核-殼技術已有數十年，但其仍未被應用在潔牙劑工業，可能是因為製造CSS研磨物質的成本高。 Colloid particles with a core-shell structure have been known for decades. The most famous example is the light-diffraction precious opal, which is slowly formed in the natural environment over thousands of years. Its core-shell structure was discovered with an electron microscope in the 1960s. Since then, various synthetic core-shell colloidal particles have been manufactured. However, the synthesis of these core-shell materials is usually complicated and requires a multi-step coating method (see Kalele et al., "Nanoshell particles: synthesis, properties and applications", current science, vol. 91, no. 8, October 25, 2006). Therefore, although the core-shell technology has been known for decades, it has not been used in the dentifrice industry, probably because of the high cost of manufacturing CSS abrasive materials.
因此，在本項技術中對於帶有多功能效應，但具有達到此多功能效應之最少所需成份的口腔護理組成物，仍有需求。對於開發適用於口腔護理組成物中之另外的抗菌劑及是九齒石控制劑，亦仍有需求。 Therefore, in this technology, there is still a need for an oral care composition that has a multifunctional effect but has the minimum required ingredients to achieve the multifunctional effect. There is still a need to develop additional antibacterial agents and nine-dentite control agents suitable for use in oral care compositions.
本發明係關於一種口腔護理組合物，包含一二氧化矽核殼顆粒，各個二氧化矽核殼顆粒包括一二氧化矽核及及一蝕刻層，蝕刻層包括形成在二氧化矽核的表面的一第I族金屬矽酸鹽。 The present invention relates to an oral care composition comprising a core-shell silica particle. Each core-shell silica particle includes a silica core and an etching layer. The etching layer includes a silicon dioxide core formed on the surface of the silicon dioxide core. A group I metal silicate.
本發明亦關於包括二氧化矽核殼顆粒之組成物。 The present invention also relates to a composition including silica core-shell particles.
本發明亦關於製造此核殼顆粒之方法，其係包括將一定量的二氧化矽顆粒在水中與一定量的鹼混合，其中該鹼係包括第I族金屬離子，用以產生二氧化矽核殼顆粒。 The present invention also relates to a method of manufacturing the core-shell particles, which includes mixing a certain amount of silica particles in water with a certain amount of alkali, wherein the alkali includes group I metal ions to produce a silica core Shell particles.
本發明亦關於降低或抑制有此需要的病患口腔中細菌之方法，其係包括將本發明組成物施用該病患的口腔表面。 The present invention also relates to a method for reducing or inhibiting bacteria in the oral cavity of a patient in need thereof, which comprises applying the composition of the present invention to the oral surface of the patient.
有關金屬CSS顆粒係指帶有適當+1電荷之金屬，例如Na-CSS，此Na為Na+，就K-CSS，此K為K+等。 Related metal CSS particles refer to metals with a proper +1 charge, such as Na-CSS, where Na is Na+, or K-CSS, where K is K+, etc.
如全文所用，範圍係用於速記供描述在此範圍內的各個和每個值。在此範圍內的任何值皆可選作此子範圍的上限。在此範圍內的任何值皆可選作此子範圍的下限。 As used throughout, ranges are used in shorthand to describe each and every value within this range. Any value within this range can be selected as the upper limit of this subrange. Any value in this range can be selected as the lower limit of this subrange.
此外，所有文中所引述的參考文獻、書籍、專利和專利申請公開案係以全文引用的方式併入本文中。在本揭示文與所引述的參考文獻、書籍、專利或專利申請公開案的定義有衝突時，則以本揭示文為主。 In addition, all references, books, patents and patent application publications cited in the text are incorporated herein by reference in their entirety. In the event that there is a conflict between the definitions of this disclosure and the cited references, books, patents or patent application publications, this disclosure shall prevail.
除非另有說明，否則有關周圍溫度或室溫係指20-25℃之溫度範圍。 Unless otherwise specified, the surrounding temperature or room temperature refers to the temperature range of 20-25°C.
除非另有說明否則文中和說明書之他處所表示的所有百分比和量，應了解係指以組成物總重量為基準之重量百分比。 Unless otherwise stated, all percentages and amounts indicated in the text and elsewhere in the specification should be understood to refer to weight percentages based on the total weight of the composition.
「及/或」一詞如文中所用，就例如選項A及/或選項B，係涵蓋(i)選項A；(ii)選項B；及(iii)選項A加上選項B之個別的具體實施例。 The term "and/or" is used in the text, for example Option A and/or Option B, which covers (i) Option A; (ii) Option B; and (iii) Option A plus Option B. example.
請了解，無論何處具體實施例在文中係以「包括」語詞來描述，另外亦提供藉由「由...組成」及/或「基本上由...組成」所描述的類似具體實施例。 Please understand that wherever specific embodiments are described in the text with the term "include", it also provides similar specific implementations described by "consisting of" and/or "consisting essentially of" example.
在本發明之態樣或具體實施例係藉由馬庫西群族(Markush group)或其他替代的群族描述之處，本發明整體上不僅涵蓋整個所列的群族，而非群族之各成員和所有主要群族之可能的子群族，以及缺少一或多個群族成員之主要群族。本發明亦設想了明顯排除在外之該申請發明中一或多個任何之群族成員。 Where aspects or specific embodiments of the present invention are described by the Markush group or other alternative groups, the present invention as a whole not only covers the entire listed group, but not the group. Possible subgroups of each member and all major groups, as well as major groups lacking one or more group members. The present invention also contemplates one or more members of any group that are clearly excluded from the invention of the application.
除非在文中另有指出或另外清楚地與內容牴觸，否則文中所述的各種元素之所有組合係在本發明之範圍內。 Unless otherwise indicated in the text or otherwise clearly in conflict with the content, all combinations of the various elements described in the text are within the scope of the present invention.
本發明進一步可應用的領域由下文詳細說明中將變得更顯而易見。應了解，詳細說明和特定的具體實施例，在指出較佳的本發明之具體實施例的同時，係希望儘為說明之目的且不希望限制本發明之範圍。 The further applicable fields of the present invention will become more apparent from the detailed description below. It should be understood that the detailed description and specific specific embodiments, while pointing out preferred specific embodiments of the present invention, are intended for illustrative purposes only and are not intended to limit the scope of the present invention.
圖1係顯示本發明二氧化矽核殼顆粒之示意圖。 Figure 1 is a schematic diagram showing the silica core-shell particles of the present invention.
圖2係顯示二氧化矽核殼顆粒之示意圖，其說明下圖中描述的光散射模型中所定義的參數。 Figure 2 shows a schematic diagram of a silica core-shell particle, which illustrates the parameters defined in the light scattering model described in the figure below.
圖3係顯示光散射及ESCA分析之圖表，用以測定透明膠體中小的奈米顆粒之存在。 Figure 3 is a chart showing light scattering and ESCA analysis to determine the presence of small nano-particles in the transparent colloid.
下列較佳具體實施例之說明本質上僅為示例性且不希望在任何方面限制本發明、其應用或用途。 The following description of the preferred specific embodiments is merely exemplary in nature and is not intended to limit the present invention, its application or use in any respect.
本發明係提供二氧化矽核殼顆粒，其中各二氧化矽核殼顆粒係包括一二氧化矽核及蝕刻上第I族金屬矽酸鹽之二氧化矽核表面。 The present invention provides silicon dioxide core-shell particles, wherein each silicon dioxide core-shell particle includes a silicon dioxide core and a silicon dioxide core surface etched on a group I metal silicate.
二氧化矽核殼顆粒係藉由以鹼蝕刻二氧化矽(SiO2)，形成核(二氧化矽)-殼(金屬矽酸鹽)結構的膠體所製備。例如使用NaOH作為鹼，形成核(二氧化矽)-殼(Na2SiO3)結構的膠體。此反應係如下：
二氧化矽核之表面係蝕刻上金屬矽酸鹽。術語「蝕刻」係指二氧化矽核的表面蝕刻上金屬矽酸鹽。術語「蝕刻」係指二氧化矽核的表面被溶解，且在二氧化矽核的上方形成第I族金屬矽酸鹽。製造本發明之二氧化矽核殼(CSS)顆粒之過程包括蝕刻原始的二氧化矽以便於形成Na2SiO3。二氧化矽顆粒與鹼的反應使得二氧化矽顆粒的徑長減少而形成一二氧化矽核，並在二氧化矽核的上方形成第I族金屬矽酸鹽。Na2SiO3層並非塗覆在原始二氧化矽表面上方的附加層。 The surface of the silicon dioxide core is etched with metal silicate. The term "etching" refers to the etching of metal silicate on the surface of the silicon dioxide core. The term "etching" means that the surface of the silicon dioxide core is dissolved and a group I metal silicate is formed on the silicon dioxide core. The process of manufacturing the silicon dioxide core-shell (CSS) particles of the present invention includes etching the original silicon dioxide to form Na 2 SiO 3 . The reaction between the silicon dioxide particles and the alkali reduces the diameter and length of the silicon dioxide particles to form a silicon dioxide core, and a group I metal silicate is formed on the silicon dioxide core. The Na 2 SiO 3 layer is not an additional layer coated on the surface of the original silicon dioxide.
藉由以矽酸鹽塗覆二氧化矽而形成顆粒之方法係描述在先前技術中(例如Kalele等人，“Nanoshell particles：synthesis,properties and applications”,current science,vol.91,no.8,2006年10月25日)。然而，這些製備二氧化矽/矽酸鹽顆粒的方法更為複雜、昂貴且與本申請書所述的蝕刻方法不同。 The method of forming particles by coating silicon dioxide with silicate is described in the prior art (for example, Kalele et al., "Nanoshell particles: synthesis, properties and applications", current science, vol. 91, no. 8, October 25, 2006). However, these methods of preparing silica/silicate particles are more complicated, expensive and different from the etching methods described in this application.
金屬矽酸鹽典型地係包括化學式M2SiO3.x H2O，其中M為第I族金屬，而x為0至10。金屬矽酸鹽可為無水的，亦即x=0，或可為水合的。較佳地，M為Na或K。 The metal silicate typically includes the chemical formula M 2 SiO3.x H 2 O, where M is a Group I metal and x is 0-10. The metal silicate can be anhydrous, i.e. x=0, or it can be hydrated. Preferably, M is Na or K.
二氧化矽核的表面可為二氧化矽核之外表面(參見圖1)。 The surface of the silicon dioxide core may be the outer surface of the silicon dioxide core (see Figure 1).
另一種選擇，或另外，二氧化矽核的表面可為二氧化矽核之內表面。 Alternatively, or in addition, the surface of the silicon dioxide core may be the inner surface of the silicon dioxide core.
在一具體實施例中，各顆粒的外部10nm深處係包括從0.1至10，視需要0.1至2重量% M2SiO3.xH2O。 In a specific embodiment, the outer 10nm depth of each particle includes M 2 SiO3.xH 2 O from 0.1 to 10, if necessary, 0.1 to 2% by weight.
在一具體實施例中，各顆粒的外部10nm深處係具有下列通式：(SiO2)p[Oo*M+ mH+ hOH- j].qH2O其中O*為矽酸鹽形式中的氧；M為一第I族金屬離子；p、o、m、h、j和q為各組份的原子百分比(p為SiO2的原子百分比，O為氧在矽酸鹽形式中的原子百分比，m為第I族金屬之原子百分比，h為H+的原子百分比，j為OH-的原子百分比而q為H2O的原子百分比)；且各二氧化矽核殼顆粒的總電荷為零。 In a specific embodiment, the outer 10nm depth of each particle has the following general formula: (SiO 2 ) p [O o *M + m H + h OH - j ].qH 2 O where O* is silicate Oxygen in the form; M is a group I metal ion; p, o, m, h, j and q are the atomic percentages of each component (p is the atomic percentage of SiO 2 and O is oxygen in the silicate form M is the atomic percentage of Group I metal, h is the atomic percentage of H + , j is the atomic percentage of OH- and q is the atomic percentage of H 2 O); and the total of each silicon dioxide core-shell particle The charge is zero.
典型地各組份的原子百分比，H+除外，係藉由化學分析電子能譜(ESCA)來測定。 Typically, the atomic percentage of each component, except H+, is determined by electronic energy spectroscopy (ESCA) for chemical analysis.
視需要，各粒子的外部10nm深處係具有下列組成之一：(SiO2)30.30Na0.41.8.70H2O If necessary, the outer 10nm depth of each particle has one of the following compositions: (Si O2 ) 30.30 N a0.41 .8.70 H2 O
(SiO2)30.67Na0.36.7.63H2O (SiO 2 ) 30.67 Na 0.36 .7.63H 2 O
(SiO2)23.25[O*11.73H10.26Na13.20].5.33H2O (SiO 2 ) 23.25 [O* 11.73 H 10.26 Na 13.20 ].5.33H 2 O
顆粒的d(0.5)或d50為將分布分成半數群族在此徑長以上及半數在此徑長以下之徑長(典型地以微米表示)。應注意，此參數為用於顆粒群族之值，且個別顆粒之徑長可能大於或小於文中所述的d(0.5)值。Dv50(或Dv0.5)為體積分布之中位數，Dn50係用於數量分布，而Ds50係用於表面分布。在本內文中，d(0.5)將用來指體積分布之中位數粒徑。 The d(0.5) or d50 of the particle is the diameter (typically expressed in micrometers) that divides the distribution into half of the groups above this diameter and half below this diameter. It should be noted that this parameter is a value for the particle group, and the diameter of individual particles may be larger or smaller than the d(0.5) value described in the text. Dv50 (or Dv0.5) is the median of volume distribution, Dn50 is used for quantity distribution, and Ds50 is used for surface distribution. In this article, d(0.5) will be used to refer to the median diameter of the volume distribution.
在一具體實施例中，CSS的d(0.5)值係從5nm至50μm。 In a specific embodiment, the d(0.5) value of CSS is from 5 nm to 50 μm.
在另外的具體實施例中，CSS顆粒的d(0.5)值可從26μm至40μm。具有在此範圍內之d(0.5)的顆粒典型地為半透明(translucent)。半透明的顆粒為該等讓光通過之顆粒，雖然不可能看見整顆粒子影像。此點不同於讓光通過並在整個組成物可看見影像之透明組成物。測定粒徑之方法以為本項技術所熟知。例如，粒徑可使用光散射法，例如使用Mastersizer 2000,Hydro 2000S,Malvern Instruments Limited，來測定。 In another specific embodiment, the d(0.5) value of the CSS particles may be from 26 μm to 40 μm. Particles with d(0.5) in this range are typically translucent. Translucent particles are particles that let light pass through, although it is impossible to see the entire particle sub-image. This is different from a transparent composition that allows light to pass through and an image can be seen throughout the composition. The method of measuring particle size is well known in this technology. For example, the particle size can be measured using a light scattering method, such as Mastersizer 2000, Hydro 2000S, Malvern Instruments Limited.
在另外的具體實施例中，CSS顆粒的d(0.5)值可從18μm至25μm。具有在此範圍內之d(0.5)的顆粒典型地為半-不透明的(semi-opaque)。 In another specific embodiment, the d(0.5) value of the CSS particles may range from 18 μm to 25 μm. Particles with d(0.5) in this range are typically semi-opaque.
在另外的具體實施例中，CSS顆粒的d(0.5)值可從10μm至15μm。具有在此範圍內之d(0.5)的顆粒典型地為不透明的(opaque)。 In another specific embodiment, the d(0.5) value of the CSS particles may range from 10 μm to 15 μm. Particles with d(0.5) in this range are typically opaque.
在另外的具體實施例中，CSS顆粒的d(0.5)值可從5μm至15μm。 In another specific embodiment, the d(0.5) value of CSS particles may range from 5 μm to 15 μm.
在另外的具體實施例中，CSS顆粒的d(0.5)值可從2.5μm至4.5μm。 In another specific embodiment, the d(0.5) value of the CSS particles may range from 2.5 μm to 4.5 μm.
在另外的具體實施例中，CSS顆粒的d(0.5)值可從5nm至20nm. In another specific embodiment, the d (0.5) value of the CSS particles can be from 5nm to 20nm.
在另外的具體實施例中，CSS顆粒的d(0.5)值可從10nm至15nm。 In another specific embodiment, the d(0.5) value of the CSS particles may range from 10 nm to 15 nm.
CSS顆粒的d(0.1)值為將分布分成10%群族在此徑長以下及90%在此徑長以上之徑長。 The d(0.1) value of CSS particles divides the distribution into 10% groups below this diameter length and 90% above this diameter length.
CSS顆粒的d(0.9)值為將分布分成90%群族在此徑長以下及10%在此徑長以上之徑長。 The d(0.9) value of CSS particles divides the distribution into groups of 90% below this diameter and 10% above this diameter.
用於描述粒徑分布之分布寬度的值為跨徑(span)：跨徑=(d(0.9)-d(0.1))/d(0.5) The value used to describe the distribution width of particle size distribution is span: span=(d(0.9)-d(0.1))/d(0.5)
根據本發明二氧化矽核殼顆粒之跨徑典型地係從1.5至3。 The span of the silica core-shell particles according to the present invention is typically from 1.5 to 3.
在一較佳的具體實施例中，CSS係具有從10至13μm之d(0.1)，從30至33μm之d(0.5)，及從61至64μm之(0.9)。 In a preferred embodiment, the CSS has d (0.1) from 10 to 13 μm, d (0.5) from 30 to 33 μm, and (0.9) from 61 to 64 μm.
在另外較佳的具體實施例中，CSS係具有從6至9μm之d(0.1)，從18至21μm之d(0.5)，及從41至45μm之(0.9)。 In another preferred embodiment, the CSS has d (0.1) from 6 to 9 μm, d (0.5) from 18 to 21 μm, and (0.9) from 41 to 45 μm.
在一更佳的具體實施例中，CSS係具從3至5μm之d(0.1)，從11至14μm之d(0.5)，及從33至36μm之(0.9)。 In a more preferred embodiment, the CSS has d (0.1) from 3 to 5 μm, d (0.5) from 11 to 14 μm, and (0.9) from 33 to 36 μm.
在較佳的具體實施例中，CSS顆粒的d(0.5)值係低於人類牙本質小管之平均直徑。此項使得CSS顆粒得以進入可能因保護的琺瑯質層損傷而暴露出的牙本質小管。在人類的牙齒中，牙本質小管的平均直徑接近牙本質-琺瑯質交界為0.9μm，牙本質小管的中間部份具有約1.2μm的直徑並接近牙髓直徑為約2.5μm。 In a preferred embodiment, the d(0.5) value of CSS particles is lower than the average diameter of human dentinal tubules. This item allows CSS particles to enter the dentin tubules that may be exposed due to damage to the protected enamel layer. In human teeth, the average diameter of the dentin tubules close to the dentin-enamel junction is 0.9 μm, the middle part of the dentin tubules has a diameter of about 1.2 μm and the diameter close to the dental pulp is about 2.5 μm.
在本發明另外的具體實施例中，二氧化矽的來源係經選擇用以產生適合進入牙本質小管之CSS顆粒(例如Aerosil® 200-一種煅製二氧化矽(合成的非晶二氧化矽)具有0.012μm之d(0.5))。在本發明之另外的具體實施例中，CSS顆粒之d(0.5)值係低於0.9μm。又在本發明另外的具體實施例中，CSS顆粒係具有在0.010μm-低於0.9μm範圍內之d(0.5)。在本發明另外的具體實施例中，本發明之CSS顆粒亦可塞住、阻塞琺瑯質中的孔洞。 In another embodiment of the present invention, the source of silica is selected to produce CSS particles suitable for entry into the dentin tubules (for example, Aerosil® 200-a fumed silica (synthetic amorphous silica) Has a d(0.5) of 0.012μm). In another embodiment of the present invention, the d(0.5) value of the CSS particles is lower than 0.9 μm. In another specific embodiment of the present invention, the CSS particles have a d(0.5) in the range of 0.010 μm to less than 0.9 μm. In another embodiment of the present invention, the CSS particles of the present invention can also plug and block the holes in the enamel.
CSS顆粒可為球形，或實質上球形的，然而應了解，顆粒可具有其他形狀，例如棒狀、針狀或橢圓形。顆粒可具有不規則狀。顆粒亦可形成較大的聚集物。 CSS particles may be spherical, or substantially spherical, however, it should be understood that the particles may have other shapes, such as rods, needles, or ellipses. The particles may have irregular shapes. The particles can also form larger aggregates.
M2SiO3.xH2O可包括多數層的M2SiO3.xH2O單層。單層之數目可從2至100，從2至40，2至12或12至40層單層。 The M 2 SiO 3 .xH 2 O may include a plurality of M 2 SiO 3 .xH 2 O single layers. The number of monolayers can be from 2 to 100, from 2 to 40, 2 to 12, or 12 to 40 monolayers.
顆粒可包括2、4、16、32或36層表面M2SiO3.xH2O單層。 The particles may include 2, 4, 16, 32, or 36 surface M 2 SiO 3 .xH 2 O monolayers.
二氧化矽較佳地係由沉澱二氧化矽、煅製二氧化矽和熔融二氧化矽組成之群中選出。 The silica is preferably selected from the group consisting of precipitated silica, calcined silica and fused silica.
二氧化矽核殼顆粒較佳地係具有高表面電荷密度和離子交換能力。視需要，二氧化矽核殼顆粒係具有從0.5至5.0meq/g之總陽離子交換能力。 The silica core-shell particles preferably have high surface charge density and ion exchange capacity. If necessary, the silica core-shell particles have a total cation exchange capacity of 0.5 to 5.0 meq/g.
在一具體實施例中，此二氧化矽核殼顆粒，使用0.20mm石英UV光學槽在從300至800nm之波長時，係具有從0.0至0.2之濁度。這些顆粒可描述為半透亮或透明的。 In a specific embodiment, the silica core-shell particles have a turbidity from 0.0 to 0.2 when using a 0.20 mm quartz UV optical cell at a wavelength from 300 to 800 nm. These particles can be described as translucent or transparent.
在另外的具體實施例中，此二氧化矽核殼顆粒，使用0.20mm石英UV光學槽在從300至800nm之波長時，係具有從0.8至1.6之濁度。這些顆粒可描述為半-不透明的。 In another specific embodiment, the silica core-shell particles have a turbidity from 0.8 to 1.6 when a 0.20mm quartz UV optical cell is used at a wavelength from 300 to 800 nm. These particles can be described as semi-opaque.
在一另外的具體實施例中，此二氧化矽核殼顆粒，使用0.20mm石英UV光學槽在從300至800nm之波長時，係具有從1.8至2.4之濁度。這些顆粒可描述為不透光的。 In another specific embodiment, the silica core-shell particles have a turbidity from 1.8 to 2.4 when a 0.20 mm quartz UV optical cell is used at a wavelength of from 300 to 800 nm. These particles can be described as opaque.
在另一方面，本發明係提供包括上述二氧化矽核殼顆粒之組成物。 In another aspect, the present invention provides a composition including the above-mentioned silica core-shell particles.
此組成物為粉狀研磨劑。此組成物不包括保濕劑。 This composition is a powdery abrasive. This composition does not include humectants.
此組成物可包括上述定義之二氧化矽核殼顆粒及載劑。 The composition may include the silicon dioxide core-shell particles as defined above and a carrier.
較佳地，此組成物為口腔護理組成物且進一步係包括一口腔可接受的載劑。 Preferably, the composition is an oral care composition and further includes an orally acceptable carrier.
此口腔護理組成物為固體、糊膏、凝膠組成物或液體組成物之形式。此組成物可採取可用於口腔投予之任何劑型。此等之說明性實施例包括(但不限於)潔牙劑，例如牙膏、牙膠、牙乳霜或牙粉；漱口水、口腔沖洗液或口腔噴霧；口腔漿液或液體潔牙劑；口香糖或其他糖果；***錠；牙線或牙膠帶；預防糊膏或粉末；單-或多-層口腔膜片或凝膠條，例如牙條或呼吸條，較佳地使用生物可降解或口腔消耗性膜片或凝膠；功能性膜片或凝膠片或功能性毫米-、微米-或奈米顆粒；包括預凝膠或預聚合物之成膜組成物，例如成膜潔牙劑、牙塗漆；牙齒硬化劑；或口腔上的塗層，例如齒顎矯正、裝置或植體。 The oral care composition is in the form of solid, paste, gel composition or liquid composition. This composition can take any dosage form that can be used for oral administration. Illustrative examples of these include, but are not limited to, dentifrice, such as toothpaste, tooth gel, dental cream or tooth powder; mouthwash, oral rinse or oral spray; oral slurry or liquid dentifrice; chewing gum or others Candies; lozenges; dental floss or dental tape; preventive pastes or powders; single- or multi-layer oral film or gel strips, such as tooth strips or breathing strips, preferably biodegradable or oral expendable Membrane or gel; functional membrane or gel sheet or functional millimeter-, micro-, or nano-particles; film-forming composition including pre-gel or pre-polymer, such as film-forming dentifrice, tooth coating Lacquer; tooth hardener; or coating on the mouth, such as orthodontics, devices, or implants.
口腔可接受的載劑較佳地為水。 The orally acceptable carrier is preferably water.
就固體潔牙劑，例如牙膏，組成物中的水量係由下列組成之量中選出：低於10%重量比，低於5%重量比，低於1%重量比。在這些各自的量中，就較低範圍的水量為0%或不超過0.1%水。 For solid dentifrices, such as toothpaste, the amount of water in the composition is selected from the following components: less than 10% by weight, less than 5% by weight, and less than 1% by weight. Among these respective amounts, the amount of water in the lower range is 0% or not more than 0.1% water.
口腔可接受的載劑可進一步包括一保濕劑。此保濕劑可為乙醇、多醇，其包括(但不限於)甘油、二醇、肌醇、麥芽糖醇、甘露醇、山梨醇、木糖醇、丙二醇、聚丙二醇(PPG)、聚乙二醇(PEG)及其混合物，和糖類，其包括(但不限於)果糖、葡萄糖、蔗糖及糖類之混合物(例如蜂蜜)。 The orally acceptable carrier may further include a humectant. The humectant can be ethanol, polyol, including (but not limited to) glycerin, glycol, inositol, maltitol, mannitol, sorbitol, xylitol, propylene glycol, polypropylene glycol (PPG), polyethylene glycol (PEG) and mixtures thereof, and sugars, which include (but are not limited to) fructose, glucose, sucrose, and mixtures of sugars (such as honey).
在一組成物的具體實施例中，二氧化矽核殼顆粒，以組成的重量為基準，係以0.1wt%至35wt%之量存在。在組成物之另外的具體實施例中，CSS顆粒係以0.1%至1%之量存在。在組成物之另外的具體實施例中，CSS顆粒係以0.5% wt.%至20wt.%之量存在。在組成物之另外的具體實施例中，CSS顆粒係以1% wt.%至10wt.%之量存在。 In a specific embodiment of the composition, the silica core-shell particles are present in an amount of 0.1 wt% to 35 wt% based on the weight of the composition. In another embodiment of the composition, CSS particles are present in an amount of 0.1% to 1%. In another specific embodiment of the composition, the CSS particles are present in an amount of 0.5% wt.% to 20 wt.%. In another embodiment of the composition, the CSS particles are present in an amount of 1% wt.% to 10 wt.%.
在一包括載劑之組成物的具體實施例中，二氧化矽核殼顆粒的折射率係在±0.1單位的載劑折射率之內。 In a specific embodiment of the composition including the carrier, the refractive index of the silica core-shell particles is within ±0.1 unit of the carrier refractive index.
載劑可包括(但不限於)水或其他水性溶劑系統。 The carrier may include, but is not limited to, water or other aqueous solvent systems.
口腔護理組成物可進一步包括一抗菌劑。可能的抗菌劑包括(但不限於)三氯沙(5-氯-2-(2,4-二氯苯氧基)酚)；8-羥基喹啉及其鹽類、鋅和亞錫離子來源例如檸檬酸鋅、硫酸鋅、甘胺酸鋅、檸檬酸鈉鋅和焦磷酸亞錫；銅(II)化合物，例如氯化銅(II)，氟化銅、硫酸酮和氫氧化銅；酞酸及其鹽類，例如酞酸鎂鉀；血根鹼；四級銨化合物，例如烷基氯化吡錠(例如十六烷基氯化吡錠(CPC)、CPC與鋅及/或酵素之混合物、十四烷基氯化吡錠和N-十四烷基-4-乙基氯化吡錠)；雙胍類，例如氯己定二葡萄糖酸(chlorhexidin digluconate)、海克替啶(hexetidine)、奧替尼啶(octenidine)、阿來西定(alexidine)；鹵素化雙酚化合物，例如2,2'伸甲基雙-(4-氯-6-溴酚)；氯化烷基二甲基苄基銨(benzalkonium chloride)；水楊醯苯胺、 溴化度米芬(domiphen bromide)；碘；磺醯胺類；雙二胍類；酚系；哌啶衍生物，例如地莫匹醇和辛哌醇(octapinol)；木蘭萃取物；百里醇；丁香酚；薄荷醇；香葉醇；香芹酚；檸檬醛；兒茶酚；4-烯丙基兒茶酚；己基間苯二酚；水楊酸甲酯；抗生素例如沃格孟汀(augmentin)、阿莫西林(amoxicillin)、四環素(tetracycline)、多西環素(doxycycline)、米諾環素(minocycline)、甲硝唑(metronidazole)、新黴素(neomycin)、卡那黴素(kanamycin)、克林黴素(clindamycin)及其混合物。 The oral care composition may further include an antibacterial agent. Possible antibacterial agents include (but are not limited to) triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol); 8-hydroxyquinoline and its salts, sources of zinc and stannous ions For example, zinc citrate, zinc sulfate, zinc glycine, zinc sodium citrate, and stannous pyrophosphate; copper (II) compounds, such as copper (II) chloride, copper fluoride, ketone sulfate, and copper hydroxide; phthalic acid And its salts, such as potassium magnesium phthalate; sanguinarine; quaternary ammonium compounds, such as alkylpyridinium chloride (such as cetylpyridinium chloride (CPC), mixture of CPC and zinc and/or enzymes) , Tetradecyl pyridinium chloride and N-tetradecyl-4-ethyl pyridinium chloride); biguanides, such as chlorhexidin digluconate, hexetidine, Octenidine, alexidine; halogenated bisphenol compounds, such as 2,2'-methylenebis-(4-chloro-6-bromophenol); chlorinated alkyl dimethyl Benzylammonium (benzalkonium chloride); salicylaniline, Domiphen bromide (domiphen bromide); iodine; sulfonamides; biguanides; phenolic series; piperidine derivatives, such as delmopinol and octapinol; magnolia extract; thymol; Eugenol; Menthol; Geraniol; Carvacrol; Citral; Catechol; 4-Allylcatechol; Hexylresorcinol; Methyl salicylate; Antibiotics such as Augmentin ), amoxicillin, tetracycline, doxycycline, minocycline, metronidazole, neomycin, kanamycin ), clindamycin and mixtures thereof.
可使用的抗菌劑之進一步的例證列表係提供於美國專利第5,776,435號中，其係以引用的方式併入本文中。鋅離子來源之進一步的例證列表包括(但不限於)乙酸鋅、硼酸鋅、丁酸鋅、碳酸鋅、氯化鋅、檸檬酸鋅、甲酸鋅、葡萄糖酸鋅、甘油酸鋅、甘醇酸鋅、乳酸鋅、氧化鋅、磷酸鋅、甲基吡啶鋅、丙酸鋅、水楊酸鋅、矽酸鋅、硬脂酸鋅、齒石酸鋅、十一碳烯酸鋅及其混合物。 A further illustrative list of antibacterial agents that can be used is provided in US Patent No. 5,776,435, which is incorporated herein by reference. A further illustrative list of zinc ion sources includes (but is not limited to) zinc acetate, zinc borate, zinc butyrate, zinc carbonate, zinc chloride, zinc citrate, zinc formate, zinc gluconate, zinc glycerate, zinc glycolate , Zinc lactate, zinc oxide, zinc phosphate, zinc picolinate, zinc propionate, zinc salicylate, zinc silicate, zinc stearate, zinc tartarate, zinc undecylenate and mixtures thereof.
在某些具體實施例中，此抗菌劑係以由下列組成之群中選出之濃度存在：0.001%至3%重量比，0.05%至2%重量比及0.075%至1.5%重量比。 In some embodiments, the antibacterial agent is present at a concentration selected from the group consisting of: 0.001% to 3% by weight, 0.05% to 2% by weight, and 0.075% to 1.5% by weight.
在一具體實施例中，除了本發明二氧化矽核殼顆粒之外，並無另外的抗菌劑。 In a specific embodiment, there is no other antibacterial agent other than the silica core-shell particles of the present invention.
組成物可進一步包括抗齲蝕劑、去敏感劑、黏度調節劑、稀釋劑、界面活性劑、乳化劑、泡沫調節劑、pH調節劑、研磨劑、口感劑、甜味劑、風味劑、色素、防腐劑、胺基酸、抗氧化劑、抗結石劑、氟化物離子來源、增稠劑、用於預防或治療口腔硬組織或軟組織之症狀或病症的活性劑和黏著劑、增白劑及其組合物。 The composition may further include anti-caries agents, desensitizers, viscosity modifiers, diluents, surfactants, emulsifiers, foam modifiers, pH modifiers, abrasives, taste agents, sweeteners, flavors, pigments, Preservatives, amino acids, antioxidants, anti-calculus agents, fluoride ion sources, thickeners, active agents and adhesives, whitening agents, and combinations thereof for preventing or treating symptoms or disorders of oral hard or soft tissues Things.
請了解，上列各物質種類之一般性作用可不同，因而可能有一些共同的作用，且在二或多種此等物質種類中任何所給予的物質可作為多重目的。較佳地，載劑係就與組成物之其他成份的相容性來選擇。 Please understand that the general effects of each substance type listed above may be different, so there may be some common effects, and any given substance in two or more of these substance types can serve multiple purposes. Preferably, the carrier is selected for compatibility with other components of the composition.
一組成物之具體實施例視需要係包括一胺基酸。適合的胺基酸包括(但不限於)精胺酸、半胱胺酸、白胺酸、異白胺酸、離胺酸、丙胺酸、天門冬醯胺酸、天門冬胺酸、***酸、麩胺酸、蘇胺酸、麩醯胺酸、色胺酸、甘胺酸、纈胺酸、脯胺酸、絲胺酸、酪胺酸和組胺酸，及其二或多種組合物。胺基酸可包括R-和L-型及其鹽類形式。胺基酸(及其鹽形式)亦可包括酸酯及/或胺基酸之脂肪醯胺衍生物(例如月桂醯精胺酸乙酯(ELAH))。 A specific embodiment of a composition optionally includes an amino acid. Suitable amino acids include (but are not limited to) arginine, cysteine, leucine, isoleucine, lysine, alanine, aspartic acid, aspartic acid, phenylalanine, Glutamic acid, threonine, glutamine, tryptophan, glycine, valine, proline, serine, tyrosine and histidine, and two or more combinations thereof. Amino acids may include R- and L-types and their salt forms. Amino acids (and their salt forms) may also include acid esters and/or fatty amide derivatives of amino acids (for example, ethyl lauric arginine (ELAH)).
一組成物之具體實施例視需要係包括一抗氧化劑。任可口腔可接受的抗氧化劑皆可使用，包括丁基羥基茴香醚(BHA)、二丁基羥基甲苯(BHT)、維生素A、類胡蘿蔔素、維生素E、類黃酮、多酚類、抗壞血酸、香草抗氧化劑、葉綠素、褪黑激素及其混合物。 A specific embodiment of a composition optionally includes an antioxidant. Any orally acceptable antioxidant can be used, including butylated hydroxyanisole (BHA), dibutylhydroxytoluene (BHT), vitamin A, carotenoids, vitamin E, flavonoids, polyphenols, ascorbic acid, Vanilla antioxidants, chlorophyll, melatonin and their mixtures.
一組成物之具體實施例視需要係包括抗結石(齒石控制)劑。適合的抗結石劑包括(不限於)磷酸鹽和聚磷酸鹽(例如焦磷酸鹽)、聚胺基丙磺酸(AMPS)、六偏磷酸鹽、檸檬酸鋅三水合物、多肽類、聚烯烴磺酸鹽、聚烯烴磷酸鹽、二膦酸鹽。抗結石劑係以約0.1%至約30%存在。口腔組成物可包括不同的抗結石劑之混合物。在一較佳的具體實施例中，係使用焦磷酸四鈉(TSPP)和三聚磷酸鈉(STPP)。抗結石劑係包括約1-2%之TSPP和約7%至約10%之STPP。 A specific embodiment of the composition optionally includes an anti-calculus (dental control) agent. Suitable anti-calculus agents include (not limited to) phosphates and polyphosphates (e.g. pyrophosphate), polyaminopropanesulfonic acid (AMPS), hexametaphosphate, zinc citrate trihydrate, polypeptides, polyolefins Sulfonates, polyolefin phosphates, bisphosphonates. The anti-calculus agent is present at about 0.1% to about 30%. The oral composition may include a mixture of different anti-calculus agents. In a preferred embodiment, tetrasodium pyrophosphate (TSPP) and sodium tripolyphosphate (STPP) are used. The anti-calculus agent includes about 1-2% of TSPP and about 7% to about 10% of STPP.
一組成物之具體實施例視需要係包括至少一種口腔可接受的氟化物離子來源。任何已知或本項技術中所開發的皆可使用。適合的氟化物離子來源包括氟化物、氟化亞錫、氟化鈉、氟化鉀、氟化胺、氟化銨、單氟磷酸亞錫、單氟磷酸鈉、單氟磷酸鉀、單氟磷酸胺、單氟磷酸銨、氟矽酸亞錫、氟矽酸鈉、氟矽酸鉀、氟矽酸胺、氟矽酸銨及其混合物。一或多種氟化物離子-釋放化合物視需要係以提供總計約100至約20,000ppm，約200至約5,000ppm，或約500至約2,500ppm氟化物離子之量存在。 A specific embodiment of the composition optionally includes at least one orally acceptable source of fluoride ions. Any known or developed in this technology can be used. Suitable sources of fluoride ions include fluoride, stannous fluoride, sodium fluoride, potassium fluoride, amine fluoride, ammonium fluoride, stannous monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, monofluorophosphoric acid Amine, ammonium monofluorophosphate, stannous fluorosilicate, sodium fluorosilicate, potassium fluorosilicate, amine fluorosilicate, ammonium fluorosilicate and mixtures thereof. One or more fluoride ion-releasing compounds are optionally present in an amount to provide a total of about 100 to about 20,000 ppm, about 200 to about 5,000 ppm, or about 500 to about 2,500 ppm fluoride ion.
一組成物之具體實施例視需要係包括各種潔牙劑成份用以調整組成物的流變學及感覺，例如表面活性成份、增稠劑或凝膠劑等等。 Specific examples of a composition include various dentifrice ingredients as needed to adjust the rheology and feel of the composition, such as surface active ingredients, thickeners or gels, and so on.
一組成物之具體實施例視需要係包括一亞錫離子或亞錫離子來源。適合的亞錫離子來源包括(不限於)氟化亞錫、其他的亞錫鹵化物，例如氯化亞錫二水合物、焦磷酸亞錫、有機羧酸亞錫鹽類例如甲酸亞錫、乙酸亞錫、葡萄糖酸亞錫、乳酸亞錫、齒石酸亞錫、草酸亞錫、丙二酸亞錫和檸檬酸亞錫、乙二醇亞錫(ethylene glyoxide)及其類似物。一或多種亞錫離子來源可視需要及說明上以約0.01%至約10%，例如約0.1%至約7%或約1%至約5%之總量存在。 A specific embodiment of a composition optionally includes a source of stannous ion or stannous ion. Suitable sources of stannous ions include, but are not limited to, stannous fluoride, other stannous halides, such as stannous chloride dihydrate, stannous pyrophosphate, stannous organic carboxylates such as stannous formate, acetic acid Stannous, stannous gluconate, stannous lactate, stannous dentate, stannous oxalate, stannous malonate and stannous citrate, ethylene glyoxide and the like. One or more sources of stannous ions may be present in a total amount of about 0.01% to about 10%, for example, about 0.1% to about 7%, or about 1% to about 5%, depending on need and description.
一組成物之具體實施例視需要係包括一表面活性劑(界面活性劑)。適合的界面活性劑包括(不限於)C8-20烷基硫酸鹽之水溶性鹽類、C8-20脂肪酸之磺酸單甘油酯、肌胺酸鹽、牛磺酸鹽、月桂基硫酸鈉、椰單甘油酯磺酸鈉、月桂基肌胺酸鈉、月桂醯羥乙基磺酸鈉、聚氧乙烯月桂醚羧酸鈉和十二烷基苯磺酸鈉以及椰油醯胺丙基甜菜鹼。 A specific embodiment of a composition optionally includes a surfactant (surfactant). Suitable surfactants include (not limited to) water-soluble salts of C 8-20 alkyl sulfates, sulfonic acid monoglycerides of C 8-20 fatty acids, sarcosine, taurates, sodium lauryl sulfate , Sodium coconut monoglyceride sulfonate, sodium lauryl sarcosine, sodium lauryl isethionate, sodium polyoxyethylene lauryl ether carboxylate and sodium dodecyl benzene sulfonate, and coco amide propyl beet Alkali.
一組成物之具體實施例視需要係包括一增稠劑。任何口腔接受的增稠劑皆可使用，包括(不限於)卡波姆(carbomer)，亦稱為羧乙烯聚合物，角叉菜膠，亦稱為愛爾蘭苔及更特言之角叉菜膠(
一組成物之具體實施例視需要係包括一風味劑、甜味劑、色劑、泡沫調節劑、口感劑及若需要，組成物中可另外包括其他試劑。 The specific embodiment of a composition optionally includes a flavoring agent, a sweetening agent, a coloring agent, a foam regulator, a mouthfeeling agent, and if necessary, other agents may be additionally included in the composition.
一組成物之具體實施例視需要係包括一或多種另外的活性成份，其可操作用於預防或治療口腔的硬組織或軟組織之症狀或病症，預防或治療生理病症或症狀，或提供美妝利益。此等另 外的活性成份之實施例包括催涎劑、唾液刺激劑、抗菌斑劑、抗發炎劑及/或去敏感劑。 A specific embodiment of a composition optionally includes one or more additional active ingredients, which can be operated to prevent or treat symptoms or disorders of hard or soft tissues of the oral cavity, prevent or treat physiological disorders or symptoms, or provide cosmetics interest. And so on Examples of other active ingredients include salivation agents, saliva stimulants, anti-plaque agents, anti-inflammatory agents and/or desensitizers.
增黏劑亦可加到口腔護理組成物中，其係包括(但不限於)蠟(包括蜂蠟)、礦物油、塑料凝膠(礦物油和聚乙烯的混合物)、石蠟油、白色石蠟油、蟲膠、versagel(液體石蠟、丁烯/乙烯/苯乙烯氫化共聚物之混合物)、聚乙烯蠟、微晶蠟、聚異丁烯、聚乙烯吡咯酮/乙酸乙烯酯共聚物，及不可溶的聚丙烯酸酯共聚物。 Tackifiers can also be added to oral care compositions, which include (but are not limited to) waxes (including beeswax), mineral oil, plastic gels (a mixture of mineral oil and polyethylene), paraffin oil, white paraffin oil, Shellac, versagel (mixture of liquid paraffin, butene/ethylene/styrene hydrogenated copolymer), polyethylene wax, microcrystalline wax, polyisobutylene, polyvinylpyrrolidone/vinyl acetate copolymer, and insoluble polyacrylic acid Ester copolymer.
亦有效作為增黏劑的有液體親水性聚合物，包括聚乙二醇、具有通式HOCH2(CH2OCH2)n1CH2OH之環氧乙烷的非離子聚合物，其中n1代表環氧乙烷基團的平均數目。可購自Dow Chemical公司之聚乙二醇係以數目來命名，例如200、300、400、600、2000，其係代表聚合物的大約平均分子量，以及下式之環氧乙烷和環氧丙烷的非離子嵌段共聚物：HO(C2H4O)a1(C3H6O)b1(C2H4O)c1H。此嵌段共聚物較佳地係選擇(就有關a1、b1和c1)使得環氧乙烷組成部份包括從約65至約75%重量比的共聚物分子及使共聚物具有從約2,000至約15,000之平均分子量，其中共聚物係以使得組成物在室溫時為液態之濃度，存在液體牙齒增白組成物中。 Also effective as thickeners are liquid hydrophilic polymers, including polyethylene glycol, non-ionic polymers of ethylene oxide with the general formula HOCH 2 (CH 2 OCH 2 ) n1 CH 2 OH, where n1 represents the ring The average number of oxyethylene groups. The polyethylene glycols available from Dow Chemical Company are named by numbers, such as 200, 300, 400, 600, 2000, which represent the approximate average molecular weight of the polymer, as well as the ethylene oxide and propylene oxide of the following formula The non-ionic block copolymer: HO (C 2 H 4 O) a1 (C 3 H 6 O) b1 (C 2 H 4 O) c1 H. This block copolymer is preferably selected (with respect to a1, b1 and c1) so that the ethylene oxide component includes from about 65 to about 75% by weight of copolymer molecules and the copolymer has from about 2,000 to With an average molecular weight of about 15,000, the copolymer is present in the liquid tooth whitening composition at such a concentration that the composition is liquid at room temperature.
就用於本發明之施行，特別所欲的嵌段共聚物可從BASF購得，且係稱為Pluraflo L1220(PEG/PPG 116/66)，其具有約9,800之平均分子量。親水性聚(環氧乙烷)嵌段，以聚合物的重量計，平均約65%。 For use in the practice of the present invention, the particularly desired block copolymer is commercially available from BASF and is called Pluraflo L1220 (PEG/PPG 116/66), which has an average molecular weight of about 9,800. The hydrophilic poly(ethylene oxide) block, based on the weight of the polymer, averages about 65%.
合成的陰離子聚羧酸酯亦可用於本發明之組成物中作為潔牙劑組成物內之任何抗細菌、抗齒石或其他活性劑的增效劑。此等陰離子聚羧酸酯一般係以其游離酸或較佳地部份或更佳地完全中和的水溶性鹼金屬(例如鉀及較佳地鈉)或銨鹽之形式來應用。較佳的為1：4至4：1之馬來酸酐或酸與另外可聚合化乙烯化不飽和單體，較佳地具有約30,000至約1,800,000，最佳地約300,000至約700,000分子量(M.W.)之甲基乙烯基醚/馬來酸酐的共聚物。這些共聚物的實施例可購自GAF公司，商品名稱GANTREZ®(甲基乙 烯基醚/馬來酸酐)，例如AN 139(M.W.500,000)、AN 119(M.W.250,000)；S-97醫藥等級(M.W.700,000)、AN 169(M.W.1,200,000-1,800,000)及AN 179(M.W.在1,800,000以上)；其中較佳的共聚物為S-97醫藥等級(M.W.700,000)。 The synthetic anionic polycarboxylate can also be used in the composition of the present invention as a synergist for any anti-bacterial, anti-tartar or other active agent in the dentifrice composition. These anionic polycarboxylates are generally used in the form of their free acids or preferably partially or preferably completely neutralized water-soluble alkali metal (such as potassium and preferably sodium) or ammonium salts. Preferably, it is 1:4 to 4:1 maleic anhydride or acid and another polymerizable ethylenically unsaturated monomer, preferably having a molecular weight of about 30,000 to about 1,800,000, and most preferably about 300,000 to about 700,000 (MW ) The copolymer of methyl vinyl ether/maleic anhydride. Examples of these copolymers can be purchased from GAF company under the trade name GANTREZ® (methyl ethyl Alkenyl ether/maleic anhydride), such as AN 139 (MW500,000), AN 119 (MW250,000); S-97 pharmaceutical grade (MW700,000), AN 169 (MW 1,200,000-1,800,000) and AN 179 (MW above 1,800,000) ); Among them, the preferred copolymer is S-97 pharmaceutical grade (MW700,000).
當存在時，陰離子聚羧酸酯係以有效達到所希望增加口腔組成物內任何抗細菌、抗齒石或其他活性劑之功效的量來使用。一般而言，此陰離子聚羧酸係以約0.05%至約4%重量比，較佳地從約0.5%至約2.5%重量比，存在口腔組成物中。 When present, the anionic polycarboxylate is used in an amount effective to achieve the desired increase in the efficacy of any anti-bacterial, anti-tartar, or other active agents in the oral composition. Generally speaking, the anionic polycarboxylic acid is present in the oral composition at a weight ratio of about 0.05% to about 4%, preferably from about 0.5% to about 2.5% by weight.
用於本發明各種具體實施例之組成物中的增黏劑係以約0%至約20%重量比之量存在。較佳地，增黏劑係以從約2%至約15%重量比之量存在。 The tackifier used in the composition of various embodiments of the present invention is present in an amount of about 0% to about 20% by weight. Preferably, the tackifier is present in an amount ranging from about 2% to about 15% by weight.
一組成物之具體實施例視需要係包括一增白劑，其包括(但不限於)過氧化氫、鹼金屬和鹼土金屬之過氧化物、有機過氧化合物、過氧酸、其醫藥上可接受鹽類及其混合物。鹼金屬和鹼土金屬之過氧化物包括過氧化鋰、過氧化鉀、過氧化鈉、過氧化鎂、過氧化鈣、過氧化鋇及其混合物。有機過氧化合物包括過氧化氫脲(亦稱為尿素過氧化氫)、甘油過氧化氫、烷基過氧化氫、二烷基過氧化物、烷基過氧酸、過氧酯、二醯基過氧化物、過氧化苯甲醯和過氧化鄰苯二甲酸酯及其混合物。過氧酸及其鹽類包括有機過氧酸，例如烷基過氧酸和過氧化鄰苯二甲酸酯及其混合物，以及無機過氧酸，例如鹼金屬和鹼土金屬，例如鋰、鉀、鈉、鎂、鈣和鋇之過硫酸鹽、二過硫酸鹽、過碳酸鹽、過磷酸鹽、過硼酸鹽及過矽酸鹽，及其混合物。在各種具體實施例中，過氧化物化合物係包括過氧化氫、過氧化尿素、過碳酸鈉及其混合物。 The specific embodiment of a composition optionally includes a whitening agent, which includes (but is not limited to) hydrogen peroxide, peroxides of alkali metals and alkaline earth metals, organic peroxy compounds, peroxyacids, and pharmaceutically acceptable Accept salts and their mixtures. The peroxides of alkali metals and alkaline earth metals include lithium peroxide, potassium peroxide, sodium peroxide, magnesium peroxide, calcium peroxide, barium peroxide and mixtures thereof. Organic peroxy compounds include urea hydrogen peroxide (also known as urea hydrogen peroxide), glycerin hydrogen peroxide, alkyl hydrogen peroxide, dialkyl peroxide, alkyl peroxy acid, peroxy ester, diacyl Peroxides, benzoyl peroxides, and peroxyphthalates, and mixtures thereof. Peroxyacids and their salts include organic peroxyacids, such as alkyl peroxyacids and peroxyphthalates and mixtures thereof, and inorganic peroxyacids, such as alkali metals and alkaline earth metals, such as lithium, potassium, Persulfate, dipersulfate, percarbonate, perphosphate, perborate and persilicate of sodium, magnesium, calcium and barium, and mixtures thereof. In various embodiments, the peroxide compound system includes hydrogen peroxide, urea peroxide, sodium percarbonate, and mixtures thereof.
在某些具體實施例中，可提供非過氧化物增白劑。在該等可用於文中之增白劑係包括非過氧化合物，例如二氧化氯、亞氯酸鹽及次氯酸鹽。亞氯酸鹽和次氯酸鹽包括該等鹼金屬和鹼土金屬，例如鋰、鉀、鈉、鎂、鈣和鋇之亞氯酸鹽及次氯酸鹽。非過氧化物增白劑亦包括色劑，例如二氧化鈦和羥磷灰石、顏料或染劑。 在某些具體實施例中，增白劑係與水性載劑隔開。在某些具體實施例中，增白劑係藉由增白劑膠囊與水性載劑隔開。 In certain embodiments, non-peroxide brighteners may be provided. The brighteners that can be used in the text include non-peroxy compounds such as chlorine dioxide, chlorite and hypochlorite. Chlorites and hypochlorites include such alkali metals and alkaline earth metals, such as chlorites and hypochlorites of lithium, potassium, sodium, magnesium, calcium, and barium. Non-peroxide brighteners also include colorants, such as titanium dioxide and hydroxyapatite, pigments or dyes. In certain embodiments, the whitening agent is separated from the aqueous carrier. In certain embodiments, the whitener is separated from the aqueous carrier by a whitener capsule.
在另一方面，本發明係提供用於製造如上所定義之二氧化矽核殼顆粒的方法，其係包括將一定量的二氧化矽顆粒於水中與一定量的鹼混合，其中該鹼係包括一第I族金屬離子，產生二氧化矽核殼顆粒。 In another aspect, the present invention provides a method for manufacturing silica core-shell particles as defined above, which includes mixing a certain amount of silica particles in water with a certain amount of alkali, wherein the alkali includes A group I metal ion, which produces silicon dioxide core-shell particles.
鹼並未特別限制，只要其包括一第I族金屬離子。該鹼典型地為一強鹼。較佳地該鹼係由下列組成之群中選出：氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、磷酸三鈉、磷酸氫二鈉、磷酸鉀、磷酸氫二鉀、焦磷酸四鈉及焦磷酸四鉀。鹼可具有在0.1至3範圍內的pKb值。例如，氫氧化鈉具有0.2之pKb值，而氫氧化鉀具有0.5之pKb值。 The base is not particularly limited as long as it includes a group I metal ion. The base is typically a strong base. Preferably the alkali is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, disodium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, tetrasodium pyrophosphate and Tetrapotassium pyrophosphate. The base may have a pKb value in the range of 0.1 to 3. For example, sodium hydroxide has a pKb value of 0.2, and potassium hydroxide has a pKb value of 0.5.
在一組成物之具體實施例中，此組成物係包括約65%-99.9%的載劑和另外包括的成份，亦即抗齲蝕劑、去敏感劑、黏度調節劑、稀釋劑、界面活性劑、乳化劑、泡沫調節劑、pH調節劑、研磨劑、口感劑、甜味劑、風味劑、色劑、防腐劑、胺基酸、抗氧化劑、抗結石劑、氟化物離子來源、增稠劑、用於預防或治療口腔硬組織或軟組織之症狀或病症的活性劑、增白劑及其組合物。在組成物之另外的具體實施例中，此組成物係包括約80%-99.5%的載劑和另外包括的成份。在組成物之另外的具體實施例中，此組成物係包括約90%-99%的載劑和另外包括的成份。 In a specific embodiment of a composition, the composition includes about 65%-99.9% of the carrier and additional ingredients, that is, anti-caries agent, desensitizer, viscosity regulator, diluent, surfactant , Emulsifiers, foam regulators, pH regulators, abrasives, taste agents, sweeteners, flavors, colorants, preservatives, amino acids, antioxidants, anti-calculus agents, fluoride ion sources, thickeners , Active agents, whitening agents and their compositions for preventing or treating symptoms or disorders of oral hard tissues or soft tissues. In another specific embodiment of the composition, the composition includes about 80%-99.5% of the carrier and additional ingredients. In another specific embodiment of the composition, the composition includes about 90%-99% of the carrier and additional ingredients.
上述視需要成份之說明亦希望包括成份之任何組合。. The above description of optional ingredients is also intended to include any combination of ingredients. .
如上所提，二氧化矽較佳地係由沉澱二氧化矽、煅製二氧化矽和熔融二氧化矽組成之群中選出。此二氧化矽可為合成的非晶沉澱二氧化矽，例如Zeodent® 114或Zeodent® 165(J.M.Huber Corp)，Absil 100 C或MFIL P(Madhu Silica)。此二氧化矽可為煅製二氧化矽，例如Aerosil 200(Evonik)。在另外的具體實施例中，此二氧化矽為熔融二氧化矽，其係包括(但不限於)由Cabot公司所製 造的CAB-O-SIL® HP-60，由C-E Minerals公司所製造的TECO-SIL® 10和TECO-SIL® 44css，及由Japanese Glass公司所製造的Spheron P1500。 As mentioned above, silica is preferably selected from the group consisting of precipitated silica, fumed silica and fused silica. The silica can be synthetic amorphous precipitated silica, such as Zeodent® 114 or Zeodent® 165 (JMHuber Corp), Absil 100 C or MFIL P (Madhu Silica). The silica can be fumed silica, such as Aerosil 200 (Evonik). In another specific embodiment, the silica is fused silica, which includes (but is not limited to) CAB-O-SIL ® HP-60 manufactured by Cabot Company, and TECO manufactured by CE Minerals Company -SIL ® 10 and TECO-SIL ® 44css, and Spheron P1500 manufactured by Japanese Glass Company.
適合用於本發明之二氧化矽亦包括膠體二氧化矽(增稠二氧化矽)有，例如氣凝膠(aerogel)Syloid 244和266(可購自W.R.Grace公司)，Aerosil(可購自DeGussa公司)和以Cab-O-Sils商品名稱販售之熱解二氧化矽(可購自Cabot公司)，Tixosil 333和Tixosil 43B(可購自Rhodia Ltda.)，Zeodent 165(可購自J.M.Huber公司)。 Silica suitable for use in the present invention also includes colloidal silica (thickened silica), such as aerogel Syloid 244 and 266 (available from WR Grace), Aerosil (available from DeGussa) Company) and pyrolytic silica sold under the trade name Cab-O-Sils (available from Cabot Company), Tixosil 333 and Tixosil 43B (available from Rhodia Ltda.), Zeodent 165 (available from JM Huber) ).
其他適合用於本發明之二氧化矽包括二氧化矽研磨劑，其相應的係包括矽膠和沉澱非晶二氧化矽。這些二氧化矽為膠體顆粒/微粒，具有範圍從約3微米至約20微米，及更佳地介於約5至約10微米之平均粒徑，及當以5%重量比之漿液測量時，pH範圍從約4至10，較佳6至9。 Other silicas suitable for use in the present invention include silica abrasives, and their corresponding systems include silica gel and precipitated amorphous silica. These silicas are colloidal particles/fine particles with an average particle size ranging from about 3 microns to about 20 microns, and more preferably between about 5 to about 10 microns, and when measured with a 5% weight ratio slurry, The pH ranges from about 4 to 10, preferably 6 to 9.
可用於施行本發明之二氧化矽研磨劑的例證係由Davison Chemical Division of W.R.Grace & Co.,Baltimore,Md.21203公司以Sylodent 650 XWA商品名稱所販售，其為由膠體二氧化矽顆粒所組成的二氧化矽水凝膠，具有29%重量比之水含量，平均從約7至約10微米之直徑。 An example of a silica abrasive that can be used in the practice of the present invention is sold under the trade name Sylodent 650 XWA by Davison Chemical Division of WRGrace & Co., Baltimore, Md. 21203, which is produced by colloidal silica particles. The composed silica hydrogel has a water content of 29% by weight and an average diameter of from about 7 to about 10 microns.
適合用於本發明之其他類型的二氧化矽研磨劑包括具有平均粒徑至高約20微米之沉澱二氧化矽，例如J.M.Huber Chemicals Division,Havre de Grace,Md.21078公司所販售的Zeodent 115，或Davison Chemical Division of W.R.Grace & Company公司所販售之Sylodent 783。 Other types of silica abrasives suitable for use in the present invention include precipitated silica having an average particle size up to about 20 microns, such as Zeodent 115 sold by JM Huber Chemicals Division, Havre de Grace, Md. 21078, Or Sylodent 783 sold by Davison Chemical Division of WRGrace & Company.
此方法可在從17℃至90℃範圍內的溫度下進行。在一具體實施例中，此方法係在室溫，亦即20至26℃進行。在另外的具體實施例中，此方法係在70至90℃之溫度下進行。當製備工業規模之二氧化矽核殼顆粒時，用於混合反應物之混合器，例如Lee mixer(Lee Industries)，較佳地係不加熱。 This method can be carried out at a temperature ranging from 17°C to 90°C. In a specific embodiment, this method is performed at room temperature, that is, at 20 to 26°C. In another specific embodiment, this method is performed at a temperature of 70 to 90°C. When preparing industrial-scale silica core-shell particles, the mixer used to mix the reactants, such as Lee mixer (Lee Industries), is preferably not heated.
在一具體實施例中，此鹼為氫氧化鈉且該方法係在70至90℃的溫度下進行。較佳地，溫度係從80至90℃。較佳地，此鹼為50%氫氧化鈉水溶液。 In a specific embodiment, the base is sodium hydroxide and the method is carried out at a temperature of 70 to 90°C. Preferably, the temperature is from 80 to 90°C. Preferably, the alkali is a 50% sodium hydroxide aqueous solution.
在另外的具體實施例中，此鹼為氫氧化鉀。當使用氫氧化鉀時，該方法可在室溫下進行。使用氫氧化鉀為較佳的，因為氫氧化鉀較高的反應性(相較於氫氧化鈉)意味著不需要加熱，且反應可在室溫下進行。室溫，有時候係指周圍溫度，典型地係從0至26℃，且為不使用外部加熱反應混合物所達到的溫度。當製備工業規模之二氧化矽核殼顆粒時，用於混合反應物之混合器，例如Lee mixer(Lee Industries)，典型地係不能加熱。 In another specific embodiment, the base is potassium hydroxide. When potassium hydroxide is used, the method can be carried out at room temperature. It is preferable to use potassium hydroxide because the higher reactivity of potassium hydroxide (compared to sodium hydroxide) means that heating is not required and the reaction can be carried out at room temperature. Room temperature, sometimes referred to as the ambient temperature, is typically from 0 to 26°C, and is the temperature reached without the use of external heating of the reaction mixture. When preparing industrial-scale silica core-shell particles, the mixer used to mix the reactants, such as the Lee mixer (Lee Industries), typically cannot be heated.
此反應為：2KOH+SiO2 
典型地，在2hrs的時間週期後，二氧化矽核殼顆粒完全形成。 Typically, after a time period of 2 hrs, the silica core-shell particles are completely formed.
鹼量(例如，50%的NaOH水溶液)與二氧化矽顆粒量之重量比率典型地係從1：1至1：20。在一較佳的具體實施例中，鹼量(例如，50%的NaOH水溶液)與二氧化矽顆粒量之重量比率係從1：1至1：6，視需要約1：4。在一典型的實施例中，係使用20%高清潔二氧化矽和4.5%NaOH(50%)，且比率為4.5%：20%=1：4.44)。此比率可用於牙膏組成物。 The weight ratio of the amount of alkali (for example, 50% NaOH aqueous solution) to the amount of silica particles is typically from 1:1 to 1:20. In a preferred embodiment, the weight ratio of the amount of alkali (for example, 50% NaOH aqueous solution) to the amount of silica particles is from 1:1 to 1:6, and about 1:4 as needed. In a typical embodiment, 20% high-cleaning silicon dioxide and 4.5% NaOH (50%) are used, and the ratio is 4.5%: 20%=1: 4.44). This ratio can be used for toothpaste compositions.
典型地，係藉由增加鹼量與二氧化矽顆粒量之重量比率來降低二氧化矽核殼顆粒的濁度。就全透明的核-殼二氧化矽(CSS)，鹼量(例如50%的NaOH)與二氧化矽顆粒量之重量比率係大於0.5：1且所有的二氧化矽顆粒已溶解。就透亮的CSS顆粒，50%的NaOH與二氧化矽之重量比率係從0.45至0.49。就半透光或不透光CSS顆粒，50%的NaOH與二氧化矽之重量比率係從0.20至0.45。就典型的CSS牙膏組成物，係使用1：4.44=0.225：1之比率。 Typically, the turbidity of the silica core-shell particles is reduced by increasing the weight ratio of the amount of alkali to the amount of silica particles. For the fully transparent core-shell silica (CSS), the weight ratio of the amount of alkali (for example, 50% NaOH) to the amount of silica particles is greater than 0.5:1 and all the silica particles have been dissolved. For transparent CSS particles, the weight ratio of 50% NaOH to silica is from 0.45 to 0.49. For semi-transparent or opaque CSS particles, the weight ratio of 50% NaOH to silica is from 0.20 to 0.45. For a typical CSS toothpaste composition, a ratio of 1:4.44=0.225:1 is used.
在一較佳的具體實施例中，二氧化矽顆粒與鹼之反應造成二氧化矽顆粒之d(0.5)值下降1至15nm，形成二氧化矽核，並 在二氧化矽核的上方形成M2SiO3.xH2O。典型地，當鹼量與二氧化矽顆粒量之重量比率增加時，二氧化矽顆粒的d(0.5)值下降更大(參見表1)。 In a preferred embodiment, the reaction between the silicon dioxide particles and the alkali causes the d(0.5) value of the silicon dioxide particles to drop by 1 to 15 nm, forming a silicon dioxide core, and forming M on the silicon dioxide core. 2 SiO 3 .xH 2 O. Typically, when the weight ratio of the amount of alkali to the amount of silica particles increases, the d(0.5) value of the silica particles decreases more (see Table 1).
二氧化矽顆粒之d(0.5)值的下降量可為1nm至6nm。二氧化矽蝕刻掉的量係依照二氧化矽顆粒的BET比面積而定。表面積較大的顆粒，例如孔狀顆粒，如非晶牙齒二氧化矽研磨劑：高清潔二氧化矽Zeodent 105；一般的二氧化矽如Zeodent 114，增 稠二氧化矽如Zeodent 165，蝕刻較淺。剛硬的二氧化矽顆粒將具有較大的蝕刻深度。 The decrease in the d(0.5) value of the silicon dioxide particles can be 1nm to 6nm. The amount of silicon dioxide etched away depends on the BET specific area of the silicon dioxide particles. Particles with larger surface area, such as porous particles, such as amorphous tooth silica abrasive: high-cleaning silica Zeodent 105; general silica such as Zeodent 114, increased Thick silica, such as Zeodent 165, has a shallower etching. The rigid silicon dioxide particles will have a larger etching depth.
當SiO2網絡之共價鍵轉成Na+和SiO3 2-之間的離子鍵時，使表面極化並吸收水和保濕劑，產生二氧化矽核殼顆粒。當反應進行時，二氧化矽核殼顆粒亦可變得透明度較低和更不透明，且反應溶液的pH下降。 When the covalent bond of the SiO 2 network is transformed into an ionic bond between Na + and SiO 3 2- , the surface is polarized and water and humectant are absorbed, producing silicon dioxide core-shell particles. When the reaction progresses, the silica core-shell particles can also become less transparent and more opaque, and the pH of the reaction solution drops.
保濕劑量與水的重量比率可由下列比率組成之群中選出：4：1至1：4；3：1至1：3；2：1至1：2；及5：3至3：5。 The weight ratio of moisturizer to water can be selected from the group consisting of: 4:1 to 1:4; 3:1 to 1:3; 2:1 to 1:2; and 5:3 to 3:5.
在一具體實施例中，以此法所形成的二氧化矽核殼顆粒之d(0.5)值大於二氧化矽起始物之d(0.5)值至少5%。應注意，雖然在作用期間二氧化矽顆粒的直徑下降，形成較小的二氧化矽核，但整顆CSS顆粒包括矽酸鹽層之直徑通常係大於原始的二氧化矽顆粒。 In a specific embodiment, the d(0.5) value of the silicon dioxide core-shell particles formed by this method is greater than the d(0.5) value of the silicon dioxide starting material by at least 5%. It should be noted that although the diameter of the silicon dioxide particles decreases during the action, a smaller silicon dioxide core is formed, but the diameter of the entire CSS particle including the silicate layer is usually larger than that of the original silicon dioxide particle.
核殼顆粒的形成可藉由測定反應混合物的pH來監測。當反應混合物的pH比最初的反應物之混合物減少至少0.5 pH單位時，則二氧化矽核殼顆粒形成。典型地，當反應混合物的pH比最初的反應物之混合物減少至少0.8 pH單位時，則二氧化矽核殼顆粒形成。在另外的具體實施例中，當反應混合物的pH比最初的反應物之混合物減少至少0.8-1.5 pH單位，且pH不再顯現任何進一步的下降時，則到達作用終點。當的pH約11時，通常二氧化矽核殼顆粒完全形成。 The formation of core-shell particles can be monitored by measuring the pH of the reaction mixture. When the pH of the reaction mixture is reduced by at least 0.5 pH units from the initial mixture of reactants, silica core-shell particles are formed. Typically, when the pH of the reaction mixture is reduced by at least 0.8 pH units from the initial mixture of reactants, then silica core-shell particles are formed. In another specific embodiment, when the pH of the reaction mixture is reduced by at least 0.8-1.5 pH units from the initial mixture of reactants, and the pH does not show any further drop, the end of action is reached. When the pH is about 11, usually silica core-shell particles are completely formed.
核殼顆粒的形成亦可藉由測定反應混合物的導電度來監測。當反應混合物的電導度下降至少250微西(micro Siemens)/cm(μS/cm)時，則為作用終點，因為電子電荷從高移動性離子(NaOH)轉移到較低移動性的二氧化矽表面(移動性
熱解二氧化矽(有時稱為煅製二氧化矽或二氧化矽灰)為非常細的微粒或膠體形式之二氧化矽。其係藉由將SiCl4置於富含氧的烴火焰中焚燒，產生SiO2的「煙」，所製備的。二氧化矽顆粒彼此融合形成支鏈、類三維鏈的聚集物。 Pyrolytic silica (sometimes called fumed silica or silica fume) is a very fine particle or colloidal form of silica. It is prepared by burning SiCl 4 in an oxygen-rich hydrocarbon flame to produce "smoke" of SiO 2. Silica particles fuse with each other to form branched, three-dimensional chain-like aggregates.
SiCl4+2 H2+O2→SiO2+4 HCl。 SiCl 4 + 2 H 2 + O 2 → SiO 2 + 4 HCl.
非晶二氧化矽，矽膠，係藉由矽酸鈉溶液之酸化作用所產生。然後清洗最先形成的明膠狀沉澱及然後脫水，產生無色的微孔二氧化矽。涉及三矽酸鹽和硫酸之理想化方程式係如下所示：Na2Si3O7+H2SO4→3 SiO2+Na2SO4+H2O Amorphous silica, silica gel, is produced by the acidification of sodium silicate solution. Then the gelatinous precipitate formed first is washed and then dehydrated to produce colorless microporous silica. The idealized equation system involving trisilicate and sulfuric acid is as follows: Na 2 Si 3 O 7 +H 2 SO 4 →3 SiO 2 +Na 2 SO 4 +H 2 O
在大部分的矽酸鹽中，Si原子係顯示四面體配位，以4個氧原子圍繞一個中心Si原子。最常見的實施例可參見二氧化矽SiO2之石英晶型。在各熱力學上最穩定的二氧化矽晶型中，平均，SiO4四面體的全部4個頂點(或氧原子)係彼此共享，產生淨化學式：SiO2。除了非晶形式外，SiO2具有許多不同的晶型(多形物)。除了超石英和纖維二氧化矽外，所有的晶型係涉及四面體SiO4單元藉由共享的頂點以不同的排列連結一起。 In most silicates, Si atoms show tetrahedral coordination, with 4 oxygen atoms surrounding a central Si atom. The most common embodiment can be found in the quartz crystal form of silicon dioxide SiO 2. In the most thermodynamically stable silicon dioxide crystal forms, on average, all four vertices (or oxygen atoms) of the SiO 4 tetrahedron are shared with each other, resulting in a net chemical formula: SiO 2 . In addition to the amorphous form, SiO 2 has many different crystal forms (polymorphs). Except for super quartz and fibrous silica, all crystalline systems involve tetrahedral SiO 4 units connected together in different arrangements by shared vertices.
矽酸鈉為帶有化學式Na2(SiO2)nO之化合物的通用名稱。此系列之熟知的成員為偏矽酸鈉Na2SiO3。亦稱為水玻璃或液體玻璃，這些物質可水溶液或以固體的形式取得。當熔化時，碳酸鈉和二氧化矽反應，形成矽酸鈉和二氧化碳：Na2CO3+SiO2→Na2SiO3+CO2 Sodium silicate is the general name for compounds with the chemical formula Na 2 (SiO 2 ) n O. A well-known member of this series is sodium metasilicate Na 2 SiO 3 . Also known as water glass or liquid glass, these substances can be obtained in aqueous solution or in solid form. When melting, sodium carbonate reacts with silicon dioxide to form sodium silicate and carbon dioxide: Na 2 CO 3 +SiO 2 →Na 2 SiO 3 +CO 2
無水矽酸鈉含有一角落共享{SiO4}四面體所組成的鏈狀聚合性陰離子，且並非離散的SiO3 2-離子。除了無水的形式外，尚有式Na2SiO3．nH2O之水合物(其中n=5、6、8、9)，其含有離散 的、帶有水合水之近乎四面體的陰離子SiO2(OH)2 2-。例如，市售的矽酸鈉五水合物Na2SiO3．5H2O係以Na2SiO2(OH)2．4H2O之化學式表示，而九水合物Na2SiO3．9H2O係以Na2SiO2(OH)2．8H2O之化學式表示。 Anhydrous sodium silicate contains a chain-like polymeric anion composed of {SiO 4 } tetrahedrons shared by one corner, and is not discrete SiO 3 2- ions. In addition to the anhydrous form, there is also the formula Na 2 SiO 3 . The hydrate of nH 2 O (where n=5, 6, 8, 9) contains discrete, nearly tetrahedral anion SiO 2 (OH) 2 2- with water of hydration. For example, the commercially available sodium silicate pentahydrate Na 2 SiO 3 . 5H 2 O is based on Na 2 SiO 2 (OH) 2 . 4H 2 O is represented by the chemical formula, and nonahydrate Na 2 SiO 3 . 9H 2 O is based on Na 2 SiO 2 (OH) 2 . The chemical formula of 8H 2 O.
在工業上，各種等級的矽酸鈉係以其SiO2：Na2O重量比來定性(重量比率可藉由乘以1.032，轉變成莫耳比)，其可在2：1至3.75：1間變化。此比率低於2.85：1之等級稱為「鹼性」。帶有較高的SiO2：Na2O比率者則稱為「中性」。 In industry, various grades of sodium silicate are qualitatively determined by their SiO 2 :Na 2 O weight ratio (the weight ratio can be converted into a molar ratio by multiplying by 1.032), which can range from 2:1 to 3.75:1 Between changes. Levels with this ratio lower than 2.85:1 are called "alkaline". Those with a higher SiO 2 :Na 2 O ratio are called "neutral".
在另外的具體實施例中，此二氧化矽為沉澱二氧化矽，其包括(但不限於)Zeodent® 114和Zeodent® 165(J.M.Huber所製造的沉澱二氧化矽顆粒-化學名稱：合成的非晶二氧化矽)，W.R.Grace所製造的Sylodent® 783，Ineos(PQ Corp.)所製造的Sorbosil® AC-43。 In another specific embodiment, the silica is precipitated silica, which includes (but is not limited to) Zeodent ® 114 and Zeodent ® 165 (precipitated silica particles manufactured by JMHuber-chemical name: synthetic amorphous Silicon dioxide), Sylodent® 783 manufactured by WR Grace, Sorbosil® AC-43 manufactured by Ineos (PQ Corp.).
在另外的具體實施例中，此二氧化矽為熔融二氧化矽，其包括(但不限於)Cabot公司所製造的CAB-O-SIL® HP-60，C-E Minerals所製造的TECO-SIL® 10和TECO-SIL®，及Japanese Glass公司所製造的Spheron P1500。 In another specific embodiment, the silica is fused silica, which includes (but is not limited to) CAB-O-SIL ® HP-60 manufactured by Cabot Company, and TECO-SIL ® 10 manufactured by CE Minerals And TECO-SIL ® , and Spheron P1500 manufactured by Japanese Glass Company.
在一具體實施例中，氫氧化鈉係與SiO2顆粒之表面反應，蝕刻一如下之Na2SiO3殼層：SiO2+2 NaOH→Na2SiO3+H2O In a specific embodiment, the sodium hydroxide reacts with the surface of the SiO 2 particles to etch a Na 2 SiO 3 shell layer as follows: SiO 2 +2 NaOH→Na 2 SiO 3 +H 2 O
如從反應流程可看出，無NaOH將不會使二氧化矽產生任何變化，而在另一極端，每1莫耳的二氧化矽與2莫耳的NaOH完全反應，將會造成完全轉化成Na2SiO3。為了得到本發明之核殼顆粒，必須控制反應過程，以便不會得到包括適當比例之Na2SiO3的顆粒。 As can be seen from the reaction process, the absence of NaOH will not cause any change in silicon dioxide. At the other extreme, every 1 mole of silicon dioxide and 2 moles of NaOH completely react, which will result in complete conversion to Na 2 SiO 3 . In order to obtain the core-shell particles of the present invention, the reaction process must be controlled so that particles including Na 2 SiO 3 in an appropriate ratio are not obtained.
二氧化矽核殼，當部份乾燥，例如風乾時則具有黏附性質，因為水合的Na2SiO3為有黏性的(水玻璃)。 The silicon dioxide core shell has adhesive properties when partially dried, such as air-dried, because the hydrated Na 2 SiO 3 is viscous (water glass).
在一具體實施例中，當至少1-6%的各二氧化矽顆粒起始物已蝕刻上一或多層的Na2SiO3單層時，則形成本發明之二氧化 矽核殼顆粒。在另外的具體實施例中，當至少2.5-5%的各二氧化矽顆粒起始物已蝕刻上一或多層的Na2SiO3時，則形成本發明之二氧化矽核殼顆粒。在另外的具體實施例中，當至少3.5-4%的各二氧化矽顆粒起始物已蝕刻上一或多層的Na2SiO3時，則形成本發明之二氧化矽核殼顆粒。 In a specific embodiment, when at least 1-6% of each silicon dioxide particle starting material has been etched on one or more layers of Na 2 SiO 3 monolayers, the silicon dioxide core-shell particles of the present invention are formed. In another specific embodiment, when at least 2.5-5% of each silicon dioxide particle starting material has been etched on one or more layers of Na 2 SiO 3 , the silicon dioxide core-shell particles of the present invention are formed. In another specific embodiment, when at least 3.5-4% of each silicon dioxide particle starting material has been etched on one or more layers of Na 2 SiO 3 , the silicon dioxide core-shell particles of the present invention are formed.
形成上述之本發明二氧化矽核殼顆粒可藉由操縱所用的鹼之量和種類，所用的二氧化矽之量、所用的保濕劑之量和各種反應溫度來進行。 The formation of the aforementioned silica core-shell particles of the present invention can be carried out by manipulating the amount and type of alkali used, the amount of silica used, the amount of humectant used, and various reaction temperatures.
在一具體實施例中，此方法進一步係包括將二氧化矽顆粒和鹼與保濕劑混合。在一具體實施例中，此方法進一步係包括保濕劑的量與水量的重量比率係介於4：1至1：4之間。在一具體實施例中，此方法進一步係包括保濕劑的量與水量的重量比率係從3：1至1：3；2：1至1：2；或從5：3至3：5。在一具體實施例中，保濕劑係包括二或多種個別的保濕劑混合物。在一具體實施例中，此方法進一步係包括一將產生的產物乾燥之步驟，以便移除一部份的H2O。 In a specific embodiment, the method further includes mixing silica particles and alkali with a humectant. In a specific embodiment, the method further includes that the weight ratio of the amount of humectant to the amount of water is between 4:1 and 1:4. In a specific embodiment, the method further includes that the weight ratio of the amount of humectant to the amount of water is from 3:1 to 1:3; 2:1 to 1:2; or from 5:3 to 3:5. In a specific embodiment, the humectant system includes a mixture of two or more individual humectants. In a specific embodiment, the method further includes a step of drying the produced product in order to remove a part of H 2 O.
在一具體實施例中，此方法進一步係包括將SiO2顆粒量與NaOH量和保濕劑於50℃至140℃反應。在一具體實施例中，此方法進一步係包括將SiO2顆粒量與NaOH量於70℃至100℃反應。在一具體實施例中，此方法進一步係包括將SiO2顆粒量與NaOH量於70℃至90℃反應。此方法進一步係包括將SiO2顆粒量與NaOH量於70℃至80℃反應。在一具體實施例中，此方法進一步係包括將SiO2顆粒量與NaOH量於74℃至76℃反應。在一具體實施例中，此方法進一步係包括將SiO2顆粒量與NaOH量於75℃反應。 In a specific embodiment, the method further includes reacting the amount of SiO 2 particles with the amount of NaOH and the humectant at 50°C to 140°C. In a specific embodiment, the method further includes reacting the amount of SiO 2 particles with the amount of NaOH at 70°C to 100°C. In a specific embodiment, the method further includes reacting the amount of SiO 2 particles with the amount of NaOH at 70°C to 90°C. The method further includes reacting the amount of SiO 2 particles with the amount of NaOH at 70°C to 80°C. In a specific embodiment, the method further includes reacting the amount of SiO 2 particles with the amount of NaOH at 74°C to 76°C. In a specific embodiment, the method further includes reacting the amount of SiO 2 particles with the amount of NaOH at 75°C.
一般而言，在反應方法中使用保濕劑而得以使用上述範圍內的較高溫度。 In general, the use of a humectant in the reaction method allows the use of higher temperatures within the above-mentioned range.
除了採樣反應混合物和檢測所形成的二氧化矽核殼顆粒，直到就殼層形成和電荷密度而言，帶有必要性質的CSS顆粒 已形成之外，本項技術之一般技術者可藉由數種方法測定何時已獲得本發明之二氧化矽核殼顆粒。 In addition to sampling the reaction mixture and detecting the formed silica core-shell particles, until the CSS particles with the necessary properties in terms of shell formation and charge density In addition to the formation, ordinary skilled in this technology can determine when the silica core-shell particles of the present invention have been obtained by several methods.
在一具體實施例中，當藉由此法所形成的二氧化矽核殼顆粒之平均粒徑比二氧化矽(SiO2)起始物之平均粒徑大至少5%時，則為作用終點。在另外的具體實施例中，此二氧化矽核殼顆粒在直徑上係比二氧化矽起始物之平均粒徑大至少5%-10%。 In a specific embodiment, when the average particle size of the silica core-shell particles formed by this method is at least 5% larger than the average particle size of the silica (SiO 2 ) starting material, it is the end point of action . In another embodiment, the silica core-shell particles are at least 5%-10% larger in diameter than the average particle diameter of the silica starting material.
在一具體實施例中，此方法進一步係包括將所產生的二氧化矽核殼顆粒與一載劑混合，製造一組成物。在一具體實施例中，此方法進一步係包括調整組成物的pH，以達到7-9 pH值，若需要，可使用酸或鹼進行調整。在一具體實施例中，係使用酸來進行pH調整。 In a specific embodiment, the method further includes mixing the produced silica core-shell particles with a carrier to produce a composition. In a specific embodiment, the method further includes adjusting the pH of the composition to achieve a pH value of 7-9, and if necessary, it can be adjusted with an acid or a base. In a specific embodiment, an acid is used for pH adjustment.
在另一方面，本發明係提供藉由上述定義之方法所得來的二氧化矽核殼顆粒。 In another aspect, the present invention provides silica core-shell particles obtained by the method defined above.
在另一方面，本發明係提供降低或抑制口腔細菌之方法，其係包括將上述定義之口腔護理組成物施用有此需要的患者，至患者的口腔表面。 In another aspect, the present invention provides a method for reducing or inhibiting oral bacteria, which comprises applying the above-defined oral care composition to a patient in need thereof to the oral surface of the patient.
在最後一方面，本發明係提供降低或抑制於病患可移除的口腔裝置中之細菌的活體外方法，其係包括將上述之口腔護理組成物施用可移除的口腔裝置之表面。較佳的該可移除口腔裝置為假牙、牙托、口件、牙齒矯正器和固定器。 In the last aspect, the present invention provides an in vitro method for reducing or inhibiting bacteria in a patient's removable oral device, which includes applying the aforementioned oral care composition to the surface of the removable oral device. Preferably, the removable oral devices are dentures, dental trays, mouthpieces, orthodontic appliances and fixtures.
本發明另外的具體實施例為使用此二氧化矽核殼顆粒供降低或抑制有此需要患者之口腔中細菌的方法，其係包括於患者的口腔表面施用本發明組成物。 Another specific embodiment of the present invention is a method of using the silica core-shell particles to reduce or inhibit bacteria in the oral cavity of a patient in need thereof, which includes applying the composition of the present invention to the oral cavity surface of the patient.
用於降低或抑制細菌之方法的另外具體實施例係包括將此二氧化矽核殼顆粒於活體外施用有此需要之患者，至患者的可移除口腔裝置。在本發明內文中，可移除口腔裝置包括(但不限於)假牙、牙托、口件、牙齒矯正器和固定器。 Another specific embodiment of the method for reducing or inhibiting bacteria includes administering the silica core-shell particles to patients in need of such particles outside the body, to the patient's removable oral device. In the context of the present invention, removable oral devices include (but are not limited to) dentures, dental trays, mouthpieces, orthodontic appliances and fixtures.
在此方法的一具體實施例中，該病患為哺乳動物，其包括(但不限於)人類和動物(例如，狗、貓、馬、牛、綿羊、羊駝等)。 In a specific embodiment of this method, the patient is a mammal, which includes (but is not limited to) humans and animals (for example, dogs, cats, horses, cows, sheep, alpacas, etc.).
本發明之另外的具體實施例為二氧化矽核殼顆粒用於製造組成物供降低或抑制有此需要患者之口腔中細菌的用途，其係包括於患者的口腔表面施用本發明組成物，或用於降低或抑制細菌係包括將此二氧化矽核殼顆粒於活體外施用此需要的患者，至患者的可移除口腔裝置。 Another specific embodiment of the present invention is the use of silica core-shell particles in the manufacture of a composition for reducing or inhibiting bacteria in the oral cavity of a patient in need, which includes applying the composition of the present invention to the oral surface of the patient, or The system for reducing or inhibiting bacteria includes administering the silica core-shell particles to patients who need them outside of the body, to the patient's removable oral device.
本發明之具體實施例係進一步以下列實施例來說明。這些實施例僅為說明性且不會在任何方面限制所描述和所申請的本發明之範圍。 The specific embodiments of the present invention are further illustrated by the following embodiments. These examples are only illustrative and do not limit the scope of the invention described and applied for in any respect.
使用如表2中所示的化合物製造二氧化矽核殼顆粒。Zeodent® 114和Zeodent®165為沉澱二氧化矽，係由J.M.Huber公司所生產(化學名稱：合成的非晶二氧化矽)。 The compounds shown in Table 2 were used to produce silica core-shell particles. Zeodent ® 114 and Zeodent ® 165 are precipitated silica, produced by JM Huber (chemical name: synthetic amorphous silica).
將本發明之核殼顆粒與其他的二氧化矽基底顆粒作比較。所用的組成物係如表3所示。 The core-shell particles of the present invention are compared with other silica base particles. The composition system used is shown in Table 3.
不希望受限於理論，咸信對照組#1所產生的顆粒並無黏附性，由於缺乏保濕劑(例如，山梨醇)將水分保持在二氧化矽顆粒中，一種離子化SiO2的較佳條件。 Without wishing to be bound by theory, it is believed that the particles produced in the control group #1 are not sticky. Due to the lack of humectant (for example, sorbitol) to keep water in the silica particles, an ionized SiO 2 is better condition.
不希望受限於理論，對照組#2所產生的顆粒亦不具有黏附性，因為無NaOH將一些SiO2轉變成Na2SiO3層，覆蓋剩餘的SiO2核。相反的，實施例2所產生的二氧化矽核殼顆粒類似上述實施例1具有黏附性。這些比較顯示，NaOH為必須的，且水及/或保濕劑為獲得本發明之核殼顆粒之較佳選擇。 Without wishing to be bound by theory, the particles produced in the control group #2 are also not adhesive, because the absence of NaOH converts some SiO 2 into a Na 2 SiO 3 layer, covering the remaining SiO 2 core. On the contrary, the silica core-shell particles produced in Example 2 have adhesive properties similar to those in Example 1. These comparisons show that NaOH is necessary, and water and/or humectants are the better choices for obtaining the core-shell particles of the present invention.
在另外的比較實施例中，以甘油取代山梨醇作為保濕劑組份，並以二種不同的對水之重量比率。所製備的組成物係如表4中所示。對照組#3與實施例1相類似，但係使用甘油取代山梨醇作為保濕劑並以8g的50% NaOH取代4g的固體NaOH。 In another comparative example, glycerin was used instead of sorbitol as the humectant component, and two different weight ratios to water were used. The prepared composition system is shown in Table 4. Control #3 is similar to Example 1, but uses glycerin instead of sorbitol as a humectant and 8g of 50% NaOH instead of 4g of solid NaOH.
不希望受限於理論，對照組#3所產生的顆粒不具有黏附性，可能係因為水量不足以將SiO2轉變成Na2SiO3。相反的，實施例3所產生的二氧化矽核殼顆粒具有黏附性。 Without wishing to be bound by theory, the particles produced in the control group #3 are not adhesive, probably because the amount of water is not enough to convert SiO 2 into Na 2 SiO 3 . In contrast, the silica core-shell particles produced in Example 3 have adhesive properties.
SiO2研磨劑與NaOH溶液反應，產生核-殼顆粒。 The SiO 2 abrasive reacts with the NaOH solution to produce core-shell particles.
此反應為：2NaOH+SiO2 
將0.8% NaOH(50%溶液)用於澄清的二氧化矽膠體(參見表5)。當NaOH與過量的SiO2反應，pH將會超過11，然後逐漸降至10.0以下(就牙膏應用，需要介於6至10之間的pH範圍)。轉變的時間在室溫下為6-24小時，但藉由加熱至較高溫度，例如75℃，則時間可能更短。反應期間膠體之光學性質改變，從透明變成不透明。 0.8% NaOH (50% solution) was used for the clear silica colloid (see Table 5). When NaOH reacts with excess SiO 2 , the pH will exceed 11 and then gradually drop below 10.0 (for toothpaste applications, a pH range between 6 and 10 is required). The transformation time is 6-24 hours at room temperature, but by heating to a higher temperature, such as 75°C, the time may be shorter. During the reaction, the optical properties of the colloid change from transparent to opaque.
因為殼上的折射率改變，而光學外觀改變。此項為合理的，因為已知SiO2能與NaOH(或Na2CO3或其他強鹼)反應，形成Na2SiO3，且符合SiO2之反折射率(1.44-1.45)變成不符合，所以透明性消失。 Because the refractive index on the shell changes, the optical appearance changes. This item is reasonable, because it is known that SiO 2 can react with NaOH (or Na 2 CO 3 or other strong bases) to form Na 2 SiO 3 , and the inverse refractive index (1.44-1.45) of SiO 2 becomes inconsistent. So transparency disappears.
本發明人假定NaOH+SiO2的產物為水合的Na2SiO3(折射率比SiO2低，或nD<1.44)。為了確認此項假設，係使用較高折射率非結晶化山梨醇(折射率=1.455-1.465)來增加水溶液 的折射率(圍繞二氧化矽顆粒)，以配合二氧化矽核殼的折射率。其並未完全變回透明的膠體。此項簡單的實驗證明，由低折射率水合Na2SiO3所組成的殼係黏附在二氧化矽核上。本發明人發現一種用於同中心的剛硬非多孔球形顆粒光散射之物理模型，用以解釋為何膠體從透明的反應物變成不透明。 The inventor assumes that the product of NaOH+SiO 2 is hydrated Na 2 SiO 3 (the refractive index is lower than that of SiO 2, or n D <1.44). In order to confirm this hypothesis, a higher refractive index amorphous sorbitol (refractive index=1.455-1.465) was used to increase the refractive index of the aqueous solution (surrounding the silica particles) to match the refractive index of the silica core-shell. It has not completely changed back to a transparent colloid. This simple experiment proved that a shell composed of low refractive index hydrated Na 2 SiO 3 adheres to the silicon dioxide core. The inventors found a physical model for light scattering of concentric rigid non-porous spherical particles to explain why colloids change from transparent reactants to opaque.
此模型係以「小粒子的光散射」為基礎，H.C.van de Hulst,2003,67-77頁。 This model is based on "light scattering of small particles", H.C. van de Hulst, 2003, pages 67-77.
散射強度係與介電常數α成比例。 The scattering intensity is proportional to the dielectric constant α.
就簡單的球形粒子：
˙m=np/nm，其中np和nm為粒子的折射率及圍繞粒子之水溶液介質(水+山梨醇+鹽類) ˙m=np/nm, where np and nm are the refractive index of the particle and the aqueous medium surrounding the particle (water + sorbitol + salt)
˙a為粒子的半徑 ˙a is the radius of the particle
就如圖2中所示之同中心粒子：就核粒子，n1為折射率，qa為半徑(q為核和殼之間的半徑比)。 Just like the concentric particles shown in Figure 2: For core particles, n1 is the refractive index and qa is the radius (q is the radius ratio between the core and the shell).
就殼而言，n2為折射率，a為半徑 As far as the shell is concerned, n2 is the refractive index and a is the radius
其中折射率(n)係如下所定義：n=n1 就0<r<qa Wherein the refractive index (n) is defined as follows: n=n1 means 0<r<qa
n=n2 就qa<r<a n=n2 is qa<r<a
n=1 就r>a(就此案例為空氣) n=1 means r>a (in this case, air)
此核-殼(同中心)顆粒之介電常數為：(僅依照4個參數：n1、n2和q、a)
吾等可看出，此介電常數或光散射強度就簡單的球形和同中心粒子為不同的。 We can see that the dielectric constant or light scattering intensity is different from simple spherical particles and concentric particles.
多數層之單層：經由ESCA、效價數據、拉曼光譜(Raman spectroscopy)和質量的計算指出，粒子的殼包括多層的矽酸鈉單層。得到2、4、16、32和36層殼單層之數值。 Single layer of multiple layers: According to ESCA, potency data, Raman spectroscopy, and mass calculations, it is pointed out that the shell of the particles includes a multi-layered sodium silicate monolayer. Get the values of 2, 4, 16, 32, and 36 shell monolayers.
使用ESCA(化學分析電子能譜儀)測定於水性媒劑中由SiO2和NaOH所製備之CSS粉末的表面組成。ESCA僅分析樣本表面的外部10nm，所以其為偵測二氧化矽粉末之表面上的矽酸鹽之理想方法。樣本分析包括乾燥的粉末以及以去離子水短暫沖洗三次，移除任何表面上的可溶性殘餘物。CSS粉末之ESCA表面組成數據係如表6中所示。 ESCA (electron spectrometer for chemical analysis) was used to determine the surface composition of CSS powder prepared from SiO 2 and NaOH in an aqueous medium. ESCA only analyzes the outer 10nm of the sample surface, so it is an ideal method for detecting silicate on the surface of silicon dioxide powder. Sample analysis includes dry powder and three brief rinses with deionized water to remove any soluble residue on the surface. The ESCA surface composition data of CSS powder is shown in Table 6.
數據顯示，相對於二氧化矽，在乾燥物質之表面發生鈉顯著增加。此外，在數據中亦觀察到低強度的氧波峰，其為矽酸鹽(OSiO3)之特徵。就SiO2並未觀察到此波峰。Na和矽酸鹽氧波峰之偵測強力地支持在二氧化矽粉末的表面上形成矽酸鈉。以去離子水沖洗乾燥的CSS粉末些微減少Na和矽酸鹽氧，其指出表面矽酸鹽具有低水溶性。因此，在水性媒劑中，矽酸鈉大量地停留在二氧化矽表面。 The data shows that compared to silica, there is a significant increase in sodium on the surface of dry matter. In addition, low-intensity oxygen peaks are also observed in the data, which are characteristic of silicate (O SiO3 ). This peak is not observed for SiO 2. The detection of Na and silicate oxygen peaks strongly supports the formation of sodium silicate on the surface of silica powder. Rinsing the dried CSS powder with deionized water slightly reduces Na and silicate oxygen, which indicates that the surface silicate has low water solubility. Therefore, in the aqueous medium, a large amount of sodium silicate stays on the surface of silicon dioxide.
經1% CaCl2溶液處理過的CSS粉末亦以ESCA進行研究，用以測定物質所吸收的Ca。就此乾燥物質之ESCA結果清楚地指出，Ca存在CSS的表面上。相對於乾燥的CSS，亦觀察到Na降低，其顯示Ca取代了CSS表面上的Na。對於經CaCl2處理過的樣本，亦偵測到低濃度的Cl，其顯示殘餘的CaCl2亦可能存在物質上。去離子水沖洗樣本移除Cl，然而大部份的Ca仍保留。因此，此數據指出，CSS能吸附及保留來自溶液的Ca離子。此結果支持上述之Ca離子吸收數據，並支持CSS作為齒石控制劑之潛在性。 CSS powder treated with 1% CaCl 2 solution was also studied with ESCA to determine the amount of Ca absorbed by the substance. The ESCA results of this dry matter clearly indicate that Ca is present on the surface of CSS. Relative to dry CSS, a decrease in Na was also observed, which shows that Ca replaced Na on the surface of the CSS. For samples treated with CaCl 2 , a low concentration of Cl was also detected, which indicates that residual CaCl 2 may also be present on the substance. Rinse the sample with deionized water to remove Cl, but most of the Ca remains. Therefore, this data indicates that CSS can adsorb and retain Ca ions from solution. This result supports the above Ca ion absorption data and supports the potential of CSS as a dental control agent.
使用中IR光譜確認矽酸鹽存在核二氧化矽的殼層上。在所有的測量中，係使用三個(多個)反射ATR(衰減全反射)配件來加強樣本之吸收光譜。這些配件僅讓光穿透1-2微米進入樣本，由此增強表面組份之訊號，與大批基質相比較。為了進一步增進對聲訊的訊號，係測量32次掃描並將各測量值平均。 IR spectroscopy in use confirmed the presence of silicate on the core silica shell. In all measurements, three (multiple) reflectance ATR (attenuated total reflectance) accessories are used to enhance the absorption spectrum of the sample. These accessories only allow light to penetrate 1-2 microns into the sample, thereby enhancing the signal of the surface composition, compared with a large number of substrates. In order to further improve the signal to the sound signal, 32 scans are measured and the measured values are averaged.
二氧化矽和矽酸鹽之中IR指紋圖譜相當不同且經完全解析。純的二氧化矽其特徵為具有接近1074cm-1之對稱的SiO振動及在大約960cm-1的吸收帶，由於SiOH鍵的伸縮振動。矽酸鹽，在另一方面，具有一介於1200cm-1和1100cm-1之間的突出不對稱肩振動。此外，發現一由二氧化矽移位的強力不對稱伸展，接近1000cm-1。 The IR fingerprints of silica and silicate are quite different and fully resolved. Pure silica is characterized by a symmetrical SiO vibration close to 1074 cm-1 and an absorption band at about 960 cm-1 due to the stretching vibration of the SiOH bond. Silicate, on the other hand, with a projection interposed between the asymmetric shoulder vibration 1200cm -1 and 1100cm -1. In addition, it was found that a strong asymmetric stretch displaced by silicon dioxide was close to 1000 cm -1 .
二氧化矽核殼糊膏之ATR光譜指紋大大地受折射率效應影響，其對於固有強力的吸收如二氧化矽和矽酸鹽中的Si-O伸展可能很大。在傳輸上，Si-O吸收帶接近1100cm-1，但在ATR中其典型地為約1060cm-1。又吸收帶並非完全對稱的。因為此等為糊膏，吸收度為寬的且可能含有非晶/晶體物質。 The ATR spectral fingerprint of the silica core-shell paste is greatly affected by the refractive index effect, and its inherently strong absorption such as Si-O in silica and silicate may stretch greatly. On the transmission, Si-O absorption band close 1100cm -1, but the ATR which is typically about 1060cm -1. Moreover, the absorption band is not completely symmetrical. Because these are pastes, the absorption is broad and may contain amorphous/crystalline substances.
除了規則的ATR測量外，係加入偏極化配件用以增進了解並確認表面矽酸鹽類係存在的。偏極化測量之利益為其給予樣本分子結構上的額外資訊，因為其係關於結晶性或分子向位。就此 應用上，因偏極化光平面沿著樣本平面，二氧化矽與矽酸鹽的比率應改變。所檢測的偏振角為：0、30、60、90、120、150和180度。計算矽酸鹽(1022cm-1)與二氧化矽(1074cm-1)的光譜比率，用以驗證殼矽酸鹽的存在。表7係顯示來自Na-CSS分析之結果。 In addition to the regular ATR measurement, polarization accessories are added to enhance understanding and confirm the presence of surface silicates. The benefit of polarization measurement is that it gives additional information about the molecular structure of the sample because it is about crystallinity or molecular orientation. For this application, since the plane of polarized light is along the plane of the sample, the ratio of silica to silicate should be changed. The detected polarization angles are: 0, 30, 60, 90, 120, 150 and 180 degrees. Calculate the spectral ratio of silicate (1022cm -1 ) to silica (1074cm -1 ) to verify the presence of shell silicate. Table 7 shows the results from Na-CSS analysis.
此分析顯示，當偏極化的平面定位時於0度時的最適濃度，其建議矽酸鹽的偶極矩改變位置係與ART表面平行。 This analysis shows that when the polarization plane is positioned at the optimal concentration at 0 degrees, it is recommended that the dipole moment change position of the silicate is parallel to the ART surface.
進行一動力學研究，用以測定原位製造Na+-CSS膠體所需的時間週期。使用下列配方，其係以Na+-CSS牙膏配方(#85 CSS牙膏)為基礎。 A kinetic study was performed to determine the time period required for in-situ production of Na+-CSS colloids. Use the following formula, which is based on the Na+-CSS toothpaste formula (#85 CSS toothpaste).
製程：於反應容器中加入水、NaOH和甘油。將Zeodent 105高清潔二氧化矽緩慢地加到此水性混合物中。使用蒸氣水-浴加熱混合物，將反應溫度維持在80-90℃的範圍內。反應歷時6小時。當冷卻至室溫時，每1小時取出一個樣本測量pH及導電度。數據係列於下：
從表9中可看出，在第1小時pH和導電度戲劇性降低及然後在2小時後達到平穩。形成CSS反應之反應在約2小時內完成。此動力學研究為重要的，因為必須將牙膏批件製造時間減至最少。 It can be seen from Table 9 that the pH and conductivity decreased dramatically in the first hour and then reached a plateau after 2 hours. The reaction to form the CSS reaction is completed in about 2 hours. This kinetic study is important because the manufacturing time of toothpaste approval parts must be minimized.
鉀二氧化矽核殼(K-CSS)膠體係以下列配方為基礎：
製程：於反應容器中加入熱水(75℃)、45% NaOH和甘油。將Zeodent 105高清潔二氧化矽緩慢地加到此水性混合物中。
在周圍溫度無另外加熱下，反應6小時。在反應期間，採取樣本測量溫度、pH及導電度。動力學數據係列於下：
表11顯示，在第1小時導電度戲劇性降低及然後在2小時後達到平穩。所以在周圍溫度(室溫)下CSS反應於約2小時後完成。 Table 11 shows that the conductivity decreased dramatically in the first hour and then reached a plateau after 2 hours. Therefore, the CSS reaction is completed after about 2 hours at ambient temperature (room temperature).
藉由將45%KOH/SiO2從101.1g/220g降至303.2g/1321g，改變上述膠體配方，製造K-CSS牙膏，並再次測量動力學：
從表13可看出，在最先的半小時導電度戲劇性降低及然後在2小時後達到平穩。因此，K-CSS牙膏之K-CSS膠體可在周圍溫度無任何外部加熱下，於約2小時內製造(參見表14之K-CSS牙膏)。此動力學研究為重要的，因為必須將牙膏批件製造時間減至最少。 It can be seen from Table 13 that the conductivity drops dramatically in the first half an hour and then reaches a plateau after 2 hours. Therefore, the K-CSS gel of K-CSS toothpaste can be manufactured in about 2 hours at ambient temperature without any external heating (see K-CSS toothpaste in Table 14). This kinetic study is important because the manufacturing time of toothpaste approval parts must be minimized.
K-CSS牙膏具有7.7的pH及8.06之10% pH(10% pH為10g牙膏加到90g水中之10%牙膏溶液的pH(就牙膏而言，10% pH應介於6至10之間)。請注意，1個Brookfield黏度單位為10,000厘泊(centipoise)。 K-CSS toothpaste has a pH of 7.7 and a 10% pH of 8.06 (10% pH is the pH of a 10% toothpaste solution with 10g toothpaste added to 90g water (for toothpaste, 10% pH should be between 6 and 10) Please note that one Brookfield viscosity unit is 10,000 centipoise (centipoise).
使用ESCA光譜儀定量K-CSS顆粒中的K元素。 The ESCA spectrometer was used to quantify the K element in the K-CSS particles.
從表15中可看出，K係在CSS研磨劑表面上發現。總言之，KOH可作為鹼，用於室溫製造K-CSS牙膏。 It can be seen from Table 15 that K is found on the surface of the CSS abrasive. In short, KOH can be used as a base to make K-CSS toothpaste at room temperature.
用於室溫下製造K-CSS之一實施例方法係如下所述：於75℃將試驗工廠水加入lee混合器中及然後加入甘油。加入SiO2(Zeodent 105)。加入KOH。混合成份。以規律的間隔移出樣本並檢測pH和導電度，用以決定何時K-CSS之形成已完全。加入H3PO4-反應混合物形成凝膠。採取樣本並於Lee混合器中加入NaF、糖精和水，歷時10分鐘。將CMC/三仙膠分散於PEG 600溶液中。於混合器中加入上述膠溶液。混合。緩慢地加入Zeodent 165增稠二氧化矽。施用25真空英吋歷經一段時間。移除真空，並加入風味劑、染劑和雲母。打開刮刀和攪拌器，顏色為淡藍色，在添加SLS之前黏度相當稀。於真空下混合物10min。停止真空/混合。加入SLS。施用真空，緩慢混合，形成具有較濃稠度之產物，但仍為稀的。測量的最終產物之密度為1.279。此產物具有淡藍的顏色。靜置2hrs後，所測量的最初黏度=156600cp。Brookfield黏度=150600cp，在1加侖的廣口瓶中幾乎為不流動的。
An example method for the manufacture of K-CSS at room temperature is as follows: add pilot plant water to the lee mixer and then add glycerin at 75°C. Add SiO2 (Zeodent 105). Join KOH. Mix the ingredients. Remove the samples at regular intervals and check the pH and conductivity to determine when the formation of K-CSS is complete. Add H 3 PO 4 -the reaction mixture forms a gel. Take a sample and add NaF, saccharin and water to the Lee mixer for 10 minutes. Disperse CMC/Sanxian gum in
在升高的溫度下(70-90℃)，將SiO2研磨劑與NaOH溶液反應，產生核-殼顆粒，此反應為：
先前，吾等係藉由將過量的SiO2與NaOH反應，製造不透明的牙膏(SiO2：50% NaOH=20%：4.5%=4.44：1重量百分比)。在此方法中，僅有小部份(表面)的SiO2顆粒與NaOH反應。並不知道有多少百分比的SiO2與NaOH反應，因為基於上述反應，SiO2與NaOH的比率為n：2(n為未知的)。 Previously, we made opaque toothpaste by reacting excess SiO 2 with NaOH (SiO 2 : 50% NaOH = 20%: 4.5% = 4.44: 1 weight percent). In this method, only a small portion (surface) of SiO 2 particles react with NaOH. It is not known what percentage of SiO 2 reacts with NaOH, because based on the above reaction, the ratio of SiO 2 to NaOH is n: 2 (n is unknown).
希望使用CSS材質製造透明或半透明漱口水產品。必須了解需要多少NaOH來完全溶解SiO2，以便於製造透明的CSS。吾等藉由將SiO2與50% NaOH的比率降至最低以達到最大的顆粒電荷密度，從下列配方製造透明的CSS膠體。 Hope to use CSS material to make transparent or translucent mouthwash products. It is necessary to know how much NaOH is needed to completely dissolve SiO2 in order to make transparent CSS. We made a transparent CSS colloid from the following formula by minimizing the ratio of SiO 2 and 50% NaOH to achieve the maximum particle charge density.
在85 C歷時4小時，SiO2完全溶於NaOH中，形成透明的液體。當計算其莫耳濃度時，SiO2與NaOH的莫耳比(4.662莫耳：2.925)=1.593：1(莫耳比)。然而，若吾等假設下列反應：
為了進一步確認此項發現，在此項研究中係使用購自PQ公司的37.5% Na2SiO3作為對照樣本。就該項市售透明的Na2SiO3液體樣本，SiO2：Na2O重量比=3.220：1或莫耳比=3.323：1。其相當於SiO2：NaOH=3.323：2=1.662：1。Na2SiO3/總SiO2=(1/2)莫耳/(1.662moles)=30.08% To further confirm this finding, 37.5% Na 2 SiO 3 purchased from PQ Company was used as a control sample in this study. For the commercially available transparent Na2SiO3 liquid sample, the weight ratio of SiO 2 :Na 2 O=3.220:1 or the molar ratio=3.323:1. It is equivalent to SiO 2 :NaOH=3.323:2=1.662:1. Na 2 SiO3/total SiO 2 =(1/2)mole/(1.662moles)=30.08%
因此，市售的Na2SiO3溶液，n>3.323。 Therefore, the commercially available Na 2 SiO 3 solution has n>3.323.
藉由光散射和ESCA分析樣本並用以測定在透明膠體中是否有一些小的奈米顆粒。基於上述表16中的配方，精確地調整SiO2與50% NaOH的比率並製造下列配方：表17用於製造不透明、半透明和透明的Na-CSS膠體之配方
可看出，半透明(#152)和透明(#148及#149)膠體具有與對照樣本相類似的濁度光譜：在介於300至800nm間的可見光區中並無散射，可能是因為缺乏SiO2顆粒，或若有二氧化矽顆粒存在，其為非常小，且在介於200至300nm之間的UV區中有一些散射或吸收。當在配方中使用更多的二氧化矽時，半-不透明(#151)和不透明(#150)樣本，在可見光和UV區中顯現高出很多的SiO2顆粒之散射背景。 It can be seen that the translucent (#152) and transparent (#148 and #149) colloids have similar turbidity spectra to the control samples: there is no scattering in the visible light region between 300 and 800 nm, which may be due to the lack of SiO 2 particles, or if silicon dioxide particles are present, are very small and have some scattering or absorption in the UV region between 200 and 300 nm. When more silica is used in the formulation, the semi-opaque (#151) and opaque (#150) samples show much higher scattering background of SiO 2 particles in the visible and UV regions.
基於上述ESCA數據，半透明樣本(#152)含有(以Na數據為基準)Na2SiO3%=37.5% X 2.53/13.20=7.19%。從#152配方，若所有的NaOH皆與二氧化矽反應，可得到6.84% Na2SiO3，其非常接近由上述ESCA數據所計算的數值(7.19%)。
Based on the above ESCA data, the translucent sample (#152) contains (based on Na data) Na 2 SiO 3 %=37.5% X 2.53/13.20=7.19%. From the
下表19係顯示，如光散射所測定的二氧化矽和CSS顆粒之粒徑分布。表19顯示煅製二氧化矽、Na-CSS膠體、Zeodent® 105沉澱二氧化矽、不透明Na-CSS(#150)、半不透明Na-CSS(#151)，以及半透明Na-CSS(#152)之粒徑分布。 Table 19 below shows the particle size distribution of silica and CSS particles as measured by light scattering. Table 19 shows fumed silica, Na-CSS colloid, Zeodent® 105 precipitated silica, opaque Na-CSS (#150), semi-opaque Na-CSS (#151), and semi-transparent Na-CSS (#152 ) The particle size distribution.
小的顆粒由於高表面積(能量)可能形成較大的叢集。此項係從市售煅製二氧化矽樣本中看出(所記錄的平均粒徑為12nm)，其表示以光散射法所得來的平均粒徑為51.90μm。SEM顆粒亦揭露煅製二氧化矽顆粒形成較大的叢集。從粒徑分布看出：(1)與NaOH反應後，粒徑分布比市售的Zeodent 105高清潔粉末(對照組)窄；(2)較小的顆粒在較大的部份之前溶解。 Small particles may form larger clusters due to high surface area (energy). This item is seen from commercially available calcined silica samples (the average particle size recorded is 12nm), which means that the average particle size obtained by the light scattering method is 51.90μm. The SEM particles also revealed that the calcined silica particles formed larger clusters. It can be seen from the particle size distribution: (1) After reacting with NaOH, the particle size distribution is narrower than the commercially available Zeodent 105 high-cleaning powder (control group); (2) The smaller particles dissolve before the larger part.
一辨別蝕刻的CSS顆粒與完全形成的金屬矽酸鹽(例如Na2SiO3)之其他方法為比較黏度。37.5% Na2SiO3在pH 11.3時固 化。當稀釋接近10x達到3.32% Na2SiO3時，溶液在約9的pH時仍為固化的。相反地，本發明之CSS顆粒在這些濃度和pH時仍保持溶液態。因此，本發明另外的具體實施例係形成CSS顆粒，其在整個pH 6-10之10% pH範圍中(10g牙膏加到90g水中之10%牙膏溶液的pH)，仍保持可流動的膠體形式，其可與其他完全形成的金屬矽酸鹽區別出，其中該完全形成的金屬矽酸鹽在約大於或等於pH 9之pH應會固化。 Another way to distinguish etched CSS particles from fully formed metal silicates (such as Na 2 SiO 3 ) is to compare viscosity. 37.5% Na 2 SiO 3 solidifies at pH 11.3. When the dilution is close to 10x to reach 3.32% Na 2 SiO 3 , the solution is still solidified at a pH of about 9. In contrast, the CSS particles of the present invention remain in solution at these concentrations and pH. Therefore, another specific embodiment of the present invention is to form CSS particles, which in the entire 10% pH range of pH 6-10 (the pH of a 10% toothpaste solution in which 10g toothpaste is added to 90g water), still maintain a flowable colloidal form It can be distinguished from other fully formed metal silicates, where the fully formed metal silicate should solidify at a pH greater than or equal to about pH 9.
CSS可從任何種類的二氧化矽物質來製作，例如硬二氧化矽顆粒、多孔二氧化矽顆粒如非晶牙二氧化矽研磨劑：高清結二氧化矽Zeodent 105；一般的二氧化矽如Zeodent 114，增稠二氧化矽如Zeodent 165。 CSS can be made from any kind of silica material, such as hard silica particles, porous silica particles such as amorphous silica abrasive: high-definition silica Zeodent 105; general silica such as Zeodent 114, thickened silica such as Zeodent 165.
蝕刻掉的二氧化矽量係依照二氧化矽顆粒的BET比面積而定。表面積越大的顆粒，蝕刻越淺。蝕刻的量亦依照二氧化矽與鹼的比率而定。已發現，當Zeodent 105二氧化矽與50% NaOH溶液的重量比率=2.02(終點)時，所有的二氧化矽皆溶解。在製造Na-CSS牙膏時，係使用20%高清潔二氧化矽(Zeodent 105)和4.5%的50% NaOH。所以SiO2：50% NaOH的比率=4.44：1。因為溶解的SiO2：50% NaOH=2.02：1，所以反應後剩餘的SiO2與NaOH(50%)=(4.44-2.02)：1=2.42：1。所以剩餘的SiO2對最初的SiO2=2.42/4.44=54.55%，或體積變化(△V/V)=54.55%-100%=-45.45%。請注意，就溶解所有二氧化矽物質之終點可能因SiO2不同而變(不同的二氧化矽可能具有不同的終點，所以就實施例煅製二氧化矽的終點可能並非2.02：1)。 The amount of silicon dioxide etched away depends on the BET specific area of the silicon dioxide particles. The larger the surface area of the particles, the shallower the etching. The amount of etching also depends on the ratio of silicon dioxide to alkali. It has been found that when the weight ratio of Zeodent 105 silica to 50% NaOH solution = 2.02 (end point), all silica is dissolved. In the manufacture of Na-CSS toothpaste, 20% high-cleaning silica (Zeodent 105) and 4.5% 50% NaOH are used. So the ratio of SiO 2 :50% NaOH=4.44:1. Since dissolution of SiO 2: 50% NaOH = 2.02 : 1, so after the reaction with the remaining SiO2 NaOH (50%) = (4.44-2.02 ): 1 = 2.42: 1. So the remaining SiO2 to the original SiO2=2.42/4.44=54.55%, or the volume change (△V/V)=54.55%-100%=-45.45%. Please note that the end point for dissolving all silicon dioxide substances may vary depending on SiO 2 (different silicon dioxide may have different end points, so the end point of the calcined silicon dioxide in the embodiment may not be 2.02:1).
使用BET比表面積(S/W)計算所有的SiO2(包括剛硬和多孔顆粒)。就高清潔二氧化矽(例如Zeodent 105,S/W=35m2/g及密度d=2.2g/cm3)，粒徑之變化(△X)係以下列方程式提供： △X=[(△V/V)/(S/W)] x 1/d Use BET specific surface area (S/W) to calculate all SiO 2 (including rigid and porous particles). For high clean silica (for example, Zeodent 105, S/W=35m 2 /g and density d=2.2g/cm 3 ), the change in particle size (△X) is provided by the following equation: △X=[(△ V/V)/(S/W)] x 1/d
△X=(-0.4545/35 x 104cm2/g) x (1/2.2g/cm3) △X=(-0.4545/35 x 10 4 cm 2 /g) x (1/2.2g/cm 3 )
△X=-5.90 x 10-7cm △X=-5.90 x 10 -7 cm
△X=-590nm(-0.590μm) △X=-590nm(-0.590μm)
就單一散體、剛硬、球形顆粒有另一種替代的計算。因為顆粒的外表面積非常小(相較於微孔顆粒)，剛硬顆粒將具有較高的蝕刻程度。取微分：
ESCA(化學分析電子能譜儀-亦稱為XPS或X-射線光電子能譜)可從表面向下穿透10nm深。1層的二氧化矽或Na2SiO3為約1Å(0.1nm)。就Na2SiO3分子：Na/Si=2：1。所以就100層的單層，Na/Si=0.02：1。但從ESCA數據：Na/Si=0.084：1。所以有0.084/0.02=4.2，約4層的Na2SiO3。 ESCA (electron spectrometer for chemical analysis-also known as XPS or X-ray photoelectron spectroscopy) can penetrate down to a depth of 10 nm from the surface. One layer of silicon dioxide or Na 2 SiO 3 is about 1 Å (0.1 nm). For Na 2 SiO 3 molecules: Na/Si=2:1. So for a single layer of 100 layers, Na/Si=0.02:1. But from ESCA data: Na/Si=0.084:1. So there are 0.084/0.02=4.2, about 4 layers of Na 2 SiO 3 .
另一種選擇，然後將過濾的實施例14之液體與DI水混合，水和Na-CSS之間的質量比率為約1：1。將混合物冷凍直到其變成固體。打開冷凍乾燥機，將冷凍室冷卻。當冷凍室的溫度降至-47℃時，將冷凍樣本置入冷凍室中並打開真空，歷經一段足以形成乾燥CSS粉末之時間。 Another option is to mix the filtered liquid of Example 14 with DI water, and the mass ratio between water and Na-CSS is about 1:1. The mixture is frozen until it becomes a solid. Turn on the freeze dryer and cool the freezer compartment. When the temperature of the freezer compartment drops to -47°C, the frozen sample is placed in the freezer compartment and the vacuum is turned on for a period of time sufficient to form dry CSS powder.
使用刃天青(resazurin)抗細菌試驗分析檢測本發明之二氧化矽核殼(CSS)顆粒的抗細菌活性，其中刃天青的還原為細菌生長下降之度量。 The resazurin antibacterial test is used to analyze the antibacterial activity of the silica core shell (CSS) particles of the present invention, wherein the reduction of resazurin is a measure of the decline in bacterial growth.
使用刃天青微分析，以用於口腔護理產品評估之恆化器接種體(含黏放線菌(A.viscosus)、口腔鏈球菌(S.oralis)、小韋榮球菌(V.parvula)、乾酪乳酸桿菌(L.casei)、和具核梭桿菌(F.nucleatum)的細菌混合液)，測量所有溶液的細菌存活力。刃天青(7-羥基-3H-啡 -3-酮10-氧化物)為一種用作氧化-還原反應，以呼吸反應效應從顏色感應定量細菌存活力的藍色染劑。 Resazurin microanalysis, for chemostat inoculum assessment of oral care products (including Actinomyces viscous (A.viscosus), Streptococcus oralis (S.oralis), Xiao Wei Rong bacteria (V.parvula), Lactobacillus casei (of L.casei), and Fusobacterium nucleatum (F.nucleatum) a mixture of bacteria), bacterial viability measurement of the total solution. Resazurin (7-hydroxy-3H-phen-3-one 10-oxide) is a blue dye used in oxidation-reduction reaction to quantify the viability of bacteria from color sensing with respiratory reaction effect.
各實驗係以含粘放線菌、口腔鏈球菌、小韋榮球菌、乾酪乳酸桿菌(L.casei)和具核梭桿菌之活的和死的細菌混合物，分別使用TSB培養液(胰蛋白大豆培養液)和乙醇來進行，且其係以適當的比率來添加，用以產生收集總計12個點，從100%活細菌至100%死細菌混合物之標準曲線。 Each experiment system used a mixture of live and dead bacteria containing Actinomyces viscosus, Streptococcus oralis, Veronococcus minor, Lactobacillus casei ( L. casei ) and Fusobacterium nucleatum, respectively, using TSB culture medium (tryptic soy culture) Liquid) and ethanol are added at an appropriate ratio to generate a standard curve that collects a total of 12 points, from 100% live bacteria to 100% dead bacteria mixture.
此分析係使用來自1ml恆化器接種體的細菌團來進行並以暴露於1：1之¼濃度的胰蛋白大豆培養液：試驗溶液的Eppendorf試管中。培養1小時後，加入1ml D/E培養液，於適當混合下進一步讓細菌生長失活，並收集菌團以1ml TSB培養液沖洗，完全移除D/E培養液(D/E=Dey-Engley)。將最後的菌團再懸浮於1.5ml TSB培養液，並將100μL量轉置於96孔盤上，在96孔盤中係含有100μL刃天青染劑溶液。於37℃培養3-5min達到較佳的染劑反應後，以刃天青分析方法進行OD測量。 This analysis was performed using bacterial clusters from 1 ml chemostat inoculum and exposed to a 1:1 ¼ concentration of tryptic soy broth: test solution in Eppendorf test tubes. After culturing for 1 hour, add 1ml D/E culture medium, further inactivate the growth of bacteria under proper mixing, and collect the colony and wash with 1ml TSB culture medium to completely remove D/E culture medium (D/E=Dey- Engley). The final colony was resuspended in 1.5 ml TSB culture medium, and 100 μL was transferred to a 96-well plate, and the 96-well plate contained 100 μL resazurin stain solution. After incubating at 37°C for 3-5 min to achieve a better dye reaction, the OD measurement was carried out by resazurin analysis method.
考慮細菌在生物學態樣每天不同，此微分析係一天進行一次，共計4-5天。最終的細菌存活力%代表平均值。呈現的成份濃度係設定在牙膏配方中的實際濃度。 Considering that the biological status of bacteria is different every day, this micro-analysis is performed once a day for a total of 4-5 days. The final bacterial viability% represents the average value. The concentration of the ingredients presented is the actual concentration set in the toothpaste formula.
從表20中的數據可看出，二氧化矽核殼顆粒提供高於氯化鋅(ZnCl2)(一種已知的抗菌劑)的抗細菌活性。 From the data in Table 20, it can be seen that the silica core-shell particles provide higher antibacterial activity than zinc chloride (ZnCl 2 ), a known antibacterial agent.
熟習本項技術者應了解，在不悖離本發明精神下，文中所述的具體實施例可做許多變化和修改。希望所有的此等變異係落在所附的申請專利之範圍內。 Those familiar with this technique should understand that many changes and modifications can be made to the specific embodiments described in the text without departing from the spirit of the present invention. Hope that all these variations fall within the scope of the attached patent application.
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