Polyamide molding materials for hypochlorite-resistant applications

Abstract

To provide polyamide molding materials for producing a molding that is resistant to an aqueous solution comprising hypochlorous acid and / or a salt thereof.SOLUTION: The present invention relates to the use of a copolyamide molding material comprising at least one amorphous or microcrystalline copolyamide (A) that contains the following monomers: (a) at least one cycloaliphatic diamine; (b) 0.25 to 10 mol% of at least one dimer fatty acid; and (c) 12 to 49.75 mol% of at least one aromatic dicarboxylic acid selected from among isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid; and (d) 0 to 37.75 mol% of at least one aliphatic dicarboxylic acid; where the molar portion of isophthalic acid is at least equal to the molar portion of terephthalic acid; and where the monomers (b), (c), and optionally (d) add up to 50 mol%.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to the use of a polyamide molding material for purposes of use where high resistance to hypochlorous acid is important. Therefore, according to the present invention, the molding material is used for a molded article suitable for contact with an aqueous solution containing hypochlorous acid.

Background Art

[0002] EP1291073A1 relates to polyamide microcapsules obtained by bringing an aqueous phase containing a diamine and an anionic polymer and / or a heteropolysaccharide in a dissolved form into contact with an oil phase containing a dissolved dicarboxylic acid halide to form a W / O emulsion, curing with a calcium salt solution, filtering, washing, and drying. The polyamide microcapsules are described as being stable to an alkaline hypochlorite solution and are used for cosmetics.

[0003] EP3502188A1 relates to a polyamide molding material, particularly a polyamide molding material for use in the field of beverages, for producing a molded article in which the processed molding material comes into contact with drinking water according to the intended use. However, the resistance to hypochlorite is not described, nor is the use of a polyamide molding material for a molded article that comes into contact with a solution containing hypochlorite according to the intended use.

[0004] EP3369761A1 relates to an amorphous or microcrystalline copolyamide (A) containing the following monomers: (a) at least one alicyclic diamine; (b) at least one dimeric fatty acid in 0.25 to 4.4 mol%; and (c) at least one aromatic dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid in 12 to 49.75 mol%; and (d) at least one aliphatic dicarboxylic acid in 0 to 37.75 mol%; where the molar ratio of isophthalic acid is equal to at least the molar ratio of terephthalic acid, furthermore, monomers (b), (c), and optionally (d) together account for 50 mol%, and furthermore, the total molar ratio of all monomers present in copolyamide (A) is 100 mol%, relating to an amorphous or microcrystalline copolyamide (A). The invention further relates to a molding material containing copolyamide (A), a molded article made therefrom, and the use of the same. The use of the aforementioned polyamide molding material is, however, limited to areas that do not come into contact with solutions containing hypochlorite. The stability of the molding material in solutions containing hypochlorite is not mentioned.

[0005] EP0469435A1 discloses copolyamides for producing molded articles having high glass transition temperature, rigidity, and impact resistance at low hygroscopicity. Furthermore, it discloses methods for producing these copolyamides and their use in producing molded articles. [Overview of the project] [Problems that the invention aims to solve]

[0006] Starting from this, the objective of the present invention was to find a polyamide suitable for use in which the polyamide molding material is exposed to a solution containing hypochlorite during use. Such use should enable improved stability with respect to applications known in the prior art. Improved stability means the smallest possible weight change when the molding material according to the present invention is stored in a solution containing hypochlorite. In the case of transparent copolyamide molding materials, improved stability means, in particular, improved maintenance of the transparency of the molding material. In the case of opaque copolyamide molding materials (e.g., molding materials containing fillers), improved stability is characterized in particular by improved maintenance of mechanical, especially tear strength. This objective is achieved by the features of claim 1. Dependent claims refer to advantageous improvements. [Brief explanation of the drawing]

[0007] [Figure 1] This is a photograph of a molded product made of copolyamide A (Example) stored in a solution containing hypochlorite. [Figure 2] This is a photograph of a molded product made of polyamide PA2, stored in a solution containing hypochlorite. [Figure 3] This is a photograph of a molded product made of polyamide PA3, stored in a solution containing hypochlorite. [Figure 4] This is a photograph of a molded product made of polyamide PA4, stored in a solution containing hypochlorite. [Modes for carrying out the invention]

[0008] Definition of Terms Notation and abbreviations for polyamides and their monomers In this invention, the term "polyamide" (abbreviated PA) is understood as a comprehensive term encompassing homopolyamides and copolyamides. The notation and abbreviations chosen for polyamides and their monomers correspond to those specified in ISO standard 1874-1(2011,(D)). The abbreviations used therein are synonymous with the IUPAC names of the monomers, as shown below. In particular, the following abbreviations are used for monomers in this application: MACM: Bis(4-amino-3-methyl-cyclohexyl)methane (also known as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane: CAS-No. 6864-37-5); TMDC: Bis(4-amino-3,5-dimethylcyclohexyl)methane (also known as 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane: CAS No. 65962-45-0); PACM: Bis(4-amino-cyclohexyl)methane (also known as 4,4'-diaminodicyclohexylmethane: CAS No. 1761-71-3); T: Terephthalic acid (CAS No. 100-21-0); I: Isophthalic acid (CAS No. 121-95-5); 36: Dimeric fatty acids having 36 carbon atoms (CAS No. 68783-41-5 or 61788-89-4); 12: Dodecanediic acid (also known as 1,10-decanedicarboxylic acid: CAS No. 693-23-2); CHD: 1,4-Cyclohexanedicarboxylic acid (CAS No. 1076-97-7)

[0009] Amorphous or microcrystalline polyamides Amorphous or microcrystalline polyamides exhibit a heat of fusion of preferably 30 J / g or less, particularly preferably 25 J / g or less, and very preferably 0 to 22 J / g, at a heating rate of 20 K / min, as measured by differential scanning calorimetry (DSC) according to ISO 11357 (2013).

[0010] Microcrystalline polyamides are semicrystalline polyamides and therefore have a melting point. However, they have a form in which the crystallites are of very small size, and a 2 mm thick plate made from them is still transparent, meaning its light transmittance is at least 75% when measured according to ASTM D 1003-13 (2013).

[0011] The microcrystalline polyamide used in the polyamide molding material according to the present invention preferably has a melting point of 255°C or lower when measured according to ISO 11357 (2013).

[0012] Amorphous polyamides have a lower heat of fusion compared to microcrystalline polyamides. Amorphous polyamides exhibit a heat of fusion of preferably 5 J / g or less, particularly preferably 3 J / g or less, and very preferably 0 to 1 J / g, at a heating rate of 20 K / min, as measured by differential scanning calorimetry (DSC) according to ISO 11357 (2013).

[0013] Amorphous polyamides have no melting point due to their amorphous nature.

[0014] Amorphous polyamides are transparent, meaning their light transmittance is at least 80%, preferably at least 85%, and particularly preferably at least 90%, when measured on a 2 mm thick plate according to ASTM D 1003-13 (2013).

[0015] non-transparent, opaque In this invention, opaque or non-transparent is understood as having a light transmittance of less than 80% when measured on a 2 mm thick plate, according to ASTM D 1003-13 (2013).

[0016] dimeric fatty acid In the present invention, the dimer fatty acid (b) has at least 28 carbon atoms (C atoms). They are obtained by dimerization of an unsaturated monocarboxylic acid to a dicarboxylic acid, where the dimerization is preferably carried out catalytically. The dimer fatty acid according to the present invention is a dicarboxylic acid. Preferably, the dimer fatty acid is partially saturated, and particularly preferably completely saturated.

[0017] Aliphatic dicarboxylic acids In the present invention, it is understood that the aliphatic dicarboxylic acid (d) is a dicarboxylic acid having 6 to 22 carbon atoms. These may be linear, branched or alicyclic and exist in a saturated form.

[0018] Monomer quantity notation The copolyamides according to the present invention contain only dicarboxylic acids and diamines. Their molar amounts are such that the sum of all diamines is 50 mol% and the sum of all dicarboxylic acids is 50 mol%, and the total amount of diamines and dicarboxylic acids is 100 mol% with respect to the copolyamide.

[0019] In the notation of the amounts of the dicarboxylic acids and diamines of the copolyamide, the sum of the molar amounts of all diamines is substantially the same as the sum of the molar amounts of all dicarboxylic acids. Substantially the same means that the maximum excess of dicarboxylic acid or diamine is 3%, i.e., the molar ratio of dicarboxylic acid to diamine is 1.03:1 to 1:1.03. Preferably, the maximum excess of dicarboxylic acid or diamine is 2%, i.e., the molar ratio of dicarboxylic acid to diamine is 1.02:1 to 1:1.02.

[0020] The excess serves to offset losses of monomers and / or to adjust the relative viscosity of the polyamide and thus the molar mass.

[0021] The notation of the amounts regarding the monomers is understood such that the corresponding molar ratios of these monomers used in the polycondensation are found again in the copolyamide produced by the polycondensation.

[0022] General overview of quantity notation The molding material according to the present invention preferably comprises only components (A), (C), and optionally (B), in which case components (A), (C), and optionally (B) total 100% by weight. The defined range for the quantity notation of individual components (A), (B), and (C) is understood to mean that any amount can be selected for each individual component within the specified range, provided that the strict requirement that the sum of components (A) to (C) is 100% by weight is met.

[0023] The amounts of diamine and dicarboxylic acid contained in copolyamide (A) are expressed as 50 mol% each. The total amount of all monomers contained in copolyamide (A) is 100 mol%. The specified range for the amount of each monomer is understood to mean that any amount can be selected for each individual component within the specified range, provided that the strict requirement that the total amount of all monomers contained in copolyamide (A) is 100 mol% is met.

[0024] Hypochlorous acid, hypochlorite In this invention, both terms are used synonymously with respect to aqueous solutions or tolerance, since the aqueous solution contains both species in equilibrium.

[0025] This equilibrium between hypochlorous acid and hypochlorites depends on the pH value (see Dissertation of Tim Schlosser, Heidelberg 2018, pp. 36-37, kinetics of water disinfection byproducts), and at pH 6.8, it is on the hypochlorous acid side. According to DIN 19643 (Water treatment for swimming pools and baths), from the Hagg (with an umlaut on 'a') diagram for the relevant pH range 6.5 ≤ pH ≤ 7.8 (Figure 2.5, p. 37), a composition of approximately 80% hypochlorous acid and approximately 20% hypochlorites can be derived at a pH of 6.8.

[0026] Solution containing hypochlorite In the present invention, the term "solution containing hypochlorite" encompasses solutions containing hypochlorite ions in water (for example, solutions of sodium hypochlorite or hypochlorous acid), and therefore also encompasses mixtures of hypochlorous acid and hypochlorite, in which case the concentration ratio depends on pH.

[0027] Sodium hypochlorite - Storage In this invention, the term "hypochlorite-storage" encompasses the storage of test specimens (tensile test specimens) in a solution containing hypochlorite ions in water (for example, a solution of sodium hypochlorite or hypochlorous acid), and therefore also encompasses storage in a mixture of hypochlorous acid and hypochlorite, in which case the concentration ratio depends on the pH.

[0028] The present invention relates to the use of a copolyamide molding material comprising at least one amorphous or microcrystalline copolyamide (A) containing the following monomers for producing molded articles resistant to aqueous solutions containing hypochlorous acid and / or salts thereof: (a) at least one alicyclic diamine; (b) 0.25 to 10 mol% of at least one dimeric fatty acid; and (c) 12 to 49.75 mol% of at least one aromatic dicarboxylic acid, selected from the group consisting of isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid; and (d) 0 to 37.75 mol% of at least one aliphatic dicarboxylic acid; Here, the molar proportion of isophthalic acid is at least the same as the molar proportion of terephthalic acid (i.e., identical to or greater than the molar proportion of terephthalic acid), and Monomers (b), (c), and optionally (d) together make up 50 mol%, and the total molar percentage of all monomers in copolyamide (A) is 100 mol%.

[0029] Resistance means that, after 8064 hours of storage, the weight change of the stored molded article, as measured according to this specification, is 2% or less, preferably 1.5% or less, and particularly preferably 1% or less. and / or, After 8064 hours of storage, the tear strength of the stored molded article, when measured as described herein, shall be at least 70%, preferably at least 75%, and particularly preferably at least 80% of the tear strength value of the unstored (pre-storage) test specimen. It means...

[0030] As a result of searching for a suitable polyamide capable of achieving the above objective, it was surprisingly found that the polyamide described in claim 1 has high resistance to solutions containing hypochlorite and is therefore suitable for the purposes of the present invention.

[0031] A preferred embodiment of use according to the present invention is use for manufacturing molded articles selected from the group consisting of: components for transporting and / or storing drinking water or hot water; components in swimming pools, whirlpools, heating systems, or components in sanitary areas (kitchens, bathrooms, saunas, toilets); taps, fittings, housings, mixers, faucets, filter housings, water meters, water meter components (bearings, propeller screws, bases), valves, valve components (housings, shut-off spheres, gate valve sliders, cylinders), distributors, cartridges, pumps, pump components (blade wheels, impellers), inspection glass, covers, lines, or containers, and their components or parts.

[0032] Particularly preferably, the at least one amorphous or microcrystalline copolyamide (A) comprises the following monomers in the following molar proportions: 40-50 mol%, preferably 48-50 mol%, particularly preferably 50 mol%, of an alicyclic diamine (a); and 1 to 7.5 mol%, preferably 1.5 to 4.4 mol%, particularly preferably 1.7 to 3.0 mol%, of dimeric fatty acids (b); and 14-44 mol%, preferably 23-38.5 mol%, particularly preferably 25.5-33.3 mol%, of aromatic dicarboxylic acid (c); and optionally 5-35 mol%, preferably 10-25.5 mol%, particularly preferably 15-22.8 mol%, of aliphatic dicarboxylic acid (d); Here, the total percentage of all monomers contained in copolyamide (A) is 100 mol%.

[0033] The use according to the present invention is more preferably characterized in that the at least one amorphous or microcrystalline copolyamide (A) also includes isophthalic acid, and preferably terephthalic acid, as the aromatic dicarboxylic acid (c), where The proportion of isophthalic acid to the total amount of all monomers in copolyamide (A) is 6 to 49.75 mol%, preferably 7 to 44 mol%, particularly preferably 11.5 to 27 mol%, even more preferably 12.75 to 20.55 mol%, and / or The proportion of terephthalic acid to the total amount of all monomers in copolyamide (A) is 0 to 24.875 mol%, preferably 0 to 22 mol%, particularly preferably 11.5 to 19.25 mol%, and even more preferably 12.75 to 16.65 mol%.

[0034] Furthermore, the at least one amorphous or microcrystalline copolyamide (A) is Pellets with a moisture content of less than 0.1% by weight are subject to ISO 11 35 The glass transition temperature measured according to 7-2(2013) is at least 155°C, preferably at least 170°C, particularly preferably at least 180°C, even more preferably at least 190°C, very preferably 200-240°C, and / or It is preferable that the light transmittance of the 2 mm thick plate manufactured thereafter, when measured according to ASTM D 1003-13 (2013), is at least 80%, preferably at least 85%, and particularly preferably at least 90%.

[0035] In a more preferred embodiment, the at least one amorphous or microcrystalline copolyamide (A) comprises, as a further monomer (d), at least one aliphatic dicarboxylic acid having 6 to 22 carbon atoms.

[0036] In a more preferred embodiment, the at least one amorphous or microcrystalline copolyamide (A) comprises at least the following monomers: (a) at least one alicyclic diamine component selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5-dimethylcyclohexyl)methane, 2,6-norbornanediamine or 2,6-bis-(aminomethyl)-norbornane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexanediamine, isophoronediamine, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane, 2,2-(4,4'-diaminodicyclohexyl)propane, and mixtures thereof; and (b) at least one dimeric fatty acid selected from the group consisting of dimeric fatty acids having 36 or 44 carbon atoms and mixtures thereof; and (c) at least one aromatic dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures thereof; and optionally (d) At least one aliphatic dicarboxylic acid selected from the group consisting of 1,6-hexanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof.

[0037] Furthermore, it is preferable that the at least one amorphous or microcrystalline copolyamide (A) contains at least the following monomers: (a) at least one alicyclic diamine component selected from the group consisting of bis-(4-amino-3-methyl-cyclohexyl)-methane, bis-(4-amino-cyclohexyl)-methane, bis-(4-amino-3,5-dimethyl-cyclohexyl)-methane and mixtures thereof, preferably selected from the group consisting of bis-(4-amino-3-methyl-cyclohexyl)-methane, bis-(4-amino-3,5-dimethyl-cyclohexyl)-methane and mixtures thereof; and (b) at least one dimeric fatty acid having 36 carbon atoms; and (c) isophthalic acid and terephthalic acid; and optionally, (d) At least one aliphatic dicarboxylic acid selected from the group consisting of 1,12-dodecanediic acid; 1,14-tetradecanediic acid; 1,18-octadecanediic acid; and mixtures thereof.

[0038] According to the present invention, as the at least one amorphous or microcrystalline copolyamide (A), a copolyamide selected from the group consisting of MACMI / MACM12 / MACM36, MACMI / MACM14 / MACM36, MACMI / MACM9 / MACM36, MACMI / MACMCHD / MACM36, MACMI / MACM11 / MACM36, MACMI / MACM13 / MACM36, MACMI / MACM18 / MACM36, MACMI / MACMT / MACM36, MACMI / MACM36, MACMI / MACMT / MACM12 / MACM36, MACMI / MACMT / MACM14 / MACM36, MACMI / MACMT / MACM18 / MACM36, MACMI / MACMT / MACM9 / MACM36, MACMI / MACMT / MACMCHD / MACM36, MACMI / MACMT / MACM12 / MACMCHD / MACM36 and mixtures thereof is used. In this case, MACM may be replaced entirely or partially with TMDC, and / or In this case, the dimeric fatty acid having 36 carbon atoms may be completely or partially replaced with a dimeric fatty acid having 44 carbon atoms.

[0039] More preferably, the present invention relates to using a copolyamide selected from the group consisting of MACMI / MACM12 / MACM36, MACMI / MACM14 / MACM36, MACMI / MACM18 / MACM36, MACMI / MACMT / MACM36, MACMI / MACM36, MACMI / MACMT / MACM12 / MACM36, MACMI / MACMT / MACM14 / MACM36, MACMI / MACMT / MACM18 / MACM36, and mixtures thereof, as the at least one amorphous or microcrystalline copolyamide (A). In this case, MACM may be replaced entirely or partially with TMDC, and / or In this case, the dimeric fatty acid having 36 carbon atoms may be completely or partially replaced with a dimeric fatty acid having 44 carbon atoms.

[0040] In particular, the present invention relates to the use of copolyamides selected from the group consisting of MACMI / MACM12 / MACM36, MACMI / MACM14 / MACM36, MACMI / MACMT / MACM36, MACMI / MACM36, MACMI / MACMT / MACM12 / MACM36, MACMI / MACMT / MACM14 / MACM36, MACMI / MACM12 / MACM36, MACMI / MACM14 / MACM36, MACMI / MACMT / MACM36, MACMI / MACM36, MACMI / MACMT / MACM12 / MACM36, MACMI / MACMT / MACM14 / MACM36, and mixtures thereof.

[0041] The aforementioned copolyamide (A) is transparent.

[0042] In use according to the present invention, the copolyamide molding material comprises at least one amorphous or microcrystalline copolyamide (A), and optionally at least one inorganic filler (B), and / or optionally at least one additive (C), and / or optionally at least one further polymer (D), wherein the polymer is different from the copolyamide (A) and also different from the additive (C).

[0043] Preferably, the copolyamide molding material does not contain other polyamides and / or copolyamides, and preferably does not contain other thermoplastic resins.

[0044] Particularly preferably, the copolyamide molding material comprises at least one amorphous or microcrystalline copolyamide (A) and at least one additive (C).

[0045] More preferably, the use described above relates to the use of a copolyamide molding material having the following composition: 46-100% by weight, preferably 57-99.99% by weight, and particularly preferably 63-99.9% by weight, amorphous or microcrystalline copolyamide (A); and Filler (B) in an amount of 0-50% by weight, preferably 0-40% by weight, and particularly preferably 0-35% by weight; and Additive (C) in an amount of 0-4% by weight, preferably 0.01-3% by weight, and particularly preferably 0.1-2% by weight; Here, the components (A) to (C) total 100% by weight.

[0046] In a more very preferred embodiment of the use of the present invention, the copolyamide molding material has the following composition: 96-100% by weight, preferably 97-99.99% by weight, and particularly preferably 98-99.9% by weight, amorphous or microcrystalline copolyamide (A); and Additive (C) in an amount of 0-4% by weight, preferably 0.01-3% by weight, and particularly preferably 0.1-2% by weight; Here, components (A) and (C) together make up 100% by weight.

[0047] Components (B) and (C) are described in more detail below.

[0048] Ingredient (B) The term "filler (component B)" includes fibrous or needle-shaped fillers, particulate fillers, and mixtures thereof.

[0049] The fillers may preferably be coated or surface-treated; that is, they may be treated with a suitable sizing system or adhesive (adhesion promoter) system, or otherwise surface-activated. For this purpose, for example, systems based on urethane, silane, epoxide (epoxy), polyamide, polyhydroxy ether, acrylate, or combinations thereof may be used. The sizing system or adhesive (adhesion promoter) system may include other additives such as antistatic agents or release agents (lubricants).

[0050] The fibrous or needle-shaped filler is preferably selected from the group consisting of glass fibers, carbon fibers, basalt fibers, boron fibers, slag fibers, metal fibers, whiskers, mineral fibers, wollastonite, aramid fibers, crushed glass fibers, crushed carbon fibers, crushed mineral fibers, and mixtures thereof. Particularly preferably, the fibrous or needle-shaped filler is selected from the group consisting of glass fibers, carbon fibers, basalt fibers, boron fibers, aramid fibers, and mixtures thereof. Very preferably, only glass fibers are used as the fibrous or needle-shaped filler.

[0051] In the case of glass fibers or carbon fibers, staple fibers or long fibers (roving) can be used.

[0052] The glass or carbon fibers may have circular, oval, elliptical, constricted elliptical (so-called cocoon fiber), angular, or rectangular cross-sections. Fibers with non-circular cross-sections, particularly oval, elliptical, constricted elliptical (so-called cocoon fiber), angular, or rectangular fibers, are also called flat fibers. Mixtures of circular and non-circular fibers may also be used.

[0053] The appearance of the glass fibers may be stretched or spiral.

[0054] Glass fibers consisting of all types of glass (e.g., A-, C-, D-, E-, E-CR-, L-, LD-, M-, NE-, S-, R-, AR- glass, or any mixture thereof) can be used. Glass fibers consisting of E- glass, S- glass, or a mixture of E- and / or S- glass fibers are preferred.

[0055] The staple glass fibers have a fiber length of 1 to 50 mm, particularly 1 to 25 mm, preferably 1.5 to 20 mm, especially preferably 2 to 12 mm, and very preferably 2 to 8 mm.

[0056] The glass fibers preferably have a diameter of 5 to 20 μm, more preferably 5 to 15 μm, and particularly preferably 6 to 12 μm.

[0057] In the pultrusion method, when glass fibers are used as long fibers (rovings), they preferably have a diameter of 20 μm or less, preferably 18 μm or less, and particularly preferably 10 to 17 μm.

[0058] The carbon fibers preferably have a diameter of 3 to 12 μm, preferably 4 to 10 μm, and particularly preferably 4 to 9 μm.

[0059] In the case of flattened fibers, the aspect ratio, i.e., the ratio of the main cross-sectional axis to the secondary cross-sectional axis, is 1.5 to 8, preferably 2 to 6, particularly preferably 2.5 to 5, and very preferably 3 to 4. Among flattened fibers, flattened glass fibers are particularly preferred. The cross-sectional axis of flattened glass fibers is 3 to 40 μm long. Preferably, the length of the secondary cross-sectional axis is 3 to 20 μm, particularly preferably 4 to 10 μm, and the length of the main cross-sectional axis is 6 to 40 μm, particularly preferably 12 to 30 μm.

[0060] The particulate filler is preferably selected from the group consisting of dolomite, silicates, quartz, talcum (talc), mica, kaolin, perlite, silica, precipitated or calcined silicon dioxide, diatomaceous earth, titanium dioxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, heavy or precipitated calcium carbonate, chalk, lime, limestone dust, slate powder, feldspar, barium carbonate, barium sulfate, synthetic layered silicates, natural layered silicates, permanently magnetic or magnetizable metals or alloys, glass flakes, glass spheres, hollow glass spheres, hollow spherical silicate fillers, and mixtures thereof. Particulate fillers are particularly preferably selected from the group consisting of silicates, quartz, talcum (talc), mica, kaolin, perlite, silica, precipitated or calcined silicon dioxide, diatomaceous earth, titanium dioxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, heavy or precipitated calcium carbonate, chalk, lime, limestone dust, slate powder, feldspar, barium carbonate, barium sulfate, synthetic layered silicates, natural layered silicates, glass flakes, glass spheres, hollow glass spheres, hollow spherical silicate fillers, and mixtures thereof. Particulate fillers are very preferably selected from the group consisting of silicates, talcum (talc), mica, kaolin, titanium dioxide, heavy or precipitated calcium carbonate, chalk, limestone dust, slate powder, synthetic layered silicates, natural layered silicates, glass flakes, glass spheres, hollow glass spheres, and mixtures thereof.

[0061] Preferably, in the polyamide molding material according to the present invention, at least one fibrous or needle-shaped filler, or a mixture of at least one fibrous or needle-shaped filler and at least one particulate filler, is used as the filler (component B).

[0062] When a mixture of at least one fibrous or needle-shaped filler and at least one particulate filler is used, the proportion of the particulate filler is half or less of the total amount of the filler, preferably 1 / 3 or less, and particularly preferably 1 / 4 or less.

[0063] In the polyamide molding material according to the present invention, it is particularly preferable to use only fibrous or needle-shaped fillers as the filler.

[0064] Ingredients (C) According to a preferred embodiment of the present invention, the at least one additive (component C) is selected from the group consisting of inorganic stabilizers and organic stabilizers, particularly antioxidants, ozone degradation inhibitors, light stabilizers, particularly UV stabilizers, UV absorbers, or UV blockers, release agents (lubricants), dyes, marking agents (tracers), pigments, carbon black, graphite, graphene, carbon nanotubes, photochromic agents, antistatic agents, release substances, antiblocking agents, chain extenders, chain shortening agents, fluorescent whitening agents, IR absorbers, NIR absorbers, and mixtures thereof.

[0065] In the case of organic stabilizers, phenol compounds, phosphite compounds, phosphonite compounds, hindered amine stabilizers (HALS), or mixtures thereof are particularly preferred.

[0066] The at least one of the aforementioned additives may be added in the form of a masterbatch. Preferably, a polyamide is used as the base polymer of the masterbatch. This polyamide is preferably selected from the group consisting of PA 12, PA 1010, PA 1012, PA 1212, PA 6 / 12, PA 612, PA MACM12 and mixtures thereof, or from the group consisting of copolyamide (A) itself.

[0067] Very preferably, the base polymer of the masterbatch is the copolyamide (A) itself.

[0068] The present invention will be described in more detail with reference to the embodiments and experiments shown below, but the present invention is not limited to the specific embodiments shown therein.

[0069] [Measurement method] Relative viscosity Relative viscosity was measured at 20°C according to ISO 307 (2007). For this purpose, 0.5 g of polymer pellets were weighed into 100 mL of m-cresol, and the relative viscosity (RV) was calculated using the formula RV = t / t0, based on Chapter 11 of the standard.

[0070] Glass transition temperature (Tg) and melting point Pellets with a moisture content of less than 0.1% by weight were measured according to ISO 11357-2 and -3 (2013). Differential scanning calorimetry (DSC) was performed during each of the two heating cycles at a heating rate of 20 K / min. After the first heating, the sample was rapidly cooled in dry ice. The melting point was measured during the second heating cycle.

[0071] The temperature at which the peak value is maximized is defined as the melting point. The center of the glass transition zone, defined as the glass transition temperature (Tg), is determined using the "half height method".

[0072] Weight change Weight changes were measured on stored ISO tensile test specimens. The weight change of tensile test specimens stored in an aqueous hypochlorite solution was subtracted from the weight change of tensile test specimens stored in water alone. This eliminated the weight increase due to water absorption that similarly occurs when stored in an aqueous hypochlorite solution.

[0073] Tear force Tear strength was measured using ISO tensile test specimens (manufactured according to standard ISO / CD3167(2003): Type A1, dimensions 170×20 / 10×4) stored in an aqueous solution of hypochlorite.

[0074] Measurements were performed at 23°C in accordance with ISO 527 (2012) for tear strength, using a tensile speed of 50 mm / min for unreinforced materials and 5 mm / min for reinforced materials. Absolute force was used directly as the measured value (i.e., without cleaving the specimen in cross-section).

[0075] light transmittance Light transmittance was determined according to ASTM D 1003-13 (2013) at 23°C using a 2mm thick 60×60mm plate (width × length) and a film gate of Byk Gardner's "Haze Gard plus" using a CIE light source C. The light transmittance value is expressed as a percentage of the amount of light irradiated.

[0076] transparency Transparency was determined according to ASTM D 1003 (2013), using a Byk Gardner "Haze Gard plus" with a CIE light source C, at the end of an ISO tensile test specimen already used for tear strength measurement, stored in an aqueous hypochlorite solution at 23°C. It was measured within an angular range of less than 2.5° of incident light and expressed as a percentage of the irradiated light intensity.

[0077] Storage conditions Sampling was performed for both storage types at the same time points, specifically at 1344 hours, 4032 hours, 5376 hours, 6720 hours, and 8064 hours, respectively. For each material and storage time, five ISO tensile test specimens (Type A1, dimensions 170 × 20 / 10 × 4, manufactured according to standard ISO / CD3167 (2003)) were stored, and the arithmetic mean of the five measurements was calculated.

[0078] Storage in water was performed in deionized water, with the temperature controlled at 60°C using a thermostat.

[0079] The storage of hypochlorite was carried out in a 100L sodium hypochlorite aqueous solution in a HyperDES-watertechnology (Crylesheim, Germany) test stand, with a thermostat adjusted to 60°C. The sodium hypochlorite solution was circulated at a rate of 6-8 L / min, while maintaining a pH of 6.8 and a conductivity of 600-1200 μS. The concentration of sodium hypochlorite, its pH, and conductivity were automatically adjusted throughout the storage period by adding 0.5 wt% sodium hypochlorite solution, 0.7 wt% sodium hydroxide solution, 0.7 wt% sulfuric acid, or deionized water. The pH value and sodium hypochlorite concentration were further checked once a week using a CHEMATEST 20s (available from Swan Analytische Instrumente, Hinwiel, Switzerland) by a colorimetric method using N,N-diethyl-1,4-phenylenediamine in accordance with DIN EN ISO 7393-2 (2012).

[0080] Manufacturing of test specimens To prepare the test specimens, pellets with a moisture content of less than 0.1% by weight were used.

[0081] ISO tensile test specimens were manufactured using an Arburg injection molding machine, model Allrounder 420 C 1000-250. The cylinder temperature, which rises and falls from the feed port to the nozzle, was used during the process.

[0082] Copolyamide molding material without fillers (Co)polyamide (A) and (PA2) Cylinder temperature: 280 / 285 / 290 / 295 / 300 / 290℃ Mold temperature: 90℃ Polyamides (PA3) and (PA4) Cylinder temperature: 265 / 270 / 275 / 280 / 285 / 280℃ Mold temperature: 80℃

[0083] Copolyamide molding material with filler Glass fiber-containing copolyamide (A) Cylinder temperature: 290 / 295 / 300 / 305 / 310 / 300℃ Mold temperature: 80℃ Glass fiber-containing polyamide (PA5) Cylinder temperature: 320 / 325 / 330 / 335 / 340 / 330℃ Mold temperature: 160℃ Glass fiber-containing polyamide (PA6) Cylinder temperature: 310 / 315 / 320 / 325 / 330 / 325℃ Mold temperature: 120℃

[0084] Unless otherwise specified, the test specimens were used in a dry state; for this purpose, after injection molding, they were stored at room temperature for at least 48 hours in a dry environment (i.e., on silica gel).

[0085] [Table 1A]

[0086] [Table 1B]

[0087] [Table 2]

[0088] [Table 3]

[0089] [Table 4]

[0090] As the experiments clearly show, surprisingly, only a specific copolyamide (copolyamide A) was found to exhibit stability in alkaline hypochlorite solutions.

[0091] Surprisingly, when molded articles were stored in an aqueous solution containing hypochlorite, a constant weight was found to be recorded only for copolyamide A. No weight increase or decrease, as observed with the other polyamides in the comparative experiment, was recorded. This suggests that the weight increase indicates oxidation of the copolyamide, accompanied by the formation of a hydrogel layer on the surface, and subsequent storage in water. The weight decrease is thought to be oxidative decomposition of the copolyamide. Thus, in both cases, damage to the copolyamide occurs.

[0092] The suitability of the (filler-free) copolyamide (A) according to the present invention is particularly evident in the observation of transparency that occurs when in prolonged contact with a solution containing hypochlorite. When using the copolyamide (A) according to the present invention, they retain a clear appearance even after prolonged contact with a solution containing hypochlorite, and do not become opaque as seen in the comparative examples. This is very clear from the molded articles produced from the molding material used according to the present invention, shown in Figure 1, which remain transparent even after being stored in a solution containing hypochlorite for 6720 hours (see Figure 1), whereas all of the molded articles of the comparative examples had already become opaque after 1344 or 2688 hours (see Figures 2-4).

[0093] Once a filler (e.g., glass fiber) is added to a copolyamide molding material, the molding material usually becomes opaque. In this case, other problems arise due to the included filler, in addition to a lack of weight stability. Glass fiber is added to such systems to improve mechanical properties, particularly tear strength. However, when such copolyamide molding materials come into contact with solutions containing hypochlorite, the tear strength stability deteriorates considerably (see Table 3, Comparative Examples 6 and 7). Surprisingly, this problem can be solved by using copolyamide A as the base for such molding materials. Clearly superior maintenance of tear strength is observed (Table 3, Example 5).

Claims

1. Use of a copolyamide molding material containing at least one amorphous or microcrystalline copolyamide (A) containing the following monomers for manufacturing molded articles used in applications requiring resistance to aqueous solutions containing hypochlorous acid and / or its salts (meaning resistance to contact with the aqueous solution [concentration 10 mg / L] for 8064 hours): (a) at least one alicyclic diamine; (b) 0.25 to 10 mol% of at least one dimeric fatty acid having at least 28 carbon atoms; and (c) 12 to 49.75 mol% of at least one aromatic dicarboxylic acid, selected from the group consisting of isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid; and (d) 0 to 37.75 mol% of at least one aliphatic dicarboxylic acid having 6 to 22 carbon atoms; Here, the molar proportion of isophthalic acid is at least the same as the molar proportion of terephthalic acid, and Monomers (b), (c), and optionally (d) together make up 50 mol%, and the total molar percentage of all monomers in copolyamide (A) is 100 mol%.

2. Components for transporting and / or storing drinking water or hot water, Components in swimming pools, bubble baths, and heating systems. Components for kitchens, bathrooms, saunas, and toilets. Mixers, faucets, water meters, valves, distributors, cartridges, or pumps, and their components. The use according to claim 1 for manufacturing a molded article selected from the group consisting of the following.

3. The above-mentioned at least one amorphous or microcrystalline copolyamide (A) contains the following monomers in the following molar proportions: 40-50 mol% of alicyclic diamine (a); and 1 to 7.5 mol% of dimeric fatty acids (b); and 14-44 mol% of aromatic dicarboxylic acid (c); and optionally 5-35 mol% of aliphatic dicarboxylic acid (d); Here, the total proportion of all monomers contained in copolyamide (A) is 100 mol%. The use described in feature 1 or 2.

4. The above-mentioned at least one amorphous or microcrystalline copolyamide (A) includes isophthalic acid as an aromatic dicarboxylic acid (c), and optionally terephthalic acid, where, The proportion of isophthalic acid to the total amount of all monomers in copolyamide (A) is 7 to 44 mol%, and / or The proportion of terephthalic acid to the total amount of all monomers in copolyamide (A) is between 0 and 24.875 mol%. The use according to any one of claims 1 to 3.

5. The above-mentioned at least one amorphous or microcrystalline copolyamide (A) The glass transition temperature measured according to ISO 11357-2 (2013) is at least 155°C, and / or The light transmittance of the 2 mm thick plate manufactured thereafter, when measured according to ASTM D 1003-13 (2013), is at least 80%. The use described in any one of claims 1 to 4.

6. The above-mentioned at least one amorphous or microcrystalline copolyamide (A) comprises at least the following monomers: (a) at least one alicyclic diamine component selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5-dimethylcyclohexyl)methane, 2,6-norbornanediamine or 2,6-bis-(aminomethyl)-norbornane, 1,3-diaminocyclohexane, isophoronediamine, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis-(aminomethyl)cyclohexane, 2,2-(4,4'-diaminodicyclohexyl)propane, and mixtures thereof; and (b) at least one dimeric fatty acid selected from the group consisting of dimeric fatty acids having 36 or 44 carbon atoms and mixtures thereof; and (c) at least one aromatic dicarboxylic acid selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures thereof: where the molar proportion of isophthalic acid is at least the same as the molar proportion of terephthalic acid; and optionally (d) at least one aliphatic dicarboxylic acid selected from the group consisting of 1,6-hexanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof; The use according to any one of claims 1 to 5.

7. The above-mentioned at least one amorphous or microcrystalline copolyamide (A) comprises at least the following monomers: (a) at least one alicyclic diamine component selected from the group consisting of bis-(4-amino-3-methyl-cyclohexyl)-methane, bis-(4-amino-cyclohexyl)-methane, bis-(4-amino-3,5-dimethyl-cyclohexyl)-methane and mixtures thereof; and (b) at least one dimeric fatty acid having 36 carbon atoms; and (c) isophthalic acid and terephthalic acid; and optionally, (d) At least one aliphatic dicarboxylic acid selected from the group consisting of 1,12-dodecanediic acid; 1,14-tetradecanediic acid; 1,18-octadecanediic acid; and mixtures thereof; The use according to any one of claims 1 to 6.

8. The at least one amorphous or microcrystalline copolyamide (A) comprises the at least one aliphatic dicarboxylic acid (d). The use according to any one of claims 1 to 5.

9. The above at least one amorphous or microcrystalline copolyamide (A) is MACMI / MACM12 / MACM36, MACMI / MACM14 / MACM36, MACMI / MACM9 / MACM36, MACMI / MACMCHD / MACM36, MACMI / MACM11 / MACM36, MACMI / MACM13 / MACM36, MACMI / MACM18 / MACM36, MACMI / MACMT / MACM36, MAC Selected from the group consisting of MI / MACM36, MACMI / MACMT / MACM12 / MACM36, MACMI / MACMT / MACM14 / MACM36, MACMI / MACMT / MACM18 / MACM36, MACMI / MACMT / MACM9 / MACM36, MACMI / MACMT / MACMCHD / MACM36, MACMI / MACMT / MACM12 / MACMCHD / MACM36 and mixtures thereof, In this case, MACM may be replaced entirely or partially with TMDC, and / or In this case, the dimeric fatty acid having 36 carbon atoms may be completely or partially replaced with a dimeric fatty acid having 44 carbon atoms. The use according to any one of claims 1 to 5.

10. The at least one amorphous or microcrystalline copolyamide (A) is selected from the group consisting of MACMI / MACM12 / MACM36, MACMI / MACM14 / MACM36, MACMI / MACM18 / MACM36, MACMI / MACMT / MACM36, MACMI / MACM36, MACMI / MACMT / MACM12 / MACM36, MACMI / MACMT / MACM14 / MACM36, MACMI / MACMT / MACM18 / MACM36, and mixtures thereof. In this case, MACM may be replaced entirely or partially with TMDC, and / or In this case, the dimeric fatty acid having 36 carbon atoms may be completely or partially replaced with a dimeric fatty acid having 44 carbon atoms. The use according to any one of claims 1 to 5.

11. The at least one amorphous or microcrystalline copolyamide (A) is selected from the group consisting of MACMI / MACM12 / MACM36, MACMI / MACM14 / MACM36, MACMI / MACMT / MACM36, MACMI / MACM36, MACMI / MACMT / MACM12 / MACM36, MACMI / MACMT / MACM14 / MACM36, and mixtures thereof. The use according to any one of claims 1 to 5.

12. The copolyamide molding material comprises at least one amorphous or microcrystalline copolyamide (A), and optionally at least one inorganic filler (B), and / or optionally at least one additive (C), and / or optionally at least one further polymer (D), wherein the polymer (D) is different from the copolyamide (A) and also different from the additive (C). The use according to any one of claims 1 to 11.

13. The aforementioned copolyamide molding material has the following composition: 46 to 100% by weight of amorphous or microcrystalline copolyamide (A); and 0-50% by weight of filler (B); and Additive (C) in a concentration of 0-4% by weight; Here, the components (A) to (C) total 100% by weight. The use according to any one of claims 1 to 12.

14. The aforementioned copolyamide molding material does not contain other polyamides and / or copolyamides. The use according to any one of claims 1 to 13.

15. The aforementioned copolyamide molding material has the following composition: 96-100% by weight of amorphous or microcrystalline copolyamide (A); and Additive (C) in a concentration of 0-4% by weight; Here, components (A) and (C) together make up 100% by weight. The use described in any one of claims 1 to 14.

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