CN114931540B

CN114931540B - Carboxymethyl bagasse-containing composite material and preparation method and application thereof

Info

Publication number: CN114931540B
Application number: CN202210631430.8A
Authority: CN
Inventors: 宁科功; 张秋林; 高峰; 郭家文; 刘萍; 蔡英; 尚慧; 潘波
Original assignee: Yunnan Baiyao Group Health Products Co ltd; Kunming University of Science and Technology; Institute of Agricultural Environment and Resources of Yunnan Academy of Agricultural Sciences; Sugarcane Research Institute of Yunnan Academy of Agricultural Sciences
Current assignee: Yunnan Baiyao Group Health Products Co ltd; Kunming University of Science and Technology; Institute of Agricultural Environment and Resources of Yunnan Academy of Agricultural Sciences; Sugarcane Research Institute of Yunnan Academy of Agricultural Sciences
Priority date: 2022-06-06
Filing date: 2022-06-06
Publication date: 2023-07-14
Anticipated expiration: 2042-06-06
Also published as: CN114931540A

Abstract

The embodiment of the invention discloses a composite material containing carboxymethylated bagasse as well as a preparation method and application thereof. The preparation method comprises the following steps: adding sodium chloroacetate aqueous solution into bagasse to carry out carboxymethylation reaction, adding calcium hydroxide to adjust the pH value to be alkaline after the reaction is finished, adding a carbonate ion source/a phosphate ion source until calcium ions in the system are completely converted into calcium carbonate/calcium phosphate salt, and carrying out centrifugal separation, drying and grinding to obtain the carboxymethylated bagasse composite material. The composite material containing the carboxymethylated bagasse fully plays the advantages of the bagasse, has the biocompatibility of an inorganic material, and can replace calcium carbonate or calcium phosphate inorganic salt to be used as a toothpaste abrasive and/or a tooth desensitizer.

Description

Carboxymethyl bagasse-containing composite material and preparation method and application thereof

Technical Field

The embodiment of the invention relates to the technical field of daily chemicals, oral medical treatment, nursing and cleaning products, in particular to a carboxymethyl bagasse-containing composite material, and a preparation method and application thereof.

Background

Toothpaste generally uses calcium carbonate and calcium phosphate inorganic salt as abrasive materials. Wherein, the calcium carbonate is the most widely existing inorganic material in nature, is also the main component of bones and shells of aquatic animals, has good biocompatibility, and is used as an abrasive for toothpaste and dentifrice and a tooth desensitizer in the field of oral care. The performance of calcium carbonate is directly related to the crystal form and morphology, natural calcium carbonate ore is generally calcite type crystal and has a hexahedral structure, even if the calcium carbonate is processed by adopting a physical crushing process, the calcium carbonate is still of an irregular hexahedral structure, the hardness of microscopic particles is high, and the calcium carbonate ore has a certain abrasion risk to enamel after long-term use.

The calcium phosphate inorganic solid particles and the hydrate thereof are toothpaste abrasive materials with the best taste and biocompatibility, the element compositions of calcium hydrophosphate dihydrate, tricalcium phosphate and hydroxyapatite are similar to the element compositions of enamel surface elements, and the toothpaste prepared by adopting the abrasive materials has unique and fine taste and outstanding performance in the aspects of enamel remineralization and dentin anti-sensitivity. However, the production cost of the calcium phosphate inorganic solid particles is relatively high, and the solid particles directly prepared by a precipitation method are large in particle size, so that the cleaning effect of the calcium phosphate inorganic solid particles on tooth gaps is prevented, the calcium phosphate inorganic solid particles are prevented from entering dentinal tubules, and the anti-sensitivity performance of the calcium phosphate abrasive is reduced. In addition, the slightly soluble calcium phosphate inorganic matters can cause eutrophication pollution to water bodies.

Therefore, how to develop an abrasive and/or tooth desensitizer that can replace calcium carbonate or calcium phosphate inorganic salts is a technical problem to be solved in the art.

Disclosure of Invention

Bagasse is a solid organic waste after sugar production of sugarcane, and is commonly used for fuel power generation, papermaking, cellulose extraction, xylitol preparation and the like, and deep processing of bagasse in the processes often causes secondary pollution, so that the requirements of energy conservation, emission reduction and carbon neutralization are difficult to realize. Bagasse mainly comprises lignin, cellulose and hemicellulose, and is harmless to human body. Lignin has certain antibacterial and antiviral properties, and edible cellulose can help digestion, and hemicellulose polysaccharide is a good prebiotic; the lignin in the bagasse wraps the cellulose and hemicellulose to form a bundle-shaped fiber structure with certain strength; the dried bagasse is easy to absorb water and swell in water at normal temperature, and the volume is increased.

Since Lignin, cellulose, hemicellulose and the like are often connected with each other in nature to form a Lignin-carbohydrate complex (Lignin-Carbohydrate Complex), no method is available at present to separate and obtain original Lignin with completely undamaged structure. From the aspect of materials science, bagasse is a material with certain mechanical rigidity (lignin) and elasticity (cellulose), and if the bagasse is directly used for toothpaste, the bagasse has poor using taste due to poor compatibility of surface organic matter composition and inorganic materials on the tooth surface.

Because active groups such as aryl, phenolic hydroxyl, alcoholic hydroxyl, carbon-based conjugated double bonds and the like exist in the molecular structure of lignin, oxidation, reduction, hydrolysis, alcoholysis, acidolysis, methoxy, carboxyl, photolysis, phthalation, sulfonation, alkylation, halogenation, nitration, polycondensation or graft copolymerization and the like can be performed, and powerful conditions are provided for modifying lignin.

The reaction of cellulose with monochloroacetic acid to produce carboxymethyl cellulose with different substitution degree is a mature technology, and carboxymethyl cellulose is a common thickener in toothpaste. The lignin and cellulose in bagasse are difficult to differentiate, but the lignin and cellulose are nontoxic to human bodies and have hydroxyl ends with similar structures, and the bagasse-acetic ether structure formed by monochloroacetic acid, lignin, cellulose and hemicellulose in bagasse can enable the hydroxyl ends on the surface of the bagasse to be carboxylated, and the carboxyl is negatively charged and can adsorb calcium ions.

In order to fully exert the application of bagasse in toothpaste, reduce environmental pollution and improve the biocompatibility and taste problem of bagasse in toothpaste application, the invention adopts chloroacetic acid to convert hydroxyl groups on the surface of bagasse into carboxyl groups, utilizes negative charges of carboxyl ends to absorb calcium ions with positive charges, and then respectively reacts with the calcium ions by using carbonates or phosphates with better biocompatibility to form carboxymethylated bagasse/calcium carbonate, or carboxymethylated bagasse/calcium phosphate core-shell composite material, so that the material fully exerts the advantages of bagasse and simultaneously has the biocompatibility of inorganic materials.

Specifically, the embodiment of the invention provides the following technical scheme:

according to a first aspect of the embodiment of the invention, the embodiment of the invention provides a preparation method of a composite material containing carboxymethyl bagasse, which comprises the steps of adding sodium chloroacetate aqueous solution into bagasse to carry out carboxymethylation reaction, adding calcium hydroxide to adjust the pH value to be alkaline after the reaction is finished, adding a carbonate ion source/phosphate ion source until calcium ions in a system are completely converted into calcium carbonate/phosphate calcium salt, and then carrying out centrifugal separation, drying and grinding to obtain the composite material containing carboxymethyl bagasse.

In the invention, the concentration of the sodium chloroacetate aqueous solution is 0.1-80%, and the mass volume ratio of bagasse to the sodium chloroacetate aqueous solution is 1:3 to 50.

In the invention, the sodium chloroacetate aqueous solution is added in a dropwise manner, and the dropwise speed is 3-5 drops/s.

In the invention, the temperature of the carboxymethylation reaction is 35-80 ℃ and the time is 1-3 h.

In the invention, the pH value is 7.5-9.

In the invention, the carbonate ion source is selected from one or more of sodium carbonate, sodium bicarbonate, dimethyl carbonate and carbon dioxide.

In the invention, the phosphate ion source is selected from one or more of trisodium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammine hydrogen phosphate and phosphorus pentoxide.

In the invention, the calcium phosphate salt is selected from one or more of tricalcium phosphate, calcium hydrophosphate and hydroxyapatite.

In the invention, the particle size of the composite material containing the carboxymethyl bagasse is 0.1-100 microns.

In the invention, the bagasse preparation method comprises the following steps: the sugar cane is squeezed, ball milled by adding water until the leaching liquid is clear and transparent, sieving with a water sieve with more than 40 meshes, removing large particles, drying the undersize and jet milling to obtain powder with the particle size of 0.1-50 microns.

According to a second aspect of embodiments of the present invention, there is provided a carboxymethylated bagasse-containing composite material, which is produced by the production process as described above.

According to a third aspect of embodiments of the present invention there is provided the use of a carboxymethylated bagasse-containing composite as described above as at least one of an abrasive, an anti-sensitization ingredient in an oral care implement.

In the present invention, the oral care product is a toothpaste, a dentifrice or a tooth desensitizing agent.

According to a fourth aspect of embodiments of the present invention there is provided a toothpaste comprising a carboxymethylated bagasse-containing composite material as described above.

In the invention, the composite material containing the carboxymethylated bagasse accounts for 0.1-70% of the mass of the toothpaste, and is preferably 10-70%.

In the invention, the toothpaste further comprises at least one of humectant, adhesive, abrasive, essence, preservative, sweetener, foaming agent and water.

Wherein the humectant is humectant conventionally used in the art, such as glycerin, sorbitol, sodium hyaluronate, etc.; the binder is a binder conventionally used in the art, such as xanthan gum, carrageenan, sodium carboxymethyl cellulose, sodium hydroxyethyl cellulose, carbomer, etc.; the abrasive is an abrasive conventionally used in the art, such as calcium carbonate, calcium phosphate salts, silica, and the like; the essence is of a type conventionally used in the art, such as peppermint type, spearmint type, wintergreen type, fruit type, tea type, medicinal type and the like; the preservative is a preservative conventionally used in the art, such as sodium benzoate, parabens, and the like; the sweetener is a sweetener conventionally used in the art, such as sorbitol, xylitol, sodium saccharin, and the like. The foaming agent is a foaming agent conventionally used in the art, such as sodium lauryl sulfate, sodium lauroyl sarcosinate, and the like.

In one embodiment of the present invention, when the toothpaste is abrasive with the carboxymethylated bagasse-containing composite, the toothpaste comprises the following components in weight percent: 1-70% of sorbitol; cellulose gum 0.3-2%; 0.1 to 2 percent of xanthan gum; 0.1 to 2 percent of carrageenan; glycerol 1-50%; 0.1 to 70 percent of composite material containing carboxymethyl bagasse; essence, preservative, sweetener, foaming agent and water are added in 100%.

In another embodiment of the invention, when the toothpaste is part of an abrasive material comprising the carboxymethylated bagasse composite material, the toothpaste comprises the following components in weight percent: 15% -80% of humectant (glycerin, sorbitol and mixture thereof in any proportion); 0.4 to 3 percent of adhesive (xanthan gum, carrageenan, sodium carboxymethyl cellulose, hydroxyethyl cellulose sodium, carbomer and any mixture thereof); 7% -60% of abrasive (at least one of calcium carbonate, calcium phosphate salt and silicon dioxide is included in addition to the carboxymethyl bagasse composite material); essence, preservative, sweetener, foaming agent and water are added in 100%.

In yet another embodiment of the present invention, when the dental anti-sensitivity toothpaste is based on the carboxymethylated bagasse-containing composite as an abrasive and an anti-sensitivity component, the dental anti-sensitivity toothpaste comprises the following components in weight percent: 15% -80% of humectant (glycerin, sorbitol and mixture thereof in any proportion); 0.4 to 3 percent of adhesive (xanthan gum, carrageenan, sodium carboxymethyl cellulose, hydroxyethyl cellulose sodium, carbomer and any mixture thereof); 7% -60% of abrasive (at least one of calcium carbonate, calcium phosphate salt and silicon dioxide is included in addition to the carboxymethyl bagasse composite material); potassium nitrate 0.5-7%; essence, preservative, sweetener, foaming agent and water are added in 100%.

The embodiment of the invention has the following advantages:

1. the carboxymethyl bagasse-containing composite material prepared by taking bagasse as a raw material fully plays the advantages of bagasse, has the biocompatibility of an inorganic material, and can replace calcium carbonate or calcium phosphate inorganic salt as a toothpaste abrasive and/or a tooth desensitizer.

2. The bagasse is applied to the oral care products, so that the anti-inflammatory and antibacterial properties of lignin can be fully exerted, and natural and safe antibacterial and antiviral properties are provided for the oral care products; the carbon neutralization is truly realized, and other toxic chemical substances are not required to be introduced; the carbon captured by the sugarcane from the air is stored in the oral care product for a long time, so that the release period of the carbon is delayed.

3. The preparation method provided by the invention has the advantages of simple and convenient operation of steps, simple process flow, great reduction of cost and contribution to industrial production.

Detailed Description

Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The test methods used in the examples are regarded as conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.

Abrasive calcium carbonate: particle size 5-70 microns, manufacturer: guangxi Ruiyun;

abrasive monocalcium phosphate: particle size 5-100 microns, manufacturer: and (5) creating in the Yunnan Tian.

In the following examples and comparative examples, bagasse was prepared as follows: after sugar is squeezed from sugarcane, 15 times of water is added for 5 times, ball milling is carried out for 3 hours at the rotating speed of 200r/min until the leaching solution is clear and transparent, sieving is carried out through a water sieve with more than 40 meshes, large particles are removed, and the undersize is dried and crushed by air flow, thus obtaining powder with the particle size of 0.1-50 microns.

Example 1

The preparation method of the carboxymethylated bagasse/calcium carbonate composite material provided by the embodiment is as follows:

1) 100g of sugar cane slag powder is weighed and placed in a 5000ml round-bottom flask, 2L of 20 percent sodium chloroacetate solution is dripped into the round-bottom flask at the speed of 3 to 5 drops/s by using a dripping funnel, after the dripping is finished, the temperature of a water bath kettle is adjusted to 75 ℃, and the mixture is stirred for 2.0h,

2) Dropwise adding 0.1% calcium hydroxide solution until the pH value is between 7.5 and 9 to obtain carboxymethyl calcified bagasse, adding 35g of sodium carbonate, and stirring for 20min;

3) Centrifuging for 20min at a rotating speed of 1000r/min, drying the obtained solid in a drying oven at 105 ℃ for 2h, grinding, and sieving with a 80-mesh sieve to obtain the carboxymethylated bagasse/calcium carbonate composite material.

Example 2

1) Weighing 100g of sugarcane slag powder, placing the sugarcane slag powder into a round 5L bottom flask, sequentially dripping 2L of 35% sodium chloroacetate solution into the round bottom flask at a speed of 3-5 drops/s by using a dropping funnel, adjusting the temperature of a water bath kettle to 70 ℃ after the dripping is finished, and stirring for 3 hours;

2) Titrating with 0.1% calcium hydroxide solution until ph=7.5-9 after the reaction is finished to obtain carboxymethyl calcified bagasse;

3) Adding 50g of sodium carbonate into the carboxymethyl calcified bagasse in the step 2), stirring for 30min, centrifuging the reaction product at a rotating speed of 1000r/min for 10min, drying the obtained solid in a drying oven at 105 ℃ for 2h, grinding, and sieving with a 100-mesh sieve to obtain the carboxymethyl bagasse/calcium carbonate composite material.

Example 3

The preparation method of the composite material containing the carboxymethyl bagasse provided by the embodiment comprises the following steps:

1) Weighing 100g of sugarcane slag powder, placing the sugarcane slag powder into a 5L round-bottom flask, sequentially dripping 2L of 45% sodium chloroacetate solution into the round-bottom flask at a speed of 3-5 drops/s by using a dropping funnel, adjusting the temperature of a water bath kettle to 80 ℃ after dripping is finished, and stirring for 3 hours;

2) After the reaction is finished, dropwise adding 0.1% calcium hydroxide solution to the pH=8 to obtain carboxymethyl calcified bagasse;

3) Adding 200g of trisodium phosphate into the carboxymethyl calcified bagasse in the step 2), stirring for 50min, centrifuging the reaction product at a rotating speed of 1000r/min for 10min, drying the obtained solid in a drying oven at 105 ℃ for 2h, grinding, and sieving with a 100-mesh sieve to obtain the carboxymethyl bagasse/calcium phosphate composite material.

Example 4

1) Weighing 100g of sugarcane slag powder, placing the sugarcane slag powder into a 5L round-bottom flask, sequentially dripping 60% sodium chloroacetate solution into the round-bottom flask at a speed of 3-5 drops/s by using a dropping funnel, regulating the temperature of a water bath kettle to 45 ℃ after the dripping is finished, and stirring for 5 hours;

2) CaCl was added to the flask ₂ 110g of the mixture is continuously stirred for 1h to obtain carboxymethyl calcified bagasse;

3) Adding 135g of monopotassium phosphate into the carboxymethyl calcified bagasse in the step 2), stirring for 90min, centrifuging the reaction product for 20min at the rotating speed of 1000r/min, drying the obtained solid in a drying oven at 105 ℃ for 2h, grinding, and sieving with a 100-mesh sieve to obtain the carboxymethyl bagasse/calcium phosphate composite material.

Example 5

The embodiment provides toothpaste, which comprises the following components in percentage by weight:

20% of the carboxymethylated bagasse/calcium carbonate composite material of the example 1, 5% of silicon dioxide, 35% of glycerol, 15% of sorbitol, 0.3% of xanthan gum, 0.5% of carrageenan, 0.5% of sodium carboxymethyl cellulose, 1.5% of peppermint flavor, 0.5% of sodium benzoate, 0.3% of saccharin sodium, 2% of sodium lauryl sulfate and the balance of water.

The preparation method of the toothpaste comprises the following steps:

1) Adding water, sodium benzoate, saccharin sodium and sorbitol into water phase pot of homogenizing emulsifying equipment, stirring to dissolve;

2) Adding glycerol into an oil phase pot of homogenizing emulsifying equipment, starting stirring at a rotation speed of 100r/min, and adding xanthan gum, carrageenan and sodium carboxymethylcellulose into the oil phase pot until the mixture is uniformly dispersed for later use;

3) Sucking the materials in the oil phase pot into the homogenizing pot through negative pressure, starting wall-mounted stirring (rotating speed of 100 r/min), sucking the materials in the water phase pot into the homogenizing pot through negative pressure, starting homogenizing stirring rotating speed (2000 r/min), stirring for 5 min until the materials are uniformly dispersed, and fully swelling;

4) Sucking the carboxymethylated bagasse/calcium carbonate composite material and silicon dioxide into a homogenizing pot under negative pressure, and stirring for 30 minutes until the system is uniform;

5) Adding peppermint essence into a homogenizing pot, stirring uniformly, and starting vacuum until the negative pressure is less than-0.06 Mp;

6) Sucking sodium laurylsulfate into the homogenizing pot under negative pressure, stirring for 10min, vacuum-starting until negative pressure is less than-0.08 MP, stirring until the system is uniform, and discharging.

Example 6

The embodiment provides a tooth anti-sensitive toothpaste, which comprises the following components in percentage by weight:

10% of the carboxymethylated bagasse/calcium carbonate composite material of the example 1, 10% of silicon dioxide, 35% of glycerol, 15% of sorbitol, 0.4% of xanthan gum, 0.4% of carrageenan, 0.5% of sodium carboxymethyl cellulose, 1.5% of peppermint flavor, 0.5% of sodium benzoate, 0.3% of saccharin sodium, 2% of sodium lauryl sulfate, 3% of potassium nitrate and the balance of water.

The preparation method of the tooth anti-sensitive toothpaste provided in the embodiment is basically the same as that in embodiment 5, wherein potassium nitrate is added in step 1).

Example 7

the carboxymethylated bagasse/calcium carbonate composite material of example 2 was 5%, silica 15%, glycerin 35%, sorbitol 15%, silica 5%, xanthan gum 0.5%, carrageenan 0.3%, sodium carboxymethylcellulose 0.5%, peppermint flavor 1.5%, sodium benzoate 0.5%, saccharin sodium 0.3%, sodium lauryl sulfate 2%, and the balance water.

The toothpaste provided in this example was prepared in the same manner as in example 5.

Example 8

20% of the carboxymethylated bagasse/calcium phosphate composite material of example 3, 10% of silicon dioxide, 35% of glycerol, 15% of sorbitol, 0.4% of xanthan gum, 0.4% of carrageenan, 0.3% of sodium carboxymethyl cellulose, 1.5% of peppermint flavor, 0.5% of sodium benzoate, 0.3% of saccharin sodium, 2% of sodium lauryl sulfate, 3% of potassium nitrate and the balance of water.

Example 9

10% of the carboxymethylated bagasse/calcium phosphate composite material of example 3, 15% of silicon dioxide, 35% of glycerol, 15% of sorbitol, 5% of silicon dioxide, 0.5% of xanthan gum, 0.3% of carrageenan, 0.5% of sodium carboxymethyl cellulose, 1.5% of peppermint flavor, 0.5% of sodium benzoate, 0.3% of saccharin sodium, 2% of sodium lauryl sulfate and the balance of water.

The toothpaste provided in this example was prepared in the same manner as in example 6.

Example 10

the carboxymethylated bagasse/calcium phosphate salt composite material of example 4 was 5%, silica 15%, glycerin 35%, sorbitol 15%, silica 5%, xanthan gum 0.5%, carrageenan 0.3%, sodium carboxymethylcellulose 0.5%, peppermint flavor 1.5%, sodium benzoate 0.5%, saccharin sodium 0.3%, sodium lauryl sulfate 2%, and the balance water.

Comparative example 1

This comparative example provides a toothpaste that differs from example 5 only in that the carboxymethylated bagasse/calcium carbonate composite material was replaced with an equivalent amount of abrasive calcium carbonate.

The toothpaste provided in this comparative example was prepared in the same manner as in example 5.

Comparative example 2

This comparative example provides a dental anti-sensitivity toothpaste which differs from example 6 only in that the carboxymethylated bagasse/calcium carbonate composite material was replaced with an equivalent amount of abrasive calcium carbonate.

The preparation method of the tooth anti-sensitive toothpaste provided in the comparative example is the same as that in example 6.

Comparative example 3

This comparative example provides a toothpaste that differs from example 7 in that the carboxymethylated bagasse/calcium carbonate composite material was replaced with an equivalent amount of abrasive calcium carbonate.

The toothpaste provided in this comparative example was prepared in the same manner as in example 7.

Comparative example 4

This comparative example provides a toothpaste that differs from example 8 only in that the carboxymethylated bagasse/calcium phosphate salt composite material was replaced with an equivalent amount of abrasive monocalcium phosphate.

The toothpaste provided in this comparative example was prepared in the same manner as in example 8.

Comparative example 5

This comparative example provides a dental anti-sensitivity toothpaste which differs from example 9 only in that the carboxymethylated bagasse/calcium phosphate salt composite material was replaced with an equivalent amount of abrasive monocalcium phosphate.

The preparation method of the tooth anti-sensitive toothpaste provided in this comparative example is the same as that of example 9.

Comparative example 6

This comparative example provides a toothpaste that differs from example 10 in that the carboxymethylated bagasse/calcium phosphate salt composite material was replaced with an equivalent amount of abrasive monocalcium phosphate.

The toothpaste provided in this comparative example was prepared in the same manner as in example 10.

Test example 1

Whiteness detection

The whiteness of the toothpaste was tested using a WSD-III type automatic whiteness meter. The whiteness test results of the toothpastes of example 5 and comparative example 1, and example 8 and comparative example 4 are shown in Table 1.

TABLE 1

Toothpaste sample	Whiteness degree	Toothpaste sample	Whiteness degree
				Example 5	91	Example 8	94
Comparative example 1	91	Comparative example 4	95

The results show that: example 5 is substantially the same as the toothpaste of comparative example 1 in whiteness, and example 8 is substantially the same as the toothpaste of comparative example 4 in whiteness, demonstrating that the carboxymethylated bagasse-containing composite material of the present invention as an abrasive for toothpaste can achieve substantially the same paste appearance properties as the abrasive calcium carbonate or monocalcium phosphate.

Test example 2

Cleaning force test

1.0g of toothpaste sample is weighed and placed on a white organic glass plate attached with special dirt on a cleaning value tester, a nose with a soft bristle toothbrush is put down, so that the bristles are in close contact with the organic glass plate, the instrument is started, and the toothbrush moves back and forth immediately to rub the organic glass plate. After rubbing for 20 times, 50 times, 100 times, 150 times, 200 times and 300 times in sequence, the organic glass plate is taken out and put into a whiteness meter to measure corresponding data. The 6 data are converted into a cleaning value CV. Higher CV values indicate more cleaning power of the toothpaste. The results of the cleaning values of the toothpastes of example 5 and comparative example 1, and example 8 and comparative example 4 are shown in Table 2.

TABLE 2

Toothpaste sample	CV value	Toothpaste sample	CV value
				Example 5	15	Example 8	24
Comparative example 1	12	Comparative example 4	18

The results show that: when 20% of the abrasive calcium carbonate in the toothpaste is replaced by the carboxymethylated bagasse/calcium carbonate composite material of the embodiment of the invention, the cleaning value of the toothpaste is improved by more than 20%; when 20% of the abrasive monocalcium phosphate in the toothpaste is replaced with the carboxymethylated bagasse/calcium phosphate salt composite material of the embodiment of the invention, the cleaning value of the toothpaste is increased from 18 to 24, and the cleaning value is improved by more than 30%. The above description shows that the carboxymethylated bagasse-containing composite material of the embodiments of the present invention has excellent tooth cleaning performance as an abrasive for toothpaste, compared to the existing abrasive calcium carbonate or monocalcium phosphate.

Test example 3

In vitro dentin tubule experiment

Cutting dentin sheet with thickness of about 3mm at 1-4mm position under enamel dentin boundary perpendicular to long axis direction of dentin with hard tissue cutter, sequentially grinding with sand paper on horizontal grinder, polishing to obtain dentin sheet with thickness of about 2mm, ultrasonic cleaning, etching with 6% citric acid for 2min, washing with distilled water for 30S, and blow drying to obtain sensitive dentin. The tooth brushing experiment was performed on sensitive dentin with the same toothbrush using the same concentration of the toothpaste slurry, and then SEM observation was performed on the surface and longitudinal section of the isolated dentin, and the occlusion rate (PR) of the isolated dentin tubule was calculated. The results of the tests for the clogging rate of the tooth anti-sensitive toothpastes of example 6 and comparative example 2, and example 9 and comparative example 5 are shown in Table 3.

TABLE 3 Table 3

Toothpaste sample	PR value	ToothpasteSample of	PR value
				Example 6	96％	Example 9	95.4％
Comparative example 2	15％	Comparative example 5	20％

The results show that: when 10% of abrasive calcium carbonate in the tooth anti-sensitive toothpaste is replaced by the carboxymethylated bagasse/calcium carbonate composite material of the embodiment of the invention, the in-vitro dentinal tubule blocking rate of the tooth anti-sensitive toothpaste reaches more than 95%; when 10% of abrasive monocalcium phosphate in the tooth anti-sensitive toothpaste is used for replacing the carboxymethylated bagasse/calcium phosphate salt composite material in the embodiment of the invention, the in-vitro dentinal tubule blocking rate of the tooth anti-sensitive toothpaste reaches more than 95%. The above description shows that the composite material containing carboxymethylated bagasse according to the embodiment of the invention has more excellent desensitizing effect as an abrasive and an antiallergic component for dental antiallergic toothpaste than the abrasive calcium carbonate or monocalcium phosphate.

Test example 4

Taste test brush

60 volunteers with healthy oral cavity were randomly selected and grouped into experiments 1-4, each group being 15. Among them, the volunteer of experiment 1 used the toothpaste of example 6, the volunteer of experiment 2 used the toothpaste of comparative example 2, the volunteer of experiment 3 used the toothpaste of example 7, and the volunteer of experiment 4 used the toothpaste of comparative example 3. All volunteers used the personal habit brushing regimen in a unified manner using a toothbrush provided by Yunnan white drug group Co., ltd. Filling out a questionnaire for the mouth feel of the toothpaste after 3 days, and obtaining a result through statistics. Wherein:

like: the taste is fine and smooth, and no granular feel exists;

generally: the taste is rough, and the friction feeling of particles is obvious;

dislike: has a rough taste and obvious granular friction feeling.

The test results are shown in Table 4.

TABLE 4 Table 4

Group of	Toothpaste sample	Xi Huan	In general	Dislike	Preference degree
						Experiment 1 group	Example 6	10	3	2	66.7％
Experiment 2 group	Comparative example 2	5	8	2	33.3％
						Experiment 3 group	Example 7	6	6	3	40％
Experiment 4 group	Comparative example 3	5	7	3	33.3％

The results show that: when 5% of the abrasive calcium carbonate in the toothpaste was replaced with the carboxymethylated bagasse/calcium carbonate composite material of the present examples, the brushing mouthfeel of the toothpaste was substantially unchanged; when 10% of the abrasive calcium carbonate in the toothpaste was replaced with the carboxymethylated bagasse/calcium carbonate composite material of the present examples, the brushing taste preference of the toothpaste increased by more than 30%.

60 volunteers with healthy oral cavity were randomly selected and grouped into experiments 1-4, each group being 15. Among them, the volunteer of experiment 1 used the toothpaste of example 9, the volunteer of experiment 2 used the toothpaste of comparative example 5, the volunteer of experiment 3 used the toothpaste of example 10, and the volunteer of experiment 4 used the toothpaste of comparative example 6. All volunteers used the personal habit brushing regimen in a unified manner using a toothbrush provided by Yunnan white drug group Co., ltd. Filling out a questionnaire for the mouth feel of the toothpaste after 3 days, and obtaining a result through statistics. Wherein:

like: the taste is fine and smooth, and no granular feel exists;

dislike: has a rough taste and obvious granular friction feeling.

The test results are shown in Table 5.

TABLE 5

Group of	Toothpaste sample	Xi Huan	In general	Dislike	Preference degree
						Experiment 1 group	Example 9	12	2	1	80％
Experiment 2 group	Comparative example 5	8	2	5	53.3％
						Experiment 3 group	Example 10	9	4	2	60％
Experiment 4 group	Comparative example 6	8	3	4	53.3％

The results show that: when 5% of the abrasive monocalcium phosphate in the toothpaste was replaced with the carboxymethylated bagasse/calcium phosphate salt composite of the present examples, the brushing mouthfeel of the toothpaste was substantially unchanged (see experiments 3-4); when 10% of the abrasive monocalcium phosphate in the toothpaste was replaced with the carboxymethylated bagasse/calcium phosphate salt composite material of the present examples, the brushing taste preference of the toothpaste increased by more than 20% (see experiments 1-2).

The above description shows that the composite material containing carboxymethylated bagasse according to the embodiment of the invention is more acceptable and favored by the public when being added into toothpaste than the abrasive calcium carbonate or monocalcium phosphate.

While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims

1. The preparation method of the composite material containing the carboxymethyl bagasse is characterized in that sodium chloroacetate aqueous solution is added into bagasse to carry out carboxymethylation reaction, after the reaction is finished, calcium hydroxide is added to adjust the pH value to be alkaline, then a carbonate ion source/a phosphate ion source is added until calcium ions in the system are completely converted into calcium carbonate/calcium phosphate, and centrifugal separation, drying and grinding are carried out to obtain the composite material containing the carboxymethyl bagasse;

the concentration of the sodium chloroacetate aqueous solution is 0.1% -80%, and the mass volume ratio of bagasse to the sodium chloroacetate aqueous solution is 1: 3-50 parts;

the sodium chloroacetate aqueous solution is added in a dropwise manner, and the dropwise speed is 3-5 drops/s;

the temperature of the carboxymethylation reaction is 35-80 ℃ and the time is 1-3 h;

the pH value is 7.5-9;

the particle size of the composite material containing the carboxymethyl bagasse is 0.1-100 microns;

the preparation method of the bagasse comprises the following steps: and (3) after the sugar is squeezed from the sugarcane, adding water for ball milling until the leaching solution is clear and transparent, sieving with a water sieve with more than 40 meshes, removing large particles, drying the undersize and carrying out jet milling to obtain powder with the particle size of 0.1-50 microns.

2. A method of preparing a carboxymethylated bagasse-containing composite material according to claim 1, wherein the carbonate ion source is selected from one or more of sodium carbonate, sodium bicarbonate, dimethyl carbonate, carbon dioxide;

and/or the phosphate ion source is selected from one or more of trisodium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, diammine hydrogen phosphate and phosphorus pentoxide.

3. A carboxymethylated bagasse-containing composite material, characterized in that it is produced by the production method according to claim 1 or 2.

4. Use of a carboxymethylated bagasse-containing composite material according to claim 3 as at least one of an abrasive, an anti-sensitization ingredient, in the manufacture of an oral care implement.

5. The use of claim 4 wherein the oral care implement is a toothpaste, a dentifrice or a tooth desensitizing agent.

6. A toothpaste comprising the carboxymethylated bagasse-containing composite material according to claim 3, wherein the carboxymethylated bagasse-containing composite material comprises 0.1-70% of the toothpaste by mass;

and/or the toothpaste further comprises at least one of humectant, binder, abrasive, essence, antiseptic, sweetener, foaming agent and water.