JPH085921B2 - Modified iota carrageenan and toothpaste using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a modified iota carrageenan, and further relates to a stabilizer for toothpaste using the modified iota carrageenan.

Carrageenan is a water-soluble natural polysaccharide mainly composed of galactose sulfate ester extracted from red algae and purified, and it is roughly classified into three kinds, katsupa, lambda and iota, due to the difference in its molecular structure. Extracted from Eumasuma Spinosum,
Refined.

Generally, Yukiuma spinosam used for extraction of iota carrageenan is roughly classified into three types according to the method of treating the seaweed. That is, raw spinosum (Raw Spinosum), seaweed collected from the sea is dried in the sun, and seaweed 70-95
Pretreated spinosum (pretreated spinosum), which was treated with a 3-10% sodium hydroxide aqueous solution at 30 ° C for 30-120 minutes, collected the solid content, washed with water and dried, and seaweed 4
These are three types of semitreated spinosum, which are treated with 0.5 to 20% aqueous potassium hydroxide solution at 0 to 60 ° C. to recover the solid content, washed with water and dried.

<Prior art> Conventionally, a known purification method using any Yukiuma spinosam, that is, "after washing the seaweed with water, heating and dissolving, and then removing the undissolved material, a water-miscible organic solvent The pure iota carrageenan obtained by "precipitating slagenan by mixing, recovering the precipitated substance, drying and pulverizing" is a 1.5% aqueous solution having a viscosity of 50 to 300 cps at 75 ° C.

There have been some reports on the modification of iota carrageenan. In USP 3,342,612, calcium hydroxide was added to dry dry algae at 3.7% to 7% when the Yukiuma spinosam was dissolved by heating to pH 10.2-11.2, and 90
A method for producing a modified iota carrageenan by a known method after reacting at -100 ° C for 45 minutes to 4 hours, preferably for 1 to 2 hours is described. This method improves the ratio of anhydrogalactose to galactose,
The purpose is to increase the calcium reactivity and to improve the gel strength. Naturally, the reduction of the molecular weight is not preferable, and the alkali treatment condition is adopted so that the molecular cleavage does not occur as much as possible. The 75 ° C viscosity of a 1.5% aqueous solution of the modified extract of Equinoma spinosum by this method is also higher than 40 cps.

USP 3,849,395 is treated with an alkali equivalent to USP 3,342,612 for the purpose of improving the solubility in cold milk, and then subjected to molecular cleavage by acid hydrolysis, and then a modified iota carrageenan is produced by a known method. The method is described and the viscosity of a 1.5% aqueous solution at 75 ° C. is specified as 0.4 to 4.0 cps.

By the way, the quality stabilizer of toothpaste has a great influence on the determination of the rheological properties of toothpaste due to its viscosity and peculiar fluidity. It prevents the separation of the toothpaste and maintains the shape and hardness of the toothpaste, and also has the role of giving a smooth texture in the mouth. Iota carrageenan is superior to Katsupa carrageenan and Lambda carrageenan in these roles.

<Problems to be solved by the invention> However, iota carrageenan extracted from Yukiuma spinosam by a known method and modified iota carrageenan subjected to alkali treatment according to USP 3,342,612 are used as quality stabilizers for toothpaste. It was found that, when the toothpaste was used, the tenacity of the toothpaste was initially good, but it increased with time, and the viscosity and hardness became too high after a certain period of time of the toothpaste, making it practically difficult to use.

Modified iota carrageenan with a viscosity as low as 1.5-75 ℃ 0.4-4.0 cps cannot be used to maintain the shape and hardness of toothpaste when used as a toothpaste quality stabilizer. It cannot be used as a stabilizer.

Therefore, there has been a demand for iota carrageenan capable of imparting stability over time to the viscosity and hardness of the toothpaste while maintaining its role as a quality stabilizer of the toothpaste.

<Means for Solving Problems> The inventors of the present invention have found that among the physical properties of iota carrageenan, the viscosity of the aqueous solution thereof is involved in the stability of toothpaste over time. Invented.

That is, the gist of the present invention resides in a modified iota carrageenan having a 1.5% aqueous solution having a viscosity at 75 ° C. of 5 to 40 cps, and further in a toothpaste containing the modified iota carrageenan.

When iota carrageenan or modified iota carrageenan whose 75 ° C viscosity of a 1.5% aqueous solution exceeds 40 cps is used as a quality stabilizer for toothpaste, the toothpaste at the beginning of production shows an appropriate viscosity, and Although there is no separation, the shape of the toothpaste is maintained, but the viscosity of the toothpaste increases over time as is clear from the results of the accelerated test of the examples described below, and the viscosity is undesirably high, exceeding 37 cps. Will end up.

On the other hand, iota carrageenan with a 1.5% aqueous solution having a viscosity of less than 5 cps at 75 ° C is used as a quality stabilizer for toothpaste when it is used as a quality stabilizer for toothpaste, because the resulting toothpaste lacks in stickiness and hardness. It is inappropriate.

A part of the iota carrageenan of the present invention may be replaced with lambda carrageenan, but in that case, the ratio of iota carrageenan to lambda carrageenan needs to be 1/4 or more. With such a ratio, the effect of stabilizing toothpaste quality is almost the same as that of iota carrageenan of the present invention alone.

The modified iota carrageenan of the present invention may be hydrolyzed in the state of an extract obtained by extracting carrageenan from Equiuma spinosum. This hydrolysis may be alkaline hydrolysis or acid hydrolysis, hydrolysis by an oxidizing agent, or hydrolysis by an enzyme or a microorganism.

Also, even if the hydrolysis is carried out under certain conditions, the viscosity of the modified iota carrageenan obtained varies depending on the type of raw material used and its state, so the hydrolysis conditions cannot be specified unconditionally. A modified iota carrageenan having a predetermined viscosity can be obtained with reference to the liquid viscosity at the time of hydrolysis in consideration of decomposition conditions and the like.

 Next, the toothpaste of the present invention will be described.

Toothpaste contains an abrasive component, a wetting agent, a foaming agent, water and, if necessary, a preservative, a sweetening agent, a flavoring agent and a coloring agent, to which a binder (a quality stabilizer in the present invention) is added. In the toothpaste of the present invention, if the modified iota carrageenan described above as a quality stabilizer or a part of which is substituted with lambda carrageenan is used, the other ingredients are usually used for toothpaste. The components may be used in the ratio usually used. That is, examples of the abrasive component include dibasic calcium phosphate, calcium carbonate, aluminum hydroxide, aluminum oxide, and magnesium hydroxide, and these can also be used as a mixture.

As a wetting agent, glycerin, propylene glycol,
Examples include sorbitol and the like, examples of the foaming agent include sodium lauryl sulfate, sodium fatty acid monoglyceride, and the like, examples of the preservative include sodium benzoate and sodium parahydroxybenzoate, and examples of the sweetener include sodium satsukarin. The quality stabilizer added to the toothpaste is preferably 0.5 to 2.0 wt% of the total toothpaste composition including water.

The toothpaste of the present invention is characterized in that its viscosity at 25 ° C. can be maintained within a preferable range of 22 to 37 cps for a long period of time and its change with time is small.

<Examples> The present invention will be described below with reference to Examples and Comparative Examples.

The compositions of the toothpastes produced in Examples and Comparative Examples were all those shown in Table 1.

Table 1 Calcium phosphate dibasic (abrasive) 43% Glycerin (wetting agent) 20% Quality stabilizer (binder) 1.3% Sodium lauryl sulfate (foaming agent) 1.5% Sodium saccharin (sweetener) 0.2% Benzoic acid Sodium (preservative) 0.01% Fragrance 1.0% Water balance 100.0% In addition, the change in tenacity and hardness of toothpaste over time was evaluated by conducting an accelerated test as follows.

After adjusting the toothpaste, fill two aluminum tubes and leave one in a thermostat bath at 25 ℃ for 24 hours, then viscosity of the toothpaste (25 ℃)
Was measured. In addition, the other one was left in a constant temperature bath of 50 ° C for 3 weeks and then in a constant temperature bath of 25 ° C for 24 hours.
The viscosity at was measured. Stability was evaluated over time based on these two changes in viscosity.

In addition, toothpaste viscosity at 25 ° C and iota carrageenan 1.
The 75 ° C. viscosities of 5% aqueous solutions are both values measured with a BL type viscometer (manufactured by Toki Sangyo).

The characteristics of toothpaste were judged by the presence or absence of separation of the abrasive and the liquid component, the ease of extrusion from the tube, and the feel in the oral cavity.

Therefore, “good” in the characteristic column of Table 2 described later means that there is no separation of the abrasive and the liquid component, the extrusion from the tube is easy, and the feeling in the mouth is good.

Example 1 1.5 kg of low spinosam was washed with water, water was added so that the total amount was about 30 kg, and the mixture was heated and dissolved at 80 ° C. for 1 hour. 10 kg of this liquid was taken, and 100 g of sodium hydroxide was added to this (pH 12.1), followed by hydrolysis treatment for 3 hours, neutralization with hydrochloric acid, addition of a super-auxiliary agent to this, and cake obtained. Three times the amount of isopropyl alcohol was added to the clear liquid to precipitate and collect iota carrageenan. The precipitate was dried and pulverized to obtain iota carrageenan powder. The viscosity of a 1.5% aqueous solution of iota carrageenan at 75 ° C was 17 cps. A toothpaste was produced using this modified iota carrageenan as a quality stabilizer, and changes in the viscosity of the toothpaste over time and the characteristics of the toothpaste were investigated. Table 2 shows the results.

Comparative Example 1 Take 10 kg of the low spinosam solution obtained in Example 1,
A powder of iota carrageenan was obtained in the same manner as in Example 1 except that the hydrolysis treatment and the subsequent neutralization treatment were not performed. The viscosity of a 1.5% aqueous solution of iota carrageenan at 78 ° C was 78 cps. The change in viscosity with time of a toothpaste using this as a quality stabilizer was investigated. Table 2 shows the results.

This toothpaste was as good as the toothpaste obtained in Example 1 after 24 hours at 25 ° C., but 50 ° C. for 3 weeks, then 25 ° C.
After being left for 24 hours, it was too hard to extrude from the tube even if force was applied, and when it was forcibly extruded and used, the feel in the mouth was not smooth and was poor.

Comparative Example 2 A modified iota carrageenan powder was obtained in the same manner as in Example 1 except that the amount of sodium hydroxide added was 50 g (pH 11.0) as the hydrolysis treatment condition of the solution. The viscosity of this modified iota carrageenan 1.5% aqueous solution at 75 ° C. was 42 cps.

Table 2 shows the evaluation results of the temporal stability and the toothpaste characteristics of the toothpaste using this.

Example 2 A modified iota carrageenan powder was obtained in the same manner as in Example 1 except that semi-treating spinosam was used instead of low spinosam. The viscosity of this 1.5% aqueous solution at 75 ° C was 33 cps. Table 2 shows the stability and characteristics of toothpaste using this over time.

Example 3 Iota carrageenan powder was obtained in the same manner as in Example 2 except that the same semi-treated tepid spinosum as used in Example 2 was not used and hydrolysis and subsequent neutralization were not performed.

The viscosity of this 1.5% aqueous solution at 75 ° C. was 280 cps.

Comparative Example 4 A modified iota carrageenan powder was obtained in the same manner as in Example 2 except that the same semi-treated spinosam as used in Example 2 was used and the hydrolysis treatment time was set to 1 hour.

 The viscosity of this 1.5% aqueous solution at 75 ° C. was 120 cps.

Comparative Example 5 A 1.5% aqueous solution having a viscosity of 64 cps was modified in the same manner as in Example 2 except that the same semi-treating spinosam as used in Example 2 was used and the hydrolysis treatment time was 2 hours. Iota carrageenan powder was obtained.

A toothpaste was prepared using the iota carrageenan or the modified iota carrageenan of Comparative Examples 3 to 5, and the change in viscosity with time was examined. Table 2 shows the results.

Example 3 Pretreated Spinosam was used in place of Low Spinosam, and 70 g of sodium hypochlorite (effective chlorine 12%) was added as a hydrolysis treatment condition, and a treatment for 30 minutes was adopted, except that neutralization was not performed. 7% of 1.5% aqueous solution in the same manner as in Example 1.
A modified iota carrageenan powder having a viscosity of 12 cps at 5 ° C. was obtained.

A toothpaste was produced by using this as a quality stabilizer, and the change in viscosity of the toothpaste with time was examined. Table 2 shows the results.

Comparative Example 6 Iota carrageenan powder was obtained in the same manner as in Example 3 except that the same pretreated spinosam as used in Example 3 was not used for hydrolysis, and this was used to obtain a toothpaste. The results of changes in the viscosity with time are shown in Table 2.

The viscosity of this 1.5% aqueous solution of iota carrageenan at 75 ° C was 95 cps.

Comparative Example 7 The viscosity of a 1.5% aqueous solution at 75 ° C. was the same as in Example 3 except that the same pretreating spinosam as used in Example 3 was used and the amount of sodium hypochlorite added was 100 g. A modified iota carrageenan of 3.5 cps was obtained, and a toothpaste was prepared using the modified iota carrageenan.

This toothpaste, which had been kept at 25 ° C. for 24 hours, was already a defective product in which the abrasive and the liquid component were separated.

Examples 4 and 5 Pretreated spinosams having a viscosity of 102 at 75 ° C. of a 1.5% aqueous solution of iota carrageenan obtained by the same treatment as in Comparative Example 1 were used, and acetic acid was used as a hydrolysis condition. PH was adjusted to 5.0 (Example 4) and 4.5 (Example 5) by addition, the liquid was maintained at 90 ° C. for 2 hours, and then neutralized with sodium hydroxide. Modified iota carrageenan (1.5
% Aqueous solution at 75 ° C. Example 4:10 cps, Example 5: 6.0
cps) powder was obtained.

A toothpaste was prepared using these modified iota carrageenan.

 Table 2 shows the change in viscosity with time and the characteristics.

Comparative Example 8 Obtained in the same manner as in Example 4 except that hydrolysis was not performed.
A toothpaste was prepared using iota carrageenan with a viscosity of 102 at 75 ° C in a 1.5% aqueous solution, and its characteristics were investigated. Table 2 shows the results.

Examples 6 and 7, Comparative Example 9 (Modified) iota carrageenan obtained in Examples 4,5 and Comparative Example 8 and Gigartena Scotts Belgium (Gigartina)
Scottsbergii) was used, and lambda carrageenan extracted and purified in the same manner as in Comparative Example 1 was used in a weight ratio of 1: 1 to prepare a toothpaste using this as a quality stabilizer, and its viscosity change with time and toothpaste characteristics were evaluated. Examined. Table 2 shows the results.

Comparative Example 10 A modified iota carrageenan was prepared according to USP 3,342,612. That is, the raw algae of low spinosum, semi-treatized spinosome and pretreatized spinosome are each 1.5 k
After washing with g each, water was added so that the total amount became 30 kg, and 7.0% of sodium hydroxide was added to dry dry algae. Then, the mixture was treated at 95 ° C. for 2 hours, neutralized with hydrochloric acid, and then treated in the same manner as in Comparative Example 1 to obtain a modified iota carrageenan powder. 1.Powder products obtained from each algae
The 5 ° C. viscosity of the 5% aqueous solution was 45 cps, 84 cps and 60 cps.

Toothpastes were produced using each modified iota carrageenan as a quality stabilizer, and the change in viscosity of toothpaste with time and the toothpaste characteristics were investigated. Table 2 shows the results.

Comparative Example 11 A modified iota carrageenan was produced according to USP 3,849,395. That is, the raw algae of low spinosum, semi-treatized spinosum, and pretreatted spinosome were each compared with Comparative Example 10
In the same manner as above, the acetic acid was added to each of the extracts that had been extracted, alkali treated, and neutralized with hydrochloric acid to adjust the pH to 4.0, treated at 90 ° C for 2 hours, and then neutralized with sodium hydroxide. Then, each modified iota carrageenan powder was obtained in the same manner as in Comparative Example 10. The 75 ° C viscosity of a 1.5% aqueous solution is
It was 1.5, 3.0 and 2.0 cps.

Toothpaste was produced using each modified iota carrageenan as a quality stabilizer. None of the toothpastes had stickiness and hardness, and any modified iota carrageenan produced in this Comparative Example was a toothpaste quality stabilizer. As inappropriate.

 The viscosity of toothpaste is shown in Table 2.

<Effect of the Invention> As is clear from the above examples and comparative examples, 1.5
% Aqueous solution having a viscosity of 5-40 cps at 75 ° C. Iota carrageenan has the excellent properties originally possessed by using it alone or in combination with lambda carrageenan as a quality stabilizer for toothpaste. While maintaining the (prevention of separation of the abrasive and the liquid component, the smooth feel in the mouth), the disadvantage of the conventional problem that the viscosity of the toothpaste increases with time and becomes hard, is solved.
It has an excellent effect, and a toothpaste using this as a quality stabilizer has the characteristic that it can maintain its original excellent properties over a long period of time.

Claims (2)

[Claims] 1. A modified iota carrageenan characterized in that a 1.5% aqueous solution has a viscosity at 75 ° C. of 5 to 40 cps. 2. A toothpaste containing a modified iota carrageenan having a viscosity at 75 ° C. of a 1.5% aqueous solution of 5 to 40 cps.