JP2010111647A - Dentifrice composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dentifrice composition having excellent shape retaining properties, liquid separation stability, and appearance of a paste preparation after high-temperature preservation. <P>SOLUTION: The dentifrice composition includes: (A) sodium carboxymethylcellulose having 0.6-0.7 degree of etherification; and (B) precipitated silica having 300-450 m<SP>2</SP>/g BET specific surface area and 1.8-2.5 mL/g liquid absorption. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dentifrice composition excellent in shape retention, liquid separation stability after storage at high temperature, and appearance of a paste formulation.

  Conventionally, carboxymethyl cellulose sodium is widely used as a binder in dentifrice compositions, and is used in many dentifrices. In general, sodium carboxymethyl cellulose is produced by introducing a carboxymethyl group into the hydroxyl group of cellulose, and by changing the degree of substitution (etherification degree), sodium carboxymethyl cellulose having various characteristics is produced. The

  However, carboxymethylcellulose sodium, which is currently widely used, is not sufficient to combine both caking property and water retention ability when blended into a dentifrice composition, and either one of shape retention or liquid separation stability. Is inferior. In order to ensure the shape retention, there is a method of ensuring the shape retention by using a higher molecular weight, that is, a highly viscous sodium carboxymethyl cellulose or increasing the amount of sodium carboxymethyl cellulose. If a high-viscosity one is used or the amount is increased, the viscosity of the dentifrice will increase and the appearance of the paste preparation will deteriorate, which is not an effective improvement measure.

  According to Patent Documents 1 and 2, water-soluble alkaline earth metal salts such as calcium chloride and magnesium chloride are used to ensure shape retention using general-purpose carboxymethylcellulose sodium without using highly viscous sodium carboxymethylcellulose. Although polyethylene glycol having a molecular weight of 200 to 600 is added, there is no detailed description about sodium carboxymethylcellulose.

Moreover, it is possible to use sodium carboxymethylcellulose having a high degree of etherification for improving the liquid separation stability, but in this case, there is a problem that the shape retention of the dentifrice cannot be ensured.
Therefore, a new technique capable of combining excellent shape retention and moisture retention capability is desired.

On the other hand, precipitating silica is available in various types of products with different properties such as specific surface area and liquid absorption due to the difference in its production method. The specific surface area is about 50 to 300 m ² / g. As precipitating silica widely used as a thickener, Patent Document 3 discloses a thickening silica having a BET specific surface area of 100 to 300 m ² / g and a high degree of etherification (degree of etherification 2.0 to 2.8). It has been proposed that by using together with sodium carboxymethylcellulose, it is possible to provide a dentifrice composition which is excellent in the gloss of the preparation, has good shape retention and good dispersibility during use. However, it is not known that the combination with a general degree of etherification improves the shape retention of dentifrice, the stability of liquid separation after high-temperature storage, and the appearance of paste formulations.

JP-A-60-75415 Japanese Patent Laid-Open No. 60-75417 JP 2006-1901 A

  This invention is made | formed in view of the said situation, and it aims at providing the dentifrice composition excellent in the shape retention property, the liquid-separation stability after high temperature storage, and a paste formulation appearance.

As a result of intensive studies to achieve the above object, the present inventors have (A) sodium carboxymethylcellulose having an etherification degree of 0.6 to 0.7, (B) a BET specific surface area of 300 to 450 m ² / g, By blending with precipitating silica with a liquid absorption of 1.8 to 2.5 mL / g, it has excellent shape retention and moisture retention ability, shape retention, liquid separation stability after high temperature storage, and kneading The present inventors have found that a dentifrice composition having a satisfactory improvement in the appearance of the preparation can be obtained, and has made the present invention.

In the present invention, sodium carboxymethylcellulose having a degree of etherification of 0.6 to 0.7 has a BET specific surface area of 300 to 450 m ² / g and a liquid absorption of 1.8 to 2.5 mL / g, and is polished. In combination with precipitating silica that does not exhibit the properties, high shape and high viscosity sodium carboxymethylcellulose is used, or even without adding a large amount of sodium carboxymethylcellulose Both can be combined.

Therefore, the present invention comprises (A) sodium carboxymethyl cellulose having a degree of etherification of 0.6 to 0.7, (B) a BET specific surface area of 300 to 450 m ² / g, and a liquid absorption amount of 1.8 to 2.5 mL / g. Provided is a dentifrice composition comprising precipitated silica.

  ADVANTAGE OF THE INVENTION According to this invention, the dentifrice composition excellent in shape retention property, the liquid-separation stability after high temperature storage, and a paste formulation appearance can be provided.

Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention can be prepared as a dentifrice such as a toothpaste, a liquid dentifrice, a liquid dentifrice, a moisturized dentifrice, particularly a paste-like dentifrice. ) Sodium carboxymethyl cellulose having a degree of etherification of 0.6 to 0.7, (B) A blended silica having a BET specific surface area of 300 to 450 m ² / g and a liquid absorption of 1.8 to 2.5 mL / g. is there.

As the component (A) sodium carboxymethylcellulose, those having an etherification degree of 0.6 to 0.7 are used. In addition, the thing with less than 0.6 etherification is difficult to obtain, and the thing exceeding 0.7 is inferior to the shape retention of a dentifrice composition.
As said carboxymethylcellulose sodium, commercial items, such as CMC Daicel 1140 by Daicel Corporation, can be used, for example.
The method for measuring the degree of etherification will be specifically described. About 1 g of purified sodium carboxymethylcellulose was precisely weighed, wrapped in filter paper for quantitative analysis, placed in a platinum crucible, gently heated and carbonized, and then heated at 600 ° C. for 3 hours for carbonization. After cooling, the crucible was transferred to a 500 mL beaker, 250 mL of water was added, 50 mL of 0.05 mol / L sulfuric acid was further added, and the mixture was boiled for 30 minutes. This was cooled, a phenolphthalein indicator was added, and titrated with a 0.1 mol / L sodium hydroxide aqueous solution. Similarly, a blank test was performed, and the degree of etherification of carboxymethylcellulose sodium purified by the following formulas 1 to 3 was calculated.
C = {(B−S) × F / D} −E (Formula 1)
E = (5F′−S × F) / D (Formula 2)
Degree of etherification = 162 × C / (10000-80C) (Formula 3)
C: Consumed alkali in 1 g sodium carboxymethylcellulose
Amount of 0.05 mol / L sulfuric acid used (mL)
B: Amount of use of 0.1 mol / L sodium hydroxide aqueous solution required for the blank test (mL)
S: Amount of 0.1 mol / L sodium hydroxide aqueous solution required for the actual test (mL)
F: titer of 0.1 mol / L sodium hydroxide aqueous solution F ': titer of 0.05 mol / L sulfuric acid D: mass of sodium carboxymethyl cellulose (g)
E: Alkalinity 162: Molecular weight of C ₆ H ₇ O ₂ (OH) ₂ (cellulose monomer) 80: Molecular weight of CH ₂ COONa-H

  The amount of the sodium carboxymethyl cellulose is preferably 0.1 to 0.7% (mass%, the same applies hereinafter), particularly 0.3 to 0.5% of the entire composition. If the blending amount is less than 0.1%, the shape retention of the dentifrice may not be maintained, and if it exceeds 0.7%, the liquid separation stability after high temperature storage may be inferior.

The precipitated silica of the component (B), BET specific surface area of 300~450m ² / g, preferably 350~450m ² / g, more preferably 370~420m ² / g, liquid absorption amount is 1.8 Use 2.5 mL / g, preferably 2.0 to 2.4 mL / g. Those having a BET specific surface area exceeding 450 m ² / g are difficult to obtain, and if it is less than 300 m ² / g, the appearance of the kneaded preparation after high-temperature storage is poor.
Moreover, there is no liquid absorption amount exceeding 2.5 mL / g and satisfying the BET specific surface area of 300 to 450 m ² / g, and it is difficult to obtain. If the liquid absorption amount is less than 1.8 mL / g, liquid separation after high-temperature storage is difficult. Inferior in stability.

The BET specific surface area is a value measured at 25 ° C. using a specific surface area measuring device (manufactured by Nikkiso Co., Ltd., automatic specific surface area meter, BET multipoint method, measurement gas; nitrogen).
The specific example of the measuring method of the said liquid absorption amount is shown. A sample (1.0 g) was weighed on a clean glass plate, and the sample was mixed with a stainless spatula while adding 42.5% glycerin dropwise little by little using a microburette. The end point was when the sample became one lump and peeled cleanly from the glass plate with a spatula. The required liquid volume (mL) was taken as the liquid absorption volume.

In addition, the precipitating silica of the component (B) is non-abrasive (not showing abrasiveness). Precipitating silica blended as an abrasive in the dentifrice composition exhibits abrasiveness. Precipitating silica blended as an abrasive usually has a BET specific surface area of 50 to ²⁰⁰ m ² / g and a liquid absorption of 0. 8 to 1.5 mL / g.

  Examples of the component (B) precipitating silica include CARPLEX # 67 manufactured by DSL Japan Co., Ltd., and commercially available products can be used.

  (B) The compounding quantity of the sedimentary silica of a component is 1 to 7% of the whole composition, and 3 to 5% is especially suitable. If the blending amount is less than 1%, the shape retention of the dentifrice may be inferior, and if it exceeds 7%, the appearance of the paste preparation after high-temperature storage may be inferior.

  The dentifrice composition of the present invention can contain other additives as optional components in addition to the above essential components, depending on the dosage form, and can be blended as long as the effects of the present invention are not hindered. It can be manufactured by the method. In the case of toothpaste, for example, an abrasive, a thickener, a binder, a surfactant, a sweetener, an antiseptic, various active ingredients, a fragrance, a colorant, and the like can be blended.

  Examples of the abrasive include silica-based abrasives such as precipitated silica, silica gel, aluminosilicate, zirconosilicate and the like, dibasic calcium phosphate dihydrate that exhibit abrasiveness when the BET specific surface area and liquid absorption amount are outside the range of component (B). , Phosphate dibasic calcium phosphate, phosphate pyrophosphates such as calcium pyrophosphate, aluminum hydroxide, alumina, titanium dioxide, crystalline zirconium silicate, polymethyl methacrylate, insoluble calcium metaphosphate, light calcium carbonate, heavy carbonate Calcium, magnesium carbonate, tribasic magnesium phosphate, zeolite, zirconium silicate, tricalcium phosphate, hydroxyapatite, fluoroapatite, calcium deficient apatite, tricalcium phosphate, tetracalcium phosphate, eighth calcium phosphate, synthetic tree System abrasives and can be blended singly or in combination.

As a thickener, one or more of glycerin, sorbit, propylene glycol, polyethylene glycol having a molecular weight of 200 to 6000, ethylene glycol, 1,3-butylene glycol, polyvalent alcohol such as reduced starch saccharified product, etc. are combined. Can be blended.
The compounding quantity of a thickener is 5 to 70% normally with respect to the composition whole quantity.

  As the binder, carboxymethylcellulose or a metal salt thereof whose etherification degree is outside the range of the component (A), a cellulose-based binder such as hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxymethylethylcellulose, methylcellulose, Xanthan gum, carrageenan, guar gum, sodium alginate, cationized cellulose, montmorillonite, gelatin, sodium polyacrylate and the like can be mentioned, and one or more of these can be blended in combination. A compounding quantity is 0.1 to 5% in total with (A) component normally with respect to the composition whole quantity.

  As the surfactant, as anionic surfactant, sodium lauryl sulfate, sodium lauroyl sarcosine, sodium alkyl sulfate such as sodium myristyl sulfate, sodium dodecylbenzenesulfonate, hydrogenated coconut fatty acid sodium monoglyceride monosulfate, sodium lauryl sulfoacetate, Examples include N-acyl glutamates such as sodium N-palmitoyl glutamate, sodium N-methyl-N-acyl taurate, sodium N-methyl-N-acylalanine, sodium α-olefin sulfonate. Nonionic surfactants include, for example, polyoxyethylene hydrogenated castor oil, sucrose fatty acid ester, alkylol amide, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, alkyl glucoside, decaglyceryl laurate, etc. Used. Among these, polyoxyethylene alkyl ether, alkyl glycoside, etc. are mentioned from the point of foaming. Examples of amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, and coconut oil fatty acid amidopropyl. Although betaine etc. are used, it is not restricted to the above. The compounding quantity of surfactant is 0 to 10% normally.

  Sweeteners include saccharin sodium, aspartame, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidyl dihydrochalcone, perilartin, etc., and preservatives include parabens such as butylparaben and ethylparaben, paraoxybenzoates And sodium benzoate.

  Various active ingredients include fluorine compounds such as sodium fluoride, sodium monofluorophosphate, tin fluoride, water-soluble phosphate compounds such as potassium salt and sodium salt of orthophosphoric acid, tranexamic acid, epsilon-aminocaproic acid, allantoin. Chlorhydroxyaluminum, hinokitiol, ascorbic acid, dl-tocopherol acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, glycyrrhetin, glycyrrhetinic acid, copper chlorophyllin sodium, chlorophyll, glycerophosphate, copper gluconate Copper compounds such as aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid and its derivatives, sodium tripolyphosphate, zeolite, metho Siethylene, maleic anhydride copolymer, polyvinyl pyrrolidone, epidihydrocholesterin, cetylpyridinium chloride, benzethonium chloride, dihydrocholesterol, trichlorocarbanilide, zinc citrate, sweet cherry extract, buckwheat extract, chamomile, clove, rosemary, Examples include extracts of plants such as ougon and safflower.

  Perfumes are peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, lime Oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, iris concrete, absolute peppermint Natural fragrances such as absolute rose and orange flower, fragrances processed with these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder fragrance, etc.), and menthol , Carvone, anethole, cineol, methyl salicylate, Namic aldehyde, eugenol, 3-l-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramentane-3-carboxamide, pinene, octylaldehyde, Citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, hexanal, ethyl alcohol, propyl alcohol, butanol , Isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, methyl lactate, ethanol Single-flavored ingredients such as luthioacetate, as well as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc., dentifrice composition The well-known perfume material used for can be used, and it is not limited to the perfume of an Example.

  Examples of the colorant include Blue No. 1, Yellow No. 4, Green No. 3, and the like. In addition, the compounding quantity of these components can be made into a normal quantity in the range which does not prevent the effect of this invention.

  The material in particular of the container which accommodates the dentifrice composition of this invention is not restrict | limited, Usually, the container used for a dentifrice composition can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the blending amount is mass%.

[Examples 1 to 11 and Comparative Examples 1 to 3]
A dentifrice composition (toothpaste composition) having the composition shown in Table 1 was prepared by the following production method and evaluated as follows. The results are shown in Table 1.

(Production method)
(I) A phase was prepared by mixing and dissolving water-soluble components (excluding binder and propylene glycol) in purified water at room temperature.
(Ii) A phase B in which a binder was dispersed at room temperature in propylene glycol was prepared.
(Iii) B phase was added and mixed in A phase under stirring, and C phase was prepared.
(Iv) In phase C, ingredients other than water-soluble ingredients such as fragrances and abrasives are mixed at room temperature using a 1.5 L kneader (manufactured by Ishiyama Kogakusho), and degassed under reduced pressure (4 kPa). The dentifrice composition 1.2kg was obtained.

The dentifrice composition thus obtained was made into a laminated tube (LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30, thickness 257 μm (Dainippon), whose innermost layer is made of linear low density polyethylene. (Printed) was filled with 50 g.
The abbreviations and names in the layer structure of the laminated tube used are as follows, and the numbers following the abbreviations indicate the thickness (μm) of each layer.
LDPE: Low density polyethylene white LDPE: White low density polyethylene LLDPE: Linear low density polyethylene AL: Aluminum PET: Polyethylene terephthalate EMAA: Ethylene / methacrylic acid copolymer resin

  The obtained dentifrice composition was evaluated for (1) shape retention, (2) liquid separation stability after high-temperature storage, and (3) appearance of the paste formulation after high-temperature storage by the following methods. The results are also shown in Table 1.

(1) Specific surface area measuring method of precipitated silica The specific surface area at 25 ° C. was measured using a specific surface area measuring device (manufactured by Nikkiso Co., Ltd., automatic specific surface area meter, BET multipoint method, measuring gas; nitrogen). A sample amount of 0.1 g was used.

(2) Measuring method of liquid absorption of precipitated silica Weigh 1.0 g of a sample on a clean glass plate and use a microburet to drop 42.5% glycerin little by little with a stainless steel spatula. The sample was mixed so as to be uniform. The end point was when the sample became one lump and peeled cleanly from the glass plate with a spatula. The required liquid volume (mL) was taken as the liquid absorption volume.

(3) Measuring method of degree of etherification About 1 g of purified sodium carboxymethylcellulose is precisely weighed, wrapped in a filter paper for quantitative analysis, put in a platinum crucible, gently heated and carbonized, and then heated at 600 ° C. for 3 hours. And carbonized. After cooling, the crucible was transferred to a 500 mL beaker, 250 mL of water was added, 50 mL of 0.05 mol / L sulfuric acid was further added, and the mixture was boiled for 30 minutes. This was cooled, a phenolphthalein indicator was added, and titrated with a 0.1 mol / L sodium hydroxide aqueous solution. Similarly, a blank test was performed, and the degree of etherification of carboxymethylcellulose sodium purified by the following formulas 1 to 3 was calculated.
C = {(B−S) × F / D} −E (Formula 1)
E = (5F′−S × F) / D (Formula 2)
Degree of etherification = 162 × C / (10000-80C) (Formula 3)
C: Consumed alkali in 1 g sodium carboxymethylcellulose
Amount of 0.05 mol / L sulfuric acid used (mL)
B: Amount of use of 0.1 mol / L sodium hydroxide aqueous solution required for the blank test (mL)
S: Amount of 0.1 mol / L sodium hydroxide aqueous solution required for the actual test (mL)
F: titer of 0.1 mol / L sodium hydroxide aqueous solution F ': titer of 0.05 mol / L sulfuric acid D: mass of sodium carboxymethyl cellulose (g)
E: Alkalinity 162: Molecular weight of C ₆ H ₇ O ₂ (OH) ₂ (cellulose monomer) 80: Molecular weight of CH ₂ COONa-H

(4) Evaluation method of shape retention on toothbrush When 50 g of the dentifrice composition shown in Table 1 is filled in the above-mentioned laminate tube having a diameter of 26 mm and a mouth diameter of 5 mm and 0.5 g is placed on the toothbrush. The shape change was evaluated and evaluated according to the following criteria.
Evaluation criteria;
4 points: No deformation on the toothbrush is observed.
3 points: Slight deformation on the toothbrush is observed.
2 points: Dislodge on the toothbrush.
1 point: Severely deforms on the toothbrush.
Degree of shape retention (score);
The evaluation results of 5 times were averaged and judged according to the following criteria, and those with ◎ and ○ were judged to be dentifrice compositions with excellent shape retention.
◎: The shape retention on the toothbrush is 3.5 or more and 4.0 points or less ○: The shape retention on the toothbrush is 3.0 or more and less than 3.5 points △: The shape retention on the toothbrush 2.0 points or more and less than 3.0 points ×: The shape retention on the toothbrush is less than 2.0 points

(5) Method for evaluating liquid separation stability of paste preparation after storage at high temperature 50 g of the dentifrice composition shown in Table 1 was filled in the above-mentioned laminate tube having a diameter of 26 mm and a mouth inner diameter of 5 mm, and 50 each of three compositions. Stored at 1 ° C. for 1 month, a 10 cm dentifrice composition was extruded onto the straw half paper, the length of the liquid exuded on the straw half paper was measured, and the degree of liquid separation was evaluated in the following four stages. In addition, the liquid separation stability of the preparation in medium and high temperature storage at 40 ° C. or more tends to promote liquid separation depending on the temperature, and the storage temperature that can be evaluated in the storage period of one month is 50 ° C. Selected.

Evaluation criteria;
4 points: No liquid separation is observed.
3 points: When extruded, a slight liquid separation is observed at the mouth.
2 points: When extruded, 1 to 3 cm of liquid separation is observed at the mouth.
1 point: When extruded, liquid separation is recognized at the mouth over 3 cm.
Degree of liquid separation (score);
The average value of the three evaluation points was determined and judged according to the following criteria, and those with ◎ and ○ were judged to be dentifrice compositions with excellent liquid separation stability of the paste formulation after high-temperature storage.
A: The degree of liquid separation is 3.5 points or more and 4.0 points or less. ○: The degree of liquid separation is 3.0 points or more and less than 3.5 points. Δ: The degree of liquid separation is 2.0 points or more and 3.0 points. Less than x: Degree of liquid separation is less than 2.0 points

(6) Method for evaluating appearance of toothpaste after storage at high temperature 50 g of the toothpaste composition shown in Table 1 was filled in the above-mentioned laminate tube having a diameter of 26 mm and a mouth inner diameter of 5 mm, and each of the three compositions at 50 ° C for one month. As the evaluation of the smoothness of the surface condition of the toothpaste composition when stored and immediately extruded 15 cm of the toothpaste composition on a straw half paper, the glossiness, crushing, wrinkle and uniformity were evaluated according to the following criteria.

Evaluation criteria 4 points: Surface is glossy, has no crushing, wrinkles, etc., and has a uniform and smooth surface
It is.
3 points: Slight wrinkles are observed in the surface state, but the surface is almost uniform and smooth.
The surface.
Two points: crushing or wrinkling is recognized in the surface state, and there is no uniformity of the kneaded surface.
1 point: Crushing or wrinkling is remarkably observed in the surface state, the surface of the kneaded surface is non-uniform and not continuous.
Degree of surface condition (score);
Determine the average value of the three evaluation points, and judge according to the following criteria, and those with ◎ and ○ are judged to be excellent dentifrice compositions that do not cause deterioration of the appearance of the paste formulation after high-temperature storage (surface roughness). did.
A: The degree of the surface state is 3.5 points or more and 4.0 points or less. A: The degree of the surface state is 3.0 points or more and less than 3.5 points. Δ: The degree of the surface state is 2.0 points or more and 3.0 points. Less than x: Degree of surface condition is less than 2.0 points

* 1: Daicel Corporation CMC Daicel 1140
* 2: Daicel Corporation CMC Daicel 1240
* 3: Precipitated silica DSL Japan Co., Ltd. CARPLEX # 67
* 4; Precipitated silica DSL Japan Co., Ltd. CARPLEX # 67
* 5: Precipitated silica DSL Japan Co., Ltd. CARPLEX FPS-101
* 6: Precipitated silica DSL Japan Co., Ltd. CARPLEX # 90
* 7: Precipitating silica Rhodia Tixosil 73

  From the results in Table 1, it was confirmed that the dentifrice composition of the present invention was excellent in shape retention, liquid separation stability after storage at high temperature, and appearance of a paste formulation.

  Next, using the same sodium carboxymethyl cellulose and precipitated silica as described above, preparing a dentifrice composition having the following composition and evaluating it in the same way, both of the shape retention, liquid separation stability after high temperature storage, It was confirmed that the appearance of the paste formulation was improved.

[Example 12] Toothpaste sodium carboxymethylcellulose (etherification degree 0.7) 0.1%
Precipitated silica (BET specific surface area 370 m ² / g, liquid absorption 2.3 mL / g) 4.0
Isopropyl methylphenol 0.05
Sodium lauryl sulfate 1.4
Lauroyl sarcosine sodium 0.13
Fragrance 1.28
POE (5) stearyl ether 0.8
POE (20) hydrogenated castor oil 0.8
Precipitated silica (polishing) 18.0
Sodium alginate 0.4
Polyvinylpyrrolidone 0.1
Sodium polyacrylate 0.4
Xanthan gum 0.6
Sorbit liquid (70%) 36.0
Saccharin sodium 0.19
Propylene glycol 3.0
Titanium oxide 0.4
Sodium fluoride 0.21
Water remaining
Total 100.0%

[Example 13] Toothpaste sodium carboxymethylcellulose (degree of etherification 0.7) 0.4%
Precipitated silica (BET specific surface area 410 m ² / g, liquid absorption 2.3 mL / g) 3.0
Sodium lauryl sulfate 0.9
Fragrance 1.2
Precipitated silica (abrasive) 20.0
Zeolite 1.5
Aluminum oxide 2.0
Sodium pyrophosphate 1.0
Sodium carboxymethylcellulose (etherification degree 1.0) 1.0
Sorbit liquid (70%) 30.0
Saccharin sodium 0.18
Propylene glycol 3.0
Sodium fluoride 0.21
Water remaining
Total 100.0%

[Example 14] Toothpaste sodium carboxymethylcellulose (degree of etherification 0.7) 0.3%
Precipitated silica (BET specific surface area 370 m ² / g, liquid absorption 2.3 mL / g) 4.0
Sodium lauryl sulfate 0.65
Lauroyl sarcosine sodium 0.05
Coconut oil fatty acid amidopropyl betaine 1.0
Polyoxyethylene (8) stearyl ether 0.7
Polyoxyethylene (20) hydrogenated castor oil 0.7
Fragrance 1.1
Aluminum hydroxide 40.0
Sodium bicarbonate 0.2
Sodium alginate 0.2
Xanthan gum 0.5
Sodium polyacrylate 0.2
Sorbit liquid (70%) 30.0
Saccharin sodium 0.15
Propylene glycol 3.0
Dextranase (13000 U / g product) 0.16
Sodium monofluorophosphate 0.73
Water remaining
Total 100.0%

[Example 15] Toothpaste sodium carboxymethylcellulose (etherification degree 0.7) 0.6%
Precipitated silica (BET specific surface area 410 m ² / g, liquid absorption 2.3 mL / g) 4.0
Sodium lauryl sulfate 1.8
Fragrance 1.2
Precipitated silica (polishing) 18.0
Titanium oxide 0.5
Sodium polyphosphate 1.0
Sodium bicarbonate 0.3
Sodium hydroxide 0.1
Carrageenan 0.3
Xanthan gum 0.6
Sorbit liquid (70%) 40.0
Saccharin sodium 0.185
Propylene glycol 3.0
Methylparaben 0.07
Butylparaben 0.01
Water remaining
Total 100.0%

[Example 16] Toothpaste sodium carboxymethyl cellulose (etherification degree 0.7) 0.5%
Precipitated silica (BET specific surface area 370 m ² / g, liquid absorption 2.3 mL / g) 3.0
Sodium lauryl sulfate 1.4
Fragrance 1.1
Precipitated silica (abrasive) 12.0
Titanium oxide 0.4
Xanthan gum 0.55
Sodium polyacrylate 0.55
Sorbit liquid (70%) 32.0
Saccharin sodium 0.17
Xylitol 5.0
Propylene glycol 3.0
Methylparaben 0.1
Butylparaben 0.01
Sodium fluoride 0.21
Water remaining
Total 100.0%

[Example 17] Toothpaste sodium carboxymethyl cellulose (etherification degree 0.7) 0.2%
Precipitated silica (BET specific surface area 370 m ² / g, liquid absorption 2.3 mL / g) 5.0
Sodium lauryl sulfate 0.8
Fragrance 0.7
Precipitated silica (abrasiveness) 7.0
Titanium oxide 0.4
Xanthan gum 0.6
Sodium polyacrylate 0.6
Glycerin 21.25
Saccharin sodium 0.1
Xylitol 9.0
Propylene glycol 3.0
Ethylparaben 0.1
Butylparaben 0.01
Sodium fluoride 0.21
Water remaining
Total 100.0%

[Example 18] Toothpaste sodium carboxymethylcellulose (etherification degree 0.7) 0.7%
Precipitated silica (BET specific surface area 410 m ² / g, liquid absorption 2.3 mL / g) 2.5
Sodium lauryl sulfate 1.2
Fragrance 0.98
Calcium hydrogen phosphate dihydrate 20.0
Calcium hydrogen phosphate anhydrate 10.0
Aluminum oxide 1.0
Sodium carboxymethylcellulose (etherification degree 1.0) 0.8
Carrageenan 0.2
Sorbit liquid (70%) 22.3
Saccharin sodium 0.125
Propylene glycol 2.5
Sodium benzoate 0.3
Methylparaben 0.2
Butylparaben 0.01
Water remaining
Total 100.0%

[Example 19] Toothpaste sodium carboxymethylcellulose (etherification degree 0.7) 0.1%
Precipitated silica (BET specific surface area 370 m ² / g, liquid absorption 2.3 mL / g) 6.0
Sodium lauryl sulfate 0.7
Polyoxyethylene (5) stearyl ether 1.0
Polyoxyethylene (30) hydrogenated castor oil 1.0
Fragrance 1.2
Precipitated silica (abrasive) 12.0
Titanium oxide 0.5
Sodium polyphosphate 1.0
Sodium carboxymethylcellulose (degree of etherification 1.0) 1.4
Sorbit liquid (70%) 50.0
Saccharin sodium 0.11
Propylene glycol 3.0
Sodium fluoride 0.21
Oat extract 0.05
Cetylpyridinium chloride 0.05
Water remaining
Total 100.0%

[Example 20] Toothpaste sodium carboxymethylcellulose (etherification degree 0.7) 0.1%
Precipitated silica (BET specific surface area 370 m ² / g, liquid absorption 2.3 mL / g) 7.0
Sodium lauryl sulfate 0.7
Polyoxyethylene (5) stearyl ether 1.0
Polyoxyethylene (20) hydrogenated castor oil 1.0
Fragrance 1.2
Precipitated silica (abrasive) 12.0
Titanium oxide 0.5
Sodium polyphosphate 1.0
Sodium carboxymethylcellulose (degree of etherification 1.0) 1.4
Sorbit liquid (70%) 50.0
Saccharin sodium 0.11
Propylene glycol 3.0
Sodium fluoride 0.21
Tocopherol acetate 0.1
Tranexamic acid 0.05
Water remaining
Total 100.0%

[Example 21] Toothpaste sodium carboxymethylcellulose (etherification degree 0.7) 0.3%
Precipitated silica (BET specific surface area 370 m ² / g, liquid absorption 2.3 mL / g) 3.0
Sodium lauryl sulfate 0.65
Lauroyl sarcosine sodium 0.05
Imidazolinium betaine 0.25
Polyoxyethylene (5) stearyl ether 0.7
Polyoxyethylene (20) hydrogenated castor oil 0.7
Fragrance 1.3
Precipitated silica (abrasive) 16.0
Sodium alginate 0.2
Xanthan gum 0.5
Sodium polyacrylate 0.2
Sorbit liquid (70%) 30.0
Saccharin sodium 0.15
Propylene glycol 3.0
Dextranase (13000 U / g product) 0.16
Sodium fluoride 0.73
Water remaining
Total 100.0%

[Example 22] Toothpaste sodium carboxymethylcellulose (degree of etherification 0.7) 0.2%
Precipitated silica (BET specific surface area 410 m ² / g, liquid absorption 2.3 mL / g) 6.0
ε-aminocaproic acid 0.03
Sodium benzoate 0.5
Sodium lauryl sulfate 1.4
Fragrance 1.2
Sodium carboxymethylcellulose (etherification degree 1.0) 0.2
Polyoxyethylene (20) hydrogenated castor oil 0.2
Calcium carbonate 15.0
Sodium polyacrylate 0.3
Zeolite 7.0
Sorbit liquid (70%) 25.0
Saccharin sodium 0.2
Propylene glycol 3.0
Methylparaben 0.2
Butylparaben 0.01
Titanium oxide 0.3
Sodium monofluorophosphate 0.21
Water remaining
Total 100.0%

Claims (2)

(A) Sodium carboxymethylcellulose having a degree of etherification of 0.6 to 0.7, and (B) precipitated silica having a BET specific surface area of 300 to 450 m ² / g and a liquid absorption of 1.8 to 2.5 mL / g. A dentifrice composition characterized by comprising.   The dentifrice composition of Claim 1 which mix | blended 0.1-0.7 mass% of carboxymethylcellulose sodium of (A) component, and 1-7 mass% of precipitation silica of (B) component.