EP2104706A1 - Additif de rheologie sous forme de pate pre-activee - Google Patents
Additif de rheologie sous forme de pate pre-activeeInfo
- Publication number
- EP2104706A1 EP2104706A1 EP07856689A EP07856689A EP2104706A1 EP 2104706 A1 EP2104706 A1 EP 2104706A1 EP 07856689 A EP07856689 A EP 07856689A EP 07856689 A EP07856689 A EP 07856689A EP 2104706 A1 EP2104706 A1 EP 2104706A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- additive
- composition
- plasticizer
- ranging
- diamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/42—Amides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q3/00—Manicure or pedicure preparations
- A61Q3/02—Nail coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/223—Packed additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
Definitions
- the present invention relates to rheology additives in the form of pre-activated paste, a specific method for preparing these additives, specific compositions comprising said additive, as well as a specific process for the preparation of said compositions, specific uses and specific coatings. obtained from said additives.
- These specific additives make it possible to modify the viscosity of compositions of mastics, glues, adhesives, coatings, such as paints, varnishes, gel coats, inks, or molding compositions.
- State-of-the-art compositions of polyurethane-based sealants, adhesives or coatings comprising a non-reactive polyamide additive are known to adjust the viscosity of said compositions.
- EP 467 533 describes a polyamide obtained from at least one polycarboxylic acid chosen from sebacic acid, azelaic acid, dodecane dioic acid and dimers or trimers of fatty acids, with at least one compound comprising a group -NH2 or -NH selected from primary and secondary monoamines, natural and synthetic, saturated or unsaturated, either ethylenically unsaturated or acetylenically unsaturated.
- the polyamide rheology additive obtained can be prepared from a powder, or in combination with a solvent or a plasticizer, to form a liquid or a paste, said polyamide to be previously diluted.
- JP 2004107543 discloses a thixotropic additive in the form of a grain-free paste, said paste being a reaction product between a diamide component and an epoxy resin added at the end of synthesis, said diamide component being chemically modified so as to react on the epoxy resin.
- JP 2002146336 describes the preparation of a rheology additive in the form of a paste obtained by mixing fatty acid diamides, dispersed in an alcohol-based solvent, a cycloaliphatic compound and a an ester. The dispersion thus obtained is then subjected to a heat treatment. The final paste does not contain a plasticizer; it is then used as a thixotropic agent in unsaturated polyester resins.
- JP 63-15876 discloses a mixture of hydrogenated castor oil and C14-C18 saturated fatty acid fatty acids with ethylene diamine or 1,4-diaminobutane, the thixotropic agent-forming mixture being usable. in single-component compositions of polyurethane mastic. However, said Thixotropic agent is not in the form of a pre-activated paste that can be used without prior activation.
- rheology additives can be used to increase the viscosity of mastic or adhesive systems in solvent or solvent phase.
- Pyrogenic silicas and calcium carbonates are of a mineral nature and require dispersion of the mixture at a very high speed.
- these mineral fillers have problems of stability and sedimentation over time, with negative effects on the mechanical properties of the final system.
- Another particular disadvantage of polyamide powders and hydrogenated castor oil derivatives is the need for activation of the system in the manufacture of the final application composition for the user (formulator).
- This activation requires high speed shearing and heating corresponding to temperature rises of up to about 120 ° C. depending on the products, as well as a minimum necessary duration, depending on the temperature and system conditions (polarity), to develop optimal final rheological properties.
- These additives give the composition to which they are incorporated a thixotropic behavior characterized by a marked rheofluidification, that is to say a reduction in viscosity when the shear increases, then a recovery in viscosity dependent on time (equivalent to an effect hysteresis).
- This type of additive provides the final composition with excellent application properties which are characterized by a high resting viscosity, good stability of this storage viscosity, good anti-settling, ease of application and extrusion and good resistance to sag when applied.
- this type of additive provides good properties to the final composition, it has as its main disadvantage the fact of needing an activation phase, sometimes difficult to control, difficult to reproduce by the end user, and expensive in time and energy.
- the technical problem of the invention compared to the state of the prior art cited, is therefore the development of an improved product having properties comparable to those provided by the polyamide powders and the derivatives of the invention.
- hydrogenated castor oil without requiring an activation phase by the end user, said product being therefore easier and faster to implement by the end user, along with other special benefits related to the resolution of this general problem.
- pre-activated paste shall be understood to mean that the additive is ready for use by the end-user (formulator of sealants, glues, adhesives, or coatings such as paints, or varnish, or gel coats, or inks or molding composition), by simple mixing in the final application formulation, without the need for any specific in situ activation in this formulation (specific conditions of temperature, shear and duration to be respected).
- the additive can be used both in solvent application compositions that in solvent-free compositions, flexibility of use and handling, the pre-activated paste being easy to disperse within the composition, at the same time as the charges at the beginning of manufacture, or at the end of manufacture, while retaining properties rheological at least comparable to those obtained from powders of polyamide type, diamides or castor oil according to the state of the prior art, and last but not least, no need for the activation step, the implementation of the additive according to the invention does not require heating, high shear or activation time, which allows a gain:
- the first subject of the invention is a rheology additive in the form of a pre-activated paste comprising:
- At least one fatty acid diamide introduced in powder form, said powder optionally being able to contain, in addition to said diamide, hydrogenated castor oil,
- the second subject of the invention is a process for preparing such rheology additives by dispersion and activation by controlled heating.
- the invention also covers an organic binder composition or pigment concentrate or fillers comprising a rheology additive according to the present invention, as well as the process for preparing such a composition.
- Another subject of the invention is the use of the rheology additive or the composition according to the invention for coating applications of paints, varnishes, inks, gel coats, PVC-based plastisols or for applications. mastics, glues, adhesives, sealants, molding compositions, or for cosmetic applications.
- a final subject of the invention relates to finished articles such as coatings, seals, composites or molded parts, or cosmetics obtained from such an additive or such a composition according to the invention.
- the first subject of the invention is therefore a rheology additive in the form of a pre-activated paste comprising:
- At least one fatty acid diamide introduced in powder form, said powder optionally being able to contain, in addition to said diamide, hydrogenated castor oil,
- Said rheology additive in pre-activated paste form preferably has an elastic dynamic modulus G ', measured on said mixture A) + B), at a temperature of 23 ° C. and at a frequency of 1 Hz, greater than or equal to 10 4 Pa, preferably greater than or equal to 8.10 4 Pa, and even more preferably greater than or equal to 5.10 5 Pa.
- said plasticizer is a polar organic plasticizer comprising at least one polar group, preferably an ether group and / or an ester group and / or an epoxy group.
- Said plasticizer may initially comprise at least one ether group, and in this case it may be chosen from polyethers such as homopolymers and / or copolymers of ethylene oxide and / or propylene oxide and / or a mixture said polyethers (homopolymers and / or copolymers) and / or their derivatives, these derivatives comprising, inter alia, said polyethers blocked at the end of the chain by a C 1 (methoxy) to C 4 (butoxy) alkoxy group, or by a C2 ester group; C4 (butyrate) acetate, said polyethers having a weight average molecular weight Mw ranging from 150 to 6000, and preferably from
- copolymer is to be understood as including both random and block copolymers.
- Said plasticizer may then comprise at least one ester group, and it may be chosen from monoesters and / or polyesters (multifunctional esters), obtained from C 4 to C 21 alcohols, optionally alkoxylated alcohols, for example with 1 to 10 units. alkoxy chosen from oxyethylene (OE) and / or oxypropylene (OP) units, and from mono- or polyacids of functionality ranging from 1 to 4, selected from: - organic acids chosen from aromatic acids having a chain length (without -CO2H function) from Ce -C 1 O and / or aliphatic acids having a chain length (without considering the functions -CO2H) ranging from C4 to C 1 S, or mineral acids.
- OE oxyethylene
- OP oxypropylene
- the aromatic acid esters may be chosen from phthalates, trimellitic or trimellitates (benzene 1, 2,4-tricarboxylates) esters and their trimesitate isomers or trimesates (benzene 1,3,5-tricarboxylates).
- the aliphatic acid esters may be chosen from adipic (adipates), citric (citrates), sebacic (sebacates) and azelaic (azelates) esters.
- the esters of mineral acids may be chosen from sulphonic esters (sulphonates), in particular alkyl sulphonates of C 1 -C 21, sulfuric (sulphates), sulfinic (sulfinates), phosphoric (phosphates), phosphonic (phosphonates) and phosphinic (phosphinates).
- said plasticizer may also comprise at least one epoxy group, and may be chosen from epoxidized oils based on fatty acids, whose chain length may range from C 10 to C 15 , such as epoxidized soy.
- said rheology additive there is no other compound selected from alcohols of molecular weight Mw ⁇ 150, such as methanol, ethanol, propanol, butanol or benzyl alcohol, or selected polar aprotic solvents such as N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, acetonitrile,
- plasticizers comprising at least one aromatic acid ester group C 8 -C 10 , in particular the plasticizers selected from mono- and / or di-alkyl phthalates, and even more preferentially from the di- -alkylphthalates, with said alkyls being identical or different, and selected from C 7 to C 1 S alkyl, and preferably C 1 O to Cu.
- plasticizers di-alkyl phthalates
- the most preferred is di-iso-undecyl phthalate.
- polyethers the most preferred are polyether homopolymers of propylene oxide (polypropylene glycols) with a weight average molecular weight Mw ranging from 1000 to 3000, and more particularly polypropylene glycol (PPG) of Mw equal to 2000, and / or their derivatives, chosen from monoesters, preferably C 2 to C 4 ) or C 1 to C 4 monoethers, such as monomethoxylated or monoethoxylated derivatives.
- PPG polypropylene glycol
- Said plasticizer may have a boiling point higher than
- the rheology additive according to the invention preferably has a consistency or maximum penetration value, measured according to ASTM D 217, less than 15 mm, more preferably less than 10 mm, and even more preferably less than 5 mm.
- Said fatty acid diamide introduced in powder form has a particle size of less than 100 ⁇ m, and preferably less than 50 ⁇ m, and more preferably at least 90% of said diamide has a particle size less than 20 microns, and preferably less than 15 microns.
- the weight ratio of the fatty acid diamide can vary from 10 to 40%, and preferably from 15 to 30% relative to the mixture A) + B).
- a fatty acid diamide suitable for the invention may be obtained by polycondensation between at least one primary C2-C12 diamine and at least one C3-C22 chain-length monocarboxylic acid, the reaction product optionally being diluted in hydrogenated castor oil, and in this case at a level ranging from 10 to 100% by weight relative to the total diamide + hydrogenated castor oil, and preferably at a level ranging from 20 to 100% by weight .
- Hydrogenated castor oil can be used to adjust the affinity of the final mixture (diamide + hydrogenated castor oil) relative to the composition of the final formulation in application.
- the addition is carried out at a temperature between 140 and 220 ° C. At the end of the addition, a solid mass is obtained which is ground.
- the rheology additive according to the invention can be obtained by a specific method, as described below.
- the specific process for the preparation of said rheology additive comprises the following steps: i) gradual dispersion of said diamide in the form of a powder, in the plasticizer until a homogeneous dispersion is obtained, controlled temperature, through a temperature control, the diamide and said plasticizer being as defined above, ii) maintaining the homogeneous dispersion obtained in step i) in at least one isotherm with a corresponding temperature of 50 at 120 0 C, and preferably ranging from 60 to 100 0 C, for a period of 1 to 100 hours, preferably from 6 to 80 hours, and even more preferably from 15 to 40 hours.
- step ii) is a function of the polarity of the plasticizer and its chemical affinity with said fatty acid diamide.
- the homogeneity of the dispersion is characterized by an absence of grains, during the application of the film of said dispersion between two glass plates (test glass plates).
- said diamide is dispersed in said plasticizer at a shear rate of preferably between 2 and 6 m. s 1 , for laboratory scale preparation on a capacity not exceeding 1 liter.
- the end of step ii), also called “activation or maturation step” is characterized by a consistency or maximum penetration value of the formed paste of less than 15 mm, preferably less than 10 mm, and even more preferably, less than 5 mm, measured according to the ASTM D 217 standard.
- This maximum penetration value is to be associated with a reference method for the preparation of said pre-activated paste, which corresponds to a preparation at laboratory scale on a capacity not exceeding 1 liter, the sample thus being perfectly homogeneous.
- the method for preparing said preactivated paste is described below in the examples according to the invention.
- the third subject of the invention relates to an organic binder composition or to a pigment concentrate or to fillers comprising at least one rheology additive as defined according to the invention or obtained according to the process as defined according to the invention, said composition being capable of be a coating composition, the latter can be used as a protective coating and / or decoration and / or surface treatment of various substrates, coating selected from paints, varnishes, gel coats pigmented or non-pigmented, inks, plastisols to PVC base, or a composition of putty, glue, adhesive, sealant, or molding composition for composites or molded parts, SMC or BMC type or laminated, types hulls of boats or panels composites, or castings, with application of the composition by spraying or brushing or rolling, or finally a composition of cosmetics.
- Said rheology additive according to the invention may be present in said composition, has a content in weight ranging from 1 to 40%, preferably from 15 to 30%, and even more preferably from 10 to 20% relative to the total weight of said composition, and said diamide may be present as a dry active ingredient at a content in weight ranging from 0.1 to 16%, preferably from 0.2 to 8%, and even more preferably from 1 to 6% relative to the total weight of said composition.
- the composition according to the invention may comprise other components such as, for example, fillers, plasticizers, wetting agents or pigments.
- the organic binder composition according to the invention is crosslinkable, either thermally or by irradiation under radiation such as VF (in the presence of at least one photoinitiator) and / or EB (beam of electrons, without initiator), including self-crosslinkable at room temperature, or it is non-crosslinkable.
- the organic binder composition may be crosslinkable single-component (a single reactive component) or bicomponent (binder based on two components reactive with each other by mixing during use).
- Said organic binder can be selected from at least one epoxy-amine reactive system (crosslinkable bi-component), an unsaturated polyester, a vinylester, an epoxidized resin, a reactive silicone resin, a polyester-grafted alkyd or a polyamide or modified diurea -diurethane, or an ungrafted alkyd, a polyurethane or a silicone, a crosslinkable bi-component polyurethane, a polysiloxane, a polysulfide polymer, a reactive acrylic polymer, a multifunctional oligomer (meth) acrylate or acrylated acrylic oligomer or multifunctional allyl oligomer, an SBR-type elastomer, polychloroprene or butyl rubber, or a silane prepolymer, preferably a silane polyether or a silane polyurethane, or a silane polyether urethane with -OH or -CO2H function.
- said organic binder may be selected from the following cross-linkable two-component reactive systems: epoxy-amine or epoxy-polyamide systems comprising at least one epoxy resin comprising at least two epoxy groups and at least one amine compound or polyamide comprising at least two amino groups, the polyurethane systems comprising at least one polyisocyanate and at least one polyol, the polyol-melamine systems, and the polyester systems based on at least one epoxy or a reactive polyol with at least one corresponding acid or anhydride.
- cross-linkable two-component reactive systems epoxy-amine or epoxy-polyamide systems comprising at least one epoxy resin comprising at least two epoxy groups and at least one amine compound or polyamide comprising at least two amino groups
- the polyurethane systems comprising at least one polyisocyanate and at least one polyol
- the polyol-melamine systems and the polyester systems based on at least one epoxy or a reactive polyol with at least one corresponding acid or anhydride.
- said organic binder can be a two-component crosslinkable polyurethane system or a polyester crosslinkable two-component system from an epoxy-acid or carboxylic anhydride reaction system, or a polyol-acid system. or carboxylic anhydride, or polyol-melamine reaction system wherein the polyol is a hydroxylated acrylic resin, or a polyester or polyether polyol.
- the organic binder composition according to the invention is a sealant, adhesive, adhesive or sealant composition, which is self-crosslinkable, and based on polyether-silane or polyurethane- silane.
- the organic binder composition according to the invention may be a silylated (or silane-based, silylated pre-polymer mono- component sealant composition, which term is to be considered synonymous with silyl for the present invention), and preferably silylated polyether or silylated polyurethane (silylated polyether urethane), such as KANEKA MS POLYMER TM and KANEKA SILYL TM.
- silylated polyether or silylated polyurethane silylated polyether urethane
- Polymeric MS can be used in: construction and building for expansion joints, glazing assembly, joinery joints, masonry joints, prefabricated (sandwich panels or refrigerated truck, for example), joints for parquet, industry for marine, automobile (industrial bodywork, windshield seals), large distribution for sealants and adhesives, with and without solvent, civil engineering.
- silylated pre-polymer single-component sealant compositions such as other types of binders, colored pigments, various plasticizers, precipitated or ground calcium carbonate fillers, glyceride derivatives, silicas, such as pyrogenic silicas, other additives such as UVA (UV antioxidants), such as 2,4-diterbutyl-6- (5-chlorobenzotriazol-2-yl) phenol (Tinuvin) ® 327 from Ciba), light stabilizers based on sterically hindered amines, such as HALS (Hindered Amine Light Stabilizers), such as bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin ® 770 of Ciba), waxes, and other types of catalysts, such as tin salts.
- UVA UV antioxidants
- HALS Hindered Amine Light Stabilizers
- HALS Hindered Amine Light Stabilizers
- the invention also comprises a process for preparing said composition according to the invention, said process comprising the following steps: i) adding said additive according to the invention to said composition, ii) homogenization of the mixture with a kneader and / or planetary mixer and / or high speed disperser, without having any need, at this stage, to apply an activation treatment.
- Said process for preparing said organic binder composition according to the invention may also comprise a preliminary step of preparation of said additive, according to the following process: i) preparation of an additive according to the invention, according to the process for the preparation of said additive of the invention, as defined above, ii) adding said additive obtained according to step i) in said composition, as defined above, iii) homogenization of the mixture in a kneader and / or planetary mixer and / or high speed disperser , without having any need, at this stage, to apply an activation treatment.
- high speed means tangential speeds ranging from 2 to 15 m. s 1 .
- Another object according to the invention relates to the use of at least one rheology additive or a composition according to the present invention, without the need for activation in situ, by simple addition and homogenization in the final formula.
- said rheology additive and said composition may be used in coating applications, such as coatings for paints, varnishes, inks, pigmented or unpigmented gels coats, or PVC-based plastisols, or in sealants, glues, adhesives, sealants, composites, moldings, SMC / BMC laminates, or in cosmetic applications such as nail polish.
- the final subject of the invention concerns finished objects such as coatings obtained from the use of at least one rheology additive or composition according to the present invention, or by the use of the methods of respective coatings, said coatings being selected from pigmented or non-pigmented paints, varnishes, inks, or gel coats, or PVC-based plastisols, or caulks, or adhesives, or adhesives, or seals, or composites, or molded parts, or SMC / BMC laminates resulting from molding compositions, or cosmetics, such as nail polish
- the following examples demonstrate without any limitation, the performance of the rheology additive according to the present invention.
- DIUP di-iso-undecyl phthalate
- Dispermat ® CV with a 4 cm diameter, at a speed of
- 100 g of grinded fatty acid diamide and 300 g of polypropylene glycol mass 2000 (PPG 2000) are dispersed for 1 hour using a Dispermat ® CV disperser equipped with a pale 4 cm in diameter, at a speed of 2000 rpm, or rpm, at a temperature not exceeding 20 ° C., by regulating the temperature by circulation of cold water.
- the rheology of the pastes is monitored at 23 ° C. using an imposed stress rheometer MCR301 (Anton Paar), with a sandblasted plane-plane geometry 25 mm in diameter, and with a gap of 0.5 mm.
- the activation of the pastes was evaluated by dynamically monitoring the elastic modulus (C) and the viscous modulus (G ”) of the pastes, as a function of the maturation time.
- the modules were measured on samples at different times. maturation (measurements were made 10 minutes after leaving the oven, the time that the temperature of the sample drops to 23 0 C).
- the stress ⁇ is chosen so as to be in the linear zone (at low deformations).
- the frequency used is 1 Hz.
- the mechanical frequency spectra of the pastes were made at 23 ° C.
- DIUP di-iso-undecyl phthalate
- the final product is a soft, white paste, characterized by a dry active ingredient content of 25%, and a penetration resistance measured according to ASTM D 217 standard of 2.00 mm.
- the rheology additive in the form of a pre-activated paste is used in the preparation of polymeric MS type mastics.
- the storage of the rheology additive is done in the absence of water and moisture to prevent any start of polymerization by crosslinking.
- the crosslinking reaction self-crosslinking occurs at the time of use, in the presence of ambient humidity, at relative humidity (RH)> 50%.
- LABMAX disperser D2 (series 2000). This equipment makes it possible to reproduce the industrial conditions but on a small scale (pilot). It is equipped with a planetary disperser 65 mm in diameter, a squeegee and a vacuum pump which excludes the entry of moisture during manufacture. This device allows the manufacture of 1500 g of product, which is equivalent to three cartridges. The cartridges used are Fischbach E310 HPDE cartridges, 310 ml - accessories KOl - DO 1A0.
- the polymeric MS and plasticizer DIUP are mixed at 1000 rpm, at a tangential velocity of 3.5 m. s 1 , for 5 minutes.
- the rheology additive is then added and dispersed at 2600 rpm (8.8 m.sup.- 1 ), the mixture being maintained at a temperature of 30 ° C. by circulation of water.
- Extrudability is expressed as an extruded weight over a defined time (g.min 1 ).
- the equipment used is as follows:
- the products to be tested are conditioned for 24 hours in an air-conditioned laboratory at 23 ° C. and 50% RH, before the start of the test.
- the end of the threaded bush of a cartridge (Fischbach E310 cartridge: HPDE, 310 ml - KO accessories l - DOlAO) must be cut to form the widest hole possible, with a diameter of at least 6 mm.
- the extrusion nozzle is then screwed onto the cartridge.
- the test is carried out at the temperature of the air-conditioned laboratory (23 ° C. and 50% RH). Three tests are performed on the same cartridge.
- the packaging prepared as before, is placed in the air gun, then the supply of compressed air is increased up to 250 KPa.
- the mastic is extruded from the package into the nozzle, to fill it completely, and thus to free any air possibly enclosed in the package.
- the gun is then placed vertically above the cylinder itself placed on the scale.
- the extrusion and the timer are started simultaneously. About 100 g of mastic are extruded.
- extrusion and stopwatch are stopped.
- the test is repeated twice.
- the flow rate of the extrusion is calculated in g.min 1 from the weight of extruded mastic as a function of the extrusion time.
- a thixotropy index (V1 / V10) equal to the ratio of the Brookfield ® viscosity obtained at 1 revolution / min on the Brookfield ® viscosity obtained at 10 revolutions / min is calculated. This relative and indicative value of thixotropic behavior is commonly used in industry.
- the consistency of the pasta is measured using a texturing apparatus according to ASTM D 217.
- the standard refers to a standard manual measuring apparatus and has been reproduced by a TAXT2i texture analyzer manufactured by
- Thermorheo (supplier: Swantech). The principle of the standard has been automated on the TAXT2i of "Stable Micro System”.
- a suitable cone as described in ASTM D 217 is used with a given force to provide a penetration value into the dough.
- This "sink” measurement is expressed in millimeters (mm).
- the resistance to penetration increases with consistency, and the penetration value decreases with this consistency.
- the equipment used is the following: - an automatic texturometer: TAXT2i, - a cone whose applied force is equivalent to its weight of 47.5 g, with a needle forming an angle of 30 °.
- the products to be tested must be conditioned in an air-conditioned laboratory under conditions of temperature and humidity of 23 ⁇ 1 0 C and 50 ⁇ 5% RH, for a period of at least 24 hours before the start of the test.
- the products are packaged after synthesis in 1-liter cans (height: 13 cm, diameter: 11 cm).
- the texture measurement is carried out after the ripening stage, and before the use of the samples.
- Procedure The test is carried out at the temperature of the air-conditioned laboratory. Three trials are done on a pot.
- the sample is placed under the cone, and the tip of the needle is placed on the surface of the dough.
- the program on the TAXT2i is then started, and the penetration is triggered.
- Example 1 putty without additive
- Example 2 putty with a powder additive Crayvallac® SL
- Example 3 Putty with Pre-Activated Paste in DIUP
- Example 4 Putty with Pre-Activated Paste in PPG 2000
- plasticizer 25 wt% polyamide in 75% by weight of plasticizer.
- Example 1 (comparative): mastic without additive of rheology
- Example 2 putty with a Crayvallac ® SL powder additive
- the dispersion is heated for two hours at 80 ° C.
- the Molteni's speed is lowered to 1500 rpm (5.1 m.s- 1 ) and the mixture is cooled by circulation of cold water to reach a temperature less than 50 ° C.
- Examples 3 and 4 putty with a pre-activated paste respectively in the DIUP and in the PPG 2000 (pre-activated pastes described previously in ⁇ III a) and b))
- the dispersion is for one hour at 2600 rpm, without heating.
- the addition of n-trimethoxysilane (2-aminoethyl-3-amino) propyl (Dynasylan ® DAMO) and vinyltrimethoxysilane (Dynasylan ® VTMO) is at a temperature below 50 0 C to avoid evaporation.
- the temperature is less than 5O 0 C
- the adhesion promoter Dynasylan ® DAMO and the dehydrating agent Dynasylan ® VTMO are added and mixed under vacuum and with gentle stirring at 1000 revolutions / min for 15 min.
- the catalyst is then added and mixed under vacuum for 10 minutes at
- the putty is then put into cartridges and then rested for at least 24 hours in an air-conditioned room at 23 ° C.
- FIG. 1 shows the evolution of the elastic and viscous modules of the reference examples (non-pre-activated composition) and of the invention (preactivated paste) in the DIUP, as a function of the maturation time.
- FIG. 2 shows the evolution of the elastic and viscous modules of the reference examples (non-pre-activated composition) and of the invention (preactivated paste) in the PPG 2000, as a function of the maturation time.
- FIG. 3 shows the evolution of the elastic and viscous dynamic modules of the reference examples (non-pre-activated composition) and of the invention (pre-activated paste) in the DIUP, as a function of frequency.
- FIG. 4 shows the evolution of the elastic and viscous dynamic modules of the reference examples (non-pre-activated composition) and of the invention (pre-activated paste) in the PPG 2000, as a function of frequency.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Sealing Material Composition (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Cosmetics (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07856689A EP2104706A1 (fr) | 2006-12-21 | 2007-12-13 | Additif de rheologie sous forme de pate pre-activee |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06292039A EP1935934B1 (fr) | 2006-12-21 | 2006-12-21 | Additif de rhéologie sous forme de pâte pré-activée |
PCT/EP2007/010943 WO2008080536A1 (fr) | 2006-12-21 | 2007-12-13 | Additif de rheologie sous forme de pate pre-activee |
EP07856689A EP2104706A1 (fr) | 2006-12-21 | 2007-12-13 | Additif de rheologie sous forme de pate pre-activee |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2104706A1 true EP2104706A1 (fr) | 2009-09-30 |
Family
ID=38051022
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06292039A Active EP1935934B1 (fr) | 2006-12-21 | 2006-12-21 | Additif de rhéologie sous forme de pâte pré-activée |
EP07856689A Withdrawn EP2104706A1 (fr) | 2006-12-21 | 2007-12-13 | Additif de rheologie sous forme de pate pre-activee |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06292039A Active EP1935934B1 (fr) | 2006-12-21 | 2006-12-21 | Additif de rhéologie sous forme de pâte pré-activée |
Country Status (11)
Country | Link |
---|---|
US (1) | US7858074B2 (fr) |
EP (2) | EP1935934B1 (fr) |
JP (1) | JP5376799B2 (fr) |
KR (1) | KR101546312B1 (fr) |
CN (1) | CN101568581B (fr) |
CA (1) | CA2671612C (fr) |
ES (1) | ES2391779T3 (fr) |
MX (1) | MX2009006427A (fr) |
PL (1) | PL1935934T3 (fr) |
TW (1) | TWI444420B (fr) |
WO (1) | WO2008080536A1 (fr) |
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CN101863792B (zh) * | 2010-05-24 | 2013-07-03 | 中科院广州化学有限公司 | 一种酰胺低聚物及其溶胀制成的聚酰胺膏体流变助剂 |
SG11201401410YA (en) * | 2011-11-08 | 2014-06-27 | Exxonmobil Res & Eng Co | Water resistant grease composition |
US10052413B2 (en) | 2013-03-14 | 2018-08-21 | Medtronic Vascular, Inc. | Medical device and plasticized nylon |
FR3012457B1 (fr) * | 2013-10-31 | 2016-01-01 | Arkema France | Additifs a base de diamides gras pour compositions reticulables sensibles aux nucleophiles |
WO2015126931A1 (fr) | 2014-02-18 | 2015-08-27 | 3M Innovative Properties Company | Articles barrières à l'air et à l'eau faciles à appliquer |
US9975122B2 (en) | 2014-11-05 | 2018-05-22 | 10X Genomics, Inc. | Instrument systems for integrated sample processing |
WO2016106273A1 (fr) | 2014-12-22 | 2016-06-30 | 3M Innovative Properties Company | Articles barrières à l'air et à l'eau |
DK3328938T3 (da) * | 2015-07-31 | 2023-06-12 | Elementis Specialties Inc | Polyamidsammensætninger til tætningsmidler og malinger med høj faststofindhold |
CN107923176B (zh) | 2015-08-18 | 2021-05-28 | 3M创新有限公司 | 包括弹性多孔层的自密封制品 |
FR3043087B1 (fr) * | 2015-11-02 | 2018-04-27 | Arkema France | Composition d'additif diamide gras pre-concentree et pre-activee dans un diluant reactif |
JP2018046900A (ja) * | 2016-09-20 | 2018-03-29 | 株式会社レンズ | 描画具 |
EP3585851A4 (fr) | 2017-02-23 | 2020-12-09 | 3M Innovative Properties Company | Article pare-air et pare-eau comprenant une couche poreuse inélastique |
WO2018231612A2 (fr) | 2017-06-12 | 2018-12-20 | Ormet Circuits, Inc. | Compositions adhésives métalliques ayant de bonnes durées de fonctionnement et une bonne conductivité thermique, procédés pour les fabriquer et utilisations associées |
FR3073843A1 (fr) * | 2017-11-21 | 2019-05-24 | Arkema France | Additifs de rheologie a base de di- ou tri-amides et de leurs melanges |
EP3502197A1 (fr) * | 2017-12-21 | 2019-06-26 | Société BIC | Encre gel d'écriture |
EP3880729B1 (fr) * | 2018-11-14 | 2023-09-27 | Sika Technology AG | Agent thixotrope pour compositions durcissables |
EP3885417B1 (fr) * | 2018-11-20 | 2024-04-03 | Kyoeisha Chemical Co., Ltd. | Agent conférant une thixotropie en poudre pour peinture non aqueuse, et composition de peinture non aqueuse à laquelle il a été ajouté |
EP3689929B1 (fr) * | 2019-02-01 | 2023-06-28 | Henkel AG & Co. KGaA | Composition adhésive comprenant un agent thixotropique |
US11760897B2 (en) | 2019-07-30 | 2023-09-19 | Axalta Coating Systems Ip Co., Llc | Coating compositions including a sag control agent and wax |
CN110885586A (zh) * | 2019-10-17 | 2020-03-17 | 苏州丰倍生物科技有限公司 | 一种植物油基油墨粘度调节剂及其制备方法 |
WO2021125051A1 (fr) * | 2019-12-17 | 2021-06-24 | 株式会社 資生堂 | Composition de produit cosmétique en émulsion huile dans l'eau |
FR3111635B1 (fr) * | 2020-06-18 | 2022-09-30 | Arkema France | Additifs de rhéologie à base de diamide, de polymère fonctionnalisé et de cire |
CN115461425B (zh) * | 2020-07-31 | 2024-02-13 | 楠本化成株式会社 | 粘度调整剂以及固化性组合物 |
EP4353219A1 (fr) * | 2021-06-08 | 2024-04-17 | ThreeBond Co., Ltd. | Composition de résine photodurcissable pour ongles ou ongles artificiels |
EP4289886A1 (fr) | 2022-06-10 | 2023-12-13 | Arkema France | Procédé continu ou semi-continu de production d'une pâte organogélatrice pré-activée |
FR3136769A1 (fr) * | 2022-06-16 | 2023-12-22 | Arkema France | Compositions d’additifs de contrôle de la rhéologie |
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JPS6315876A (ja) | 1986-07-05 | 1988-01-22 | Mitsui Toatsu Chem Inc | 一成分形ウレタンシ−リング材組成物 |
DE4019074C1 (fr) | 1990-06-15 | 1991-07-18 | Teroson Gmbh, 6900 Heidelberg, De | |
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NZ243136A (en) * | 1991-08-16 | 1995-06-27 | Rheox Int | Rheological additive comprising the reaction product of a polycarboxylic acid, two different active hydrogen containing compounds and a monocarboxylic capping agent |
US5902841A (en) * | 1992-11-25 | 1999-05-11 | Tektronix, Inc. | Use of hydroxy-functional fatty amides in hot melt ink jet inks |
CN1090594A (zh) * | 1993-02-04 | 1994-08-10 | 西安近代化学研究所 | 金属焊缝用密封胶 |
CN1109086A (zh) * | 1994-03-24 | 1995-09-27 | 丁铁龙 | 新型厚浆型防水涂料 |
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JP2002146336A (ja) | 2000-11-15 | 2002-05-22 | Kusumoto Kasei Kk | アマイド系ペースト状チクソトロピック剤 |
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-
2006
- 2006-12-21 PL PL06292039T patent/PL1935934T3/pl unknown
- 2006-12-21 ES ES06292039T patent/ES2391779T3/es active Active
- 2006-12-21 EP EP06292039A patent/EP1935934B1/fr active Active
-
2007
- 2007-12-13 MX MX2009006427A patent/MX2009006427A/es active IP Right Grant
- 2007-12-13 EP EP07856689A patent/EP2104706A1/fr not_active Withdrawn
- 2007-12-13 CN CN2007800477057A patent/CN101568581B/zh not_active Expired - Fee Related
- 2007-12-13 KR KR1020097012903A patent/KR101546312B1/ko not_active IP Right Cessation
- 2007-12-13 CA CA2671612A patent/CA2671612C/fr not_active Expired - Fee Related
- 2007-12-13 WO PCT/EP2007/010943 patent/WO2008080536A1/fr active Application Filing
- 2007-12-17 TW TW096148208A patent/TWI444420B/zh active
- 2007-12-17 US US11/957,805 patent/US7858074B2/en active Active
- 2007-12-21 JP JP2007330382A patent/JP5376799B2/ja not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO2008080536A1 * |
Also Published As
Publication number | Publication date |
---|---|
US7858074B2 (en) | 2010-12-28 |
US20080153924A1 (en) | 2008-06-26 |
MX2009006427A (es) | 2009-08-20 |
CN101568581B (zh) | 2012-07-04 |
JP5376799B2 (ja) | 2013-12-25 |
PL1935934T3 (pl) | 2012-12-31 |
ES2391779T3 (es) | 2012-11-29 |
TWI444420B (zh) | 2014-07-11 |
KR20090103884A (ko) | 2009-10-01 |
WO2008080536A1 (fr) | 2008-07-10 |
CA2671612C (fr) | 2016-02-02 |
CA2671612A1 (fr) | 2008-07-10 |
TW200838907A (en) | 2008-10-01 |
CN101568581A (zh) | 2009-10-28 |
EP1935934A1 (fr) | 2008-06-25 |
EP1935934B1 (fr) | 2012-07-18 |
KR101546312B1 (ko) | 2015-08-25 |
JP2008174743A (ja) | 2008-07-31 |
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