Thermoplastic moulding composition for extrusion with high melt stability

Abstract

The invention relates to thermoplastic molding compositions based on semi-aromatic polyesters, which are particularly suitable for extrusion coating processes, in particular on paper substrates. The invention also relates to molded articles and films comprising the thermoplastic molding, in particular to coated articles. In another aspect, the invention relates to methods for producing thermoplastic molding compositions and to extrusion methods using these thermoplastic molding compositions. The invention also relates to a packaging material comprising a coated article coated with a thermoplastic molding composition according to the invention.

Description

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[0001] This invention relates to thermoplastic molding compositions based on semi-aromatic polyesters, which are particularly suitable for extrusion coating processes, especially on paper substrates. The invention also relates to molding articles and films comprising thermoplastic moldings, particularly coated articles. In another aspect, the invention relates to methods for producing thermoplastic molding compositions and to extrusion methods using these thermoplastic molding compositions. The invention further relates to packaging materials comprising coated articles coated with thermoplastic molding compositions according to the invention.

[0002] Polymer extrusion coating is a widely practiced technique that involves applying thin layers of polymer material to various substrates, such as paper, cardboard, fabrics, and metal foil. During extrusion coating, molten polymer material is extruded through a flat die to produce a film only a few micrometers thick. This film is then coated onto the substrate and cooled, allowing the polymer material to adhere to the substrate surface.

[0003] For extrusion coating processes, the polymer material used should have a good combination of flowability, melt stability, and viscosity. The polymer material should possess good melt flow characteristics, allowing it to be easily extruded through a flat die. Additionally, it should exhibit sufficient adhesion properties to ensure proper bonding to the substrate surface. Sufficient melt stability is required to achieve a thin and uniform coating on the substrate and a stable production process.

[0004] Polyesters exhibit a good combination of properties as barrier coatings, such as high moisture and oxygen barrier properties, combined with good grease and oil barrier properties and resistance. Commercial thermoplastic polyesters, such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), are also highly temperature stable. Therefore, coated articles using these polymers can be used in high-temperature applications.

[0005] However, polyesters, such as PET and PBT, exhibit several drawbacks in extrusion coating processes, such as low melt stability during film extrusion, leading to an unstable melt curtain and so-called "edge wavy" (i.e., the outer edge of the extruded film is wavy and a constant coating width is not achieved). Therefore, these polymers can only be coated onto substrates at low speeds. Furthermore, the adhesion of these polyesters, particularly on paper and paperboard, is very low, especially at high processing rates (i.e., high substrate speeds). Another problem that can occur in the coating process is the so-called "neck-in," the effect where the width of the product film becomes significantly narrower than the width of the die exit.

[0006] WO 2011 / 110750 discloses a heat-sealable, biodegradable packaging material comprising a fibrous substrate coated with a polymer layer by extrusion or co-extrusion. The polymer layer contains polylactide and a biodegradable polyester. A small amount of acrylic copolymer may be blended into the polymer layer to improve adhesion to the substrate. WO 2011 / 110750 does not address the production speed of the coating process.

[0007] JP5995471 describes a PBT laminate on a paper-based material, the laminate containing 0.1 wt% to 0.7 wt% of an organic compound having at least two epoxy groups in one molecule. This laminate exhibits reduced necking during processing. Surface adhesion is not addressed in JP5995471.

[0008] WO 2005 / 100015 discloses a lamination method using olefin copolymers to provide improved adhesion of foils to thermoplastic compositions. The disclosed olefin copolymers may be, for example, ethylene / methacrylate copolymers or ethylene / acrylic acid copolymers. In contrast to this invention, the disclosed articles are multilayer structures rather than single-layer coatings, wherein the olefin copolymers are laminated as separate layers.

[0009] US 7,507,473 discloses a coated paper article containing a primer to enhance the adhesion of polyethylene terephthalate to paperboard. The primer used to enhance adhesion is an ammonium-catalyzed self-crosslinking copolymer of ethylene-vinyl acetate, wherein N-hydroxymethylacrylamide functional groups are attached to the polymer backbone to be applied to the paper.

[0010] WO 2009 / 133016 describes a two-component adhesive composition suitable for extrusion coating on paper substrates, comprising (A) a high melt strength polypropylene and a second component (B) to increase melt strength and adhesion to paperboard, the second component being selected from the group consisting of (i) maleic anhydride-modified polypropylene (MAPP), (ii) maleic anhydride-modified polypropylene wax, (iii) a polypropylene homopolymer having a high melt flow rate, or (iv) an ethylene-vinyl acetate-based hot melt adhesive. This invention is limited to polypropylene, and other classes of additives (B) are used to improve the properties of the composition.

[0011] Therefore, the object of this invention is to develop thermoplastic polyester molding compositions that have a good combination of flowability, melt stability, and viscosity, and thus can be easily processed at high process speeds in extrusion coating processes and also exhibit good adhesion to coated substrates. The thermoplastic molding compositions should form a stable melt curtain during the extrusion process and reduce the so-called “edge waviness” and “necking” effects caused by low melt stability.

[0012] It has been found that this problem can be solved by a thermoplastic molding composition (M) comprising:

[0013] (A) 30% to 100% by weight of at least one thermoplastic polymer blend (A), the thermoplastic polymer blend comprising or consisting of the following (based on (A)):

[0014] (A-1) 81.5% to 99.39% by weight of at least one semi-aromatic polyester (A-1).

[0015] (A-2) 0.01% to 2% by weight of at least one acrylic polymer (A-2), wherein the at least one acrylic polymer comprises the following:

[0016] (a-2a) is based on 70% to 100% by weight of acrylic acid (a-2a) in the formula (A-2), and

[0017] (a-2b) Based on (A-2) from 0% to 30% by weight of at least one other olefinic unsaturated monomer (a-2b) capable of copolymerizing with acrylic acid, wherein the other olefinic unsaturated monomer is selected from the group consisting of monoolefinic unsaturated carboxylic acids;

[0018] (A-3) 0.05% to 5% by weight of at least one epoxy-containing vinyl aromatic copolymer (A-3).

[0019] (A-4) 0.5% to 10% by weight of at least one epoxy-containing olefin copolymer (A-4).

[0020] (A-5) 0.05% to 1.5% by weight of at least one polyolefin wax (A-5) prepared by a metallocene catalyst, wherein the polyolefin wax is a homopolymer of ethylene, a copolymer of ethylene and one or more 1-olefins, or a homopolymer of propylene, wherein the one or more 1-olefins can be linear or branched, substituted or unsubstituted, and have 3 to 18 carbon atoms.

[0021] Among them, polyolefin wax (A-5) is polarized by reacting polyolefin wax with α,β-unsaturated carboxylic acids or their derivatives;

[0022] The total proportions of components (A-1), (A-2), (A-3), (A-4), and (A-5) are 100% by weight.

[0023] and

[0024] (B) 0% to 70% by weight of one or more other additives (B).

[0025] The sum of the proportions of component (A) and component (B) is 100 by weight.

[0026] The thermoplastic molding composition (M) according to the invention exhibits high melt stability and reduced necking during extrusion, which enables extrusion coating processes at high linear speeds, i.e., high conveying speeds of the material to be coated along the extrusion die. Furthermore, the composition according to the invention exhibits good adhesion to substrates, particularly paper, cardboard, and corrugated board, without requiring pretreatment of the substrate surface, such as by applying an adhesive layer, glue, primer, etc.

[0027] Preferably, the thermoplastic molding composition (M) has a 1 cm² thickness as determined according to ISO 1133-1 at 250°C / 2.16 kg. 3 / 10min to 100cm 3 / 10min, more preferably at 1cm 3 / 10min and 20cm 3 Between 10 min and the optimal value is 2 cm. 3 / 10min and 10cm 3 Melt volume flow rate (MVR) between 10 min and 10 min.

[0028] According to the present invention, the thermoplastic molding composition (M) comprises at least 30% by weight, preferably 50% by weight to 100% by weight, of at least one thermoplastic polymer blend (A) and at most 70% by weight, preferably 0% by weight to 50% by weight, of other additives (B).

[0029] At least one thermoplastic polymer blend (component A) comprises or is composed of the following (based on A):

[0030] (A-1) 81.5% to 99.39% by weight, preferably 87.5% to 99.33% by weight, for example 91.3% to 99.05% by weight of at least one semi-aromatic polyester (A-1).

[0031] (A-2) 0.01% to 2% by weight, preferably 0.05% to 1.5% by weight, for example 0.05% to 1.2% by weight of at least one acrylic polymer (A-2).

[0032] (A-3) 0.05% to 5% by weight, preferably 0.05% to 2.5% by weight, for example 0.05% to 1% by weight of at least one epoxy-containing vinyl aromatic copolymer (A-3).

[0033] (A-4) 0.5% to 10% by weight, preferably 0.5% to 7.5% by weight, for example 0.75% to 6% by weight of at least one epoxy-containing olefin copolymer (A-4).

[0034] (A-5) 0.05% to 1.5% by weight, preferably 0.07% to 1% by weight, for example 0.1% to 0.5% by weight of at least one polyolefin wax (A-5).

[0035] Preferably, the thermoplastic polymer blend (A) has a 1 cm² thickness as determined according to ISO 1133-1 at 250°C / 2.16 kg. 3 / 10min to 100cm 3 / 10min, more preferably at 1cm 3 / 10min and 20cm 3 Between 10 min and the optimal value is 2 cm. 3 / 10min and 10cm 3 Melt volume flow rate (MVR) between 10 min and 10 min.

[0036] Components (A-1), (A-2), (A-3), (A-4) and (A-5), as well as optional component B, are described in further detail below.

[0037] Component A-1

[0038] According to the present invention, the thermoplastic polymer blend (A) comprises at least one semi-aromatic polyester (A-1). A suitable semi-aromatic polyester (A-1) is generally based on repeating units of at least one phthalic acid and its derivatives and repeating units of at least one aliphatic dihydroxy compound.

[0039] According to the present invention, the repeating unit of the term phthalic acid and its derivatives includes repeating units derived from phthalic acid, its esters, or other esterifying derivatives. The aromatic ring may also be substituted, for example, by halogens such as chlorine and bromine, or by C1-C6-alkyl groups such as methyl, ethyl, isopropyl, and n-propyl, as well as n-butyl, isobutyl, or tert-butyl or (iso-)hexyl groups. A semi-aromatic polyester (A-1) preferably comprises repeating units of terephthalic acid and isophthalic acid or mixtures thereof, especially terephthalic acid. According to one embodiment, up to 60 mol%, preferably no more than 10 mol%, of the terephthalic acid repeating unit may be substituted with isophthalic acid, 2,6-naphthalenedicarboxylic acid, or aliphatic or alicyclic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanoic acid, and cyclohexanedicarboxylic acid, especially with isophthalic acid repeating units. The preferred semi-aromatic polyester (A-1) is a semi-aromatic polyester having 2 to 10 carbon atoms in the diol component.

[0040] Among the repeating units derived from aliphatic dihydroxy compounds, diols having 2 to 6 carbon atoms are preferred, especially 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, and neopentyl glycol or mixtures thereof.

[0041] Particularly preferred semi-aromatic polyesters (A-1) include semi-aromatic polyesters derived from alkanediols having 2 to 6 carbon atoms. Particularly preferred are polyethylene terephthalate (PET), polypropylene terephthalate (PTT), and polybutylene terephthalate (PBT), or mixtures thereof. PET and / or PBT also preferably contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as additional monomer units.

[0042] The melt volumetric flow rate (MVR) of semi-aromatic polyester (A-1), measured according to ISO 1133-1 at 250°C / 2.16 kg, is typically 5 cm. 3 / 10min to 120cm 3 / 10min, more preferably at 5cm 3 / 10min and 20cm 3 Between 10 min and 5 cm, with the optimal time being between 10 min and 5 cm. 3 / 10min and 12cm 3 Between 10 minutes.

[0043] Particularly preferred are semi-aromatic polyesters (A-1) with a carboxyl end group content of 0 mmol / kg to 100 mmol / kg, more preferably 10 mmol / kg to 50 mmol / kg, and especially 15 mmol / kg to 40 mmol / kg of polyester. Such polyesters can be produced, for example, by the method of DE-A 4401 055. The carboxyl end group content is usually determined by titration (e.g., potentiometry).

[0044] A particularly preferred thermoplastic molding composition (M) comprises a semi-aromatic polyester (A-1) selected from PET, PTT and PBT, or a mixture of semi-aromatic polyesters (A-1) selected from PET, PTT and PBT as component A-1.

[0045] Semi-aromatic polyesters (A-1) are known and described in the literature. These semi-aromatic polyesters (A-1) can be produced by polycondensation of phthalic acid, its esters or other ester derivatives with aliphatic dihydroxy compounds in a manner known per se.

[0046] Recycled materials, especially recycled PET (also known as waste PET), can also be used, optionally blended with other semi-aromatic polyesters such as PBT and / or PTT.

[0047] Recyclables are generally understood to mean:

[0048] 1) So-called “post-industrial recyclables”: These are production wastes from polycondensation or processing, such as slag from injection molding, start-up waste from injection molding or extrusion, or edge scraps from extruded sheets or films.

[0049] 2) So-called "post-consumer recyclables": These are plastic products collected and processed by end consumers after use. The majority of these are blow-molded PET bottles used for mineral water, soft drinks, and juices.

[0050] Both types of recyclables can be in the form of regrind or granules. In the latter case, the raw material recyclables are melted and granulated in an extruder after separation and cleaning. This generally facilitates handling, dumping, and metering for further processing steps.

[0051] Recyclables in the form of granular recyclables and re-grindable materials can be used, wherein the maximum edge length should be 10 mm, preferably less than 8 mm.

[0052] Suitable semi-aromatic polyesters can be marketed under the trade name Ultradur. ® For example, Ultradur ® B6550 was purchased from BASF SE.

[0053] Component A-1 is typically present in the thermoplastic polymer blend (A) in an amount of 81.5% to 99.39% by weight, preferably 87.5% to 99.33% by weight, and especially 91.3% to 99.05% by weight, based on the thermoplastic polymer blend (A).

[0054] Component A-2

[0055] According to the present invention, the thermoplastic polymer blend (A) comprises at least one acrylic polymer as component A-2, the acrylic polymer being composed of the following:

[0056] (a-2a) is based on (A-2), comprising 70% to 100% by weight, preferably 85% to 100% by weight, more preferably 95% to 100% by weight of acrylic acid (a-2a), and

[0057] (a-2b) Based on (A-2), 0% to 30% by weight, preferably 0% to 15% by weight, more preferably 0% to 5% by weight of at least one other olefinic unsaturated monomer (a-2b) capable of copolymerizing with acrylic acid, wherein the other olefinic unsaturated monomer is selected from the group consisting of monoolefinic unsaturated carboxylic acids.

[0058] The sum of the proportions of components (a-2a) and (a-2b) is 100 by weight.

[0059] Component A-2 is typically present in the thermoplastic polymer blend (A) in an amount of 0.01% to 2% by weight, preferably 0.05% to 1.5% by weight, and especially 0.05% to 1.2% by weight.

[0060] It has been surprisingly found that for thermoplastic molding compositions (M) containing at least 0.01% by weight of component A-2, improved surface adhesion can be achieved in coating applications, while increasing the speed of the coating process without negative effects such as edge waviness or defects in the coated film. However, on the other hand, it has been found that amounts greater than 2% by weight result in a decrease in the viscosity of the thermoplastic molding composition (M) and an increase in necking when the composition is used in the coating process.

[0061] The monomer (a-2a) is acrylic acid.

[0062] Preferred suitable olefinically unsaturated monomers (a-2b) are monoolefinically unsaturated carboxylic acids, such as methacrylic acid, maleic acid, fumaric acid, itaconic acid, mesoconic acid, methylene malonic acid, and citraconic acid, or mixtures thereof. In a preferred embodiment, the acrylic polymer (A-2) substantially does not contain the olefinically unsaturated monomer (a-2b), i.e., it contains less than 0.5% by weight, preferably less than 0.1% by weight, and more preferably less than 0.01% by weight of the olefinically unsaturated monomer (a-2b) based on the total weight of the acrylic polymer (A-2). Therefore, in a preferred embodiment, the acrylic polymer (A-2) is made from acrylic monomers (i.e., containing 100% by weight of repeating units derived from acrylic acid).

[0063] The aforementioned monomers containing acidic groups (a-2a) and / or (a-2b) can be used in polymerization as free acids or as salts, such as sodium, potassium, or ammonium salts.

[0064] Specifically, the molecular weight of the acrylic polymer (A-2) according to the present invention is in the range of 1,000 g / mol to 100,000 g / mol (M w=weight average molecular weight). Preferably, the weight average molecular weight of the acrylic polymer (A-2) is in the range of 1,000 g / mol to 12,000 g / mol, more preferably in the range of 1,500 g / mol to 8,000 g / mol. Typically, the weight average molecular weight of the acrylic polymer (A-2) is in the range of 3,500 g / mol to 6,500 g / mol. Within these ranges, the molecular weight can be specifically adjusted by the amount of chain regulator used during the preparation of the acrylic polymer (A-2). Based on the total polymer, the proportion of polymer with a molecular weight <1,000 g / mol is typically ≤10% by weight, preferably ≤5% by weight. Generally, the polydispersity index Mw / Mn of the acrylic polymer (A-2) is ≤2.5, preferably 1.5 to 2.5, for example 2. The molecular weight of the acrylic polymer (A-2) is determined by gel permeation chromatography (GPC) of an aqueous solution of the polymer buffered to pH 7, using a hydroxyethyl methacrylate copolymer network as the stationary phase and sodium polyacrylate standards.

[0065] The inventors have discovered that acrylic polymers (A-2) conforming to these molecular weights are particularly useful and do not adversely alter the viscosity of the thermoplastic molding composition.

[0066] The K value for a 1% by weight softened aqueous solution, determined by the Fikentscher method, is typically from 10 to 50, preferably from 15 to 35, and particularly preferably from 20 to 30. The K value determined by the Fikentscher method is typically determined according to EN ISO 1628-1.

[0067] Specifically, the preferred acrylic polymer (A-2) has a pH value of less than 4, particularly less than 3, which means that the acrylic polymer used is preferably only partially neutralized or not neutralized at all, which means that there are free acidic groups or acidic groups that are only partially neutralized by alkali ions.

[0068] To produce low molecular weight polyacrylic acid, a molecular weight regulator or chain transfer agent is added during the free radical polymerization of acrylic acid. The regulator must be suitable as a polymerization initiator and also as a polymerization method. Examples of known initiators are inorganic and organic peroxides (such as peroxydisulfate, peroxides, hydroperoxides, and peresters), azo compounds (such as 2,2'-azobisisobutyronitrile), and redox systems having both inorganic and organic components. The regulators used typically comprise inorganic sulfur compounds (such as bisulfites, disulfites, and dithionites), organic sulfides, sulfoxides, sulfones, and mercapto compounds (such as mercaptoethanol and mercaptoacetic acid), as well as inorganic phosphorus compounds (such as hypophosphite (phosphonic acid)) and their salts (e.g., sodium hypophosphite).

[0069] Methods for producing the acrylic polymer (A-2) according to the invention are described, for example, in DE-A 19950941 and WO 2012 / 104401 A.

[0070] Acrylic polymer (A-2) can be used in substantially pure form, as a masterbatch (e.g., in combination with a polyester matrix) or as a solution (e.g., an aqueous solution).

[0071] Component A-3

[0072] According to the present invention, the thermoplastic polymer blend (A) comprises at least one epoxy-containing vinyl aromatic copolymer (component A-3). The epoxy-containing vinyl aromatic copolymer (component A-3) preferably comprises repeating units derived from vinyl aromatic monomers and acrylic monomers.

[0073] Component A-3 is typically present in the thermoplastic polymer blend (A) at an amount of 0.05% to 5% by weight, preferably 0.05% to 2.5% by weight, and particularly 0.05% to 1% by weight. It has been found that the claimed amount of component A-3 improves the melt stability of the thermoplastic polymer blend (A).

[0074] The vinyl aromatic monomer is preferably selected from styrene and styrene derivatives, wherein the styrene derivative is substituted at the α, β, ortho, meta, and / or para positions with at least one alkyl group having one to six carbon atoms. Preferably, the vinyl aromatic monomer is selected from styrene and styrene derivatives, wherein the styrene derivative is substituted at the α and / or para positions, preferably at the α position, with at least one alkyl group having one to three carbon atoms, preferably one carbon atom. Preferably, the vinyl aromatic monomer is selected from styrene and α-methylstyrene, especially styrene.

[0075] Examples of suitable esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the corresponding esters of decyl acrylate / methacrylic acid. Among these, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate are particularly preferred.

[0076] Epoxy functional groups can be introduced by monomers containing epoxy groups. Suitable monomers containing epoxy groups include glycidyl methacrylate and glycidyl acrylate. The repeating unit with an epoxy group is preferably glycidyl (meth)acrylate. It will be found that copolymers with a glycidyl methacrylate content of more than 20% by weight, more preferably more than 30% by weight, and even more preferably more than 50% by weight, based on the copolymer content, are particularly advantageous.

[0077] Preferably, the epoxy-containing copolymer (component A-3) is a random copolymer or block copolymer represented by the following formula (I):

[0078] (I),

[0079] in

[0080] R1, R2, R3, R4 and R5 are independently selected from hydrogen atoms and are alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms;

[0081] R6 is independently selected from alkyl groups having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms; and

[0082] x, y, and z are integers from 1 to 20.

[0083] R1 is preferably selected from -H or -CH3, with -H being preferred.

[0084] R2 is preferably selected from H.

[0085] R3 is preferably selected from -H or -CH3, with -H being preferred.

[0086] R4 is preferably selected from -H or -CH3.

[0087] R5 is preferably selected from -H or -CH3.

[0088] R6 is preferably selected from -CH3

[0089] The preferred epoxy-containing vinyl aromatic copolymer (A-3) is based on styrene, acrylate and / or methacrylate, and is preferably poly(styrene-glycidyl ether-methyl methacrylate).

[0090] The epoxy equivalent (EEW) in the epoxy-containing copolymer (component A-3) is preferably in the range of 150 g / mol to 3,000 g / mol, more preferably in the range of 150 g / mol to 1,500 g / mol, for example in the range of 150 g / mol to 1,000 g / mol, or in the range of 150 g / mol to 750 g / mol. More preferably, the EEW is in the range of 200 g / mol to 650 g / mol, particularly in the range of 200 g / mol to 500 g / mol. The epoxy equivalent (EEW) is defined as the number of grams of epoxy-containing copolymer (component A-3) required to provide 1 mole of epoxy groups, and is determined according to ASTM D1652.

[0091] The weight-average molecular weight (Mw) of the epoxy-containing copolymer (component A-3) is preferably in the range of 2,000 g / mol to 25,000 g / mol, and particularly in the range of 3,000 g / mol to 8,000 g / mol. The number-average molecular weight (Mn) of the polymer is preferably in the range of 400 g / mol to 6,000 g / mol, and particularly in the range of 1,000 g / mol to 4,000 g / mol. The polydispersity (Q = Mw / Mn) is generally between 1.5 and 5. The molecular weight of the epoxy-containing copolymer (component A-3) was determined by gel permeation chromatography (GPC) of an aqueous solution of the polymer buffered to pH 7, using a hydroxyethyl methacrylate copolymer network as the stationary phase and sodium polyacrylate standards.

[0092] The epoxy-containing vinyl aromatic copolymer (A-3) can be prepared by random or block copolymerization of the reaction mixture of the above monomers contained in a free radical polymerization reaction, an ionic polymerization reaction or a catalytic polymerization reaction.

[0093] The above-mentioned type of epoxy-containing copolymers can be, for example, from BASF Resins BV in the form of Joncryl ® Acquired from ADR brand store. Joncryl ® ADR 4468 and Joncryl ® The ADR 4400 is particularly useful.

[0094] Component A-4

[0095] According to the present invention, the thermoplastic polymer blend (A) comprises at least one epoxy-containing olefin copolymer (component A-4).

[0096] The preferred epoxy-containing olefin copolymer (component A-4) comprises a copolymer consisting of the following components:

[0097] (a-4a) 40% to 99% by weight of at least one α-olefin having 2 to 8 carbon atoms.

[0098] (a-4b) 0% to 45% by weight of C1-C of acrylic acid or methacrylic acid 12 Alkyl esters or mixtures of such esters,

[0099] (a-4c) 0 wt% to 40 wt% olefinic unsaturated C2-C 20 Monocarboxylic acids or dicarboxylic acids or functional derivatives of such acids,

[0100] (a-4d) 0% to 40% by weight of monomers containing epoxy groups.

[0101] (a-4e) 0% to 50% by weight diene monomers, and

[0102] (a-4f) 0% to 5% by weight of other free radical polymerizable monomers

[0103] Components (a-4b), (a-4c) and (a-4d) together account for at least 1% to 45% by weight based on components (a-4a) to (a-4f).

[0104] Component A-4 is typically present in the thermoplastic polymer blend (A) at an amount of 0.5% to 10% by weight, preferably 0.5% to 7.5% by weight, and particularly 0.75% to 6% by weight. It has been found that at least 0.5% by weight of component A-4 improves the adhesion of the thermoplastic molding composition (M) to the substrate surface. However, if the amount of component A-4 is too high, the melt stability of the thermoplastic molding composition (M) decreases, and the processing speed must be reduced during the extrusion coating process to obtain a qualified coated article.

[0105] Examples of suitable α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 2-methylpropene, 3-methyl-1-butene, and 3-ethyl-1-butene, with ethylene and propylene being preferred.

[0106] Examples of suitable esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the corresponding esters of decyl acrylate / methacrylic acid. Among these, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate are particularly preferred.

[0107] In addition to or in addition to these esters, olefin polymers may also contain acid-functionalized monomers and / or potentially acid-functionalized monomers of olefinically unsaturated monocarboxylic or dicarboxylic acids.

[0108] Examples of olefinically unsaturated monocarboxylic or dicarboxylic acids include acrylic acid, methacrylic acid, tertiary alkyl esters of these acids (especially tert-butyl acrylate), and dicarboxylic acids (such as maleic acid and fumaric acid) or derivatives of these acids, as well as their monoesters.

[0109] "Potentially acidic functional monomers" should be understood to mean compounds that form free acidic groups under polymerization conditions or during the incorporation of olefin polymers into molding materials. Examples include anhydrides of dicarboxylic acids (especially maleic anhydride) having 2 to 20 carbon atoms and tertiary C1-C groups of the aforementioned acids. 12 Alkyl esters (especially tert-butyl acrylate and tert-butyl methacrylate).

[0110] Suitable monomers containing epoxy groups include glycidyl methacrylate and glycidyl acrylate.

[0111] Suitable diene monomers include, for example, conjugated dienes having 4 to 8 carbon atoms, such as isoprene and butadiene; non-conjugated dienes having 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene; cyclic dienes, such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene; and alkenyl norbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methylallyl-5-norbornene and 2-isopropenyl-5-norbornene; and tricyclic dienes, such as 3-methyltricyclo[5.2.1.0.2.6]-3,8-decadiene; or mixtures thereof. The preferred materials are 1,5-hexadiene, 5-ethylidene norbornene, and dicyclopentadiene.

[0112] Other useful monomers include, for example, vinyl esters and vinyl ethers.

[0113] Preferably, component A-4 is a copolymer composed of the following:

[0114] (a-4a) 50% to 94.8% by weight, preferably 55% to 79.5% by weight, of at least one α-olefin having 2 to 8 carbon atoms, preferably ethylene.

[0115] (a-4b) 5% to 40% by weight, preferably 20% to 40% by weight of C1-C of acrylic acid or methacrylic acid 12 Alkyl esters or mixtures of such esters, preferably esters of acrylic acid or methacrylic acid;

[0116] (a-4c) 0.1 wt% to 20 wt%, preferably 0.5 wt% to 20 wt%, of an olefinically unsaturated monocarboxylic acid or dicarboxylic acid or a functional derivative thereof, preferably acrylic acid and / or maleic anhydride; and

[0117] (a-4d) 0.1% to 20% by weight, preferably 0.2% to 20% by weight, of monomers containing epoxy groups, preferably glycidyl acrylate and / or glycidyl methacrylate.

[0118] Particularly suitable functionalized rubbers are random (ethylene-methyl acrylate-glycidyl methacrylate) copolymers, (ethylene-methyl methacrylate-glycidyl methacrylate) copolymers, (ethylene-methyl acrylate-glycidyl acrylate) copolymers, and (ethylene-methyl methacrylate-glycidyl acrylate) copolymers. Random (ethylene-methyl acrylate-glycidyl methacrylate) copolymers are particularly preferred.

[0119] The aforementioned polymer can be produced by methods known per se, preferably by random copolymerization under high pressure and high temperature. The melt flow index of the copolymer (A-4) is typically in the range of 1 g / 10 min to 80 g / 10 min (measured at 190 °C under a load of 2.16 kg).

[0120] The above-mentioned type of epoxy-containing copolymers can be obtained, for example, from SK Functional Polymers via Lotader. ® Purchased from the brand. Lotader ® The AX8900 is particularly useful.

[0121] Component A-5

[0122] According to the present invention, the thermoplastic polymer blend (A) comprises at least one polyolefin wax (A-5) prepared by a metallocene catalyst, wherein the polyolefin wax is a homopolymer of ethylene, a copolymer of ethylene and one or more 1-olefins, or a homopolymer of propylene, wherein the one or more 1-olefins may be linear or branched, substituted or unsubstituted, and have 3 to 18 carbon atoms, wherein the polyolefin wax (A-5) is polarly modified by reacting the polyolefin wax with α,β-unsaturated carboxylic acids or their derivatives.

[0123] The thermoplastic molding composition (M) according to the invention is characterized in particular by the presence of component A-5, which is a polyolefin wax prepared by a metallocene catalyst, in an amount of 0.05% to 1% by weight, preferably 0.07% to 0.7% by weight, more preferably 0.1% to 0.5% by weight, based on the total weight of the molding composition. The polyolefin wax is a homopolymer of ethylene, a copolymer of ethylene and one or more 1-olefins, or a homopolymer of propylene. The one or more 1-olefins may be linear or branched, substituted or unsubstituted, and have 3 to 18 carbon atoms. The polyolefin wax is polarly modified by reacting it with α,β-unsaturated carboxylic acids or their derivatives.

[0124] The use of component A-5 in the described amount improves processing characteristics, particularly in extrusion, i.e., no additive deposition or reduced additive deposition during processing, and in particular, no die drooling or reduced die drooling is observed.

[0125] The 1-olefin can be straight-chain or branched, substituted or unsubstituted, and has 3 to 18 carbon atoms, preferably 3 to 6 carbon atoms. Examples are propylene, 1-butene, 1-hexene, 1-octene, and 1-octadecene, as well as styrene. Copolymers of ethylene with propylene or 1-butene are preferred. The copolymer has an ethylene content of 70% to 99.9% by weight, preferably 80% to 99% by weight. If the 1-olefin is substituted, the substituent is preferably an aromatic group conjugated with the double bond of the 1-olefin.

[0126] Particularly suitable polyolefin waxes for use as raw materials, i.e., unpolarized polyolefin waxes, are homopolymers of ethylene or copolymers of ethylene with one or more 1-olefins, preferably having a dropping point in the range of 90°C to 130°C, more preferably 100°C to 120°C, as determined according to ASTM D 3954; a melt viscosity at 140°C preferably in the range of 10 mPa·s to 10,000 mPa·s, more preferably 50 mPa·s to 5,000 mPa·s; and a melt viscosity at 20°C, preferably 0.89 g / cm³, as determined according to ISO 1183. 3 Up to 1.05 g / cm 3 More preferably 0.91 g / cm 3 Up to 0.99 g / cm 3 Density within a certain range. In the case of copolymers of ethylene with one or more 1-olefins as comonomers, the comonomer units may be predominantly random or predominantly block-based. In the case of propylene as the 1-olefin, the propylene sequence may be isotactic, syndiotactic, or partially atactic.

[0127] Other suitable polyolefin waxes used as raw materials, i.e., unpolarized polyolefin waxes, are propylene homopolymers prepared using metallocene catalysts and preferably with a melt viscosity of 20 mPa·s to 50,000 mPa·s measured at 170 °C. The softening point (ring / sphere) of such waxes is typically from 90 °C to 165 °C, preferably from 90 °C to 145 °C. Suitable waxes are highly crystalline products with a high proportion of isotactic or syndiotactic structures and those with low crystallinity and a predominantly atactic structure. The crystallinity of propylene homopolymers can be varied within a wide range in a known manner by appropriately selecting the catalyst used for polymerization and by the polymerization conditions.

[0128] Synthesis of unmodified, i.e., nonpolar starting waxes via metallocene catalysts is known from numerous documents, such as EP-A-0 571 882 and EP-A-0416 566.

[0129] The metallocene catalyst used to prepare the starting polyolefin wax is of formula M. 1 L X Chiral or achiral transition metal compounds. Transition metal compound M 1 L X Contains at least one central metal atom M 1 It has at least one p-ligand, such as a cyclopentadienyl ligand, attached to it. Additionally, substituents such as halogen atoms or alkyl, alkoxy, or aryl groups can be attached to the central metal atom M. 1 M 1 Preferably, the elements are group III, IV, V, or VI elements of the periodic table, such as Ti, Zr, or Hf. For the purposes of this invention, the cyclopentadienyl ligand is an unsubstituted cyclopentadienyl group or a substituted cyclopentadienyl group, such as methylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenyl-indenyl, tetrahydroindenyl, or octahydrofluorenyl groups. The p-ligand can be bridged or unbridged, and can have a single bridge or multiple bridges, including bridges via a ring system.

[0130] The term metallocene also encompasses compounds having more than one metallocene fragment, called polynuclear metallocenes. These can have any substitution mode and bridging form. The individual metallocene fragments of such polynuclear metallocenes can be of the same type or different from each other. Examples of such polynuclear metallocenes are described, for example, in EP-A-0 632 063.

[0131] The structural formulas of metallocenes and examples of their activation by co-catalysts are given in particular in EP-A-0 571 882 and EP-A-0416 566.

[0132] Polyolefin waxes are polarized by reacting them with α,β-unsaturated carboxylic acids or their derivatives, preferably in the presence of a free radical forming agent.

[0133] Examples of suitable α,β-unsaturated carboxylic acids or their derivatives are acrylic acid or methacrylic acid or their esters or amides, maleic acid, maleic anhydride, maleic acid monoesters (e.g., monoalkyl maleate), maleic acid diesters (e.g., dialkyl maleate), or maleic acid amides (e.g., maleimides or N-alkyl-substituted maleimides). Mixtures of these compounds may also be used. Maleic acid and its derivatives are preferred; maleic anhydride is particularly preferred. The amount of α,β-unsaturated carboxylic acids or their derivatives used is from 0.1% by weight to 20% by weight based on the starting polyolefin wax.

[0134] Suitable free radical forming agents are compounds that decompose into free radicals to a sufficient extent under reaction conditions. Particularly suitable free radical forming agents are organic peroxides, such as alkyl, aryl, or aralkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; peroxide esters, such as tert-butyl peracetate or tert-butyl perbenzoate; or hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide. Other possible free radical forming agents are aliphatic azo compounds, such as azobis-(2-methylpropionitrile) or 2,2'-azobis-(2,4-dimethylpentanonitrile). Dialkyl peroxides are preferred, and di-tert-butyl peroxide is particularly preferred. The free radical forming agent is used at a concentration of 0.1% to 5% by weight based on the starting polyolefin wax.

[0135] The reaction of starting polyolefin wax with α,β-unsaturated carboxylic acids or their derivatives can be carried out continuously or intermittently. In an intermittent process, the wax is heated to a temperature above its softening point, and the α,β-unsaturated carboxylic acids or their derivatives and a free radical forming agent are introduced into the melt while stirring. This introduction can be continuous over an appropriate time period or in one or more portions, and if desired, under an inert gas atmosphere. The reaction temperature is above the softening point of the wax, preferably 100°C to 200°C, particularly preferably 130°C to 180°C. After the metered addition is complete, the mixture can be further reacted at the same or different temperatures, if desired, after the addition of an additional amount of free radical forming agent. Volatile components formed during the reaction or excess volatile starting components can be removed, for example, by vacuum distillation or by stripping with an inert gas.

[0136] The polar wax, namely component A-5 of the present invention, preferably has an acid value or saponification value (determined according to DIN EN ISO 2114) of 0.5 mg KOH / g to 120 mg KOH / g, more preferably 1 mg KOH / g to 100 mg KOH / g, and most preferably 5 mg KOH / g to 80 mg KOH / g; preferably 20 mPa·s to 50,000 mPa·s, more preferably 25 mPa·s to 5,000 mPa·s, and most preferably 30 mPa·s to 500 mPa·s; and a preferred softening point (ring / sphere) of 90°C to 165°C, preferably 90°C to 145°C.

[0137] Preferably, component A-5 is a homopolymer of ethylene or a copolymer of ethylene with one or more 1-olefins, which may be linear or branched, substituted or unsubstituted, and have 3 to 18 carbon atoms. This component is polar modified by reacting a polyolefin wax with maleic anhydride.

[0138] More preferably, it is a homopolymer of ethylene, which is polarized by reacting a polyolefin wax with maleic anhydride.

[0139] This type of product can be, for example, as Licocene. ® PE MA 4221 fine particles were commercially available from Clariant Plastics & Coatings (Deutschland) GmbH.

[0140] Component B

[0141] According to the present invention, the thermoplastic molding composition (M) may further contain 0% to 70% by weight of other additives, different from components (A-1) to (A-5), as component B, based on 100% by weight of the total of components A and components B. Specifically, the thermoplastic molding composition (M) may contain up to 50% by weight of other additives and processing aids, different from components (A-1) to (B-1), based on 100% by weight of the total of components A and components B.

[0142] Generally, all known additives and processing aids commonly used in polyester-based thermoplastic molding compositions are suitable as component B. These are generally known to those skilled in the art. As component B, the thermoplastic molding composition (M) according to the invention may contain conventional processing aids such as stabilizers, oxidation inhibitors, agents resistant to thermal and UV degradation, flow aids and release agents, nucleating agents such as sodium phenylphosphine, alumina, silica, nylon 22, and colorants such as dyes and pigments or plasticizers. Other polymers may also be included, especially impact modifiers or polyesters different from component A-1.

[0143] According to one embodiment of the invention, the thermoplastic molding composition (M) may optionally contain at least one epoxidized oil or oil mixture as a component (B-1) to further improve the processability of the thermoplastic molding composition (M). In the epoxidized oil or oil mixture, at least some of the unsaturated fatty acids in the parent fatty acid ester of the oil or oil mixture have 12 to 22 carbon atoms. Such oils as raw materials for epoxidation may be petrochemical, vegetable, or animal-derived, and may exist in pure form and be mixed with each other, and thus added to the thermoplastic polymer blend (A) as pure epoxidized oil or a mixture of such epoxidized oils.

[0144] Various oils and mixtures thereof that can withstand epoxidation are described in column 2, line 33 to column 3, line 12 of US 9,034,965 B2, and these oils and mixtures thereof are also suitable for use as components according to the invention (B-1).

[0145] Suitable epoxidized oils as component (B-1) include epoxidized oils based on vegetable oils selected from the group consisting of soybean oil, linseed oil, rapeseed oil, castor oil, cottonseed oil, olive oil, peanut oil, sunflower oil, corn oil, and hemp seed oil, and these epoxidized oils are preferred. Epoxidized oils based on vegetable oils selected from the group consisting of soybean oil, linseed oil, rapeseed oil, and castor oil are particularly suitable.

[0146] Epoxidized oil (B-1) and its mixtures are typically used in amounts of 0% to 5% by weight based on thermoplastic polymer blends (A), and are typically used in amounts of 0% to 3% by weight.

[0147] The thermoplastic molding composition (M) according to the invention may contain 0% to 5% by weight of talc as a preferred nucleating agent B. This is preferably used in an amount of 0.001% to 4% by weight, especially 0.01% to 1% by weight.

[0148] Talc is hydrated magnesium silicate, in which other trace elements may be present, such as Mn, Ti, Cr, Ni, Na and K, and the OH groups may be replaced by fluorides.

[0149] Talc is particularly preferred, having a particle size of less than 20 μm to a 100% degree extent. The particle size distribution is typically determined by sedimentation analysis and is preferably <20 μm: 100 wt%, <10 μm: 99 wt%, <5 μm: 85 wt%, <3 μm: 60 wt%, <2 μm: 43 wt%. Such products are commercially available from Micro-Talc IT extra.

[0150] Examples of oxidation inhibitors and heat stabilizers are hindered phenols and / or phosphites, hydroquinone, aromatic secondary amines (such as diphenylamine), various substituted representatives of these groups, and mixtures thereof, with a concentration of at most 1 wt% based on the weight of the thermoplastic molding material.

[0151] Examples of UV stabilizers (typically used in amounts of up to 2% by weight based on the molding material) include various substituted resorcinols, salicylates, benzotriazoles, and benzophenones.

[0152] Inorganic and organic pigments and dyes such as aniline black and anthraquinone can be added as colorants. Particularly suitable colorants are described, for example, in EP 1 722 984 B1, EP 1 353 986 B1 or DE 10054859 A1.

[0153] As an additive (“lubricant, flow aid and release agent”) in component B, the thermoplastic molding composition (M) according to the invention may contain an ester or amide of a saturated or unsaturated aliphatic carboxylic acid having 10 to 40, preferably 16 to 22 carbon atoms and an aliphatic saturated alcohol or amine having 2 to 40, preferably 2 to 6 carbon atoms.

[0154] Carboxylic acids can be mono- or di-carboxylic. Examples include nonanoic acid, palmitic acid, lauric acid, heptadecanic acid, dodecanoic acid, benzalkonium chloride, and particularly preferred are stearic acid, decanoic acid, and linalic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0155] Aliphatic alcohols can be mono- to tetra-membered. Examples of alcohols include n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, with glycerol and pentaerythritol being preferred here.

[0156] Aliphatic amines can be monofunctional to trifunctional. Examples include stearamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Therefore, preferred esters or amides are correspondingly glyceryl distearate, glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobehenate, and pentaerythritol tetrastearate.

[0157] Mixtures of different esters or amides can also be used, or combinations of esters and amides in any desired mixing ratio can be used.

[0158] Monocarboxylic or polycarboxylic acids, preferably fatty acid-esterified or etherified polyether polyols or polyester polyols, are also suitable. Suitable products are commercially available, for example, Loxiol. ® EP 728 was purchased from Henkel KGaA.

[0159] Preferred ethers derived from alcohols and ethylene oxide have the following general formula:

[0160] RO(CH2CH2O) n H

[0161] Where R is an alkyl group having 6 to 40 carbon atoms, and n is an integer greater than or equal to 1. Particularly preferred R is a group that can be soluble in Lutensol. ® The AT 50 was purchased from BASF and is saturated with C 16 To C 18 Fatty alcohols, where n is approximately 50.

[0162] Other examples of such additives (“lubricants, flow aids, and release agents”) are long-chain fatty acids (such as stearic acid or behenic acid), their salts (such as calcium stearate or zinc stearate), or lignite waxes (a mixture of straight-chain saturated carboxylic acids with a chain length of 28 to 32 carbon atoms) and calcium or sodium lignite, as well as low molecular weight polyethylene or polypropylene waxes.

[0163] The additives (“lubricants, flow aids and release agents”) of component B above are typically used in an amount of up to 1% by weight based on the total mixture.

[0164] Examples of plasticizers used as additives for component B are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, and N-(n-butyl)benzenesulfonamide.

[0165] The molding material according to the invention may also contain 0% to 2% by weight of a fluorinated ethylene polymer. These are ethylene polymers with a fluorine content of 55% to 76% by weight, preferably 70% to 76% by weight.

[0166] Examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers, or tetrafluoroolefin copolymers containing a small proportion (usually up to 50% by weight) of copolymerizable olefinically unsaturated monomers. These are described, for example, by Schildknecht in “Vinyl and Related Polymers”, Wiley-Verlag, 1952, pp. 484–494, and by Wall in “Fluoropolymers” (Wiley Interscience, 1972).

[0167] These fluorinated vinyl polymers are uniformly distributed in the molding material and preferably have a particle size d50 (number average) in the range of 0.05 μm to 10 μm, especially 0.1 μm to 5 μm. These small particle sizes are particularly preferably achieved by using an aqueous dispersion of the fluorinated vinyl polymer and introducing it into the polymer melt.

[0168] Other conventional additives B include, for example, up to 40% by weight, preferably up to 15% by weight, an amount of an elastomeric polymer (also commonly referred to as an impact modifier, elastomer, or rubber).

[0169] Examples of impact modifiers include rubbers that may have functional groups. A mixture of two or more different impact-modified rubbers may also be used.

[0170] Rubbers that enhance the toughness of molding materials typically comprise an elastomer portion with a glass transition temperature of less than -10°C, preferably less than -30°C, and contain at least one functional group capable of reacting with polyamide. Suitable functional groups include, for example, carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic amides, carboxylic imides, amino groups, hydroxyl groups, epoxides, carbamates, or oxazoline groups, preferably carboxylic anhydride groups.

[0171] Suitable rubbers include core-shell grafted rubbers. These are grafted rubbers produced in an emulsion, consisting of at least one hard component and one soft component. The hard component is typically a polymer with a glass transition temperature of at least 25°C, while the soft component is a polymer with a glass transition temperature not exceeding 0°C. These products have a structure consisting of a core and at least one shell, the structure of which is determined by the order in which the monomers are added. The soft component is typically derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates, or siloxanes and optionally other comonomers. Suitable siloxane cores can be generated, for example, from cyclic oligomeric octamethyltetrasiloxane or from tetravinyltetramethyltetrasiloxane. These can be reacted, for example, with γ-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization reaction, preferably in the presence of sulfonic acid, to form a soft siloxane core. Siloxanes can also be crosslinked, for example, by polymerization in the presence of silanes having hydrolyzable groups such as halogens or alkoxy groups, such as tetraethoxysilane, methyltrimethoxysilane, or phenyltrimethoxysilane. Suitable comonomers include, for example, styrene, acrylonitrile, and crosslinking or grafting monomers having more than one polymerizable double bond, such as diallyl phthalate, divinylbenzene, butanediol diacrylate, or triallyl (iso)cyanurate. The hard components are typically derived from styrene, α-methylstyrene, and their copolymers; preferred comonomers are acrylonitrile, methacrylonitrile, and methyl methacrylate.

[0172] Preferred core-shell grafted rubbers comprise a soft core and a hard shell, or a hard core, a first soft shell, and at least one other hard shell. The incorporation of functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, carbamate, urea, lactam, or halobenzyl groups is preferably achieved here by adding suitable functionalizing monomers during the polymerization of the final shell. Suitable functionalizing monomers include, for example, maleic acid, maleic anhydride, monoesters or diesters of maleic acid, tert-butyl (meth)acrylate, acrylic acid, glycidyl (meth)acrylate, and vinyloxazoline. Based on the total weight of the core-shell grafted rubber, the proportion of monomers having functional groups is typically from 0.1% to 25% by weight, preferably from 0.25% to 15% by weight. The weight ratio of the soft component to the hard component is typically from 1:9 to 9:1, preferably from 3:7 to 8:2.

[0173] Such rubbers are known in themselves and are described, for example, in publication EP 0 208 187. The incorporation of oxazine groups for functionalization can be achieved, for example, according to EP 0 791606.

[0174] Another suitable group of impact modifiers is thermoplastic polyester elastomers. Polyester elastomers are block coether esters comprising long segments typically derived from poly(alkylene)ether glycols and short segments derived from low molecular weight glycols and dicarboxylic acids. Such products are known in themselves and described in the literature, for example, in U.S. Patent No. 3,651,014. A corresponding product may also be named Hytrel. ™ (Du Pont), Arnitel ™ (Akzo) and Pelprene ™ Obtained through commercial purchase from Toyobo Co., Ltd.

[0175] It should be understood that mixtures of different rubbers can also be used.

[0176] Other additives B may include polyesters or polycarbonates that are different from component A-1.

[0177] Process for producing a thermoplastic molding composition (M)

[0178] The thermoplastic molding composition (M) according to the invention can be produced and subsequently extruded by methods known per se, in conventional mixing equipment such as a (twin)-screw extruder, Brabender mill, or Banbury mill, by mixing starting components (A-1), (A-2), (A-3), (A-4), and (A-5) and optional component (B). After extrusion, the extrudate can be cooled and pulverized. Alternatively, the individual components can be premixed, and then the remaining raw materials can be added separately and / or similarly as a mixture. Components (A-2), (A-3), (A-4), (A-5), and optional (B) can be added in the form of one or more masterbatches, preferably using a polymer compatible with component (A-1) as the matrix. For example, a masterbatch comprising 30% to 90% by weight, preferably 50% to 85% by weight, of a semi-aromatic polyester based on the total weight of the masterbatch, and 10% to 70% by weight, preferably 15% to 50% by weight, of at least one of components (A-2), (A-3), (A-4), (A-5), and optionally (B), or a mixture of at least two of the above, based on the total weight of the masterbatch. The mixing temperature is typically about 230°C to 320°C. Specifically, the individual components can also be added as “hot feed” or directly to the feed section of the extruder. It will be apparent to those skilled in the art that the thermoplastic polymer blend (A) can be obtained by the same method without adding component (B). Therefore, the thermoplastic molding composition (M) can be obtained by mixing the thermoplastic polymer blend (A) and optionally component (B).

[0179] Use of a thermoplastic molding composition (M)

[0180] The thermoplastic molding composition (M) can be used to prepare molded articles and extrusion applications, including films, coated films, sheets, profiles, fibers, and bristles. According to one embodiment, the thermoplastic molding composition (M) is preferably used to prepare coated films, especially films obtained by extrusion coating.

[0181] The thermoplastic molding composition (M) exhibits high melt stability and only slight necking during extrusion, which enables extrusion coating processes at high line speeds. Therefore, it can be advantageously used as a coating material, for example, in coating processes such as extrusion coating.

[0182] Coated article (S)

[0183] In another aspect, the present invention relates to a coated article (S) comprising:

[0184] (S-1) At least one substrate layer (S-1), and

[0185] (S-2) At least one coating (S-2).

[0186] in

[0187] At least one coating (S-2) is applied to at least one surface of at least one substrate layer (S-1), and wherein

[0188] At least one coating (S-2) comprises or is composed of the thermoplastic molding composition (M) according to the invention.

[0189] The substrate layer (S-1) can be any known material. Typically, materials such as polymers, fibrous materials (such as paper-based materials), fabrics, and metal foils, or combinations thereof, can be used. Preferred materials are selected from paper-based substrate materials, and particularly include paper, paperboard, cardboard, and corrugated cardboard.

[0190] The thickness of the substrate layer (S-1) is generally not limited, that is, the present invention is not limited to coated articles (S) having a specific minimum or maximum thickness of the substrate layer (S-1).

[0191] The thickness of the coating (S-2) is generally not limited, meaning the invention is not limited to a coated article (S) having a specific minimum or maximum thickness of the coating (S-2). According to one embodiment of the invention, the thickness of the coating (S-2) may not exceed 50 μm, for example, in the range of 1 μm to 30 μm, preferably in the range of 5 μm to 25 μm. According to an alternative embodiment of the invention, the thickness of the coating (S-2) may exceed 50 μm. The thickness of the coating (S-2) can be calculated from the weight of the coated article (S), the density of the thermoplastic molding composition (M), and the weight of the substrate layer (S-1).

[0192] The thermoplastic molding composition (M) exhibits high adhesion to various substrate materials used as the substrate layer (S-1), particularly paper-based substrate materials, and especially including paper, paperboard, cardboard, and corrugated cardboard. Therefore, it is unnecessary to apply an adhesive layer, glue, primer, etc., to the surface of the paper-based material before applying the thermoplastic molding composition (M) to the surface of the substrate layer (S-1). Thus, in one embodiment, the coated article (S) is characterized in that the coating (S-2) is directly located on the surface of the substrate layer (S-1), i.e., no additional material is located between the surface of the substrate layer (S-1) and the coating (S-2).

[0193] Process for producing a coated article (S)

[0194] In another aspect, the present invention also relates to a method for producing a coated article (S) according to the present invention, wherein the method comprises at least the following method steps:

[0195] (i) Provide a substrate layer (S-1);

[0196] (ii) Providing a thermoplastic molding composition (M) according to the invention;

[0197] (iii) a melt thermoplastic molding composition (M), and

[0198] (iv) Apply the molten thermoplastic molding composition (M) obtained in step (iii) to at least a portion of at least one surface of the substrate layer (S-1) to obtain a coating (S-2) comprising the thermoplastic molding composition (M) or composed of the thermoplastic molding composition.

[0199] The substrate layer (S-1) can be provided by any known method. Typical substrate layers, such as paper-based substrate materials, are commercially available. For example, commercially available paper-based substrate materials include Magno Star paper (e.g., Magno Star 58gsm) available from Sappi Ltd. or Cupforma paper (e.g., Cupforma Natura) available from Stora Enso Oyj. ™ 195gsm).

[0200] The thermoplastic molding composition (M) can be provided by components (A-1), (A-2), (A-3), (A-4), and (A-5), and optionally (B), for example, by the method described above. The thermoplastic molding composition (M) can also be provided by directly melt-blending its components in step (iii) of the method. Melting of the thermoplastic molding composition (M) or its components as a blend can be achieved by known methods, for example in conventional mixing equipment such as a (twin)screw extruder, a Brabender mill, or a Banbury mill, followed by extrusion. To obtain a substantially liquid melt, the thermoplastic molding composition (M) or its components as a blend are brought to a temperature above the melting temperature of the thermoplastic molding composition (M), typically in the range of 230°C to 320°C, preferably 250°C to 300°C. Preferably, a twin-screw extruder is used.

[0201] According to method step (iv), the molten thermoplastic molding composition (M) obtained in step (iii) is applied to at least a portion of at least one surface of the substrate layer (S-1). Application can be achieved by known coating processes, such as extrusion coating, dip coating, brush coating, roll coating, spray coating, spin coating, and flow coating. Preferably, an extrusion coating process is selected.

[0202] Preferably, the molten thermoplastic molding composition (M) obtained in step (iii) is applied to at least a portion of at least one surface of the substrate layer (S-1) by an extrusion coating process, for example, by immersing the molten thermoplastic molding composition (M) obtained in step (iii) through a slit die approaching at least one surface of the substrate layer (S-1). Preferably, the substrate layer (S-1) is continuously conveyed along the slit die such that the melt curtain is oriented tangentially or perpendicularly to the substrate layer (S-1). The substrate is typically conveyed at a speed greater than 0.1 m / min, typically greater than 1 m / min, for example greater than 20 m / min or greater than 50 m / min. The maximum possible conveying speed is not particularly limited by the thermoplastic molding composition (M) according to the invention. By adjusting the conveying speed, the amount of molten thermoplastic molding composition (M) applied to a certain surface area of ​​the substrate layer (S-1) can be adjusted to obtain the desired thickness of the coating (S-2).

[0203] Preferably, the method for producing the coated article (S) according to the invention includes at least one additional step (v), wherein the coated article (S) obtained in step (iv) is cooled to a temperature below the melt temperature of the thermoplastic molding composition (M), for example, below 200°C, preferably below 150°C, and for example below 100°C. Rapid cooling of the coating (S-2) reduces the risk of crystal formation in the coating (S-2), thereby improving its properties. Furthermore, rapid cooling allows for direct rewinding of the coated substrate (S) after the coating process.

[0204] According to one embodiment of the method for producing the coated article (S) according to the invention, the substrate layer (S-1) is a paper-based substrate material, and the method includes an additional method step (before step iv), wherein the paper-based substrate material is pretreated by flame treatment and / or corona treatment of at least one surface to which the coating (S-2) is applied before performing method step (iv). This method step (before step iv) can be performed at any point after method step (i) and before method step (iv). Preferably, the method set (before step iv) is performed in parallel with method step (iii) and directly before method step (iv), for example, less than 30 seconds before method step (iv), particularly less than 10 seconds before method step (iv). This allows the thermoplastic molding composition (M) to adhere better to the surface of the substrate layer (S-1). Preferably, the method step (before step iv) is performed by a combination of flame treatment and corona treatment of at least one surface to which the coating (S-2) is applied.

[0205] Preferably, the method for producing the coated article (S) according to the invention does not include a method step in which an additional chemical compound or chemical composition is applied to the surface of the substrate layer (S-1) prior to method step (iv) to improve the adhesion of the thermoplastic molding composition (M) to it. Specifically, no adhesive layer, glue, primer, etc., is applied to the surface of the substrate layer (S-1) prior to method step (iv).

[0206] Use of a coated article (S)

[0207] The resulting coated article (S) can be used in many applications, such as as packaging material (P), such as packaging materials for solid, liquid and / or oily substances, especially for food, for animal feed, for medical or pharmaceutical products, for industrial or waterproof packaging materials.

[0208] Other suitable applications include coatings for structural materials such as laminates, wood, chipboard, or fiber wood, or chemicals (concrete, plastics, etc.).

[0209] Packaging material (P)

[0210] In another aspect, the present invention also relates to a coating article (S) according to the invention or a packaging material (P) composed of such a coating article according to the invention. The coating article (S) exhibits a good combination of properties, such as high moisture and oxygen barrier properties, combined with good grease and oil barrier properties and grease and oil resistance, and even with a low layer thickness of the coating (S-2), the coating (S-2) has good adhesion to the substrate layer (S-1), i.e., reduced consumption of the thermoplastic molding composition (M).

[0211] Use of a packaging material (P)

[0212] Packaging materials (P) can be used as packaging materials for liquids and / or oily substances, especially for food, animal feed, medical or pharmaceutical products, industrial or waterproof packaging materials.

[0213] The present invention will be further illustrated by the following embodiments and claims.

[0214] Experimental examples

[0215] Examples and comparative examples were prepared using the following materials in the proportions given in Table 1:

[0216] A-1 poly(butylene terephthalate), wherein the melt volume rate is 8 cm³ / min to 10 cm³ / min (measured at 250°C under a 2.16 kg load), can be Ultradur ® B6550 (BASF SE) obtained.

[0217] A-2 aqueous solution of polyacrylic acid (approximately 49% wt dry content, determined according to ISO 3251, 150°C, 2 hours), with a weight-average molecular weight of 5 kg / mol (determined by GPC), a viscosity of approximately 500 mPa·s (determined according to EN12092, Brookfield 25°C), and a K value of approximately 25 (determined according to ISO 1628-1, 1% water), can be used in Sokalan. ® PA 25 XS (BASF SE) obtained.

[0218] A-3 is an epoxy-containing styrene copolymer that can be used with Joncryl ® ADR 4400 (SK FunctionalPolymer) was obtained.

[0219] A-4 random ethylene-methyl acrylate-glycidyl methacrylate (EMA-GMA) terpolymer can be used as a lotader. ® Obtained from AX8900 (SK Functional Polymer).

[0220] A-5 maleic anhydride-grafted metallocene polyethylene wax can be ligocene. ® PE MA4221 (Clariant AG) was obtained.

[0221] B-1 epoxidized linseed oil, Vikoflex ® 7190 (Arkema Group) acquired it.

[0222] Substrate

[0223] The paper-based substrate is selected from Magno Star 58gsm (further referred to as Magno Star) purchased from Sappi or Cupforma Natura purchased from Stora Enso. ™ 195gsm (further known as Cuforma).

[0224] Thermoplastic molding compositions were produced using a ZE-40 twin-screw extruder with vacuum degassing at an average throughput of 75 kg / h. The screw speed was set to 200 rpm, and the melt temperature was maintained at 280°C. Thermoplastic molding compositions were obtained as granules by granulation.

[0225] Melt volumetric flow rate (MVR, 250℃ / 2.16 kg [cm³ / 10 min]) was determined according to ISO 1133-1. The values ​​are reported in Table 1.

[0226] Table 1. Compositions of examples and comparative examples (amounts of the constituent parts A-1 to A-5 and B-1 used to form the compositions given in wt.-%) .

[0227]

[0228] Extrusion coating experiments were conducted on a roll-to-roll extrusion coating machine using two different substrates: paper (Magno Star) and cardboard (Cupforma). The substrates (paper or cardboard) were continuously fed and could be pretreated with both flame bars and / or corona discharge. The polymer melt was then extruded onto the continuously conveyed substrate, and the coated paper was rewound after immersion in cooling rolls. The substrate could be conveyed at speeds ranging from 80 m / min to 300 m / min. The polymer was extruded through a heated 50 cm slit die at a melt temperature of approximately 300°C using a single-screw extruder with a screw diameter of 60 mm (length / diameter ratio = 30). The maximum conveying speed was determined for each thermoplastic molding composition combined with the corresponding substrate. The maximum conveying speed was reached when an unstable coating was observed (unstable melt curtain, wavy edges, or defective coating). The maximum conveying speeds are given in m / min in Tables 2 to 5 below and refer to the speed at which the substrate is conveyed along the extruder die.

[0229] To determine the adhesion between the coating and the substrate surface, each substrate was coated with the corresponding thermoplastic molding composition at four different conveying speeds (100 m / min, 120 m / min, 200 m / min, and 250 m / min). To evaluate the adhesion between the coating and the substrate, the coating was peeled off the substrate, and the results were categorized by a trained person. The categorization of the five levels of adhesion is defined as follows:

[0230] 1 = There is no adhesion between the coating and the substrate; peeling off the coating does not damage the paper.

[0231] 2 = Poor adhesion, some paper fibers are torn off.

[0232] 3 = Poor adhesion; the separated polymer film tears off less than 50% of the paper area.

[0233] 4 = Medium adhesion; more than 50% of the peeled polymer film is still covered by the detached substrate.

[0234] 5 = Perfect adhesion, cohesive breakdown of the coated substrate, 100% peelable polymer covered by adhesive paper.

[0235] Table 2 summarizes the results for paper substrates (Magnostar) pretreated with corona, Table 3 summarizes the results for paper substrates (Magnostar) pretreated with a combination of corona and flame treatment, Table 4 summarizes the results for cardboard substrates (Cupforma) pretreated with corona, and Table 5 summarizes the results for cardboard substrates (Cupforma) pretreated with a combination of corona and flame treatment.

[0236] Table 2. Results of paper coating (Mangostar) with paper substrate treated by corona .

[0237]

[0238] As can be seen from the experimental data in Table 2, the composition according to Reference Example Ref. 1 produces unsatisfactory adhesion and only allows for a limited maximum conveying speed. A comparison of Ref. 1 with Comparative Examples 1, 2, and 3 demonstrates that the addition of component A-4 improves both adhesion and maximum conveying speed. However, while higher amounts of component A-4 tend to produce better adhesion (Comparative Examples 1 to 3), the maximum conveying speed decreases at 5% by weight (Comparative Example 3). A comparison of Comparative Examples 3 and 4 shows that the maximum conveying speed is improved in the presence of component A-5. Therefore, component A-5 is essential for achieving high linear speeds. A comparison of Comparative Example 5 and Example 1 of the present invention shows that the best results are obtained regarding both the maximum possible conveying speed and the adhesion between the coating and the substrate material using the thermoplastic molding composition according to the present invention. Component A-2 is able to increase both adhesion and linear speed and can compensate for the loss of linear speed caused by the addition of a large amount of A-4.

[0239] Table 3. Results of paper coating (Mangostar) with paper substrate treated by a combination of corona and flame .

[0240]

[0241] The experimental data provided in Table 3 confirm the observations in Table 2 regarding the maximum possible conveying speed and the adhesion between the coating and the substrate material. Furthermore, by comparing the results in Table 3 with those in Table 2, it can be seen that pretreatment of the paper substrate material using a combination of corona and flame pretreatment further improves the surface adhesion.

[0242] Table 4. Results of cardboard coating (Cupforma) with paper substrate treated by corona .

[0243]

[0244] The experimental data provided in Table 4 confirm the observations obtained in Table 2 regarding the maximum possible conveying speed and the adhesion between the coating and the substrate material. Furthermore, by comparing the results in Table 4 with those in Table 2, it can be seen that the cardboard substrate material exhibits better surface adhesion compared to the paper substrate material. A higher concentration of component A-2 further increases adhesion (comparison between Example 1 and Example 2).

[0245] Table 5. Results of cardboard coating (Cupforma) with paper substrate treated by a combination of corona and flame .

[0246]

[0247] The experimental data provided in Table 5 further confirm the previous observations obtained in Tables 2 and 4 regarding the maximum possible conveying speed and the adhesion between the coating and the substrate material. Furthermore, by comparing the results in Table 5 with those in Table 4, it can be seen that surface adhesion is further improved when the paper substrate material is pretreated with a combination of corona and flame pretreatment.

[0248] In summary, component A-4 is essential for excellent adhesion; however, at higher concentrations, there is a trade-off in the maximum achievable linear velocity. Component A-2 can compensate for component A-4 and further increase adhesion. Component A-5 is essential for good processability.

Claims

1. A thermoplastic molding composition (M) comprising: (A) 30% to 100% by weight of at least one thermoplastic polymer blend (A), said at least one thermoplastic polymer blend comprising or consisting of the following: (A-1) 81.5% to 99.39% by weight of at least one semi-aromatic polyester (A-1). (A-2) 0.01% to 2% by weight of at least one acrylic polymer (A-2), said at least one acrylic polymer being composed of the following: (a-2a) is based on 70% to 100% by weight of acrylic acid (a-2a) in the formula (A-2), and (a-2b) Based on (A-2) from 0% to 30% by weight of at least one other olefinic unsaturated monomer (a-2b) capable of copolymerizing with acrylic acid, said other olefinic unsaturated monomer being selected from the group consisting of monoolefinic unsaturated carboxylic acids; (A-3) 0.05% to 5% by weight of at least one epoxy-containing vinyl aromatic copolymer (A-3). (A-4) 0.5% to 10% by weight of at least one epoxy-containing olefin copolymer (A-4). (A-5) 0.05% to 1.5% by weight of at least one polyolefin wax (A-5) prepared by a metallocene catalyst, wherein the polyolefin wax is a homopolymer of ethylene, a copolymer of ethylene and one or more 1-olefins, or a homopolymer of propylene, wherein the one or more 1-olefins can be linear or branched, substituted or unsubstituted, and have 3 to 18 carbon atoms. The polyolefin wax (A-5) is polarized by reacting the polyolefin wax with α,β-unsaturated carboxylic acids or their derivatives. The total proportions of components (A-1), (A-2), (A-3), (A-4), and (A-5) are 100% by weight. and (B) 0% to 70% by weight of one or more other additives and processing aids (B). The sum of the proportions of component (A) and component (B) is 100 by weight.

2. The thermoplastic molding composition (M) according to claim 1, wherein the at least one acrylic polymer (A-2) comprises the following: (a-2a) is based on 85% to 100% by weight of acrylic acid (a-2a) in the formula (A-2), and (a-2b) Based on (A-2) at least 0% to 15% by weight of at least one other olefinic unsaturated monomer (a-2b) capable of copolymerizing with acrylic acid, said other olefinic unsaturated monomer being selected from the group consisting of said monoolefinic unsaturated carboxylic acids.

3. The thermoplastic molding composition (M) according to claim 1 or 2, wherein the at least one acrylic polymer (A-2) has a weight-average molecular weight M in the range of 1,000 g / mol to 12,000 g / mol. W .

4. The thermoplastic molding composition (M) according to any one of claims 1 to 3, wherein the thermoplastic molding composition (M) comprises 0.05% to 1.5% by weight of the at least one acrylic polymer (A-2).

5. The thermoplastic molding composition (M) according to any one of claims 1 to 4, wherein the thermoplastic molding composition (M) comprises 0.05% to 2.5% by weight of at least one epoxy-containing vinyl aromatic copolymer (A-3) selected from poly(styrene-glycidyl ether-methyl methacrylate).

6. The thermoplastic molding composition (M) according to any one of claims 1 to 5, wherein the at least one epoxy-containing olefin copolymer (A-4) is selected from one or more copolymers comprising: (a-4a) 50% to 94.8% by weight of at least one α-olefin having 2 to 8 carbon atoms; (a-4b) 5% to 40% by weight of C1-C of acrylic acid or methacrylic acid 12 Alkyl esters or mixtures of such esters; (a-4c) 0.1 wt% to 20 wt% of olefinically unsaturated monocarboxylic or dicarboxylic acids or functional derivatives of such acids; and (a-4d) 0.1 wt% to 20 wt% of monomers containing epoxy groups, The sum of the proportions of the components (a-4a), (a-4b), (a-4c), and (a-4d) is 100 by weight.

7. The thermoplastic molding composition (M) according to any one of claims 1 to 5, wherein the at least one thermoplastic polymer blend (A) comprises or is composed of the following: (A-1) 87.5% to 99.33% by weight of at least one semi-aromatic polyester (A-1). (A-2) 0.05% to 1.5% by weight of the at least one acrylic polymer (A-2). (A-3) 0.05% to 2.5% by weight of the at least one epoxy-containing vinyl aromatic copolymer (A-3). (A-4) 0.5% to 7.5% by weight of the at least one epoxy-containing olefin copolymer (A-4). (A-5) 0.07% to 1% by weight of the at least one polyolefin wax (A-5).

8. The thermoplastic molding composition (M) according to any one of claims 1 to 7, wherein the thermoplastic molding composition (M) comprises 0% to 5% by weight of an epoxidized oil (B-1) or an oil mixture, wherein at least a portion of the unsaturated fatty acids in the base fatty acid ester of the oil or oil mixture contain 12 to 22 carbon atoms.

9. A method for producing a thermoplastic molding composition (M) according to any one of claims 1 to 8, wherein the method comprises at least the step of melt-mixing components (A-1), (A-2), (A-3), (A-4), (A-5) and optionally component (B).

10. Use of the thermoplastic molding composition (M) according to any one of claims 1 to 8 as a coating material.

11. Coated articles (S), including: (S-1) At least one substrate layer (S-1), and (S-2) At least one coating (S-2). in The at least one coating (S-2) is applied to at least one surface of the at least one substrate layer (S-1), and wherein The at least one coating (S-2) comprises or is composed of the thermoplastic molding composition (M) according to any one of claims 1 to 8.

12. The coated article (S) according to claim 11, wherein the substrate layer (S-1) comprises or is composed of the fiber substrate, wherein the fiber substrate is preferably selected from paper-based substrate materials.

13. A method for producing a coated article (S) according to claim 11 or 12, wherein the method comprises at least the following method steps: (i) Provide a substrate layer (S-1); (ii) Providing a thermoplastic molding composition (M) according to any one of claims 1 to 8; (iii) Melting the thermoplastic molding composition (M), and (iv) Apply the molten thermoplastic molding composition (M) to at least one surface of the substrate layer (S-1) to obtain a coating (S-2) comprising the thermoplastic molding composition (M) or composed of the thermoplastic molding composition.

14. A method for producing a coated article (S) according to claim 13, wherein the substrate layer (S-1) is a paper-based substrate material, and the method includes an additional method step (before iv), wherein the paper-based substrate material is pretreated by flame treatment or corona treatment of the at least one surface on which the coating (S-2) is applied prior to method step (iv).

15. Use of the coated article (S) according to claim 11 or 12 as a packaging material (P) or a structural material.

16. Packaging material (P), comprising or consisting of the coated article (S) according to claim 11 or 12.

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