DK157900B - DENTAL CREAM - Google Patents

Description

DK 157900 B

The present invention relates to a toothpaste, as claimed in the preamble of claim 1, which has a desirable rheological character. In particular, it relates to a toothpaste with a smooth texture with little tendency to form grains, especially in aging at low temperature.

Calcium carbonate or chalk has long been used as a tooth polish. In spite of its effectiveness in polishing teeth, it had previous disadvantages in that it tended to give a toothpaste a somewhat slimy feel. Recently, however, grades of calcium carbonate have emerged which essentially avoid this problem.

Nevertheless, it has been observed that in toothpaste containing 15 calcium carbonate, including modern grades of the material, granular formation occurs after storage at low temperatures, e.g. between -7 and 7 ° C when the cream further contains sodium alkyl sulphate as a surfactant and especially sodium alkyl sulfate with a wide distribution of alkyl chain lengths such as 20 to 1% C10, 40 to 70¾ C12, 13 to 30% C14, 5- 16% C16 and 0-23% C18.

Sodium alkyl sulfate has long been used in toothpastes, but it has generally been used as a low dispersion material in the composition wherein at least 90%, even 99%, of the alkyl groups are C 2. Toothpaste containing calcium carbonate and low alkyl sodium sulfate in the composition is not granulated even when aging at low temperatures. It is when using sodium lauryl sulfate with a broad alkyl distribution that problems occur with grain after aging at low temperatures.

From Norwegian Patent Specification No. 142,653, it is known to use calcium carbonate in toothpastes together with alkyl sulfate.

35 As alkyl sulfate, among others, sodium aryl sulfate is mentioned.

In Anthony M. Schwartz and James W. Perry, Surface Active Agents (New York 1949), pages 53-55, section "Sulfated Alcohols", it is stated that a mixture of "coconut fatty alcohol" is often referred to as "lauryl alcohol". Ibid, pages 448-449 is mentioned the use of alkyl sulfates in toothpastes.

2

DK 157900 B

US Patent No. 2,812,284 discloses a dentifrice which is said to have superior rapid foaming and improved taste properties, the dentifrice containing a mixture of water-soluble salts of fatty acid monoglyceride sulfonates and water-soluble salts of fatty alcohol sulfates containing 10 to 18 carbon atoms per fat. Dicalcium phosphate is mentioned as a polishing agent in these dentifrices.

U.S. Patent No. 2,041,473 discloses dentifrice polishing materials comprising a powder of the tricalcium phosphate and calcium and magnesium carbonate group and a minor amount of an alkali metal pyrophosphate, the latter being present in a substantially smaller amount than that which will be sufficient to dissolve the calcium or magnesium present. It is not stated in this US patent that alkyl sulfates should be included in the dentifrices described.

U.S. Patent No. 337,532 discloses the use of tetrasodium pyrophosphate as an additive to stabilize chlorophyll in dentifrices which will usually contain a surfactant or a cleaning ingredient. Examples of suitable materials are soaps and additionally synthetic surfactants. As an example of synthetic surfactant, among others, sodium lauryl sulfate is mentioned.

British Patent Nos. 1,475,251 and 1,475,252 disclose oral care products, especially toothpastes, containing 20-75% by weight of a polishing material comprising α-alumina trihydrate and in which an anionic surfactant is used. phosphate ester comprising a mixture of monoester 35 of formula 3

DK 157900 B

0 I) R (° c2H4) n0P ”0M and

5 OM

diester of the formula 0 10 0

R (0C2H4) n 0-P-0 (C2H40) n

ABOUT

Wherein R is an alkyl group of 10-20 carbon atoms, n is an integer from 1 to 5 and M is hydrogen, alkali metal or ammonium.

The surfactant is incorporated into such toothpastes to eliminate the adverse effects of the alkalinity of α-alumina trihydrate on unlined aluminum containers.

20

From Swiss Patent Specification No. 569,477 it is known to use tetrasodium pyrophosphate in combination with calcium carbonate and sodium alauryl sulfate in toothpastes. However, the amount of calcium carbonate in the prior art toothpastes is low, in Example 2 of the patent 25 given at 4.97% by weight.

It is an object of the present invention to provide a toothpaste comprising calcium carbonate and sodium alkyl sulphate having a wide distribution of alkyl chain lengths, which toothpaste has 30 desirable rheological properties and is essentially grain-free.

The invention thus relates to a toothpaste containing from 20 to 75% by weight of a calcium carbonate as a polishing material and from 0.1 to 35% by weight of a surfactant including sodium C10-C18 alkyl sulfate having a wide distribution of alkyl groups, with C 2 content is 40 to 70% by weight, in an amount of 4

DK 157900 B

preferably 1-2% by weight, which toothpaste is free of granulation after storage at low temperature, and is characterized in that it contains as a granular agent 0.2 to 1% by weight of an M4 pyrophosphate or an anionic phosphate ester about 5%. forming a mixture of monoester of formula 0

II

R (OC2H4) n ° P-0M and

10 ... I

ABOUT

diester of formula 0

II

R (0C2H4) n 0-P-0 (C2H40) n

ABOUT

Wherein M is hydrogen, alkali metal or ammonium, R is an alkyl group having 10 to 20 carbon atoms and n is a number from 1 to 5.

Calcium carbonate is available in various grades, especially as chalk. Qualities used in the present invention may e.g. have an apparent density of 0.47 to 0.61 g per cm 3, a flow point of 1.2-1.5 mg / g, a moisture loss at 105 ° C of 1 to 2%, a particle size of at least 99, 7% of the particles are finer than 74 microns, the average size being 4 to 9 microns and no more than 90% 30 being less than 18m of crown, and the material is composed of calcite and aragon it in a ratio of 1: 9 to 3: 1, typically 1:10, 1: 1 or 3: 1. Suitable grades can be obtained from John and E. Sturge Ltd., Birmingham, England, e.g. as "Sturcal" H and from Johann Schaefer Kalkwerke, Dies West Germany as "Schaefer" AC.

35

The polishing material preferably comprises from 40 to 55% of the toothpaste and preferably at least 95% of the polishing material is calcium.

DK 157900 B

carbonate. In addition to calcium carbonate, the polishing material may optionally contain up to 5% of its content of an additional polishing material such as dicalcium phosphate (anhydrous or dihydrate), tricalcium phosphate, dimagnium phosphate, trimagneium phosphate, insoluble sodium metaphosphate, hydrated alumina or silica.

A particular sodium Cig-Cjg alkyl sulphate used for the present invention contains approx. 3% Cj / 58% C12> 21% C14 »10 9% C1g and 11% C3 alkyl groups and are commercially available in the form of needles, such as" LZV "from the Marchon Division of Albright and Wilson, Whitehaven, England. Other grades of sodium C 10 -C 18 alkyl sulfate with broad alkyl distributions that can be used are "Tensopol ACL 17" from Tensia S.A. Liege, Belgium and Texapon® ZHC 15 from Henkel and Cie, Dlisseldorf, West Germany. These grades of sodium C ^ o-C ^allallallyl sulfate contain 40 to 70% C₂₂ in their cooling distribution. In particular, they typically have a cooling distribution of 1 to 8% C10, 4 to 70% C12, 13 to 30% C14, 5 to 15% C16, and 0 to 23% C All of the cooling groups are substantially straight chain (normal).

In addition to Natriurn-C ^-Curn-alkyl alkyl sulfate with wide cooling distribution, the toothpaste may optionally contain an additional surfactant. These agents may include anionic materials, e.g. water-soluble salts of higher fatty acid monoglyceride monosulfate (e.g., sodium coconut fatty acid monoglyceride monosulfate), alkylarylsulfonate (e.g., sodium dodecylbenzene sulfonate), higher fatty acid esters of 1,2-dihydroxypropanesulfonate (e.g. phosphate ester of the type shown above that is also effective as an additive to reduce grain formation.

A nonionic or ampholytic surfactant may also be present, which agents include nonionic agents such as sorbitan monosterarate having about. 60 moles of ethylene oxide, condensates of ethylene oxide with propylene glycol (available under the trade name Pluronic®) and amphoteric agents such as quaternization 6

DK 157900 B

prepared imidazole derivatives available under the trade name Miranol, such as Miranol® C2M. It is preferred that the total amount of surfactant does not exceed 5% by weight of the oral care agent. The total surfactant content of the 5 toothpaste is 0.1 to 5% by weight. Preferably, 1 to 2% by weight of sodium C1-C1-6 alkyl sulfate with wide alkyl distribution is found.

The additive which lowers the grain formation at low temperature storage such as from -7 to 7 ° C is an M4 pyrophosphate or the anionic phosphate ester mixture of monoester and diester as defined above. When the anionic phosphate ester is used, it can also serve as part of the surfactant.

The M4 pyrophosphate may be tetrasodium pyrophosphate in its anhydrous or hydrated forms. (Ν84Ρ2θγ, IOH2O) is a preferred material. The corresponding tripolyphosphate is not believed to be effective in reducing grain.

The anionic phosphate esters are mixtures of mono- and diesters of the above formulas. They are available from the M0D0 Kemi Aktie company, formerly Bero! Aktiebolaget, Sweden under the name Bero! ® and may include an anionic triester moiety, as well as a nonionic moiety. Berol® 729 has an all cool chain length of 16 25 to 18 carbon atoms and contains rows of 4 ethylene oxide units. Since the acid form of Berol® 729 typically provides a finished oral composition with a pH value below 6, this material is generally used in neutralized or partially neutralized form to ensure a pH value above about 10%. 6 in the finished oral care.e-30 ml ddel.

Other anionic phosphate esters which can be used in acidic or neutralized form are Berol® 525 containing alkyl groups of 10 to 18 carbon atoms and rows of 5 ethylene oxide units, 35 and Berol® 513 containing alkyl groups of 16 to 18 carbon atoms. The use of B'erol® 525 can also provide a finished oral preparation with a pH value below 6, and it is preferred that 7

DK 157900 B

use it in neutralized or partially neutralized form. Other Bero! ® anionic phosphate esters are available such as Bero! ® 521, Berol ® 724 and Berol ® 733. 1:10 to 10: 1.

5

The grain reduction additive is used in an amount of from 0.2 to 1% by weight, preferably 0.2 to 0.5%. When a dentifrice containing calcium carbonate and sodium lauryl sulfate is prepared with a wide alkyl group distribution but not containing the anti-grain additive, the granulation can be observed after aging for a month at low temperatures such as -7 to 7 ° C, typically 4 ° C.

The toothpaste contains as a carrier for the polishing material additive for grain reduction and the other constituents, liquids and solids adapted to form an extensible crumb mass of the desired consistency. In general, fluids in the toothpaste will comprise mainly water, glycerine, sorbit, propylene glycol or suitable mixtures thereof. It is generally advantageous to use a mixture of both water and a binder or moisture-binding agent such as glycerine and / or sorbit. It is preferred to use glycerine or mixtures of glycerine with sorbit. The moisture binding agent is generally used in an amount between 20 and 25% and preferably about 20%.

22%. The total liquid content will generally be 20 to 25 65% by weight of the composition as the water is contained in an amount which brings the total components up to 100%.

It is also preferred to use a gelling agent in toothpastes such as the natural and synthetic rubbers and rubber = 30 like materials, e.g. Irish moss, tragacanth, sodium car = boxymethyl cellulose, polyvinyl pyrrolidone, starch and the like, all referred to as rubber. Irish moss and sodium carboxymethyl cellulose are particularly compatible and are preferred gelling agents. The rubber content is usually in an amount of up to about 5 to approx. 10% and preferably 0.5 to 5% by weight of the composition, with rubber in an amount of 0.9 to 1.3% being particularly preferred.

8

DK 157900 B

The total amount of liquid and gelling agent (rubber) forms the tandem carrier in which the other components are dispersed or dissolved.

Various other materials can be incorporated into the toothpaste of the invention. Examples of these are staining and whitening agents, flavoring agents, sweetening agents, preservatives, silicones, chlorophyll compounds and ammoniated materials such as urea, diammonium phosphate and mixtures thereof. These additives are incorporated in the present compositions in amounts which do not substantially damage the properties of the particular type of composition concerned.

A fluoride-releasing compound may also be present. These 15 compounds may be slightly soluble in water or may be completely water soluble. They are characterized by their ability to release fluoride ions in water and by being essentially free of reaction with other compounds in the oral composition. Among these materials are inorganic fluoride salts such as suitable alkali metal, alkaline earth metal and heavy metal salts, e.g. sodium fluoride, potassium fluoride, ammonium fluoride, copper fluoride, such as copper fluoride, zinc fluoride, tin fluoride such as stannofluoride or stanochlorofluoride, barium fluoride, sodium fluoride, sodium ammonium fluoride, sodium ammonium fluoride Alkali metal and tin fluorides such as sodium and stannofluoride and also sodium monofluorophosphate are preferred.

The following examples further illustrate the nature of the invention. Oral care products are prepared in the usual manner except where indicated and all quantities are by weight unless otherwise stated. Preparation A is according to the prior art and Preparation B and C are according to the invention.

35 9

DK 157900 B

Example

The following dentifrices were prepared which were placed in unlined aluminum tubes: 5

Components Parts

A B C

Glycerin 6.060 6.060 6.060

Sodium carboxymethyl = 1,200 1,200 1,200 µl of cellulose

Sodium saccharin 0.200 0.200 0.200

Sodium silicate 0.200 0.200 0.200

Sorbit (70%) 16,000 16,000 16,000

Tetrasodium pyro = --- 0.500 --- phosphate Berol ^ l3X --- --- 0.500

Deionized water 23,433 22,933 22,933

Calcium carbonate 42,000 42,000 42,000

Natgium-C---C g alkyl sulfate 1,807 1,807 1,807

LZV

Aroma 1,100 1,100 1,100 pH 8,65 9,44 8,20 x Berol®> 13 used in dentifrice C is a mixture of anionic phosphate monoesters and diesters of the previously mentioned formulas, wherein the alkyl group contains 16 to 18 carbon atoms. It is a paste-like material with a weight = density of approx. 1.050 / cm 2 at 30 ° C. It is available from MoDo Kemi Aktiebolaget, Sweden.

** The calcium carbonate used in dentifrices A, B and C is "Sturcal® H" chalk available from John & E. Sturge Ltd., Bir mingham, England. 1

The sodium C10-C18 alkyl sulfate used in dentifrices A, 35 B and C is "LZV", a broad spectrum needle material available from the Marchon Division at Albright and Wilson.

Claims (2)

A toothpaste containing from 20 to 75% by weight of a calcium 30 carbonate as a polishing material and from 0.1 to 5% by weight of a surfactant including sodium C C--C g gyalkyl sulfate having a wide distribution of alkyl groups, wherein Cj₂ the content is 40 to 70% by weight, in an amount of preferably 1-2% by weight, which toothpaste is free from granulation after low temperature storage 35, characterized in that the toothpaste contains 0.2 to 1% by weight of the toothpaste. an m4 pyrophosphate or an anionic phosphate ester comprising a mixture of monoester of formula DK 157900 B 0 II R (OC2H4) nOP-0M and t 5 OM diester of formula 0 10 II R (OC2H4) nO-P-O (C2H40) nR OM 15 where M is hydrogen, alkali metal or ammonium, R is an alkyl group having 10 to 20 carbon atoms and n is a number from 1 to 6. A toothpaste according to claim 1, characterized in that it contains as an additive an anionic phosphate ester and R 20 has 15-18 carbon atoms. 25 30 35