WO1993008230A1 - Cellulose ether thickening compositions - Google Patents
Cellulose ether thickening compositions Download PDFInfo
- Publication number
- WO1993008230A1 WO1993008230A1 PCT/GB1992/001914 GB9201914W WO9308230A1 WO 1993008230 A1 WO1993008230 A1 WO 1993008230A1 GB 9201914 W GB9201914 W GB 9201914W WO 9308230 A1 WO9308230 A1 WO 9308230A1
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- WO
- WIPO (PCT)
- Prior art keywords
- composition
- cellulose ether
- thickening agent
- electrolyte
- silicate
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 229920003086 cellulose ether Polymers 0.000 title claims abstract description 40
- 230000008719 thickening Effects 0.000 title claims abstract description 14
- 239000002562 thickening agent Substances 0.000 claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006467 substitution reaction Methods 0.000 claims abstract description 17
- 230000008961 swelling Effects 0.000 claims abstract description 10
- 229910000271 hectorite Inorganic materials 0.000 claims abstract description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 229920006321 anionic cellulose Polymers 0.000 claims description 2
- 239000004927 clay Substances 0.000 abstract description 3
- 238000005553 drilling Methods 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 14
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 13
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 12
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 12
- 229940105329 carboxymethylcellulose Drugs 0.000 description 12
- 229940094522 laponite Drugs 0.000 description 11
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 235000010356 sorbitol Nutrition 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000000230 xanthan gum Substances 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- 235000010493 xanthan gum Nutrition 0.000 description 3
- 229940082509 xanthan gum Drugs 0.000 description 3
- 229920000715 Mucilage Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 229940106681 chloroacetic acid Drugs 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 235000012243 magnesium silicates Nutrition 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000000606 toothpaste Substances 0.000 description 2
- 229940034610 toothpaste Drugs 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002882 anti-plaque Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000551 dentifrice Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940050526 hydroxyethylstarch Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/731—Cellulose; Quaternized cellulose derivatives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
- C09D7/44—Combinations of two or more thickening agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
- C09K8/18—Clay-containing compositions characterised by the organic compounds
- C09K8/20—Natural organic compounds or derivatives thereof, e.g. polysaccharides or lignin derivatives
- C09K8/206—Derivatives of other natural products, e.g. cellulose, starch, sugars
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/44—Thickening, gelling or viscosity increasing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/16—Esters of inorganic acids
Definitions
- This invention relates to cellulose ether-containing thickening compositions, a method for their production, and to thickened compositions containing them.
- Cellulose ethers are widely used to thicken aqueous or organic liquids. It has been found that combinations of cellulose ethers with other thickening agents show a synergistic thickening effect and there are a number of publications which disclose particular synergistic thickening compositions. Examples of such compositions are mixtures of cellulose ethers with polyacrylamidomethyl propane sulphonic acid as disclosed in United States Patent Specification No. 4540510, with Xanthan gum as disclosed in US Patent Specification No. 4,313,765, with a ' maleic anhydride/olefin copolymer as disclosed in US Patent Specification No. 4172055, with a cross-linked acrylic copolymer as disclosed in US Patent Specification No. 4798682 or with hydroxyethyl starch as disclosed in GB Patent Specification No. 2110698 and 2110699.
- SUBSTITUTESHEET the medium to be thickened is a high electrolyte composition.
- the present invention therefore relates to cellulose ether thickening compositions which are suitable for use to thicken high-electrolyte compositions.
- a high electrolyte concentration is regarded as one above which the performance of a cellulose ether thickener other than as claimed is impaired.
- this effect may show itself at around 0.02 to 0.2 meq/g of electrolyte in the total solution.
- compositions containing a high solids concentration such as a toothpaste formulation it may show itself around 0.5-0.8 meq/g of the total composition.
- the high electrolyte effect may occur between these figures.
- the present invention provides a composition suitable for use to thicken electrolyte containing compositions comprising a cellulose ether thickening agent and another thickening agent, the composition being characterised in that the cellulose ether is a substituted cellulose ether having an average degree of substitution of at least from 0.7 and not more than l.l, and in that the other thickening agent is a swelling silicate thickening agent.
- the cellulose molecule is reacted with alkali and then with a reagent such as chloroacetic acid to cause conversion of one or more of the three hyroxyl groups present in each anhydroglucose unit in the cellulose chain, first to the alkali metal salt and then ro tne alkali metal acetate ether.
- the chloroacetic acid may be replaced by other reagents to produce other cellulose ethers.
- the degree of substitution can be controlled by, amongst other factors, the concentration of the alkali.
- the degree of substitution is the number of hydroxyl groups per anhydroglucose unit which are substituted and is usually stated as a range defining the minimum and maximum degree of substitution.
- the average degree of substitution is the weight mean average appropriate to a range. It is envisaged that to practical purposes a cellulose ether product will be outside the invention if any substantial part of the range, for example 20% or more is outside the range selected according to the invention.
- the average degree of substitution of the cellulose ether is advantageous for the average degree of substitution of the cellulose ether to be above 0.7 and up to 1.1, Cellulose ethers having a range of substitution which extends substantially below 0.65 are undesirably difficult to dissolve while those having a degree of substitution which extends substantially above 1.1 or even above 1.0, show a diminution of synergism to some degree.
- the cellulose ether has a minimum degree of substitution of above 0.7 for example of at least 0.8.
- the cellulose ether utilised herein is preferably on anionic cellulose ether such as for example sodium carboxymethyl cellulose.
- silicates have swelling or thickening properties. These are layered silicates, which swell by the entry of water or other polar liquids between the layers thereby causing an increase in the basal spacing, and are typified by the layered clay minerals of the smectite series such as the saponites, including saponite and hectorite or the montmorillonites. There also exists a range of synthetic silicates having structures of the smectite type which show greatly enhanced swelling properties. Detail concerning the identification of structure types in clay minerals is given in "X-ray identification and crystal structure of clay minerals" Minerlogical Society (G. Brown) 1961. Suitable synthetic silicates are described in US Patent ' Specification No. 4049780 together with a process for their preparation and are hydrous magnesium silicates having a crystal structure similar to that of a hectorite and a composition
- Such hydrous magnesium silicates are available under the LAPONITE Trade Mark from Laporte Industries Limited.
- the particular effectiveness of the combination according to the invention may be connected to an inter-reaction between the anionic sites on the cellulose ether and hydroxyl sites on the silicate and that an extended cage type of structure is thereby obtained when the degree of substitution of the cellulose ether is as selected herein which structure is sufficiently stable to resist degradation in the presence of high electrolyte concentrations.
- This theory is supported by the fact that certain non-ionic cellulose ethers such as methyl cellulose and hydroxyethyl cellulose have been found not to be operative in the present invention.
- the silicates preferably contains at least 1 hydroxyl group for each 8 silicon atoms in the framework e.g.
- y in the above general formula is preferably 3 or less. To maximise the opportunities for inter-reaction between the silicate and the cellulose ether it is preferred that the number of hydroxyl groups on the silicate is as high as possible. Preferably therefore in the above general formula "y" is less than 1 or 0.
- the relative weights of the cellulose ether and the clay may, for example, be from 5:95 to 95:5, preferably from 30:70 to 70:30.
- the present invention may be utilised in the production of thickened high-electrolyte compositions by including the cellulose ether and the silicate, together or separately in an aqueous or suitable polar medium containing the other components of the composition to be thickened.
- the cellulose ether and the 'silicate' are both included in a liquid medium before contact with a high concentration of electrolyte.
- the cellulose ether and the silicate may be premixed into a liquid medium which is then added to the main composition or they may be added to the main composition before any substantial quantity of electrolyte, sufficient to give a high electrolyte concentration, is included with the main composition. It is believed that an interaction between the cellulose ether and the electrolyte could prevent the desired cellulose ether/silicate structure from developing.
- the present invention may be utilised in many differing applications in which high electrolyte concentration liquids require to be thickened.
- Dentrifice compositions intended for special "purposes, for example antiplaque dentrifices can contain high concentrations of electrolyte in the form of sodium pyro- or poly-phosphates.
- Other examples of high electrolyte systems which require to be thickened are drilling muds in situations where high salt strata are penetrated, concrete mixes, aqueous emulsion paints and coating mixes which may contain highly charged polymers such as polyacrylic copolymers, and the like.
- Samples of water containing varying quantities of sodium sulphate were thickened with 2% by weight of the total composition of a 50/50- weight blend of a silicate thickener (Laponite RD) and one of 3 different carboxy methyl cellulose (CMC) ethers having degrees of substitution of 0.65-0.9, 0.8-0.95 and 1.15-1.45 denoted hereafter for convenience CMC/.65, CMC/.8 and CMC/1.15.
- the solutions were stored for 24 hours and the viscosities of the samples was determined using a Brookfield LVT (T-bar) viscometer at 0.6 rpm. The results are depicted in Figure 1 attached hereto.
- Example numbered 6 The subject of these Examples is a typical high electrolyte dentrifice composition.
- sorbitol syrup 70% aq
- 6.0 g of a sodium carboxymethyl cellulose (CMC .65 or CMC .8) was added to a polythene beaker, stirred under high shear whilst adding 6.0 g of a sodium carboxymethyl cellulose (CMC .65 or CMC .8) and mixing was continued for 15 minutes until the cellulose was completely dispersed.
- CMC .65 or CMC .8 a sodium carboxymethyl cellulose
- the Laponite dispersion was added to the cellulose/Sorbitol mucilage and mixed thoroughly. Then 15.0 g sodium saccharin solution (10% aq) , 10.0 g sodium fluoride solution (25% aq) and 50.0 g tetrasodiu pyrophosphate was added to the mucilage which was transferred to a vacuum mixer and to which was added 200 g of dentifrice grade silica abrasive and 10.0 g of titanium dioxide. Mixing under vacuum was continued for 5 minutes to deaerate the composition.
- flavour oil 0.5 mg of preservative and 50.0 g of sodium lauryl sulphate solution (30% aq ⁇ were added and the resulting product was then further mixed under vacuum until completely deaerated.
- TSPP Tetrasodium pyrophosphate
- TKPP Tetrapotassium pyrophosphate
- CMC Carboxymethyl cellulose
- CMC .65 Grade 7M4XF available from Aqualon Corp.
- CMC .8 Grade 9M31XF available from Aqualon Corp.
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
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Abstract
The combination of a cellulose ether thickening agent having an average degree of substitution of from 0.7 to 1.1 with a swelling silicate thickening agent such as smectite clay or a synthetic clay having a structure resembling hectorite gives excellent thickening performance in electrolyte containing compositions such as, for example, tooothpastes. Other potential applications are in drilling muds, concrete mixes and emulsion paints.
Description
Cellulose ether thickening compositions
This invention relates to cellulose ether-containing thickening compositions, a method for their production, and to thickened compositions containing them.
Cellulose ethers are widely used to thicken aqueous or organic liquids. It has been found that combinations of cellulose ethers with other thickening agents show a synergistic thickening effect and there are a number of publications which disclose particular synergistic thickening compositions. Examples of such compositions are mixtures of cellulose ethers with polyacrylamidomethyl propane sulphonic acid as disclosed in United States Patent Specification No. 4540510, with Xanthan gum as disclosed in US Patent Specification No. 4,313,765, with a'maleic anhydride/olefin copolymer as disclosed in US Patent Specification No. 4172055, with a cross-linked acrylic copolymer as disclosed in US Patent Specification No. 4798682 or with hydroxyethyl starch as disclosed in GB Patent Specification No. 2110698 and 2110699.
The presence of any substantial quantity of electrolyte in a polar aqueous and/or organic medium which requires to be thickened can in at least some instances greatly disturb the thickening effect of cellulose ethers and particularly the synergistic effect mentioned above. The Applicants have found however that a combination of a suitably selected carboxymethyl cellulose thickening agent in combination with a swelling silicate thickening agent can give useful thickening or even synergistically enhanced thickening when
SUBSTITUTESHEET
the medium to be thickened is a high electrolyte composition.
The present invention therefore relates to cellulose ether thickening compositions which are suitable for use to thicken high-electrolyte compositions. For the purposes of the present invention a high electrolyte concentration is regarded as one above which the performance of a cellulose ether thickener other than as claimed is impaired. In a low solids medium consisting only of water thickener and electrolyte this effect may show itself at around 0.02 to 0.2 meq/g of electrolyte in the total solution. In other compositions containing a high solids concentration such as a toothpaste formulation it may show itself around 0.5-0.8 meq/g of the total composition. In other compositions of intermediate constitution the high electrolyte effect may occur between these figures. The term high electrolyte concentration should accordingly be interpreted from the point of view of effect on a cellulose ether thickener having a degree of substitution other than that now claimed. The use of the invention in relation to compositions containing up to 1 or even up to 2 or 2-5 m.eq/g of electrolyte is also envisaged.
The present invention provides a composition suitable for use to thicken electrolyte containing compositions comprising a cellulose ether thickening agent and another thickening agent, the composition being characterised in that the cellulose ether is a substituted cellulose ether having an average degree of substitution of at least from 0.7 and not more than l.l, and in that the other thickening agent is a swelling silicate thickening agent.
In the manufacture of the substituted cellulose ethers usually used for thickening purposes the cellulose molecule is reacted with alkali and then with a reagent such as chloroacetic acid to cause conversion of one or more of the three hyroxyl groups present in each anhydroglucose unit in the cellulose chain, first to the alkali metal salt and then
ro tne alkali metal acetate ether. The chloroacetic acid may be replaced by other reagents to produce other cellulose ethers. The degree of substitution can be controlled by, amongst other factors, the concentration of the alkali. The degree of substitution is the number of hydroxyl groups per anhydroglucose unit which are substituted and is usually stated as a range defining the minimum and maximum degree of substitution. The average degree of substitution is the weight mean average appropriate to a range. It is envisaged that to practical purposes a cellulose ether product will be outside the invention if any substantial part of the range, for example 20% or more is outside the range selected according to the invention.
It is found that while acceptable thickening properties may be attained over the above stated range of degree of substitution it is advantageous for the average degree of substitution of the cellulose ether to be above 0.7 and up to 1.1, Cellulose ethers having a range of substitution which extends substantially below 0.65 are undesirably difficult to dissolve while those having a degree of substitution which extends substantially above 1.1 or even above 1.0, show a diminution of synergism to some degree. Particularly preferably the cellulose ether has a minimum degree of substitution of above 0.7 for example of at least 0.8.
The cellulose ether utilised herein is preferably on anionic cellulose ether such as for example sodium carboxymethyl cellulose.
Many silicates have swelling or thickening properties. These are layered silicates, which swell by the entry of water or other polar liquids between the layers thereby causing an increase in the basal spacing, and are typified by the layered clay minerals of the smectite series such as the saponites, including saponite and hectorite or the montmorillonites. There also exists a range of synthetic
silicates having structures of the smectite type which show greatly enhanced swelling properties. Detail concerning the identification of structure types in clay minerals is given in "X-ray identification and crystal structure of clay minerals" Minerlogical Society (G. Brown) 1961. Suitable synthetic silicates are described in US Patent 'Specification No. 4049780 together with a process for their preparation and are hydrous magnesium silicates having a crystal structure similar to that of a hectorite and a composition
[Si8(MgaLibHc)O20(OH) -yFy]Z"ZM+
wherein a,b,c,y,z and M have the values: a is > 0 to 6 preferably 4.95 to 5.7 b is from 0 to <6 preferably 0 to 1.05 c is from 0 to <2 preferably 0 to 2 a-r-b+c is from >4 to <8 preferably 4 to 8 y is from 0 to <4 z = 12-2a-b-c M is Na+ or Li+
Such hydrous magnesium silicates are available under the LAPONITE Trade Mark from Laporte Industries Limited.
It is postulated without intending to limit the invention to the correctness of the following theory, that the particular effectiveness of the combination according to the invention may be connected to an inter-reaction between the anionic sites on the cellulose ether and hydroxyl sites on the silicate and that an extended cage type of structure is thereby obtained when the degree of substitution of the cellulose ether is as selected herein which structure is sufficiently stable to resist degradation in the presence of high electrolyte concentrations. This theory is supported by the fact that certain non-ionic cellulose ethers such as methyl cellulose and hydroxyethyl cellulose have been found not to be operative in the present invention. The silicates preferably contains at least 1 hydroxyl group for each 8 silicon atoms in the framework e.g. "y" in the above general
formula is preferably 3 or less.. To maximise the opportunities for inter-reaction between the silicate and the cellulose ether it is preferred that the number of hydroxyl groups on the silicate is as high as possible. Preferably therefore in the above general formula "y" is less than 1 or 0.
The relative weights of the cellulose ether and the clay may, for example, be from 5:95 to 95:5, preferably from 30:70 to 70:30.
The present invention may be utilised in the production of thickened high-electrolyte compositions by including the cellulose ether and the silicate, together or separately in an aqueous or suitable polar medium containing the other components of the composition to be thickened. According to the invention however it is preferred that the cellulose ether and the 'silicate' are both included in a liquid medium before contact with a high concentration of electrolyte. Thus the cellulose ether and the silicate may be premixed into a liquid medium which is then added to the main composition or they may be added to the main composition before any substantial quantity of electrolyte, sufficient to give a high electrolyte concentration, is included with the main composition. It is believed that an interaction between the cellulose ether and the electrolyte could prevent the desired cellulose ether/silicate structure from developing.
The present invention may be utilised in many differing applications in which high electrolyte concentration liquids require to be thickened. Dentrifice compositions intended for special "purposes, for example antiplaque dentrifices, can contain high concentrations of electrolyte in the form of sodium pyro- or poly-phosphates. Other examples of high electrolyte systems which require to be thickened are drilling muds in situations where high salt strata are penetrated, concrete mixes, aqueous emulsion paints and
coating mixes which may contain highly charged polymers such as polyacrylic copolymers, and the like.
The invention will now be illustrated by the following examples thereof which are not intended to be limiting on the general scope of the invention.
Example 1
Samples of water containing varying quantities of sodium sulphate were thickened with 2% by weight of the total composition of a 50/50- weight blend of a silicate thickener (Laponite RD) and one of 3 different carboxy methyl cellulose (CMC) ethers having degrees of substitution of 0.65-0.9, 0.8-0.95 and 1.15-1.45 denoted hereafter for convenience CMC/.65, CMC/.8 and CMC/1.15. The solutions were stored for 24 hours and the viscosities of the samples was determined using a Brookfield LVT (T-bar) viscometer at 0.6 rpm. The results are depicted in Figure 1 attached hereto.
Examples 2-11
The subject of these Examples is a typical high electrolyte dentrifice composition. To carry out the Example numbered 6 herein 495 g of sorbitol syrup (70% aq) was added to a polythene beaker, stirred under high shear whilst adding 6.0 g of a sodium carboxymethyl cellulose (CMC .65 or CMC .8) and mixing was continued for 15 minutes until the cellulose was completely dispersed.
In a separate beaker 4.0 g of synthetic silicate thickening agent (Laponite D) was added to 149.5 g of demineralised water with stirring. The mixture was heated to 40°C and mixing continued for 15 minutes.
The Laponite dispersion was added to the cellulose/Sorbitol mucilage and mixed thoroughly.
Then 15.0 g sodium saccharin solution (10% aq) , 10.0 g sodium fluoride solution (25% aq) and 50.0 g tetrasodiu pyrophosphate was added to the mucilage which was transferred to a vacuum mixer and to which was added 200 g of dentifrice grade silica abrasive and 10.0 g of titanium dioxide. Mixing under vacuum was continued for 5 minutes to deaerate the composition.
Lastly 10.0 g of flavour oil, 0.5 mg of preservative and 50.0 g of sodium lauryl sulphate solution (30% aq} were added and the resulting product was then further mixed under vacuum until completely deaerated.
After storage for 24 hours the rheological properties of the toothpaste were measured on a Brookfield viscometer.
To carry out Examples 2-5 and 7-11 the same procedure was followed with variations in the identity and quantity of the carboxymethyl cellulose, the quantity of the Laponite gelling agent and the identity and quantity of the electrolyte as indicated in Table l. The rheological results for each shear rate used are set out in Table 2.
SUBSTITUTESHEET
Ex Laponite
0.6 II
1.0 II
0.5 0.75 100% Sorbitol
0 0.35 0.5 " " 10 SrCl2.6H20 1 0 35 0.5 " " " "
TSPP = Tetrasodium pyrophosphate
TKPP = Tetrapotassium pyrophosphate
CMC = Carboxymethyl cellulose
CMC .65 = Grade 7M4XF available from Aqualon Corp.
CMC .8 = Grade 9M31XF available from Aqualon Corp.
DS = Degree of Substitution
Table 2
Viscosity (Poise) at given
Shear Rate after 24 hours
In comparison tests using the same procedure but in which the Laponite gellant and/or the CMC were replaced by other products an inferior rheology was found.
1.8% Laponite combined with 0.6% xanthan gum in a formulation otherwise identical to Examples 8 and 9 gave viscosities of 1438, 270, 61, 21 respectively despite this relatively very large quantity of Laponite while the same quantity of xanthan gum in the absence of any Laponite gave viscosities of 1010, 206, 50 and 18 respectively. The replacement of the Laponite by 0.2% of polyacrylic acid polymer gave viscosities of 1450, 286, 59 and 18 respectively.
SUBSTITUTE SHEET
Claims
1. A composition, suitable for use to thicken electrolyte containing compositions, comprising a cellulose ether thickening agent and another thickening agent, the composition being characterised in that the cellulose ether is a substituted cellulose ether having an average degree of substitution of from 0.7 to 1.1 and in that the other thickening agent is a swelling silicate thickening agent.
2. A composition suitable for use to thicken electrolyte- containing compositions comprising a cellulose ether thickening agent and another thickening agent, the composition being characterised in that the cellulose ether is a substituted cellulose ether having a degree of substitution confined to a range having a minimum of 0.65 and a maximum of 1.1 and in that the other thickening agent is a swelling silicate thickening agent.
3. A composition as claimed in claim l or 2 wherein the cellulose ether is an anionic cellulose ether.
4. A composition as claimed in any preceding claim wherein the swelling silicate thickening agent is a layered natural or synthetic layered silicate of the smectite series.
5. A composition as claimed in claim 4 wherein the swelling silicate is a synthetic layered silicate having a crystal structure similar to that of hectorite.
6. A composition as claimed in any preceding claim wherein the swelling silicate thickening agent comprises hydroxyl groups.
7. A composition as claimed in any preceding claim wherein the relative weights of the cellulose ether and the other thickening agent are from 5 to 95 to 95 to 5.
8. A composition as claimed in any preceding claim also comprising a liquid polar medium.
9. A composition as claimed in claim 8 wherein the polar medium comprises water.
10. A thickening composition comprising a composition as claimed in any one of claims 8 or 9 also containing at least 0.02 m.eq/g of electrolyte.
11. A composition as claimed in claim 10 containing not more than 2.5 m.eq/g electrolyte.
12. A process for the production of a thickened composition as claimed in claim 10 or 11 by mixing the thickening agents, a source of electrolyte and a polar liquid medium characterised in that the cellulose ether thickening agent and the swelling silicate thickening agent are mixed together, before contact with the source of electrolyte.
13. A composition as claimed in any preceding claim and substantially as described in the Examples herein.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB919122607A GB9122607D0 (en) | 1991-10-24 | 1991-10-24 | Cellulose ether thickening compositions |
GB9122607.6 | 1991-10-24 |
Publications (1)
Publication Number | Publication Date |
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WO1993008230A1 true WO1993008230A1 (en) | 1993-04-29 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/GB1992/001914 WO1993008230A1 (en) | 1991-10-24 | 1992-10-19 | Cellulose ether thickening compositions |
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WO (1) | WO1993008230A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0691381A4 (en) * | 1994-01-24 | 1996-07-17 | Sumitomo Chemical Co | COMPOSITION, FILM AND MOLDING OF BIODEGRADABLE RESIN |
EP0773198A1 (en) * | 1995-11-10 | 1997-05-14 | Hoechst Aktiengesellschaft | Thickening system for building material mixtures |
EP0786249A1 (en) | 1996-01-23 | 1997-07-30 | L'oreal | Stable gel composition containing an amount of an electrolyte |
EP0795320A1 (en) | 1996-03-12 | 1997-09-17 | L'oreal | Stable gelified composition with high electrolyte content |
WO2002062310A1 (en) * | 2001-02-05 | 2002-08-15 | Amcol International Corporation | Multifunctional particulate additive for personal care and cosmetic compositions, and the process of making the same |
WO2003004562A1 (en) * | 2001-07-03 | 2003-01-16 | Henkel Kommanditgesellschaft Auf Aktien | Binding agent composition for roller paste preparation |
EP1553152A3 (en) * | 2004-01-09 | 2008-12-03 | Clariant Produkte (Deutschland) GmbH | Deicing and antifreeze composition thickened by layered silicates |
US7744908B2 (en) * | 2003-10-28 | 2010-06-29 | Taro Pharmaceuticals U.S.A., Inc. | Spill resistant formulations containing clays |
ITVA20100020A1 (en) * | 2010-03-05 | 2011-09-05 | Lamberti Spa | RHEOLOGY MODIFIER FOR CERAMIC ENAMELS |
EP2591825A1 (en) * | 2011-11-08 | 2013-05-15 | PeGoMa B.V. | Composition for the treatment of teeth, and use |
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US4267062A (en) * | 1977-10-21 | 1981-05-12 | Nl Industries, Inc. | Abandoned borehole compositions |
US4497919A (en) * | 1983-09-22 | 1985-02-05 | Turtle Wax, Inc. | Emulsion polish compositions |
US4818293A (en) * | 1985-08-01 | 1989-04-04 | Betz Laboratories, Inc. | Stable slurries comprising powdered activated carbon |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6146750A (en) * | 1994-01-24 | 2000-11-14 | Sumitomo Chemical Co., Ltd. | Bio-degradable resin composition, film and shaped article |
EP0691381A4 (en) * | 1994-01-24 | 1996-07-17 | Sumitomo Chemical Co | COMPOSITION, FILM AND MOLDING OF BIODEGRADABLE RESIN |
EP0773198A1 (en) * | 1995-11-10 | 1997-05-14 | Hoechst Aktiengesellschaft | Thickening system for building material mixtures |
EP0786249A1 (en) | 1996-01-23 | 1997-07-30 | L'oreal | Stable gel composition containing an amount of an electrolyte |
EP0795320A1 (en) | 1996-03-12 | 1997-09-17 | L'oreal | Stable gelified composition with high electrolyte content |
WO2002062310A1 (en) * | 2001-02-05 | 2002-08-15 | Amcol International Corporation | Multifunctional particulate additive for personal care and cosmetic compositions, and the process of making the same |
US6500411B2 (en) | 2001-02-05 | 2002-12-31 | Amcol International Corporation | Multifunctional particulate additive for personal care and cosmetic compositions, and the process of making the same |
WO2003004562A1 (en) * | 2001-07-03 | 2003-01-16 | Henkel Kommanditgesellschaft Auf Aktien | Binding agent composition for roller paste preparation |
US8211451B2 (en) | 2003-10-28 | 2012-07-03 | Taro Pharmaceuticals U.S.A., Inc. | Spill resistant formulations containing clays |
US7744908B2 (en) * | 2003-10-28 | 2010-06-29 | Taro Pharmaceuticals U.S.A., Inc. | Spill resistant formulations containing clays |
US7981435B2 (en) | 2003-10-28 | 2011-07-19 | Taro Pharmaceuticals U.S.A. Inc. | Spill resistant formulations containing clays |
EP1553152A3 (en) * | 2004-01-09 | 2008-12-03 | Clariant Produkte (Deutschland) GmbH | Deicing and antifreeze composition thickened by layered silicates |
WO2011107563A1 (en) * | 2010-03-05 | 2011-09-09 | Lamberti Spa | Rheology modifier for ceramic glazes |
ITVA20100020A1 (en) * | 2010-03-05 | 2011-09-05 | Lamberti Spa | RHEOLOGY MODIFIER FOR CERAMIC ENAMELS |
CN102906052A (en) * | 2010-03-05 | 2013-01-30 | 蓝宝迪有限公司 | Rheology modifier for ceramic glazes |
US8628611B2 (en) * | 2010-03-05 | 2014-01-14 | Lamberti Spa | Rheology modifier for ceramic glazes |
EP2591825A1 (en) * | 2011-11-08 | 2013-05-15 | PeGoMa B.V. | Composition for the treatment of teeth, and use |
WO2013068495A3 (en) * | 2011-11-08 | 2013-09-26 | Pegoma B.V. | Composition for the treatment of teeth, and use |
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