JP2000038327A - Toothpaste composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toothpaste composition having fluidity as well as shape- retainability. SOLUTION: Carboxymethyl cellulose or its salt (CMC) to be used in the objective composition has a viscosity ratio η24/η1 of >=1.4 wherein η1 and η24 are viscosity values of a sorbitol aqueous solution measured after 1 hr and 24 hr from the preparation of the solution, respectively. The CMC has (l) a turbidity of >=30% when dissolved in 4 wt.% salt solution at a concentration of 1 wt.%, (2) a viscosity of 20-500 (mPa.s) as a 1 wt.% aqueous solution or (3) an average etherification degree of 0.6-1.0. Such CMC can be produced by setting the reaction temperature to 20-50 deg.C in a process to produce an alkali cellulose by the reaction of cellulose with an alkali.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a toothpaste composition containing carboxymethylcellulose or a salt thereof.

[0002]

2. Description of the Related Art Conventionally, the fluidity, shape retention,
In order to control physical properties such as moisture retention and surface gloss, carboxymethyl cellulose or a salt thereof (hereinafter, simply referred to as CMC) is used.

[0003] Such a toothpaste composition is required to have fluidity for filling in a container, and when used, to have shape retention opposite to fluidity. For example, when filling a toothpaste composition into a container, a composition with high fluidity is easier to fill, but when a composition with high fluidity is used, there is no shape retention, so from the container When the filling is taken out, the shape may be lost or sagged. Conversely, in order to impart shape retention, the viscosity of the composition is increased. However, if the viscosity of the composition is increased, the fluidity and, consequently, the filling property of the container decrease.

As described above, when the conventional CMC is used, it is difficult to achieve a balance between various physical properties, particularly, a balance between fluidity and shape retention.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a toothpaste composition containing CMC and capable of achieving both high levels of fluidity (or filling in a container) and shape retention. It is in.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that the use of CMC having a specific viscosity characteristic can achieve both high fluidity and high shape retention. We have found and completed the present invention.

That is, the CMC used in the present invention is:
When an aqueous sorbitol solution was prepared, the viscosity η after one hour
₁ and the viscosity ratio eta ₂₄ / eta ₁ of the viscosity eta ₂₄ after 24 hours 1.
4 or more.

In the present invention, there is provided a toothpaste composition containing CMC obtained by reacting cellulose and alkali at a temperature of 20 to 50 ° C. to produce alkali cellulose and reacting the alkali cellulose with monochloroacetic acid.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the salt type of CMC used in the present invention include alkali metal salts such as sodium and potassium, ammonium salts and the like, and a mixture of these salts may be used. As CMC, carboxymethyl cellulose sodium salt is usually used.

The CMC used in the present invention is suitable for use in combination with a saccharide. That is, the CMC used in the present invention, when preparing an aqueous sorbitol solution,
Viscosity eta ₁ after 1 hour and the viscosity ratio eta ₂₄ / eta ₁ of the viscosity eta ₂₄ after 24 hours 1.4 or higher (e.g., about 1.5 to 10), preferably 1.8 or more (e.g., 2 ５5), and usually about 1.5-5. Viscosity ratio η ₂₄ / η ₁
If it is less than 1.4, the increase in viscosity after filling the toothpaste composition into a container is small, and it is difficult to impart high shape retention.

When CMC having such a viscosity ratio is used, the viscosity is low immediately after the toothpaste composition is prepared and the fluidity is high, so that the composition is easily filled in a container. On the other hand, after a while, the viscosity of the toothpaste composition is greatly increased due to the interaction between the CMC and a saccharide (for example, sorbitol), and high shape retention can be maintained.

Furthermore, the CMC used in the present invention is 4
The turbidity of a 1% by weight solution is 30% or more (for example, about 30 to 90%), and preferably 35% or more (for example, about 35 to 85%) when using a 1% by weight saline solution as a solvent. Immediately after preparing the toothpaste composition, the CMC having such turbidity has a low fluidity (fillability in a container) because of low viscosity, and after filling, a short time after filling, the CMC and a saccharide (eg, sorbitol) By virtue of the interaction, the viscosity of the composition is greatly increased, and high shape retention can be maintained. If the turbidity is less than 30%, the composition containing CMC and the saccharide has a small increase in viscosity after filling into a container and cannot provide high shape retention.

Further, the CMC used in the present invention is 1
The weight% aqueous solution has a viscosity of 20 to 500 (mPa · s), preferably 50 to 300 (mPa · s), and more preferably 9 (mPa · s).
It is about 0 to 200 (mPa · s). A toothpaste composition containing CMC having such a viscosity can improve fluidity (fillability in a container) and shape retention. In addition, the viscosity is 20
When the viscosity is less than (mPa · s), the viscosity of the toothpaste composition is low, and the shape retention tends to decrease.
The viscosity of the toothpaste composition becomes too high, so that the fluidity and the filling property of the container are likely to decrease.

The average degree of etherification of the CMC used in the present invention is, for example, 0.6 to 1.0, preferably 0.7 to 1.0.
0.95, more preferably about 0.8 to 0.95. If the average degree of etherification is less than 0.6, the gloss of the surface required for the toothpaste composition may not be obtained, or the dispersion stability may decrease, and sufficient fluidity may not be obtained. On the other hand, if the average degree of etherification exceeds 1.0, it may not be possible to impart high shape retention after filling.

The average degree of polymerization of CMC can be adjusted within the above-mentioned range of properties, and is, for example, about 10 to 1,000, preferably about 50 to 900, and more preferably about 200 to 800.

Such CMC can be obtained by various methods such as a conventional slurry method and a kneader method, for example, a step of reacting cellulose with an alkali to form alkali cellulose (arcelizing step or mercerizing step), It can be produced by a method comprising a step (carboxymethylation step or etherification step) of producing carboxymethyl cellulose by reacting cellulose with monochloroacetic acid.

As the cellulose, various raw materials such as wood pulp and linter pulp can be used. As the alkali, alkali (lithium, potassium, sodium, etc.), ammonia and the like can be used. Sodium is usually used as the alkali. The alkali is usually used as a hydroxide or an aqueous solution.

The amount of alkali (such as sodium hydroxide) used in the acellulization process is usually
40-80 parts by weight, preferably 45-80 parts by weight per 0 parts by weight
It can be selected from a range of about 75 parts by weight. In the slurry method, the amount of the alkali (such as sodium hydroxide) used is usually 40 to 7 parts per 100 parts by weight of cellulose.
0 parts by weight, preferably about 45 to 65 parts by weight. In the slurry method, in many cases, the cellulization is performed at a cellulose concentration of about 1 to 7% by weight, and in the kneader method, the cellulose is formed at a cellulose concentration of about 10 to 20% by weight. In addition, the alkali concentration in the alcerization step varies depending on the slurry method, the kneader method, and the like. In the slurry method, the alkali concentration can be generally performed in an aqueous medium of about 1 to 20% by weight.
It can be carried out in an aqueous medium having a concentration of about 1 to 5% by weight.

The step of converting into an alucell may be carried out in the presence of a suitable solvent. Examples of the solvent include water, alcohols (such as ethanol and isopropanol), ketones (acetone), and cellosolves (such as methyl cellosolve and ethyl cellosolve).

In the present invention, in the step of producing alkali cellulose, the temperature is 20 to 50 ° C., preferably 25 to 40 ° C.
C., more preferably at 25-35.degree. C., is advantageous. When the reaction temperature is low, CMC having the above characteristics
Is difficult to obtain.

In the carboxymethylation step, the amount of monochloroacetic acid to be used can be selected according to the degree of carboxymethylation, and is, for example, about 40 to 100 parts by weight, preferably about 45 to 75 parts by weight, per 100 parts by weight of cellulose. Can be selected from the range.

The CMC thus formed is dewatered,
It can be purified by washing and drying. If necessary, after the completion of the reaction, it may be treated with a peroxide such as hydrogen peroxide or peracetic acid to adjust the viscosity.

As described above, the toothpaste composition of the present invention can be used in combination with sugars, and can be prepared by mixing them. The saccharide used includes a monosaccharide (eg, triose, tetroses, pentose, hexose, etc.) or a substituted derivative thereof. Preferably, a sugar alcohol in which the aldehyde group or keto group of the monosaccharide is reduced (for example, arabitol, xylitol derived from pentose, or sorbitol or annitol derived from hexose), more preferably sorbitol.

The amount of saccharide used is, for example, C
The amount can be selected from the range of 0.01 to 1000 parts by weight, preferably 0.1 to 500 parts by weight, more preferably about 1 to 300 parts by weight, based on 100 parts by weight of MC.

The dentifrice composition is usually made of a filler or an abrasive (calcium carbonate, magnesium carbonate, silicon dioxide, calcium phosphate, titanium oxide, etc.), a wetting agent (sorbitol, xylitol, lactose, fructose, sucrose, etc.). Sugars, glycerin, glycols, etc.), binders (CM
C, carrageenan, xanthan gum, locust bean gum, guar gum, pectin, polysaccharides such as carrageenin, methylcellulose, hydroxyethylcellulose,
Cellulose ethers such as hydroxypropylcellulose, aqueous polymers such as polyvinyl alcohol and polyvinylpyrrolidone), stabilizers (such as antioxidants), dispersion stabilizers such as surfactants, disinfectants, anti-inflammatory agents, breath fresheners, It can be composed of vitamins, flavors, sweeteners, pigments, water and the like.

[0026]

According to the present invention, a CM exhibiting a specific viscous behavior is used.
Since C is used, it is possible to obtain a toothpaste composition in which fluidity (or filling in a container) and shape retention are compatible at a high level.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 1684 parts by weight of isopropyl alcohol, 124 parts by weight of water, and 70 parts by weight of pulverized pulp were charged into a 3 L separable flask equipped with a stirrer and stirred. About 30
After adjusting the temperature to 0 ° C, an aqueous solution of 41.6 parts by weight of sodium hydroxide and 40.7 parts by weight of water was added, and the temperature was adjusted to 30 to 35 ° C.
The mixture was stirred and mixed at 60 ° C. for 60 minutes to prepare alkali cellulose. Next, a mixed solution of 44.2 parts by weight of monochloroacetic acid and 35.8 parts by weight of isopropyl alcohol was charged and mixed, and the temperature was raised to 70 ° C., and the reaction was performed for 1 hour. After the reaction is completed, take out the contents from the reactor, remove the liquid with a centrifuge, wash the cotton wool with about 80% by weight aqueous methyl alcohol solution, adjust the viscosity with hydrogen peroxide, remove the liquid, and dry. Produced carboxymethylcellulose sodium salt (CMC).

Example 2 A mixed solution of 883 parts by weight of isopropyl alcohol, 141 parts by weight of sodium hydroxide and 190 parts by weight of water was charged into a 5 L reactor having a biaxial stirring blade, and 200 parts by weight of pulverized pulp Was added and stirred and mixed at 30 to 35 ° C. for 60 minutes. After a mixed solution of 140 parts by weight of monochloroacetic acid and 113 parts by weight of isopropyl alcohol was charged into the reactor, the temperature was raised to 70 ° C., and the reaction was carried out for 1 hour. After the completion of the reaction, the contents were taken out of the reactor and drained with a centrifuge. The cotton wool was washed with an aqueous solution of about 80% by weight of methyl alcohol, the viscosity was adjusted with hydrogen peroxide, and the liquid was drained and dried. ,
Carboxymethyl cellulose sodium salt (CMC) was produced.

Example 3 1664 parts by weight of isopropyl alcohol, 160 parts by weight of water, and 70 parts by weight of pulverized pulp were put into a 3 L separable flask equipped with a stirrer and stirred. About 20
C., and a mixed solution of 34.0 parts by weight of sodium hydroxide and 33.3 parts by weight of water was added thereto.
The mixture was stirred and mixed at 60 ° C. for 60 minutes to prepare alkali cellulose. Next, a mixed solution of 33.7 parts by weight of monochloroacetic acid and 27.3 parts by weight of isopropyl alcohol was added and mixed, and the mixture was heated to 70 ° C. and reacted for 1 hour. After the reaction is completed, take out the contents from the reactor, remove the liquid with a centrifuge, wash the cotton wool with an aqueous solution of about 80% by weight methyl alcohol, adjust the viscosity with hydrogen peroxide, remove the liquid, and dry it. Produced carboxymethylcellulose sodium salt (CMC).

Comparative Example 1 In the process of preparing alkali cellulose, the temperature was 10 to 20 ° C.
CMC was obtained in the same manner as in Example 1 except that the content was less than the above.

Comparative Example 2 In the preparation process of alkali cellulose, the temperature was 10 to 20 ° C.
CMC was obtained in the same manner as in Example 2 except that the content was less than the above.

Comparative Example 3 1675 parts by weight of isopropyl alcohol, 114 parts by weight of water, and 70 parts by weight of pulverized pulp were charged into a 3 L separable flask equipped with a stirrer and stirred. About 20
After adjusting the temperature to 5 ° C., a mixed solution of 51.9 parts by weight of sodium hydroxide and 50.9 parts by weight of water was added, and the mixture was heated to a temperature of 20 to 30 parts by weight.
The mixture was stirred and mixed at 60 ° C. for 60 minutes to prepare alkali cellulose. Next, a mixed solution of 33.7 parts by weight of monochloroacetic acid and 27.3 parts by weight of isopropyl alcohol was added and mixed, and the mixture was heated to 70 ° C. and reacted for 1 hour. After the reaction is completed, take out the contents from the reactor, remove the liquid with a centrifuge, wash the cotton wool with an aqueous solution of about 80% by weight methyl alcohol, adjust the viscosity with hydrogen peroxide, remove the liquid, and dry it. Produced carboxymethylcellulose sodium salt (CMC).

With respect to the CMC thus obtained,
Turbidity of 1% by weight solution (saline turbidity) using 4% by weight saline solution as a solvent, and 1 hour and 2 hours after sorbitol aqueous solution
The viscosity (sorbitol viscosity) after 4 hours was measured.

[Brine turbidity] To a predetermined amount of a 4% by weight saline solution, precisely weighed CMC was added with stirring, and the coagulated product (Mamako) was crushed with a pencil mixer. Then, the concentration 1
A solution was prepared by adding a 4% by weight saline solution to a concentration of 4% by weight. After standing for a certain period of time in a thermostat at a temperature of 25 ° C., the solution was stirred so as to be uniform, and the turbidity of the solution was measured using a turbidimeter (T-2600D turbidimeter, manufactured by Tokyo Denshoku Co., Ltd. : Integral sphere method using a halogen lamp, cell length 50 mm). Turbidity (%) = scattered light / total transmitted light × 100 [Sorbitol viscosity] 136 g of water and 100.5 g of a 70% by weight sorbitol aqueous solution were put into a 500 ml beaker and stirred. Add this mixture to a CMC in a 50 ml beaker.
A solution in which 6.0 g was dispersed in 7.5 g of a 94% aqueous ethanol solution was added, and the adhered substance of the beaker was washed with 50 g of water.
, And homogenized at 24000 rpm for 5 minutes using a homogenizer (Ultratax T-25, manufactured by Squid). The homogenized solution was allowed to stand in a constant temperature bath at 25 ° C. for a certain period of time (1 hour and 24 hours) after the stirring was stopped, and then the viscosity was measured (Brookfield BH type viscometer, 10 rpm, value after 3 minutes). ).

The results are shown in Table 1.

[0037]

[Table 1]

[Toothpaste composition] A toothpaste paste was prepared by mixing the following components.

Abrasive (calcium carbonate) 15% by weight Abrasive (calcium hydrogen phosphate) 31% by weight CMC 1% by weight obtained in Examples and Comparative Examples 1% by weight Glycerin 20% by weight 70% Sorbitol 10% by weight Sodium lauryl sulfate 1 0.5% by weight Saccharin sodium 0.1% by weight Peppermint 0.9% by weight Water 20.5% by weight The ease of filling the obtained toothpaste into tubes (fluidity) was measured. The measurement criteria are shown below.・ Fluidity, easy to fill ○ ・ No flowability, difficult to fill × Next, paste filled in tube was squeezed out on paper and shape change (shape retention) after 3 minutes was visually judged. . The criteria are shown below.・ No change ○ ・ Almost no change △ ・ Change (sagging) × The results are shown in Table 2.

[0040]

[Table 2]

Claims (8)

[Claims] A dentifrice composition comprising carboxymethylcellulose or a salt thereof, wherein carboxymethylcellulose or a salt thereof is prepared by preparing an aqueous sorbitol solution.
A toothpaste composition having a viscosity ratio η ₂₄ / η ₁ of at least 1.4 when the viscosity η ₁ after 24 hours and the viscosity η ₂₄ after 24 hours are measured. 2. The toothpaste composition according to claim 1, wherein the turbidity of a 1% by weight solution of carboxymethyl cellulose or a salt thereof is 30% or more when 4% by weight saline is used as a solvent. 3. A 1% by weight aqueous solution of carboxymethylcellulose or a salt thereof has a viscosity of 20 to 500 (mPa · s).
The toothpaste composition according to claim 1, which is: 4. The carboxymethyl cellulose or a salt thereof having an average degree of etherification of 0.6 to 1.0.
The toothpaste composition according to any one of the preceding claims. 5. A method according to claim 1, wherein the cellulose and the alkali are reacted at a temperature of 20 to 5%.
The toothpaste composition according to claim 1, wherein the composition is reacted at 0 ° C to produce alkali cellulose, and contains carboxymethylcellulose or a salt thereof obtained by reacting alkali cellulose with monochloroacetic acid. 6. The toothpaste composition according to claim 1, further comprising a saccharide. 7. The method according to claim 6, wherein the saccharide is a sugar alcohol.
The toothpaste composition according to any one of the preceding claims. 8. The method according to claim 6, wherein the saccharide is sorbitol.
The toothpaste composition according to any one of the preceding claims.