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    • 专利摘要:
    polymer composition, automotive interior article, and use of a triazine derivative (t) The present invention relates to a polymer composition comprising a heterophasic propylene copolymer, talc, an organic antioxidant and a triazine derivative.
    公开号:BR112012003913B1
    申请号:R112012003913-0
    申请日:2010-08-17
    公开日:2019-11-19
    发明作者:Kastner Erwin；Siebert Hartmut；Lederer Klaus；Otte Michael；Dicke René
    申请人:Borealis Ag；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for POLYMERIC COMPOSITION, INTERNAL AUTOMOTIVE ARTICLE, AND USE OF A TRIAZINE DERIVATIVE (T).
    [0001] The present invention relates to polypropylene compositions comprising phenolic antioxidants and the use of a triazine derivative in polymeric compositions.
    [0002] Polypropylene is the material of choice for many applications. For example, polypropylene in combination with talc is used as bubble wrap back sheets as well as in automotive interior items. Said polypropylene / talc compositions are generally speaking - good to process and can be individually customized. However, such materials must also provide long-term stability against environmental impacts, such as oxidative degradation, keeping the properties specifically made of the polypropylene / talc composition at the desired level. In this way, antioxidants are added to impair the degradation of the polypropylene / talc compositions. During the past few years the standard needs for long-term stability have been constantly narrowed, which in turn has increased the quantities of additives to satisfy craved desires, such as heat resistance and / or mechanical properties. On the other hand, such a large amount of additives intensifies the risk of side reactions. Such side reactions lead to by-products, such as aldehyde compounds or ketone compounds, to be frequently volatile. Certainly volatile compounds must be kept at low levels, particularly since they are not accepted by consumers. In addition, it has been observed that such compounds suffer from bad odor.
    [0003] In this way, the objective of the present invention is to reduce the sensory impression of the smell of polymers, in particular of automotive internal articles. An additional object of the present invention is REPETITION 870190094194, of 20/09/2019, p. 4/40
    2/29 reduce the amount of volatile polymer compounds and / or an automotive interior article. In particular, there is a desire to reduce the sensory smell impression measured according to VDA 270 and optionally the amount of headspace emission according to VDA 277. In addition, volatile reduction and / or odor reduction should preferably not be achieved at at the expense of mechanical properties. [0004] The first finding of the present invention is that the main cause of bad odor are aldehydes and / or ketones being inter alia the degradation products of polymers, such as polyethylene. The second finding of the present invention is that triazine derivatives act as scavengers of these degradation products.
    [0005] In this way, the present invention relates to a polymeric composition and / or automotive interior article comprising said polymeric composition, wherein the polymeric composition comprises:
    (a) polyolefin, such as polypropylene (A), (b) optionally talc (B), (c) optionally an organic antioxidant (C), and (d) a triazine derivative (T).
    [0006] Preferably, the polyolefin, such as polypropylene (A), is present in the composition of the invention in the amount of at least 50.0% by weight, more preferably at least 60.0% by weight, even more preferably at least 70.0% by weight, even more preferably at least 75.0% by weight. In addition, it is understood that polyolefin, preferably polypropylene (A), is the only polymer component within the polymeric composition.
    [0007] The polymeric composition defined above may further comprise a phosphorous antioxidant (E), a hindered amine light stabilizer (HALS) and / or a glidant (S).
    [0008] In this way, the present invention relates in particular
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    3/29 to a polymeric composition and / or an automotive interior article comprising said polymeric composition, where the polymeric composition comprises (a) at least 50% by weight of polyolefin, such as polypropylene (A), (b) optionally, 1,000 to 550,000 ppm of talc (B), (c) optionally 100 to 5,000 ppm of the organic antioxidant (C), such as phenolic antioxidant, (d) 1,000 to 50,000 ppm of the triazine derivative (T), and (e) optionally 100 to 5,000 ppm of a phosphorous antioxidant (E), (f) optionally 1,000 to 2,500 ppm of a hindered amine light stabilizer (HALS), and (g) optionally 1,000 to 2,000 ppm of a glidant (S) based in the composition.
    [0009] In general, 1 ppm of additive corresponds to 1 mg of additive in 1 kg of composition.
    [00010] Surprisingly it was found that the use of the triazine derivative (T) in a polymeric composition containing talc (B) and organic antioxidants (C) solves the problem of bad odor measured according to VDA 270. Additionally, the use of derivatives of triazine (T) allows to significantly reduce the amount of volatiles measured according to headspace emission according to VDA 277 compared to standard polypropylene compositions comprising talc and organic antioxidants without any sequestrant. Even more surprisingly, this benefit is not offset by the loss of mechanical properties, such as tension modules and / or flexural modules (see table 1).
    [00011] In this way, the present invention also refers to the use of a triazine derivative (T) in a polymeric composition, I preferred
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    A polyolefin composition (especially poly-a-olefin composition), such as a polypropylene composition or polyethylene composition, or an automotive interior article comprising said composition to obtain (a) a measured headspace emission of according to VDA 277 of all volatiles together of said polymeric composition of 50 pgC / g or less, preferably below 40 pgC / g, more preferably below 30 pgC / g, even more preferably below 25 pgC / g , and / or (b) a sensory impression of smell measured according to VDA 270 below 4.0, more preferably not more than
    3.5.
    [00012] To obtain the desired improvement of sensory impression according to VDAA 270 and / or the reduction of volatiles according to VDA 277 when maintaining the mechanical properties at the desired level, it is estimated to use the triazine derivative (T) in a composition polymeric in an amount of from 1,000 to 5,000 ppm, preferably from 2,000 to 20,000, more preferably from 5,000 to 10,000 ppm.
    [00013] Preferably the triazine derivative (T) is used in a polymeric composition comprising in addition talc (B) and / or an organic antioxidant (C). Most preferably, the polymeric composition comprises a polyolefin, such as polypropylene (A). Even more preferably, polyolefin, such as polypropylene (A), is the only polymer component within said composition. In especially preferred embodiments, talc (B), organic antioxidant (C) and polypropylene (A) are those as defined in the present invention. In this way, the triazine derivative (T) is used in polymeric compositions according to the present invention.
    [00014] Without being limited by theory, the triazine derivative (T) contains
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    5/29 used in the present invention is capable of reducing the amount of aldehyde compounds and / or ketone compounds occurring as products of degradation of polymeric material. In this way, the triazine (T) derivatives of the present invention are used as scavengers of aldehydes and / or ketones occurring in a polymeric composition, in particular in a polymeric composition according to the present invention.
    [00015] The term volatiles is understood according to the present invention as substances that tend to vaporize from the polymeric composition. More precisely, volatiles are substances having a very high vapor pressure and then vaporize easily from the polymeric composition. Preferred volatiles are those being gaseous at 130 ° C or below (atmospheric pressure), more preferably at 120 ° C or below (atmospheric pressure). Volatiles according to the present invention are in particular substances that are detectable according to VDA 277. Volatiles can be any substance part of the polymeric composition and are in particular degradation products caused by chemical and / or physical reactions (processes) within the polymeric compositions. Typically volatiles are degradation products of the polymer (s) and / or additives of the polymeric composition, such as degradation products of polypropylene and / or organic antioxidants, such as phenolic (hindered) antioxidants as defined herein. The amount of volatiles in the polymeric composition is determined using VDA 277. The exact measurement method is described in the example section. The amount of volatiles analyzed is given by the ratio of the amount [gC] of volatiles to the total amount [g] of the polymeric composition.
    [00016] In this way, in one aspect the use of the triazine derivative (T) in a polymeric composition provides a headspace emission measured according to VDA 277 of all volatiles together in the
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    6/29 said polymeric composition equal to, or below 50 pgC / g, preferably below 40 pgC / g, more preferably below 30 pgC / g, even more preferably below 25 pgC / g.
    [00017] In a second aspect or alternatively the use of the triazine derivative (T) in a polymeric composition provides a sensory impression of smell measured according to VDA 270 below 4.0, more preferably not more than 3.5.
    [00018] The polypropylene (A) used in the polymeric composition can be any polypropylene, in particular polypropylene suitable for the automotive interior and / or for back blister packaging sheets, such as heterophasic polypropylene (A1) or a propylene homopolymer (A2) . Thus, in the case of automotive compounds, a preferred polymeric composition comprises, more preferably it comprises, as the only polymer component a heterophasic propylene copolymer (A1), while in the case of blister backing sheets a preferred polymeric composition comprises, more preferably it comprises, as the only polymer component, a polypropylene (A2) homopolymer.
    The expression propylene homopolymer used in the present invention refers to a polypropylene that consists substantially, that is, of more than 99.5% by weight, still preferably at least 99.7% by weight, as in at least 99.8% by weight of propylene units. In a preferred embodiment, only propylene units in the propylene homopolymer are detectable. The comonomer content can be determined with FT infrared spectroscopy, as described below in the examples.
    [00020] Heterophasic polypropylene systems are well known in the art and are systems in particular obtained in a process of at least two stages resulting in a multiphase structure comprising a polypropylene (A 1 ) matrix, preferably one
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    7/29 isotactic polypropylene matrix, and inclusions dispersed therein comprising amorphous elastomer (A 2 ). Such systems can be easily made specifically for the required requirements by adjusting the comonomer content in the polypropylene matrix and the amorphous elastomer, respectively. Such a heterophasic propylene copolymer (A1) can have an MFR2 in the range of 2.0 to 80.0 g / 10 min., More preferably in the range of 5.0 to 50.0 g / 10 min., Even more preferably in the range from 7.0 to 20.0 g / 10 min. Typically, such a heterophasic polypropylene (A1) copolymer has an amorphous elastomer being a propylene-ethylene (EPR) rubber. The polypropylene matrix can be a propylene homopolymer or a propylene copolymer, the latter being especially preferred. The total comonomer content, preferably ethylene, is in the range of 2 to 25% by weight based on the total heterophasic propylene copolymer (A1). The amount of xylene soluble can be in the range of 10 to 40% by weight, preferably 15 to 30% by weight.
    [00021] Of course, polypropylene can comprise, in addition to the heterophasic propylene copolymer (A1), a high density polyethylene (HDPE) having, for example, a density in the range of 0.954 to 0.966 g / cm 3 and a flow rate melting point (MFR2 at 190 ° C) from 0.1 to 15.0 g / 10 min. In addition, polypropylene (A) may also further comprise EPR, propylene-ethylene copolymers and / or ethylene-octene copolymers.
    [00022] However, it is preferred that polypropylene (A) is the only polymer component in the polymeric composition.
    [00023] In this way, it is understood that polypropylene (A) is present in the polymeric composition in the amount of at least 50.0% by weight, more preferably at least 60.0% by weight, even more preferably at least 70% by weight. weight, even more preferably at least 75.0% by weight.
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    8/29 [00024] In addition to polypropylene (A), the polymeric composition is in particular defined by its additives.
    [00025] Thus, to be useful in the applications mentioned above, the polymeric composition of the invention must comprise an inorganic reinforcing agent. Talc is usually the additive of choice. Talc (B) is generally used to support the crystallization behavior of the polymer material. It can also be used as a crosslink reduction additive and / or reinforcing agent. In any case, talc (B) has been recognized in the applications mentioned above as an indispensable part of polypropylene compositions. Talc (B) is a mineral composed of hydrated magnesium silicate and can comprise low amounts of residues, such as iron oxide (FeO; Fe2O3) and / or iron silicate. In general, the quantities of waste do not exceed 5.0% by weight. In this way, it is preferred that the talc (B) comprises 0.1 to 3.5% by weight, more preferably 0.1 to 3.0% by weight, of residues, that is, residues comprising iron, such as oxide of iron or iron silicate. Of course, talc (B) can also be a chloride-talc like the commercial product Steamic T1 C A from Luzenac.
    [00026] Preferably, the talc (B) according to the present invention has a particle size (d50%) below 3.0 pm (d50% indicates that 50% of the talc has a particle size below 3.0 pm pm) and / or particle size (d98%) below 15.0 pm (d98% indicates that 98% by weight of talc has a particle size below 15.0 pm), more preferably a particle size (d50 %) below 2.0 pm and / or a particle size (d98%) below 10.0 pm, even more preferably a particle size (d50%) below 1.0 pm and / or a particle size (d98%) below 5.0 pm.
    [00027] However, it has been found that in the present invention talc (B) promotes the degradation of organic antioxidants and then increases
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    9/29 undesirably the amount of volatiles. Problems with smell are also increased. Such degradation of organic antioxidants is particularly pronounced if the talc comprises a considerable amount of residues within the talc, such as iron oxide (FeO, Fe2Ü3) and / or iron silicate. The degradation of organic oxidants can be very easily deduced in the headspace emission according to VDA 277.
    [00028] Also the smell problems possibly caused by the degradation of antioxidants, but also the degradation of the polymer, such as polypropylene, can be measured according to the smell detection method according to VDA 270.
    [00029] The present invention has now found that the reduction of odor and / or volatile problems is provided by adding a triazine derivative (T) to a polymeric composition comprising (a) polyolefin, such as polypropylene (A), and (b) optionally talc (B) and an organic antioxidant (C), such as a phenolic antioxidant.
    [00030] Advantageously, the triazine derivative (T) does not impede the mechanical properties of the polymeric composition necessary for final applications, for example, for automotive interior articles.
    [00031] Any triazine (T) derivatives are suitable, but 1,3,5 triazine (T) derivatives are preferred. In this way, derivatives of 1,3,5 triazine (T) of Formula (I)
    R N '^ N /
    (I)
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    10/29 where [00032] R 'and R are independently selected from the group NHZ', NZ'Z, C1 to C10 alkyl, phenyl and benzyl [00033] Z 'and Z are independently selected from the group H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl and n-pentyl. [00034] More preferably, residues R and NZ'Z are both NH2, and
    R 'is or NZ'Z, preferably NH2, methyl or phenyl.
    [00035] Especially good results can be obtained with triazine derivatives (T) of Formulas (Ia), (Ib) and (Ic) [melamine derivative]
    (la) (lb) (Ic) where [00036] Z 'and Z are independently selected from the group consisting of H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl and n-pentyl , preferably independently selected from the group consisting of H, methyl, ethyl, iso-propyl and tert-butyl.
    [00037] In this way, especially suitable are triazine derivatives (T) of Formulas (Id), (le) and (If) [melamine]
    (Ld)
    (1c)
    df)
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    11/29 [00038] Melamine is most preferred as a triazine derivative.
    [00039] As indicated above, problems with smell and the increase in volatiles are also observed due to the presence of organic antioxidants since they can degrade due to the polymeric environment, that is, due to other additives, such as talc (B) . However, antioxidants are needed to impair oxidative degradation of polypropylene. In this way, the polymeric composition for which the triazine derivative (T) is used preferably contains organic antioxidants (T). The term organic antioxidant (C) according to the present invention preferably means all possible compounds capable of decreasing or preventing oxidation of the polymer component, for example, polypropylene (A). However, in a preferred embodiment the phosphorus antioxidant (E) as defined in the present invention is not included in the term organic antioxidant (C). Particularly preferred is the organic antioxidant (C) a phenolic antioxidant.
    [00040] The term phenolic antioxidant as used in the present invention means any compound capable of decreasing or preventing oxidation of the polymer component, for example, polypropylene (A). In addition, such a phenolic antioxidant must certainly comprise a phenolic residue.
    [00041] Better results can be obtained if the organic antioxidant (C), preferably the phenolic antioxidant, is sterically prevented. The term Sterically hindered according to the present invention means that the hydroxyl group (HO-) of the organic antioxidant (C), preferably the phenolic antioxidant, is surrounded by steric alkyl residues.
    [00042] In this way, the phenolic antioxidant preferably comprises the residue of Formula (II)
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    12/29
    A | (II) where
    Ri being located in the ortho- or meta- position for the hydroxyl group and Ri is (CHsjsC-, CH3- or H, preferably (CHsjsC-, and
    Ai constitutes the remainder of the phenolic antioxidant and is preferably located in the para- to hydroxyl group. [00043] Preferably the phenolic antioxidants preferably comprise the residue of Formula (IIa)
    A | (Ha) where
    R1 is (CHsjsC-, CH3- or H, preferably (CHsjsC-, and
    Ai forms the remainder of the phenolic antioxidant.
    [00044] Preferably A1 is in the para- to 0 hydroxyl group.
    [00045] Additionally, the organic antioxidant (C), preferably the phenolic antioxidant, should preferably exceed a specific molecular weight. In this way, the organic antioxidant (C), preferably the phenolic antioxidant, preferably has a molecular weight of more than 785 g / mol, more preferably greater than 1100 g / mol. On the other hand, the molecular weight should not be too high, that is, not more than 1300 g / mol. A preferred range is from 785 to 1,300 g / mol, more preferably from 1,000 to 1,300 g / mol, even more preferably from 1,100 to 1,300 g / mol.
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    13/29 [00046] Also, the organic antioxidant (C), preferably the phenolic antioxidant, can be additionally defined by the amount of phenolic residues, in particular the amount of phenolic residues of formula (II) or (IIa). In this way, the phenolic antioxidant can comprise 1, 2, 3, 4 or more phenolic residues, more preferably 1,2, 3, 4 or more phenolic residues of Formula (II) or (IIa).
    [00047] In addition, the organic antioxidant (C), preferably the phenolic antioxidant, mainly comprises only carbon atoms, hydrogen atoms and small amounts of O atom, mainly caused due to the hydroxyl group (HO-) of the phenolic residues. However, the organic antioxidant (C), preferably the phenolic antioxidant, can still comprise small amounts of N, S and P atoms. Preferably the organic antioxidant (C), preferably the phenolic antioxidant, consists of C, H atoms , O, N and S only, more preferably the organic antioxidant (C), preferably the phenolic antioxidant, consists of C, H and O only.
    [00048] As stated above, the organic antioxidant (C), preferably the phenolic antioxidant, must have a very high molecular weight. A high molecular weight is an indicator of several phenolic residues. In this way, it is particularly understood that the antioxidant (C), preferably the phenolic antioxidant, has 4 or more, especially 4, phenolic residues, such as the phenolic residue of Formula (II) or (IIa).
    [00049] As particularly suitable, phenolic antioxidants have been recognized compounds comprising at least one residue of Formula (III)
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    14/29
    on what
    R4 is (ChhhC-, CH3- or H, preferably (CHsjsC-, and
    A2 constitutes the remainder of the phenolic antioxidant.
    [00050] Considering the needs above, phenolic antioxidants are preferably selected from the group consisting of
    2,6-di-tert-butyl-4-methylphenol (CAS No. 128-37-0; M 220 g / mol), (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate pentaerythrityl-tetrakis (CAS No. 6683-19-8; M 1178 g / mol),
    Octadecyl 3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 2082-79-3; M 531 g / mol)
    1.3.5- trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (CAS No. 1709-70-2; M 775 g / mol), (3, 2,2'tiodiethylenebis 5-di-tert-butyl-4-hydroxyphenyl) (CAS No. 41484-35-9; M 643 g / mol), bis (3,5-di-tert-butyl-4- hydroxybenzylphosphonate) of calcium (CAS No. 65140-91-2; M 695 g / mol),
    1.3.5- tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) -isocyanurate (CAS No. 27676-62-6, M 784 g / mol),
    1.3.5- tris (4-tert-butyl-3-h idroxy-2,6-d imethyl benzyl) -1,3,5 triazine-2,4,6- (1H, 3H, 5H) -trione (CAS No 40601-76-1, M 813 g / mol), bis (3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butanoic acid glycol ester (CAS No. 32509-66-3; M 794 g / mol),
    4,4'-thiobis (2-tert-butyl-5-methylphenol) (CAS No. 96-69-5; M 358 g / mol),
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    15/29
    2,2'-methylene-bis- (6- (1-methyl-cyclohexyl) -para-cresol) (CAS No.
    77-62-3; M 637 g / mol),
    3,3'-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'hexamethylenedipropionamide (CAS No. 223128-74-7; M 637 g / mol),
    2,5,7,8-tetramethyl-2- (4 ', 8', 12'-trimethyltridecyl) -chroman-6-ol (CAS No. 10191-41-0; M 431 g / mol),
    2,2-ethylidenobis (4,6-di-tert-butylphenol) (CAS No. 35958-30-6; M 439 g / mol),
    1,1,3-tris (2-methyl-4-hydroxy-5'-tert-butylphenyl) butane (CAS No.
    1843-03-4; M 545 g / mol),
    3,9-bis (1,1-dimethyl-2- (beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl-2,4,8,10-tetraoxaspira [5.5] undecane (CAS No. 9049890-1; M 741 g / mol),
    1.6- hexanediyl-bis (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzene) propanoate (CAS No. 35074-77-2; M 639 g / mol),
    2.6- di-tert-butyl-4-nonylphenol (CAS No. 4306-88-1; M 280 g / mol),
    4,4'-butylenobis (6-tert-butyl-3-methylphenol (CAS No. 85-60-9;
    M 383 g / mol);
    2,2'-methylene bis (6-tert-butyl-4-methylphenol) (CAS No. 119-471; M 341 g / mol), triethylene glycol-bis- (3-tert-butyl-4-hydroxy-5methylphenyl) propionate (CAS No. 36443-68-2; M 587 g / mol), a mixture of linear and branched C13 to C15 alkyl esters of 3- (3'-di-t-butyl-4'-hydroxyphenyl) propionic acid ( CAS No. 171090-93-0; Mw 485 g / mol),
    6,6'-di-tert-butyl-2,2'-thiodip-cresol (CAS No. 90-66-4; M 359 g / mol), diethyl- (3,5-di-tert-butyl-4 -hydroxybenzyl) phosphate (CAS No. 97656-7; M 356 g / mol),
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    4.6- bis (octylthiomethyl) -o-cresol (CAS No. 110553-27-0; M 425 g / mol), benzenepropanoic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-, linear and branched C7-C9 alkyl esters (CAS No. 125643-61-0; Mw 399 g / mol),
    1,1,3-tris [2-methyl-4- [3- (3,5-di-tert-butyl-4hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane (CAS No. 180002-86-2; M 1326 g / mol), mixed styrene phenols (M ca 320 g / mol; CAS No. 6178844-1; M ca 320 g / mol), butylated, octyl phenols (M ca 340 g / mol; CAS No. 68610- 06-0; M ca 340 g / mol), and butylated reaction product of p-cresol and dicyclopentadiene (Mw 700 to 800 g / mol; CAS No. 68610-51-5; Pm 700-800 g / mol). [00051] More preferably, the phenolic antioxidant is selected from the group consisting of (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate pentaerythrityl-tetrakis (CAS No. 6683-19-8; M 1178 g / mol),
    Octadecyl 3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate (CAS No. 2082-79-3; M 531 g / mol, bis (3,3-bis ( 3'-tert-butyl-4-hydroxyphenyl) butanic) CAS No. 32509-66-3; M 794 g / mol),
    3,3'-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -N, N'hexamethylenepropionamide (CAS No. 23128-74-7; M 637 g / mol),
    3,9-bis (1,1-dimethyl-2- (beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl-2,4,8,10-tetraoxasposp [5.5] undecane ( CAS No. 9049890-1; M 741 g / mol),
    1.6- hexanediyl-bis (3,5-bis (1,1-dimethylethyl) -4-hydroxybenzene) propanoate (CAS No. 35074-77-2; M 639 g / mol), triethylene glycol-bis- (3- tert-butyl-4-hydroxy-5methylphenyl) propionate (CAS No. 36443-68-2; M 587 g / mol),
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    17/29 a mixture of linear and branched C13 to 15 alkyl esters of 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionic acid (CAS No. 171090-93-0; Pm 485 g / mol), and benzenepropanoic acid, 3,5-bis (1,1-dimethyl-ethyl) -4-hydroxy-, branched and linear C7-C9 alkyl esters (CAS No. 125643-610; Pm 399 g / mol).
    [00052] The most preferred phenolic antioxidant is (3- (3,5-di-tert-butyl-
    4-hydroxyphenyl) propionate pentaerythrityl-tetrakis (CAS No. 6683-19-8; M 1178 g / mol) preferably having Formula (IV)
    L J 4 (IV) [00053] The present polymeric composition can comprise different phenolic antioxidants as defined in the present invention, however, it is preferred that it comprises only one type of phenolic antioxidant as defined herein.
    [00054] The polymeric composition may further comprise one or more phosphorous antioxidants (E). Most preferably, the polymeric composition comprises only one type of phosphorous antioxidant (E). Preferred phosphorous (E) antioxidants are selected from the group consisting of tris- (2,4-di-tert-butylphenyl) phosphite (CAS No. 31570-04-4; M 647 g / mol), tetrakis (2,4- di-tert-butylphenyl) -4,4'-biphenylen-di-phosphonite (CAS No. 38613-77-3; M 991 g / mol), bis- (2,4-di-tert-butylphenyl) -pentaerythrityl- di-phosphite (CAS No.
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    26741-53-7; M 604 g / mol), di-stearyl-pentaerythrityl-di-phosphite (CAS No. 3806-34-6; M 733 g / mol), tris-nonylphenyl phosphite (CAS No. 26523-78-4; M 689 g / mol), bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl-di-phosphite (CAS No. 80693-00-1; M 633 g / mol),
    2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl-phosphite (CAS No.
    126050-54-2; M 583 g / mol),
    1.1.3- tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane (CAS No. 68958-97-4; M 1831 g / mol),
    4,4'-butylidenobis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite (CAS No. 13003-12-8; M 1240 g / mol), bis- (2,4-dicumylphenyl) pentaerythritol diphosphite (CAS No. 15486243-8; M 852 g / mol), bis (2-methyl-4,6-bis (1,1dimethylethyl) phenyl) phosphorous acid ethyl ester (CAS No. 145650-60-8; M 514 g / mol), triethyl-tris (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite) 2,2', 2 -nitrile (CAS No. 80410-33-9; M 1465 g / mol),
    2,4,6-tris (tert-butyl-phenyl-2-butyl-2-ethyl-1,3-propanediolphosphite (CAS No. 161717-32-4, M 450 g / mol),
    2,2'-ethylidene-bis (4,6-di-tert-butylphenyl) fluorphosphonite (CAS No.
    118337-09-0; M 487 g / mol),
    6- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy) -2,4,8,10tetra-tert-butyldibenzo [d, f] [1.3.2] dioxafosfepine (CAS No. 203255 -81-6; M 660 g / mol), tetrakis- (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylen-diphosphite (CAS No. 147192-62-9; M 1092 g / mol), and
    1.3- bis- (diphenylphosphino) -2,2-dimethylpropane (CAS No. 8032698-3; M 440.5 g / mol).
    [00055] Especially suitable are organic phosphites, in particular
    Petition 870190094194, of 9/20/2019, p. 21/40
    19/29 to label those as defined in the above list as phosphorous antioxidants (E).
    [00056] The most preferred phosphorous antioxidant (E) is tris- (2,4-ditherc-butylphenyl) phosphite (CAS No. 31570-04-4; M 647 g / mol).
    [00057] As additional additives the polypropylene composition preferably comprises at least one hindered amine light stabilizer. In this way, such hindered amine light stabilizers (HALS) are present in an amount of 800 to 2500 ppm, more preferably from 900 to 2,000 ppm, even more preferably from 1,200 to 1,600 ppm, in the polypropylene composition.
    [00058] Impeded amine light stabilizers (HALS) are known in the art. Preferably such hindered amine light stabilizers (HALS) are 2,6-alkyl-piperidine derivatives, in particular 2,2,6,6-tetramethyl-piperidine derivatives. Especially suitable are hindered amine light stabilizers (HALS) of Formula (V)
    u (V) where U is the remainder of the hindered amine light stabilizer (HALS).
    [00059] Impeded amine light stabilizers (HALS) do not absorb UV radiation, but act to inhibit degradation of polypropylene. They slow down the photochemically initiated degradation reactions, to some extent in a similar way to antioxidants.
    [00060] Impeded amine light stabilizers (HALS) show high efficiency and longevity due to a cyclical process where
    Petition 870190094194, of 9/20/2019, p. 22/40
    20/29 hindered amine light stabilizers (HALS) are generated instead of being consumed during the stabilization process. Thus, an advantage of these hindered amine light stabilizers (HALS) is that significant levels of stabilization are obtained at relatively low concentrations.
    [00061] Preferred hindered amine light stabilizer (s) (HALS) is (are) 1,3,5-triazine-2,4,6-triamine, NsN'M, 2-ethanedi-ylbis [N [3 - [[4,6-bis [butyl (1,2,2,6,6-pentamethyl-4-piperidinyl) amino] -1,3,5-triazin-
    2-yl] amino] propyl] -N ', N-dibutyl-N'N-bis (1,2,2,6,6-pentamethyl-4piperidinyl) - (CAS No. 106990-43-6; Pm 2286 g / mol) of Formula (VI)
    poly ((6- (1,1,3,3-tetramethylbutyl) amino) -1,3,5-triazin-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino) -hexamethylene- (2,2,6,6-tetramethyl-4piperidyl) imino)) (CAS No. 71878-19-8; Pm> 2,500 g / mol), and sebacate bis- (2,2,6, 6-tetramethyl-4-piperidyl) (CAS No.
    52829-07-9; Mp 481 g / mol) of Formula (VII).
    Petition 870190094194, of 9/20/2019, p. 23/40
    21/29
    (VII).
    [00062] Additionally, it is estimated that the polypropylene composition comprises at least one glidant being a fatty acid amide. In this way, such glidants are present in an amount of 1,000 to 2,000 ppm and, more preferably, from 1,200 to 1,600 ppm, in the polypropylene composition. More preferably, the polypropylene composition part comprises only a glidant. Preferred types of glidants are unsaturated fatty acid amides. The amount of fatty acid carbons is preferably in the range of C10 to C25 carbon atoms.
    [00063] In this way, the sliding agent (s) is (are) preferably selected from the group consisting of cis-13-docosenoic amide (CAS No. 112-84-5; Pm 337.6 g / mol), cis-9,10-octadecenoamide (CAS No. 301-02-0; Pm 281.5 g / mol), octadecanoylamide (CAS No. 124-26-5; Pm 283.5 g / mol), beenamide (CAS No. 3061-75-4; Pm 339.5 g / mol), Ν, Ν'-ethylene-bis-stearamide (CAS No. 110-30-5; Pm 588 g / mol),
    N-octadecyl-13-docosenamide (CAS No. 10094-45-8; Pm 590 g / mol), and oleylpalmitamide (CAS No. 16260-09-6; Pm 503 g / mol).
    [00064] Especially suitable is (are) cis-13-docosenoic amide (CAS No. 112-84-5; Pm 337.6 g / mol) and / or cis-9.10
    Petition 870190094194, of 9/20/2019, p. 24/40
    22/29 octadecenoamide (CAS No. 301-02-0; Pm 281.5 g / mol).
    [00065] The present invention relates especially to a polymeric composition comprising (a) at least 50% by weight, preferably at least 70% by weight, more preferably at least 75% by weight, of polypropylene (A), such as copolymer of heterophasic propylene (A1) or a polypropylene homopolymer (A2), (b) 1,000 to 550,000 ppm, preferably 50,000 to 500,000 ppm, more preferably 100,000 to 400,000 ppm, even more preferably 150,000 to 300,000 ppm, of talc (B), (c) 100 to 5,000 ppm, preferably 500 to 5,000 ppm, more preferably 500 to 3,000 ppm, even more preferably 200 to 1,000 ppm, of organic antioxidants, especially phenolic antioxidants, such as (3- (3,5-di-tert -butyl-4-hydroxyphenyl) propionate pentaerythritol-tetrakis (CAS No. 6683-19-8; M 1178 g / mol), (d) 1,000 to 50,000 ppm, preferably from 2,000 to 20,000 ppm, more preferably from from 5,000 to 10,000 ppm, of the triazine derivative (T), such as derivative that of triazine (T) of Formula (Ia), (Ib) or (Ic), especially (Id), (Ie), (If), more preferably melamine, (e) optionally 100 to 5,000 ppm, preferably 500 to 3,000 ppm, more preferably 500 to 1,500 ppm, even more preferably 1,000 to 1,500 ppm, of phosphorus (E) antioxidants, such as tris- (2,4-di-tert-butylphenyl) phosphite (CAS No. 31570-04-4 ; M 647 g / mol), (f) optionally 800 to 2500 ppm, more preferably
    900 to 2,000 ppm, preferably 1,200 to 1,600 ppm, of hindered amine light stabilizer (s) with Pm greater than 1,000 g / mol, more preferably greater than 2,000 g / mol, such as 1,3,5-triazine-
    2,4,6-triamine, N5N'-1,2-ethanedi-ylbis [N- [3 - [[4,6-bis [butyl (1,2,2,6,6-pentamethyl-4-piperidinyl) amino] -1,3,5-triazin-2-yl] amino] propyl] -N ', NPetition 870190094194, of 9/20/2019, p. 25/40
    23/29 dibutyl-N ', N-bis (1,2,2,6,6-pentamethyl-4-piperidinyl) - (CAS No. 10699043-6; Pm 2286 g / mol) of Formula (VIII) and / or poly ((6- (1,1,3,3tetramethylbutyl) amino) -1,3,5-triazin-2,4-diyl) - (2,2,6,6-tetramethyl-4piperidyl) imino) -hexamethylene - ((2,2,6,6-tetramethyl-4-piperidyl) imino)) (CAS No. 71878-19- (g) 8; Pm> 2,500 g / mol), (h) optionally 1,000 to 2,000 ppm, preferably 1,200 to 1,600 ppm, of slip agent being a fatty acid amide, preferably cis-13-docosenoic amide (CAS No. 11284-5; Pm 337.6 g / mol) and / or cis-9.10 -octadecenoamide (CAS No. 30102-0; Pm 281.5 g / mol), more preferably cis-9.10 octadecenoamide (CAS No. 301-02-0; Pm 281.5 g / mol), based on the composition polypropylene. As stated above, it is preferred that the polypropylene composition comprises polypropylene (A) polymer only.
    [00066] The polymeric composition of the present invention is preferably obtained by extruding the polymer and then adding the additives as mentioned in the present invention. Preferably a twin screw extruder is used, such as a ZSK40 twin screw extruder. The polymeric composition pelleted with the ZSK 40 twin screw extruder is used in the headspace emission test according to VDA 277.
    [00067] Still, as stated above, the present invention relates to an automotive interior article comprising at least 50% by weight, more preferably at least 70% by weight, more preferably at least 90% by weight, even more preferably 99, 0% by weight, such as 100% by weight, based on said article of a polypropylene composition as defined in the present invention.
    [00068] The term automotive internal article in the present invention
    Petition 870190094194, of 9/20/2019, p. 26/40
    24/29 tion means all articles, preferably injection molded articles, from the automotive interior. Preferred articles are selected from the group consisting of panels, auxiliary step, inner edges, ashtrays, inner body panels and changes.
    [00069] The invention also relates to the blister pack, in particular to the blister back sheets, comprising the polymeric composition of the present invention.
    [00070] The present invention is further described by way of examples.
    EXAMPLES [00071] The definitions of terms and method determination that follow apply to the above general description of the invention as well as the examples below unless otherwise defined.
    Molecular weights, molecular weight distribution (Mn, Pm, MWD) [00072] Pm / Mn / MWD are measured using Gel Permeation Chromatography (GPC) according to the following method:
    The average molecular weight Pm and the molecular weight distribution (MWD = Pm / Mn where Mn is the numerical average molecular weight and Pm is the average molecular weight) are measured using the method based on ISO 16014-1: 2003 and ISO 16014-4: 2003. A Waters Alliance GPCV 2000 instrument, equipped with refractive index detector and online viscometer, was used with TosoHaas 3x TSK gel columns (GMHXL-HT) and 1,2,4-trichlorobenzene (TCB, stabilized with 200 mg / L of 2,6-Di-tert-butyl-4-methyl-phenol) as a solvent at 145 ° C and at a constant flow rate of 1 mL / min. 216.5 pL of sample solution was injected by analysis. The column set was calibrated using relative calibration with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg / mol to 11500 kg / mol and a well-characterized broad set of polypropylene standards. All samples were prepared by dissolving 5-10 mg of polymer
    Petition 870190094194, of 9/20/2019, p. 27/40
    25/29 ro in 10 mL (at 160 ° C) of stabilized TCB (same as the mobile phase) and holding for 3 hours with continuous agitation before sampling on the GPC instrument.
    [00073] MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C,
    2.16 kg of load).
    [00074] Ethylene content is measured with Fourier transform infrared (FTIR) spectroscopy calibrated with 13 C-NMR. When measuring the ethylene content in polypropylene, a thin film of the sample (thickness of about 250 pm was prepared using hot pressure). The area of absorption peaks 720 and 733 cm -1 was measured with a Perkin Elmer FTIR 1600 spectrometer. The method was calibrated by ethylene content data measured using 13 C-NMR.
    [00075] The particle size is measured according to ISO 13320-1: 1999.
    [00076] Xylene soluble (XS,% by weight): The content of Xylene soluble (XS) is determined at 23 ° C according to ISO 6427.
    [00077] Flexural Module: The flexural module was determined in a 3-point bend according to ISO 178 in 80 x 10 x 4 mm injection molded specimens prepared in accordance with ISO 294: 1: 1996.
    [00078] VDA 277 (available, for example, from Dokumentation Kraftfahrwesen (DKF); Ulrichstrape 14, 74321 Bietigheim Bissingen) [00079] The volatile content is determined according to VDA 277: 1995 using a gas chromatography device (GC ) with a WCOT capillary column (wax type) of 0.25 mm internal diameter and 30 m long. The GC settings were as follows: 3 minutes isothermal at 50 ° C, heat to 200 ° C at 12 K / min, 4 minutes isothermal at 200 ° C, injection temperature: 200 ° C, temperature-detection: 250 ° C , carrier helium, 1:20 flow mode split, and
    Petition 870190094194, of 9/20/2019, p. 28/40
    26/29 medium carrier 22-27 cm / s.
    [00080] In addition to the FID detector for the assessment of volatile summary, an MS detector is used for the evaluation of simple volatile components. A specific Quadropol MS was used with the following settings: transfer line temperature 280 ° C, scanning method with a scan rate of 15-600 amu, with respect to the EMV mode, mass calibration with standard spectrum auto-adjustments, MS source temperature of 230 ° C and Quad MS temperature of 150 ° C.
    [00081] The samples used (minimum 5 mL; sample of 1,000 + / 0,001 g per 10 mL of container volume) were conditioned at 120 +/- 1 ° C (5 hours +/- min) in a gas-tight container and 5 ml of gas from the vessel are subsequently injected through injection of pl into the GC apparatus. In the present invention, sample pellets were used.
    [00082] VDA 270 method for detecting sensory impression of smell (available, for example, from Dokumentation Kraftfahrwesen (DKF); Ulrichstrape 14, 74321 Bietigheim Bissingen)
    Test settings
    a) heat the chamber with circulating air according to DIN 50 011-12; accuracy class 2
    b) 1 or 3 liter glass test cup with odorless seal and lid; the cup, seal and lid must be cleaned before use.
    Table 1: Specimen
    Variant Examples Sample quantity per 1 liter cup Sample quantity per 3 liter cup THE Staples, plugs, other small parts 10 +/- 1 g 30 +/- 3 g
    Petition 870190094194, of 9/20/2019, p. 29/40
    27/29
    Variant Examples Sample quantity per 1 liter cup Sample quantity per 3 liter cup B Armrest, ashtray, palm rest, sun shade and other medium sized parts 20 +/- 2 g 60 +/- 6 g Ç Insulating material, sheets, leather, cover fabric, cellular material, foam type, carpets and other large scale parts 50 + / 5 g 150 +/- 15 g [00083] In the case of variant C the thickness of the evil material should be
    in those of 3 mm, in the 1 liter test cup a specimen of 200 + / 20 cm 2 is used, while in the 3 liter test cup a specimen of 600 +/- 60 cm 2 is used. In case the material thickness is more than 20 mm, the specimen used must be trimmed to a size below 20 mm. Sandwich assemblies are tested as a whole. In the case of small parts, several specimens have to be used to obtain the desired quantity to be tested.
    Procedure [00084] Three different storage conditions are available (table 2). In the present application, variant 3 was used.
    Table 2: Storage conditions
    Variant Temperature Storage Period Note 1 23 +/- 2 ° C 24 +/- h a B C D F 2 40 + / - 2 ° C 24 +/- h a B C D F 3 80 +/- 2 ° C 2 h +/- 10 min a, c and f
    a) for variants 1 and 2, 50 ml of deionized water were added to the 1 liter test cup and 150 ml of deionized water are added to the 3 liter test cup
    b) the specimen (s) is / are placed in a way to avoid
    Petition 870190094194, of 9/20/2019, p. 30/40
    28/29 direct contact with water
    c) the test cup is stored tightly closed in the preheated heating chamber
    d) for variants 1 and 2 the test takes place immediately after removing the test cup from the heating chamber
    e) for variant 3 the test cup must be cooled to a temperature of 60 +/- 5 ° C after removal of the heating chamber before being tested; after testing by three tasters the test cup must be stored for 30 minutes at 80 - / - 2 ° C in the heating chamber before further testing is carried out
    f) the classification must be carried out by at least three tasters; To differ the individual classifications of the tasters in graduation by two points, a repetition of the test by at least five tasters must follow.
    Analysis [00085] Scent classification for all variants is performed by the scale as provided in table 3. Degrees are provided from 1 to 6, with which half degrees are possible.
    Table 3: Scent classification
    Degree Classification 1 Not notable 2 Remarkable; does not bother 3 Clearly remarkable; but it still doesn't bother 4 Nuisance 5 Severely uncomfortable 6 Intolerable [00086] The resull is given as an average value, rounded
    by half degrees. The variant used is indicated with the result. [00087] In the present application, variant C / 3 was used. Preparation of examples
    Petition 870190094194, of 9/20/2019, p. 31/40
    29/29
    Table 1: Example properties
    CE 1 E1 HECO [% by weight] 65% 65% AO 1 [% by weight] 0.25% 0.25% Baby powder [% by weight] 20% 20% Melamine [% by weight] - 1% Odor [VDA 270] [1-6] 4 3 Total volatile content[VDA 277] [MgC / g] 30 23 Voltage Module [MPa] 2,000 2,000
    HECO: heterophasic propylene copolymer, namely the commercial product EE188HP from Borealis (MFR2 of 13 g / 10 min; soluble xylene content of 20% by weight)
    AO 1: phenolic antioxidant, namely (3- (3 ', 5'-di-tert-butyl-4hydroxyphenyl) -propylate pentaerythrityl-tetrakis (CAS No. 6683-19-8) [IRGANOX 1010]
    Talc: Jetfine 3CA commercial talc from Luzenac Europe, F
    Melamine: the commercial product MELAMIN from Borealis Agrolinz Melamine GmbH, as per PCT amendments.
    Petition 870190094194, of 9/20/2019, p. 32/40
    权利要求:
    Claims (10)
    [1]
    1. Polymeric composition, characterized by the fact that it comprises:
    (a) at least 70% by weight of a heterophasic propylene copolymer (A1), (b) 150,000 to 300,000 ppm of talc (B), (c) 500 to 5,000 ppm of an organic antioxidant (C), (d) 2,000 to 20,000 ppm of a 1,3,5 triazine derivative (T), and (e) optionally 500 to 3,000 ppm of a phosphorous antioxidant (E), based on the composition, with derivatives of 1,3,5 triazine (T) are of Formula (D

    in which
    R 'and R are independently selected from the group, NHZ', NZ'Z, C1 to C10 alkyl, phenyl and benzyl
    Z 'and Z are independently selected from the group H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl and n-pentyl.
    [2]
    2. Polymeric composition according to claim 1, characterized by the fact that the triazine derivative (T) is melamine.
    [3]
    Polymeric composition according to claim 1 or 2, characterized by the fact that the heterophasic propylene copolymer (A1) comprises a polypropylene matrix (A 1 ) and an elastomer
    Petition 870190094194, of 9/20/2019, p. 33/40
    2/3 mere amorphous (A 2 ).
    [4]
    Polymeric composition according to any one of claims 1 to 3, characterized in that the organic antioxidant (C) is a phenolic antioxidant, preferably a sterically hindered phenolic antioxidant.
    [5]
    Polymeric composition according to any one of claims 1 to 4, characterized by the fact that the organic antioxidant (C) is a phenolic antioxidant comprising the residue of Formula (I)

    (0 in which
    Ri is located in the ortho- or meta- position for the hydroxyl group and Ri is (CHsjsC-, CH3- or H, preferably (CHsjsC-, and
    Ai forms the remainder of the phenolic antioxidant.
    [6]
    6. Polymeric composition, according to the claim
    5, characterized by the fact that the phenolic antioxidant comprises at least one residue of Formula (II)

    in which
    R4 is (CHsjsC-, CH3- or H, preferably (CHsjsC-, and
    A2 constitutes the remainder of the phenolic antioxidant.
    [7]
    7. Polymeric composition, according to any one
    Petition 870190094194, of 9/20/2019, p. 34/40
    3/3 of claims 1 to 6, characterized by the fact that it further comprises:
    (a) 1,000 to 2,500 ppm of hindered amine light stabilizer (s) and / or (b) 1,000 to 2,000 ppm of gliding agent (s) being a fatty acid amide (s).
    [8]
    8. Automotive interior article, characterized by the fact that it comprises at least 50% by weight, based on said article, of a polymeric composition, as defined in any one of claims 1 to 7.
    [9]
    9. Use of a triazine derivative (T) in an automotive interior article comprising a polyolefin composition, as defined in any one of claims 1 to 7, characterized by the fact that it is to obtain:
    (a) a headspace emission measured according to VDA 277 of all volatiles together of said polymeric composition equal to or below 50 pgC / g and / or (b) a sensory smell impression measured according to VDA 270 below 4 , 0.
    [10]
    10. Use according to claim 9, characterized by the fact that the polyolefin composition comprises in addition to the triazine derivative (T) talc (B) and / or an organic antioxidant (C).
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    同族专利:
    公开号 | 公开日
    CN102482458B|2014-08-27|
    EP2470600A1|2012-07-04|
    CN102482458A|2012-05-30|
    WO2011023594A1|2011-03-03|
    BR112012003913A2|2016-03-29|
    EP2530116B1|2017-10-11|
    EP2470600B1|2013-07-17|
    EP2530116A1|2012-12-05|
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    CN109679210A|2018-12-25|2019-04-26|浙江普利特新材料有限公司|It is a kind of to adorn apperance performance, high-performance, the low preparation method for distributing polypropylene material for automobile interior exterior|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-02-12| B06T| Formal requirements before examination|
    2019-07-09| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-10-15| B09A| Decision: intention to grant|
    2019-11-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/08/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/08/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09168893|2009-08-28|
    PCT/EP2010/061967|WO2011023594A1|2009-08-28|2010-08-17|Polypropylene-talc composite with reduced malodour|
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