MXPA97001807A - Granula compositions - Google Patents
Granula compositionsInfo
- Publication number
- MXPA97001807A MXPA97001807A MXPA/A/1997/001807A MX9701807A MXPA97001807A MX PA97001807 A MXPA97001807 A MX PA97001807A MX 9701807 A MX9701807 A MX 9701807A MX PA97001807 A MXPA97001807 A MX PA97001807A
- Authority
- MX
- Mexico
- Prior art keywords
- water
- insoluble
- microns
- particle size
- weight
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000002245 particle Substances 0.000 claims abstract description 76
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 239000011236 particulate material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 238000005054 agglomeration Methods 0.000 claims description 9
- 230000002776 aggregation Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002537 cosmetic Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- KOYYEPZTIWTHDY-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;zinc;dihydrate Chemical compound O.O.[Zn].[Zn].[Zn].OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O KOYYEPZTIWTHDY-UHFFFAOYSA-N 0.000 claims description 6
- JUNWLZAGQLJVLR-UHFFFAOYSA-J Calcium pyrophosphate Chemical class [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 6
- 229940068475 ZINC CITRATE Drugs 0.000 claims description 6
- 235000010216 calcium carbonate Nutrition 0.000 claims description 6
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 6
- 239000008262 pumice Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000011746 zinc citrate Substances 0.000 claims description 6
- 235000006076 zinc citrate Nutrition 0.000 claims description 6
- NEFBYIFKOOEVPA-UHFFFAOYSA-K Dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims description 5
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L Magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- AQMNWCRSESPIJM-UHFFFAOYSA-M Sodium metaphosphate Chemical compound [Na+].[O-]P(=O)=O AQMNWCRSESPIJM-UHFFFAOYSA-M 0.000 claims description 5
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 229940038472 dicalcium phosphate Drugs 0.000 claims description 5
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 239000011776 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 235000019362 perlite Nutrition 0.000 claims description 5
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 5
- 238000005296 abrasive Methods 0.000 claims description 4
- 230000001225 therapeutic Effects 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 2
- 239000011049 pearl Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000005341 metaphosphate group Chemical group 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 description 21
- 239000000606 toothpaste Substances 0.000 description 21
- 239000008187 granular material Substances 0.000 description 16
- 229940034610 Toothpaste Drugs 0.000 description 15
- 238000009826 distribution Methods 0.000 description 15
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000003814 drug Substances 0.000 description 8
- 210000000214 Mouth Anatomy 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 239000000796 flavoring agent Substances 0.000 description 6
- 235000019634 flavors Nutrition 0.000 description 6
- 235000010215 titanium dioxide Nutrition 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000001680 brushing Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005029 sieve analysis Methods 0.000 description 4
- 210000000515 Tooth Anatomy 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 239000008368 mint flavor Substances 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 235000019615 sensations Nutrition 0.000 description 2
- 230000001953 sensory Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229940075484 D&C red no. 30 Drugs 0.000 description 1
- 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 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J Pyrophosphate Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 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
- 229940081974 Saccharin Drugs 0.000 description 1
- 210000003296 Saliva Anatomy 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M Sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- BFDWBSRJQZPEEB-UHFFFAOYSA-L Sodium monofluorophosphate Chemical compound [Na+].[Na+].[O-]P([O-])(F)=O BFDWBSRJQZPEEB-UHFFFAOYSA-L 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K Tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 230000024126 agglutination involved in conjugation with cellular fusion Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 235000019622 astringency Nutrition 0.000 description 1
- 235000019606 astringent taste Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004075 cariostatic agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- VLCINIKIVYNLPT-UHFFFAOYSA-J dicalcium;hydrogen phosphate Chemical compound [Ca+2].[Ca+2].OP(O)([O-])=O.[O-]P([O-])([O-])=O VLCINIKIVYNLPT-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 238000007908 dry granulation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 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
- 229960004711 sodium monofluorophosphate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- VSJRDSLPNMGNFG-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate;trihydrate Chemical compound O.O.O.[Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VSJRDSLPNMGNFG-UHFFFAOYSA-H 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Abstract
A granular composition comprising from 45 to 98% w / w of a water-insoluble particle is described, wherein from 10 to 75% of the water-insoluble particle is made from a water-soluble particulate material, having a size of medium particle by weight less than 20 microns and an oil absorption capacity of 60 to 180g / 100g, and from 10 to 75% of the water-insoluble particle is made of a water-insoluble particulate material, which has a size of medium particle by weight below 20 microns and an oil absorption of 200 to 350g / 100g, the granulated composition having a particle size, by screening analysis, of 95% below 600 microns, and 95% above of 40 micr
Description
GRANULATED COMPOSITIONS
FIELD OF THE INVENTION
The present invention relates to granular compositions, which provide "useful sensory-perceived benefits in toothpaste compositions.
BACKGROUND OF THE INVENTION
The use of water as a binder for silica particles has been described in GB 1,365,516, and water is known to be a common binder for size enlargement (Handbook of Powder Technology - Vol. 1 - Particle Size Enlarge ent - page 41 , Table 2.3 - Elsevier). Formulations of toothpastes containing a granular composition comprising a water-insoluble material and a water-insoluble binder have been described in EP-B-269, 966. Such granulated compositions may contain functional substances such as drugs, enzymes and agents. polishers. The problem addressed in this document is that it is not possible to agglutinate the particles within the granulated composition with water-soluble binders for use in formulations containing large amounts of water, such as toothpastes. The reason is that the water-soluble binder will dissolve in the aqueous component of the formulation and weaken the granulated composition, making it impossible to detect coarse particles in the mouth. The addition of a zinc salt, as an agent against the plate, to the composition of the toothpaste, has already been described in GB 1,373,001. It was found that granular compositions containing only water insoluble particles of a low to medium structure, particularly those with a low oil absorption capacity favored as abrasives and polishing agents in dental formulations, joined with water and dried, are too weak to survive the normal procedures in the manufacture of toothpastes, and, therefore, could not be felt in the subsequent procedure of tooth cleaning. In addition, granular compositions containing highly insoluble water-insoluble particles (ie, with a high oil absorption capacity) for example, silicas, favored as thickening agents in toothpaste formulations, are considered to have much more strength and provide unacceptable levels of sensation to the mouth.
To overcome this problem, it has been discovered that granulated compositions with sufficient strength can be prepared by mixing a highly structured water insoluble particle with low to medium structuring prior to the agglutination process. Surprisingly, the addition of powdered therapeutic agents, for example, zinc citrate, opacifiers, for example, titanium dioxide, and color pigments, have been shown to have no significant harmful effect on the properties of the granulated composition.
Normal Procedures
The granular compositions of the invention are defined in terms of the properties and textures of the water-insoluble particles used to produce the agglomerate, its particle size distribution, and strength.
i) Oil Absorption
The oil absorption is determined by the ASTM spatula friction method (American Society of Test Material Standards D, 281).
The test is based on the principle of mixing flaxseed oil with the water-insoluble particle, rubbing with a spatula on a smooth surface, until a firm, putty type paste is formed, which will not break or separate when Cut with a spatula. The volume of oil used is converted to weight and expressed as grams of oil / 100 g of insoluble particles in water.
ii) Average particle size in weight
The average particle size by weight of the water-insoluble particle before agglomeration is determined using an X Malvern Mastersizer model, made by Malvern Instruments, Malvern, Worcestershire with the sample presentation unit MS15. This instrument uses the principle of dissemination, using a low energy He / Ne laser. The water-insoluble particles are ultrasonically dispersed in water for 5 minutes to form an aqueous suspension, and then mechanically agitated before they are subjected to the measurement procedure underlined in the instruction manual for the instrument, using a 45 mm lens in the detector system. The Malvern Particle Sizer measures the particle size by weight of the insoluble particle in water. The average particle size by weight (or-50) or 50th percentile, 10th percentile (d10) and 90th percentile (ó-90) are easily obtained from the data generated by the instrument.
iii) Resistance of the Granular Composition
The average particle size distribution by weight of the granulated composition is measured using the same Malvern instrument and the general method described above, but with the following differences: a) the granules are measured with a 300 mm lens in the detector system . b) an initial particle size distribution of the granules is taken without any ultrasonic dispersion
(0-ultrasonic) that is, the sample dispersed only with mechanical agitation. c) the granules are dispersed using ultrasonics for two minutes, setting at 50, and then subjecting them to the usual measurement method (ultrasonic 50). d) the granules are dispersed using ultrasonics for two minutes, setting at 100, and then subjecting them to the usual measurement procedure (100 ultrasonics).
The dlO, d50 and d90 can then be interpolated from the particle size distribution generated by the instrument, and the larger the values obtained after exposure to the ultrasonics, the stronger the granulated composition.
iv) Distribution of the particle size by sieve analysis
A more accurate measurement of the true particle size distribution of the granulated composition is made using the sieve analysis. 100 g of the sample is placed on the upper sieve of a series of BS sieves, at intervals of about 50 microns between 45 and 600 microns. The sieves are arranged in the order of the thinnest in the background and the thickest at the top of the row. The sieves are placed in a mechanical vibrator, for example, Inclyno Mechanical Sieve Shaker by Pascall Engineering Co Ltd., covered with a lid and shaken for 10 minutes. Each sieve fraction is exactly weighed and the results are calculated:
Waste% = weight of the waste * 100 weight of the sample Next, a particle size distribution can be plotted from the data.
General Description of the Invention
It is a first object of the present invention to provide a granular composition comprising from 45 to 98% w / w of a water-insoluble particle, whereby from 10 to 75% of the water-insoluble particle is made of a material which is insoluble in water. insoluble particles in water, which has the average particle size by weight less than 20 microns and an absorbency of oil 60 to 180g / l00g, and selected from the group consisting of amorphous silicas, aluminas, calcium carbonates, phosphate dicalcium phosphate tribasic calcium, insoluble sodium metaphosphate, calcium pyrophosphates, hydroxyapatites, perlites, zeolites, magnesium carbonate, pumice, and 10 to 75% of water insoluble particles is made of a material water-insoluble particle which has a mean particle size per weight below 20 microns and an oil absorption of 200 to 350g / 100g, selected from the group consisting of amorphous silicas, low density aluminas and pearls and xpandidas, the granulated composition having a particle size, by sieve analysis, of 95% below 600 microns, and 95% above 40 microns.
This granulated composition is substantially free of organic or inorganic binder. It is preferable that the granulated composition should have a particle size distribution, as measured by the sieve analysis, so that 95% of the granules are less than 400 microns and 95% of the particles are above 100. microns, more preferably 150 microns. Due to the porous nature of the agglomerates, it is possible that these act as delivery vehicles for substances that provide cosmetic benefits, such as coloring pigments, flavors, perfumes or other cosmetics. The agglomerates may also contain other therapeutic and / or oral cosmetic and / or dental actives, and release them in the mouth. Such substances may be contained within the pores of the material. The inclusion of a material that has a therapeutic or cosmetic effect on the gums or teeth, or oral cavity, in these agglomerates, provides an additional benefit since by breaking or crushing these agglomerates, the therapeutic / cosmetic agent is slowly released, thus delivering the therapeutic agent over the entire mouth for a long period. Suitable examples of such therapeutic agents are zinc salts, such as zinc citrate; antimicrobial agents such as Triclosan; anti-caries agents such as sodium fluoride and sodium monofluorophosphate; agents against plaque formation such as stannous pyrophosphate, etc. In this respect, it has surprisingly been found that the inclusion of zinc citrate in the agglomerates (in an amount up to 15%, preferably up to 12% by weight of the agglomerates) significantly reduced the level of astringency, perceived by a group trained after trying a toothpaste with such agglomerates for its sensory properties. The addition of Ti02, as an opacifying agent, at a concentration of 1 to 5% w / w, usually at the expense of the water-insoluble particles, ensures that the granules have a white appearance, and therefore persist in the formulations of toothpaste with color. If colored granules are required, then you can be added color pigment food grade, for example pigment dispersions under the trade name Cosmenyl or pigment powders under the trade name Hostaperm or Cosmetic Pink RC 01 (D &C Red No. 30) supplied by Hoechst, to the composition of the granule, without affecting the strength of the same. If the titanium dioxide and the therapeutic agent are omitted from the granular composition, which contains abrasive and thickener silicas, then the coarse particles are invisible in the transparent gel formulations. In addition, the strength of the agglomerate can be varied over a wide variety of scales by changing the structure of the water-insoluble particle, i.e., the insoluble particles in water of low structure reduce the strength, while the insoluble particles in water of high structure increase the strength of the agglomerate. The use of water insoluble particles, which have proven to play an important role in toothpaste formulations, such as toothpaste abrasive silicas [e.g., Sorbosil AC77 (obtained from Crosfield Limited - England)], as The low / medium structure component is an added advantage, since such silicas are able to provide extra cleaning to the formulation and have good compatibility with the formulation. Actually, the insoluble particles particularly preferred water, which make up the granular composition are mixtures of synthetic thickening silicas, amorphous [for example, Sorbosil TC15 (obtainable from Crosfield Limited - England)] and abrasive silicas. The agglomerates must be insoluble in the medium of the composition of the toothpaste to which they are incorporated. In this context, "insoluble" means that it has an insufficient solubility at room temperature, since the agglomerates remain undissolved or substantially undissolved in the composition, so that its friability under the conditions of use of the composition and thus its ability to perform its cleaning / polishing function are not in a harmful way affected. Preferably, the level of insolubility of the agglomerates extends to their insolubility in the oral environment, where the composition is to be used, which may often contain higher levels of water, than, for example, a toothpaste, caused by the presence of saliva and added water frequently used in the brushing regime. When the granules are incorporated into a toothpaste composition, it is important that they break under the shear stresses generated by the toothbrush in a relatively short period, thereby eliminating the gritty feeling experienced by the user. This means, that the agglomerates must have a particle resistance, so that they will crush within the scale of shear and / or crushing forces, normally produced in the relevant brushing regime, since the considerably variable forces produced in a particular location for a time, they allow at least some of the agglomerates to remain intact enough to perform their cleaning function to a satisfactory degree.
It is still possible to develop the break time of the agglomerates, such as controlling the contact time for a given duration of brushing the composition, controlling the average deformation resistance of the agglomerates, for example, selecting a particular type of source of particulate materials and / or the manner in which they are agglomerated in the manufacturing process. When the agglomerates are broken under the action of shear and / or deformation forces, the resulting average particle size (diameter) will typically be less than about 40 microns. Such reduced particle sizes will generally prevent any gritty feeling in the mouth, and impart a feeling of polished teeth. It is another object of the present invention to provide a process for producing a granular composition wherein, from 10 to 75 parts by weight of a water-insoluble particulate material, having a mean particle size per weight of less than 20 microns and a capacity of of oil absorption from 60 to 180g / 100g and selected from the group consisting of amorphous silicas, aluminas, calcium carbonates, dicalcium phosphate, tribasic calcium phosphates, insoluble sodium metaphosphate, calcium pyrophosphates, hydroxyapatites, pearlites, zeolites, carbonate of magnesium, pumice, are mixed with 10 to 75 parts by weight of a particulate material insoluble in water, having a mean particle size per weight below 20 microns and an oil absorption of 200 to 350g / 100g, selected from the group consisting of amorphous silicas, low density aluminas and expanded perlites, then agglomerated with water, the resulting product being then dried. Preferably, the water-insoluble particulate powders are amorphous silica particles of high structure and low to medium, and a therapeutic agent is mixed therewith prior to agglomeration. If opaque granules are required, then Ti02 is added to the powder mixture. If colored granules are required, a pigment dispersion with a suitable color, food grade, can be added. By drying the product after agglomeration, a granular composition is obtained, which is stable in a toothpaste composition. Agglomeration can be achieved, for example, by tray granulation, extrusion, spray granulation or spinning disk granulation. Preferably, the agglomeration is operated in a tray granulator, when the ratio of water: solids (ie water-insoluble particles with optionally Ti02 / mixed therapeutic agent etc.) is on the scale of 1.1-1.35: 1. This relationship is important to obtain agglomerates of correct resistance, since below this, the material remains as a powder and above it a paste is formed. Afterwards, the agglomerates are dried. This drying can be carried out in various ways, for example, in an oven or in a fluidized bed. During this drying step, the required degree of resistance develops in the agglomerates. It has also been found that agglomeration can be obtained by compacting the powder mixture and in this process a drying step is not required. Therefore, another object of the present invention is to provide a process for producing a granular composition, wherein, from 10 to 75 parts by weight of a particulate water insoluble material, having a mean particle size by weight less than 20 microns and an oil absorption capacity of 60 to 180g / l00g, and is selected from the group consisting of amorphous silicas, aluminas, calcium carbonates, dicalcium phosphate, tribasic calcium phosphates, insoluble sodium metaphosphate, calcium pyrophosphates, hydroxyapatites, pearlites, zeolites, magnesium carbonate, pumice, are mixed with 10 to 75 parts by weight of a particulate material insoluble in water, having a mean particle size per weight below 20 microns and an oil absorption from 200 to 350g / 100g, selected from the group consisting of amorphous silicas, low density aluminas and expanded perlites, the resulting mixture being agglomerated by compaction. To be incorporated into toothpastes, it is important that virtually all particles are below 600 μm, preferably below 400 μm, since gritty particles give unpleasant sensation properties in the mouth. Therefore, a size reduction step using a minimum energy is required to avoid unnecessary breakage of the agglomerate. Then, one or more screening steps are desirable to ensure that no size oversize and also provide a background cut, for example, at 150 microns.
Specific Description of the Invention
The present invention will be further illustrated in the following examples.
Comparative Example 1
Two highly structured silicas [Sorbosil TC15 (obtained from Crosfield Limited - England)] and a medium structure (almost low) [Sorbosil AC77 (obtained from Crosfield Limited -England)] were agglomerated individually, at a batch size of dust of 200g, laboratory scale with deionized water (water ratio: 1.33: 1 solids) using a Sirman CV6 mixer, supplied by Metcalfe Catering Equipment Ltd, Blaenau Ffestiniog, Víales. The resulting wet agglomerates were then dried in an oven at 150 ° C for 4 hours, moderately forced through a 420 micron sieve and sieved at 150 microns to adjust the particle size distribution. Silicas have the following properties:
(*) - obtained from Crosfield Limited - England Granulated silicas after agglomeration have the following properties:
Ultrasonic dlO d50 d90
Sorbosil TC15 0 268 415 549 50 249 410 553 100 70 265 469
Sorbosil AC77 0 16 187 346 50 3.2 10 37.4 100 2.9 8.5 21.2
The highly structured silica TC15 (obtained from Crosfield Limited - England) forms an agglomerate, which is too strong and will not break in the required time with brushing in a toothpaste composition, while the silica with a structure of medium / low AC77 (obtained from Crosfield Limited England), produces an agglomerate, which is too weak to survive the normal procedures in the manufacture of toothpastes.
Example 1
The silicas used in Comparative Example 1 were mixed together with titanium dioxide in the following matrix, which includes the individual silicas with TiO2:
(*) - which is obtained from Joseph Crosfield & Sons - England
Deionized water was added to the powder mixtures to give a water: solids ratio of 1.33 to 1 and the resulting 200g mixtures were agglomerated using a laboratory-scale Sir an CV6 mixer, supplied by Metcalfe Catering Equipment Ltd, Blaenau Ffestiniog, Wales.
The resulting wet agglomerates were then dried in an oven at 150 ° C for 4 hours, moderately forced through a 420 micron sieve and screened at 150 microns to adjust the particle size distribution. The resulting agglomerates have the following properties:
Ultrasonic dlO d50 d90
Composition 1 0 258 404 555 50 254 389 547 100 128 309 500
Composition 2 0 228 370 542 50 201 355 530 100 118 277 474
Composition 3 0 207 351 534 50 167 320 509 100 5.3 73 220
Composition 4 0 176 324 506 50 4 15.6 71 100 3.4 11 29.8 Composition 5 0 8. 8 186 332 50 2. 8 9. 4 31. 6 100 2. 6 8. 3 21. 1
Compositions 1 and 5 show that the addition of
Ti02 does not have any harmful effect on the strength of the agglomerate particle. It can be seen that the particle resistance varies according to the relative amounts of high and medium / low structure silicas present in the agglomerate. Compositions 1 and 2 are considered too strong, and compositions 4 and 5 too weak for a granule of optimum strength. Composition 3, since it is not considered optimal within the desired scale of resistance.
Example 2
The following powders were mixed together to give an intimate mixture:
parts by weight parts by weight
Sorbosil AC77 (*) 43.15 48.5 Sorbosil TC15 (*) 43.15 48.5 Titanium dioxide 3.0 3.0 Zinc trihydrate-citrate 10.7 or (*) - obtained from Crosfield Limited - England
Water was added to this mixture to give a water: solids ratio of 1.33 to 1, the resulting mixture being granulated in a 100 liter CMG mixer / granulator manufactured by Eurovent Ltd, Fenton, Stoke-on-Trent, with an intermittent load of 6 kg. The resulting wet agglomerates were then partially dried for 30 minutes in a fluid bed dryer and terminated in a furnace for 2 hours at a temperature of 120 ° C. The particle size distribution was subjected by sieving to 150 and 400 microns. The properties of the granulated composition are presented below.
Ultrasonic dlO d50 d90
Composition 1 0 193 334 502 50 112 289 475 100 3.3 14.3 41.5
Composition 2 0 268 391 539 50 224 365 526 100 3.3 12 39 Clearly, the presence of zinc citrate has a small effect on the strength of the granular compositions, and the granules of this strength have been shown to survive the normal processing conditions used in the manufacture of toothpastes, they are stable and have good sensory properties in a toothpaste composition.
Examples 3-7:
The following homogeneous powder mixtures were made:
Deionized water was added to the powder mixes (200g) to give a water: solids ratio of 1.33 to 1, for examples 3, 4 and 7, and 0.72 to for examples 5 and 6. The resulting mixtures were agglomerated using a laboratory-scale Sirman CV6 mixer, supplied by Metcalfe Catering Equipment Ltd, Blaenau Ffestiniog, Wales. The resulting wet agglomerates were then dried in an oven at 150 ° C for 12 hours, moderately forced through a 420 micron sieve and screened at 150 microns to adjust the particle size distribution. The resulting agglomerates have the following properties:
Ultrasonic dlO d50 d90
Example 3 0 186 306 488 50 14 222 425 100 3.8 23 62
Example 4 0 223 385 530 50 9.4 151 423 100 4 16 41
Example 5 0 32 233 460 50 11 128 376 100 3.9 17 45
Example 6 0 199 386 554 50 8 180 412 100 3 13 41 Example 7 0 190 346 532 50 30 286 510 100 4 16 46
Examples 8-10
The following homogeneous powder mixtures were made:
I INNGRADIENT EJ. 8 EJ. 9 EJ. 10
SORBOSIL AC77 26.3 43.1 60.0 SORBOSIL C15 26. 3 43. 1 40 0 PYROPHOSPHATE OF 24. 6 POTASSIUM
PIROPHOSPHATE OF 19.8 SODIUM
ZINC TRIHYDRATE-CITRATE 10 .8
TITANIUM DIOXIDE 3.0 3.0
The powder mixes were fed through a Fitzpatrick Chilsonator model L83 roller compactor (manufactured by Fitzpatrick Company, Elmhurst, Illinois, USA), which was configured as Figure 1 in the article "Preconditioning process powders with dry granulation" by Calvin E. Johnson (The Fitzpatrick Company), cited in Powder and Bulk Engineering, December 1987. The upper sieve size was 425 microns and the lower sieve was 250 microns. The resulting agglomerate product had the following properties:
Ultrasonic dlO d50 d90
Example 8 0 150 326 526 50 17 162 383 00 4 29 69
Example 9 0 176 331 530 50 74 292 516 100 6.9 72 314
Example 10 0 160 300 497 50 120 288 495 100 3 15 69
Examples 11-14
The following homogeneous powder mixtures were made:
Deionized water was added to the powder mixtures (200g) to give a water: solids ratio of 1.33 to 1, for Examples 11, 12 and 14 and from 0.72 to 1 for Example 13. The resulting mixtures were agglomerated using a Sirman CV6 laboratory scale mixer, supplied by Metcalfe Catering Equipment Ltd, Blaenau Ffestiniog, Wales. The resulting wet agglomerates were then dried in an oven at 150 ° C for 12 hours, moderately forced through a 420 micron sieve and sieved at 150 microns to adjust the particle size distribution. The resulting agglomerates have the following properties:
Ultrasonic dlO d50 d90
Example 11 0 197 354 526 50 10 213 465 100 3.3 15 50
Example 12 0 187 311 498 50 16 250 471 100 5 34 297
Example 13 0 190 333 518 50 14 210 455 00 4 24 69
Example 14 0 196 326 514 50 96 282 476 100 4 29 104
Examples 15-16
The following homogeneous powder mixtures were made:
Deionized water was added to the powder mixes
(200g) to give a water ratio: solids of 1.33 to 1. The resulting mixtures were agglomerated using a mixer of
Sirman CV6 laboratory scale, supplied by Metcalfe Catering Equipment Ltd, Blaenau Ffestiniog, Wales. The resulting wet agglomerates were then dried in an oven at 150 ° C for 12 hours, moderately forced through a 420 micron sieve and screened at 150 microns to adjust the particle size distribution. The resulting agglomerates have the following properties:
Ultrasonic dlO d50 d90
Example 15 0 219 379 536 50 194 355 524 100 6.7 43 186 Example 16 0 215 373 534 50 177 339 517 100 3 37 95
Examples 17-19
The following mixtures were made:
Deionized water was added to the powder mixes (200g) to give a water: solids ratio of 1.33 to 1. With examples 17 and 19, the Cosmenyl pigment dispersions were added to the deionized mixing water, which was then added to the powder mixture. The resulting mixtures were agglomerated using a laboratory-scale Sirman CV6 mixer, supplied by Metcalfe Catering Equipment Ltd, Blaenau Ffestiniog, Wales. The resulting wet agglomerates were then dried in an oven at 150 ° C for 12 hours, moderately forced through a 420 micron sieve and screened at 150 microns to adjust the particle size distribution. The resulting agglomerates have the following properties:
Ultrasonic dlO d50 d90
Example 17 0 182 301 487 50 41 251 447 00 4 22 62
Example 18 0 191 344 532 50 163 347 534 100 5.6 39 210
Example 19 0 192 345 537 50 77 285 511 100 4 19 49 Example 20
A toothpaste having the following composition was produced:
INGREDIENT% BY WEIGHT Sorbitol 45 Water 22. .12 Sorbosil AC77 10. .0 Silica of the invention 7. .0 Sorbosil TC15 6. .0 PEG 1500 5. .0 SLS 1. .5 TÍO2 1 .0 Mint flavor DP5017 0 .5 SMPF 0 .8 SCMC 0 .8 Saccharin 0 .2 Sodium Benzoate 0 .08
The above formulations were made under vacuum, using conventional preparative procedures in a Lang mixer. In preparation 1, the flavor component was added on the side of the container, near the end of the formulation.
An identical additional preparation 2 was performed, with the exception that the flavor was added to the silica granule of the invention by means of a pipette, before its introduction to the toothpaste mixer. The granule of the invention, containing the flavor, was mixed dry with the other two silicas and the resulting powder mixture was added in portions for 40 minutes under a closed vacuum. The two pastas were then examined "blindly" by 6 people, who were asked to analyze the flavor properties. The 6 people established that the pasta 2 had a significantly stronger mint flavor, indicating that the granule of the invention can carry and deliver the flavor more effectively than by simply adding it to the dental platte mixture, separately.
Claims (10)
1. A granulated composition, characterized in that it comprises from 45 to 98% w / w of a water-insoluble particle, whereby from 10 to 75% of the water-insoluble particle is made of a water-insoluble particulate material, which has a average particle size per weight less than 20 microns and an oil absorption capacity of 60 to 180g / 100g, and is selected from the group consisting of amorphous silicas, aluminas, calcium carbonates, dicalcium phosphate, tribasic calcium phosphates, metaphosphate of insoluble sodium, calcium pyrophosphates, hydroxyapatites, pearlites, zeolites, magnesium carbonate, pumice, and 10 to 75% water-insoluble particles are made from a water-insoluble particulate material, which has a mean particle size by weight below 20 microns and an oil absorption of 200 to 350g / l00g, selected from the group consisting of amorphous silicas, low density aluminas and expanded perlites, the granulated composition endo a particle size, by screening analysis, 95% below 600 microns, and 95% above 40 microns.
2. The granulated composition according to claim 1, characterized in that it comprises from 1 to 5% w / w of Ti023.
The granulated composition according to claims 1 and 2, characterized in that it comprises up to 15% zinc citrate.
4. The granulated composition according to claims 1-3, characterized in that the agglomerate contains a material that has a therapeutic cosmetic dental benefit.
5. The granulated composition according to claims 1-3, characterized in that the material having a therapeutic cosmetic benefit is a flavoring compound.
6. The granular composition according to claims 1-3, characterized in that it comprises a high structure silica thickener and a low structure silica abrasive.
7. A process for producing a granular composition, according to claim 1, characterized in that from 10 to 75 parts by weight of a water-insoluble particulate material, having a mean particle size per weight of less than 20 microns and a capacity of oil absorption of 60 to 180g / 100g, and is selected from the group consisting of amorphous silicas, aluminas, calcium carbonates, dicalcium phosphate, tribasic calcium phosphates, insoluble sodium metaphosphate, calcium pyrophosphates, hydroxyapatites, pearlites, zeolites, Magnesium carbonate, pumice, are mixed from 10 to 75 parts by weight of a water-insoluble particulate material, which has a mean particle size per weight below 20 microns and an oil absorption of 200 to 350g / l00g , selected from the group consisting of amorphous silicas, low density aluminas and expanded perlites, then agglomerated with water, and the resulting product is then dried.
8. A process for producing a granular composition, characterized in that from 10 to 75 parts by weight of a water-insoluble particulate material, having a mean particle size per weight of less than 20 microns and an oil absorption capacity of 60 to 180g / l00g, and is selected from the group consisting of amorphous silicas, aluminas, calcium carbonates, dicalcium phosphate, tribasic calcium phosphates, insoluble sodium metaphosphate, calcium pyrophosphates, hydroxyapatites, pearlites, zeolites, magnesium carbonate, pumice, 10 to 75 parts by weight of a water-insoluble particulate material having a mean particle size per weight below 20 microns and an oil absorption of 200 to 350g / 100g, selected from the group consisting of Amorphous silicas, low density aluminas and expanded pearls, the resulting mixture agglomerated by compaction.
9. The process according to claim 7 or 8, characterized in that Ti02 and zinc citrate are added to the amorphous silica particles before agglomeration.
10. The process according to claim 7, characterized in that the agglomeration with water is carried out with a water: solids ratio of 1.1: 1 to 1.35: 1.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94306904 | 1994-09-21 | ||
EP94306904.7 | 1994-09-21 | ||
PCT/EP1995/003560 WO1996009033A1 (en) | 1994-09-21 | 1995-09-09 | Granular compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
MXPA97001807A true MXPA97001807A (en) | 1998-04-01 |
MX9701807A MX9701807A (en) | 1998-04-30 |
Family
ID=8217854
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
MX9701807A MX9701807A (en) | 1994-09-21 | 1995-09-09 | Granular compositions. |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0783293B1 (en) |
JP (1) | JP3202751B2 (en) |
CN (1) | CN1089231C (en) |
AT (1) | ATE208607T1 (en) |
AU (1) | AU3565195A (en) |
BR (1) | BR9508962A (en) |
DE (1) | DE69523938T2 (en) |
ES (1) | ES2167462T3 (en) |
MX (1) | MX9701807A (en) |
TW (1) | TW408019B (en) |
WO (1) | WO1996009033A1 (en) |
ZA (1) | ZA957609B (en) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6140301A (en) * | 1995-04-27 | 2000-10-31 | The Procter & Gamble Company | Process for producing granular detergent components or compositions |
GB9602797D0 (en) * | 1996-02-12 | 1996-04-10 | Unilever Plc | Inorganic material in particles form |
JP3854719B2 (en) * | 1997-04-24 | 2006-12-06 | サンスター株式会社 | Oral composition |
US6294155B1 (en) | 1998-04-08 | 2001-09-25 | W. R. Grace & Co. -Conn. | Abrasive silica compositions and dentifrice compositions prepared therefrom |
JP3834732B2 (en) * | 1998-08-05 | 2006-10-18 | 株式会社ロッテ | Chewing gum |
EP1050293A1 (en) * | 1999-05-06 | 2000-11-08 | HAWE NEOS DENTAL Dr. H. V. WEISSENFLUH AG | Dentifrice compositions |
EP1183006B1 (en) * | 1999-06-04 | 2003-02-05 | Unilever N.V. | Oral composition containing perlite |
FR2808267B1 (en) * | 2000-04-28 | 2002-06-14 | Rhodia Chimie Sa | HIGH-STRUCTURE PRECIPITATION SILICA GRANULES OBTAINED BY GRANULATION AND THEIR USE AS THICKENING AGENTS IN DENTAL COMPOSITIONS |
FR2808266B1 (en) * | 2000-04-28 | 2002-06-14 | Rhodia Chimie Sa | THICKENING PRECIPITATION SILICA GRANULES OBTAINED BY GRANULATION AND THEIR USE AS A THICKENING AGENT IN DENTAL COMPOSITIONS |
JP2002068947A (en) * | 2000-08-23 | 2002-03-08 | Lion Corp | Composition for oral cavity |
FR2815335B1 (en) * | 2000-10-12 | 2002-12-13 | Rhodia Chimie Sa | HIGH STRUCTURE SILICA GRANULES AND THEIR USE IN DENTAL COMPOSITIONS |
AU1029901A (en) * | 2000-10-16 | 2002-04-29 | Biocosmetics Sl | Use of olive oil in the preparation of a product for oral hygiene for eliminating or reducing bacterial plaque and/or bacteria in the mouth |
WO2002092509A1 (en) * | 2001-05-11 | 2002-11-21 | Rhodia Chimie | Thickening precipitated silica granules obtained by granulation and use thereof as thickening agent in dental composition |
WO2002092508A1 (en) * | 2001-05-11 | 2002-11-21 | Rhodia Chimie | Precipitated thickening silica granules obtained by granulation and use thereof as thickening agent in dental compositions |
DE10250328A1 (en) * | 2002-10-29 | 2004-05-13 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Production of suspensions of hydrophobic oxide particles |
GB0400415D0 (en) * | 2004-01-09 | 2004-02-11 | Ineos Silicas Ltd | Dental abrasive system |
FR2960434B1 (en) * | 2010-05-26 | 2012-08-17 | Oreal | COSMETIC COMPOSITION BASED ON A SUPRAMOLECULAR POLYMER AND AN ABSORBENT CHARGE |
JP6236773B2 (en) * | 2012-11-28 | 2017-11-29 | ライオン株式会社 | Opaque dentifrice composition |
DE102013004088A1 (en) | 2013-03-11 | 2014-09-11 | Voco Gmbh | Particularly storage-stable and thixotropic stable prophylaxis paste for professional dental use |
WO2014205623A1 (en) * | 2013-06-24 | 2014-12-31 | The Procter & Gamble Company | Oral composition indicative of proper tooth cleaning |
WO2014205622A1 (en) * | 2013-06-24 | 2014-12-31 | The Procter & Gamble Company | Oral composition indicative of proper tooth cleaning |
GB201322510D0 (en) * | 2013-12-19 | 2014-02-05 | Glaxo Group Ltd | Novel composition |
CN107921469A (en) * | 2016-03-24 | 2018-04-17 | 中外炉工业株式会社 | The holding pallet of curved surface base material |
CN106361626A (en) * | 2016-08-29 | 2017-02-01 | 陈思 | Method for preparing toothpaste with efficacy of diminishing inflammation |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4089943A (en) * | 1974-02-08 | 1978-05-16 | Colgate-Palmolive Company | Toothpaste formulations |
DE3639844A1 (en) * | 1986-11-21 | 1988-06-01 | Degussa | DENTAL CARE |
DE3639845A1 (en) * | 1986-11-21 | 1988-06-01 | Degussa | FELLING SILICS, METHOD FOR THE PRODUCTION AND USE THEREOF |
US4871396A (en) * | 1986-11-25 | 1989-10-03 | Kao Corporation | Granular composition and dentifrice containing the same |
DE68910125T2 (en) * | 1989-08-04 | 1994-02-10 | Unilever Nv | Oral preparations. |
ATE159232T1 (en) * | 1990-08-06 | 1997-11-15 | Crosfield Joseph & Sons | SILICIC ACIDS |
MY106919A (en) * | 1990-08-31 | 1995-08-30 | Kao Corp | Composition for use in oral cavity. |
GB2272640A (en) * | 1992-11-24 | 1994-05-25 | Unilever Plc | Oral compositions |
-
1995
- 1995-09-09 WO PCT/EP1995/003560 patent/WO1996009033A1/en active IP Right Grant
- 1995-09-09 CN CN95195194A patent/CN1089231C/en not_active Expired - Lifetime
- 1995-09-09 BR BR9508962A patent/BR9508962A/en not_active IP Right Cessation
- 1995-09-09 ES ES95932706T patent/ES2167462T3/en not_active Expired - Lifetime
- 1995-09-09 DE DE69523938T patent/DE69523938T2/en not_active Expired - Lifetime
- 1995-09-09 EP EP95932706A patent/EP0783293B1/en not_active Expired - Lifetime
- 1995-09-09 AT AT95932706T patent/ATE208607T1/en not_active IP Right Cessation
- 1995-09-09 JP JP51056296A patent/JP3202751B2/en not_active Expired - Lifetime
- 1995-09-09 MX MX9701807A patent/MX9701807A/en unknown
- 1995-09-09 AU AU35651/95A patent/AU3565195A/en not_active Abandoned
- 1995-09-11 ZA ZA957609A patent/ZA957609B/en unknown
- 1995-10-26 TW TW084111273A patent/TW408019B/en not_active IP Right Cessation
Similar Documents
Publication | Publication Date | Title |
---|---|---|
MXPA97001807A (en) | Granula compositions | |
EP0783293B1 (en) | Granular compositions | |
US5976506A (en) | Oral compositions | |
US5891473A (en) | Granular Compositions | |
EP0269966B1 (en) | Granular composition and dentifrice containing the same | |
MXPA97002006A (en) | Ora compositions | |
US3935306A (en) | Toothpaste formulations | |
EP1976482B1 (en) | Silicas | |
US3929987A (en) | Toothpaste | |
US7731110B2 (en) | Method for making precipitated silica compositions and products thereof | |
JPH0621053B2 (en) | Toothpaste | |
KR20180083940A (en) | Oral care composition for remineralization and whitening of teeth | |
WO2007005231A2 (en) | Method for making particulate compositions and products thereof | |
KR20010033013A (en) | Particle Agglomerates | |
JPH0912436A (en) | Dentifrice | |
KR20220005059A (en) | Magnesium Ion-Containing Substances as White Pigments in Oral Care Compositions | |
JP2010275273A (en) | Dentifrice composition | |
WO2006081913A1 (en) | Multiphase toothpaste composition |