Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
• • 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
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
  • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00

Definitions

• Copolyamide composition comprising such a copolyamide and their use
• the present invention relates to a copolyamide and its use, especially as adhesive or glue, hot melt.
• the invention also relates to a composition comprising such a copolyamide as well as to the use of this composition.
• the copolyamides comprise at least two distinct repeating units, these distinct units being formed from the two corresponding comonomers.
• the copolyamides are thus prepared from two or more comonomers selected from an amino acid, a lactam and / or a dicarboxylic acid and a diamine.
• copolyamides which correspond to the following general formula: A / (diamine Cz). (diacid in Cw), in which: z represents the number of carbons of the diamine and w represents the number of carbons of the diacid, and
• A is selected from a unit obtained from an amino acid, a lactam and a unit having the formula (diamine Cx). (diacid in
• Cy where x represents the number of carbons of the diamine and y represents the number of carbons of the diacid.
• the patent application DE OS 1594233 describes copolyamides resulting either from the condensation of lauryllactam and caprolactam, or from the condensation of (i) lauryllactam and (ii) hexamethylenediamine and adipic acid in stoichiometric proportions, or further condensation (i) of lauryllactam, (ii) caprolactam and (iii) hexamethylenediamine and adipic acid in stoichiometric proportions.
• the patent application DE OS 2324160 describes copolyamides resulting from the condensation of lauryllactam, amino-11-undecanoic acid, caprolactam and hexamethylenediamine with one or more diacids having from 6 to 13 carbon atoms.
• the patent application EP 0 627 454 describes copolyamides resulting from the condensation of at least 10% by weight of lauryllactam or of 11-amino-undecanoic acid and hexamethylenediamine with one or more diacids having from 6 to 12 atoms. of carbon.
• the patent application EP 1 153 957 describes copolyamides resulting from the condensation of caprolactam, lauryllactam or amino-11-undecanoic acid and a diamine with at least two diacids containing from 6 to 14 carbon atoms.
• copolyamides described by the documents of the prior art which have just been cited are used, alone or as a mixture, as adhesives of the "hot melt adhesives" (or HMA) type, that is to say that the melt deposits on the surfaces to be bonded, the adhesion being then obtained by cooling, by the return to the solid state of the copolyamides.
• HMA hot melt adhesives
• copolyamides are obtained from monomers, mostly from the petroleum industry and therefore do not meet at least one of the concerns of sustainable development that is the reduction of fossil resources that are at the base of petrochemistry.
• the application WO 94/10257 describes adhesive compositions of the HMA type comprising from 20 to 80% by weight of poly lactic acid (PLA), from 2 to 20% by weight of a polar adhesive resin and, optionally, a plasticizer or a stabilizer.
• PVA poly lactic acid
• a plasticizer or a stabilizer a plasticizer or a stabilizer
• PLA because of its biodegradability, the use of PLA is not conceivable in all applications, particularly in the field of adhesive compositions of the HMA type where such PLA-based compositions are not entirely satisfactory.
• the greatest disadvantage of the compositions based on PLA is the poor resistance to water at temperatures from 50 ° C.
• Hot melt glues based on starch or its derivatives have a high sensitivity to water and can not therefore be used in certain applications in the presence of high relative humidity.
• the purpose of the present invention is therefore to meet some of the concerns of sustainable development while overcoming the disadvantages of adhesive compositions such as those based on PLA or starch.
• renewable raw material is a natural resource, animal or vegetable, whose stock can be reconstituted over a short period on a human scale. In particular, this stock must be renewed as quickly as it is consumed.
• renewable raw materials contain 14C . All carbon samples from living organisms (animals or plants) are actually a mixture of 3 isotopes: 12 C (representing about 98.892% ), 13 C (about 1, 108%) and 14 C
• the ratio 14 CV 12 C of living tissues is identical to that of the atmosphere.
• 14 C exists in two main forms: in mineral form, that is to say carbon dioxide (CO2), and in organic form, that is to say carbon incorporated into molecules organic.
• CO2 carbon dioxide
• organic form that is to say carbon incorporated into molecules organic.
• the ratio 14 CV 12 C is kept constant by the metabolism because the carbon is continuously exchanged with the environment.
• the proportion of 14 C is constant in the atmosphere, it is the same in the body, as long as it is alive, since it absorbs this 14 C as it absorbs the 12 C.
• the average ratio of 14 CV 12 C is equal to 1, 2x10 "12.
• n is the number of 14 C atoms remaining at the end of time t
• - a is the disintegration constant (or radioactive constant); it is connected to the half-life.
• the half-life of 14 C is
• the 14 C content is substantially constant from the extraction of renewable raw materials, to the manufacture of copolyamides according to the invention and even the end of their use.
• copolyamides according to the invention consist of 100% organic carbon derived from renewable raw materials, which could be certified by determination of the 14 C content according to one of the methods described in ASTM D6866, in particular according to the mass spectrometry method or the liquid scintillation spectrometry method described in this standard.
• copolyamides are obtained which have chemical and thermal properties that are entirely equivalent to those of the copolyamides of the art. obtained with caprolactam and / or lauryllactam, but which, moreover, meet at least one of the concerns of sustainable development mentioned above.
• the implementation and use of the copolymers according to the invention do not generate or few volatile organic compounds (VOC) and significantly reduces the phenomena of "fogging".
• these comonomers can be derived from renewable resources such as vegetable oils or natural polysaccharides such as starch or cellulose, the starch being extractable from, for example, corn or potato.
• These comonomers, or starting materials can in particular come from various transformation processes, in particular from conventional chemical processes, but also from processes for enzymatic transformation or else by bio-fermentation.
• copolyamides according to the invention therefore consist of 100% organic carbon derived from renewable resources, which could be certified according to the ASTM D6866 standard. These copolyamides can also receive JBPA's "Biomass PIa” certification, which is also based on ASTM D6888. The copolyamides according to the invention may also be validly labeled "JORA”.
• these copolyamides can be used in a large number of applications. applications, as will be seen below, particularly in the textile and automotive fields and, at least, in already known for copolyamides obtained for example with caprolactam or lauryllactam.
• the invention also relates to a composition comprising at least one copolyamide as described above.
• the composition according to the invention may be an adhesive composition.
• Such an adhesive composition has many applications in the textile, electronics and automotive industry, for example.
• the invention also relates to the use of such a copolyamide as well as to the use of a composition comprising at least one such copolyamide, such uses particularly aimed at adhesives of the "hot melt adhesive” (HMA) type. .
• HMA hot melt adhesive
• the invention also relates to the use of copolyamides and compositions according to the invention for the manufacture of masterbatches (or "masterbatch").
• the copolyamides and compositions according to the invention have a real advantage because they can be used directly, without a complementary washing step after polymerization, since they no longer contain toxic monomers, unlike the copolyamides obtained, for example , from caprolactam. It is observed that the copolyamides according to the invention melt relatively low temperature, especially at melting temperatures between 70 and 170 0 C, preferably between 80 and 150 0 C, or between 80 and 130 0 C. Thus, the The present invention retains all the advantages of copolyamides based on monomers from the petroleum industry while being composed of 100% organic carbon from renewable resources.
• the copolyamides comprise at least two units and correspond to the formula A / (C-diamine). (diacid in Cw).
• the (diamine in C z) denotes a diamine of formula HbN- (CHb) Z-NHb in which z indicates the number of atoms of carbon, or number of carbons, present in the diamine, z being of course an integer strictly greater than O.
• the (diacid in Cw) denotes a diacid of formula HOOC- (CH 2 ) w 2 -COOH in which w indicates the total number of carbon atoms, or number of carbons, present in the diacid, w being of course an integer strictly greater than 2.
• the number of carbons z of the diamine and the number of carbons w of the diacid of the comonomer or unit (diamine in Cz). (C 8 diacid) of the copolyamide according to the invention are preferably each between 4 and 36.
• the diamine in Cz is chosen from butanediamine
• the diacid Cw is selected from succinic acid
• fatty acid dimers Preferred fatty acid dimers and corresponding diamines, which are compounds containing predominantly 36 carbons, are preferred. This is due to their natural origin.
• the molar proportions of (diamine in Cz) and (diacid in Cw) are preferentially stoichiometric.
• the comonomer or unit A, in the general formula A / (diamine in Cz). (diacid in Cw) is obtained from an amino acid, this amino acid being obtained from a renewable raw material, still according to ASTM D6866.
• amino acid A is chosen from 9-aminononanoic acid, 10-aminodecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid and its derivatives, especially N-heptyl-11-aminodecanoic acid. -aminoundecanoic acid, and mixtures thereof.
• (Cw diacid) can be any combination of diamine and diacid possible and, in particular, any combination of diamines and diacids that have been listed above.
• the following monomers 4.4, 4.6, 4.9, 4.7, 4.10, 4.11, 4.12, 4.13, 4.14, 4.16, 4.18, 4.20, 4.22 and 4.36 when considering butane diamine.
• copolyamides are of particular interest: they are copolyamides corresponding to one of the formulas chosen from 11 / 9.18, 11 / 10.9, 11 / 10.10, 11 / 10.13, 11 / 10.14, 11 /10.18, 11 / 9.36 and 11 / 10.36. Indeed, such copolyamides, according to their composition, and more specifically the molar proportions of A on the one hand and (diamine in Cz).
• melting Cw may have a melting temperature, measured by DSC (Differential Scanning Calorimetry), which is between 70 0 C and 170 0 C, preferably between 80 ° C and 150 0 C, and a melt flow index (MFI) of between 1 and 80 g / 10 min (2.16 kg -180 ° C).
• DSC Different Scanning Calorimetry
• these copolyamides alone or mixed with one or more other polymers derived from renewable resources according to the ASTM standard D6866, such as poly lactic acid (PLA), poly glycolic acid, polyhydroxyalkanoates and polysaccharides, the latter can be modified and / or formulated, can form adhesives, used in the textile or automotive industry.
• PVA poly lactic acid
• poly glycolic acid polyhydroxyalkanoates
• polysaccharides the latter can be modified and / or formulated, can form adhesives, used in the textile or automotive industry.
• the comonomer or unit A in the general formula A / (diamine in Cz). (diacid in Cw) is a unit corresponding to the formula (diamine in Cx).
• x indicating the number of carbon atoms, or number of carbon, present in the diamine of formula HbN- (CHb) x -NHb and y indicating the number of carbon atoms, or number of carbons present in the diacid of formula HOOC- (CH 2 ) y 2 -
• x and y are, of course, integers, x being strictly greater than O and y being strictly greater than 2.
• x and y are preferably between 4 and 36.
• copolyamides according to their composition, have a melting temperature, measured by DSC (Differential Scanning Calorimetry), which is included between 70 ° C. and 170 ° C., advantageously between 80 ° C. and 150 ° C., and a melt flow index (MFI) of between 1 and 80 g / 10 min (2.16 kg -180 ° C.).
• DSC Different Scanning Calorimetry
• the comonomer or unit A could also be obtained from a lactam, a mixture of two or more lactams, this or these lactams which can also be in admixture with one, two or more amino acid (s).
• the copolyamides further comprise at least one third comonomer or unit, thus fulfilling the following general formulation:
• the (diamine in Ct) denotes a diamine of formula H 2 N- (CH 2 ) I -NH 2 in which t indicates the number of carbon atoms present in the diamine, t being of course a number Integer strictly greater than 0.
• the (diacid in Cu) denotes a diacid of formula HOOC- (CH 2 ) u 2 -COOH in which u indicates the total number of atoms carbon present in the diacid, u being of course an integer strictly greater than 2.
• the number of carbons t of the diamine and the number of carbons u of the diacid of the comonomer or unit (diamine in Ct). (Cu diacid) of the copolyamide according to the invention are preferably each between 4 and 36.
• diamines and diacids of the comonomer or unit diamine in Ct.
• Cu diacid reference will be made to what has been previously described for the preferred diamines and diacids of the comonomer or unit (Cz diamine).
• the invention also relates to a composition, especially to an adhesive composition, comprising at least one copolyamide according to the first and second aspects of the invention, with the comonomer or unit A being chosen from a unit obtained from an amino acid , a lactam and a unit having the formula (diamine Cx). (diacid in Cy).
• composition may further comprise one or more of each of the following compounds:
• At least a second polymer preferably obtained from a renewable raw material, still according to ASTM D6866.
• This second polymer may in particular be chosen from starch, which may be modified and / or formulated, cellulose or its derivatives such as cellulose acetate or cellulose ethers, poly lactic acid, poly glycolic acid and polyhydroxyalkanoates; at least one additive, preferably of natural origin and renewable according to ASTM D6866, this additive being especially suitable for use among fillers, fibers, dyes, stabilizers, plasticizers, impact modifiers, pigments, brighteners, antioxidants, UV stabilizers and natural waxes such as those commonly used in formulations.
• the comonomers or starting materials envisaged in the present description are effectively linear, nothing forbids to consider that they can in all or part be branched, cycloaliphatic, partially unsaturated, aromatic or aryl aromatic, provided that these comonomers are well obtained from a raw material renewable according to ASTM D6866.
• the C18 dicarboxylic acid may be octadecanoic acid, which is saturated, or octadecenoic acid, which has an unsaturation.
• the copolyamide according to the invention or the composition can be used (e) to manufacture glues or adhesives, in particular hot melt glues of the "HMA" type.
• the latter may be shaped so as to be in the form of a film, powder, filaments (monofilament or multifilament), a fabric nonwoven, pellet or net.
• copolyamides and compositions of the invention may be manufactured according to the usual methods described in the prior art. Reference is made in particular to DE 4318047 or US 6 143 862. The present invention will now be described in the examples below, such examples being given for illustrative purposes only, and obviously not limiting.
• Example B Evaluation of the properties of copolyamides 11 / 10.10 / 10.36, 11 / 10.36 and 10.10 / 10.36 with respect to copolyamide 6 / 6.10 / 6.12
• copolyamides according to the invention melt relatively at low temperature, especially at melting temperatures. between 80 and 150 ° C. Therefore, the present invention retains all the advantages of HMA based on petroleum resources while adding the appearance of 100% organic carbon from renewable resources.
• the melting temperature of the copolyamide according to the invention can be varied as a function of the molar proportion of each of the comonomers or units and / or depending on the nature of the monomers (amino acid, diacid, diamine) used. artwork.
• Example D Example of Composition According to the Invention
• a decrease in the apparent viscosity (melted) is observed.
• the fact of being able to influence the viscosity, in particular to reduce it, can facilitate the processes of transformation and bonding according to the intended application (film, fabric, net, filaments).
• amino acids, diamines and diacids mentioned in the present patent application are currently known to be derived from renewable raw material within the meaning of ASTM D6866.
• 9-Aminononanoic acid can be obtained from oleic acid, for example.
• the 10-aminodecanoic acid can be obtained from decyleneic acid, the latter being itself obtained by metathesis of oleic acid, for example.
• Oleic acid comes from vegetable oils such as palm oil, sunflower, soy, olive ...
• the 11-aminoundecanoic and 12-aminododecanoic acids can be obtained from castor oil, for example.
• the diacids C4 (succinic acid) and C6 (adipic acid) can be obtained from glucose, for example. Glucose can be obtained itself from sugarcane or starch (wheat, maize, potato ). .
• the diacid C9 (azelaic acid) can be obtained from oleic acid, for example by ozonolysis. .
• the diacids C7 (heptanedioic acid) and C10 (sebacic acid) can be obtained from castor oil, for example.
• the diacid C12 (dodecanedioic acid) can be obtained by bio-fermentation of dodecanoic acid, also called lauric acid, lauric acid can be extracted from the rich oil formed kernal palm and coconut, for example .
• the diacid C13 (brassylic acid) can be obtained from erucic acid (especially by ozonolysis), it being specified that erucic acid is found in rapeseed, for example.
• the C14 diacid (tetradecanedioic acid) can be obtained by bio-fermentation of myristic acid, myristic acid can be extracted from the rich oil of kernal palm and coconut, for example.
• the diacid C16 (hexadecanedioic acid) can be obtained by bio-fermentation of palmitic acid, the latter being found in palm oil mainly, for example.
• the diacid C18 (octadecanedioic acid) can be obtained by bio-fermentation of stearic acid, it being specified that stearic acid be present in all vegetable oils but especially in animal fats, for example.
• the diacid C20 (eicosanedioic acid) can be obtained by bio-fermentation of arachidic acid that is found mainly in rapeseed oil, for example.
• the C22 diacid (docosanedioic acid) can be obtained by metathesis of undecylenic acid which is extracted from castor oil, for example.
• C36 diacid is a fatty acid dimer derived from softwood by-products processed by Kraft processes. - For obtaining diamines:
• the diamine C4 (butanediamine) can be obtained by amination of succinic acid.
• diamines that can be used in the context of the present invention, and in particular the C6, C7, C9, C10 and C12 diamines.
• the diamine C5 (pentanediamine) can be obtained enzymatically from lysine.
• copolyamides which may be obtained from amino acids, lactams, diamines and / or diacids, for which will be developed, in the future, synthetic routes from renewable raw materials according to said ASTM D6866 standard.
• copolyamides comprising two or three distinct motifs have been explicitly described.
• copolyamides comprising more than three distinct units for example four or five distinct units, each of these multiple units being obtained either from an amino acid or from a lactam, or with the formula (diamine). (diacid), the different reasons being of course strictly separate two by two.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Proteomics, Peptides & Aminoacids (AREA)
• Polyamides (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesive Tapes (AREA)
• Biological Depolymerization Polymers (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=38474272

Family Applications (1)

Country Status (9)

Families Citing this family (28)

Family Cites Families (11)

• 2007
  • 2007-02-16 FR FR0753319A patent/FR2912753B1/fr active Active
• 2008
  • 2008-02-15 US US12/526,982 patent/US20100105812A1/en not_active Abandoned
  • 2008-02-15 CN CN201410200350.2A patent/CN103937438B/zh active Active
  • 2008-02-15 WO PCT/FR2008/050251 patent/WO2008104719A2/fr active Application Filing
  • 2008-02-15 CN CN200880004989A patent/CN101679627A/zh active Pending
  • 2008-02-15 KR KR1020097019263A patent/KR20090123885A/ko not_active Application Discontinuation
  • 2008-02-15 JP JP2009549844A patent/JP5650909B2/ja active Active
  • 2008-02-15 CA CA002678023A patent/CA2678023A1/fr not_active Abandoned
  • 2008-02-15 EP EP08762099A patent/EP2118170A2/fr not_active Withdrawn
  • 2008-02-18 TW TW097105565A patent/TW200906907A/zh unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events