EP3512901A1 - Polymerfilm enthaltend ein copolyamid eines diamins, einer dimersäure und eines lactams - Google Patents
Polymerfilm enthaltend ein copolyamid eines diamins, einer dimersäure und eines lactamsInfo
- Publication number
- EP3512901A1 EP3512901A1 EP17761524.2A EP17761524A EP3512901A1 EP 3512901 A1 EP3512901 A1 EP 3512901A1 EP 17761524 A EP17761524 A EP 17761524A EP 3512901 A1 EP3512901 A1 EP 3512901A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolyamide
- polymer film
- component
- film
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/02—Wrappers or flexible covers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/04—Polyamides derived from alpha-amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/04—Polyamides derived from alpha-amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
- C08J2377/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
Definitions
- the present invention relates to a polymer film (P) containing at least one copolyamide, wherein the copolyamide is prepared by polymerizing at least one lactam (A) and one monomer mixture (M). Moreover, the present invention relates to a process for producing the polymer film (P) and to the use of the polymer film (P) as a packaging film.
- Polyamides are industrially of particular importance, since they are characterized by very good mechanical properties, in particular they have a high strength and toughness, good chemical resistance and high abrasion resistance. They are used for example for the production of fishing lines, climbing ropes and carpets. In addition, polyamides are used for the production of packaging films and packaging bags.
- EP 0 352 562 describes films of copolyamides, wherein the copolyamides are prepared from ⁇ -caprolactam and preferably 1 to 10 parts by weight of a dimer acid and a diamine.
- the copolyamides can then be used for the production of flat or blown films. Likewise, they are suitable for the production of composite films.
- a disadvantage of the copolyamide films described in EP 0 352 562 is that they have a relatively low tear strength, a high modulus of elasticity and a low penetration energy.
- the object underlying the present invention was to provide a polymer film containing a polyamide and having the disadvantages of the prior art polymer films described not or only to a reduced extent.
- the polymer film should also be as simple and inexpensive to produce.
- (B2) contains at least one C4-Ci2-diamine, wherein the weight percent of components (A) and (B) are each based on the sum of the weight percent of components (A) and (B).
- the polymer film (P) according to the invention has a high tear strength both in the direction of extrusion and perpendicular thereto. This is particularly advantageous when the polymer film (P) according to the invention is used as a packaging film.
- the polymer film (P) according to the invention has a high transparency and a high low-temperature toughness. It is also advantageous that the polymer film (P) according to the invention is less stiff than the polymer films (P) described in the prior art which contain a polyamide or a copolyamide. In addition, the polymer film (P) of the present invention has a low modulus of elasticity and a high puncture resistance in the dry state. The high puncture resistance is also particularly important when the polymer film (P) is used as a packaging film.
- the polymer film (P) contains at least one copolyamide.
- the polymer film (P) has, for example, a thickness in the range from 0.1 ⁇ m to 1 mm, preferably a thickness in the range from 5 to 500 ⁇ m, and particularly preferably in the range from 20 to 100 ⁇ m.
- the present invention therefore also relates to a polymer film (P) in which the polymer film (P) has a thickness in the range from 0.1 ⁇ m to 1 mm.
- the polymer film (P) may contain, in addition to the at least one copolyamide, at least one further polymer (wP).
- At least one further polymer (wP) means both exactly one further polymer (wP) and a mixture of two or more further polymers (wP) It goes without saying that the at least one further polymer (wP) is different from the at least one copolyamide.
- the at least one further polymer (wP) is preferably selected from the group consisting of polyolefins, poly (ethylvinyl alcohols), poly (ethylvinylacetates), polyethylene terephthalates, polyvinylidene chlorides, maleic anhydride-grafted polyolefins, polyesters and ionomers.
- the at least one further polymer (wP) is particularly preferably selected from the group consisting of polyolefins, poly (ethylvinyl alcohols), poly (ethylvinylacetates), polyethylene terephthalates, polyvinylidene chlorides and polyolefins treated with maleic anhydride.
- the at least one other polymer (wP) is selected from the group consisting of polyolefins, maleic anhydride-grafted polyolefins, and ethylvinyl alcohols.
- At least one further polymer (wP) selected from the group consisting of polyolefins it is preferred that polyolefins additionally grafted with maleic anhydride be used as at least one further polymer (wP). It is possible that a mixture of polyolefins and polyolefins grafted with maleic anhydride is used as the at least one further polymer (wP).
- the polymer film (P) contains at least a first further layer of at least one further polymer (wP), wherein the at least one further polymer (wP) of the first another layer is selected from the group consisting of polyolefins grafted with maleic anhydride and the polymer film (P) comprises at least one second further layer of at least one further polymer (wP), wherein the at least one further polymer (wP) of the second further layer is selected from Group consisting of polyolefins.
- the polymer film (P) then preferably contains the first further layer between the first layer containing the at least one copolyamide and the second further layer.
- Polyolefins as such are known to those skilled in the art.
- Preferred polyolefins are polypropylene (PP), low-density polyethylene (LDPE), linear-low-density polyethylene (LLDPE) and very-low-density polyethylene (VLDPE).
- Linear low-density polyethylene (LLDPE) is a copolymer of ethylene and at least one C4-C8 ⁇ -olefin.
- Linear-low-density polyethylene (LLDPE) is characterized by long polymer chains with short side chains. The length of the side chains in linear-low-density polyethylene (LLDPE) is usually shorter than in low-density polyethylene (LDPE) and in medium-density polyethylene (MDPE).
- the melting point of linear-low-density polyethylene (LLDPE) is preferably in the range of 1 10 to 130 ° C, its density is in the range of 0.91 to 0.93 g / cm 3 .
- VLDPE Very-low-density polyethylene
- C 4 - Cs- ⁇ -olefin usually have a melting point in the range of 1 10 to 130 ° C and a density in the range of 0.86 to ⁇ 0.91 g / cm 3 .
- the proportion of C 4 -C 8 ⁇ -olefins in VLDPE is generally higher than in LLDPE.
- C 4 -C 8 - ⁇ -olefin is understood to mean linear and branched, preferably linear, alkylenes having 4 to 8 carbon atoms which are unsaturated in the a position, ie have a C-C double bond in the ⁇ position
- Examples of these are 1-butene, 1-pentene, 1-hexene, 1-heptane and 1-octene.1-butene, 1-hexene and 1-octene are preferred.
- Preferred poly (ethylene vinyl acetates) are copolymers of ethylene with vinyl acetate.
- ethylene ethylene vinyl acetates
- Preferred poly (ethylene vinyl acetates) are copolymers of ethylene with vinyl acetate.
- ethylene in the range of 82 to 99.9 wt.% Of ethylene and in the range of 0.1 to 18 wt.% Of vinyl acetate, preferably in the range of 88 to 99.9 wt.% Of ethylene and in the range of 0, 1 to 12 wt .-% vinyl acetate used for the preparation.
- Preferred poly (ethylenevinyl alcohols) are obtainable by complete or partial saponification of the above-described poly (ethylenevinylacetates).
- the poly (ethylene vinyl alcohols) contain in the range of 50 to 75 mole% ethylene and in the range of 25 to 50 mole% vinyl alcohol, based on the total amount of poly (ethylene vinyl alcohols).
- the polymer film (P) may contain the at least one further polymer (wP) as a blend (mixture) with the at least one copolyamide.
- the polymer film (P) to contain at least one first layer which contains the at least one copolyamide and the polymer film (P) to contain at least one further layer which contains the at least one further polymer (wP) , In this embodiment, it is preferred that the at least one first layer containing the at least one copolyamide contains no further polymer (wP).
- At least one first layer in the context of the present invention means both exactly one first layer and two or more first layers.
- At least one further layer means both exactly one further layer and two or more further layers, two or more further layers being preferred.
- the polymer film (P) comprises at least one first layer which contains the at least one copolyamide, and the polymer film (P) also contains at least one further layer, wherein the at least one further layer comprises at least one further polymer (wP). selected from the group consisting of polyolefins, poly (ethylene vinyl alcohols), poly (ethylene vinyl acetates), polyethylene terephthalates,
- Polyvinylidenchloriden and gelled with maleic anhydride polyolefins contains.
- the present invention thus also provides a polymer film (P) in which the polymer film (P) contains at least one first layer containing the at least one copolyamide, and the polymer film (P) contains at least one further layer, wherein the at least one further Layer at least one further polymer (wP) selected from the group consisting of polyolefins, poly (ethylene vinyl alcohols), poly (ethylene vinyl acetates), polyethylene terephthalates, polyvinylidene chlorides and maleic anhydride gegrafteten polyolefins containing.
- the polymer film (P) contains at least one first layer containing the at least one copolyamide
- the polymer film (P) contains at least one further layer
- the at least one further Layer at least one further polymer (wP) selected from the group consisting of polyolefins, poly (ethylene vinyl alcohols), poly (ethylene vinyl acetates), polyethylene terephthalates, polyvinylidene chlorides and maleic anhydride gegrafteten polyo
- the polymer film (P) contains no further layer in addition to the at least one first layer, then the polymer film (P) is also referred to as monofilm. If the polymer film (P) is a monofilm, it may contain exactly one first layer and no further layer, and it is also possible that it contains two or more first layers and no further layer. If the polymer film (P) contains two or more first layers and is a monofilm, the two or more first layers all have the same composition.
- the polymer film (P) contains at least one first layer which contains the at least one copolyamide, and at least one further layer which contains the at least one further polymer (wP), the polymer film (P) is also referred to as multilayer film.
- the polymer film (P) then contains 1 to 11 first layers containing the at least one copolyamide and 1 to 13 further layers containing the at least one further polymer (wP).
- the polymer film (P) contains 1 to 5 first layers containing the at least one copolyamide, and 1 to 1 1 further layers containing the at least one further polymer (wP).
- the polymer film (P) contains 1 to 3 first layers containing the at least one copolyamide, and 1 to 7 further layers containing the at least one further polymer (wP).
- the at least one first layer consists of the at least one copolyamide. It is likewise preferred that the at least one further layer consists of the at least one further polymer (wP).
- polymer film (P) in the context of the present invention thus comprises both monofilms and multilayer films.
- the present invention therefore also relates to a polymer film (P), wherein the polymer film (P) is a monofilm or a multilayer film.
- the polymer film (P) usually has a thickness in the range of 0.1 ⁇ to 1 mm, preferably in the range of 5 to 500 ⁇ and particularly preferably in the range of 10 to 100 ⁇ .
- the first layer has the same thickness as the polymer film (P), for example in the range of 0.1 ⁇ m to 1 mm, preferably in the range of 5 to 500 ⁇ and particularly preferably in the range of 10 to 100 ⁇ . If the polymer film (P) is monofilm and it contains two or more first layers, the thickness of each first layer is usually smaller than the thickness of the polymer film (P). The sum of the thicknesses of the individual first layers then generally corresponds to the thickness of the polymer film (P).
- the at least one first layer containing the at least one copolyamide then has a thickness in the range of 0.1 to 100 ⁇ , preferably in the range of 0.5 to 50 ⁇ and particularly preferably in the range of 0.5 to 15 ⁇ on.
- the thickness of the individual layers of the polymer film is (P), that is, the thickness of the at least one first layer containing the at least one copolyamide, and the thickness of the at least one further layer containing the contains at least one further polymer (wP), usually smaller than the thickness of the polymer film (P).
- the sum of the thicknesses of the individual layers then generally corresponds to the thickness of the polymer film (P).
- the at least one first layer containing the at least one copolyamide then has a thickness in the range from 0.1 to 100 ⁇ m, preferably in the range from 0.5 to 50 ⁇ m, and particularly preferably in the range from 0.5 to 15 ⁇ .
- the at least one further layer which contains the at least one further polymer (wP) then has, for example, a thickness in the range from 0.1 to 100 ⁇ m, preferably in the range from 0.5 to 50 ⁇ m, and particularly preferably in the range from 0 , 5 to 15 ⁇ .
- the polymer film (P) may contain at least one adhesion promoter. This embodiment is preferable when the polymer film (P) is a multilayer film.
- At least one adhesion promoter in the context of the present invention means both exactly one adhesion promoter and a mixture of two or more adhesion promoters.
- the at least one adhesion promoter can be contained together with the at least one copolyamide in the at least one first layer. It is likewise possible for the at least one adhesion promoter to be present together with the at least one further polymer (wP) in the at least one further layer. Moreover, it is possible for the at least one adhesion promoter to be present as at least one additional layer in the polymer film (P). This embodiment is preferred.
- the at least one adhesion promoter is present as at least one additional layer in the polymer film (P), then this at least one additional layer is preferably between the at least one further layer containing the at least one further polymer (wP) and the at least one first Layer containing the at least one copolyamide arranged.
- the at least one layer of the adhesion promoter has, for example, a thickness of 0.1 to 100 ⁇ m, preferably in the range of 0.5 to 50 ⁇ m, and particularly preferably in the range of 0.5 to 15 ⁇ m.
- adhesion promoters are known to those skilled in the art.
- Preferred adhesion promoters are copolymers of ethylene with maleic anhydride or a copolymer of ethylene with vinyl acetate.
- a copolymer of linear-low-density polyethylene (LLDPE) and maleic anhydride or a copolymer of ethylene and vinyl acetate is preferred, with> 18% by weight of vinyl acetate and ⁇ 82% by weight of ethylene being used for the preparation of the copolymer.
- LLDPE linear-low-density polyethylene
- These copolymers are commercially available, for example under the trade name Bynel 4105 from DuPont or Escorene FL001 19 from Exxon.
- Copolymers of ethylene with maleic anhydride and maleic anhydride grafted polymers or copolymers of ethylene are preferred as adhesion promoters.
- the polymer film (P) may also contain additives.
- additives are known to the person skilled in the art and are selected, for example, from the group consisting of stabilizers, dyes, antistatic agents, tackifiers, anti-block, processing aids, antioxidants, light stabilizers, UV absorbers, lubricants and nucleating agents.
- Suitable dyes are organic and inorganic pigments, such as, for example, sized titanium dioxide.
- Suitable tackifiers are, for example, polyisobutylene (PIB) or ethylvinylacetate (EVA).
- Suitable antiblocking agents are, for example, silica or calcium carbonate particles.
- Suitable light stabilizers are, for example, so-called HALS (hindered amine light stabilizers).
- HALS hinderedered amine light stabilizers
- ethylenebisstearamide (EBS) wax can be used as ethylenebisstearamide (EBS) wax can be used.
- Nucleating aids may be, for example, all types of organic or inorganic nucleating agents, such as talc.
- the additives may be contained both in the at least one first layer and in the at least one further layer. They can be contained in only one of these layers, as well as they are likely to be included in each of these layers.
- the polymer film (P) contains at least one copolyamide which is prepared by polymerization of the components
- component (A) and “at least one lactam” are used synonymously in the context of the present invention and therefore have the same meaning.
- component (B) and “a monomer mixture (M)”. These terms are also used synonymously in the context of the present invention and therefore have the same meaning.
- At least one lactam means both exactly one lactam and one mixture of two or more lactams, with exactly one lactam being preferred.
- the at least one copolyamide is prepared by polymerization of from 15 to 84% by weight of component (A) and from 16 to 85% by weight of component (B); the copolyamide is preferably prepared by polymerization from 40 to 83% by weight. % of component (A) and from 17 to 60% by weight of component (B), particularly preferably at least one copolyamide prepared by polymerization of from 60 to 80% by weight of component (A) and 20 to 40 wt .-% of component (B), wherein the weight percent of components (A) and (B) are each based on the sum of the weight percent of components (A) and (B). Preferably, the sum of the weight percent of components (A) and (B) gives 100 wt .-%.
- weight percentages of components (A) and (B) relate to the weight percentages of components (A) and (B) before the polymerization, that is, when components (A) and (B) are not yet together have reacted. During the polymerization, the weight ratio of the components (A) and (B) may change, if necessary.
- the copolyamide is prepared by polymerization of components (A) and (B).
- the polymerization of components (A) and (B) is known to the person skilled in the art.
- the polymerization of components (A) with (B) is a condensation reaction.
- component (A) reacts with components (B1) and (B2) contained in component (B) and optionally with component (B3) described below, which may likewise be present in component (B).
- component (A) during the polymerization is at least partially open-chain, ie as an amino acid.
- Suitable catalysts are all catalysts known to those skilled in the art, which catalyze the polymerization of components (A) and (B). Such catalysts are known in the art.
- Preferred catalysts are phosphorus compounds such as sodium hypophosphite, phosphorous acid, triphenylphosphine or triphenyl phosphite.
- the copolyamide is formed, which thus obtains building units derived from component (A) and building units derived from component (B). Building units derived from component (B) contain building blocks derived from components (B1) and (B2) and optionally from component (B3).
- the copolyamide forms as a copolymer.
- the copolymer may be a random copolymer, as well as it is possible that it is a block copolymer.
- blocks of units derived from component (B) and blocks of units derived from component (A) form. These alternate.
- units derived from component (A) alternate with units derived from component (B). from. This alternation occurs statistically, for example, two units derived from component (B) may be followed by a unit derived from component (A), followed by another unit derived from component (B), to which then a structural unit follows, containing three units derived from component (A).
- the at least one copolyamide is a random copolymer.
- the present invention therefore also provides a polymer film in which the at least one copolyamide is a random copolymer.
- the preparation of the at least one copolyamide preferably comprises the following steps: a) polymerization of components (A) and (B) to obtain at least one first copolyamide, b) granulation of the at least one first copolyamide obtained in step a) to obtain at least one granulated copolyamide c) extraction of the at least one granulated copolyamide obtained in step b) with water to obtain at least one extracted copolyamide; d) drying of the at least one extracted copolyamide obtained in step c) at a temperature (Tr) to obtain the at least one copolyamide.
- the present invention therefore also provides a polymer film (P) in which the copolyamide is prepared in a process comprising the following steps: a) polymerization of the components (A) and (B) to obtain at least one first copolyamide, b) granulation of the c) extraction of the at least one granulated copolyamide obtained in step b) with water to obtain at least one extracted copolyamide, d) drying of the at least one extracted extract obtained in step c) Copolyamides at a temperature (Tr) to obtain the at least one copolyamide.
- the polymerization in step a) can take place in all reactors known to those skilled in the art. Preference is given to stirred tank reactors.
- additives known to the person skilled in the art may be used to improve the reaction, such as defoamers such as polydimethylsiloxane (PDMS) can be used.
- PDMS polydimethylsiloxane
- step b) the at least one first copolyamide obtained in step a) can be granulated by all methods known to the person skilled in the art, for example by means of strand granulation or underwater granulation.
- step c) can be carried out by all methods known to the person skilled in the art.
- by-products formed during the polymerization of components (A) and (B) in step a) are usually extracted from the at least one granulated copolyamide.
- step d) the at least one extracted copolyamide obtained in step c) is dried.
- Methods for drying are known in the art.
- the at least one extracted copolyamide is dried at a temperature (Tr).
- the temperature (Tr) is preferably above the glass transition temperature (TG ⁇ C)) of the at least one copolyamide and below the melting temperature (TM ⁇ C)) of the at least one copolyamide.
- the drying in step d) is usually carried out for a period in the range of 1 to 100 hours, preferably in the range of 2 to 50 hours and more preferably in the range of 3 to 40 hours.
- step d the molecular weight of the at least one copolyamide is further increased.
- the at least one copolyamide usually has a glass transition temperature (TG ⁇ C)).
- the glass transition temperature (TG ⁇ O) is for example in the range of 20 to 50 ° C, preferably in the range of 23 to 47 ° C and particularly preferably in the range of 25 to 45 ° C, determined according to ISO 1 1357-2: 2014.
- the present invention therefore also provides a polymer film (P) in which the at least one copolyamide has a glass transition temperature (TG ⁇ C)), the glass transition temperature (TG ⁇ O) being in the range from 20 to 50 ° C.
- a polymer film (P) in which the at least one copolyamide has a glass transition temperature (TG ⁇ C)), the glass transition temperature (TG ⁇ O) being in the range from 20 to 50 ° C.
- the glass transition temperature (TG ⁇ C)) of the at least one copolyamide according to ISO 1 1357-2: 2014 in the context of the present invention refers to the glass transition temperature (TG ⁇ O) of the dry copolyamide.
- dry means that the at least one copolyamide contains less than 1% by weight, preferably less than 0.5% by weight and more preferably less than 0.1% by weight, based on water the total weight of the at least one copolyamide. More preferably, “dry” means that the at least one copolyamide does not contain water, and most preferably, the at least one copolyamide contains no solvent, and the at least one copolyamide usually has a melting temperature (M (C)).
- TM ⁇ O TM ⁇ O of the at least one copolyamide is for example in the range of 150 to 21 0 ° C, preferably in the range of 160 to 205 ° C and particularly preferably in the range of 1 60 to 200 ° C, determined according to ISO 1 1 357-3
- the present invention therefore also relates to a polymer film (P) in which the at least one copolyamide has a melting temperature (TM ⁇ C)), wherein the melting temperature (TM ⁇ C)) in the range of 150 to 21 0 ° C. lies.
- the at least one copolyamide generally has a viscosity number (VZ (o) in the range of 150 to 300 ml / g, determined in a 0.5 wt .-% solution of at least one copolyamide in a mixture of phenol / o-dichlorobenzene in the weight ratio 1: 1.
- VZ (o) viscosity number
- the viscosity number (VZ ⁇ o) of the at least one copolyamide is preferably in the range from 160 to 290 ml / g and particularly preferably in the range from 170 to 280 ml / g, determined in a 0.5% strength by weight solution of the at least one Copolyamide in a mixture of phenol / o-dichlorobenzene in the weight ratio 1: 1.
- the present invention therefore also relates to a polymer film (P) in which the at least one copolyamide has a viscosity number (VZ ⁇ o) in the range from 150 to 300 ml / g, determined in a 0.5% by weight solution of the at least a copolyamide in a mixture of phenol / o-dichlorobenzene in the weight ratio 1: 1.
- VZ ⁇ o viscosity number
- Component (A) is at least one lactam.
- Lactams are known to those skilled in the art. Lactams having 4 to 12 carbon atoms are preferred according to the invention.
- lactams are understood to mean cyclic amides which have in the ring preferably 4 to 12, particularly preferably 5 to 8, carbon atoms.
- Suitable lactams are for example selected from the group consisting of
- 6-aminohexanoic acid lactam hexano-6-lactam: ⁇ -lactam; ⁇ -caprolactam
- 7-aminoheptanoic acid lactam heptano-7-lactam; ⁇ -lactam; ⁇ -heptanolactam
- the present invention therefore also provides a polymer film (P) in which component (A) is selected from the group consisting of 3-aminopropanoic acid lactam, 4-aminobutanoic acid lactam, 5-aminopentanoic acid lactam, 6-aminohexanoic acid lactam, 7-aminoheptanoic acid lactam, 8-aminooctanoic acid lactam , 9-aminononanoic acid lactam, 10-aminodecanoic acid lactam, 1-amino undecanoic acid lactam and
- the lactams may be unsubstituted or at least monosubstituted. In the event that at least monosubstituted lactams are used, they may carry on the nitrogen atom and / or on the carbon atoms of the ring one, two or more substituents independently selected from the group consisting of C 1 to C 10 alkyl, C 5 - to C6-cycloalkyl and C5- to Cio-aryl.
- C 1 to C 10 -alkyl substituents are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
- a suitable C5 to C6 cycloalkyl substituent is, for example, cyclohexyl.
- Preferred C5 to Cio-aryl substituents are phenyl and anthranyl.
- Unsubstituted lactams are preferably used, with ⁇ -lactam ( ⁇ -butyrolactam), ⁇ -lactam ( ⁇ -valerolactam) and ⁇ -lactam ( ⁇ -caprolactam) being preferred. Particularly preferred are ⁇ -lactam ( ⁇ -valerolactam) and ⁇ -lactam ( ⁇ -caprolactam), with ⁇ -caprolactam being particularly preferred.
- component (B) is a monomer mixture (M).
- the monomer mixture (M) contains the components (B1), at least one C32-C4o dimer acid and (B2) at least one C4-C12 diamine.
- a monomer mixture (M) is understood as meaning a mixture of two or more monomers, where at least the components (B1) and (B2) are contained in the monomer mixture (M).
- component (B1) and “at least one C32-C4o dimer acid” are used synonymously in the context of the present invention and therefore have the same meaning.
- component (B2) and “at least one C4-C12 diamine”. These terms are also used synonymously in the context of the present invention and therefore have the same meaning.
- the monomer mixture (M) contains, for example, in the range from 45 to 55 mol% of component (B1) and in the range from 45 to 55 mol% of component (B2) in each case based on the sum of the molar percentages of components (B1) and ( B2), preferably based on the total amount of substance of component (B).
- Component (B) preferably contains in the range from 47 to 53 mol% of component (B1) and in the range from 47 to 53 mol% of component (B2) in each case based on the sum of the molar percentages of components (B1) and ( B2), preferably based on the total amount of substance of component (B).
- Component (B) particularly preferably contains in the range from 49 to 51 mol% of component (B1) and in the range from 49 to 51 mol% of component (B2), in each case based on the sum of the molar percentages of components (B1). and (B2), preferably based on the total amount of component (B).
- the present invention therefore also provides a polymer film (P) in which component (B) contains in the range from 45 to 55 mol% of component (B1) and in the range from 45 to 55 mol% of component (B2), in each case based on the total amount of component (B).
- component (B1) The sum of the molar percentages of components (B1) and (B2) contained in component (B) is usually 100 mol%.
- the component (B) may additionally contain a component (B3), at least one C 4 - C 20 diacid.
- the present invention therefore also provides a polymer film (P) in which component (B) additionally contains a component (B3), at least one C 4 -C 20 diacid.
- component (B3) and “at least one C 4 -C 20 diacid” are used synonymously in the context of the present invention and therefore have the same meaning.
- component (B) additionally contains component (B3), it is preferred that component (B) be used in the range from 25 to 54.9 mol% of component (B1), in the range from 45 to 55 mol%. % of component (B2) and in the range of 0.1 to 25 mol% of component (B3), in each case based on the total amount of component (B).
- the component (B) then particularly preferably contains in the range from 13 to 52.9 mol% of component (B1), in the range from 47 to 53 mol% of component (B2) and in the range from 0.1 to 13 mol% of component (B3), in each case based on the total amount of substance of component (B).
- component (B) then contains in the range of 7 to 50.9 mol% of component (B1), in the range of 49 to 51 mol% of component (B2) and in the range of 0.1 to 7 mol% of component (B3), in each case based on the total amount of substance of component (B).
- component (B) additionally contains component (B3)
- the mole percentages of components (B1), (B2) and (B3) usually add up to 100 mole percent.
- the monomer mixture (M) may also contain water.
- component (B1) and (B2) and optionally (B3) of the component (B) may react with each other to give amides. This reaction is known to those skilled in the art. Therefore, component (B) may contain components (B1) and (B2) and optionally (B3) in fully reacted form, in partially reacted form or in unreacted form. Component (B) preferably contains the components (B1) and (B2) and optionally (B3) in unreacted form.
- unreacted form means that component (B1) is present as the at least one C 32 -C 40 dimer acid and component (B2) is present as the at least one C 4 -C 12 diamine and optionally the component ( B3) as the at least one C4-C2o diacid.
- the component (B1) is according to the invention at least one C32-C4o dimer acid.
- At least one C32-C4o dimer acid in the context of the present invention means both exactly one C32-C4o dimer acid and one mixture of two or more C32-C40 dimer acids.
- Dimer acids are also referred to as dimer fatty acids.
- C32-C4o dimer acids are known to those skilled in the art and are usually prepared by dimerization of unsaturated fatty acids. This dimerization can be catalyzed by clays, for example.
- Suitable unsaturated fatty acids for preparing the at least one C 32 -C 40 dimer acid are known to the person skilled in the art and, for example, unsaturated C 16 -fatty acids, unsaturated cie fatty acids and unsaturated C 20 fatty acids.
- the component (B1) is therefore preferably prepared starting from unsaturated fatty acids selected from the group consisting of unsaturated C 16 -fatty acids, unsaturated cis-fatty acids and unsaturated C 20 fatty acids, the unsaturated cie fatty acids being particularly preferred.
- the present invention therefore also provides a polymer film (P) in which component (B1) is prepared starting from unsaturated fatty acids selected from the group consisting of unsaturated C 16 -fatty acids, unsaturated cis-fatty acids and unsaturated C 20 -fatty acids.
- a suitable unsaturated C 16 -fatty acid is, for example, palmitoleic acid ((9Z) -hexadeca-9-enoic acid).
- Suitable unsaturated cis-fatty acids are, for example, selected from the group consisting of petroselinic acid ((6Z) -octadeca-6-enoic acid), oleic acid ((9Z) -octadeca-9-enoic acid), elaidic acid ((9E) -octadeca-9-enoic acid ), Vaccenic acid ((1 1 E) - octadeca-1 1 -enoic acid), linoleic acid ((9Z, 12Z) -octadeca-9,12-dienoic acid), alpha-linolenic acid ((9Z, 12Z, 15Z) -Octadeca-9 , 12,15-trienoic acid), gamma-linolenic acid ((6Z, 9Z, 12Z) octadeca-6,9,12-trienoic acid), calendulic acid ((8E, 10E,
- Alpha-elaeostearic acid (9Z, 11E, 13E) -octadeca-9,1 1, 13-trienoic acid) and beta-elaeostearic acid ((9E, 11E, 13E) -octadeca-9, 11, 13-trienoic acid ).
- unsaturated cis-fatty acids selected from the group consisting of petroselinic acid ((6Z) octadeca-6-enoic acid), oleic acid ((9Z) octadeca-9-enoic acid), elaidic acid ((9E) octadeca- 9-enoic acid ), Vaccenic acid ((1 1 E) -octadeca-1-enoic acid), linoleic acid ((9Z, 12Z) -octadeca-9,12-dienoic acid).
- Suitable unsaturated C2o-fatty acids are, for example, selected from the group consisting of gadoleic acid ((9Z) -eicosa-9-enoic acid), icosenoic acid ((11Z) -eicosa-1-enoic acid), arachidonic acid ((5Z, 8Z, 1 1Z, 14Z) -eicosa-5,8,11,14-tetraenoic acid) and timnodonic acid ((5Z, 8Z, 11Z, 14Z, 17Z) -eicosa-5,8,1,1,14,7-pentaenoic acid).
- the component (B1) is particularly preferably at least one C36 dimer acid.
- the at least one C36 dimer acid is preferably prepared starting from unsaturated cis fatty acids. More preferably, the C36 dimer acid is prepared from cis fatty acids selected from the group consisting of petroselinic acid ((6Z) -octadeca-6-enoic acid), oleic acid ((9Z) -octadeca-9-enoic acid), elaidic acid (9E ) -Octadeca-9-enoic acid), Vaccenic acid ((1 L) octadeca-1-enoic acid) and linoleic acid ((9Z, 12Z) -octadeca-9,12-dienoic acid).
- cis fatty acids selected from the group consisting of petroselinic acid ((6Z) -octadeca-6-enoic acid), oleic acid ((9Z) -octadeca-9-enoic acid), elaidic acid
- trimer acids can form in the preparation of component (B1) from unsaturated fatty acids, and residues of unreacted unsaturated fatty acid can also be left over.
- component (B1) preferably contains at most 0.5% by weight of unreacted unsaturated fatty acid and at most 0.5% by weight of trimer acid, more preferably at most 0.2% by weight of unreacted unsaturated fatty acid and at most 0.2 % By weight of trimer acid, in each case based on the total weight of component (B1).
- Dimer acids also known as dimerized fatty acids or dimer fatty acids
- mixtures referred to which are prepared by oligomerization of unsaturated fatty acids.
- They can be prepared, for example, by catalytic dimerization of vegetable, unsaturated fatty acids, using as starting materials in particular unsaturated C 16- to C 20 -fatty acids.
- the linkage proceeds primarily according to the Diels-Alder type and, depending on the number and position of the double bonds of the fatty acids used to prepare the dimer acids, mixtures of predominantly dimeric products which are cycloaliphatic, linear-aliphatic, branched aliphatic and also between the carboxyl groups C6 have aromatic hydrocarbon groups.
- the aliphatic radicals may be saturated or unsaturated and also the proportion of aromatic groups may vary.
- the residues between the carboxylic acid groups then contain, for example, 32 to 40 carbon atoms.
- fatty acids containing 18 carbon atoms are used for the preparation, so that the dimeric product thus has 36 carbon atoms.
- the radicals linking the carboxyl groups of the dimer fatty acids have no unsaturated bonds and no aromatic hydrocarbon radicals.
- Linolenic, linoleic and / or oleic acid are particularly preferably used.
- dimer acids generally contain at least 80% by weight of dimeric molecules, up to 19% by weight of trimeric molecules and at most 1% by weight of monomeric molecules and other by-products. It is preferred to use dimer acids which consist of at least 90% by weight, preferably at least 95% by weight, very particularly preferably at least 98% by weight, of dimeric fatty acid molecules.
- the determination of the proportions of monomeric, dimeric and trimeric molecules and other by-products in the dimer acids can be carried out, for example, by means of gas chromatography (GC).
- GC gas chromatography
- the dimer acids are converted before the GC analysis via the boron trifluoride method to the corresponding methyl esters (see DIN EN ISO 5509) and then analyzed by GC.
- the basic characteristic of "dimer acids” is that their preparation comprises the oligomerization of unsaturated fatty acids, which is predominantly formed, ie preferably at least 80% by weight, more preferably at least 90% by weight. %, very particularly preferably at least 95% by weight and in particular at least 98% by weight of dimeric products
- unsaturated fatty acids which is predominantly formed, ie preferably at least 80% by weight, more preferably at least 90% by weight. %, very particularly preferably at least 95% by weight and in particular at least 98% by weight of dimeric products
- the dimer acids to be used can be obtained as commercial products. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976 and Radiacid 0977 from Oleon, Pripol 1006, Pripol 1009, Pripol 1012, and Pripol 1013 Croda, Empol 1008, Empol 1012, Empol 1061 and Empol 1062 from BASF SE and Unidyme 10 and Unidym Tl from Arizona Chemical.
- the component (B1) has, for example, an acid number in the range from 190 to 200 mg KOH / g.
- Component (B2) has, for example, an acid number in the range from 190 to 200 mg KOH / g.
- the component (B2) is according to the invention at least one C4-Ci2-diamine.
- At least one C 4 -C 12 -diamine in the context of the present invention means both exactly one C 4 -C 12 -diamine and a mixture of two or more C 4 -C 12 diamines.
- C 4 -C 12 -diamine is understood to mean aliphatic and / or aromatic compounds having four to twelve carbon atoms and two amino groups (-NH 2 groups)
- the aliphatic and / or aromatic compounds may be unsubstituted or additionally at least monosubstituted
- they may carry one, two or more substituents which are involved in the polymerization of Components (A) and (B) do not participate.
- substituents are, for example, alkyl or cycloalkyl substituents. These are known to those skilled in the art.
- the at least one C 4 -C 12 -diamine is preferably unsubstituted.
- Suitable components (B2) are, for example, selected from the group consisting of 1,4-diaminobutane (butane-1,4-diamine, tetramethylenediamine, putrescine), 1,5-diaminopentane (pentamethylenediamine, pentane-1,5-diamine, cadaverine) , 1, 6-diaminohexane
- Component (B2) is preferably selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.
- the present invention therefore also provides a polymer film in which component (B2) is selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.
- component (B3) is selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine.
- the component (B3) optionally contained in component (B) is at least one C4-C20 diacid according to the invention.
- "At least one C4-C2o-diacid” means in the context of the present invention, both exactly one C 4 -C2o-diacid and a mixture of two or more C 4 -C2o-diacids.
- C 4 -C 20 diacid is understood to mean aliphatic and / or aromatic compounds having two to eighteen carbon atoms and two carboxy groups (-COOH groups)
- the aliphatic and / or aromatic compounds may be unsubstituted or additionally at least monosubstituted
- they may carry one, two or more substituents which do not participate in the polymerization of the components (A) and (B)
- substituents are, for example, alkyl
- the at least one C 4 -C 20 diacid is preferably unsubstituted.
- Suitable components (B3) are, for example, selected from the group consisting of butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid, suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), Undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid and hexadecanedioic acid.
- the component (B3) is preferably selected from the group consisting of pentanedic acid (glutaric acid), hexanedioic acid (adipic acid), decanedioic acid (sebacic acid) and dodecanedioic acid.
- the polymer film (P) according to the invention is preferably prepared in a process comprising the following steps: i) providing at least one copolyamide; produced by polymerization of the components
- the present invention therefore also provides a process for producing a polymer film (P) according to the invention, comprising the steps of i) providing at least one copolyamide prepared by polymerization of the components
- At least one C4-Ci2-diamine wherein the weight percent of components (A) and (B) are each based on the sum of the weight percent of components (A) and (B), in molten form in a first extruder,
- step i) Extruding the at least one copolyamide in molten form provided in step i) from the first extruder through a die to give a film of the at least one copolyamide in molten form, iii) cooling the film of the at least one copolyamide in molten form obtained in step ii); wherein the at least one copolyamide solidifies to obtain the polymer film (P).
- step i) the at least one copolyamide is provided in molten form in a first extruder.
- a first extruder means both exactly one first extruder and two or more first extruders. Usually as many first extruders are used as first layers which contain the at least one copolyamide in which the polymer film (P) is contained should.
- the polymer film (P) contains exactly one first layer which contains the at least one copolyamide, exactly one first extruder is used. If the polymer film (P) contains exactly two first layers containing the at least one copolyamide, exactly two first extruders are used. If the polymer film (P) contains exactly five first layers containing the at least one copolyamide, exactly five first extruders are used. For example, 1 to 1 1 first extruder used, preferably 1 to 5 first extruder and more preferably 1 to 3 first extruder.
- step i) For the at least one copolyamide which is provided in step i), the previously described embodiments and preferences for the at least one copolyamide contained in the polymer film (P) apply correspondingly.
- the at least one copolyamide is provided in molten form.
- “In molten form” in the context of the present invention means that the at least one copolyamide is provided at a temperature which is above the melting temperature (TM ⁇ C)) of the at least one copolyamide.
- “In molten form” means that the at least a copolyamide has a temperature which is above the melting temperature (TM ⁇ C)) of the at least one copolyamide. If the at least one copolyamide is in molten form, the at least one copolyamide is free-flowing.
- Flowable means that the at least one copolyamide can be promoted in the first extruder and that the at least one copolyamide can be extruded from the first extruder.
- the at least one copolyamide in step i) is provided at a temperature in the range from 170 to 300 ° C., preferably in the range from 200 to 290 ° C. and particularly preferably in the range from 230 to 280 ° C., in each case with the proviso the temperature at which the at least one copolyamide is provided is above the melting temperature (TM ⁇ C)) of the at least one copolyamide.
- the at least one copolyamide can be provided in molten form in the first extruder by all methods known to those skilled in the art.
- the at least one copolyamide may be supplied in molten or solid form to the first extruder. If the at least one copolyamide is fed to the first extruder in solid form, it can be fed to the first extruder, for example, as granules and / or as a powder. The at least one copolyamide is then melted in the first extruder and thus provided in molten form in the first extruder. This embodiment is preferred.
- the components (A) and (B) are polymerized directly in the first extruder and thus the at least one copolyamide in molten form is provided in the first extruder. Processes for this are known to the person skilled in the art.
- step ii) the at least one copolyamide in molten form is extruded from the first extruder through a die to give a film of the at least one copolyamide in molten form.
- a nozzle means both exactly one nozzle and two or more nozzles. According to the invention, exactly one nozzle is preferred.
- Suitable nozzles are all nozzles known to those skilled in the art, which make it possible to extrude a film of the at least one copolyamide in molten form.
- Such nozzles are, for example, annular nozzles or slot nozzles. Suitable annular nozzles and slot nozzles are known in the art as such.
- step ii) the at least one copolyamide in molten form from the first extruder with the at least one further polymer (wP) in molten form from the further extruder in the Nozzle, for example in the annular nozzle or in the slot nozzle, is brought together.
- step ii) the at least one copolyamide in molten form from the first extruder with the at least one further polymer (wP) in molten form from the further extruder are combined in the nozzle in such a way that the film of the at least one obtained in step ii) Copolyamide and the at least one other polymer (wP), each in molten form, at least one first layer containing the at least one copolyamide in molten form, and at least one further layer containing the at least one further polymer (wP) in molten Contains form.
- the thickness of the film of the at least one copolyamide in molten form is in the range of 0.1 ⁇ m to 1 mm, preferably in the range of 5 to 500 ⁇ m, and particularly preferably in the range of 20 to 100 ⁇ m.
- the film of the at least one copolyamide in molten form may be, for example, a flat film or a tubular film.
- a tubular film is usually obtained when an annular nozzle is used as a nozzle, a flat film is obtained when a slit nozzle is used as a nozzle.
- step iii) the film of the at least one copolyamide obtained in step ii) is cooled in molten form.
- the at least one copolyamide solidifies to obtain the polymer film (P).
- the film of the at least one copolyamide may be cooled in molten form by air or water cooling or by contact with a cold surface.
- the film of the at least one copolyamide in molten form is cooled in step iii), for example to a temperature below the melting temperature (TM ⁇ O) of the at least one copolyamide, to obtain the polymer film (P).
- the film of the at least one copolyamide in molten form in step iii) is cooled to a temperature which is below the glass transition temperature (TG ⁇ C)) of the at least one copolyamide.
- the film of the at least one copolyamide in molten form is cooled to a temperature in the range of 0 to 100 ° C, preferably in the range of 10 to 80 ° C and particularly preferably in the range of 15 to 50 ° C, wherein the temperature, on in which the film of the at least one copolyamide is cooled in molten form, below the melting temperature (TM ⁇ O), preferably below the glass transition temperature (TG ⁇ O) of the at least one copolyamide.
- TM ⁇ O melting temperature
- the present invention therefore also provides a process for the preparation of a polymer film (P), in which in step iii) the film of the at least one copolyamide in molten form at a temperature below the melting temperature (TM ⁇ C)) of the at least one copolyamide is, is cooled.
- Steps ii) and iii) can be carried out successively or simultaneously.
- a step i 1) is preferably carried out, in which at least one further polymer (wP) is provided in molten form in a further extruder.
- the process for producing the polymer film (P) then comprises the following steps: i) providing at least one copolyamide prepared by polymerizing the components
- (B2) contains at least one C 4 -C 12 -diamine, the percentages by weight of components (A) and (B) in each case being based on the sum of the percentages by weight of components (A) and (B), in molten form in a first extruder, i1) providing at least one further polymer (wP) in molten form in a further extruder, ii) extruding the at least one copolyamide in molten form provided in step i) from the first extruder through a die and extruding the at least one further polymer (wP) provided in step i 1) in molten form from the further extruder through the die to obtain a film of the at least one copolyamide and of the at least one further polymer (wP), each in molten form, iii) cooling the film obtained in step ii) of the at least one copolyamide and the at least one other polymer (wP), each in molten form, wherein the at least one cop
- step i1) the at least one further polymer (wP) is provided in molten form in another extruder.
- another extruder means both exactly one further extruder and two or more further extruders, two or more further extruders are preferred, and as many further extruders are preferred as further layers containing the at least one further polymer.
- the polymer film (P) is to contain exactly one further layer, If the polymer film (P) contains exactly two further layers which contain the at least one further polymer (wP), exactly two further extruders are used, which contain at least one further polymer (wP) If the polymer film (P) exactly five further layers containing the at least one further polymer (wP) entha If so, exactly five more extruders are used.
- the previously described designs and preferences for the first extruder apply accordingly.
- the at least one further polymer (wP) the above-described embodiments and preferences for the optionally in the polymer film (P) contained at least one further polymer (wP) apply accordingly.
- the at least one further polymer (wP) in step i1) is provided in molten form.
- “In molten form” means that the at least one further polymer (wP) is provided at a temperature above the melting temperature (TM ⁇ W P)) of the at least one other polymer (wP)
- the "form” means that the at least one further polymer (wP) has a temperature which is above the melting temperature (TM ⁇ W P)) of the at least one further polymer (wP) Form before, then the at least one further polymer (wP) is flowable.
- Flowable means that the at least one further polymer (wP) can be conveyed in the further extruder and that the at least one further polymer (wP) can be extruded from the further extruder Step i 1) at a temperature in the range of 120 to 350 ° C, preferably in the range of 130 to 300 ° C and particularly preferably in the range of 140 to 250 ° C, provided, respectively, provided that the temperature at which the at least one further polymer (wP) is provided, above the melting temperature (TM ⁇ W P)) of the at least one further polymer (wP).
- the at least one further polymer (wP) can be provided in molten form in the further extruder by all methods known to those skilled in the art.
- the at least one further polymer (wP) can be supplied in molten or solid form to the other extruder. If the at least one further polymer (wP) is fed to the further extruder in solid form, then it can be fed to the further extruder, for example as granules and / or as a powder.
- the at least one further polymer (wP) is then melted in the further extruder and thus provided in molten form in the further extruder.
- Step i1) is usually carried out simultaneously with step i).
- the film obtained in step ii) of the at least one copolyamide and the at least one further polymer (wP), in each case in molten form, contains the at least one copolyamide in at least one first layer and the at least one further polymer (wP) in at least one further layer ,
- the film obtained in step ii) contains as many first layers containing the at least one copolyamide in molten form as were first extruders used in step i) and as many further layers containing the at least one further polymer (wP) in contain molten form, as more extruders have been used in step i1).
- the polymer film (P) obtained in step iii) is a multilayer film.
- the polymer film (P) is stretched.
- the polymer film (P) can be stretched after step iii), it is also possible to remove the polymer film (P) during step iii), ie during the cooling of the film of the at least one copolyamide and optionally the at least one further polymer (wP) to stretch.
- the subject of the present invention is therefore also a process in which additionally the following step is carried out: iv) drawing of the polymer film (P) to obtain a stretched polymer film (vP).
- Steps iii) and iv) can be performed sequentially or simultaneously.
- the polymer chains of the at least one copolyamide align and the crystallinity of the at least one copolyamide can be increased.
- the polymer chains of the at least one further polymer (wP) optionally present in the polymer film (P) also align during stretching.
- the crystallinity of the at least one further polymer (wP) can also increase.
- the stretching can be carried out by all methods known to the person skilled in the art.
- the polymer film (P) can be stretched by passing it over at least one roller, preferably a roller system, or by stretching it to its width.
- the polymer film (P) is obtained as a tube, it is also possible that the polymer film (P) is stretched by blowing air into the tube of the polymer film (P) and thereby stretching the polymer film (P).
- the polymer film (P) is guided over at least one roller, preferably via a roller system, then the polymer film (P) is stretched in the extrusion direction, ie in its length. If the polymer film (P), however, stretched in its width, it is stretched perpendicular to the extrusion direction.
- the polymer film (P) is guided for stretching over at least one roller, preferably via a roller system, then the polymer chains of the at least one copolyamide and, if appropriate, of the at least one further polymer (wP) are oriented parallel to the direction in which they are drawn , The resulting stretched polymer film (vP) is then uniaxially oriented. Also, the obtained stretched polymer film (vP) is uniaxially oriented when the polymer film (P) is stretched to stretch in width. Even then, the polymer chains of the at least one copolyamide and optionally of the at least one further polymer (wP) are oriented parallel to the direction in which they are drawn. "Uniaxially oriented" means that the polymer chains are oriented substantially in one direction.
- the polymer film (P) is guided over a roller system for stretching and additionally stretched in its width, then the polymer chains of the at least one copolyamide and optionally of the at least one further polymer (wP) are oriented parallel to both directions to be drawn.
- the resulting stretched polymer film (vP) is then biaxially oriented.
- "Biaxially oriented" means that the polymer chains are oriented substantially in two different directions, preferably perpendicular to each other.
- the polymer film (P) is obtained as a tube and the polymer film (P) is stretched by blowing air into the tube of the polymer film (P), the obtained stretched polymer film (vP) is uniaxially oriented.
- the polymer film (P) is obtained as a tube and the polymer film (P) is stretched by blowing air into the tube of the polymer film (P) and simultaneously passing it over rollers is also stretched, the obtained stretched polymer film (vP) is biaxially oriented.
- the polymer film (P) is usually stretched at a temperature which is above the glass transition temperature (TG ⁇ C)) of the at least one copolyamide and which is below the melting temperature (TM ⁇ C)) of the at least one copolyamide. If the polymer film (P) is a multilayer film, it is further preferred that the polymer film (P) be stretched at a temperature lower than the melting temperature (TM ( W P)) of the at least one other polymer (wP), particularly preferably at a temperature which is below the melting temperature of the melting at least one further polymer (wP) at the lowest temperature.
- the polymer film (P) of the present invention can be produced, for example, by a casting method, a blown method, a biaxially-oriented polyamide film method (BOPA method), or a multiblas method.
- the subject of the present invention is therefore also a polymer film (P) which is produced in a casting process, in a blown process, in a biaxially-oriented polyamide film process or in a multiblas process.
- the casting process, the blown process, the biaxially-oriented polyamide film process and the multi-glass process are known to those skilled in the art.
- the Polymer film (P) stretched in these methods so that a stretched polymer film (P) is obtained.
- a casting process for producing the polymer film (P) preferably comprises the following steps i-c) to iv-c): i) providing at least one copolyamide prepared by polymerizing the
- (B2) contains at least one C 4 -C 12 -diamine, the percentages by weight of components (A) and (B) in each case being based on the sum of the percentages by weight of components (A) and (B), in molten form in a first extruder, ii c) extruding the at least one copolyamide provided in step ic) from the first extruder through a die to give a film of the at least one copolyamide in molten form, iii c) cooling the film obtained in step ii-c) c) stretching the at least one copolyamide in molten form, the at least one copolyamide solidifying to obtain the polymer film (P), iv) c) stretching the polymer film (P) obtained in step iii-c) by passing the polymer film (P) over at least one roll , preferably via a roller system, is passed to obtain a stretched polymer film (vP).
- the nozzle used in the casting process in step ii-c) is usually a slot die.
- the film of the at least one copolyamide in molten form obtained in step ii-c) is therefore preferably a flat film, so that the polymer film (P) obtained in step iii-c) and the stretched polymer film (vp) obtained in step iv-c) are preferably a flat sheet is.
- steps iii-c) and iv-c) may be performed sequentially or simultaneously.
- steps iii-c) and iv-c) are carried out simultaneously, more preferably, steps iii-c) and iv-c) are carried out simultaneously and directly after step ii-c).
- the at least one roll used in step iv-c), preferably the roll system, is cooled during step iv-c).
- a blowing method for producing the polymer film (P) preferably comprises the following steps i-b) to iv-b): i) providing at least one copolyamide prepared by polymerizing the
- Components (A) 15 to 84% by weight of at least one lactam
- (B2) contains at least one C 4 -C 12 -diamine, the percentages by weight of components (A) and (B) in each case being based on the sum of the percentages by weight of components (A) and (B), in molten form in a first extruder, ii b) extruding the at least one copolyamide in molten form provided in step ib) from the first extruder through a die which is an annular die to melt a tubular film of the at least one copolyamide
- Copolyamides in molten form wherein the at least one copolyamide solidifies to obtain the polymer film (P), iv-b) stretching the polymer film (P) obtained in step iii-b) by blowing air into the hose of the polymer film (P) Obtaining a stretched polymer film (vP).
- the nozzle used in step ii-b) of the blowing process is preferably a stack dye, a helical distributor dye or a mixed form thereof. These nozzles are known in the art and described for example in "Blown Film Extrusion” by Kirk Cantor, 2nd Edition, Carl Hanser Verlag, Kunststoff 201 1.
- Steps iii-b) and iv-b) can be carried out simultaneously or sequentially in the blowing process.
- steps iii-b) and iv-b) are carried out simultaneously.
- step iii-b) the tubular film of the at least one copolyamide obtained in step ii-b) is cooled in molten form and simultaneously being drawn by blowing air into the tubular film to obtain the stretched polymer film (vP).
- a biaxially-oriented polyamide film process for preparing the polymer film (P) preferably comprises the following steps i-o) to iv-o): i) providing at least one copolyamide prepared by polymerizing the
- (B2) contains at least one C 4 -C 12 -diamine, the percentages by weight of components (A) and (B) in each case being based on the sum of the percentages by weight of components (A) and (B), in molten form in a first extruder, ii- o) extruding the at least one copolyamide provided in step io) in molten form from the first extruder through a die to obtain a film of the at least one copolyamide in molten form, iii o) cooling the film obtained in step ii-o) the at least one copolyamide in molten form, the at least one copolyamide solidifying to give the polymer film (P), iv-o) stretching the polymer film (P) obtained in step iii-o) by passing the polymer film (P) over at least one roll, preferably a roll system, and stretching it to obtain the stretched polymer film (vP) ,
- the nozzle used in the biaxially-oriented polyamide film process in step ii-o) is usually a slot die.
- the film of the at least one copolyamide in molten form obtained in step ii-o) is therefore preferably a flat film so that the polymer film (P) obtained in step iii-o) and the stretched polymer film (vP) obtained in step iv-o) is preferably one Flat film is.
- steps iii-o) and iv-o) can be carried out successively or simultaneously, preferably steps iii-o) and iv-o) are carried out successively.
- steps iii-o) and iv-o) are carried out successively and the polymer film (P) obtained in step iii-o) is heated before step iv-o). It is preferred that the polymer film (P) before step iv-o) is heated to a temperature which is above the glass transition temperature (TG ⁇ C)) of the at least one copolyamide contained in the polymer film (P) and which below the melting temperature ( TM ⁇ C)) of the at least one copolyamide contained in the polymer film (P). The polymer film (P) is then preferably stretched in step iv-o) at the temperature to which it is heated prior to step iv-o).
- TG ⁇ C glass transition temperature
- TM ⁇ C melting temperature
- a multi-glass process for producing the polymer film (P) preferably comprises the following steps i-m) to iv-m): i-m) providing at least one copolyamide prepared by polymerizing the
- the weight percentages of components (A) and (B) are each based on the sum of the weight percentages of components (A) and (B), in molten form in a first extruder, ii-m) extrusion of the one provided in step im) a copolyamide in molten form from the first extruder through a die which is an annular die to obtain a tubular film of the at least one copolyamide in molten form; iii-m) cooling the tubular film of the at least one copolyamide obtained in step ii-m) into molten one Mold, wherein the at least one copolyamide solidifies to obtain the polymer film (P), iv-m) stretching the polymer film (P) obtained in step iii-m) by blowing air into the hose of the polymer film (P) and simultaneously exposing the polymer film (P) Polymer film (P) over at least one roller, preferably a roller system,
- the tubular film of the at least one copolyamide is cooled in molten form in step iii-m) in a water bath.
- steps iii-m) and iv-m) can be carried out simultaneously or successively, preferably steps iii-m) and iv-m) are carried out successively. Particularly preferably, steps iii-m) and iv-m) are carried out successively and the polymer film (P) obtained in step iii-m) is heated before step iv-m).
- the polymer film (P) before step iv-m) is heated to a temperature which is above the glass transition temperature (TG ⁇ C)) of at least one copolyamide contained in the polymer film (P) and below the melting temperature (TM ⁇ C)) of the at least one copolyamide contained in the polymer film (P).
- the polymer film (P) is then preferably stretched in step iv-m) at the temperature to which it is heated prior to step iv-m).
- step i1) in which at least one further polymer (wP) in a further extruder in molten form and then according to step ii) of the process for producing the polymer film (P) in step ii-c), in step ii-b), in step ii-o) and in step ii-m) Film of the at least one copolyamide and the at least one other polymer (wP), in each case in molten form, is obtained and this is cooled according to step iii) of the process for producing the polymer film (P) in step iii-c), in step iii-b), in step iii-o) and in step iii-m).
- the previously described embodiments and preferences for the optionally performed step i1) of the method for producing the polymer film (P) apply accordingly.
- no step i1) is performed.
- no further polymer (wP) is preferably provided in a further extruder.
- the contained stretched polymer film (P) can be wound up after its production, for example. Processes for this are known to the person skilled in the art. If the stretched polymer film (vP) is contained as a tube, such as blow molding and the multi-glass process, the tube may also be slit prior to winding. A slit film can then be wound on one or more rollers.
- the polymer film (P) of the present invention is preferably used as a packaging film.
- the present invention therefore also relates to the use of the polymer film (P) according to the invention as a packaging film.
- the polymer film (P) of the present invention may be used as a tubular bag package, a side sealed bag package, a thermoformed package, sealable bags, and / or a pillow package.
- the properties of the polymer films (P) were determined as follows.
- the viscosity number of copolyamides containing units derived from a C 32 -C 40 dimer acid was determined in a 0.5% strength by weight solution of phenol / o-dichlorobenzene in a weight ratio of 1: 1 at 25 ° C.
- the viscosity number of copolyamides and polyamides containing no units derived from a C 32 -C 40 dimer acid was measured in a 0.5% by weight solution in 96% strength by weight sulfuric acid at 25 ° C. in accordance with EN ISO 307: 2007 + Amd 1: 2013 determined.
- the glass transition temperatures and melting temperatures were determined according to ISO 1 1357-1: 2009, ISO 1 1357-2: 2013 and ISO 1 1357-3: 201 1. For this purpose, two heating runs were carried out and the glass transition and melting temperatures were determined on the basis of the second heating run.
- the densities of the polyamides were determined by the gas pyknometer method according to EN ISO 1 183-3: 1999.
- the copolyamide was hydrolyzed in dilute hydrochloric acid (20%).
- the units derived from hexamethylenediamine are protonated, the chloride ion of the hydrochloric acid forming the counterion.
- this chloride ion was then exchanged for a hydroxide ion with liberation of hexamethylenediamine.
- the hexamethylenediamine concentration is then determined by titration with 0.1 molar hydrochloric acid, from which the content of polyamide 6.36 in the copolyamide can be determined.
- the tear strength is determined according to Elmendorf, DIN ISO 6383-2: 2004 in the direction of extrusion (MD) and perpendicular thereto (TD).
- MD direction of extrusion
- TD perpendicular thereto
- the films were conditioned in standard climate for non-tropical countries according to DIN EN ISO 291: 2008.
- the modulus of elasticity is determined according to ISO 527-3: 1995.
- the impact strength of the polymer film (P) was determined in accordance with DIN ISO 7765-2: 1994 with 5 test specimens at a relative air humidity of 0%, the puncture work being indicated in the present case.
- P-1 polyamide 6 from BASF SE® sold under the brand name Ultramid B40L with a viscosity number of 250 ml / g, a glass transition temperature of 57 ° C, a melting temperature of 220 ° C and a density of 1, 153 g / ml.
- P-2 polyamide 6 from BASF SE® sold under the brand name Ultramid B33L with a viscosity number of 195 ml / g, a glass transition temperature of 56 ° C, a melting temperature of 220 ° C and a density of 1.145 g / ml.
- P-3 copolymer of polyamide 6 and polyamide 6.6 (PA 6 / 6.6) from BASF SE® sold under the brand name Ultramid C40L with a viscosity number of 250 ml / g, a Glass transition temperature of 53 ° C, a melting temperature of 190 ° C and a density of 1, 143 g / ml.
- P-4 copolymer of polyamide 6 and polyamide 6.6 (PA 6 / 6.6) from BASF SE® sold under the brand name Ultramid C33L with a viscosity number of 195 ml / g, a
- component (B2) Hexamethylenediamine solution (component (B2)) in water, 100 g polyapp 2557-CTW antifoam reagent from Polymethylsiloxane from Polysteil do Brazil and 100 kg of water were mixed in a 1930 liter kettle and blanketed with nitrogen. The outside temperature of the kettle was heated to 290 ° C and the mixture contained in the kettle stirred for 1 1 hour
- the copolyamide was dried at 90 to 140 ° C in a stream of nitrogen for 10 hours.
- the viscosity number was 246 ml / g, the glass transition temperature at 49 ° C and the melting temperature at 21 1 ° C.
- the proportion of polyamide 6.36 in the copolyamide based on the total weight of the copolyamide was 10.5% by weight, the density was 1.116 g / ml.
- the copolyamide obtained had a viscosity number of 244 ml / g, a glass transition temperature of 44 ° C and a melting temperature of 203 ° C.
- the proportion of polyamide 6:36 in the copolyamide based on the total weight of the copolyamide was 20.8 wt .-%, the density was 1, 095 g / ml.
- a copolyamide of polyamide 6 and polyamide 6.36 prepared by the following procedure:
- the resulting granules of the copolyamide were extracted with 95 ° C hot water for 4 times 6 hours and then dried at 90 to 140 ° C in a stream of nitrogen for 10 hours.
- the copolyamide obtained had a viscosity number of 259 ml / g, a glass transition temperature of 38 ° C and a melting temperature of 188 ° C.
- the proportion of polyamide 6:36 in the copolyamide based on the total weight of the copolyamide was 30.3 wt .-%, the density was 1, 076 g / ml.
- a copolyamide of polyamide 6 and polyamide 6.36 prepared by the following procedure:
- the resulting granules of the copolyamide were extracted with 95 ° C hot water for 4 times 6 hours and then dried at 90 to 140 ° C in a stream of nitrogen for 10 hours.
- the copolyamide obtained had a viscosity number of 212 ml / g, a glass transition temperature of 38 ° C and a melting temperature of 187 ° C.
- the proportion of polyamide 6:36 in the copolyamide based on the total weight of the copolyamide was 28.9 wt .-%, the density was 1, 076 g / ml.
- WP-1 low density polyethylene from LyondellBasell® sold under the brand name Lupolen 2420 F with a MFR (melt flow rate) (190 ° C / 2.16 kg) of 0, 75 g / 10 min.
- WP-2 low density polyethylene from LyondellBasell® sold under the brand name Lupolen 3020 K with a MFR (melt flow rate) (190 ° C / 2.16 kg) of 4 g / 10 min.
- wP-3 anhydride-modified linear low density polyethylene from DuPont® sold under the brand name Bynel 4104 with a melt flow rate MFR (190 ° C / 2, 16 kg) of 1.1 g / 10 min.
- wP-4 anhydride-modified linear low density polyethylene from DuPont® sold under the trade name Bynel 4105 with MFR (melt flow rate) (190 ° C / 2.16 kg) of 4 g / 10 minute wP-5 a poly (ethylvinyl alcohol) (EVOH) from Kuraray®, sold under the brand name EVAL F171 B with an MFR (melt flow rate, melt mass flow rate)
- a 7-layer cast film plant from Collin® with a nozzle head width of 800 mm was used. So 7 extruders were used. Six of the extruders had a diameter of 30 mm (extruder B, C, D, E, F, G) and one extruder had a diameter of 45 mm (extruder A). Each of the 7 extruders was loaded with the same component. The melt of extruder A was in contact with the castroll, the melt of extruder G farthest from this. The order of the layers was A, B, C, D, E, F, G.
- the polymer films produced had a thickness of 100 ⁇ and the layers have a layer thickness of 15/14/14/14/14/14/15 ⁇ .
- the components used as well as the results of the measurement of the tear strength, modulus of elasticity and puncture resistance are given in Table 1.
- the percentages by weight of component (B) given in Table 1 are understood as meaning the percent by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide. Table V.
- Multilayer films with three different polymers were produced on the above-described 7-layer cast film plant from Collin®.
- the resulting multilayer films had a thickness of 100 ⁇ and the layers have a layer thickness of 15/14/14/14/14/14/15 ⁇ .
- the extruders of the Castfolienstrom were applied in accordance with the structure of the multilayer films shown in Table 2 with the components.
- % By weight of component (B) given in Table 2 is understood as meaning the% by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide.
- Table 2 also shows the properties of the multilayer film produced.
- Multilayer films with five different polymers were produced on the above-described 7-layer cast film line from Collin®.
- the resulting multilayer films had a thickness of 100 ⁇ and the layers have a layer thickness of 15/14/14/14/14/14/15 ⁇ .
- the extruders of the Castfolienstrom were applied according to the structure of the multilayer films specified in Table 3 with the components.
- the percentages by weight of component (B) given in Table 3 are understood as meaning the percent by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide.
- Table 3 also shows the properties of the multilayer film produced.
- Monofilms were produced on a 7-layer blown film line from Collin® with a die head diameter of 180 mm.
- 6 had a diameter of 30 mm (extruder B, C, D, E, F, G) and a diameter of 45 mm (extruder A).
- the melt of extruder was inside the bladder, the melt of extruder G was outside.
- the monofilms produced had a thickness of 100 ⁇ m and the layers had a layer thickness of 15/14/14/14/14 / 14/15 ⁇ in the monofilms. All extruders were loaded with the same component.
- the films were slit before winding.
- component (B) The components used and the properties of the monomaterial films are given in Table 4.
- the percentages by weight of component (B) given in Table 4 are understood as meaning the percent by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide.
- Component (B) [Wt. 10.5 20.8 30.3
- Pendulum pendulum) pendulum) pendulum) pendulum) pendulum) pendulum) pendulum)
- Multilayer films with three different materials were produced on a 7-layer blown film line from Collin® with a die head diameter of 180 mm. Of the 7 extruders, 6 had a diameter of 30 mm and a diameter of 45 mm. The resulting multilayer films had a thickness of 100 ⁇ and the layers have a layer thickness of 15/14/14/14/14/15 ⁇ .
- the extruders of the blown film line were charged with the components according to the structure of the multilayer films given in Table 5.
- Table 5 also shows the properties of the multilayer films produced.
- the percentages by weight of component (B) given in Table 5 are understood to mean the percent by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide.
- Multilayer films with five different polymers were produced on a 7-layer blown film line from Collin® with a die head diameter of 180 mm. Of the 7 extruders, 6 had a diameter of 30 mm and a diameter of 45 mm. The resulting multilayer films had a thickness of 100 ⁇ and the layers have a layer thickness of 15/14/14/14/14/15 ⁇ .
- the extruders of the blown film line were charged with the components according to the structure of the multilayer films given in Table 6. Table 6 also shows the properties of the multilayer films produced.
- the percentages by weight of component (B) given in Table 6 are understood to mean the percent by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide.
- Monofilms were produced on a 7-layer blown film line from Collin® with a die head diameter of 180 mm. Of the 7 extruders, 6 had a diameter of 30 mm and a diameter of 45 mm. The Monomaterialfilme produced had a thickness of 100 ⁇ and the layers have a layer thickness of 15/14/14/14/14/14/15 ⁇ . All extruders were loaded with the same component.
- component (B) The components used and the properties of the monofilaments are given in Table 7.
- the percentages by weight of component (B) given in Table 7 are understood to mean the percent by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide.
- Component (B) [wt%] - - 28.9
- Multilayer films were produced on a 7-layer blown film line from Collin® with a die head diameter of 180 mm. Of the 7 extruders, 6 had a diameter of 30 mm and a diameter of 45 mm. The Monomaterialfilme produced had a thickness of 100 ⁇ and the layers have a layer thickness of 15/14/14/14/14/14/15 ⁇ . All extruders were loaded with the same component.
- component (B) The components used and the properties of the monomaterial films are given in Table 8.
- the percentages by weight of component (B) given in Table 8 are understood as meaning the percent by weight of units derived from component (B) (polyamide 6.36 units) in the copolyamide, based on the total weight of the copolyamide.
- the copolyamide according to the invention can significantly increase the tear strength of the polymer films (P) both along the direction of extrusion and perpendicular to it.
- the modulus of elasticity and the puncture resistance of the polymer films (P) according to the invention are also in an acceptable range for practical use, so that the polymer films (P) according to the invention have overall advantageous properties, in particular as packaging films.
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Abstract
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PCT/EP2017/072225 WO2018050487A1 (de) | 2016-09-14 | 2017-09-05 | Polymerfilm enthaltend ein copolyamid eines diamins, einer dimersäure und eines lactams |
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BR112019004925B8 (pt) * | 2016-09-14 | 2023-03-14 | Basf Se | Uso de um filme agrícola (af) e processo para a produção de um filme agrícola (af) |
AU2018249397B2 (en) * | 2017-04-05 | 2020-06-25 | Advansix Resins & Chemicals Llc | Branched, terminated polyamide compositions |
US11155692B2 (en) | 2017-12-18 | 2021-10-26 | Basf Se | Polyamide molding compositions with improved optical properties and use of colorants therein |
CN111630122B (zh) | 2018-01-23 | 2023-07-28 | 伊士曼化工公司 | 新型聚酯酰胺、其制备方法以及聚酯酰胺组合物 |
KR20210034051A (ko) | 2018-07-18 | 2021-03-29 | 바스프 에스이 | 장쇄 폴리아미드계 폼 재료 입자 |
EP3962979A1 (de) | 2019-04-30 | 2022-03-09 | Basf Se | Blends aus tpu und polyamid |
US20220340727A1 (en) | 2019-09-17 | 2022-10-27 | Basf Se | High crystallinity polyamide foam particles and foam moldings |
KR20230110595A (ko) | 2020-11-24 | 2023-07-24 | 바스프 에스이 | 락탐, 디아민 및 이량체 산으로부터 코폴리아미드를 연속적으로 제조하는 방법 |
KR20230118631A (ko) * | 2020-12-14 | 2023-08-11 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | 텔레킬릭 n-알킬화된 폴리아미드 중합체 및 공중합체 |
IL311404A (en) * | 2021-09-17 | 2024-05-01 | Basf Se | Copolyamide and a polymer layer containing at least one diamine, dicarboxylic acid and 5,1-diamino-3-oxapentane |
EP4402193A1 (de) * | 2021-09-17 | 2024-07-24 | Basf Se | Copolyamid und polymerfilm enthaltend mindestens ein lactam, eine dicarbonsäure und 1,5-diamino-3-oxapentan |
WO2023041369A1 (de) * | 2021-09-17 | 2023-03-23 | Basf Se | Schlauchhülle (s) für lebensmittel, enthaltend mindestens ein copolyamid aus mindestens einem lactam, einer dicarbonsäure und 1,5-diamino-3-oxapentan |
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BE792796A (fr) * | 1971-12-16 | 1973-03-30 | Du Pont | Interpolymeres de polyamide condenses a l'etat fondu solubles ala temperature ambiante |
JPS5114997A (ja) * | 1974-07-30 | 1976-02-05 | Showa Denko Kk | Kyojugohoriamidojushino seizohoho |
FR2407227A1 (fr) * | 1977-10-28 | 1979-05-25 | Rhone Poulenc Ind | Procede d'obtention de copolyamides souples ayant des proprietes mecaniques ameliorees |
DE3825411A1 (de) * | 1988-07-27 | 1990-02-08 | Bayer Ag | Verfahren zur herstellung von polyamidfolien |
JPH0641514B2 (ja) * | 1988-08-17 | 1994-06-01 | 三菱化成株式会社 | ブロックコポリアミドの製造法 |
US5744570A (en) * | 1995-08-17 | 1998-04-28 | Akzo Nobel Nv | Copolyether amide and water vapour permeable film made therefrom |
DE10120453A1 (de) | 2001-04-26 | 2002-10-31 | Bayer Ag | Polyamid-Formmassen zur Herstellung besonders transparenter Folien |
US7001979B2 (en) | 2002-06-14 | 2006-02-21 | H.B. Fuller Licensing & Financing Inc. | Polyamide and composition and article including same |
WO2005037337A1 (en) | 2003-10-17 | 2005-04-28 | Invatec S.R.L. | Catheter balloons |
CA2785673C (en) | 2009-12-28 | 2015-07-21 | Mitsubishi Gas Chemical Company, Inc. | Polyamide compound |
JP5816691B2 (ja) | 2010-09-06 | 2015-11-18 | アルケマ フランス | コポリアミド |
JP6425369B2 (ja) | 2012-09-20 | 2018-11-21 | 四国化工株式会社 | 多層延伸フィルムの製造方法 |
US9463609B2 (en) * | 2012-12-20 | 2016-10-11 | Dsm Ip Assets B.V. | Process for producing multilayer blown film and film obtained by the process |
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2017
- 2017-09-05 CN CN201780066923.9A patent/CN109890872B/zh active Active
- 2017-09-05 AU AU2017326287A patent/AU2017326287B2/en active Active
- 2017-09-05 BR BR112019004928-2A patent/BR112019004928B1/pt active IP Right Grant
- 2017-09-05 JP JP2019514097A patent/JP7143285B2/ja active Active
- 2017-09-05 US US16/332,255 patent/US11149124B2/en active Active
- 2017-09-05 WO PCT/EP2017/072225 patent/WO2018050487A1/de unknown
- 2017-09-05 EP EP17761524.2A patent/EP3512901A1/de active Pending
- 2017-09-05 RU RU2019110965A patent/RU2759905C2/ru active
- 2017-09-05 KR KR1020197010567A patent/KR102407950B1/ko active IP Right Grant
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CN109890872B (zh) | 2022-07-08 |
BR112019004928A2 (pt) | 2019-06-04 |
IL265334A (en) | 2019-05-30 |
IL265334B2 (en) | 2023-07-01 |
US20200123335A1 (en) | 2020-04-23 |
KR102407950B1 (ko) | 2022-06-13 |
RU2019110965A (ru) | 2020-10-15 |
US11149124B2 (en) | 2021-10-19 |
AU2017326287B2 (en) | 2021-12-09 |
AU2017326287A1 (en) | 2019-05-02 |
KR20190053895A (ko) | 2019-05-20 |
BR112019004928B1 (pt) | 2022-12-13 |
RU2759905C2 (ru) | 2021-11-18 |
IL265334B1 (en) | 2023-03-01 |
CL2019000652A1 (es) | 2019-05-24 |
RU2019110965A3 (de) | 2020-12-23 |
CN109890872A (zh) | 2019-06-14 |
WO2018050487A1 (de) | 2018-03-22 |
JP2019529638A (ja) | 2019-10-17 |
JP7143285B2 (ja) | 2022-09-28 |
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