EP1771515A1 - Utilisation d'un polyamide micro-cristallin pour obtenir un etat de surface particulier - Google Patents
Utilisation d'un polyamide micro-cristallin pour obtenir un etat de surface particulierInfo
- Publication number
- EP1771515A1 EP1771515A1 EP05775537A EP05775537A EP1771515A1 EP 1771515 A1 EP1771515 A1 EP 1771515A1 EP 05775537 A EP05775537 A EP 05775537A EP 05775537 A EP05775537 A EP 05775537A EP 1771515 A1 EP1771515 A1 EP 1771515A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamide
- microcrystalline
- crystalline
- use according
- microcrystalline polyamide
- 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- Withdrawn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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
Definitions
- the present invention relates to the use of a microcrystalline polyamide to obtain a particular surface condition. More precisely it is the use of a transparent material of a particular type, solid but malleable, particularly adapted to reproduce the surface states (small scale relief), and to be shaped (large scale relief, deep relief), and to adhere on itself or on a substrate possibly with anf ractuosities, all in order to achieve an object having visual and tactile properties aesthetic, attractive, quality, and resistant to mechanical aggression, chemical and physical.
- This outer layer may also be the outer layer of a multilayer structure which covers a substrate.
- the structure is also called film or sheet when its thickness is at most of the order of 0.5 to
- the structure consists of a single layer of microcrystalline polyamide or the multilayer structure comprising an outer layer (or upper) that is to say the surface layer of the object is fixed on the object by any means.
- the structure is disposed in an injection mold, the upper layer being disposed on the side of the wall of the mold and then the substrate is injected in the molten state on the opposite side.
- the structure can be thermoformed before being placed in the mold. After cooling and opening of the mold, the substrate covered with the structure is recovered.
- micro-crystalline polyamides of the invention make it possible to have an upper face capable of taking the grain well and to make the surface conditions, ie able to become smooth and shiny (in contact with a metal wall). polished mold sufficiently hot) or to become matte and grained (in contact with a metal wall mat or grained sufficiently hot mold), or to take a brushed appearance.
- the texturing walls of the mold or any other texturing device
- the ability of our microcrystalline material to be able to make very complex surface conditions of non-metallic materials such as fabrics, papers, leathers , woods, plants, etc.
- plastics are difficult to render complex surface conditions. Either the plastics are solid and too rigid to take enough relief, or they are in the liquid state and will adhere too much to the surface, and it will then be impossible, once the plastic re-solidified, to take off the last of the texturing wall (eg fabric). It is well known that plastics generally have aspects of surfaces that are not very complex and unattractive. It is known that plastics are generally regarded as poor quality materials compared to more traditional materials such as metals, fabrics, woods, leathers ...
- the invention is the use of a particular polyamide polymer material called "microcrystalline" in order to obtain decorative and functional objects having visual and tactile properties aesthetic, attractive and quality. It is also desirable for these visio-tactile properties to be durable in the face of mechanical (shock, scratch), chemical (solvent) and physical (UV) aggression.
- the manufacture of the object comprises hot stages, in particular between the Tg (glass transition temperature or “glass temperature”) and the Tm (melting temperature or “melting temperature”) also referred to by Tf) of this micro-crystalline polyamide.
- Tg glass transition temperature or "glass temperature”
- Tm melting temperature or “melting temperature”
- Tf melting temperature
- the use of the object will be at a temperature below the Tg of this microcrystalline polyamide.
- the amorphous polymers have the advantage of being transparent. In addition to this inherent aesthetic advantage, they help protect and enhance an underlying décor.
- these amorphous polymers include PMMA, PC, amorphous PA. These The latter are particularly efficient (EP 550308, EP 725101). Nevertheless, when they are used in molten form, they have the disadvantage of rapidly passing to the solid state (because of their high Tg, 100-200 ° C.) during their cooling and are therefore not very apt to transcribe the surface and feel of the mold and, more generally, of a complex texturing surface. Being typically very rigid and not malleable under their Tg, they are not very suitable for being shaped in the solid state (for example embossing).
- amorphous polymer of low Tg ( ⁇ 60 ° C) is in turn unimaginable because it goes to the liquid state above its Tg, which makes it obviously unsuitable to play its role of protection of the decorated object as soon as the temperature rises a little.
- Another disadvantage of amorphous polymers, and even amorphous PAs with higher carbon monomers is the chemical resistance (stress cracking) and physical (UV radiation) less compared to semiconducting polymers.
- crystalline, especially semicrystalline polyamides with higher carbon monomers such as PAU or PAI 2.
- the semi-crystalline polymers thus have the advantage of better chemical and physical resistance.
- semi-crystalline polyamides are a good choice.
- those made from higher carbon monomers, such as PA-11 and PA-12 are preferred because their physicochemical behavior is even greater and their recovery in water and the consequences in terms of variations. dimensions (and other properties) are less than in the case of common semicrystalline polyamides such as PA-6 and PA-6.6.
- these semicrystalline polyamides have the disadvantage of a limited transparency and rapidly pass to the solid state (because of their rapid and strong recrystallization) during their cooling and are therefore poorly able to accurately transcribe the surface state. and the touch of the mold.
- micro-crystalline polyamide in other words a transparent but nevertheless semi-crystalline polyamide but with a particular degree of crystallinity, could make it possible to provide a particularly advantageous solution. to get decorative and functional objects with visual and tactile aesthetic, attractive and quality properties.
- the polyamides used in the invention are, among the semi-crystalline polyamides, those which are microcrystalline, ie they consist of a crystalline structure (spherulite) of a size small enough not to diffract the light and thus allow a good transparency. They are referred to in the rest of the text as "micro-crystalline".
- They can also be characterized by a transparency such that the light transmission at 560 nm on a polished article of 1 mm thick is> 80%, advantageously> 88% (the object being obtained by the usual methods of implementation such as injection sheet extrusion by calendering).
- This micro-crystalline polyamide has many advantages. Indeed, such a material does not have the disadvantages of:
- such a material has the key advantage of being able to be shaped in the solid state (or partially solid) between its Tg and its Tm, easily, thanks to its malleability in this area of T °.
- shaping in the solid state (or partially solid) we mean various "hot” or “hot” thermo ⁇ mechanical treatments, between Tg and Tm, aiming at conferring a finish having an aesthetic, attractive visual and tactile character. of quality to the polymeric material (and to the object of which this polymeric material is one of the constituents).
- these formatting in the solid state let us quote:
- a "2D" shape in 2 dimensions
- a "3D" shape in 3 dimensions
- the transition from one surface state to another typically by a step and a method of contacting with a textured surface (eg rough metal or fabric, compression molding or overmolding), between Tg and Tm , under pressure, for a while.
- a textured surface eg rough metal or fabric, compression molding or overmolding
- the complexing, lamination, or assembly for example of a sheet of 600 .mu.m, on a substrate having anfractuosities (wood, fabrics), for example during a step of a coating or rolling process.
- the complexing or transfer for example on a sheet of 600 .mu.m of the polymer material, fibrils or powder (pigmented or not), for example during a step of a transfer process.
- This method consists for example in contacting, at T ° between Tg and Tm, under pressure P °, for a time t, a sheet of polymeric material and substrate containing the fibrils (eg a tissue), the latter being transferred from the substrate to the polymer material in which they will be anchored mechanically (or in addition, chemically), which gives a particularly soft and warm touch.
- a bed of polymer powder eg PA11
- the total transparency typically greater than or equal to that of a conventional amorphous polymer such as polycarbonate (PC), that for identical thicknesses and less than 2mm.
- PC polycarbonate
- the present invention relates to the use of a micro-crystalline polyamide to obtain an object having all or part of its outer surface made of this micro-crystalline polyamide having a particular surface state and in which: "the manufacture of the object has hot stages between the Tg
- the transparency of the microcrystalline polyamide is such that the light transmission at 560 nm on a polished article 1 mm thick is> 80%, advantageously> 88%, the transparency being measured on the object obtained by the usual methods of setting implemented as the injection sheet extrusion by calendering.
- the microcrystalline polyamide is such that its degree of crystallinity is> 10% and ⁇ 30% (first DSC heating according to ISO 11357 at 40 ° C./min), and the heat of fusion> 25J / g and ⁇ 75J / g (1st DSC heating according to ISO 11357 at 40 ° C / min).
- Tg glass transition temperature
- Tm melting temperature
- Microcrystalline polyamide is also understood to mean copolyamides, compositions predominantly based on these, or in which the microcrystalline polyamide is the matrix constituent. These compositions may be alloys, mixtures, composites, for example compositions including plasticizers, stabilizers, dyes, inorganic fillers, and other miscible polymers, compatible or compatibilized by a third component.
- the invention also relates to objects made in this microcrystalline polyamide and to objects having wholly or partly their outer surface made of this micro-crystalline polyamide having a particular surface state.
- PA11 denotes a PA 11 Atofina Rilsan BESNO TL
- Amorphous PA denotes PA-BMACM.
- T / BMACM.1 / 12 obtained by condensation of BMACM, T (terephthalic acid), I (isophthalic acid) and lactam
- ⁇ -crystalline PA means a microcrystalline polyamide of composition by weight:
- Tg and Tm we will therefore particularly focus on the area between Tg and Tm, where we typically consider fabricating the object or at least perform part of the manufacturing steps, including finishing to give it the visual and tactile properties that are desired.
- Fig 1 we observe that below Tg, the 3 polymers are good and sufficiently rigid (to protect the object during use, not to give formability during the manufacture of the object). Above its Tg the amorphous PA becomes liquid: it is therefore unfit to be worked and shaped in the solid state above its Tg, it could not keep integrates its visual decoration (and below its Tg it is obviously much too rigid and not malleable to be worked and shaped).
- the semi-crystalline PA sees its rigidity drop below Tg, and it remains in the solid state up to its Tm.
- the ⁇ -crystalline PA between Tg and Tm, is itself sufficiently flexible and malleable to be easily worked and shaped in the solid state. But the ⁇ -crystalline PA, between Tg and Tm, is still sufficiently crystalline and rigid not to flow or liquefy. We understand all the practical interest of such a material.
- the ratio "es / r" also represents approximately the degree of crystallinity. We understand that this one is too high.
- the ratio "c ⁇ / r" also represents approximately the degree of crystallinity.
- Tg and which Tm to choose corresponds in some way to the temperature where the key steps of the fabrication of the finished object will take place. In many industrial processes this temperature must remain reasonable, ie remain not too high so that the other constituents of the object do not undergo degradation (for example the liquefaction of a third constituent polymer ABS, which is liquefies at about 100 ° C). It is therefore preferable to choose a Tg lower than 90 ° C (but significantly higher than the ambient temperature or the service temperature of the object). A microcrystalline PA with a Tg of 140 ° C., for example, will impose a manufacturing process (of the final object) greater than 140 ° C., which can therefore be restrictive.
- microcrystalline polyamides By way of example of microcrystalline polyamides, mention may be made of the transparent composition comprising, by weight, the total being 100%:
- diamine chosen from cycloaliphatic diamines and aliphatic diamines and at least one diacid chosen from cycloaliphatic diacids and aliphatic diacids, at least one of these diamino or diacid units being cycloaliphatic
- a flexible polyamide chosen from polyamide block and polyether block copolymers and copolyamides, 0 to 20% of a compatibilizer (D) of (A) and (B),
- composition is microcrystalline. Without being bound by this explanation the inventors think that it is due to the very small size of crystalline buildings size sufficiently small not to diffract the light as
- aliphatic alpha omega amino carboxylic acid mention may be made of amino-11-undecanoic and amino-12-dodecanoic acids.
- lactam mention may be made of lauryllactam.
- aliphatic diamines examples include hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
- aliphatic diacids mention may be made of adipic, azelaic, suberic, sebacic and dodecanedicarboxylic acids.
- polyundecanamide PA11
- PA-12 polylauryllactam
- PA-6.9 polyhexamethylene sebacamide
- PA-6,10 polyhexamethylene dodecanamide
- PA-6,12 polydecamethylene dodecanamide
- PA-10,12 polydecamethylene sebacanamide
- PA-12,12 polydodecamethylene dodecanamide
- (A) is PA 11 and PA 12. It would not be outside the scope of the invention if (A) was a mixture of aliphatic polyamides.
- the diamines are, for example, cycloaliphatic diamines comprising two cycloaliphatic rings. These diamines correspond to the general formula (I)
- R1 to R4 represent identical or different groups chosen from a hydrogen atom or alkyl groups of 1 to 6 carbon atoms and X represents either a single bond or a divalent group consisting of: a linear or branched aliphatic chain of 1 to 10 carbon atoms, a cycloaliphatic group of 6 to 12 carbon atoms, a linear or branched aliphatic chain of 1 to 10 carbon atoms, substituted by cycloaliphatic groups of 6 to 8 carbon atoms of a group of 8-12 carbon atoms consisting of a dialkyl, linear or branched, with a cyclohexyl or benzyl group.
- the cycloaliphatic diamines may be the isomers of bis- (4-aminocyclohexyl) -methane (BACM), bis- (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4) aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM).
- BMACP bis- (4-aminocyclohexyl) -methane
- BMACP bis- (3-methyl-4-aminocyclohexyl) methane
- PAMN para-amino-di-cyclohexyl methane
- IPDA isophoronediamine
- BAMN 2,6-bis (aminomethyl) norbornane
- amorphous polyamide (B) may optionally contain at least one monomer or comonomer selected from: alpha omega amino carboxylic acids, aliphatic diacids, aliphatic diamines, these products have been described above.
- PA-IPDA 1, 10, coPA-IPDA, 10/12, PA-IPDA. It would not be outside the scope of the invention if (B) was a mixture of several amorphous polyamides.
- the flexible polyamide (C) and firstly the polyamide block and polyether block copolymers result from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, inter alia: 1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends.
- Polyamide sequences having dicarboxylic chain ends with polyoxyalkylene sequences having diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic alpha-omega dihydroxylated polyoxyalkylene sequences known as polyetherdiols.
- copolymers (C) are advantageously of this type.
- the polyamide sequences with dicarboxylic chain ends result, for example, from the condensation of alpha-omega-aminocarboxylic acids, lactams or dicarboxylic and diamine diacids in the presence of a dicarboxylic acid chain-limiting agent.
- the molar mass in number Mn of the polyamide sequences is between 300 and 15,000 and preferably between 600 and 5,000.
- Mn polyether sequences is between 100 and 6000 and preferably between 200 and 3000.
- Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
- polyetherdiol, a lactam (or an alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water.
- a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly are obtained which are distributed statistically along the polymer chain.
- polymers with polyamide blocks and polyether blocks whether they come from the copolycondensation of previously prepared polyamide and polyether blocks or from a one-step reaction, have, for example, Shore D durations which can be between 20 and 75 and advantageously between 30 and 75. and 70 and an intrinsic viscosity between 0.8 and 2.5 measured in metacresol at 25 0 C for an initial concentration of 0.8 g / 100 ml.
- the MFI can be between 5 and 50 (235 ° C. under a load of 1 kg)
- the polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated to be converted into polyether diamines and condensed. with polyamide blocks with carboxylic ends.
- polyamide block and polyether block copolymers can also be mixed with polyamide precursors and a chain limiter to make the polyamide block and polyether block polymers having statistically distributed patterns.
- these polyamide block and polyether block copolymers have polyamide blocks of PA 11, PA 12 or PA 6 and polyether blocks of PTMG (polytetramethylene glycol) or PPG (polypropylene glycoi).
- the flexible polyamide (C) consisting of copolyamide, it results either from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid is condensation of at least two alpha omega aminocarboxylic acids (or their corresponding lactams or a lactam and the other in alpha omega aminocarboxylic acid form). These constituents have already been defined above.
- copolyamides By way of examples of copolyamides, mention may be made of copolymers of caprolactam and lauryl lactam (PA 6/12), copolymers of caprolactam, adipic acid and hexamethylenediamine (PA 6 / 6-6), copolymers caprolactam, lauryl lactam, adipic acid and hexamethylenediamine (PA 6/12 / 6-6), copolymers of caprolactam, lauryl lactam, amino 11 undecanoic acid, azelaic acid and hexamethylenediamine (PA 6 / 6-9 / 11/12), copolymers of caprolactam, lauryl lactam, amino undecanoic acid, adipic acid and hexamethylenediamine (PA 6 / 6-6 / 11 / 12), copolymers of lauryl lactam, azelaic acid and hexamethylenediamine (PA 6-9 / 12).
- the preferred copolyamides are copolyamides with a marked copolymer character, that is to say with substantially equivalent proportions of the various comonomers, which leads to the properties furthest away from the corresponding polyamide homopolymers. It would not be departing from the scope of the invention if (C) was a mixture of several polyamide block copolymers and polyether blocks or of several copolyamides or any combination of these possibilities.
- compatibilizer (D) of (A) and (B) it is any product that lowers the temperature necessary to make the mixture of (A) and (B) transparent.
- it is a polyamide.
- (A) is PA 12 then (D) is PA 11.
- PA 11 is a catalyzed aliphatic polyamide.
- the polyamide (D) catalyzed it is a polyamide as described above for (A) but containing a polycondensation catalyst such as a mineral or organic acid, for example phosphoric acid.
- the catalyst may be added to the polyamide (D) after it has been prepared by any method, or simply, and it is preferred, to be the remainder of the catalyst used for its preparation.
- Catalyzed polyamide means that the chemistry will continue beyond the steps of synthesis of the base resin and therefore during the subsequent stages of the preparation of the compositions of the invention. Polymerization and / or depolymerization reactions may be very substantially carried out during the mixing of the polyamides (A) and (B) and (D) to prepare the compositions of the present invention.
- the amount of catalyst may be between 5 ppm and 15000 ppm phosphoric acid relative to the resin (D).
- the contents will be different and can be chosen appropriately according to the usual polycondensation techniques of polyamides.
- the flexible modifier (M) by way of example, mention may be made of functionalized polyolefins, grafted aliphatic polyesters, polyether block copolymers and optionally grafted polyamide blocks, copolymers of ethylene and a (meth) acrylate. alkyl and / or a vinyl ester of saturated carboxylic acid.
- the polyether block and polyamide block copolymers may be chosen from those mentioned above for (C), flexible copolymers are preferred, that is to say having a flexural modulus of less than 200 MPa.
- the modifier may also be a polyolefin chain having polyamide or polyamide oligomer grafts; thus it has affinities with polyolefins and polyamides.
- the flexible modifier may also be a block copolymer having at least one block compatible with (A) and at least one block compatible with (B).
- a flexible modifier mention may also be made of: copolymers of ethylene, an unsaturated epoxide and optionally an ester or an unsaturated carboxylic acid salt or a saturated carboxylic acid vinyl ester. These are, for example, ethylene / vinyl acetate / glycidyl (meth) acrylate copolymers or ethylene / alkyl (meth) acrylate / glycidyl (meth) acrylate copolymers.
- Zn metal
- Li alkali
- the functionalized polyolefin is chosen from ethylene / (meth) alkyl acrylate / maleic anhydride copolymers, ethylene / vinyl acetate / maleic anhydride copolymers, and ethylene propylene predominantly propylene copolymers grafted with maleic anhydride then condensed with monoamino polyamide 6 or monoamino oligomers of caprolactam.
- the alkyl (meth) acrylate may be chosen from methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, ethyl-2-hexyl acrylate, ethyl acrylate and the like. cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
- grafted aliphatic polyesters mention may be made of polycaprolactone grafted with maleic anhydride, glycidyl methacrylate and esters. vinyl or styrene. These products are described in application EP 711 791.
- the modifier (M) is useful for further softening or conferring a particular property (hence its modifying name) without losing the advantageous properties of transparency, of low T ° production. and aptitude for sublimation.
- additional properties that can be made by the modifier include: impact modifier to improve the impact resistance, modifying reactive function carrier to improve the adhesion of the material to the substrates, modifying to give a matte appearance, modifying to give a silky touch or sliding, modifying to make more viscous the material to implement it by blowing. It is advantageous to mix the modifiers to combine their effects.
- compositions are those in which the proportions of the constituents are as follows (the total being 100%) and are described in the following Table 1: Table 1
- compositions are manufactured by melt blending of the various constituents (twin-screw extruders, BUSS®, single screw) according to the usual techniques of thermoplastics.
- the compositions can be granulated for later use (it is sufficient to recast) or else injected into a mold or an extrusion or coextrusion device to make plates, films.
- Those skilled in the art can easily adjust the compounding temperature to obtain a transparent material, as a rule it is sufficient to increase the compounding temperature, for example to 280 or 290 ° C.
- compositions may comprise stabilizers, antioxidants, anti-UV agents.
- microcrystalline polyamides By way of another example of microcrystalline polyamides, mention may be made of the transparent composition comprising, by weight, the total being 100%: • 5 to 40% of an amorphous polyamide (B) which essentially results from the condensation of at least an optionally cycloaliphatic diamine, from at least one aromatic diacid and optionally at least one monomer chosen from: alpha omega amino carboxylic acids, aliphatic diacids, aliphatic diamines,
- a soft polyamide (C) chosen from polyamide block and polyether block copolymers and copolyamides,
- the proportion of (B) is between 10 and 40% and preferably between 20 and 40%.
- the proportion of (C) + (D) is between 5 and 40% and preferably 10 and 40%.
- the amorphous polyamide (B) in this other microcrystalline polyamide composition essentially results from the condensation of at least one optionally cycloaliphatic diamine and at least one aromatic diacid.
- the cycloaliphatic diamines may be the isomers of bis- (4-aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2 -2-bis- (3-methyl-4-aminocyclohexyl) propane (BMACP).
- diamines commonly used may be isophoronediamine (IPDA) and 2,6-bis (aminomethyl) -norbornane (BAMN).
- IPDA isophoronediamine
- BAMN 2,6-bis (aminomethyl) -norbornane
- aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
- the amorphous polyamide (B) may optionally contain at least one monomer chosen from: alpha omega amino carboxylic acids, aliphatic diacids, aliphatic diamines, these products have been described above.
- (B) By way of example of (B), mention may be made of the amorphous semi-aromatic polyamide PA-12 / BMACM, TA / BMACM.IA synthesized by melt polycondensation from bis- (3-methyl-4-aminocyclohexyl) ) -methane (BMACM), lauryllactam (L12) and iso- and terephthalic acids (IA and TA). It would not be outside the scope of the invention if (B) was a mixture of several amorphous polyamides.
- BMACM bis- (3-methyl-4-aminocyclohexyl) ) -methane
- L12 lauryllactam
- IA and TA iso- and terephthalic acids
- micro-crystalline polyamide overmolding with decoration in the mold (called "IMD", “In-Mold Decoration”)
- IMD In-Mold Decoration
- This micro-crystalline polyamide material is particularly suitable for its use in the IMD process.
- In-Mold-Decoration or decoration in the mold This process consists in placing at the bottom of the mold a foil or film previously decorated (and optionally thermoformed beforehand) and overmolded (it would be better to use the term under-mold) , but usually the term overmould be used) then a polymer to give body to the object, the sheet or the film then becoming the surface (decorated) of the object.
- the micro-crystalline polyamide is particularly suitable because it allows not only a visual decoration "in the mold” but also a tactile decoration by the faculty that it possesses to make the texture of the surface of the mold
- the micro-crystalline polyamide, semi-crystalline in and not too strongly crystalline, is indeed particularly suitable for decoration by sublimation between its Tg and its Tm (and preferentially near its Tm
- micro-crystalline polyamide Among the other advantages of our micro-crystalline polyamide, let's emphasize its ability superior to thermoforming (often used before overmolding), its chemical resistance far superior to amorphous polymers (for example polycarbonate, I 1 ABS), its excellent resistance to mechanical attack, UV radiation (much better than that of polycarbonate).
- thermoforming often used before overmolding
- amorphous polymers for example polycarbonate, I 1 ABS
- UV radiation ultraviolet radiation
- the molded and overmolded film process is just one example and that our micro-crystalline polyamide is advantageous with other manufacturing processes, such as compression molding, injection molding, thermoforming and all processes where the ductility and malleability of the material is an asset, it being understood that said process takes place at least partially at a temperature between Tg and Tm (and it being understood that thereafter the service temperature of the object will be less than this Tg, or that this Tg is substantially greater than the ambient temperature).
- a “solid paint” advantage of the micro-crystalline polyamide and the IMD process on painting.
- paint or screen printing ink has the advantage of being able to give not only aesthetic visual effects but also attractive tactile effects.
- the paint has the disadvantage of requiring an often long application process and the presence of solvents, which is ecologically undesirable.
- paints for example those based on polyurethane, are not as efficient as a polyamide micro-crystalline coating. Between its Tg and its Tm, the micro-crystalline polyamide is particularly flexible and malleable while remaining in the solid state.
- a smooth, shiny sheet of micro-crystalline PA is placed against a metal surface with a seed relief, all at 110 ° C, between Tg and Tm, under 20bar, for 3 minutes.
- the composition PA 11 No. 6 (it has a Tg of about 55 ° C. and a Tm of about 188 ° C.) may be used.
- the Microcrystalline PA sheet has the advantage of having acquired a surface relief, a visual appearance, a touch very faithfully reproduced.
- a bilayer smooth sheet of microcrystalline polyamide material // polypropylene grafted with maleic anhydride is placed at the bottom of a seed mold at 60 ° C., face PA side mold seed.
- This mold is an injection mold.
- An overmolding operation will be performed: PP (molten) is then injected at 210-230 ° C., with a holding pressure of 500 bar. When leaving the mold, the surface on the side leaf perfectly acquired the seed relief of the mold.
- PA 11 No. 6 // Orevac® 18729.
- a bilayer smooth sheet of microcrystalline polyamide material // polypropylene grafted with maleic anhydride is placed at the bottom of a mold polished at 60 0 C, side PA side polished mold.
- This mold is an injection mold.
- An overmolding operation will be performed: PP (molten) is then injected at 210-230 ° C., with a holding pressure of 500 bar. At the end of the mold, the leaf side surface has perfectly acquired the polish of the mold.
- PA 11 No. 6 // Orevac® 18729.
- a smooth, shiny sheet of microcrystalline PA is now placed against a wooden surface at T ° sufficiently high (but still in the range Tg - Tm) so that there is adhesion between the wood and the PA (the AP penetrating the crevices of the wood surface thus creating a mechanical anchorage).
- T ° sufficiently high but still in the range Tg - Tm
- Visio-tactile fabric structure A smooth and glossy sheet of microcrystalline PA is now placed against a "non-woven" textile surface (for example at 110 ° C., under 20 bar, for 5 minutes). As described above, the surface condition of the "nonwoven” will be faithfully retranscribed, but in addition, if T ° is sufficiently high but still in the range Tg-Tm, textile fibrils will remain trapped in the sheet of Microcrystalline PA, which will give a soft touch particularly marked, type fabric.
- the fabric can be replaced by a bed of powder or a substrate impregnated with powder, for example PA11 powder.
- powder for example PA11 powder.
- the hot contact between Tg and Tm is put under a pressure P ° and during a time t, and a material with a touch "powder" is obtained.
- powder and fibrils can be colored or pigmented, which will give an additional visual effect.
- composition of the micro-crystalline polyamide which will allow the degree of crystallinity (the lower it will be, the more adhesion there will be), the thickness of the micro-crystalline polyamide sheet (the finer it is, the more adhesion there will be); temperature during the implementation (the higher it is, the more there will be adhesion); time during implementation (the higher it is, the more membership there will be); pressure during the implementation (the higher it is, the more there will be adhesion).
- Adhesion / weldability A smooth, glossy sheet of micro ⁇ crystalline PA is now placed partly superimposed on another microcrystalline PA sheet. The whole is pressed at T ° (for example 180 ° C, 30bar, 3min) between Tg and Tm.
- T ° for example 180 ° C, 30bar, 3min
- the material has the double advantage of being weldable and that this weld has almost the same thickness as the sheet (this thanks to the flexibility and heat workability of this microcrystalline material).
- Adhesion / sintering Superior ability to sinter a powder of the micro-crystalline polyamide. Sintering is an operation which consists in making the powder mass by heating it below its Tm. Ceramics are typically manufactured by sintering. This sintering ability is to be compared with the weldability described in the previous paragraph. More generally, the microcrystalline polyamide of the invention has a superior ability to interdiffuse between Tg and Tm, that is to say that 2 objects (for example grains of powder and plates) put in contact between Tg and Tm are going to see a superior aptitude to join together. As one places between Tg and Tm, the default comparison material is a semi-crystalline (an amorphous material having no Tm, it is in the liquid state above its Tg).
- Malleability / all that is hot forming between Tg and Tm In general malleability is greater between Tg and Tm, it is the superior formability between Tg and Tm. For example, between Tg and Tm, if a flat sheet of the microcrystalline polyamide of the invention is placed in a bowl-shaped mold, it will take less force to force the material to adopt this bowl shape. Compared to the grain intake (see previous paragraphs), the forming is not so different, finally it can be seen as a simple change of scale: the grained surface is a relief of small scale (hollow and boss of a hundred microns), the bowl is a relief of large scale (tens of cm).
- Thermoforming Overmolding Decoration Two antagonistic advantages are desired. The first is that hot (between Tg and Tm, it requires a malleable material to be able to thermoform in a deep way (strong 3rd dimension, high relief) . The second is that after having manufactured the object by IMD, it requires a sufficiently hard and tough surface to withstand mechanical aggression type scratches, nicks, shock, etc.
- thermoformable because particularly soft / malleable in the temperature zone between its Tg and its Tm, during its manufacture, while being thereafter, during its use, T ⁇ Tg, sufficiently hard, rigid and tenacious to provide a very good resistance to mechanical attack type scratches, cuts and shocks.
- the micro-crystalline polyamide of the invention is advantageous for reproducing surface states, during a liquid-state processing operation such as injection.
- a liquid-state processing operation such as injection.
- the injection is a process in the liquid state, so above Tm and not between Tg and Tm.
- the skin of the object is in the solid state and the heart in the liquid state, the latter exerting pressure on the skin against the surface of the mold.
- a significant part of the thickness is therefore in the solid state, in fact between Tg and Tm, and subjected to pressure from the heart of the workpiece.
- the micro-crystalline polyamide of the invention will also have a greater capacity to reproduce the surface texture of the mold than more conventional materials such as amorphous thermoplastic polymer materials or "standard”"non-transparent" semi-crystalline polymeric materials. .
- Adhesion to a substrate The superior ability to adhere to a substrate having anfractuosities (ie a sufficiently pronounced relief so that hook points can be created with another material) is described.
- the microcrystalline polyamide of the invention can be pressed onto wood or fabric, beyond Tm, under pressure and for a time, and generate good adhesion with this substrate. (A conventional semi-crystalline material will not adhere or less where it will require more time, temperature or pressure).
- Micro-crystalline polyamide filled fiberglass, surface appearance, touch and color Another example of an advantageous use of the micro-crystalline polyamide of the invention is the case of the composites or polymers loaded with an isotropic (for example calcium carbonate) or anisotropic mineral material, such as a fiber (for example a fiber of glass or carbon).
- the microcrystalline polyamide may contain 30% by weight of fillers such as, for example, glass fibers. This material loses its transparency and becomes opaque. This does not prevent the composition from having 2 advantages related to its semi-crystalline and microcrystalline character and its low crystallinity level.
- Microcrystalline polyamide highly charged with mineral powder To obtain mineral-looking objects (such as granite or other stone), transparent amorphous polymers such as PMMA can be used and can be loaded to 30-80% powder or mineral filler. Then we give it a 3-dimensional shape to make a finished object, for example a sink.
- Using micro-crystalline PA instead of PMMA will provide better formability (shape in 3 deep dimensions) and also allow to obtain better texturing (type anti-scratch embossing type structuring facilitating the flow of water type touch pleasant and reproducing more faithfully that of stone) and much more easily.
- polyamide very loaded with mineral powder or pigment is no longer transparent, but its intrinsic transparency makes the color of the mineral filler or pigments appear more vividly and aesthetically.
- Microcrystalline polyamide with anti-scratch and anti-wear texturing To obtain scratch and wear resistant objects, the intrinsic strength of the material is not the only factor. Adequate surface texturing is also beneficial, this is known. Thanks to the character (malleable but not melted between its tg and its Tm) of the microcrystalline PA we can use as texturing a net or a loose fabric. It will print in our material and leave a negative surface, that is to say a surface consisting of bumps and grooves. This surface is particularly resistant to wear. Similar effects can be achieved with embossed paper or textile. A particularly interesting case is the one where one generates brilliant bumps and dull valleys with a soft touch. It combines good wear resistance (visual) and a soft touch.
- Another advantage of the polyamide of the invention is its ability to be repaired. Indeed, in case of scratches or defects, it is possible to blow a blowtorch near its surface and, under the effect of heat, the scratch or the defect will heal, will fill, without for all that the whole object does not become liquefied or deformed in a prejudicial way.
- this advantage relating to compositions loaded with a mineral material, consider a slab of soil loaded with 50 parts of calcium carbonate.
- Manufacturing step 1 the transparent sheet.
- the micro-crystalline polyamide is extruded by calendering in sheet form.
- the thickness may for example be between 200 and 800 ⁇ m.
- This polymer material has the advantage of being easy to extrude (crystallizes and freezes less quickly on the calendering rolls).
- a standard semi-crystalline polyamide and to be transparent (for example the standard PA11 is only translucent).
- PA 11 # 6 can be used.
- Production step n ° 2 Sublimation decoration.
- a colored decoration (supported on a sheet of paper) and bearing a logo and inscription in letters and in figures is given to the sheet during a process of sublimation (one places the sheet bearing the decoration against the sheet of micro-crystalline polyamide and then heated so that the dyes sublimate and pass into the micro-crystalline polyamide).
- This sublimation is usually done at 170 ° C. for 2 minutes and under 2 bars.
- This decoration does not cover the entire sheet, there are still undecorated areas, therefore colorless and transparent.
- the sublimated decor is placed on the underside of the transparent sheet: it will be protected and the thickness of transparent material that covers it reinforces its aesthetics (varnished appearance).
- Manufacturing step 3 thermoforming.
- the decorated microcrystalline polyamide sheet is then thermoformed in the form of a 3-dimensional object (for example a car cover).
- the micro-crystalline polyamide is particularly suitable for this hot-forming operation, between Tg and Tm.
- the reaction was carried out at about 170 ° C. for 3 minutes.
- Manufacturing step n ° 4 overmolding and finishing.
- the decorated thermoformed sheet is then placed in an injection mold, the undecorated face being against the wall of the mold.
- This wall of the mold next to the future face of the finished object, has a finish of "brushed" type, that is to say that it is textured by unidirectional stripes. Nevertheless, in the center of this mold wall, there is a polished and glossy area in the shape of a logo.
- the mold is closed and then injected semi-crystalline standard polyamide (for example PA 12) pigmented gray metal.
- This polyamide (PA12) is then overmoulded on the face internal decorated with the micro-crystalline polyamide sheet, over a thickness for example of the order of 1 to 5 mm.
- This object is visually and tactfully decorated.
- the following decorative areas can be observed: A metallic gray color zone with a brushed aluminum look and feel (corresponding to an area not decorated by sublimation),
- micro-crystalline polyamide material is particularly advantageous for obtaining complex and attractive visi-tactile decorations. It allows more freedom than other materials such as amorphous polymers, semi-crystalline polymers and paints.
- the paint has the advantage of offering various touches (but only one type at a time) but the disadvantage of being limited in visual decorations and protections (letters, numbers, logos).
- the usual polymers are limited in touch but advantageous in visual scenery.
- the micro-crystalline PA combines all these advantages.
- the first inventive step of the process is to insert between the mold and the film of our material a sheet of texturing paper or fabric (or other).
- This has the advantage of avoiding texturing of the metal of the injection mold, to make it possible to change texturing very easily without changing the mold.
- 2nd variant can also use a film of our already textured material (in another operation, at another time) and used as texturing, texturing another film of our material.
- One can thus very well use as texturizer another solid polymer, and advantageously this same polymer.
- thermoforming plaxing, compression or overmoulding (as described in the first variants)
- the texturing of our film will not disappear but will be further improved. It is not essential to texturize during the last hot manufacturing step.
- thermoplastic processing methods such as extrusion coating, thermoforming, injection molding with.
- thermoset processing technologies we can use thermoset processing technologies. For example, we can line a mold bottom with a film of our polymeric material and then deposit and bake a thermosetting resin (with its impregnated fiberglass fabric).
- inventive variant e we can use multilayer films or sheets, made of a top layer (aspect) of our microtips crystalline material and a lower layer of a second polymer (and the need for a layer a binder between them).
- the advantage of this second polymer is to be able to better adhere to a third material, typically a molten polymer (typically introduced during a subsequent overmolding step).
- the second polymer being of the same nature as the third, or being compatible and adhering with it.
- the adhesion between the molten polymer and the PEBA side of the film is excellent.
- molten TPU and not PEBA
- molten TPU is then injected.
- the adhesion between the molten polymer and the PEBA side of the film is excellent.
- the adhesion between the molten polymer and the PEBA side of the film is excellent. As we have mentioned above other methods may be employed.
- a micro-crystalline PA multilayer film / PEBA can be used alone, without overmolding, in thermoforming alone.
- the ratio of the thicknesses of PA and PEBA will be adjusted according to the overall compromise of properties sought.
- the micro-crystalline polyamide sheet may itself consist of different layers (in particular made of this same PA), the upper layer being slightly pigmented by metallic pigments and nevertheless transparent and the lower layer being heavily pigmented. by a color so as to be sufficiently opaque.
- This multilayer sheet will have a beautiful metallized appearance, a good depth and, by its sufficient opacity, mask all the defects of the substrate which will be overmoulded (or under-molded to be more precise). Por accentuated the effect of varnish and depth, it is even possible to envisage an additional upper layer of completely transparent microcrystalline polyamide.
- the textu ration (and the resulting touch) can be obtained by any lukewarm process (Tg - Tm) and generating enough pressure to press our material (solid) on the texturing surface.
- Tg - Tm lukewarm process
- the non-liquid nature would stick too much
- not too rigid would not take texturing
- the tactile (and visual) rendering of materials of totally different nature such as fabric, paper, leather, wood, plants, etc.
- this advantage can be combined with other advantages, such as the visual decorability, such as the protective properties (durability against wear, shock, UV radiation, chemicals).
- micro-crystalline polyamide objects of high quality, both perceived and real.
- objects may for example be interior or exterior vehicle parts, sports equipment parts such as shoes, skis, household appliances parts, telephone parts, computer housings, furniture, floors, etc.
- Example of microcrystalline compositions that can be used in the present invention.
- alloys of polymers mainly consisting of polyamide monomers C9 and more, made at a sufficient temperature such that the resulting polymer is sufficiently transparent.
- These alloys consist, on the one hand, of a sufficient quantity of crystalline polymer (for example polyamide 11) so that the final alloy has a melting point and a melting enthalpy greater than 25 J / g, and on the other hand a sufficient amount of polymers amorphous (for example the IPDA.12 polymer) so that the final alloy is a sufficient transparency.
- Copolymers predominantly consisting of C9 and higher monomers, with on the one hand a sufficient amount of crystalline monomer (e.g. monomer unit 11) for the final copolymer to have a melting point and a melting enthalpy greater than 25J / g, and on the other hand a sufficient quantity of amorphous monomer (for example the monomer unit IPD.10) so that the final copolymer is a sufficient transparency.
- Polyamide compositions are mainly composed of C9 monamers and better chemical, UV and shock protection, less dimensional variations). Nevertheless it is possible to use polymer mixtures or alloys predominantly consisting of polyamide monomers C9 and less, made at a sufficient temperature such that the resulting polymer is sufficiently transparent. These alloys are formed on the one hand with a sufficient quantity of crystalline polymer (for example polyamide 6) so that the final alloy is a melting point and an enthalpy of melting greater than 25J / g, and secondly a sufficient amount of amorphous polymers (for example the PA-6.1 polymer) so that the final alloy is a sufficient transparency.
- a sufficient quantity of crystalline polymer for example polyamide 6
- amorphous polymers for example the PA-6.1 polymer
- Copolymers predominantly consisting of C9 and lower monomers, with on the one hand a sufficient amount of crystalline monomer (e.g. monomeric unit 6.6) for the final copolymer to have a melting point and a melting enthalpy greater than 25J / g, and on the other hand a sufficient quantity of amorphous monomer (for example the monomeric unit IPD.6) so that the final copolymer is a sufficient transparency.
- crystalline monomer e.g. monomeric unit 6.6
- amorphous monomer for example the monomeric unit IPD.6
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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)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Polyamides (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0406757A FR2871808B1 (fr) | 2004-06-22 | 2004-06-22 | Utilisation d'un polyamide micro-cristallin pour obtenir un etat de surface particulier |
PCT/FR2005/001406 WO2006008358A1 (fr) | 2004-06-22 | 2005-06-08 | Utilisation d’un polyamide micro-cristallin pour obtenir un état de surface particulier |
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Publication Number | Publication Date |
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EP1771515A1 true EP1771515A1 (fr) | 2007-04-11 |
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EP05775537A Withdrawn EP1771515A1 (fr) | 2004-06-22 | 2005-06-08 | Utilisation d'un polyamide micro-cristallin pour obtenir un etat de surface particulier |
Country Status (6)
Country | Link |
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EP (1) | EP1771515A1 (fr) |
JP (2) | JP2008503631A (fr) |
KR (1) | KR100879495B1 (fr) |
CN (1) | CN101006137B (fr) |
FR (1) | FR2871808B1 (fr) |
WO (1) | WO2006008358A1 (fr) |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2871808B1 (fr) * | 2004-06-22 | 2006-10-13 | Arkema Sa | Utilisation d'un polyamide micro-cristallin pour obtenir un etat de surface particulier |
JPWO2007034905A1 (ja) * | 2005-09-22 | 2009-03-26 | 富士通株式会社 | 植物系樹脂含有組成物及びそれを用いた植物系樹脂含有成形体 |
FR2902431B1 (fr) * | 2006-06-14 | 2013-04-26 | Arkema France | Copolymeres a motif amides et a motif ethers ayant des proprietes optique ameliorees |
FR2902436B1 (fr) * | 2006-06-14 | 2008-08-01 | Arkema France | Melanges et alliages a base d'un copolymere amorphe a semi-cristallin, a motif amides et a motif ethers, ces materiaux ayant des proprietes optiques ameliorees |
JP5376773B2 (ja) * | 2007-04-12 | 2013-12-25 | ユニチカ株式会社 | ポリアミド樹脂フィルム |
DE102008002599A1 (de) | 2008-06-24 | 2009-12-31 | Evonik Degussa Gmbh | Bauteil mit Deckschicht aus einer PA613-Formmasse |
US20110047860A1 (en) * | 2009-09-03 | 2011-03-03 | Fmc Corporation | Bed bug capturing device |
US9744722B2 (en) * | 2012-11-21 | 2017-08-29 | Stratasys, Inc. | Additive manufacturing with polyamide consumable materials |
FR3018280B1 (fr) * | 2014-03-04 | 2017-05-26 | Arkema France | Composition transparente a base de polyamide chargee de verre |
FR3019181B1 (fr) * | 2014-03-31 | 2020-06-19 | Arkema France | Compositions de polyamide et de peba pour l'injection de pieces rigides resistant a la fatigue |
JP6440446B2 (ja) * | 2014-10-10 | 2018-12-19 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | ポリアミド混合物 |
JP6068737B1 (ja) * | 2015-03-18 | 2017-01-25 | 旭化成株式会社 | ポリアミド系樹脂発泡成形体、及びポリアミド系樹脂発泡成形体の製造方法 |
CN108779306A (zh) * | 2017-07-10 | 2018-11-09 | 东莞市森特塑胶制品有限公司 | 一种塑料膜层以及应用该塑料膜层的塑料膜 |
CN108698391A (zh) * | 2017-07-10 | 2018-10-23 | 东莞市森特塑胶制品有限公司 | 一种塑料膜 |
CN109294222A (zh) * | 2018-09-20 | 2019-02-01 | 安徽江淮汽车集团股份有限公司 | 一种pa6-pmma复合材料及其制备方法 |
FR3094912B1 (fr) | 2019-04-12 | 2021-03-05 | Arkema France | Procede de texturation d’un polyamide |
JP7008287B2 (ja) * | 2019-10-18 | 2022-01-25 | 株式会社豊田中央研究所 | 透明ポリアミド樹脂組成物及びその製造方法 |
EP4053199A4 (fr) * | 2019-10-30 | 2023-11-08 | UBE Corporation | Composition de résine de polyamide |
Family Cites Families (8)
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---|---|---|---|---|
ATE119465T1 (de) * | 1988-12-01 | 1995-03-15 | Curt Niebling | Verfahren zur herstellung tiefgezogener kunststoff-formteile. |
DE4122211A1 (de) * | 1991-07-04 | 1993-01-21 | Inventa Ag | Thermoplastische formmassen aus semikristallinem und amorphem polyamid, deren verwendung und verfahren zu ihrer herstellung |
FR2685703B1 (fr) * | 1991-12-31 | 1995-02-24 | Atochem | Compositions polyamides transparentes a tenue aux agents chimiques elevee. |
FR2706474B1 (fr) * | 1993-06-11 | 1995-08-25 | Atochem Elf Sa | Compositions polyamides transparentes sans déformation à chaud. |
CH685500A5 (de) * | 1993-12-23 | 1995-07-31 | Inventa Ag | Schwerentflammbare Polyamide. |
FR2820141B1 (fr) * | 2001-01-26 | 2003-03-21 | Atofina | Composition transparente a base de polyamide |
DE60209862T2 (de) * | 2001-01-26 | 2007-01-04 | Arkema | Transparente, Polyamid enthaltende Zusammensetzung |
FR2871808B1 (fr) * | 2004-06-22 | 2006-10-13 | Arkema Sa | Utilisation d'un polyamide micro-cristallin pour obtenir un etat de surface particulier |
-
2004
- 2004-06-22 FR FR0406757A patent/FR2871808B1/fr not_active Expired - Lifetime
-
2005
- 2005-06-08 WO PCT/FR2005/001406 patent/WO2006008358A1/fr active Application Filing
- 2005-06-08 JP JP2007517344A patent/JP2008503631A/ja active Pending
- 2005-06-08 KR KR1020067027238A patent/KR100879495B1/ko active IP Right Grant
- 2005-06-08 EP EP05775537A patent/EP1771515A1/fr not_active Withdrawn
- 2005-06-08 CN CN200580028290XA patent/CN101006137B/zh active Active
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2010
- 2010-09-21 JP JP2010211420A patent/JP2011001560A/ja active Pending
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Also Published As
Publication number | Publication date |
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CN101006137A (zh) | 2007-07-25 |
FR2871808B1 (fr) | 2006-10-13 |
KR20070033372A (ko) | 2007-03-26 |
KR100879495B1 (ko) | 2009-01-20 |
JP2008503631A (ja) | 2008-02-07 |
CN101006137B (zh) | 2012-05-16 |
JP2011001560A (ja) | 2011-01-06 |
FR2871808A1 (fr) | 2005-12-23 |
WO2006008358A1 (fr) | 2006-01-26 |
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