CA1152433A - Copper compound and a plastic polishing agent in toothpaste - Google Patents

Copper compound and a plastic polishing agent in toothpaste

Info

Publication number
CA1152433A
CA1152433A CA000376135A CA376135A CA1152433A CA 1152433 A CA1152433 A CA 1152433A CA 000376135 A CA000376135 A CA 000376135A CA 376135 A CA376135 A CA 376135A CA 1152433 A CA1152433 A CA 1152433A
Authority
CA
Canada
Prior art keywords
copper
toothpaste composition
polishing agent
toothpaste
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000376135A
Other languages
French (fr)
Inventor
Helmut Raaf
Dieter Becker
Franz Frosch
Helmut Harth
Helmar R. Wagner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Blendax GmbH
Original Assignee
Blendax Werke R Schneider and Co GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Blendax Werke R Schneider and Co GmbH filed Critical Blendax Werke R Schneider and Co GmbH
Application granted granted Critical
Publication of CA1152433A publication Critical patent/CA1152433A/en
Expired legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses

Abstract

ABSTRACT OF THE DISCLOSURE

This invention relates to a novel toothpaste and more particularly, to a new toothpaste which includes a finely divided synthetic plastic material as a polishing agent and at least one copper compound. This toothpaste has proven effective against plaque formation on teeth but does not exhibit any of the untoward side effects of the prior art formulations such as discolouring.

Description

1 This invention generally relates to toothpaste and, more particularly, to a new toothpaste having excellent properties for the prevention of the formation of dental plaque on teeth and accordingly makes a significant contribution to the maintenance of healthy teeth and gums.
According to modern dental science, there is no doubt that dental plaque is an important factor in the de-velopment of dental caries and also parodontopathies. Therefore, a substantial portion of medico-dental research is directed to discover new substances and means which will prevent plaque formation on teeth. Substantial advances have already been made in ~his respect. One of the most investigated compounds is 1,6-di-4'-(chlorophenyldiguanido)-hexane, commonly known as "chlorhexidine". This compound not only has an outstanding effect upon bacteria which are responsible for forming dental plaque, it also adheres to the enamel and thùs ensures long-lasting action.
In spite of this undisputed success in preventing and combatting parodontopathies, chlorhexidine unfortunately has certain side-effects which although being harmless per se, have hitherto apparently prevented its continuous use in tooth and mouth care preparations.
Extended use of preparations containing chlorhexidine produced discolouration of the teeth and the mucous membranes.
This effect is harmless and can be eliminated mechanically, but it is cosmetically undesirable. Its use may also lead to gustatory stimulation or irritat10n.
More recent1y, various attempts have been made to dlscover substances which do not produce these side effects but which st111 effectively prevent plaque formation on the teeth For example, the effectiveness of copper ions has already been discussed in this respect, as shown in AADR
Abstracts 1975, No. 117 (Journal of Dental Research 1975 Special Issue A, page 74). Although compounds supplying copper ions have produced satisfactory results in the prevention of plaque formation on teeth when used in solutions in accor-dance to this reference, surprisingly, it has hitherto been impossible to obtain these results with corresponding tooth-pastes.

' . - ,. ... .. . .

- - .
- 2 - ~ ~52433 1 Accordingly, it is an object of the present invention to overcome these disadvantages by providing a novel toothpaste composition containing conventional basic and additive sub-stances, at least one copper compound, ànd at least one polishing agent which is composed at least for the major part ~divided synthetic plastic material.
Further objects and advantages of the invention will appear from the following description Surprisingly, it has been found, tha~t by using a polishing agent which consists mainly of a finely divided synthetic material a toothpaste containing a copper compound is outstandingly effective against plaque formation on teeth.
The polishing agents consisting of finely divided, powdered synthetic plastic materials are products which are known for this purpose. Usually, they have an average particle diameter of preferably from about 0.5 to about 40 microns and more particulary, from about 2 to about 20 microns. They are present in toothpaste compositions in amounts from about 20 % to about 60 ~ by weight.
The preferred polishing agent is polymethyl metha-crylate, preferably with an average particle diameter of between about 0.2 and about 5 microns It is also possible to use other synthetic plastic materials as a polishing agent in the toothpaste composition.
Some of these agents have been disclosed in the prior art and include polyvinyl chloride, polystyrene, polycarbonates, copolymers of methyl methacrylate and other co-monomers, wh~ch do not have a negative effect on the hardness and the abrasivity of the methyl methacrylate copolymer; the amount of methyl methacrylate in the copolymer being preferably of at least 80 % by weight.
Other suitable polishing agents include polyamides such as powdered nylon, urea-formaldehyde resins, melamine-formaldehyde resins, phenol-formaldehyde resins, powdered cured epoxy resins, polyesters and the like. Suitable finely divided synthetic polishing agents are discribed for example in US, Patents Nos. 2,130,034; 3,070,510; 3,151,927; 3,251,800 and in German Accepted Patent Application No. 1,617,306.

1 In a preferred embodiment, the finely divided synthetic plastic powder is used as the sole polishing agent. However, it is possible to add other polishing agents in minor amounts, that means, in each case, less than 50 % of the total amount of polishing agent, provided that the additional polishing agent or agents do not inactivate the copper compounds present.
Such additional polishing agents include, for example, alkali aluminium silicates and in particular, the various s~licon dioxides which may be obtained by precipitation.
Reference is made to German Published Patent Applications Nos. 2,206,285; 2,446,03~ and 2,610,207; British Patent Nos. 1,433,743 and 1,447,663 and U.S. Patent No. 3,122,160.
These products are commercially available under the names "Neosyl*" and "Sident*".
Also suitable for this purpose are the silica xerogels described in U.S. Patent No. 3,538,230 with specific surfaces of between about 150 and about 800 m /9 which are commercially available from Grace & Co. under the name Syloid*. Partially dehydrated silica hydrogels as described in German Published Patent Application Nos. 2,704,504 and 2,920,906 may also be used as secondary polishing agent components in the tooth-paste composition of the present invention.
The amount of the copper compound used in the tooth-paste of this invention may be between about 0.001 and about 5 % by weight of the total toothpaste, calculated on Cu, The preferred range is from about 0.05 to about 1.5 % of coppe~ and the most preferred amount is from about 0.1 to 0.5 % of copper.
Suitable copper compounds which supply copper ions are, in principle, all copper compounds being toxicologically harmless, compatible with mucous membranes and, to some extent, water-soluble.
The following inorganic copper salts may be used:
Copper chloride, CuCl2, and the dihydrate thereof; copper fluoride, CuF2, and the dihydrate thereof; copper fluorosili-cate, CuSiF6, and the hexahydrate thereof; copper sulphate, CuS04, and the pentahydrate thereof; copper nitrate and the tri- and hexa-hydrates thereof, and also less popular copper salts, such as copper bromide, CuBr2, copper metaborate, *Trade Marks ~lSZ433 1 Cu(B02)2; copper bromate, Cu(BrO3)2. 6H20; copper clorate, Cu(C~03)2 . 6 H20; copper iodate, Cu(I03)2, and copper fluoro-phosphate, CuP03F.
Preferred copper salts of organic acids include copper acetate, copper formiate, copper benzoate, copper citrate, copper tartrate, copper lactate, copper malate, copper mandelate, copper sorbate, copper pantothenate, copper gluconate, copper phytate, copper glycerophosphate, ~pper cinnamate, copper butyrate, copper propionate, copper laurate, copper oxalate, copper glycinate, and copper salicylate.
As stated before, the toothpastes of the present invention contain the usual additives and compounds in addition to the finely divided, powdered synthetic plastic polishing agent and one or more copper compounds.
These include moisturizers such as glycerol and other polyalcohols, for example, propylene glycol, 1,3-butane-diol and polyethylene glycols having low molecular weights.
Also various sugar alcohols such as sorbitol or mannitol or xylitol may be used.
In addition to these compounds, toothpastes usually contain additional compounds such as thickeners and binding agents. Most suitable in this respect are the various cellu-lose derivatives (for example, hydroxyalkyl celluloses, and more particulary, hydroxyethyl cellulose), vegetable gums (for example, xanthan gum, carrageen) and inorganic thickeners which are inert to copper ions. The amount of these compounds is generally between about 0.25 ~ and about
3.5 % by weight of the toothpaste.
The toothpaste according to the present invention may also contain surfactants which are mainly used to produce a foaming effect which is desired by the customer. Suitable surfactants include water-soluble salts of higher alkyl sul-phates or alkyl ether sulphates (e.g. sodium lauryl sulphate), aliphatic acyl amides of saturated monoaminocarboxylic acids (e.g. sodium-N-lauroyl sarcosinate), taurine fatty acid amides (e.g., sodium N-alkyl-N-myristoyl-tauride), salts of sulphonated monoglycerides of higher fatty acids (e.g., sodium monoglyceride sulphonate), fatty acid esters of is-ethionic acid and salts thereof, non-ionic tensides (e.g., alkylene oxide condensates with fatty alcohols and mono-, ,.-- ., . *, , ~

~LlSZ433 1 or polyamines), sugar esters (for example, sucrose monolaurate), sorbitol polyoxyethylene stearate, long-chain amine oxides (e.g., dimethyllauryl amine oxide), ampholytic tensides (e.g., betaine or long-chain alkyl amino carboxylic acids), and cationic tensides (e.g., quaternary ammonium compounds such as cetyltrimethylammonium bromide).
The amount of surfactants in the toothpaste accor-ding to the invention is bètween O and about 5 % by weight of the total composition.
Toothpastes usually contain flavouring substances, preservatives, etc.. These are known per se and have been described in numerous publications.
In a preferred embodiment of the invention, fluorine compounds are used in amounts providing a fluorine concentra-tion in the paste between 0.01 and 1 ~, preferably between 0.1 and 0.5 % by weight of the toothpaste.
Suitable fluorine compounds are particulary the various salts of monofluorophosphoric acid, especially sodium, potassium, lithium, ca1cium and aluminum mono- and difluoro-phosphates, and the various fluorides containing fluorine in ionic form, especially alkali fluorides such as sodium, lithium, potassium and ammonium fluoride, stannous fluoride, manganese fluoride, zirconium fluoride, aluminum fluoride, and mixtures and addition products of these fluorides with each other or with other fluorine compounds, e,g. sodium or potassium manganese fluorlde.
Other fluorides that may be used are, e.g., zinc fluoride, germanium fluoride, palladium fluoride, titanium f1uoride, alkall fluorozirconates, e.g. sodium or potassium fluorozirconate, stannous fluorozirconate, fluoroborate or fluorosulphate, e.g., sodium or potassium fluorosulphate.
Fluorine and coppper ions may also released in a toothpaste according to the invention in the form of one compound, e.g. as copper fluoride, copper monofluorophos-phate and copper fluorosilicate.
Organic fluorine compounds may also be used, especially known addition products from long-chain amines or amino acids and hydrogen fluoride, monoethanolamine hydrofluoride or methyltriethylammonium fluoride.
,.

1 The toothpaste according to the invention may also contain further substances known per se for use in such agents, e.g. enzymes such as proteases and carbohydrases, e.g. amy-lase, dextranase, levanase or ~-1,3-glucan-3-glucanohydrolase;
tartar-preventing substances such as phosphonic acids, e.g.
hydroxy-ethane-1,1-diphosphonic acid, or bisbiguanidines known for plaque-prevention and their water-soluble salts.
A detailed review of the production of dentif~ice preparations and the substances used therefor is given in M.S. BALSAM and E. SAGARIN, "Cosmetics-Science and Technology", 2nd Ed., Vol.1, pages 423 to 531 (1972).
Examples of toothpastes according to the invention are given hereinafter.

.. O

7 ~ ~52433 1 Example 1 Xanthan gum o.90 % by weight Glycerol 15.00 Sorbitol 12.00 CuS04 5 H20 0.40 Sodium monofluorophosphate 0.76 Sodium lauryl sulphate 1.40 Polymethyl methacrylate powder (average particle diameter~4~um) 42.00 Pyrogenic silica 2.20 Flavour mixture 1.00 Sodium saccharin 0.25 Methyl p-hydroxybenzoate 0.20 Deionized water 23.89 Example 2 Carrageen 0.05 % by weight Xanthan gum 0,05 Glycerol 7,50 Sorbitol 22.00 Copper formiate . 4 H20 0.30 Copper fluoride (CuF2) 0.25 Sodium lauroyl sarcosinate ~.40 Cured melamine-formaldehyde condensate (av. particle diam. ~ 1 - lO~um) 28.50 Titan~um dioxide 0.50 Sod1um saccharin 0.10 Flavour mixture 1.00 Methyl p-hydroxybenzoate 0.10 n-Propy1 p-hydroxybenzoate 0.05 Deionized water 37,~0 Example 3 Hydroxyethyl cellulose 1.10 % by weight Glycerol 10.00 Sorbitol 20.00 Copper fluorosilicate (CuSiF6. 6 H20) 0.95 Sodium lauryl sulphate 1.50 - 8 - 1~52433 1 Finely divided polymethyl methacrylate powder (av.part.diam.~ 5 - 5~m) 25.00 Silica aerogel ("Syloid 244", specific surface about 260 m /9) 1.80 Polyvinyl chloride powder (av.part.diam. ~1 - 10 ,um) 7.30 Flavour mixture 1.00 Sodium saccharin 0.15 Methyl p-hydroxybenzoate 0.20 Deionized water 31.00 Example 4 Methyl cellulose 1.20 % by weight 1,3-Butanediol 6.00 Glycerol 13.00 Sorbitol 10.00 Sodium lauryl sulphate (10 % suspension 1n glycerol) 3.50 Copper fluoride (CuF2 . 2 H20) 0 30 Copper pantothenate 0.80 Finely divided urea-formaldehyde condensate, cured, av.part.diam. ~2 - 8~um) 37.00 Flavour mixture 1.20 Sodium saccharin 0.20 Ethyl p-hydroxybenzoate 0.13 Benzo1c ac1d 0.10 Tartar1c ac1d 0.55 De1On1zed water 26.02 Example 5 Glycerol 19.00 ~ by weight Sorbitol (70 %) 7.00 Polyethylene glycol 300 3.00 Copper lactate dihydrate 1.20 Stannous fluoride (SnF2) 0.40 Hydroxyethane-1,1-diphosphonic acid, trisodium salt 1.25 Bromochlorophene 0.05 Benzoic acid 0.15 Dehydrace~ic acid 0.10 g .

- 1~52433 1 n-Propyl p-hydroxybenzoate 0.05 Polymethyl methacrylate powder (av.part.diam. ~ 3 - 8 ~um) 20~00 Silica xerogel (of the ~Syloid 701l type, specific surface about 290 m2/g) 8.50 Pyrogenic silica (of the "Aerosil "
type) 1.20 Sodium lauryl ether sulphate (25 % in ethanol)10.00 Xanthan gum ~ 0.80 Deionized water 27.30 Although preferred embodiments of the invention are described and illustrated it is to be understood that the invention is not restricted to these particular embo-diments.

~,o

Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An aqueous toothpaste composition containing at least one water-soluble copper compound reducing or preventing the formation of dental plaque and at least one polishing agent, the major part of the polishing agent being finely divided synthetic plastic material.
2. A toothpaste composition as claimed in claim 1, wherein said polishing agent consists, at least partially, of finely divided polymethyl methacrylate.
3. A toothpaste composition as claimed in claim 1, wherein said polishing agent consists, at least partially, of a finely divided aminoplast resin.
4. A toothpaste composition as claimed in claim 1, wherein said synthetic material is selected from the group consisting of polymethyl methacrylate, aminoplast resin, polyvinyl chloride, polystyrene, polycarbonate, powdered nylon, urea-formaldehyde resins, melamine-formaldehyde resins, phenol-formaldehyde resins, and powdered cured epoxy resins.
5. A toothpaste composition as claimed in claim 1, further including one or more additional compatible polishing agents which constitute less than 50% of the total amount of polishing agent.
6. A toothpaste composition as claimed in claim 1, wherein said copper compound is at least one copper salt of an organic acid.
7. A toothpaste composition as claimed in claim 4, wherein said copper compound is at least one water-soluble inorganic copper salt.
8. A toothpaste composition as claimed in claim 6, wherein said copper compound is at least one compound selected from the group consisting of copper citrate, copper tartrate, copper pantothenate, copper lactate, copper malate, copper mandelate, copper sorbate, copper benzoate, copper salicylate, copper gluconate, copper phytate, copper glycerophosphate, copper glycinate and copper cinnamate
9. A toothpaste composition as claimed in claim 1, wherein said copper compound is present in an amount of between about 0.001 % and about 5 % by weight, calculated on copper, of the total composition
10. A toothpaste composition as claimed in claim 9, wherein said copper compound is present in an amount of between about 0.05 and about 0.5 % by weight, calculated on copper, of the total composition.
CA000376135A 1980-04-29 1981-04-24 Copper compound and a plastic polishing agent in toothpaste Expired CA1152433A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP80102305A EP0038868B1 (en) 1980-04-29 1980-04-29 Toothpaste
EP80102305.2 1980-04-29

Publications (1)

Publication Number Publication Date
CA1152433A true CA1152433A (en) 1983-08-23

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ID=8186672

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000376135A Expired CA1152433A (en) 1980-04-29 1981-04-24 Copper compound and a plastic polishing agent in toothpaste

Country Status (9)

Country Link
US (1) US4339429A (en)
EP (1) EP0038868B1 (en)
JP (1) JPS56169620A (en)
AR (1) AR224191A1 (en)
AT (1) ATE4776T1 (en)
AU (1) AU537684B2 (en)
CA (1) CA1152433A (en)
DE (1) DE3065016D1 (en)
ES (1) ES501712A0 (en)

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Also Published As

Publication number Publication date
DE3065016D1 (en) 1983-11-03
JPS6234004B2 (en) 1987-07-24
JPS56169620A (en) 1981-12-26
ES8207424A1 (en) 1982-09-16
AU6941981A (en) 1981-11-05
EP0038868B1 (en) 1983-09-28
ATE4776T1 (en) 1983-10-15
EP0038868A1 (en) 1981-11-04
AR224191A1 (en) 1981-10-30
ES501712A0 (en) 1982-09-16
AU537684B2 (en) 1984-07-05
US4339429A (en) 1982-07-13

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