[go: up one dir, main page]

WO1991011986A1 - Produits pour soins buccaux et dentaires - Google Patents

Produits pour soins buccaux et dentaires Download PDF

Info

Publication number
WO1991011986A1
WO1991011986A1 PCT/EP1991/000164 EP9100164W WO9111986A1 WO 1991011986 A1 WO1991011986 A1 WO 1991011986A1 EP 9100164 W EP9100164 W EP 9100164W WO 9111986 A1 WO9111986 A1 WO 9111986A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
phosphoric acid
oxide
tris
hydroxyethyl
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.)
Ceased
Application number
PCT/EP1991/000164
Other languages
German (de)
English (en)
Inventor
Hinrich Möller
Hans-Jürgen Klüppel
Peter Wülknitz
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1991011986A1 publication Critical patent/WO1991011986A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/416—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55—Phosphorus compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses

Definitions

  • the invention relates to oral and dental care products with an improved action against tooth decay by virtue of a content of an active ingredient which reduces the solubility of hydroxylapatite and inhibits crystal growth and the phosphate ion exchange of hydroxylapatite.
  • Oral and dental care products are products that serve to clean and care for the teeth, the oral cavity and the throat.
  • its task is to prevent dental diseases such as tooth decay and periodontitis and to prevent the formation of tartar.
  • water-soluble organic phosphates have a caries-prophylactic effect.
  • mono- and disodium glycerophosphate, fructose-6-phosphate, sorbitol-1-phosphate, sorbitol-6-phosphate, glucose-1-phosphate and glucose-6-phosphate have been proposed as additives to oral and dental care products.
  • Salts of phosphoric acid esters of lactose and sucrose have also been described as cariostatic components. Although these products have a certain action which reduces the solubility of the hydroxyapatite and inhibits crystal growth, the effects are not sufficient for effective protection against demineralization of the tooth enamel.
  • DE-OS 34 39 094 phosphoric acid ester salts of ethoxylated polyols have been proposed as caries prophylactic agents. These show a significantly higher effect; However, there is still a need for substances with an improved effect, in particular with a view to reducing the hydroxylapatite solubility.
  • the invention therefore relates to oral and dental care products with improved activity against tooth decay, which comprise, as active ingredient (A), a phosphoric acid ester of an amino alcohol with the general formula (I)
  • n and p are independently numbers from 2 to 5
  • s and t are independently numbers from 0 to 8
  • x is a number from 1 to 5
  • y is a number from 0 to 4, the sum (x + y) being not greater than 6
  • M is hydrogen, an alkali metal or alkaline earth metal ion, an ammonium group or a mono-, bis- or tris (hydroxy - alkyljamonium distr having 1-4 carbon atoms in the alkyl group and hydroxy
  • R 2 and R 3 are independently
  • R 4 and R ⁇ are hydrogen, a group of the formula (II), an alkyl group having 1 to 4 carbon atoms or a carboxyalkyl group having 1 to 4 carbon atoms, or
  • (C) a quaternization product of a compound of the general formula (I) which is formed by alkylation with a compound R6 U X, where R6 represents an alkyl or carboxyalkyl group having 1 to 4 carbon atoms or a group of the formula (II), in which x can also be 0, X represents halogen, a phosphate group, a sulfate group, a methyl sulfate group, a tosylate group or a sulfonate group and u is an integer which corresponds to the valence of the group X and / or a (D) alkoxyl Production product of the compounds (A), (B) or (C), which is formed by reacting these compounds with ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and / or pentylene oxide.
  • Phosphoric acid esters according to formula (I) are further understood to mean both the phosphoric acid esters of the amino alcohols according to formula (
  • alkylene oxides with 2-5 carbon atoms i.e. ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and pentene oxide
  • basic catalysts such as e.g. NaOH, KOH, Na methylate and Ca acetate
  • acidic catalysts such as e.g. Boron trifluoride, antimony pentachloride, triethyloxoniu fluoroborate and SnClj. or without catalysts.
  • alkylene oxides When alkylene oxides are attached to primary or secondary amines in stoichiometric or substoichiometric ratios of alkylene oxide to hydrogen atoms on the amine nitrogen, it is generally possible to dispense with a catalyst. At higher molar ratios, sodium methylate is a preferred catalyst.
  • the salts of the substrates, in particular the hydrochlorides, are preferably used for the quaternization with alkylene oxides.
  • the phosphorylation of the amino alcohols and their alkylene oxide storage products can be carried out, for example, by reaction with phosphorus pentoxide or polyphosphoric acid with a high content of phosphorus pentoxide, for example by the process described in US Pat. No. 4,311,662.
  • phosphorus pentoxide By varying the amount of phosphorus pentoxide used, both predominantly monophosphoric acid esters and predominantly those compounds can be prepared in which the majority of the OH groups of the amino alcohols are phosphorylated.
  • a short-term hydrolytic treatment in the acidic pH range is advantageous in the workup, since POP bonds still present are thus split. This has an advantageous effect on the storage stability of the formulated products.
  • Detailed synthesis instructions can be found in the examples.
  • the products contain, as a by-product, inorganic phosphates, predominantly orthophosphate, which is not detrimental to the cariostatic activity of the products and can therefore remain in the product.
  • the phospho- Degree of rylation PG ie the number of phosphorylated OH groups divided by the number of OH groups available for phosphorylation, can be determined from the analytical values for the content of inorganic phosphate and the total phosphate content as well as the amounts of substrate and phosphorylation used - Agens (for example phosphorus pentoxide) are calculated
  • the use ratio EV is defined as the ratio of the amount of substance P2O5 used to the number of gram equivalents of the substrate, based on the hydroxyl groups (hydroxy equivalents).
  • the phosphoric acid esters of the amino alcohols can be neutralized with inorganic or organic bases and in this way converted into physiologically compatible, water-soluble salts.
  • Preferred compounds H U X are the hydrogen halides; preferred compounds R6 and ⁇ are the alkyl and carboxyalkyl halides and sulfates, each having 1 to 4 carbon atoms. The chlorides are very particularly preferred.
  • Phosphoric acid esters of the formula (I) which meet one or more of the following conditions are preferably used: m is a number from 2 to 5, n is 2 or 3, p is 2 or 3, s is a number from 0 to 3, t is a number from 0 to 3,
  • M stands for an alkali metal ion, especially sodium, a
  • phosphoric acid esters according to formula (I) in which R2 and / or R 3 represent a group of formula (II) or a group -C q H2 q -NR 4 R 5 .
  • the quaternization product (C) according to claim 1 and the alkoxylation products (D) according to claim 1 are preferably used.
  • Preferred compounds are, for example, phosphorylated N- [tris (hydroxymethyl) methyl] ethanolamine, N- [tris (hydroxymethyl) methylj-diethanolamine + 1 EO, tris (2-hydroxyethyl) - [tris (hydroxymethyl) methyl] ammonium chloride, N- [tris (hydroxymethyl) methyl] di-ethanolamine + 3 EO and 2- [bis (2-hydroxyethyl) amino] -2-methylpropane-1,3-diol.
  • the oral and dental care compositions according to the invention containing phosphoric acid esters of the formula (I) can be prepared in the various versions customary for such products, for example as mouthwashes, toothpastes or tooth powder.
  • the content of phosphoric acid esters according to formula (I) should be in the range from 0.01 to 5.0% by weight of the preparation.
  • toothpastes, dental Powders and dental gels Amounts of 0.05-2% by weight are usually sufficient.
  • mouthwashes to be used undiluted sufficient effects can be achieved with 0.01-1.0% by weight, in mouthwashes that are diluted before use with higher concentrations according to the intended dilution ratio.
  • Oral and dental care products can also be prepared in the form of chewing gum, mouth lozenges and dental treatment ointments.
  • Oral care products of this type which may be used several times a day and are inevitably swallowed, may also contain the phosphoric acid esters of the formula (I). In these cases, however, the dosage should not exceed 1% by weight of the preparation.
  • the oral and dental care compositions according to the invention can contain the carriers and additives customary for the particular preparation.
  • a combination with the aqueous-alcoholic solutions of essential oils, emulsifiers, astringent and toning drug extracts, tartar-inhibiting and antibacterial additives and flavor corrections is readily possible.
  • surface-active substances e.g. Anionic, nonionic, zwitterionic and ampholytic surfactants can be added in the usual amounts.
  • Toothpastes or toothpastes are generally understood to mean gel-like or pasty preparations made from water, thickeners, moisturizing agents, abrasive or cleaning bodies, surfactants, sweeteners, flavorings, deodorising active ingredients and active ingredients against mouth and tooth diseases.
  • all customary cleaning bodies such as chalk, dicalcium phosphate, insoluble sodium metaphosphate, aluminum silicates, calcium pyrophosphate, finely divided synthetic resins, silicas, aluminum oxide and aluminum oxide trihydrate can be used.
  • Particularly suitable cleaning bodies for the toothpaste according to the invention are, in particular, finely divided xerogel silicas, hydrogel silicas, precipitated silicas, aluminum oxide trihydrate and finely divided aluminum oxide or mixtures of these cleaning articles in amounts of 15-40% by weight of the toothpaste.
  • Low molecular weight polyethylene glycols, glycerol, sorbitol or mixtures of these products in amounts of up to approx. 50% by weight are mainly suitable as humectants.
  • Known thickeners include the thickening, finely divided gel silicas and hydrocolloids, such as, for example, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl guar, hydroxyethyl starch, polyvinyl pyrrolidone, high molecular weight polyethylene glycol, vegetable gums such as tragacanth, agar agar, caragar gum, and gum arabic, gum Carboxyvinyl polymers (e.g. Carbopol ( R ) types) are suitable.
  • surface-active substances preferably anionic high-foaming surfactants, such as, for example, linear sodium alkyl sulfates with 12-18 C atoms in the alkyl group, sodium salts of alkyl polyglycol ether sulfates with 12-16 C atoms in the linear alkyl group and 2-6 glycol ether groups in the molecule , of alkyl (Cl2-16) "* Denzo ⁇ su ⁇ ona't 'linear alkane (Ci2-i8) sulfonates, sulfosuccinic acid monoalkyl (Ci2_.i8) beta star, sulfated fatty acid monoglycerides, sulfated fatty acid alkanolamides, sulfo- acetic acid alkyl (Ci2-i8) esters ⁇ acyl sarcosides, acyl taurides and acyl isethionates each containing 8 to 18 carbon atoms in the alkyl
  • Preservatives and antimicrobial substances such as p-Hydroxybenzoic acid methyl, ethyl or propyl ester, sodium sorbate, sodium benzoate, bromochlorophene, phenylsalicylic acid ester, thymol etc.
  • Anti-calculus agents e.g. Organophosphonates such as 1-hydroxyethane-l. L-diphosphonic acid, l-phosphonopropane-l, 2,3-tricarboxylic acid and others, e.g. from US-PS 3,488,419, DE-OS 2224430 and DE-OS 2343 196 are known;
  • caries-inhibiting substances such as Sodium fluoride, sodium monofluorophosphate, tin fluoride,
  • Sweeteners such as Saccharin sodium, sodium cyclamate, sucrose, lactose, maltose, fructose,
  • Flavors such as Peppermint oil, spearmint oil, eucalyptus oil, anise oil, fennel oil, caraway oil, menthyl acetate, cinnamaldehyde, ethanol, vanillin, thymol and mixtures of these and other natural and synthetic aromas,
  • Buffer substances such as primary, secondary or tertiary alkali phosphates or citric acid / sodium citrate,
  • wound healing and anti-inflammatory substances such as allantoin, urea, azulene, chamomile active ingredients and acetylsalicylic acid derivatives.
  • the oral and dental care products according to the invention not only have a caries-inhibiting activity due to the addition of phosphate esters of the formula (I), but also successfully counteract the formation of tartar.
  • New and thus the subject of the invention are the phosphoric acid esters (A) of an amino alcohol of the general formula (I) according to Claim 1, in which R 2 and / or R 3 represent a group —CqH2q-NR 4 R 5 , in which q is a number is from 2 to 6 and R 4 and R5 are hydrogen, a group of the formula (II), an alkyl group with 1 to 4 carbon atoms or a carboxyalkyl group with 1 to 4 carbon atoms, their salts (B), which are formed by salt formation with a compound H U X, and their quaternizing products (C), which are formed by alkylation with a compound R ⁇ u X, where R ⁇ represents an alkyl or carboxyalkyl group having 1 to 4 carbon atoms or a group of the formula (II), in the x too
  • X represents halogen, a phosphate group, a sulfate group, a methyl sulfate group, a tosylate group or a sulfonate group and u is an integer which corresponds to the valency of the group X, and the alkoxylation products of the compounds (A) , (B) or (C) which are formed by reacting these compounds with ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and / or pentylene oxide.
  • the invention also relates to the quaternization products (C) of the compounds of the general formula (I) which are formed by alkylation with a compound R ⁇ U X, where R6 is an alkyl or carboxyalkyl group
  • X represents halogen, a phosphate group, a sulfate group, a methyl sulfate group, a tosylate group or is a sulfonate group and u is an integer which corresponds to the valence of group X, and the alkoxylation products (D) of the compounds (C) mentioned, which are formed by reacting these compounds with ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and / or pentylene oxide become.
  • the alkylene oxides were added to the amino alcohols by a process known from the literature by reaction in a pressure vessel at temperatures of 40-150.degree. Catalytic amounts of sodium methylate were used in the case of additions to primary and secondary amines in a superstoichiometric ratio of alkylene oxide to amine protons. In these cases the reaction temperature was 150-160 ° C.
  • the hydrochlorides of the substrate were used for the quaternization with alkylene oxides; the reaction temperature was then 100-110 ° C.
  • the active substance content of the solutions was determined after the
  • % Active ingredient (% WS) 100% -% phosphate inorganic -
  • N- [Tris (hydroxymethyl) methyl] diethanolamine was obtained by adding 2 moles of ethylene oxide to 1 mole of [tris (hydroxymethyl) methyl] amine at 40 ° C. and a pressure of 3 bar.
  • the product had a melting point of 99-100 ° C and was converted into the hydrochloride by reaction with 10% hydrochloric acid and subsequent drying.
  • Active substance content 43% 1.5
  • Preparation of phosphorylated, ethoxylated (1 EO) ⁇ 2- [bis (2-hydroxyethyl) amino] ethyl ⁇ tris (2-hydroxyethyl) ammonium chloride (reaction with EV 0.7) (active ingredient 71)
  • the effectiveness of the substances according to the invention is determined with regard to a) the reduction in hydroxylapatite solubility (ALR) and b) the inhibition of hydroxylapatite crystal growth (KWI).
  • the quantities given relate to the active substance.
  • hydroxylapatite powder (specific surface area 60 m 2 / g, from Merck) was placed in a reaction vessel thermostatted at 37 ° C. with 300 ml of demineralized water.
  • the amount of 0.1 m lactic acid solution consumed for pH stabilization was registered by a writer. The consumption of lactic acid registered after 2 hours corresponded to the solubility of the untreated hydroxylapatite (Lu).
  • the measurement was carried out analogously to a). Before the addition of the hydroxyapatite powder, 30 mg of the active ingredient to be tested were dissolved. The milk consumption registered after 2 hours acid corresponded to the solubility of the treated apatite powder (b).
  • the measurement was carried out analogously to a). Before the pH was adjusted, 6 mg of the active ingredient to be tested were dissolved.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cosmetics (AREA)

Abstract

Des produits pour soins buccaux et dentaires, renfermant comme substances actives des esters d'acide phosphorique d'amino-alcools déterminés, ou de leurs sels ou des produits de quaternisation, ou des produits d'alcoxylation des composés précités, présentent une action améliorée contre la formation de caries. Des substances actives préférées sont, par exemple, la N-[tris(hydroxyméthyl)méthyl]-éthanolamine phosphorylée, la N-[tris(hydroxyméthyl-méthyl]-diéthanolamine + 1 EO, le chlorure de tris(2-hydroxyéthyl)-[tris(hydroxyméthyl)méthyl]ammonium, la N-[tris(hydroxyméthyl)-méthyl]-diéthanolamine + 3 EO et le 2-[bis(2-hydroxyéthyl)amino]-2-méthylpropane-1,3-diol.
PCT/EP1991/000164 1990-02-07 1991-01-29 Produits pour soins buccaux et dentaires Ceased WO1991011986A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4003662.6 1990-02-07
DE19904003662 DE4003662A1 (de) 1990-02-07 1990-02-07 Mund- und zahnpflegemittel

Publications (1)

Publication Number Publication Date
WO1991011986A1 true WO1991011986A1 (fr) 1991-08-22

Family

ID=6399626

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1991/000164 Ceased WO1991011986A1 (fr) 1990-02-07 1991-01-29 Produits pour soins buccaux et dentaires

Country Status (2)

Country Link
DE (1) DE4003662A1 (fr)
WO (1) WO1991011986A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101402576B (zh) * 2008-10-23 2011-03-23 浙江大学 制备二(2－羟乙基)亚氨基三(羟甲基)甲烷的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140235776A1 (en) * 2011-07-28 2014-08-21 Angus Chemical Company Aminoalcohol compounds and their use as zero or low voc additives for paints and coatings

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2224560A1 (de) * 1972-05-19 1973-11-29 Henkel & Cie Gmbh Zahnsteinbildung verhindernde mundund zahnpflegemittel
US4311662A (en) * 1978-02-13 1982-01-19 Petrolite Corporation Corrosion inhibitor for highly oxygenated systems
DE3439094A1 (de) * 1984-10-25 1986-05-07 Henkel KGaA, 4000 Düsseldorf Mund- und zahnpflegemittel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2224560A1 (de) * 1972-05-19 1973-11-29 Henkel & Cie Gmbh Zahnsteinbildung verhindernde mundund zahnpflegemittel
US4311662A (en) * 1978-02-13 1982-01-19 Petrolite Corporation Corrosion inhibitor for highly oxygenated systems
DE3439094A1 (de) * 1984-10-25 1986-05-07 Henkel KGaA, 4000 Düsseldorf Mund- und zahnpflegemittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Band 81, no. 4, 29 Juli 1974, (Columbus, Ohio, US), siehe Seite 223, Zusammenfassung 16716w, & JP, A, 7337824 (Dentifrices) 14 November 1973 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101402576B (zh) * 2008-10-23 2011-03-23 浙江大学 制备二(2－羟乙基)亚氨基三(羟甲基)甲烷的方法

Also Published As

Publication number Publication date
DE4003662A1 (de) 1991-08-08

Similar Documents

Publication Publication Date Title
EP0179396B1 (fr) Compositions pour les soins bucco-dentaires
DE2756078C2 (fr)
CH620359A5 (fr)
EP0150374B1 (fr) Compositions pour les soins bucco-dentaires
CH662352A5 (de) Morpholinverbindungen und mittel, welche solche verbindungen enthalten und ihre herstellung.
DE2600709A1 (de) Zahnpasta
EP0382020A2 (fr) Compositions buccales et dentaires contenant des enzymes lysant des polysaccharides
WO1988008697A1 (fr) Pate dentifrice
DE2428227C2 (de) Mundhygienisches Mittel
CH672596A5 (fr)
DE2736155C2 (fr)
CH620358A5 (fr)
DE2456693A1 (de) Verfahren zum stabilisieren von calcium-hydrogenphosphat-anhydrid gegen die umsetzung mit fluorionen
EP0071025B1 (fr) Sel de zinc d'un acide tricarboxylique hydrolysé obtenu à partir des composés d'addition de l'anhydride maléique avec l'acide undécylénique, son procédé de préparation et son utilisation
WO1991011986A1 (fr) Produits pour soins buccaux et dentaires
CH651204A5 (de) Mittel zur foerderung der mundhygiene.
DE2523363B2 (de) Mund- und Zahnpflegemittel
WO1991002510A1 (fr) Produits inhibiteurs du tartre pour les soins de la bouche et des dents
DE2265735C3 (de) Mittel zur Verhütung von Zahnstein
CH638676A5 (de) Karies verhinderndes mittel.
DE2755847A1 (de) Antibakterielles mundpflegemittel
DE69512910T2 (de) Alkylsulfoacetat-zusammensetzungen und verfahren zu ihrer herstellung
WO1991009589A2 (fr) Produit d'hygiene bucco-dentaire
DE10238537A1 (de) Zusammensetzung
DE3239976A1 (de) Gegen zahnstein wirkendes mundpflegemittel

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA