JPH1025303A - Toothpaste containing lambda-carrageenan and modified iota-carrageenan - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toothpaste from which such a defect is eliminated as viscosity increases with the lapse of time as to become hard while being prevented from syneresis of liquid components from polishing agents and maintaining smooth touch in mouth. SOLUTION: This toothpaste comprises lambda-carrageenan and modified carrageenan the aqueous 1.5% solution of which has viscosity of 5-40cPs at 75 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a toothpaste containing carrageenans as a stabilizer for toothpaste.

[0002]

2. Description of the Related Art Carrageenan is a water-soluble natural polysaccharide composed mainly of galactose sulfate extracted and purified from red algae. Carrageenan is roughly classified into three types, kappa, lambda and iota, depending on the molecular structure. Carrageenan is mainly Euchema Spinosam
inosum) and purified.

[0003] In general, eukyuma spinosum used for the extraction of iota carrageenan depends on the method of treating the seaweed.
They are roughly classified into species. That is, raw spinach (raw spinosum) obtained by simply drying seaweed collected from the sea in the sun.
sum), seaweed at 70-95 ° C for 30-120 minutes for 3-
A pretreated spinosum (Pre) treated with a 10% aqueous solution of potassium hydroxide to recover solids, washed with water and dried
treated spinosum) and seaweed in 4
A semi-treated spinosum (Semitreated Spinosum) treated with a 0.5 to 2.0% aqueous potassium hydroxide solution at 0 to 60 ° C to collect solids, washed with water and dried.
um).

Conventionally, any of the eukuma spinosams can be purified by a known purification method, that is, washing the seaweed with water, heating and dissolving it, removing the undissolved matter, and then mixing with a water-miscible organic solvent. The carrageenan is precipitated, and the precipitated substance is recovered, dried and pulverized. "
0 to 300 cps.

There have been several reports on the modification of iota carrageenan. USP3,34
At 2,612, calcium hydroxide was added at 3.7% to 7% to the dry original alga at the time of heating and dissolving Eucuma spinosam to adjust the pH to 10.2 to 11.2, and 90 ° C to 100 ° C.
For 45 minutes to 4 hours, preferably 1 to 2 hours, and then producing a modified iota carrageenan by a known method. This method aims at increasing the ratio of anhydrogalactose to galactose, increasing calcium reactivity, and improving gel strength. Naturally, reduction in molecular weight is not preferable, and alkali which does not cause molecular cleavage as much as possible Processing conditions are adopted. The 75 ° C. viscosity of a 1.5% aqueous solution of the modified extract of Eucuma spinosam according to this method is also higher than 40 cps.

[0006] USP 3,849,395 is subjected to an alkali treatment equivalent to that of USP 3,342,612 for the purpose of improving solubility in cold milk, followed by molecular cleavage by acid hydrolysis, followed by a known method. Describes a method for producing a modified iota carrageenan, wherein the viscosity of a 1.5% aqueous solution at 75 ° C. is specified to be 0.4 to 4.0 cps.

[0007] By the way, the quality stabilizer of toothpaste has a great influence on the determination of the rheological properties of toothpaste because of its viscosity and peculiar fluidity. It has the role of preventing the separation of liquid and liquid components, keeping the shape and hardness of the toothpaste and giving a smooth tactile sensation in the mouth. Iota carrageenan excels in these roles compared to kappa carrageenan and lambda carrageenan.

[0008]

However, as a quality stabilizer for toothpaste, iota carrageenan extracted from Eucuma spinosam by a known method and modified iota carrageenan subjected to alkali treatment according to US Pat. No. 3,342,612 are used. When used, toothpaste has good toughness / hardness at first, but increases over time, and after a certain period of toothpaste, it becomes too sticky and too hard to be practically difficult to use did.

[0009] 1.5% 75 ° C viscosity is 0.4-4.0 cp
When a modified iota carrageenan such as s is used as a toothpaste quality stabilizer, it cannot maintain the shape and hardness of the toothpaste and cannot be used as a toothpaste quality stabilizer. It is.

[0010] Therefore, there has been a demand for iota-carrageenan, which can impart the stability over time to the stickiness and hardness of the toothpaste while maintaining the role of the toothpaste as a quality stabilizer.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies and found that among the physical properties of iota-carrageenan, the viscosity of the aqueous solution is involved in the temporal stability of toothpaste. Reached.

That is, the gist of the present invention is that lambda carrageenan and a 1.5% aqueous solution at 75 ° C. have a viscosity of 5 to 40 cp.
s is a modified toothpaste containing modified iota carrageenan.

A 75% viscosity of a 1.5% aqueous solution is 40 cps.
If iota-carrageenan or modified iota-carrageenan is used as a toothpaste quality stabilizer, the toothpaste at the beginning of production will have an appropriate viscosity, no separation of the abrasive and liquid components, and the shape of the toothpaste will be Although it is maintained, the viscosity of the toothpaste increases with time, as is apparent from the results of the acceleration test in the examples described later, and the viscosity becomes undesirably high, exceeding 37 cps.

On the other hand, the viscosity of a 1.5% aqueous solution at 75 ° C. is 5c
When iota-carrageenan of less than ps is used as a quality stabilizer for toothpaste, the resulting toothpaste is insufficient in stickiness and hardness and is unsuitable as a quality stabilizer for toothpaste.

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

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

Further, even if the hydrolysis is carried out under a certain condition, the viscosity of the modified iota carrageenan obtained varies depending on the kind of the raw material used and the state thereof, so that the hydrolysis conditions cannot be specified unconditionally. A modified iota carrageenan having a predetermined viscosity can be obtained by referring to the liquid viscosity at the time of hydrolysis in consideration of hydrolysis 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 sweetener, a flavor, and a colorant, and further contains a binder (a quality stabilizer in the present invention). In the toothpaste of the present invention, if the modified iota carrageenan and lambda carrageenan described above are used as quality stabilizers, other components usually used in toothpaste are usually used. The ratio may be used. That is, as the abrasive component, dicalcium phosphate,
Examples thereof include calcium carbonate, aluminum hydroxide, aluminum oxide, and magnesium hydroxide, and these may be used in combination.

Examples of the humectant include glycerin, propylene glycol, and sorbitol; examples of the foaming agent include sodium lauryl sulfate and sodium fatty acid monoglyceride; examples of the preservative include sodium benzoate and sodium parahydroxybenzoate; Examples include saccharin sodium. The quality stabilizer added to the toothpaste is 0.5 to 2.0 of the total toothpaste composition including water.
It is preferably wt%.

The toothpaste of the present invention has a viscosity at 25 ° C. of 2
It has a feature that it can be maintained in a preferable range of 2 to 37 cps for a long period of time and there is little change with time.

[0022]

The present invention will be described below with reference to examples and comparative examples.

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

[0024]

[Table 1] The change over time in the stickiness and hardness of the toothpaste was evaluated by performing an acceleration test as described below.

After adjusting the toothpaste, two aluminum tubes were filled, and one of the tubes was left in a thermostat at 25 ° C. for 24 hours, and then the viscosity (25 ° C.) of the toothpaste was measured. Another one is 50 ℃
After being left in a thermostat for 3 weeks, the viscosity of the toothpaste at 25 ° C after being left in a thermostat at 25 ° C for 24 hours was measured. The evaluation of stability over time was carried out from these two changes in viscosity.

Both the toothpaste viscosity at 25 ° C. and the 75 ° C. viscosity of a 1.5% aqueous solution of iota carrageenan are values measured by a BL viscometer (manufactured by Toki Sangyo Co., Ltd.).

The characteristics of the toothpaste were determined based on the separation of the abrasive and the liquid component, the ease of extrusion from the tube, and the feeling in the oral cavity.

Accordingly, "good" in the property column of Table 2 described below means that there is no separation between the abrasive and the liquid component, the extrusion from the tube is easy, and the feel in the mouth is good.

REFERENCE EXAMPLE 1 After washing 1.5 kg of low spinosum with water, water was added so that the total amount was about 30 kg.
The mixture was dissolved by heating at 0 ° C. for 1 hour. Take 10 kg of this solution and add 100 g of sodium hydroxide (pH 12.
1) After hydrolyzing for 3 hours, neutralize with hydrochloric acid, add a filter aid to this, and add 3% to the clear solution obtained by cake filtration.
Iota carrageenan was precipitated and recovered by adding twice the volume of isopropyl alcohol. The precipitate was dried and pulverized to obtain powder of iota carrageenan. The viscosity at 75 ° C. of this 1.5% aqueous solution of iota carrageenan was 17 cps. A toothpaste was manufactured using this modified iota carrageenan as a quality stabilizer, and the change in the toothpaste viscosity with time and the characteristics of the toothpaste were examined. Table 2 shows the results.

Comparative Example 1 10 kg of the low spinosum solution obtained in Reference Example 1 was taken and powdered with iota-carrageenan was prepared in the same manner as in Reference Example 1 except that hydrolysis and subsequent neutralization were not performed. Obtained. The viscosity of this 1.5% aqueous solution of iota carrageenan at 75 ° C. is 78 cp.
s. The change in viscosity over time of toothpaste using this as a quality stabilizer was examined. Table 2 shows the results.

This toothpaste was as good as the toothpaste obtained in Reference Example 1 after 24 hours at 25.degree.
After being left for 24 hours at 25 ° C. for a week, it was too hard to extrude from the tube even if force was applied. When it was forcibly extruded and used, the feel in the mouth was not smooth and poor.

Comparative Example 2 The amount of sodium hydroxide added was set to 50 g (pH 1)
A modified iota carrageenan powder was obtained in the same manner as in Reference Example 1 except for 1.0). This modified iota carrageenan 1.5
% Aqueous solution at 75 ° C. was 42 cps.

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

Reference Example 2 A modified iota carrageenan powder was obtained in the same manner as in Reference Example 1 except that a semi-treated spinosum was used instead of the low spinosum. This 1.5
% Aqueous solution at 33 ° C. was 33 cps.
Table 2 shows the aging stability and properties of toothpaste using this.

Comparative Example 3 An iota-carrageenan powder was obtained in the same manner as in Reference Example 2, except that hydrolysis and subsequent neutralization were not carried out using the same semi-treated spinosum as used in Reference Example 2.

The viscosity of the 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 Reference Example 2 except that the same semi-treated spinosum as used in Reference Example 2 was used and the hydrolysis treatment time was changed to 1 hour.

The viscosity of this 1.5% aqueous solution at 75 ° C. is 1
It was 20 cps.

Comparative Example 5 Using the same semi-treated spinosum as used in Reference Example 2, the hydrolysis treatment time was 2
A modified iota carrageenan powder having a viscosity of 64 cps at 75 ° C. of a 1.5% aqueous solution was obtained in the same manner as in Reference Example 2 except for changing the time.

Toothpastes were prepared using the iota-carrageenan or the modified iota-carrageenan of Comparative Examples 3 to 5, and the time-dependent change in viscosity was examined. Table 2 shows the results.

[Reference Example 3] Pretreated spinosum was used in place of low spinosum, and 70 g of sodium hypochlorite (effective chlorine 12%) was added as a hydrolysis treatment condition, and a 30 minute treatment was employed to neutralize. Except when not performed, the viscosity of the 1.5% aqueous solution at 75 ° C. was 12 in the same manner as in Reference Example 1.
A modified iota carrageenan powder of cps was obtained.

Using this as a quality stabilizer, toothpaste was manufactured, and the viscosity change of the toothpaste over time was examined. Table 2 shows the results.

Comparative Example 6 Iota-carrageenan powder was obtained in the same manner as in Reference Example 3 except that hydrolysis was not performed using the same pretreated spinosum as used in Reference Example 3, and toothpaste was used with this. Obtained. Table 2 shows the results of the time-dependent changes in the viscosity.

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

Comparative Example 7 A 1.5% aqueous solution was prepared in the same manner as in Reference Example 3, except that the same pretreated spinosum as used in Reference Example 3 was used and the amount of sodium hypochlorite added was changed to 100 g. A modified iota carrageenan having a viscosity of 3.5 cps at 75 ° C. was obtained, and a toothpaste was prepared using the modified iota carrageenan.
Table 2 shows the results of the time-dependent changes in the viscosity.

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

[Reference Examples 4 and 5] A pretreated spinosum having a viscosity of 102 cps at 75 ° C. of a 1.5% aqueous solution of iota-carrageenan obtained by performing the same treatment as in Comparative Example 1 was used. The pH was adjusted to 5.0 (Reference Example 4) and 4.5 (Reference Example 5) by adding acetic acid as a hydrolysis condition, and the solution was maintained at 90 ° C. for 2 hours, and then neutralized with sodium hydroxide. The modified iota-carrageenan (1.
Viscosity of 5% aqueous solution at 75 ° C. Reference Example 4: 10 cp
s, Reference Example 5: 6.0 cps) powder was obtained.

A toothpaste was prepared using these modified iota carrageenans.

Table 2 shows the time-dependent changes and characteristics of the viscosity.

Comparative Example 8 A toothpaste was prepared by using iota-carrageenan having a viscosity of 102 cps at 75 ° C. of a 1.5% aqueous solution obtained in the same manner as in Reference Example 4 except that hydrolysis was not carried out. Examined. Table 2 shows the results.

[Examples 1 and 2, Comparative Example 9] Reference Examples 4 and 5
And (modified) iota carrageenan obtained in Comparative Example 8 and Gigartena Scotts Belgium (Gigartina).
Lambda carrageenan extracted and purified in the same manner as in Comparative Example 1 except that Scottsbergii) was used at a weight ratio of 1: 1 to prepare a toothpaste as a quality stabilizer. Was examined. Table 2 shows the results.

Comparative Example 10 USP 3,342,612
To produce a modified iota carrageenan. That is, after 1.5 kg each of the raw algae of low spinosum, semi-treated spinosum and pretreated spinosum was washed with water, water was added so that the total amount became 30 kg each, and sodium hydroxide was added to the dried raw algae by 7 kg. 0.0% was added. Next, after treatment at 95 ° C. for 2 hours, the mixture was neutralized with hydrochloric acid.
The same treatment as in Comparative Example 1 was performed to obtain a powder of modified iota carrageenan. 1.5 of the powder product obtained from each original algae
The 75 ° C. viscosities of the% aqueous solutions were 45 cps, 84 cps and 60 cps.

Toothpastes were prepared using each of the modified iota carrageenans as a quality stabilizer, and the viscosity change of the toothpaste over time and the toothpaste characteristics were examined. Table 2 shows the results.

Comparative Example 11 USP 3,849,395
To produce a modified iota carrageenan. That is, raw algae of low spinosum, semi-treated spinosum, and pretreated spinosum were each extracted and alkali-treated in the same manner as in Comparative Example 10, and then acetic acid was added to the extract neutralized with hydrochloric acid, followed by pH adjustment. Was adjusted to 4.0, treated at 90 ° C. for 2 hours, and then neutralized with sodium hydroxide. Thereafter, powders of each modified iota carrageenan were obtained in the same manner as in Comparative Example 10. The 75 ° C. viscosity of the 1.5% aqueous solution is 1.
5, 3.0 and 2.0 cps.

A toothpaste was produced using each of the modified iota-carrageenans as a quality stabilizer. However, none of the toothpastes was sticky or hard, and any of the modified iota-carrageenans produced in this comparative example had the same quality as the toothpaste. Not suitable as stabilizer.

The viscosity of toothpaste is shown in Table 2.

[0057]

[Table 2]

[0058]

[Table 3] * 1 Viscosity: The viscosity of a 1.5% aqueous solution at 75 ° C. * 2 Viscosity and hardness were insufficient, and separation of the abrasive and the liquid component was observed. * 3 It was too hard to be extruded or difficult to extrude from the tube, and the tactile sensation in the mouth was poor.

[0059]

As is clear from the above Examples and Comparative Examples, the viscosity of a 1.5% aqueous solution at 75 ° C. was 5 to 40 cp.
The combination of modified iota carrageenan and lambda carrageenan, which are s, is used as a quality stabilizer for toothpaste to provide superior properties inherent to iota carrageenan (prevention of separation of abrasive and liquid components, While maintaining the smooth touch), the problem of the conventional problem that the toothpaste increases in viscosity over time and becomes hard,
It has an excellent effect, and toothpaste using it as a quality stabilizing agent has the feature that it can maintain its original excellent properties for a long period of time.

Claims (1)

[Claims] 1. A toothpaste comprising lambda carrageenan and modified iota carrageenan having a 1.5% aqueous solution having a viscosity at 75 ° C. of 5 to 40 cps.