WO2020140402A1 - 一种高磨擦高透明牙膏用二氧化硅及其制备方法 - Google Patents

一种高磨擦高透明牙膏用二氧化硅及其制备方法 Download PDF

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WO2020140402A1
WO2020140402A1 PCT/CN2019/092327 CN2019092327W WO2020140402A1 WO 2020140402 A1 WO2020140402 A1 WO 2020140402A1 CN 2019092327 W CN2019092327 W CN 2019092327W WO 2020140402 A1 WO2020140402 A1 WO 2020140402A1
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silica
toothpaste
sodium silicate
solution
sulfuric acid
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PCT/CN2019/092327
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English (en)
French (fr)
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任振雪
李丽峰
林超聪
林英光
高文颖
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广州市飞雪材料科技有限公司
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Publication of WO2020140402A1 publication Critical patent/WO2020140402A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
    • C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the invention belongs to the technical field of silicon dioxide for toothpaste, and in particular relates to a silicon dioxide for high friction and high transparent toothpaste and a preparation method thereof.
  • silica is a spherical porous structure, does not wear teeth without sharp edges, and has stable physical and chemical properties, strong cleaning ability, good compatibility with toothpaste systems, and can be used for the preparation of transparent toothpaste, etc. Characteristics, has been widely used in the toothpaste industry.
  • the copper consumption value of ordinary silica is within 2.0 mg; the copper consumption value of medium friction silica is between 2.0 and 10.0 mg; the copper consumption value of high friction silica is greater than 10.0 mg, Generally not more than 20.0mg, otherwise it is easy to wear enamel.
  • the frictional cleaning power of silica and the light transmittance are two opposing factors. The denser the general silica structure, the better the friction force and the worse the light transmittance.
  • the silica with high light transmittance friction The value is low, the cleaning effect is not good, and the high friction value silica has low light transmittance and cannot be applied well, even if it has both high light transmittance (light transmittance above 90%) and high friction (copper consumption) Silicon dioxide with a value of 10 mg or more), but its refractive index (approximately 1.4425) is low, and it can only be made into a translucent toothpaste after it is applied to an anhydrous toothpaste formula.
  • the refractive index of the liquid phase system and the solid phase system of the paste must be close, or even reach the same.
  • the main component of the low-water/anhydrous toothpaste liquid system is a wetting agent, while sorbitol, polyethylene glycol and glycerin are all commonly used wetting agents.
  • the refractive index of silica is in the range of 1.4350 to 1.4600
  • the refractive index of 70% sorbitol is 1.457
  • the refractive index of polyethylene glycol is 1.46.
  • the light transmittance of silica is also very important, generally requiring more than 90%. As long as the above two conditions are met at the same time, there will be no diffuse reflection, thus forming a paste with good transparency. Therefore, the transmittance of silica with a refractive index of 1.46 or higher must be greater than 90% to prepare a water-less/anhydrous transparent toothpaste.
  • patent document CN105776230A discloses a method for preparing silica for tooth cleaning transparent toothpaste.
  • the method includes (1) disposing 25-28wt% sodium carbonate solution, and then adding 1.6-2.2M sodium silicate solution, A mixed solution is obtained; (2) Add 11.0 ⁇ 15.0wt% sodium sulfate solution 4 ⁇ 8m 3 to the reactor, heat to 70 ⁇ 80°C, and add 2.5 ⁇ 3.2M sodium silicate solution (modulus is 3.3 ⁇ 3.45) 3 ⁇ 5m 3 and 10.0 ⁇ 12.0M sulfuric acid solution, keep the process pH at 7.5 ⁇ 9.5, after the sodium silicate solution is added dropwise, continue to add the sulfuric acid solution dropwise to pH 6.0 ⁇ 7.0, stirring for 10 ⁇ 15min (3) Continue to add water 4 ⁇ 6m 3 to the above reaction kettle, heat to 70 ⁇ 80°C, and drop the mixed solution 8 ⁇ 10m 3 and 10.0 ⁇ 12.0M sulfuric acid solution while stirring, keeping the process pH at 5.5 ⁇ 7.5.
  • silica After the mixed dropwise addition is completed, control the pH of the reaction end point to 6.0 ⁇ 7.0, stir for 10 ⁇ 15 min, filter press, wash, spray dry, and airflow crushing to obtain silica.
  • the silica has high frictional cleaning value and light transmittance, and has a thickening effect, but the silica has high transparency at a low refractive index (1.4300 to 1.4400) and is only suitable for water content It is 16-21% of transparent toothpaste, and its copper consumption value is about 6-8mg, which belongs to medium friction silica.
  • the preparation method is simple, and the transmittance of silicon dioxide in the range of refractive index 1.438 to 1.450 can reach more than 95%. It has the characteristics of high light transmittance at low refractive index. It is also suitable for use in aqueous transparent toothpaste. At the same time, the copper consumption value of the silica is relatively low, below 5 mg, and the frictional cleanliness is not good.
  • the present invention first provides a high friction high The preparation method of silica for transparent toothpaste.
  • This method adopts a two-step hydrothermal precipitation method to strictly control the material concentration, reaction temperature and pH value.
  • the light transmittance is greater than 90% at a refractive index of 1.448 to 1.460, and the copper consumption value ⁇ 15mg, silica with high light transmittance and high friction cleaning performance under high refractive index.
  • the preparation method of silica for high friction and high transparent toothpaste provided by the present invention includes the following steps:
  • the formed silica is press-filtered, washed, and spray-dried to break the airflow to a particle size of 8-12 ⁇ m to obtain silica for high-friction and high-transparent toothpaste.
  • concentration concentration of the sodium sulfate solution is 4.0-6.0%.
  • the sodium silicate solution has a modulus of 3.4 to 3.5 and a concentration of 1.5 to 2.0 mol/L.
  • the concentration of the sulfuric acid solution is 14-16mol/L.
  • the flow rate of the sodium silicate solution is 14-15 m 3 /h.
  • the rotation speed of the stirring is 35-40 Hz.
  • the present invention also provides the silica prepared by the above-mentioned method for preparing silica for high-friction and high-transparency toothpaste.
  • the silica has a light transmittance of ⁇ 90% at a refractive index of 1.448 to 1.460. Copper The consumption value is ⁇ 15mg. It is suitable for the formulation of transparent toothpaste with little or no water. It provides a suitable toothpaste system for special functional raw materials such as peroxide, hydrogen peroxide and probiotics, and improves the quality of transparent toothpaste.
  • reaction mechanism of the method for preparing silica for high friction and high transparent toothpaste of the present invention is as follows:
  • the invention adopts a two-step hydrothermal precipitation method, using sodium silicate solution with a modulus of 3.4 to 3.5 and concentrated sulfuric acid with a concentration of 14 to 16 mol/L as reaction raw materials.
  • sodium sulfate solution is used as a reaction aid.
  • the acid-dropping alkali feeding method directly using concentrated sulfuric acid reaction, under high-speed stirring and relatively low reaction temperature, the initial loose gel particles are quickly formed.
  • This step of the reaction produces high seed crystals with a high refractive index, corresponding to the transparent The light rate is also high.
  • the second step of the same acid-base drip is continued; during the second step of the acid-base drip, with the addition of concentrated sulfuric acid, the system continues to exotherm, making the temperature of the reaction system of the same drop It can be maintained at a high temperature of 85-95°C.
  • the seed crystals continue to grow. While maintaining high light transmittance, the structure of the silicon dioxide becomes dense, and the friction performance is effectively improved. Therefore, by adopting two different reaction methods, silica has both high light transmittance and high frictional cleaning performance at high refractive index.
  • the preparation method of silicon dioxide for high friction and high transparent toothpaste of the present invention uses sodium silicate solution and sulfuric acid solution of the same modulus and concentration to participate in the reaction.
  • the process is simple and stable, the conditions are easy to control, and concentrated sulfuric acid is used for the reaction directly It uses concentrated sulfuric acid to continuously release heat to reach the temperature required for the reaction, saves energy consumption, and obtains silica with high light transmittance and high friction and cleaning performance under high refractive index.
  • the silica for high friction and high transparent toothpaste of the present invention has a light transmittance of ⁇ 90% and a copper consumption value of ⁇ 15mg at a refractive index of 1.448 to 1.460.
  • Special functional raw materials such as substances, hydrogen peroxide and probiotics provide a suitable toothpaste system, and at the same time improve the quality of transparent toothpaste and have a wide range of application prospects.
  • Example 1 Silica for high friction and transparent toothpaste of the present invention and preparation method thereof
  • the formed silica is press-filtered, washed, and spray-dried to break the airflow to a particle size of 10 ⁇ m to obtain silica with high friction and high transparency toothpaste.
  • the modulus of the sodium silicate solution is 3.4 and the concentration is 1.5 mol/L; the concentration of the sulfuric acid solution is 14 mol/L.
  • the formed silica is press-filtered, washed, and spray-dried to break the airflow to a particle size of 10 ⁇ m to obtain silica with high friction and high transparency toothpaste.
  • the modulus of the sodium silicate solution is 3.5 and the concentration is 2.0 mol/L; the concentration of the sulfuric acid solution is 16 mol/L.
  • the formed silica is press-filtered, washed, and spray-dried to break the airflow to a particle size of 10 ⁇ m to obtain silica with high friction and high transparency toothpaste.
  • the modulus of the sodium silicate solution is 3.4 and the concentration is 1.8 mol/L; the concentration of the sulfuric acid solution is 15 mol/L.
  • Embodiment 4 Silica for high-friction and high-transparency toothpaste of the present invention and preparation method thereof
  • the formed silica is press-filtered, washed, and spray-dried to break the airflow to a particle size of 10 ⁇ m to obtain silica with high friction and high transparency toothpaste.
  • the modulus of the sodium silicate solution is 3.4 and the concentration is 1.5 mol/L; the concentration of the sulfuric acid solution is 16 mol/L.
  • this comparative example differs only in that the sodium silicate solution has a modulus of 3.0 and a concentration of 1.2 mol/L.
  • this comparative example differs only in that the modulus of the sodium silicate solution is 3.4 and the concentration is 2.5 mol/L.
  • this comparative example differs only in that the concentration of the sulfuric acid solution is 8 mol/L.
  • this comparative example differs only in that the sodium sulfate solution has a concentration of 7% by weight.
  • this comparative example differs only in that the pH value of the control process in step S3 is 9.5.
  • Example 3 Compared with Example 3, this comparative example differs only in that after the stirring is turned on, the control rotational speed is 45 Hz.
  • Test Example 1 Performance test of silica for high friction and transparent toothpaste of the present invention
  • the light transmittance and copper consumption value in the range of refractive index 1.448 to 1.460 (method for measuring copper consumption value: dispersing silica in 70 % Sorbitol, the laboratory hard particle tester rubs back and forth 9999 times on the copper sheet immersed in the dispersion, and the loss value before and after the copper sheet is weighed is the copper consumption value).
  • Table 1 The results are shown in Table 1 below.
  • the silica of Examples 1 to 4 of the present invention has a light transmittance ⁇ 90% in the range of refractive index 1.448 to 1.460, and a copper consumption value ⁇ 15 mg, but not exceeding 20 mg, suggesting that the silica of the present invention has high It has the characteristics of high light transmittance under refractive index, and has excellent friction and cleaning performance. It is used in low water/anhydrous toothpaste formulations, which not only gives toothpaste a transparent and clear appearance, but also gives toothpaste good oral cleaning performance.
  • Comparative Example 1 reduces the modulus and concentration of the sodium silicate solution, and its light transmittance is significantly reduced; Comparative Example 2 increases the concentration of the sodium silicate solution, and its light transmittance The ratio decreased significantly, and the copper consumption value increased significantly; Comparative Example 3 reduced the concentration of the sulfuric acid solution, its light transmittance gradually decreased in the range of 1.448 to 1.460, and the copper consumption value also decreased; Comparative Example 4 increased Concentration of sodium sulfate solution, as a result, not only the light transmittance of silica gradually decreased, but also the copper consumption value increased; Comparative Example 5 increased the reaction pH value, and its light transmittance and copper consumption value decreased; Comparative Example 6 increased When the stirring speed is increased, the light transmittance is obviously reduced, and the copper consumption value is increased. It is suggested that each parameter and step in the preparation method of the present invention complement each other, thereby preparing silica for high friction and high transparency toothpaste.
  • Test Example 2 Application effect of silica for high friction and transparent toothpaste of the present invention
  • the silica for high-friction high-transparency toothpaste of Examples 1 to 4 of the present invention is applied to a low-water/anhydrous toothpaste to prepare toothpastes 1 to 4, respectively.
  • the specific formula of anhydrous toothpaste is as follows (mass percentage): Example silica 15%, thickened silica 5%, sorbitol 62%, polyethylene glycol 8%, carboxymethyl cellulose 0.6%, carrageenan Gum 0.4%, saccharin 0.2%, sodium benzoate 0.2%, color 0.2%, flavor 1%, sodium lauryl sulfate 2% and water 5.4%.
  • the above toothpaste was tested according to GB/T 8372 toothpaste standard.
  • the appearance of the paste was smooth and delicate, crystal clear, high transparency, pH value was 7.4, and the consistency was moderate, 14mm.
  • the main test index results all met the requirements of toothpaste standards.

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Abstract

提供一种高磨擦高透明牙膏用二氧化硅及其制备方法。方法包括S1、往反应罐中加入硫酸钠溶液，升温至60~65℃；S2、搅拌下加入硅酸钠溶液后升温至60~65℃，滴加硫酸溶液，当pH值为8.5~9.5时，停止加酸，陈化；S3、同时加入硅酸钠溶液和硫酸溶液进行反应，控制过程pH值为8.0~9.0，硅酸钠溶液添加完毕后，继续滴加硫酸溶液至pH值为4.5~5.0；S4、将形成的二氧化硅进行压滤，洗涤，喷雾干燥，气流破碎，得到二氧化硅。该方法得到的二氧化硅在折光率1.448~1.460下透光率≥90%，铜耗值≥15mg，同时具备高折光率下高透光率和高磨擦清洁性能。

Description

一种高磨擦高透明牙膏用二氧化硅及其制备方法 技术领域
本发明属于牙膏用二氧化硅技术领域，具体涉及一种高磨擦高透明牙膏用二氧化硅及其制备方法。
背景技术
近年来，透明牙膏越来越受到人们的青睐，尤其是高磨擦清洁性的透明型牙膏，其既具有晶莹剔透、色泽鲜艳的外观，又具有美白牙齿的功效，深受消费者的喜爱。同时随着社会的进步，牙膏的品种、档次和技术含量也不断提高，一些特殊功能性原料，如生物活性玻璃、过氧化物、双氧水和益生菌等也开始加入到牙膏产品中。这些特殊功能性原料遇水溶解后发生水解或发生变化，导致功能性原料失效或牙膏胀气，如过氧化物、双氧水和小苏打等。因此，为了满足这些特殊功能原料在牙膏配方中的应用要求，需要少水/无水的透明牙膏配方。
目前，二氧化硅是球状的多孔结构，没有尖锐的棱角不会过多的磨损牙齿，且具有物理化学性质稳定、清洁能力强、与牙膏体系相容性好、能用于透明牙膏的制备等特点，目前已被广泛应用于牙膏行业中。一般来说，普通二氧化硅的铜耗值在2.0mg以内；中等磨擦型二氧化硅的铜耗值在2.0～10.0mg之间；高磨擦型二氧化硅的铜耗值则大于10.0mg，一般不超过20.0mg为宜，否则易磨损牙釉质。然而二氧化硅的磨擦清洁力与透光率是对立的两个因素，一般的二氧化硅结构越密实，磨擦力越好，透光率越差，因此，透光率高的二氧化硅磨擦值低，清洁效果不佳，而高磨擦值的二氧化硅透光率较低，不能很好地应用，即使同时具有高透光率(透光率为90％以上)和高磨擦(铜耗值为10mg以上)的二氧化硅，但其折光率(约为1.4425)低，应用于无水牙膏配方后只能做成半透明牙膏。
要制作透明牙膏，必须使膏体的液相体系和固相体系的折光率相接近，甚至达到了一致。少水/无水牙膏液相体系的主要成分为润湿剂，而山梨醇、聚乙二醇和甘油均属于常用的润湿剂。一般来说，二氧化硅折光率在1.4350～1.4600范围内，而70％山梨醇折光率为1.457，聚乙二醇的折光率为1.46。通过调节各润湿剂的比例使液相与固相的折光率一致，从而达到透明效果。除了折光率以外，二氧化硅的透光率也非常重要，一般要求在90％以上。只要同时具备以上两项条件，就不会产生漫反射，从而形成透明度好的膏体。因此，二氧化硅在折光率1.46以上的透光率必须大于90％，才可制备少水/无水透明牙膏。
如专利文献CN105776230A公开了一种洁齿透明牙膏用二氧化硅的制备方法，其该方法包括(1)配置25～28wt％的碳酸钠溶液，然后加入1.6～2.2M的硅酸钠溶液中，得到混合液；(2)往反应釜中加入11.0～15.0wt％的硫酸钠溶液4～8m 3，加热至70～80℃，搅拌下同时滴加2.5～3.2M硅酸钠溶液(模数为3.3～3.45)3～5m 3和10.0～12.0M的硫酸溶液，保持过程pH为7.5～9.5，硅酸钠溶液滴加完毕后，继续滴加硫酸溶液至pH为6.0～7.0，搅拌10～15min；(3)往上述反应釜中继续加入水4～6m 3，加热至70～80℃，搅拌下同时滴加所述混合液8～10m 3和10.0～12.0M的硫酸溶液，保持过程pH为5.5～7.5，混合液滴加完毕后，控制反应终点pH为6.0～7.0，搅拌10～15min，压滤，洗涤，喷雾干燥、气流破碎，得到二氧化硅。该二氧化硅既有高的磨擦清洁值性和透光率，又具有增稠作用，但是该二氧化硅属于在低折光率(1.4300～1.4400)下具备高透明性，仅适合应用于含水量为16～21％的透明牙膏中，并且其铜耗值约为6～8mg，属于中等磨擦型二氧化硅。
又如专利文献CN107792861A公开了一种低折光率高透明磨擦型二氧化硅的制备方法，该方法包括(1)往反应罐中加入硫酸钠溶液11～13m 3，加热至80～95℃，搅拌下同时滴加硅酸钠溶液8.5～12m 3(模数为2.5～3.0)和4.0～5.0M硫酸溶液，控制硫酸溶液的滴加速度以保证反应过程pH值为3.0～4.5，滴加完毕后继续搅拌10～15min；(2)将形成的二氧化硅进行压滤、洗涤，喷雾干燥、气流粉碎，制得二氧化硅。该制备方法简单，且其二氧化硅在折光率1.438～1.450范围内的透光率可达95％以上，具备低折光率下高透光率的特性，同样只适合应用于含水透明牙膏中，同时该二氧化硅的铜耗值偏低，在5mg以下，磨擦清洁性欠佳。
综上所述，生产一种高磨擦、高折光、高透明牙膏用二氧化硅是非常必要的。
发明内容
为了解决现有技术中存在的问题(如现有二氧化硅在折光率1.450以上的透光率低于85％、且其铜耗值偏低)等，本发明首先提供了一种高磨擦高透明牙膏用二氧化硅的制备方法，该方法通过两步水热沉淀法，严格控制物料浓度和反应温度及pH值，制得了在折光率1.448～1.460下透光率≥90％，铜耗值≥15mg，同时具备高折光率下高透光率和高磨擦清洁性能的二氧化硅。
本发明提供的高磨擦高透明牙膏用二氧化硅的制备方法，包括以下步骤：
S1、往反应罐中加入硫酸钠溶液13～15m 3，开启搅拌，升温至60～65℃；
S2、搅拌下加入硅酸钠溶液3～5m 3，硅酸钠溶液加入完毕后，升温至60～65℃，开始 滴加硫酸溶液，当pH值为8.5～9.5时，停止加酸，控制加酸时间为20～30min，接着陈化10min；
S3、同时加入硅酸钠溶液11～12m 3和硫酸溶液进行并流中和反应，控制过程pH值为8.0～9.0，硅酸钠溶液添加完毕后，继续滴加硫酸溶液至pH值为4.5～5.0，停止加酸，搅拌10min；
S4、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为8～12μm，得到高磨擦高透明牙膏用二氧化硅。
进一步地，所述硫酸钠溶液的质量百分比浓度为4.0～6.0％。
进一步地，所述硅酸钠溶液的模数为3.4～3.5，浓度为1.5～2.0mol/L。
进一步地，所述硫酸溶液的浓度为14～16mol/L。
进一步地，所述步骤S3中，硅酸钠溶液的加入流速为14～15m 3/h。
进一步地，所述搅拌的转速为35～40Hz。
相应地，本发明还提供了由上述的高磨擦高透明牙膏用二氧化硅的制备方法所制得的二氧化硅，该二氧化硅在折光率1.448～1.460下透光率≥90％，铜耗值≥15mg，适合应用于少水或无水的透明牙膏配方中，为过氧化物、双氧水和益生菌等特殊功能性原料提供了一个合适的牙膏体系，同时提高了透明牙膏的品质。
本发明高磨擦高透明牙膏用二氧化硅的制备方法的反应机理如下：
本发明采用两步水热沉淀法，以模数为3.4～3.5的硅酸钠溶液以及浓度为14～16mol/L的浓硫酸作为反应原料，第一步，以硫酸钠溶液作为反应助剂，通过酸滴碱的加料方式，直接使用浓硫酸反应，在高速搅拌及相对较低的反应温度下，使得初始疏松的凝胶粒子快速形成，这一步反应生成的晶种折光率高，对应的透光率也高，在此基础上继续进行第二步酸碱同滴；在第二步酸碱同滴的过程中，随着浓硫酸的加入，体系持续放热，使得同滴的反应体系温度可以维持在85～95℃的高温，同时在体系pH值为8.0～9.0下，晶种继续生长，二氧化硅在保持高透光率的同时结构变得致密，磨擦性能获得有效提高。因此，通过采用两种不同的反应方式，使二氧化硅兼备高折光率下高透光率和高磨擦清洁性能。
因此，与现有技术相比，本发明的优势在于：
(1)本发明高磨擦高透明牙膏用二氧化硅的制备方法采用同一种模数和浓度的硅酸钠溶液和硫酸溶液参与反应，工艺简单、稳定，条件易控，并且直接使用浓硫酸反应，利用浓硫酸持续放热达到反应所需的温度，节约了能耗，且获得了在高折光率下透光率高和磨擦清洁性能强的二氧化硅。
(2)本发明高磨擦高透明牙膏用二氧化硅在折光率1.448～1.460下透光率≥90％，铜耗值≥15mg，适合应用于少水/无水透明牙膏配方中，为过氧化物、双氧水和益生菌等特殊功能性原料提供了一个合适的牙膏体系，同时提高了透明牙膏的品质，具有广泛的应用前景。
具体实施方式
下面将结合具体实施例来详细说明本发明，在此本发明的示意性实施例以及说明用来解释本发明，但并不作为对本发明的限定。
实施例1、本发明高磨擦高透明牙膏用二氧化硅及其制备方法
S1、往反应罐中加入质量百分比浓度为4.0％的硫酸钠溶液13m 3，开启搅拌，控制转速为35Hz，升温至60℃；
S2、搅拌下加入硅酸钠溶液3m 3，硅酸钠溶液加入完毕后，升温至60℃，开始滴加硫酸溶液，当pH值为8.5时，停止加酸，控制加酸时间为20min，接着陈化10min；
S3、同时加入硅酸钠溶液11m 3和硫酸溶液进行并流中和反应，控制硅酸钠溶液的加入流速为14m 3/h，并且通过调节硫酸溶液的流速以控制过程pH值为8.0，硅酸钠溶液添加完毕后，继续滴加硫酸溶液至pH值为4.5，停止加酸，搅拌10min；
S4、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为10μm，得到高磨擦高透明牙膏用二氧化硅。
所述硅酸钠溶液的模数为3.4，浓度为1.5mol/L；所述硫酸溶液的浓度为14mol/L。
实施例2、本发明高磨擦高透明牙膏用二氧化硅及其制备方法
S1、往反应罐中加入质量百分比浓度为6.0％的硫酸钠溶液15m3，开启搅拌，控制转速为40Hz，升温至65℃；
S2、搅拌下加入硅酸钠溶液5m 3，硅酸钠溶液加入完毕后，升温至65℃，开始滴加硫酸溶液，当pH值为9.5时，停止加酸，控制加酸时间为30min，接着陈化10min；
S3、同时加入硅酸钠溶液12m 3和硫酸溶液进行并流中和反应，控制硅酸钠溶液的加入流速为15m 3/h，并且通过调节硫酸溶液的流速以控制过程pH值为9.0，硅酸钠溶液添加完毕后，继续滴加硫酸溶液至pH值为5.0，停止加酸，搅拌10min；
S4、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为10μm，得到高磨擦高透明牙膏用二氧化硅。
所述硅酸钠溶液的模数为3.5，浓度为2.0mol/L；所述硫酸溶液的浓度为16mol/L。
实施例3、本发明高磨擦高透明牙膏用二氧化硅及其制备方法
S1、往反应罐中加入质量百分比浓度为5.0％的硫酸钠溶液14m 3，开启搅拌，控制转速为40Hz，升温至60℃；
S2、搅拌下加入硅酸钠溶液4m 3，硅酸钠溶液加入完毕后，升温至65℃，开始滴加硫酸溶液，当pH值为9.0时，停止加酸，控制加酸时间为25min，接着陈化10min；
S3、同时加入硅酸钠溶液11m 3和硫酸溶液进行并流中和反应，控制硅酸钠溶液的加入流速为14m 3/h，并且通过调节硫酸溶液的流速以控制过程pH值为8.0，硅酸钠溶液添加完毕后，继续滴加硫酸溶液至pH值为4.5，停止加酸，搅拌10min；
S4、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为10μm，得到高磨擦高透明牙膏用二氧化硅。
所述硅酸钠溶液的模数为3.4，浓度为1.8mol/L；所述硫酸溶液的浓度为15mol/L。
实施例4、本发明高磨擦高透明牙膏用二氧化硅及其制备方法
S1、往反应罐中加入质量百分比浓度为5.0％的硫酸钠溶液13m 3，开启搅拌，控制转速为40Hz，升温至65℃；
S2、搅拌下加入硅酸钠溶液4m 3，硅酸钠溶液加入完毕后，升温至65℃，开始滴加硫酸溶液，当pH值为9.5时，停止加酸，控制加酸时间为30min，接着陈化10min；
S3、同时加入硅酸钠溶液11m 3和硫酸溶液进行并流中和反应，控制硅酸钠溶液的加入流速为15m 3/h，并且通过调节硫酸溶液的流速以控制过程pH值为9.0，硅酸钠溶液添加完毕后，继续滴加硫酸溶液至pH值为4.5，停止加酸，搅拌10min；
S4、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为10μm，得到高磨擦高透明牙膏用二氧化硅。
所述硅酸钠溶液的模数为3.4，浓度为1.5mol/L；所述硫酸溶液的浓度为16mol/L。
对比例1
与实施例3相比，本对比例的区别仅在于：硅酸钠溶液的模数为3.0，浓度为1.2mol/L。
对比例2
与实施例3相比，本对比例的区别仅在于：硅酸钠溶液的模数为3.4，浓度为2.5mol/L。
对比例3
与实施例3相比，本对比例的区别仅在于：硫酸溶液的浓度为8mol/L。
对比例4
与实施例3相比，本对比例的区别仅在于：硫酸钠溶液的重量百分比浓度为7％。
对比例5
与实施例3相比，本对比例的区别仅在于：步骤S3中控制过程pH值为9.5。
对比例6
与实施例3相比，本对比例的区别仅在于：开启搅拌后，控制转速为45Hz。
试验例一、本发明高磨擦高透明牙膏用二氧化硅的性能检测
对本发明实施例1～4、对比例1～6制得的二氧化硅在折光率1.448～1.460范围内的透光率及铜耗值(铜耗值的测定方法：将二氧化硅分散于70％的山梨醇，实验室过硬颗粒测定仪在浸没了分散液的铜片上来回磨擦9999次，最后称量铜片磨擦前后的损耗值即为铜耗值)进行检测，结果见下表1。
表1各二氧化硅的性能检测结果
Figure PCTCN2019092327-appb-000001
Figure PCTCN2019092327-appb-000002
由上表1可知：
(1)本发明实施例1～4二氧化硅在折光率1.448～1.460范围内的透光率≥90％，且铜耗值≥15mg，但不超过20mg，提示本发明二氧化硅既具有高折光率下透光率高的特性，又具有优异的磨擦清洁性能，应用于少水/无水牙膏配方中，不仅为牙膏带来透明清亮的外观，同时也赋予牙膏良好的口腔清洁性能。
(2)与本发明实施例3相比，对比例1降低了硅酸钠溶液的模数和浓度，其透光率明显降低；对比例2则提高了硅酸钠溶液的浓度，其透光率明显下降，且铜耗值则大幅升高；对比例3降低了硫酸溶液的浓度，其透光率在折光率1.448～1.460范围内逐步降低，铜耗值也有所降低；对比例4提高了硫酸钠溶液的浓度，结果其二氧化硅不仅透光率逐步下降，并且铜耗值提高；对比例5提高了反应pH值，其透光率和铜耗值均有所下降；对比例6提高了搅拌速度，其透光率明显降低，铜耗值升高。提示本发明制备方法中各参数与步骤相辅相成，从而制备得到高磨擦高透明牙膏用二氧化硅。
试验例二、本发明高磨擦高透明牙膏用二氧化硅的应用效果
将本发明实施例1～4的高磨擦高透明牙膏用二氧化硅应用于少水/无水牙膏中，分别制得牙膏1～4。无水牙膏的具体配方如下(质量百分比)：实施例二氧化硅15％、增稠型二氧化硅5％、山梨醇62％、聚乙二醇8％、羧甲基纤维素0.6％、卡拉胶0.4％、糖精0.2％、苯甲酸钠0.2％、色素0.2％、香精1％、十二烷基硫酸钠2％和水5.4％。
按GB/T 8372牙膏标准对上述牙膏进行检测，膏体外观幼滑细腻，晶莹剔透、透明度高，pH值为7.4，稠度适中，为14mm，主要检测指标结果均符合牙膏标准的要求。
其中，各牙膏的透视程度如下表2所示。
表2各牙膏透明度检测结果
Figure PCTCN2019092327-appb-000003
Figure PCTCN2019092327-appb-000004
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (7)

  1. 一种高磨擦高透明牙膏用二氧化硅的制备方法，其特征在于，包括以下步骤：
    S1、往反应罐中加入硫酸钠溶液13～15m 3，开启搅拌，升温至60～65℃；
    S2、搅拌下加入硅酸钠溶液3～5m 3，硅酸钠溶液加入完毕后，升温至60～65℃，开始滴加硫酸溶液，当pH值为8.5～9.5时，停止加酸，控制加酸时间为20～30min，接着陈化10min；
    S3、同时加入硅酸钠溶液11～12m3和硫酸溶液进行并流中和反应，控制过程pH值为8.0～9.0，硅酸钠溶液添加完毕后，继续滴加硫酸溶液至pH值为4.5～5.0，停止加酸，搅拌10min；
    S4、将形成的二氧化硅进行压滤，洗涤，通过喷雾干燥后气流破碎至粒径为8～12μm，得到高磨擦高透明牙膏用二氧化硅。
  2. 根据权利要求1所述的高磨擦高透明牙膏用二氧化硅的制备方法，其特征在于，所述硫酸钠溶液的质量百分比浓度为4.0～6.0％。
  3. 根据权利要求1所述的高磨擦高透明牙膏用二氧化硅的制备方法，其特征在于，所述硅酸钠溶液的模数为3.4～3.5，浓度为1.5～2.0mol/L。
  4. 根据权利要求1所述的高磨擦高透明牙膏用二氧化硅的制备方法，其特征在于，所述硫酸溶液的浓度为14～16mol/L。
  5. 根据权利要求1所述的高磨擦高透明牙膏用二氧化硅的制备方法，其特征在于，所述步骤S3中，硅酸钠溶液的加入流速为14～15m 3/h。
  6. 根据权利要求1所述的高磨擦高透明牙膏用二氧化硅的制备方法，其特征在于，所述搅拌的转速为35～40Hz。
  7. 根据权利要求1～6任一项所述的高磨擦高透明牙膏用二氧化硅的制备方法所制得的二氧化硅，其特征在于，所述二氧化硅在折光率1.448～1.460下透光率≥90％，铜耗值≥15mg。
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