WO2009007651A2 - Seal for valve or pump - Google Patents
Seal for valve or pump Download PDFInfo
- Publication number
- WO2009007651A2 WO2009007651A2 PCT/FR2008/051234 FR2008051234W WO2009007651A2 WO 2009007651 A2 WO2009007651 A2 WO 2009007651A2 FR 2008051234 W FR2008051234 W FR 2008051234W WO 2009007651 A2 WO2009007651 A2 WO 2009007651A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- seal
- inorganic filler
- basic inorganic
- valve
- basic
- Prior art date
Links
- 239000012530 fluid Substances 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 18
- 239000012764 mineral filler Substances 0.000 claims abstract description 15
- 239000000806 elastomer Substances 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011256 inorganic filler Substances 0.000 claims description 28
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229920002943 EPDM rubber Polymers 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 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 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 description 13
- 239000003380 propellant Substances 0.000 description 11
- 239000012632 extractable Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical compound C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- -1 ethylene propylene diene Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 125000000484 butyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 125000004968 halobutyl group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D83/00—Containers or packages with special means for dispensing contents
- B65D83/14—Containers for dispensing liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant
-
- 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
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
-
- 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
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0617—Polyalkenes
- C09K2200/062—Polyethylene
-
- 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
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0642—Copolymers containing at least three different monomers
Definitions
- the present invention relates to a valve seal and a fluid dispenser device comprising such a seal.
- the seals of the invention are suitable for use on the one hand in devices for dispensing fluid under pressure comprising a valve, in particular a metering valve, and on the other hand in fluid dispensing devices. non-pressurized having a pump.
- Seals used in pressurized fluid dispensing devices must meet a number of conditions and meet certain requirements.
- these seals must provide good mechanical properties, have suitable swelling properties to the propellant, provide an adequate coefficient of friction, be impervious to the propellant and ensure good resistance to moisture.
- seals used in non-pressurized fluid dispensing devices, and especially in pumps must also meet several conditions and fulfill a number of requirements.
- these seals must have good heat resistance, be impervious to gases, and be obviously non-toxic. They must also have good resistance to solutions, especially water / ethanol solutions. They must provide good resistance to moisture, chemicals, solvents, acids, bases and ensure a good resistance to preservatives, such as quaternary ammoniums, as well as resistance to microbiological attack and solutions. of mineral salts.
- a poor chemical compatibility between the seal and the product contained by the dispenser may result in migrations between the seal and the contents.
- vis-à-vis pharmaceutical formulations with which these seals are in contact
- extractables can be highlighted, which are potential migrants.
- oligomer residues, residual solvents, vulcanizing agents, antioxidants, lubricants, plasticizers, and other products can be found.
- the fluids in contact with the seal can in particular have several types of harmful influences.
- the seal is susceptible to chemical attack by fluids in contact. In this case, there is degradation of the material, the seal may become brittle, soft or cracked. Of course, there is then a risk of leakage.
- the absorption by the seal of the fluid in contact may cause swelling of the seal, which may have several consequences, such as a change in the properties of the material of the seal, a stiffening, an expulsion of the seal for lack of square. Removal of a seal component by the fluid in contact may also result in a change in the properties of the material, and a decrease in seal section may cause leakage.
- Elasticity properties such as DRC (Remanent Compression Deformation)
- DRC Remanent Compression Deformation
- the DRC is essentially a measure of the seal's ability to maintain its sealing strength and thus to ensure its function.
- the value of the DRC depends on the operating conditions and the duration. It is therefore an object of the present invention to provide valve or pump seals which optimally fulfill the above requirements.
- the present invention aims to provide a valve or pump seal to improve the elastic properties, the sealing properties and the compatibility of the seal with the active ingredients.
- the present invention also aims to provide valve or pump seals which are simple and inexpensive to manufacture.
- the present invention therefore aims to provide seal materials suitable for use with these HFC gases, ensuring sealing properties, compatibility and chemical resistance of the seal, both vis-à-vis the propellants and other active ingredients of the fluid in contact with the seal.
- the present invention therefore also aims to provide seals capable of withstanding high concentrations of alcohol.
- the present invention therefore relates to a valve or pump seal for a fluid dispenser device, said seal comprising at least one elastomer obtained by metallocene catalysis and at least one basic inorganic filler.
- said at least one elastomer obtained by metallocene catalysis comprises EPDM and / or EP.
- said at least one basic inorganic filler comprises aluminum hydroxide (Al (OH) 3).
- said at least one basic inorganic filler comprises aluminum oxide hydroxide (AIOOH).
- said at least one basic inorganic filler comprises magnesium hydroxide (Mg (OH) 2).
- said at least one basic inorganic filler comprises diatomaceous earth.
- said at least one basic mineral filler comprises wollastonite.
- said at least one basic inorganic filler comprises silica at basic pH (> 7).
- said at least one basic inorganic filler comprises chalk.
- said at least one basic inorganic filler comprises aluminosilicate of sodium and magnesium.
- the seal further comprises at least one other mineral filler associated with said at least one basic mineral filler.
- said at least one other associated mineral filler comprises kaolin and / or silica (pH ⁇ 7).
- said seal is a gasket, such as a neck seal disposed between a valve or a pump and a reservoir, and / or a seal dynamic, in contact with a movable member, such as a pump piston rod or a valve valve.
- FIG. 1 represents a graph illustrating the influence of the elastomer on the extractables
- FIG. 2 represents a graph illustrating the influence of the type of inorganic filler on the DRC
- FIGS. 5 represent graphs illustrating the influence of the type of inorganic filler on the degradation of active ingredients, respectively A, B and C.
- the seal according to the invention can be used both in a device for dispensing fluid under pressure as well as in a non-pressurized fluid dispenser device. It can serve both as a gasket, for example a neck seal sealing between a pump or a valve and a reservoir, and a dynamic seal, in contact with a movable member, for example a piston rod. a pump or a valve valve.
- the device comprises a valve provided with a movable valve, said valve being mounted on a reservoir containing the fluid and a propellant with or without alcohol.
- the thruster comprises a HFC-134a or HFC-227 type gas.
- the seal according to the invention can then be used as a neck seal between the valve and the reservoir and / or as a dynamic seal in which the valve slides.
- the dispenser (unpressurized) comprises a pump mounted on a reservoir containing fluid.
- the seal according to the invention can then be used for example between the pump body and the reservoir (gasket) or against the piston rod (dynamic seal).
- the seal formulations usually comprise one or more base polymers, to which may be added, in particular, mineral fillers or black carbon fillers, additives, vulcanizing agents, colorants, setting agents and the like. in use or plasticizers.
- the valve or pump seal according to the present invention may comprise at least one elastomer based on EP or EPDM.
- EP or EPDM gives the joint a good level of mechanical properties.
- EPDM-based seals have better inertness to active ingredients and have low levels of extractables.
- the use of elastomers obtained by metallocene catalysis in the composition of the joints according to the invention makes it possible to significantly improve the level of cleanliness in the joints.
- the metallocene catalysts, complexes of zinc and zirconium have a unique active site with well-defined steric and electronic characteristics, which makes it possible to easily initiate the polymerization and lead to stereo-regular polymers, guaranteeing improved and reproducible properties.
- the metallocene catalyzed polymerization offers essential advantages: better polymerization yield, narrow molecular weight distribution, large possibilities of copolymerization with homogeneous distribution of the comonomer (s) used.
- Extractable measurements made in the joints showed that metallocene grade elastomers, especially metallocene EP or EPDM, had significantly lower extractable amounts than other elastomeric materials.
- Extractives measurements consist in extracting 1 g of seal with an aggressive solvent (ethyl acetate, dichloromethane) and assaying by gas chromatography (GC) and / or liquid (LC) the extractables present in the extract obtained.
- an aggressive solvent ethyl acetate, dichloromethane
- LC liquid
- the amount of extractables is much lower (1800 mg / g) than the extractables found with the nitrile-based gaskets (14000 mg / ml). g) or chloroprene (5000 mg / g).
- the graph of FIG. 1 shows an even smaller amount of extractables (500 mg / g) measured in the case of metallocene EPDM-based gaskets. Greater cleanliness is thus obtained with a metallocene EPDM.
- seals according to the invention based on metallocene grade elastomer have very good properties of dimensional stability, rigidity and resistance to stress cracking.
- the seal may contain an elastomer alloy obtained by metallocene catalysis, such as EP or metallocene EPDM, with other elastomers (metallocene or otherwise), such as ethylene propylene (EP) , ethylene propylene diene (EPDM), polyoctene ethylene (POE), nitrile (NBR), hydrogenated nitrile (HNBR), butyl (NR), halobutyl (CIIR or BIIR), ethylene acetate vinyl (EVA).
- EP ethylene propylene
- EPDM ethylene propylene diene
- POE polyoctene ethylene
- NBR nitrile
- HNBR hydrogenated nitrile
- NR butyl
- CIIR or BIIR halobutyl
- EVA ethylene acetate vinyl
- the seal materials according to the invention also comprise one or more basic inorganic fillers having a pH greater than 7, preferably greater than 8, in combination with at least one elastomer, such as those described above.
- the seal according to the invention comprises at least one basic inorganic filler, preferably selected from the group consisting of aluminum hydroxide (Al (OH) 3 ), aluminum oxide hydroxide (AIOOH), magnesium hydroxide (Mg (OH) 2 ), earth of diatomaceous earth, wollastonite, silica at basic pH (> 7), chalk, sodium aluminosilicate and magnesium.
- the basic inorganic fillers employed in the seals according to the present invention may further be associated with one or more other mineral fillers, such as kaolin and / or silica at acidic pH.
- the DRC compression set
- compression Set also called “Compression Set”
- the DRC test consists of crushing a rubber pad (diameter 6 mm, thickness 6 mm) by 25% of its initial height. This stress is maintained for 22 hours at 40 ° C. After removing the stress, the rubber stud is left for 30 minutes at rest. Then we measure its height again.
- the DRC is calculated as follows:
- Hf final height
- Hc compressed height
- the joints which comprise silica with basic pH combined with kaolin or silica with basic pH associated with earth of diatom have a lower DRC (respectively 9% and 6%) at the joint DRC comprising silica at acidic pH associated with kaolin (15%) or silica at acidic pH associated with magnesium dihydroxide (14%). %).
- the seals according to the invention comprising the type of basic mineral fillers mentioned above, have, in comparison with the joints comprising silicas at acidic pH, a lower value of DRC, and therefore a higher elasticity.
- tests, such as the degradation test of the active ingredient have demonstrated that the use of basic inorganic fillers in the joints according to the present invention provides a better compatibility of these joints vis-à-vis the active ingredients.
- the quantity of active ingredient remaining is greater (between 27% and 87%), than in the case of joints using acidic silica (between 2 and 15%).
- the seals according to the present invention which use at least one basic mineral filler, are therefore more compatible with the active ingredient than seals using only an acidic mineral filler.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Details And Applications Of Rotary Liquid Pumps (AREA)
- Details Of Reciprocating Pumps (AREA)
Abstract
Description
Joint de valve ou de pompe Valve or pump seal
La présente invention concerne un joint de valve et un dispositif de distribution de produit fluide comportant un tel joint.The present invention relates to a valve seal and a fluid dispenser device comprising such a seal.
Plus particulièrement, les joints de l'invention sont adaptés à être utilisés d'une part dans des dispositifs de distribution de produit fluide sous pression comportant une valve, notamment une valve doseuse, et d'autre part dans les dispositifs de distribution de produit fluide non pressurisés comportant une pompe.More particularly, the seals of the invention are suitable for use on the one hand in devices for dispensing fluid under pressure comprising a valve, in particular a metering valve, and on the other hand in fluid dispensing devices. non-pressurized having a pump.
Les joints utilisés dans le cadre de dispositifs de distribution de produit fluide sous pression, tels que des dispositifs aérosols, doivent satisfaire un certain nombre de conditions et remplir certaines exigences. Ainsi, ces joints doivent fournir de bonnes propriétés mécaniques, présenter des propriétés de gonflement appropriées au propulseur, fournir un coefficient de frottement adéquat, être étanches au propulseur et assurer une bonne résistance à l'humidité. Ces caractéristiques sont notamment particulièrement importantes pour les joints dynamiques qui forment l'étanchéité entre la soupape mobile de la valve et la chambre de valve qui contient la dose à expulser.Seals used in pressurized fluid dispensing devices, such as aerosol devices, must meet a number of conditions and meet certain requirements. Thus, these seals must provide good mechanical properties, have suitable swelling properties to the propellant, provide an adequate coefficient of friction, be impervious to the propellant and ensure good resistance to moisture. These features are particularly important for the dynamic seals which form the seal between the movable valve of the valve and the valve chamber which contains the dose to be expelled.
D'autre part, les joints utilisés dans des dispositifs de distribution de produit fluide non pressurisés, et notamment dans les pompes, doivent également satisfaire plusieurs conditions et remplir un certain nombre d'exigences. Ainsi, ces joints doivent présenter une bonne résistance à la chaleur, être imperméables aux gaz, et être évidemment non toxiques. Ils doivent aussi présenter une bonne tenue aux solutions, notamment aux solutions eau/éthanol. Ils doivent fournir une bonne résistance à l'humidité, aux agents chimiques, aux solvants, acides, bases et garantir une bonne tenue aux agents de conservation, tels que les ammoniums quaternaires, ainsi qu'une résistance à l'attaque microbiologique et aux solutions de sels minéraux. Une mauvaise compatibilité chimique entre le joint et le produit contenu par le distributeur, peut entraîner des migrations entre le joint et le contenu.On the other hand, seals used in non-pressurized fluid dispensing devices, and especially in pumps, must also meet several conditions and fulfill a number of requirements. Thus, these seals must have good heat resistance, be impervious to gases, and be obviously non-toxic. They must also have good resistance to solutions, especially water / ethanol solutions. They must provide good resistance to moisture, chemicals, solvents, acids, bases and ensure a good resistance to preservatives, such as quaternary ammoniums, as well as resistance to microbiological attack and solutions. of mineral salts. A poor chemical compatibility between the seal and the product contained by the dispenser may result in migrations between the seal and the contents.
Par exemple, vis-à-vis des formulations pharmaceutiques, avec lesquelles ces joints sont en contact, des extractibles peuvent être mis en évidence, qui sont des migrants potentiels. Parmi ces composés : des résidus d'oligomères, des solvants résiduels, des agents de vulcanisation, antioxydants, lubrifiants, plastifiants, et autres produits peuvent être retrouvés. Les fluides en contact avec le joint peuvent notamment avoir plusieurs types d'influences néfastes.For example, vis-à-vis pharmaceutical formulations, with which these seals are in contact, extractables can be highlighted, which are potential migrants. Among these compounds: oligomer residues, residual solvents, vulcanizing agents, antioxidants, lubricants, plasticizers, and other products can be found. The fluids in contact with the seal can in particular have several types of harmful influences.
Le joint risque de subir une attaque chimique par des fluides en contact. Dans ce cas, il y a dégradation de la matière, le joint pouvant devenir cassant, mou ou parcouru de craquelures. Bien entendu, il y a alors risque de rupture d'étanchéité.The seal is susceptible to chemical attack by fluids in contact. In this case, there is degradation of the material, the seal may become brittle, soft or cracked. Of course, there is then a risk of leakage.
Par ailleurs, l'absorption par le joint du fluide en contact peut entraîner un gonflement du joint, ce qui peut avoir plusieurs conséquences, telles qu'une modification des propriétés de la matière du joint, une rigidification, une expulsion du joint par manque de place. L'extraction d'un composant du joint par le fluide en contact peut aussi entraîner une modification des propriétés de la matière, et une diminution de la section du joint pouvant entraîner des fuites.Furthermore, the absorption by the seal of the fluid in contact may cause swelling of the seal, which may have several consequences, such as a change in the properties of the material of the seal, a stiffening, an expulsion of the seal for lack of square. Removal of a seal component by the fluid in contact may also result in a change in the properties of the material, and a decrease in seal section may cause leakage.
Les propriétés mécaniques, physico-chimiques tout autant que la compatibilité chimique sont à prendre en considération. La flexibilité du joint, sa résistance à la flexion répétée et sa résistance au frottement ont une influence considérable sur la longévité du joint.The mechanical, physical and chemical properties as well as the chemical compatibility are to be taken into consideration. The flexibility of the joint, its resistance to repeated bending and its resistance to friction have a considerable influence on the longevity of the joint.
Les propriétés d'élasticité, telles que la DRC (Déformation Rémanente à la Compression), peuvent influencer la bonne tenue du joint à une application particulière. La DRC est essentiellement une mesure de la capacité du joint à maintenir sa force d'étanchéité et donc à assurer sa fonction. La valeur de la DRC dépend des conditions de fonctionnement et de la durée. La présente invention a donc pour but de fournir des joints de valve ou de pompe qui remplissent de manière optimale les exigences susmentionnées.Elasticity properties, such as DRC (Remanent Compression Deformation), can influence the good behavior of the joint to a particular application. The DRC is essentially a measure of the seal's ability to maintain its sealing strength and thus to ensure its function. The value of the DRC depends on the operating conditions and the duration. It is therefore an object of the present invention to provide valve or pump seals which optimally fulfill the above requirements.
La présente invention a pour but de fournir un joint de valve ou de pompe permettant d'améliorer les propriétés élastiques, les propriétés d'étanchéité et la compatibilité du joint avec les principes actifs.The present invention aims to provide a valve or pump seal to improve the elastic properties, the sealing properties and the compatibility of the seal with the active ingredients.
La présente invention à ainsi pour but de fournir des joints capables d'offrir des durées de vie et de fonctionnement accrues, grâce à la combinaison de leurs propriétés d'élasticité, de DRC et de compatibilité chimique.It is an object of the present invention to provide seals capable of providing increased service and life times by combining their elasticity, DRC and chemical compatibility properties.
La présente invention a aussi pour but de fournir des joints de valve ou de pompe qui sont simples et peu coûteux à fabriquer.The present invention also aims to provide valve or pump seals which are simple and inexpensive to manufacture.
Il est connu, notamment pour distribuer des produits pharmaceutiques, d'utiliser des dispositifs du type aérosol, dans lesquels le produit est distribué au moyen d'un gaz propulseur. Pour des raisons écologiques, les propulseurs utilisés précédemment, qui étaient généralement à base de CFC, ont été remplacés par d'autres gaz propulseurs, et notamment des gaz propulseurs du type HFC- 134a ou HFC-227. Il s'est avéré que cette modification du gaz propulseur engendrait des contraintes différentes sur les joints, que ce soit au niveau de la performance d'étanchéité dudit joint, ou au niveau des extractibles lorsque ledit joint était en contact avec ces nouveaux gaz propulseurs. Par conséquent, les matériaux de joint habituellement utilisés dans les valves aérosol en conjonction avec des gaz CFC ne peuvent pas être simplement appliqués aux nouveaux gaz propulseurs. La présente invention a donc pour but de fournir des matériaux de joint adaptés pour être utilisés avec ces gaz HFC, en garantissant des propriétés d'étanchéité, de compatibilité et de résistance chimique du joint, à la fois vis-à-vis des gaz propulseurs et des autres principes actifs du fluide en contact avec le joint. Un autre problème qui peut se poser avec les gaz HFC, lorsqu'ils sont utilisés avec un cosolvant, tel que l'éthanol, est la tendance de l'alcool à se séparer car il est moins soluble dans la phase liquide des HFC. Ceci expose les joints à une plus grande concentration d'alcool que cela était le cas précédemment avec les gaz CFC.It is known, particularly for dispensing pharmaceutical products, to use aerosol-type devices in which the product is distributed by means of a propellant. For ecological reasons, the thrusters used previously, which were generally CFC-based, have been replaced by other propellants, including HFC-134a or HFC-227 type propellants. It turned out that this modification of the propellant gas caused different constraints on the joints, either in terms of the sealing performance of said seal, or in terms of extractables when said seal was in contact with these new propellants. Therefore, seal materials commonly used in aerosol valves in conjunction with CFC gases can not be simply applied to new propellants. The present invention therefore aims to provide seal materials suitable for use with these HFC gases, ensuring sealing properties, compatibility and chemical resistance of the seal, both vis-à-vis the propellants and other active ingredients of the fluid in contact with the seal. Another problem that may arise with HFC gases, when used with a cosolvent, such as ethanol, is the tendency of the alcohol to separate because it is less soluble in the liquid phase of HFCs. This exposes the joints at a higher concentration of alcohol than was previously the case with CFC gases.
La présente invention a donc aussi pour but de fournir des joints capables de résister aux fortes concentrations d'alcool. La présente invention a donc pour objet un joint de valve ou de pompe destiné à un dispositif de distribution de produit fluide, ledit joint comprenant au moins un élastomère obtenu par catalyse métallocène et au moins une charge minérale basique.The present invention therefore also aims to provide seals capable of withstanding high concentrations of alcohol. The present invention therefore relates to a valve or pump seal for a fluid dispenser device, said seal comprising at least one elastomer obtained by metallocene catalysis and at least one basic inorganic filler.
Avantageusement, ledit au moins un élastomère obtenu par catalyse métallocène comprend de l'EPDM et/ou de l'EP.Advantageously, said at least one elastomer obtained by metallocene catalysis comprises EPDM and / or EP.
Avantageusement, ladite au moins une charge minérale basique comprend de l'hydroxyde d'aluminium (AI(OH)3).Advantageously, said at least one basic inorganic filler comprises aluminum hydroxide (Al (OH) 3).
Avantageusement, ladite au moins une charge minérale basique comprend de l'hydroxyde d'oxyde d'aluminium (AIOOH). Avantageusement, ladite au moins une charge minérale basique comprend de l'hydroxyde de magnésium (Mg(OH)2).Advantageously, said at least one basic inorganic filler comprises aluminum oxide hydroxide (AIOOH). Advantageously, said at least one basic inorganic filler comprises magnesium hydroxide (Mg (OH) 2).
Avantageusement, ladite au moins une charge minérale basique comprend de la terre de diatomée.Advantageously, said at least one basic inorganic filler comprises diatomaceous earth.
Avantageusement, ladite au moins une charge minérale basique comprend de la wollastonite.Advantageously, said at least one basic mineral filler comprises wollastonite.
Avantageusement, ladite au moins une charge minérale basique comprend de la silice à pH basique (>7).Advantageously, said at least one basic inorganic filler comprises silica at basic pH (> 7).
Avantageusement, ladite au moins une charge minérale basique comprend de la craie. Avantageusement, ladite au moins une charge minérale basique comprend de l'aluminosilicate de sodium et magnésium.Advantageously, said at least one basic inorganic filler comprises chalk. Advantageously, said at least one basic inorganic filler comprises aluminosilicate of sodium and magnesium.
Avantageusement, le joint comprend en outre au moins une autre charge minérale associée à ladite au moins une charge minérale basique.Advantageously, the seal further comprises at least one other mineral filler associated with said at least one basic mineral filler.
Avantageusement, ladite au moins une autre charge minérale associée comprend du kaolin et/ou de la silice (pH<7).Advantageously, said at least one other associated mineral filler comprises kaolin and / or silica (pH <7).
Avantageusement, ledit joint est un joint statique, tel qu'un joint de col disposé entre une valve ou une pompe et un réservoir, et/ou un joint dynamique, en contact avec un élément mobile, tel qu'une tige de piston de pompe ou une soupape de valve.Advantageously, said seal is a gasket, such as a neck seal disposed between a valve or a pump and a reservoir, and / or a seal dynamic, in contact with a movable member, such as a pump piston rod or a valve valve.
Avantageusement, ladite au moins une charge minérale basique a un pH supérieur à 8. La présente invention a aussi pour objet un dispositif de distribution de produit fluide, comprenant au moins un joint tel que décrit ci-dessus. Sur les dessins : - la figure 1 représente un graphe illustrant l'influence de l'élastomère sur les extractibles, - la figure 2 représente un graphe illustrant l'influence du type de charge minérale sur la DRC, et les figures 3, 4 et 5 représentent des graphes illustrant l'influence du type de charge minérale sur la dégradation de principes actifs, respectivement A, B et C. Le joint selon l'invention peut être utilisé aussi bien dans un dispositif de distribution de produit fluide sous pression que dans un dispositif de distribution de produit fluide non pressurisé. Il peut servir à la fois de joint statique, par exemple un joint de col faisant l'étanchéité entre une pompe ou une valve et un réservoir, et de joint dynamique, en contact d'un élément mobile, par exemple une tige de piston d'une pompe ou une soupape de valve.Advantageously, said at least one basic inorganic filler has a pH greater than 8. The present invention also relates to a fluid dispenser device comprising at least one seal as described above. In the drawings: FIG. 1 represents a graph illustrating the influence of the elastomer on the extractables; FIG. 2 represents a graph illustrating the influence of the type of inorganic filler on the DRC, and FIGS. 5 represent graphs illustrating the influence of the type of inorganic filler on the degradation of active ingredients, respectively A, B and C. The seal according to the invention can be used both in a device for dispensing fluid under pressure as well as in a non-pressurized fluid dispenser device. It can serve both as a gasket, for example a neck seal sealing between a pump or a valve and a reservoir, and a dynamic seal, in contact with a movable member, for example a piston rod. a pump or a valve valve.
Dans un distributeur sous pression, le dispositif comprend une valve pourvue d'une soupape mobile, ladite valve étant montée sur un réservoir contenant le produit fluide et un propulseur avec ou sans alcool. Le propulseur comprend un gaz de type HFC-134a ou HFC-227. Le joint selon l'invention peut alors être utilisé comme joint de col entre la valve et le réservoir et/ou comme joint dynamique dans lequel coulisse la soupape.In a pressure distributor, the device comprises a valve provided with a movable valve, said valve being mounted on a reservoir containing the fluid and a propellant with or without alcohol. The thruster comprises a HFC-134a or HFC-227 type gas. The seal according to the invention can then be used as a neck seal between the valve and the reservoir and / or as a dynamic seal in which the valve slides.
Dans le deuxième cas, le distributeur (non pressurisé) comprend une pompe montée sur un réservoir contenant du produit fluide. Le joint selon l'invention peut alors être utilisé par exemple entre le corps de pompe et le réservoir (joint statique) ou contre la tige de piston (joint dynamique). Les formulations de joints comprennent habituellement un ou plusieurs polymères de base, au(x)quel(s) peuvent être ajoutés notamment des charges minérales ou des charges noir de carbone, des additifs, des agents de vulcanisation, des colorants, des agents de mise en oeuvre ou des plastifiants.In the second case, the dispenser (unpressurized) comprises a pump mounted on a reservoir containing fluid. The seal according to the invention can then be used for example between the pump body and the reservoir (gasket) or against the piston rod (dynamic seal). The seal formulations usually comprise one or more base polymers, to which may be added, in particular, mineral fillers or black carbon fillers, additives, vulcanizing agents, colorants, setting agents and the like. in use or plasticizers.
Le joint de valve ou de pompe selon la présente invention peut comporter au moins un élastomère à base d'EP ou d'EPDM.The valve or pump seal according to the present invention may comprise at least one elastomer based on EP or EPDM.
Les EP ou EPDM confèrent au joint un bon niveau de propriétés mécaniques. De plus, comparés à d'autres joints à base de nitrile ou de chloroprène, les joints à base d'EPDM possèdent une meilleure inertie vis-à- vis des principes actifs et ont des niveaux d'extractibles peu élevés.EP or EPDM gives the joint a good level of mechanical properties. In addition, compared to other nitrile or chloroprene-based seals, EPDM-based seals have better inertness to active ingredients and have low levels of extractables.
L'emploi d'élastomères obtenus par catalyse métallocène dans la composition des joints selon l'invention permet d'améliorer de manière significative le niveau de propreté dans les joints. Les catalyseurs métallocènes, complexes du zinc et du zirconium, présentent un site actif unique à caractéristiques stériques et électroniques bien définies, permettant d'amorcer facilement la polymérisation et de conduire à des polymères stéréo-réguliers, gage de propriétés améliorées et reproductibles. La polymérisation par catalyse métallocène offre des avantages essentiels : meilleur rendement de polymérisation, distribution étroite des masses moléculaires, importantes possibilités de copolymérisation avec répartition homogène du ou des co-monomères utilisés.The use of elastomers obtained by metallocene catalysis in the composition of the joints according to the invention makes it possible to significantly improve the level of cleanliness in the joints. The metallocene catalysts, complexes of zinc and zirconium, have a unique active site with well-defined steric and electronic characteristics, which makes it possible to easily initiate the polymerization and lead to stereo-regular polymers, guaranteeing improved and reproducible properties. The metallocene catalyzed polymerization offers essential advantages: better polymerization yield, narrow molecular weight distribution, large possibilities of copolymerization with homogeneous distribution of the comonomer (s) used.
Les mesures d'extractibles réalisées dans les joints ont montré que les élastomères de grade métallocène, notamment l'EP ou l'EPDM de grade métallocène, présentaient des quantités d'extractibles nettement inférieures à celles d'autres matériaux élastomères.Extractable measurements made in the joints showed that metallocene grade elastomers, especially metallocene EP or EPDM, had significantly lower extractable amounts than other elastomeric materials.
Les mesures d'extractibles consistent à extraire 1g de joint avec un solvant agressif (acétate d'éthyle, dichlorométhane) et à doser par chromographie gazeuse (GC) et/ou liquide (LC) les extractibles présents dans l'extrait obtenu. Comme visible sur le graphe de la figure 1 , avec les joints à base d'EPDM, la quantité d'extractibles est très inférieure (1800 mg/g) aux quantités d'extractibles trouvées avec les joints à base de nitrile (14000 mg/g) ou de chloroprène (5000 mg/g). Le graphe de la figure 1 montre une quantité d'extractibles encore plus faible (500 mg/g) mesurée dans le cas des joints à base d'EPDM métallocène. Une plus grande propreté est ainsi obtenue avec un EPDM métallocène.Extractives measurements consist in extracting 1 g of seal with an aggressive solvent (ethyl acetate, dichloromethane) and assaying by gas chromatography (GC) and / or liquid (LC) the extractables present in the extract obtained. As can be seen in the graph of FIG. 1, with the EPDM-based gaskets, the amount of extractables is much lower (1800 mg / g) than the extractables found with the nitrile-based gaskets (14000 mg / ml). g) or chloroprene (5000 mg / g). The graph of FIG. 1 shows an even smaller amount of extractables (500 mg / g) measured in the case of metallocene EPDM-based gaskets. Greater cleanliness is thus obtained with a metallocene EPDM.
De plus, les joints selon l'invention à base d'élastomère de grade métallocène présentent de très bonnes propriétés de stabilité dimensionnelle, de rigidité et de résistance à la fissuration sous contraintes.In addition, the seals according to the invention based on metallocene grade elastomer have very good properties of dimensional stability, rigidity and resistance to stress cracking.
Selon la présente invention, le joint peut contenir un alliage d'élastomère obtenu par catalyse métallocène, tel que l'EP ou l'EPDM métallocène, avec d'autres élastomères (métallocènes ou non), tels que l'éthylène propylène (EP), l'éthylène propylène diène (EPDM), le polyoctène éthylène (POE), le nitrile (NBR), le nitrile hydrogéné (HNBR), le Butyl (NR), l'halobutyl (CIIR ou BIIR), l'éthylène acétate de vinyle (EVA). Ce type d'alliage permet d'optimiser les propriétés des joints, notamment en fonction du type de propulseur et/ou du principe actif à distribuer. Les charges minérales sont généralement utilisées dans les joints pour améliorer certaines de leurs caractéristiques (propriétés mécaniques, frottement, compatibilité...).According to the present invention, the seal may contain an elastomer alloy obtained by metallocene catalysis, such as EP or metallocene EPDM, with other elastomers (metallocene or otherwise), such as ethylene propylene (EP) , ethylene propylene diene (EPDM), polyoctene ethylene (POE), nitrile (NBR), hydrogenated nitrile (HNBR), butyl (NR), halobutyl (CIIR or BIIR), ethylene acetate vinyl (EVA). This type of alloy makes it possible to optimize the properties of the joints, in particular as a function of the type of propellant and / or of the active ingredient to be dispensed. Mineral fillers are generally used in joints to improve some of their characteristics (mechanical properties, friction, compatibility ...).
Les matériaux de joints selon l'invention comportent en outre une ou plusieurs charges minérales basiques ayant un pH supérieur à 7, de préférence supérieur à 8, en association avec au moins un élastomère, tel que ceux décrits ci-dessus.The seal materials according to the invention also comprise one or more basic inorganic fillers having a pH greater than 7, preferably greater than 8, in combination with at least one elastomer, such as those described above.
Alors que des silices à pH acide sont généralement employées dans les applications de valves doseuses, le joint selon l'invention comporte au moins une charge minérale basique, avantageusement choisie dans le groupe constitué de l'hydroxyde d'aluminium (AI(OH)3), l'hydroxyde d'oxyde d'aluminium (AIOOH), l'hydroxyde de magnésium (Mg(OH)2), la terre de diatomée, la wollastonite, la silice à pH basique (>7), la craie, de l'aluminosilicate de sodium et magnésium.While acidic acid silicas are generally employed in metering valve applications, the seal according to the invention comprises at least one basic inorganic filler, preferably selected from the group consisting of aluminum hydroxide (Al (OH) 3 ), aluminum oxide hydroxide (AIOOH), magnesium hydroxide (Mg (OH) 2 ), earth of diatomaceous earth, wollastonite, silica at basic pH (> 7), chalk, sodium aluminosilicate and magnesium.
Les charges minérales basiques employées dans les joints selon la présente invention peuvent en outre être associées à une ou plusieurs autres charges minérales, telles que le kaolin et/ou la silice à pH acide.The basic inorganic fillers employed in the seals according to the present invention may further be associated with one or more other mineral fillers, such as kaolin and / or silica at acidic pH.
L'utilisation d'une ou plusieurs charges minérales basiques dans les matériaux de joint selon l'invention permet d'améliorer les propriétés d'élasticité telles que la DRC et/ou la compatibilité avec le principe actif.The use of one or more basic inorganic fillers in the seal materials according to the invention makes it possible to improve the elasticity properties such as the DRC and / or the compatibility with the active principle.
La DRC (déformation rémanente à la compression) appelée également « Compression Set », s'exprime en pourcentage et permet de déterminer la rémanence ou capacité du caoutchouc à retrouver ses dimensions initiales après avoir subi une déformation.The DRC (compression set), also called "Compression Set", is expressed as a percentage and determines the remanence or ability of the rubber to recover its original dimensions after being deformed.
Le test de DRC consiste à écraser un plot de caoutchouc (diamètre 6 mm, épaisseur 6 mm) de 25% de sa hauteur initiale. Cette contrainte est maintenue pendant 22 heures à 400C. Après suppression de la contrainte, le plot de caoutchouc est laissé 30 minutes au repos. Puis on mesure de nouveau sa hauteur.The DRC test consists of crushing a rubber pad (diameter 6 mm, thickness 6 mm) by 25% of its initial height. This stress is maintained for 22 hours at 40 ° C. After removing the stress, the rubber stud is left for 30 minutes at rest. Then we measure its height again.
La DRC est calculée de la façon suivante :The DRC is calculated as follows:
DRC(%) = ™zK DRC (% ) = ™ zK
Hi - Hc Hi : hauteur initialeHi - Hc Hi: initial height
Hf : hauteur finale Hc : hauteur compriméeHf: final height Hc: compressed height
Plus la valeur (pourcentage de DRC) est faible, plus le matériau est considéré comme élastique. Comme visible sur le graphe de la figure 2, représentant l'influence du type de charge minérale sur la DRC, les joints qui comportent de la silice à pH basique associée à du kaolin ou de la silice à pH basique associée à de la terre de diatomée ont une DRC inférieure (respectivement égale à 9% et 6%) à la DRC du joint comprenant de la silice à pH acide associée à du kaolin (15%) ou de la silice à pH acide associée à du dihydroxyde de magnésium (14%). Ainsi les joints selon l'invention, comportant le type de charges minérales basiques évoquées ci-dessus, présentent, en comparaison avec les joints comportant des silices à pH acide, une valeur de DRC inférieure, et donc une élasticité supérieure. En outre, des tests, tels que le test de dégradation du principe actif, ont démontré que l'utilisation de charges minérales basiques dans les joints selon la présente invention apporte une meilleure compatibilité de ces joints vis-à-vis des principes actifs.The lower the value (percentage of DRC), the more the material is considered elastic. As can be seen in the graph of FIG. 2, showing the influence of the inorganic filler type on the DRC, the joints which comprise silica with basic pH combined with kaolin or silica with basic pH associated with earth of diatom have a lower DRC (respectively 9% and 6%) at the joint DRC comprising silica at acidic pH associated with kaolin (15%) or silica at acidic pH associated with magnesium dihydroxide (14%). %). Thus, the seals according to the invention, comprising the type of basic mineral fillers mentioned above, have, in comparison with the joints comprising silicas at acidic pH, a lower value of DRC, and therefore a higher elasticity. In addition, tests, such as the degradation test of the active ingredient, have demonstrated that the use of basic inorganic fillers in the joints according to the present invention provides a better compatibility of these joints vis-à-vis the active ingredients.
Le test de dégradation du principe actif consiste à introduire cinq pastilles de caoutchouc dans un bidon, puis à y ajouter une formulation avec un principe actif en solution. Ces bidons pressurisés sont placés en étuve pour vieillissement accéléré. La quantité d'actif restante dans chaque bidon est quantifié par HPLC à chaque point de stabilité (TO, T=2 semaines et T=5 semaines pour l'actif étudié). Plus la quantité d'actif restante est importante, plus le matériau testé est compatible avec l'actif.The degradation test of the active ingredient consists in introducing five rubber pellets into a can, and then adding a formulation with an active ingredient in solution. These pressurized cans are placed in an oven for accelerated aging. The remaining amount of active ingredient in each can is quantified by HPLC at each point of stability (TO, T = 2 weeks and T = 5 weeks for the active agent). The greater the amount of the remaining asset, the more the tested material is compatible with the asset.
Les résultats de test représentés sur les graphiques des figures 3, 4 et 5, pour trois principes actifs A, B et C différents, montrent que pour les joints comportant des charges minérales basiques, telles que la silice à pH basique, le kaolin (surtout s'il est calciné), la craie, le trihydrate d'aluminium, le dihydroxyde de magnésium, la wollastonite ou la terre de diatoméeThe test results shown in the graphs of FIGS. 3, 4 and 5, for three different active ingredients A, B and C, show that for the joints comprising basic mineral fillers, such as silica with basic pH, kaolin (especially if calcined), chalk, aluminum trihydrate, magnesium dihydroxide, wollastonite or diatomaceous earth
(surtout si elle est calcinée), la quantité de principe actif restante est plus importante (entre 27% et 87%), que dans le cas des joints utilisant de la silice acide (entre 2 et 15%). Les joints selon la présente invention, qui utilisent au moins une charge minérale basique, sont donc plus compatibles avec le principe actif, que les joints utilisant uniquement une charge minérale acide.(especially if it is calcined), the quantity of active ingredient remaining is greater (between 27% and 87%), than in the case of joints using acidic silica (between 2 and 15%). The seals according to the present invention, which use at least one basic mineral filler, are therefore more compatible with the active ingredient than seals using only an acidic mineral filler.
La facilité de fabrication et le coût modéré sont également des aspects avantageux des joints de la présente invention.The ease of manufacture and the moderate cost are also advantageous aspects of the seals of the present invention.
Bien que des exemples d'élastomères et de charges minérales basiques entrant dans la composition des joints selon la présente invention aient été décrits ci-dessus en référence aux diverses variantes possibles de formulation des joints, la présente invention n'est pas limitée à ces exemples, et la portée du brevet est définie par les revendications annexées. Although examples of elastomers and basic inorganic fillers used in the composition of the seals according to the present invention have been described above with reference to the various possible variants of formulation of the seals, the present invention is not limited to these examples, and the scope of the patent is defined by the appended claims.
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0756266 | 2007-07-04 | ||
| FR0756266A FR2918436B1 (en) | 2007-07-04 | 2007-07-04 | VALVE OR PUMP SEAL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2009007651A2 true WO2009007651A2 (en) | 2009-01-15 |
| WO2009007651A3 WO2009007651A3 (en) | 2009-05-07 |
Family
ID=39008901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR2008/051234 WO2009007651A2 (en) | 2007-07-04 | 2008-07-02 | Seal for valve or pump |
Country Status (2)
| Country | Link |
|---|---|
| FR (1) | FR2918436B1 (en) |
| WO (1) | WO2009007651A2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4191172A (en) * | 1971-05-14 | 1973-11-08 | Ici Ltd | Seals |
| FR2787424B1 (en) * | 1998-12-18 | 2001-03-02 | Valois Sa | VALVE OR PUMP SEAL |
| FR2855829B1 (en) * | 2003-06-06 | 2005-09-09 | Valois Sas | VALVE JOINT AND FLUID PRODUCT DISPENSING DEVICE COMPRISING SUCH A JOINT |
| GB2406096B (en) * | 2003-09-16 | 2008-05-21 | Bespak Plc | A pharmaceutical metered dose aerosol inhaler device |
-
2007
- 2007-07-04 FR FR0756266A patent/FR2918436B1/en active Active
-
2008
- 2008-07-02 WO PCT/FR2008/051234 patent/WO2009007651A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| FR2918436B1 (en) | 2011-01-21 |
| WO2009007651A3 (en) | 2009-05-07 |
| FR2918436A1 (en) | 2009-01-09 |
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