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    • 专利摘要:
    The invention relates to a composition comprising: - (A) a rigid block and soft block copolymer (TPE), - (B) a non-crosslinked polysiloxane silicone, preferably a non-crosslinked polyorganosiloxane, - optionally (C) a compatibilizer, improving the compatibility between the TPE and the silicone, the compatibilizer (C) being chosen from a polyolefin or a mixture of several polyolefins.
    公开号:FR3076834A1
    申请号:FR1850303
    申请日:2018-01-15
    公开日:2019-07-19
    发明作者:Sebastien Merzlic；Philippe Blondel；Florent Abgrall；Karine Loyen；Damien Rauline；Sebastien-Jun Mougnier
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    ELASTOMERIC THERMOPLASTIC COMPOSITION - SILICONE
    TECHNICAL AREA
    The present invention relates to thermoplastic elastomer-silicone polymer compositions as well as articles made from these compositions.
    TECHNICAL BACKGROUND
    Elastomeric thermoplastic polymers (TPE) such as thermoplastic polyurethanes (TPU) or copolymers with polyamide blocks and polyether blocks (PEBA) are used in various applications such as sports, electronics, optics, automotive, and appliances. Their typical hardness is from 25 to 80 Shore D. Their main advantages are their processability (that is to say ease of implementation in injection molding and extrusion), their elastomeric mechanical properties, their high resilience, their good resistance. impact and their low density.
    However, existing VSEs have certain limitations:
    -it is not possible to target a hardness (in Shore D) less than 25 shore D, or (in Shore A) a hardness less than 80 shore A, while keeping good processability especially in injection;
    - the exudation of low molecular weight components is observed, in particular for the flexible grades, with a high rate of flexible polyether blocks, in particular due to the limited compatibility between the blocks of hard polyamide and the flexible polyether blocks;
    -they have limited resistance to abrasion;
    - they have low chemical resistance to oily components such as sebum;
    -They have limited resistance to soiling, i.e. color transfer from an external product
    -they have limited thermomechanical resistance;
    their haptic properties are not entirely satisfactory.
    In contrast, silicone-based materials are generally used in consumer applications due to a number of advantages:
    - low hardness (<80 shore A);
    -good haptic properties;
    -good chemical resistance, in particular to sebum;
    -good thermomechanical properties.
    Their processability is their main drawback, because of the long cycle times required. Their mechanical properties (tear resistance, abrasion resistance) are limited. In addition, their bond or compatibility with other thermoplastics is generally poor or requires the use of a primer or compatibilizer.
    There is therefore a need for polymer systems without the various drawbacks mentioned above, for the manufacture of a material having a good compromise between:
    - the flexibility and durability of the TPE material: abrasion and tear resistance, sufficient chemical and mechanical resistance for repeated common use, and
    - the esthetics and the soft and silky touch (in particular "peach skin"), expected by the users.
    The present invention targets at least some, if not most, of the following properties, the measurement standards of which are specified below in Table 2 of this description:
    - Hardness, instantaneous (Shore A) <80
    - Hardness, 15 s (Shore A) <75
    - Tensile tests, strain stress of 25% (MPa) <2.0
    - Tensile test, stress at 100% deformation (MPa) <4.0
    - Tensile test, tensile strength (MPa)> 10
    - Tensile test, Elongation at break (%)> 500
    - Flexural modulus (MPa) <or = 12
    - Tear resistance (kN / m)> 40
    - Taber abrasion resistance - H18 grinding wheel (mass loss in mg / 1000 revolutions) <50
    - Taber abrasion resistance - CS10 grinding wheel (mass loss in mg / 1000 revolutions)
    - Remanent compression deformation at 23 ° C (%) <20
    - Ease of implementation and demolding.
    - Recyclability
    - Density <1.00
    - Resistance to exudation
    - Chemical resistance (including sebum)
    - Resistance to stains and soiling.
    SUMMARY OF THE INVENTION
    The subject of the present invention is therefore a composition comprising:
    - (A) a copolymer with rigid blocks and flexible blocks (TPE),
    - (B) a non-crosslinked silicone, that is to say polysiloxane, such as linear polydimethylsiloxane, preferably a polyorganosiloxane
    - Optionally (C) a compatibilizer, improving the compatibility between TPE and silicone, and advantageously chosen from a polyolefin or a mixture of several polyolefins.
    Advantageously, said rigid blocks comprise at least one block chosen from: polyamide, polyurethane, polyester, and their copolymers. Advantageously, said flexible blocks comprise at least one block chosen from: polyether, polyester, polysiloxane, polyolefin, polycarbonate, and their copolymers.
    Preferably, the block copolymer is chosen from copolymers with polyester blocks and polyether blocks, copolymers with polyurethane blocks and polyether blocks and copolymers with polyamide blocks and polyether blocks, and preferably it is a copolymer with polyamide blocks and blocks polyether.
    According to one embodiment, the weight ratio of TPE (A) relative to silicone (B) is from 10:90 to 95: 5, preferably 50:50 to 90:10, or even better from 60:40 to 85 15.
    Preferably, the composition of the invention comprises, by weight:
    - from 55 to 95% of copolymer (A), preferably from 60 to 80%,
    - from 5 to 45% of silicone (B), preferably from 10 to 40%, possibly
    - from 0 to 45% of compatibilizer (C), preferably from 5 to 30%,
    - from 0 to 15% of additives (D), preferably from 0.1 to 10%, on the total weight of the composition, this being 100%.
    The percentage by weight of silicone is thus fixed to improve the abrasion resistance, touch and soil resistance properties of the product. This solution also makes it possible to eliminate the phenomena of exudation observed on the most flexible TPEs and to facilitate the implementation of the product, the silicone limiting the adhesion of the mixture to the metal walls.
    According to one embodiment, the flexible blocks are polyether blocks in the copolymer (A), and are preferably polytetramethylene glycol blocks.
    According to one embodiment, the rigid blocks are polyamide blocks in the copolymer (A), and are preferably PA 11 or PA 12 blocks.
    According to one embodiment, the number-average molar mass Mn of the flexible blocks, in particular polyether, is greater than 800 g / mol, preferably greater than 1000 g / mol, preferably greater than 1200 g / mol, preferably greater than 1400 g / mol, preferably greater than 1600 g / mol, preferably greater than 1800 g / mol and preferably greater than or equal to 2000 g / mol
    Advantageously, the weight ratio of the rigid blocks, in particular polyamide, to the flexible blocks, in particular polyether, in the copolymer (A) is less than or equal to 1.2, preferably less than or equal to 1, preferably less than or equal to 0.8 and preferably less than or equal to 0.5.
    According to one embodiment, the composition of the invention further comprises one or more additives (D).
    The invention also relates to a process for manufacturing the above composition, comprising the production of the mixture of at least one block copolymer (A) and of a non-crosslinked silicone. According to one embodiment, the method is carried out in a mixing device in the molten state, preferably in a twin-screw extruder, preferably at a temperature of the order of 150 to 250 ° C, preferably 160 ° C to 220 ° C.
    The invention also relates to an article comprising at least one part having a composition in accordance with the present invention.
    According to one embodiment, the article is produced by a manufacturing process involving a step of injection molding, overmolding, extrusion or co-extrusion of the composition according to the invention.
    The applications of the composition according to the invention advantageously include consumer products containing a flexible part exposed to daily wear and tear (shoes, interior decorative parts in cars), a part in regular contact with the skin (glasses, medical, electronics ) or industry (conveyor belts).
    According to one embodiment, the article is an electrical or electronic article comprising a protective casing or casing made from the composition according to the invention, said article preferably being a laptop computer, a mobile phone or a tablet.
    The present invention overcomes the drawbacks of the prior art. In particular, the invention provides compositions combining the advantageous properties of TPEs and silicones and in particular:
    -good formability (in injection molding and extrusion),
    -elastomeric mechanical properties,
    -high resilience,
    - low density,
    - low hardness,
    -good abrasion resistance,
    -good compression properties,
    -good haptic and aesthetic properties;
    -good chemical resistance, in particular to sebum;
    -high thermomechanical properties;
    good properties of adhesion to other materials such as polyamides, including polyamides mixed with fillers such as glass fibers, polyether block amides (PEBA), copolyetheresters (COPE), thermoplastic polyurethanes (TPU), polycarbonate (PC), ABS and PC-ABS.
    This is achieved by providing a thermoplastic elastomer in the form of a composition according to the invention, based on TPE, preferably based on PEBA, and on non-crosslinked silicone.
    It has proven particularly advantageous to use a copolymer (A) in which the flexible blocks, preferably polyether, have a relatively high molar mass. Without wishing to be bound by theory, it is assumed that the polyether blocks aid compatibility with the non-crosslinked silicones of the composition according to the invention.
    DESCRIPTION OF EMBODIMENTS
    The invention is now described in more detail and without limitation in the description which follows.
    In the present description, it is specified that when reference is made to intervals, the expressions of the type "going from ... to" or "comprising / comprising from ... to" include the limits of the interval. Conversely, expressions of the type "between ... and ..." exclude the limits of the interval.
    Unless otherwise stated, the percentages expressed are mass percentages. Unless otherwise stated, the parameters to which reference is made are measured at atmospheric pressure and ambient temperature (20-25 ° C, generally 23 ° C).
    The composition of the present invention is a thermoplastic elastomer, obtained by mixing a TPE (A) and a non-crosslinked silicone (B), and optionally a compatibilizing polymer (C), improving the compatibility between the TPE and the silicone.
    The composition according to the invention is an intimate mixture or alloy of polymers, that is to say a macroscopically homogeneous mixture of at least two polymers (A) and (B), or even polymers (A), (B) and (C).
    Additional components, such as various additives (D) can also be added to the composition according to the invention.
    Copolymer (A):
    By block copolymer according to the invention is meant thermoplastic elastomeric polymers (TPE), which comprise, alternately, so-called hard or rigid blocks or segments (with a rather thermoplastic behavior) and so-called flexible or flexible blocks or segments (at rather elastomeric behavior). For example, polyamide blocks are known to be so-called rigid segments with a melting temperature (Tf) or glass transition temperature (Tg) higher than the temperature of use of the polymer, while polyether blocks are so-called flexible segments at Tf or Tg lower than the temperature of use of said polymer.
    More specifically, a block is said to be “flexible” if it has a low glass transition temperature (Tg). By low glass transition temperature is meant a glass transition temperature Tg of less than 15 ° C, preferably less than 0 ° C, advantageously less than -15 ° C, even more advantageously at -30 ° C, possibly less than - 50 ° C.
    By flexible or soft blocks which can be envisaged in the copolymer according to the invention, is meant in particular those chosen from polyether blocks, polyester blocks, polysiloxane blocks, such as polydimethylsiloxane or PDMS blocks, polyolefin blocks, polycarbonate blocks, and their mixtures. The flexible blocks that can be envisaged are described for example in French patent application n °: 0950637 page 32 line 3 to page 38 line 23. By way of example, the polyether blocks are chosen from poly (ethylene glycol) (PEG), poly (1,2-propylene glycol) (PPG), poly (1,3-propylene glycol) (PO3G), poly (tetramethylene glycol) (PTMG), and their copolymers or mixtures.
    The rigid blocks can be based on polyamide, polyurethane, polyester or a mixture of these polymers. These blocks are described in particular in French patent application No. 0856752. The rigid blocks are preferably based on polyamide. The polyamide blocks (abbreviated PA) may contain homopolyamides or copolyamides. The polyamide blocks which can be envisaged in the composition of the invention are in particular those defined in application FR0950637 from page 27 line 18 to page 31 line 14.
    Advantageously, said at least one block copolymer comprises at least one block chosen from: polyether blocks, polyester blocks, polyamide blocks, polyurethane blocks, and mixtures thereof. By way of example of a copolymer with rigid blocks and flexible blocks, mention may be made respectively of (a) copolymers with polyester blocks and polyether blocks (also called COPE or copolyetheresters), (b) copolymers with polyurethane blocks and polyether blocks (called also TPU abbreviation of thermoplastic polyurethanes) and (c) copolymers with polyamide blocks and polyether blocks (also called PEBA according to IUPAC, or even polyether-block amide).
    Preferably, said at least one block copolymer (A) comprises a copolymer with polyamide blocks and polyether blocks (PEBA).
    PEBAs result from the polycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia polycondensation:
    1) polyamide blocks with diamine chain ends with polyoxyalkylene blocks with dicarboxylic chain ends;
    2) polyamide blocks with ends of dicarboxylic chains with polyoxyalkylene blocks with ends of diamine chains, obtained for example by cyanoethylation and hydrogenation of polyoxyalkylene blocks α, ω- aliphatic dihydroxylates called polyetherdiols
    J
    3) of polyamide blocks having dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.
    The polyamide blocks with dicarboxylic chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid. The polyamide blocks with diamine chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain limiting diamine.
    Three types of polyamide blocks can advantageously be used.
    According to a first type, the polyamide blocks originate from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms, and from an aliphatic or aromatic diamine. , in particular those having from 2 to 20 carbon atoms, preferably those having from 6 to 14 carbon atoms.
    As examples of dicarboxylic acids, mention may be made of 1,4cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acid and terephthalic and isophthalic acids, but also dimerized fatty acids.
    As examples of diamines, mention may be made of tetramethylene diamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylene diamine, isomers of bis- (4-aminocyclohexyl) -methane (BACM), bis - (3-methyl-4aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4aminocyclohexyl) -propane (BMACP), para-amino-di-cyclo-hexyl-methane (PACM), l 'isophoronediamine (IPDA), 2,6-bis- (aminomethyl) -norbornane (BAMN) and piperazine (Pip).
    Advantageously, polyamide blocks PA 4.12, PA 4.14, PA 4.18, PA 6.10, PA 6.12, PA 6.14, PA 6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18 are used. In the notation PA X.Y, X represents the number of carbon atoms derived from diamine residues, and Y represents the number of carbon atoms derived from diacid residues, in a conventional manner.
    According to a second type, the polyamide blocks result from the condensation of one or more α, ω-aminocarboxylic acids and / or of one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to 12 carbon atoms or a diamine. Examples of lactams include caprolactam, enantholactam and lauryllactam. By way of examples of α, ω-amino carboxylic acid, mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids.
    Advantageously, the polyamide blocks of the second type are PA 11 (polyundecanamide), PA 12 (polydodecanamide) or PA 6 (polycaprolactam) blocks. In the notation PA X, X represents the number of carbon atoms originating from the amino acid residues.
    According to a third type, the polyamide blocks result from the condensation of at least one α, ω-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
    In this case, the polyamide PA blocks are prepared by polycondensation:
    - linear or aromatic aliphatic diamine (s) having X carbon atoms;
    - Carboxylic acid (s) having Y carbon atoms; and
    - the comonomer (s) {Z}, chosen from lactams and α, ωaminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X1 carbon atoms and at least one dicarboxylic acid having Y1 atoms of carbons, (X1, Y1) being different from (X, Y),
    - Said comonomer (s) {Z} being introduced in a proportion by weight ranging advantageously up to 50%, preferably up to 20%, even more advantageously up to 10% relative to all of the polyamide precursor monomers;
    - In the presence of a chain limiter chosen from dicarboxylic acids.
    Advantageously, the chain limiter is used the dicarboxylic acid having Y carbon atoms, which is introduced in excess relative to the stoichiometry of the diamine (s).
    According to a variant of this third type, the polyamide blocks result from the condensation of at least two α, ω-aminocarboxylic acids or of at least two lactams having from 6 to 12 carbon atoms or from a lactam and a aminocarboxylic acid not having the same number of carbon atoms in the possible presence of a chain limiter. As examples of α, ipaminocarboxylic aliphatic acid, mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids. Examples of lactams include caprolactam, enantholactam and lauryllactam. As examples of aliphatic diamines, mention may be made of hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylene diamine. As examples of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid. Mention may be made, as examples of aliphatic diacids, of butane-dioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids and dimerized fatty acids. These dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated; these are for example products marketed under the PRIPOL brand by the company CRODA, or under the EMPOL brand by the company BASF, or under the Radiacid brand by the company OLEON, and polyoxyalkylenes α, ω-diacids. Mention may be made, as examples of aromatic diacids, of terephthalic (T) and isophthalic (I) acids. As examples of cycloaliphatic diamines, mention may be made of the isomers of bis- (4aminocyclohexyl) -methane (BACM), bis- (3-methyl-4-aminocyclohexyl) methane (BMACM) and 2-2-bis- (3 -methyl-4-aminocyclohexyl) -propane (BMACP), and paraamino-di-cyclo-hexyl-methane (PACM). Other commonly used diamines can be isophoronediamine (IPDA), 2,6-bis- (aminomethyl) norbornane (BAMN) and piperazine.
    As examples of polyamide blocks of the third type, the following may be cited:
    - PA 6.6 / 6, where 6.6 denotes hexamethylenediamine units condensed with adipic acid and 6 denotes units resulting from the condensation of caprolactam;
    PA 6.6 / 6.10 / 11/12, where 6.6 denotes hexamethylenediamine condensed with acid-adipic acid, 6.10 denotes hexamethylenediamine condensed with sebacic acid, 11 denotes units resulting from the condensation of aminoundecanoic acid and 12 designates patterns resulting from the condensation of lauryllactam.
    PA X / Y, PA X / Y / Z, etc. relate to copolyamides in which X, Y, Z, etc. represent homopolyamide units as described above.
    Advantageously, the polyamide blocks of the copolymer used in the invention comprise polyamide blocks PA 6, PA 11, PA 12, PA 5.4, PA 5.9, PA
    5.10, PA 5.12, PA 5.13, PA 5.14, PA 5.16, PA 5.18, PA 5.36, PA 6.4, PA 6.9, PA
    6.10, PA6.12, PA6.13, PA6.14, PA6.16, PA6.18, PA6.36, PA 10.4, PA 10.9, PA 10.10, PA 10.12, PA 10.13, PA 10.14, PA 10.16, PA 10.18, PA 10.36, PA 10.T, PA 12.4, PA 12.9, PA 12.10, PA 12.12, PA 12.13, PA 12.14, PA 12.16, PA 12.18, PA 12.36, PA 12.T, or mixtures or copolymers thereof; and preferably comprise polyamide blocks PA 6, PA 11, PA 12, PA
    6.10, PA 10.10, PA 10.12, or mixtures or copolymers thereof.
    Polyether blocks are made up of alkylene oxide units. The polyether blocks may in particular be PEG blocks (polyethylene glycol), that is to say made up of ethylene oxide units, and / or PPG blocks (propylene glycol), that is to say made up of propylene oxide units, and / or PO3G blocks (polytrimethylene glycol), that is to say made up of polytrimethylene ether glycol units, and / or PTMG blocks, that is to say made up of tetramethylene glycol units also called polytetrahydrofuran. PEBA copolymers can comprise in their chain several types of polyethers, the copolyethers possibly being block or random.
    It is also possible to use blocks obtained by oxyethylation of bisphenols, such as for example bisphenol A. These latter products are described in particular in document EP 613919.
    The polyether blocks can also consist of ethoxylated primary amines. By way of example of ethoxylated primary amines, mention may be made of the products of formula:
    H - i OCH ; CH ; u - N— * C'H ; CH ; OR - H 'Z * · TT rw.
    in which m and n are integers between 1 and 20 and x an integer between 8 and 18. These products are for example commercially available under the brand name NORAMOX® from the company CECA and under the brand GENAMIN® from the company Clariant.
    The flexible polyether blocks can comprise polyoxyalkylene blocks with NH 2 chain ends, such blocks being able to be obtained by cyanoacetylation of polyoxyalkylene α, ω-dihydroxylated aliphatic blocks called polyetherdiols. More particularly, the commercial products Jeffamine or Elastamine can be used (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from the company Huntsman, also described in documents JP 2004346274, JP 2004352794 and EP 1482011).
    The polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or aminated to be transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends. The general method for preparing two-stage PEBA copolymers having ester bonds between the PA blocks and the PE blocks is known and is described, for example, in document FR 2846332. The general method for preparing the PEBA copolymers of the invention having amide bonds between the PA blocks and the PE blocks is known and described, for example in document EP 1482011. The polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to prepare polymers with polyamide blocks and polyether blocks having randomly distributed patterns (one-step process).
    Of course, the designation PEBA in the present description of the invention relates as well to PEBAX® marketed by Arkema, to Vestamid® marketed by Evonik®, to Grilamid®, to Griflex marketed by EMS, as to Pelestat® type PEBA marketed by Sanyo or any other PEBA from other suppliers.
    If the block copolymers described above generally comprise at least one polyamide block and at least one polyether block, the present invention also covers all the copolymer alloys comprising two, three, four (or even more) different blocks chosen from those described in this description.
    For example, the copolymer according to the invention can be a segmented block copolymer comprising three different types of blocks (or "triblock"), which results from the condensation of several of the blocks described above. Said triblock is preferably chosen from copolyetheresteramides and copolyetheramideurethanes.
    PEBA copolymers which are particularly preferred in the context of the invention are: PA12-PEG, PA6-PEG, PA6 / 12-PEG, PA11-PEG, PA12-PTMG, PA6-PTMG, PA6 / 12-PTMG, PA11-PTMG, PA12-PEG / PPG, PA6-PEG / PPG, PA6 / 12PEG / PPG, PA11-PEG / PPG, PA11 / PO3G, PA6.10 / PO3G and / or PA10.10 / PO3G.
    Preferably, the PA blocks comprise at least 30%, preferably at least 50%, preferably at least 75%, preferably 100% by weight of PA 11 and / or PA 12 with regard to the total weight of the PA blocks .
    The polyether blocks preferably represent 50% to 80% of the total weight of the block copolymer (A) used in the composition according to the invention.
    Advantageously, the number-average molar mass of the polyamide blocks in the PEBA copolymer is from 200 to 2000 g / mol; the number-average molar mass of the polyether blocks is from 800 to 2500 g / mol; and the mass ratio of the polyamide blocks to the polyether blocks of the copolymer is from 0.1 to 1.2.
    The number-average molar mass is fixed by the content of chain limiter. It can be calculated according to the relation:
    Mn = (nmonomer / nlimitor) * M repeating pattern + Mlimiter nmonomer = number of moles of monomer nlimitor = number of moles of excess diacid
    M repeat pattern = Molar mass of the repeat pattern
    Mlimitor = Molar mass of excess diacid
    According to particular embodiments, the copolymers are defined by the following ranges of number-average molar masses M n :
    M n of block polyamides M n of polyether blocks # 1 200 to 300 g / mol 800 to 1000 g / mol # 2 300 to 400 g / mol 800 to 1000 g / mol # 3 400 to 500 g / mol 800 to 1000 g / mol # 4 500 to 600 g / mol 800 to 1000 g / mol N ° 5 600 to 700 g / mol 800 to 1000 g / mol N ° 6 700 to 800 g / mol 800 to 1000 g / mol
    M n of block polyamides M n of polyether blocks # 7 800 to 900 g / mol 800 to 1000 g / mol # 8 900 to 1000 g / mol 800 to 1000 g / mol N ° 9 200 to 300 g / mol 1000 to 1200 g / mol # 10 300 to 400 g / mol 1000 to 1200 g / mol # 11 400 to 500 g / mol 1000 to 1200 g / mol # 12 500 to 600 g / mol 1000 to 1200 g / mol N ° 13 600 to 700 g / mol 1000 to 1200 g / mol N ° 14 700 to 800 g / mol 1000 to 1200 g / mol # 15 800 to 900 g / mol 1000 to 1200 g / mol N ° 16 900 to 1000 g / mol 1000 to 1200 g / mol N ° 17 1000 to 1100 g / mol 1000 to 1200 g / mol N ° 18 200 to 300 g / mol 1200 to 1400 g / mol N ° 19 300 to 400 g / mol 1200 to 1400 g / mol # 20 400 to 500 g / mol 1200 to 1400 g / mol # 21 500 to 600 g / mol 1200 to 1400 g / mol N ° 22 600 to 700 g / mol 1200 to 1400 g / mol N ° 23 700 to 800 g / mol 1200 to 1400 g / mol N ° 24 800 to 900 g / mol 1200 to 1400 g / mol N ° 25 900 to 1000 g / mol 1200 to 1400 g / mol N ° 26 1000 to 1100 g / mol 1200 to 1400 g / mol N ° 27 1100 to 1200 g / mol 1200 to 1400 g / mol # 28 1200 to 1300 g / mol 1200 to 1400 g / mol N ° 29 200 to 300 g / mol 1400 to 1600 g / mol N ° 30 300 to 400 g / mol 1400 to 1600 g / mol # 31 400 to 500 g / mol 1400 to 1600 g / mol N ° 32 500 to 600 g / mol 1400 to 1600 g / mol # 33 600 to 700 g / mol 1400 to 1600 g / mol N ° 34 700 to 800 g / mol 1400 to 1600 g / mol N ° 35 800 to 900 g / mol 1400 to 1600 g / mol N ° 36 900 to 1000 g / mol 1400 to 1600 g / mol N ° 37 1000 to 1100 g / mol 1400 to 1600 g / mol N ° 38 1100 to 1200 g / mol 1400 to 1600 g / mol N ° 39 1200 to 1300 g / mol 1400 to 1600 g / mol N ° 40 1300 to 1400 g / mol 1400 to 1600 g / mol
    M n of block polyamides M n of polyether blocks # 41 1400 to 1500 g / mol 1400 to 1600 g / mol N ° 42 200 to 300 g / mol 1600 to 1800 g / mol N ° 43 300 to 400 g / mol 1600 to 1800 g / mol # 44 400 to 500 g / mol 1600 to 1800 g / mol N ° 45 500 to 600 g / mol 1600 to 1800 g / mol N ° 46 600 to 700 g / mol 1600 to 1800 g / mol N ° 47 700 to 800 g / mol 1600 to 1800 g / mol N ° 48 800 to 900 g / mol 1600 to 1800 g / mol N ° 49 900 to 1000 g / mol 1600 to 1800 g / mol N ° 50 1000 to 1100 g / mol 1600 to 1800 g / mol N ° 51 1100 to 1200 g / mol 1600 to 1800 g / mol N ° 52 1200 to 1300 g / mol 1600 to 1800 g / mol N ° 53 1300 to 1400 g / mol 1600 to 1800 g / mol N ° 54 1400 to 1500 g / mol 1600 to 1800 g / mol N ° 55 200 to 300 g / mol 1800 to 2000 g / mol N ° 56 300 to 400 g / mol 1800 to 2000 g / mol N ° 57 400 to 500 g / mol 1800 to 2000 g / mol N ° 58 500 to 600 g / mol 1800 to 2000 g / mol N ° 59 600 to 700 g / mol 1800 to 2000 g / mol N ° 60 700 to 800 g / mol 1800 to 2000 g / mol N ° 61 800 to 900 g / mol 1800 to 2000 g / mol N ° 62 900 to 1000 g / mol 1800 to 2000 g / mol N ° 63 1000 to 1100 g / mol 1800 to 2000 g / mol N ° 64 1100 to 1200 g / mol 1800 to 2000 g / mol N ° 65 1200 to 1300 g / mol 1800 to 2000 g / mol N ° 66 1300 to 1400 g / mol 1800 to 2000 g / mol N ° 67 1400 to 1500 g / mol 1800 to 2000 g / mol N ° 68 200 to 300 g / mol 2000 to 2200 g / mol N ° 69 300 to 400 g / mol 2000 to 2200 g / mol N ° 70 400 to 500 g / mol 2000 to 2200 g / mol N ° 71 500 to 600 g / mol 2000 to 2200 g / mol N ° 72 600 to 700 g / mol 2000 to 2200 g / mol N ° 73 700 to 800 g / mol 2000 to 2200 g / mol N ° 74 800 to 900 g / mol 2000 to 2200 g / mol
    M n of block polyamides M n of polyether blocks N ° 75 900 to 1000 g / mol 2000 to 2200 g / mol N ° 76 1000 to 1100 g / mol 2000 to 2200 g / mol N ° 77 1100 to 1200 g / mol 2000 to 2200 g / mol N ° 78 1200 to 1300 g / mol 2000 to 2200 g / mol N ° 79 1300 to 1400 g / mol 2000 to 2200 g / mol N ° 80 1400 to 1500 g / mol 2000 to 2200 g / mol N ° 81 200 to 300 g / mol 2200 to 2500 g / mol N ° 82 300 to 400 g / mol 2200 to 2500 g / mol N ° 83 400 to 500 g / mol 2200 to 2500 g / mol N ° 84 500 to 600 g / mol 2200 to 2500 g / mol N ° 85 600 to 700 g / mol 2200 to 2500 g / mol N ° 86 700 to 800 g / mol 2200 to 2500 g / mol N ° 87 800 to 900 g / mol 2200 to 2500 g / mol N ° 88 900 to 1000 g / mol 2200 to 2500 g / mol N ° 89 1000 to 1100 g / mol 2200 to 2500 g / mol N ° 90 1100 to 1200 g / mol 2200 to 2500 g / mol N ° 91 1200 to 1300 g / mol 2200 to 2500 g / mol N ° 92 1300 to 1400 g / mol 2200 to 2500 g / mol N ° 93 1400 to 1500 g / mol 2200 to 2500 g / mol
    Preferably, the mass ratio of the polyamide blocks relative to the polyether blocks of the copolymer is from 0.1 to 1.2. This mass ratio can be calculated by dividing the average molar mass in number of the polyamide blocks by the average molar mass in number of the polyether blocks.
    According to particular embodiments, this ratio is from 0.1 to 0.2; or from 0.2 to 0.3; or from 0.3 to 0.4; or from 0.4 to 0.5; or from 0.5 to 0.6; or from 0.6 to 0.7; OU from 0.7 to 0.8; or from 0.8 to 0.9.
    Preferably, the copolymer used in the invention has an instantaneous hardness less than or equal to 45 Shore D, more preferably less than or equal to 35 Shore D, more preferably still less than or equal to 25 Shore D. The hardness measurements can be performed according to ISO 868.
    Advantageously, the copolymer has an inherent viscosity of 2 or less; preferably 1.5 or less; preferably 1.4 or less; preferably 1.3 or less; preferably 1.2 or less. In the present description, the inherent viscosity is determined according to standard ISO 307: 2007 in m-cresol at a temperature of 20 ° C., at a polymer concentration of 0.5% by weight in solution in metacresol over weight total solution, using an Ubbelohde viscometer.
    Silicone (B)
    The silicone or “polysiloxane” used in the composition of the present invention is non-crosslinked and non-crosslinkable. It can advantageously be polyorganosiloxane comprising one or more organic chains, or even comprise groups, preferably polar functions, which promote its compatibility or its mixture with the other components, in particular TPE, of the present composition.
    For the purposes of the present invention, the following are understood:
    - By "non-crosslinked silicone", a silicone which is neither crosslinked nor crosslinkable, even in situ, in the composition according to the invention or during its use to obtain the final product. In particular, the term “non-crosslinked / non-crosslinkable silicone” means a silicone not containing alkenyl groups having from 2 to 20 carbon atoms in the molecule, in particular a silicone not containing any group: vinyl, allyl, butenyl, pentenyl, hexenyl or decenyl capable of causing the silicone to crosslink.
    This requirement for the silicone of the present composition not only ensures the processing capacity (processability), the ease of implementation, but also the recyclability of the composition according to the invention.
    - By "polysiloxane", a polymer comprising a polymer backbone composed of repeating siloxy units - (Si (R2) -O -) - which may be units, cyclic, linear or branched, for example lower dialkyl units siloxy such as in particular dimethylsiloxy units and optionally organic side groups.
    The organic groups (i.e., non-alkenyl) bonded through silicon are preferably independently derived from hydrocarbons or halogenated hydrocarbon groups which contain no aliphatic unsaturation. These can be specifically illustrated by alkyl groups having from 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl and hexyl; cycloalkyl groups such as cyclohexyl and cycloheptyl; aryl groups of 6 to 12 carbon atoms, such as phenyl, tolyl and xylyl; aralkyl groups of 7 to 20 carbon atoms, such as benzyl and phenethyl; and halogenated alkyl groups having from 1 to 20 carbon atoms, such as 3,3,3-trifluoropropyl and chloromethyl.
    Mention may in particular simply be made of linear polydimethylsiloxane (PDMS).
    - by "polyorganosiloxane", a polymer which combines repeating siloxy units - (Si (R2) -O -) - silicones with hydrocarbons or repeating units with main hydrocarbon chain. It can then be copolymers. An example of interest is polysiloxane-co-urethane (for example in the Carbosil® range from DSM). It can also be a branched copolymer. An example is the CoatOSil® range from Momentive, which carries a polyether group pendant on a silicone skeleton. Conversely, a branched hydrocarbon skeleton of silicone chain is also possible and included in the definition of the polyorganosiloxane usable in the composition according to the invention.
    - by “polar poly (organo) siloxane”, a poly (organo) siloxane having at least one polar radical, the polar radical being present at one of the ends of the poly (organo) siloxane skeleton or on the poly ( organo) siloxane.
    - “polar radical” means a radical which confers polar properties on the organopolysiloxane. Examples of polar radicals according to the present invention are: hydroxy, hydroxyl, urea, amine, amide, carboxylate, ester, ether, acrylate, thiol, sulfonate, sulfate, and phosphate. By way of example, mention may be made of the Baysilone® range from Momentive, which in particular comprises an amine-functionalized polyorganosiloxane.
    The compatibilizer (C):
    The compatibilizer is advantageously constituted by a polymer having a flexural modulus of less than 100 MPa measured according to standard ISO 178 and of Tg of less than 0 ° C (measured according to standard 11357-2 at the point of inflection of the DSC thermogram) , in particular a polyolefin.
    The polyolefin of the compatibilizer can be functionalized or non-functionalized or be a mixture of at least one functionalized and / or at least one non-functionalized. To simplify, the polyolefin has been designated by (C) and functionalized polyolefins (C1) and non-functionalized polyolefins (C2) have been described below.
    A non-functionalized polyolefin (C2) is conventionally a homopolymer or copolymer of alpha olefins or of diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene. As an example, we can cite
    - homopolymers and copolymers of polyethylene, in particular LDPE, HDPE, LLDPE (linear low density polyethylene, VLDPE (very low density polyethylene, or polyethylene very low density) and metallocene polyethylene.
    - homopolymers or copolymers of propylene.
    - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
    - block copolymers of styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS).
    - copolymers of ethylene with at least one product chosen from the salts or esters of unsaturated carboxylic acids such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of carboxylic acids saturated such as vinyl acetate (EVA), the proportion of comonomer up to 40% by weight.
    The functionalized polyolefin (C1) can be a polymer of alpha olefins having reactive units (functionalities); such reactive units are the acid, anhydride or epoxy functions. By way of example, mention may be made of the preceding polyolefins (C2) grafted or co- or ter polymerized by unsaturated epoxides such as glycidyl (meth) acrylate, or by carboxylic acids or the corresponding salts or esters such as l (meth) acrylic acid (this can be totally or partially neutralized by metals such as Zn, etc.) or also by anhydrides of carboxylic acids such as maleic anhydride. A functionalized polyolefin is for example a PE / EPR mixture, the weight ratio of which can vary within wide limits, for example between 40/60 and 90/10, said mixture being co-grafted with an anhydride, in particular maleic anhydride, according to a grafting rate for example of 0.01 to 5% by weight.
    The functionalized polyolefin (C1) can be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the grafting rate is for example from 0.01 to 5% by weight
    - PE, PP, copolymers of ethylene with propylene, butene, hexene, or octene containing for example from 35 to 80% by weight of ethylene;
    - ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
    - block copolymers of styrene / ethylene-butene / styrene (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), styrene / ethylene-propylene / styrene (SEPS).
    - ethylene and vinyl acetate (EVA) copolymers, containing up to 40% by weight of vinyl acetate;
    - ethylene and alkyl (meth) acrylate copolymers, containing up to 40% by weight of alkyl (meth) acrylate;
    - ethylene and vinyl acetate (EVA) and alkyl (meth) acrylate copolymers, containing up to 40% by weight of comonomers.
    The functionalized polyolefin (C1) can also be chosen from ethylene / propylene copolymers predominantly in propylene grafted with maleic anhydride and then condensed with monoamino polyamide (or a polyamide oligomer) (products described in EP-A-0342066) .
    The functionalized polyolefin (C1) can also be a co- or ter polymer of at least the following units: (1) ethylene, (2) alkyl (meth) acrylate or vinyl ester of saturated carboxylic acid and (3) anhydride such as maleic anhydride or (meth) acrylic acid or epoxy such as glycidyl (meth) acrylate.
    By way of example of functionalized polyolefins of the latter type, mention may be made of the following copolymers, where the ethylene preferably represents at least 60% by weight and where the ter monomer (the function) represents for example from 0.1 to 10% by weight of the copolymer:
    - ethylene / (meth) acrylate / (meth) acrylic acid or maleic anhydride or glycidyl methacrylate copolymers;
    - ethylene / vinyl acetate / maleic anhydride or glycidyl methacrylate copolymers;
    - ethylene / vinyl acetate or (meth) acrylate / (meth) acrylic acid or maleic anhydride or glycidyl methacrylate copolymers.
    In the above copolymers, (meth) acrylic acid can be salified with Zn or Li.
    The term alkyl (meth) acrylate in (C1) or (C2) denotes methacrylates and C1 to C8 alkyl acrylates, and can be chosen from methyl acrylate, ethyl acrylate, l n-butyl acrylate, iso butyl acrylate, ethyl-2-hexyl acrylate, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
    The copolymers mentioned above, (C1) and (C2), can be copolymerized in a statistical or sequenced fashion and have a linear or branched structure.
    The molecular weight, the MFI index, the density of these polyolefins can also vary to a large extent, which a person skilled in the art will appreciate. MFI, short for Melt Flow Index, is the melt flow index. It is measured according to ISO 1133 standard.
    Advantageously, the non-functionalized polyolefins (C2) are chosen from homopolymers or copolymers of polypropylene and any homopolymer of ethylene or copolymer of ethylene and of a comonomer of higher alpha olefinic type such as butene, hexene, octene or 4-methyl 1Pentene. Mention may be made, for example, of PPs, high density PEs, medium density PEs, linear low density PEs, low density PEs, very low density PEs. These polyethylenes are known to those skilled in the art as being produced by a "radical" process, by a "Ziegler" type catalysis or, more recently, by a so-called "metallocene" catalysis.
    Advantageously, the functionalized polyolefins (C1) are chosen from any polymer comprising alpha olefinic units and units carrying polar reactive functions such as epoxy, carboxylic acid or carboxylic acid anhydride functions. As examples of such polymers, mention may be made of the ter polymers of ethylene, of alkyl acrylate and of maleic anhydride or of glycidyl methacrylate such as the Lotaders® of the Applicant or of polyolefins grafted with l maleic anhydride such as Orevac® from the Applicant as well as ter polymers of ethylene, alkyl acrylate and (meth) acrylic acid. Mention may also be made of homopolymers or copolymers of polypropylene grafted with a carboxylic acid anhydride and then condensed with polyamides or monoamino oligomers of polyamide.
    The MFI of the copolymer (A) and the MFI of the compatibilizer (C) can be chosen within a wide range. However, to facilitate the dispersion of (C), it is recommended that the MFI of the copolymer (A) be greater than that of (C).
    additives
    Advantageously, the composition of the invention comprises at least one additive selected from organic or inorganic fillers, reinforcing agents, plasticizers, stabilizers, antioxidants, anti-UV, flame retardants, carbon black, carbon nanotubes, pigments, dyes, release agents, lubricants, foaming agents, impact resistant agents, flame retardants, nucleating agents, surface modifiers, and mixtures thereof.
    Manufacturing process
    The process for manufacturing the composition according to the invention comprises producing the mixture of block copolymer (A) and non-crosslinked silicone (B), and any other components (C) and / or (D).
    The mixing is preferably carried out in a mixing device in the molten state, such as a twin-screw or single-screw extruder, or else in a device using buss co-kneaders.
    Preferably, said mixing is carried out in a twin-screw extruder.
    It is preferably carried out at a temperature of the order of 150 to 250 ° C, preferably from 160 ° C to 220 ° C.
    The thermoplastic elastomer composition according to the invention can then be implemented by conventional techniques, such as extrusion, vacuum forming, injection molding, blow molding, overmolding or compression molding. In addition, the compositions according to the invention can be retransformed (recycled) with little or no degradation of the mechanical properties.
    applications
    The new thermoplastic elastomers of composition in accordance with the present invention can be used to manufacture insulators of wires and cables; sound and vibration dampening components; electrical connectors; automotive components and devices, such as belts, pipes, air lines, bellows, gaskets and fuel line components; furniture components; soft-touch handles for portable devices (eg tool handles); joints for architecture; closing bottles; medical devices ; sport stuff ; and other parts of parts generally of rubber appearance which can be replaced by parts of composition according to the invention.
    The subject of the present invention is in particular an article or a part of an article chosen from a shoe sole, in particular a sports sole, such as an insole, midsole, or outsole, a ski boot, a sock, a racket. , a ball, a ball, a float, gloves, personal protective equipment, a helmet, a rail sole, an automotive part, a stroller part, a tire, a wheel, a tire-like wheel , a handle, a seat element, a child car seat part, a construction part, a piece of electrical and / or electronic equipment, a piece of electronic protection, a piece of audio equipment, insulation acoustic and / or thermal, a part intended to absorb shocks and / or vibrations, such as those generated by a means of transport, a padding element, a toy, a medical object, such as a splint, an orthosis, a collar cervical tie, a dressing, in particular an antimicrobial foam dressing, an art or craft object, a life jacket, a backpack, a membrane, a mat, a sports mat, a sports flooring, a carpet pad, and any article comprising a mixture of these articles.
    The thermoplastic elastomers of the present invention are particularly useful for manufacturing the following articles:
    -shoes and in particular sports shoes, in particular the soles, external, internal or intermediate soles; in fact, the compositions of the invention have properties of good adhesion to PEBA and to polyamide, in particular by molding, good resistance to abrasion and they can be easily transformed into shoe components;
    -in the optical industry: components of spectacle frames, nose pads or pads, protective elements on frames; in fact, the compositions of the invention have a soft-silky feel, adhere well to polyamide and more precisely to transparent polyamide by overmolding, and resist sebum;
    -in the automotive industry: interior decorative elements; in fact, the compositions of the invention have a soft touch, good haptic properties, adhere perfectly by overmolding, are resistant to sebum and resistant to abrasion;
    - in the manufacturing industry: transmission or transport belts, silent gears; in fact, the compositions of the invention are resistant to heat, resistant to abrasion, and easy to use by overmolding;
    - in the medical sector: patches, biofeedback (bioretroaction) patches, drug delivery devices, sensors;
    -in the electronics industry: headsets, earphones, jewelry and Bluetooth® watches, display screens, connected watches, connected glasses, interactive game components and devices, GPS, connected shoes, monitors and bioactivity sensors, belts and interactive bracelets, child or pet tracker, scanner or handheld computer, location sensors, trackers, vision aid.
    In a preferred embodiment, the compositions of the invention are used for the manufacture of a protective casing or casing in electrical or electronic equipment, such as in particular a laptop computer, a mobile phone or a tablet.
    EXAMPLES
    The following examples illustrate the invention without limiting it.
    Materials used in the examples:
    Compositions according to the invention
    AT:
    PEBA 2 + 30% of polyorganosiloxane polycarbonate polyurethane copolymer (Carbosil® 20 80A silicone from DSM).
    B:
    PEBA 2 + 15% of polyorganosiloxane polycarbonate polyurethane copolymer (Carbosil® 20 80A from DSM) + 15% of styreneethylene / butylene-styrene block copolymer grafted with maleic anhydride (Kraton® FG-1924).
    comparative
    VS :
    PEBA 1: PA 12-PTMG (Mn: 600-2000)
    PEBA 1 is a copolymer with PA 12 blocks and PTMG blocks with respective number average molecular weights (Mn) 600 - 2000.
    The mass ratio: PA blocks / PE blocks = 0.3
    D:
    PEBA 2: PA 12-PTMG (Mn: 850-2000)
    PEBA 2 is a copolymer according to the invention, with PA 12 blocks and PTMG blocks with respective number average molecular weights (Mn) 850 - 2000.
    The mass ratio: PA blocks / PE blocks = 0.4
    E:
    PEBA 3: PA 12-PTMG (Mn: 2000-2000)
    PEBA 3 is a copolymer according to the invention, with PA 12 blocks and PTMG blocks with respective number average molecular weights (Mn) 2000 - 2000.
    The mass ratio: PA blocks / PE blocks = 1
    F:
    TPU-based thermoplastic crosslinked silicone (TPSiV® 4000-75A SR, Multibase)
    G:
    TPU (Desmopan® 9370AU, Covestro)
    Formulations A to G are prepared (by mixing in the case of A or B) in a twin-screw extruder at a temperature of 210 ° C.
    Plates and drawbars are produced by injection molding at 200 ° C in a mold at 30 ° C.
    The results of measurement of the properties of these plates and bars, of respective compositions A to G, are indicated in Table 1 below.
    Table 1:
    Target values sought by the invention and results of measurement of the properties measured on dumbbells (plates or bars) of the compositions
    AAG
    target AT B VS D E F G Physicochemical properties Density <1.00 0.96 0.98 1.00 1.00 1.00 1.1 1.06 Resistance to exudation O O O X X X Chemical resistance (including sebum) (++) Resistance to stains / soiling (++) Mechanical properties Hardness, instantaneous (Shore A) <80 75 75 77 85 90 Hardness, 15 s (Shore A) <75 70 70 74 80 89 Tensile test, strain stress of 25% (MPa) <2.0 1.7 1.8Tensile test, stress at 100% deformation(MPa) <4.0 2.9 3.1Tensile test, tensile strength (MPa) > 10 > 10 > 11 32 39 40 Tensile test, Elongation at break (%) > 500 > 500 > 500 > 750 > 600 > 450 Flexural modulus (MPa) <or = 12 12 12 12 21 77 Tear resistance (kN / m) > 40 35 45 66 78 116 Abrasion resistance Taber-grinding wheel H18 (loss of mass in mg / 1000 revolutions) <50 70 40 99 77 62 Abrasion resistance Taber - CS10 grinding wheel (mass loss in mg / 1000 revolutions) Remaining compression deformation at 23 ° C (% <20 19 22 32 Remaining compression deformation at 70 ° C (%) 62 54 21 Ease of implementation Melt Flow Index at 235 ° C, 1kg (g / 10min) > 10 10 8 5 ease of demolding O O O X X O recyclability O O O O O O X O
    The protocols for measuring the properties characterized according to the present invention and measured according to the examples are described in Table 2 below:
    Table 2:
    Property measurement methods and standards
    Measured property Standard /method Specifications Density ISO 1183-3 Measured at 23 ° C Resistance to exudation Internal method Measured after packaging in a Blinder container at 70 ° C and 62% relative humidity (RH) for 7 days. The samples were 100 x 100 x 2 mm plates.Classification by visual observation:O = No exudationX = Surface exudation Resistance to stains / soiling Internal method Measured after conditioning in an oven at 23 ° C and 50% RH for 7 days. The color change is evaluated by measuring the chromatic aberration before and after exposure to chemicals and everyday products, generating a Delta E value. The samples are plates of 100 x 100 x 2 mm.Classification by visual observation 0 = No color change on the surface2 = Slight change in color on the surface5 = significant coloration on the surface
    Chemical resistance to sebum Internal method Measured after conditioning in an oven at 23 ° C and 50% H R for 7 days. A given mass of sebum is spread over the surface of the samples, then removed after conditioning. The samples thus exposed are weighed after cleaning and the solidification (%) of the sample during the test is calculated. Any visual changes are also recorded.The samples are 50x50x2mm plates.Classification scale:(++) = low caking, no visual changes(+) = low caking, slight visual changes(-) = strong bulking, slight visual changes Hardness ISO 868 23 ° C Tensile test ISO 527 50mm / min at 23 ° C Flexural module ISO 178 23 ° C Tear resistance ISO 34-B 500mm / min, samples not cut Abrasion resistance Taber ISO 9352 1000g load, CS10 abrasive wheel, 1000 revolutions or revolutions per cycle. The samples are 100 x 100 x 2 mm plates. Remanent compression deformation ISO 815 Constant deformation of 25% applied for 72 hours at 23 ° C and for 22 hours at 70 ° C. The samples are type B cylinders. Melt Flow Index (MFI) ISO 1133 235 ° C, 1kg Easy release Internal method Classification according to:O = easy release, no stickingX = difficult release, sticky material
    recyclability Internal method Recyclability is defined as the possibility of reprocessing an already molded part, by melting and re-molding the material, without impacting the quality of the reprocessed part. Classification according to:X = not recyclable 0 = recyclable
    The characterizations are carried out on samples conditioned for 2 weeks at 23 ° C, 50% relative humidity.
    The compositions of the invention have low shore A hardness, especially formulations A and B, having a shore A hardness less than or equal to 70 after 15 s, while retaining good transformability in injection molding, and no exudation. . These formulations show the haptic properties required by consumer applications such as sports devices, portable devices for example in electronic equipment, or optical accessories such as glasses.
    The compositions of the invention also combine a low flexural modulus while retaining very good transformability in injection molding and no exudation, as well as good resistance to high temperatures.
    The compositions of the invention, in composition B comprising a maleized SEBS compatibilizer, exhibit better abrasion resistance than PEBA materials and than TPSiV® derived from TPU. The surface characteristics after abrasion are improved: the surface remains smooth and homogeneous without deep scratches. The visual appearance is retained after abrasion, and there is no risk of injury to the skin, which is necessary for the materials used in the components of the shoe, for example the heel of the shoe, or for sports equipment.
    The formulations of the invention are a solution to avoid the bonding step necessary today to bond the thermosetting rubber outsole to the thermoplastic parts of the ski boot. This bonding step takes time, requires the use of primer and glue which may contain solvents, and requires a crosslinking step at high temperature.
    On the contrary, the formulations of the invention can be combined directly with the thermoplastics used in ski boots such as PEBA, TPU.
    The compositions of the invention have a matte surface and a softer feel than the PEBA reference materials.
    The compositions of the invention do not exhibit visible exudation, unlike PEBAs.
    The compositions of the invention have lower moisture absorption than the PEBA reference materials. This contributes to giving greater resistance to stains, especially against hydrophilic stains (coffee, tea, wine, ...).
    The compositions of the invention have a lower residual compression deformation compared to PEBAs (comparative C, D and E) and to TPSiV® (F) from TPU, especially at 70 ° C. This contributes to obtaining better performance under stress or stress, for example in sports equipment or industrial applications such as sealants.
    It has been found that soft PEBA materials (typical with a hardness less than 35 shore D) are difficult to inject because they tend to stick to the mold and to deform during demolding. The composition (comprising silicone) of the invention is a solution for solving this injection problem while retaining the various advantageous properties of PEBAs, this for even more flexible materials.
    In addition, when the design of the mold becomes complex, the standard PEBA cannot be injected (because of its rigidity), whereas there is no problem for injecting the composition (PEBA-silicone) according to the invention.
    权利要求:
    Claims (21)
    [1" id="c-fr-0001]
    1. Composition including:
    - (A) a rigid block and flexible block copolymer (TPE), and
    - (B) a non-crosslinked polysiloxane silicone.
    [2" id="c-fr-0002]
    2. Composition according to claim 1 in which the silicone is a non-crosslinked polyorganosiloxane.
    [3" id="c-fr-0003]
    3. Composition according to any one of claims 1 or 2, further comprising:
    - (C) a compatibilizer, improving the compatibility between TPE and silicone, chosen from a polyolefin or a mixture of several polyolefins.
    [4" id="c-fr-0004]
    4. Composition according to one of the preceding claims, in which said rigid blocks comprise at least one block chosen from: polyamide, polyurethane, polyester, and their copolymers.
    [5" id="c-fr-0005]
    5. Composition according to one of the preceding claims, in which said flexible blocks comprise at least one block chosen from: polyether, polyester, polysiloxane, polyolefin, polycarbonate, and their copolymers.
    [6" id="c-fr-0006]
    6. Composition according to one of the preceding claims, in which the block copolymer is chosen from copolymers with polyester blocks and polyether blocks, copolymers with polyurethane blocks and polyether blocks and copolymers with polyamide blocks and polyether blocks, preferably chosen among the copolymers with polyamide blocks and polyether blocks.
    [7" id="c-fr-0007]
    7. Composition according to one of the preceding claims, in which the flexible blocks in the copolymer (A) are polyether blocks chosen from PTMG, PPG, PO3G and / or PEG, preferably PTMG.
    [8" id="c-fr-0008]
    8. Composition according to one of the preceding claims, in which the polyamide blocks in the copolymer (A) are PA 11 and / or PA 12 blocks.
    [9" id="c-fr-0009]
    9. Composition according to any one of the preceding claims, in which the weight ratio of TPE (A) relative to the silicone (B) is from 10:90 to 95: 5, preferably 50:50 to 90:10, even better from 60:40 to 85:15.
    [10" id="c-fr-0010]
    10. Composition according to any one of the preceding claims, comprising, by weight:
    - from 55 to 95% of copolymer (A), preferably from 60 to 80%,
    - from 5 to 45% of silicone (B), preferably from 10 to 40%, possibly
    - from 0 to 45% of compatibilizer (C), preferably from 5 to 30%,
    - from 0 to 15% of additives (D), preferably from 5 to 10%, on the total weight of the composition, this being 100%.
    [11" id="c-fr-0011]
    11. Composition according to any one of the preceding claims, in which the number-average molar mass Mn of the flexible blocks, in particular polyether, is greater than 800 g / mol, preferably greater than 1000 g / mol, preferably greater than 1200 g / mol, preferably greater than 1400 g / mol, preferably greater than 1600 g / mol, preferably greater than 1800 g / mol and preferably greater than or equal to 2000 g / mol.
    [12" id="c-fr-0012]
    12. Composition according to any one of the preceding claims, in which the weight ratio of the rigid blocks, in particular polyamide, to the flexible blocks, in particular polyether, in the copolymer (A) is less than or equal to 1.2, preferably less than or equal to 1, preferably less than or equal to 0.8 and preferably less than or equal to 0.5.
    [13" id="c-fr-0013]
    13. Composition according to any one of claims 3 to 12, in which the polyolefin or the mixture of polyolefins of the compatibilizer (C) carries a function chosen from the functions maleic anhydride, carboxylic acid, carboxylic anhydride and epoxide, and is in particular chosen from ethylene / octene copolymers, ethylene / butene copolymers, ethylene / propylene elastomer (EPR), ethylene-propylene diene elastomeric copolymers (EPDM), ethylene / (meth) acrylate copolymers, and copolymers styreneethylene / butylene-styrene (SEBS).
    [14" id="c-fr-0014]
    14. Composition according to any one of claims 1 to 13, further comprising at least one additive (D) selected from: organic or inorganic fillers, reinforcing agents, plasticizers, stabilizers, antioxidants, anti-UV, flame retardants, carbon black, carbon nanotubes, pigments, dyes, mold release agents, lubricants, foaming agents, impact resistant agents, flame retardants, nudants, surface modifiers, and mixtures thereof.
    [15" id="c-fr-0015]
    15. A method of manufacturing the composition according to any one of the preceding claims, comprising producing the mixture of block copolymer (A) and non-crosslinked silicone (B), and any components (C) and / or (D ).
    [16" id="c-fr-0016]
    16. The method as claimed in claim 15, in which the mixing is carried out in a mixing device in the molten state, preferably in a twin-screw extruder, preferably at a temperature of the order of 150 to 250 ° C, preferably from 160 ° C to 220 ° C.
    [17" id="c-fr-0017]
    17. Article comprising at least one part having a composition according to any one of claims 1 to 14.
    [18" id="c-fr-0018]
    18. Article according to claim 17, characterized in that it is manufactured by a process involving at least one of the following steps: injection molding, overmolding, extrusion or co-extrusion of the composition according to any one of claims 1 to 14.
    [19" id="c-fr-0019]
    19. Article according to any one of claims 17 or 18, which is chosen from a shoe sole, in particular a sports sole, such as an insole, midsole, or outsole, a ski boot, a sock, a racket, ball, ball, float, gloves, personal protective equipment, helmet, sole for rail, auto part, stroller part, tire, wheel, soft-rolling wheel like tire, handle, seat element, child car seat part, construction part, electrical and / or electronic equipment part, electronic protective part, audio equipment part, acoustic and / or thermal insulation, a part intended to absorb shocks and / or vibrations, such as those generated by a means of transport, a padding element, a toy, a medical object, such as a splint, an orthosis , a cer necklace vical, a dressing, including an antimicrobial foam dressing, an art or craft object, a life jacket, a backpack, a membrane, a mat, a sports mat, a sports flooring, a underlay, and any article comprising a mixture of these articles.
    [20" id="c-fr-0020]
    20. Article according to any one of claims 17 to 19, the article being an article or element of an article:
    - shoes and in particular sports shoes;
    - optics: components of spectacle frames, nose pads or pads, protective elements on frames;
    - automobile: interior decorative element;
    - the manufacturing industry: transmission or transport belt, silent gear;
    - medical: patch, drug delivery device, J sensor
    - electronics: headphones, earphones, jewelry or Bluetooth® watch, display screen, connected watch, connected glasses, interactive game component or device, GPS, connected shoe, monitor or bioactivity sensor, interactive belt or bracelet, tracker for children or pets, scanner or handheld computer, location sensors, tracker, visual assistance device.
    [21" id="c-fr-0021]
    21. Article according to any one of claims 17 to 20, the article being an electrical or electronic article comprising a housing or protective casing made from the composition according to any one of claims 1 to 13, said article being preferably tablet.
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    同族专利:
    公开号 | 公开日
    US20210087399A1|2021-03-25|
    CN111601852A|2020-08-28|
    KR20200108052A|2020-09-16|
    EP3740535A1|2020-11-25|
    FR3076834B1|2020-08-21|
    WO2019138202A1|2019-07-18|
    引用文献:
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    法律状态:
    2018-12-13| PLFP| Fee payment|Year of fee payment: 2 |
    2019-07-19| PLSC| Publication of the preliminary search report|Effective date: 20190719 |
    2019-12-16| PLFP| Fee payment|Year of fee payment: 3 |
    2020-12-10| PLFP| Fee payment|Year of fee payment: 4 |
    2021-12-17| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1850303A|FR3076834B1|2018-01-15|2018-01-15|ELASTOMERIC THERMOPLASTIC COMPOSITION - SILICONE|
    FR1850303|2018-01-15|FR1850303A| FR3076834B1|2018-01-15|2018-01-15|ELASTOMERIC THERMOPLASTIC COMPOSITION - SILICONE|
    EP19703776.5A| EP3740535A1|2018-01-15|2019-01-15|Thermoplastic elastomer-silicone composition|
    US16/961,984| US20210087399A1|2018-01-15|2019-01-15|Thermoplastic elastomer-silicone composition|
    KR1020207023301A| KR20200108052A|2018-01-15|2019-01-15|Thermoplastic elastomer-silicone composition|
    CN201980008550.9A| CN111601852A|2018-01-15|2019-01-15|Thermoplastic elastomer-silicone composition|
    PCT/FR2019/050075| WO2019138202A1|2018-01-15|2019-01-15|Thermoplastic elastomer-silicone composition|
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