Enhanced fire-resistant polyamide molded composition

Abstract

The present invention relates to a polyamide molded composition comprising at least one polyamide (PA), glass fiber (GF), and at least one flame retardant (FR), wherein the composition has a breakage time (t F A polyamide molding composition comprising at least 5.0 minutes, preferably at least 6.0 minutes, and more preferably at least 10.0 minutes, and a polyamide molding composition comprising at least one PA, GF, and at least one FR, wherein the length distribution of GF is 220 μm or more in arithmetic mean length (L av The present invention relates to a polyamide molding composition characterized by, and wherein the proportion of GF having a length exceeding 400 μm is at least 20% (in number). The present invention also relates to articles comprising the said composition and to the use of glass fibers and flame retardants in improving the heat resistance of polyamide molding compositions.

Description

Technical Field

[0001] This application claims the priority of U.S. Patent Application No. 63 / 490812, filed on March 17, 2023, and European Patent Application No. 23196163.2, filed on September 8, 2023, the contents of which are hereby incorporated by reference in their entirety for all purposes. In case of any contradiction between this application and the two applications that may affect the clarity of terms or expressions, only this application shall be referred to.

[0002] The present invention relates to a polyamide molding composition that can be used in the production of battery housings and other battery components.

Background Art

[0003] With the development of electric vehicles (EVs) and the need to lightweight many components, original equipment manufacturers (OEMs) are demanding battery housings and other battery components made of polymeric materials.

[0004] Lithium-ion batteries can enter a state of uncontrollable self-heating, resulting in "thermal runaway" that can release harmful substances while causing fires, smoke, and extreme high temperatures.

[0005] The performance of batteries remains an ongoing challenge in the efficiency of EVs. The battery housing system plays an important role in reducing the impact of thermal runaway, a risk associated with lithium-ion batteries. Unwanted thermal runaway should be contained within the battery housing to prevent the rapid release of heat and energy from escaping to the rest of the vehicle.

[0006] Furthermore, as the temperature of a battery cell experiencing thermal runaway rises, it can cause the temperature of adjacent cells within the battery to also rise, potentially leading to a chain reaction of instability in adjacent cells and causing thermal runaway. Therefore, the battery configuration may include walls that separate cells or cell packs within the battery housing. The materials for these walls and other components of the battery housing should be resistant to thermal runaway and have sufficient resistance to contain it.

[0007] Polymer-based materials should preferably exhibit a combination of excellent mechanical properties (such as impact resistance and tensile strength) and heat resistance, especially in the case of thermal runaway.

[0008] Therefore, there is a need to develop polymer-based materials used in the manufacture of battery casings and other battery components that can withstand and contain all types of thermal runaway, and withstand the dynamic stresses caused by such runaway.

[0009] The present invention and its polymer-based materials aim to solve this technical problem.

[0010] While flame-retardant polymer materials have been known for a long time, the materials developed are not intended to solve the problem of dynamic thermal runaway.

[0011] Chinese Patent No. 115785663 (D1) provides a halogen-free flame-retardant nylon-based material for battery pack shells, comprising 40 to 67 parts polyamide 6 or 66, 20 to 30 parts GF, 5 to 10 parts modified melamine polyphosphate, 4 to 10 parts diethylaluminum hypophosphite, 0.1 to 0.5 parts chain extender, 3 to 8 parts reinforcing agent, and 1 to 2 parts other additives. The reinforcing agent is a polymer containing maleic anhydride.

[0012] U.S. Patent Application Publication No. 2014 / 0363654A1 (D2) (EMS-Patent AG) discloses a polyamide molded composition comprising at least one polyamide, glass fibers (the arithmetic mean length of these glass fibers in the polyamide molded composition is 100 to 220 μm), at least one phosphinate and / or at least one diphosphinate, and optionally at least one additive, which exhibits a V0 rating at 3.2 mm according to UL-94 (Underwriters Laboratories-94: Tests for flammability of plastic materials for parts in devices and appliances).

[0013] U.S. Patent Application Publication 2012 / 029124 (D3) discloses a polymer composition comprising at least one semi-aromatic polyamide having a melting point of at least 270°C, at least one organophosphorus compound selected from the group consisting of phosphinates, diphosphinates, and condensation products thereof, and at least 0.01% by weight of calcium oxide based on the total weight of the composition. D3 does not disclose the breakage time and size of GF in the polyamide composition.

[0014] U.S. Patent Application Publication 2023 / 183454 (D4) discloses an electrical or electronic product comprising semicrystalline polyamide and glass fibers. D4 does not disclose the breakage time and size of GF in the polyamide composition.

[0015] U.S. Patent Application Publication 2023 / 183452(D5) discloses a composition comprising a semicrystalline polyamide and glass fibers. D5 does not disclose the breakage time and size of GF in the polyamide composition.

[0016] European Patent No. 4191757A1 (D6) discloses a thermal runaway protection film for lithium-ion batteries comprising at least one protective layer, the protective layer comprising at least one silicone and at least one silicate compound in an amount of at least 40% by weight based on the total weight of the at least one protective layer. D6 does not disclose the composition of the present invention.

[0017] U.S. Patent Application Publication No. 2014 / 0275367A1 (Cheil Industries Inc.) discloses the addition of polyphenylene sulfide to a reinforced polyamide composition, which exhibits satisfactory flame retardancy while reducing the amount of flame retardant required.

[0018] U.S. Patent No. 10,435,540B2 (SABIC) discloses another approach using pellets having a specific structure consisting of a core and a sheath, wherein the core comprises glass fibers and an impregnating agent, and the sheath surrounding the core comprises polypropylene and a mixture of an organophosphate compound as a flame retardant, an organophosphoric acid compound, and zinc oxide.

[0019] International Publication No. 2024 / 022878 discloses battery packs and battery housings. The polyamide molded composition of the present invention is not disclosed. [Overview of the Initiative]

[0020] The present invention is disclosed below and in the appended claims.

[0021] The present invention relates, firstly, to a polyamide molding composition according to any one of claims 1 to 36.

[0022] The present invention also relates to the article described in any one of claims 37 to 38.

[0023] The present invention also relates to a method for preparing the pellet(p) described in claim 39 or 40.

[0024] The present invention also relates to the pellet(p) described in claim 41.

[0025] The present invention also relates to the use described in claim 42 or 43 and the manufacturing method described in claim 44.

[0026] The present invention also relates to the use described in claim 45.

[0027] Various aspects, advantages, and features of the present invention will be more readily understood and recognized by referring to the detailed description and examples. [Brief explanation of the drawing]

[0028] [Figure 1] The number-weighted distribution of glass fiber length with respect to fiber length (μm) as a function of density is shown for Example 1 (E1) and Comparative Example 1 (CE1). [Figure 2] The equipment configuration for torch test T1 is shown. [Modes for carrying out the invention]

[0029] In relation to the present invention, the term "weight percent" (weight%) indicates the content of a particular component in a mixture, calculated as the ratio between the weight of the component and the total weight of the mixture.

[0030] The term "(C)" is a technical term for organic groups used in this specification. n ~C m The notation ")" (where n and m are integers) indicates that this group may contain n to m carbon atoms per group.

[0031] The “semi-crystalline” polyamides used herein have a heat of fusion (H) of at least 5.0 joules per gram (J / g), as measured by differential scanning calorimetry (DSC) according to ASTM D3418 at a heating rate of 20°C / min. mSimilarly, the “amorphous” polyamides used herein have a heat of fusion (H) less than 5.0 J / g, preferably less than 3.0 J / g, and more preferably less than 2.0 J / g, as measured using DSC at a heating rate of 20°C / min. m ) indicates.

[0032] As used herein, the term "alkyl" group includes saturated hydrocarbons having one or more carbon atoms, including linear alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl; cyclic alkyl groups (or "cycloalkyl," "alicyclic," or "carbocyclic" groups) such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; branched alkyl groups such as isopropyl, tert-butyl, sec-butyl, and isobutyl; and alkyl-substituted alkyl groups such as alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups. As used herein, the term "alkylene" group refers to a divalent saturated hydrocarbon having one or more carbon atoms, and the term "cycloalkylene" group refers to a divalent saturated cyclic hydrocarbon having at least three carbon atoms.

[0033] The term "aliphatic group" typically refers to C1-C11. 50 It contains organic moieties characterized by linear or branched chains. In complex structures, the chains can be branched, cross-linked, or bridging. Aliphatic groups include alkyl groups, alkenyl groups, and alkynyl groups.

[0034] As used herein, the term "aryl" group includes aromatic hydrocarbons, such as phenyl, indanyl, and naphthyl groups. An aryl group may contain one or more alkyl groups, in which case it may be called an "alkylaryl," and may consist of, for example, an aromatic group and two C1-C6 groups. An aryl group may also contain one or more heteroatoms, such as N, O, or S, in which case it may be called a "heteroaryl" group, and these heteroaromatic rings may be condensed with other aromatic systems. Such heteroaromatic rings include, but are not limited to, furanyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridadyl, pyrimidyl, pyrazinyl, and triazinyl ring structures. The aryl substituent or heteroaryl substituent may be unsubstituted or halogen, hydroxyl, C1-C6 alkoxy, sulfo, C1-C6 alkylthio, C1-C6 acyl, formyl, cyano, C6-C 15 Aryloxy or C6~C 15 The group may be substituted with one or more substituents selected from, but not limited to, aryl groups, provided that the substituents are sterically appropriate and satisfy the rules of chemical bonding and strain energy. As used herein, the term "arylene" refers to a divalent aromatic hydrocarbon such as phenylene.

[0035] The term "halogen" or "halo" includes fluorine, chlorine, bromine, and iodine.

[0036] In this application, unless otherwise indicated, any particular embodiment or technical feature relating to one of the subject matter of the present invention is applicable to and interchangeable with other embodiments or technical features relating to the subject matter and disclosed elsewhere in this application.

[0037] Regarding polyamide molding compositions The polyamide molding composition of the present invention, - At least one type of polyamide (PA), - Glass fiber (GF), and - At least one flame retardant (FR), and - At least one additive (Add) other than a flame retardant (FR), optionally selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical blowing agents, nucleating agents, and any combination thereof. Includes.

[0038] Glass fibers (GF) are present in the molded composition in a blended state with PA and FR.

[0039] All components of a polyamide molding composition (e.g., polyamide (PA), GF, FR, and additives (Add) (if any)) are typically blended.

[0040] In one embodiment of the present invention, the proportion of GF is 20.0 to 60.0% by weight or 30.0 to 55.0% by weight. This proportion may be 30.0 to 50.0% by weight.

[0041] In another embodiment of the present invention, the proportion of FR is 10.0 to 30.0% by weight. This proportion may be 10.0 to 20.0% by weight.

[0042] In another embodiment of the present invention, the proportion of PA is 35.0 to 65.0% by weight. This proportion may be 35.0 to 60.0% by weight or 35.0 to 55.0% by weight.

[0043] In another embodiment of the present invention, the proportion of the additive (Add) is 0 to 10.0% by weight.

[0044] All these percentages, expressed in weight percent, are given relative to the weight of the polyamide molded composition.

[0045] More specifically, the polyamide molding composition of the present invention is - 35.0 to 65.0% by weight of at least one type of polyamide (PA), - 20.0-60.0% by weight of glass fiber (GF), - 10.0 to 30.0% by weight of at least one flame retardant (FR), and - 0 to 15.0% by weight of at least one additive (Add) other than flame retardants (FR), selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical blowing agents, nucleating agents, and any combination thereof. It includes or consists of.

[0046] More specifically, the polyamide molding composition of the present invention is - 35.0 to 60.0% by weight of at least one type of polyamide (PA), - 30.0-55.0% by weight of glass fiber (GF), - 10.0 to 30.0% by weight of at least one flame retardant (FR), and - 0 to 15.0% by weight of at least one additive (Add) other than flame retardants (FR), selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical blowing agents, nucleating agents, and any combination thereof. It includes or consists of.

[0047] The polyamide molding composition may contain one or more polyamides (PA). According to one embodiment, the polyamide molding composition contains only one polyamide (PA). Preferably, the polyamide molding composition does not contain polyamides other than polyamide (PA).

[0048] According to another embodiment, the polymer component of the polyamide molding composition consists of one or more polyamides (PA).

[0049] Distribution of GF in polyamide molded compositions Polyamide molded compositions are also characterized by a specific size distribution of glass fibers (GF) within the polyamide molded composition. This distribution corresponds to the length distribution of GF dispersed in the polyamide molded composition. This distribution is usually obtained by microscopically observing a statistically significant number n (e.g., at least 200, and even more so, at least 5000) of glass fibers separated from the polyamide molded composition.

[0050] Observation and determination of the distribution can be performed automatically, for example, as disclosed in International Publication No. 2008 / 033789.

[0051] Polyamide molded compositions may be characterized in particular by a set of parameters (S1) or (S2) or by a set of parameters (S1) and (S2), as defined herein. Polyamide molded compositions may also be characterized by a set of parameters (S1*) or (S2*) or by a set of parameters (S1*) and (S2*), as defined herein.

[0052] Number-weighted distribution of GF length The number-weighted distribution provides the number of fibers with a given length L. In the number-weighted distribution, each GF is given equal weighting regardless of its length.

[0053] The arithmetic mean length of GF can be calculated from this number-weighted distribution. av The formula is as follows:

number

[0054] Furthermore, this number-weighted distribution reveals that a significant proportion of GFs have a specific length L, which characterizes the polyamide molded composition.

[0055] The polyamide molding composition can be characterized by a set (S1) of the following parameters.

[0056] [Table 1]

[0057] Therefore, the polyamide molding composition of the present invention - the arithmetic mean length (L av ) is 220 μm or more, and - the proportion of GF having a length exceeding 400 μm is at least 20% (by number), preferably at least 25% (by number), preferably at least 30% (by number), preferably at least 35% (by number), preferably at least 40% (by number), preferably at least 45% (by number), preferably at least 50% (by number) can be characterized by.

[0058] [[ID=2,4]] The polyamide molding composition of the present invention is more specifically - the arithmetic mean length (L av ) is 300 to 750 μm, preferably 300 to 700 μm, and - the proportion of GF having a length exceeding 400 μm is at least 45% (by number), preferably at least 50% (by number) can be characterized by.

[0059] The proportion of GF having a length exceeding 400 μm is typically 45% (by number) to 90% (by number).

[0060] The polyamide molding composition of the present invention - the arithmetic mean length (L av ) is 220 μm or more, and - The proportion of GF having a length exceeding 500 μm is at least 15.0% (in terms of number), preferably at least 20.0% (in terms of number), preferably at least 25.0% (in terms of number), and preferably at least 30.0% (in terms of number). It can also be characterized by...

[0061] More specifically, the polyamide molding composition of the present invention is - Arithmetic mean length (L av The thickness of the material is 300 to 750 μm, preferably 300 to 700 μm, and - The proportion of GFs with a length exceeding 500 μm must be at least 30.0% (in terms of number). It can be characterized by:

[0062] The proportion of GFs with lengths exceeding 500 μm is typically between 30.0% (by number) and 80.0% (by number).

[0063] Glass fibers have an arithmetic mean length (L) of 220 μm or more. av ) has. Lav is preferably more than exactly 220 μm. Lav is preferably at least 300 μm or at least 400 μm.

[0064] In one embodiment, L av The thickness is 220 μm to 600 μm. More specifically, Lav is 250 μm to 600 μm, preferably 270 μm to 550 μm. Lav is more preferably 300 to 400 μm.

[0065] In one embodiment, L av The range is 220 μm to 750 μm or 220 μm to 700 μm. av More specifically, this is 300-750 μm or 300-700 μm.

[0066] Typically, this number-weighted distribution suggests that at least 90.0% (in terms of number) of the GFs have a length of 3000 μm or less, preferably 2500 μm or less.

[0067] Volume-weighted distribution of GF length The volume-weighted distribution shows the volume (or weight) of a fiber with a specific length L. Here, the contribution of each fiber to the distribution is related to its volume. The volume Vi of the i-th fiber is given by Vi = (πr²). 2 It is expressed as ) × Li (where r is the radius of GF). The radius of GF used in the preparation of polyamide molded compositions is known (corresponding to the diameter of GF used as the starting material) and is considered to be the same for all GF.

[0068] In a number-weighted distribution, percentages are expressed as numbers, whereas in a volume-weighted distribution, percentages are expressed as volumes.

[0069] From the volume-weighted distribution, the following average length L of GF can be calculated using the following formula. p It is possible to calculate this.

number

[0070] Furthermore, from this volume-weighted distribution, it can be observed that the polyamide molded composition is characterized by a significant proportion of GF having a specific length L.

[0071] Polyamide molded compositions can be characterized by the following set of parameters (S2):

[0072] [Table 2]

[0073] Therefore, the polyamide molding composition of the present invention, - Average length (L p ) is between 400 μm and 1800 μm. - The proportion of GF having a length exceeding 400 μm is at least 50.0%, preferably at least 60.0%, preferably at least 65.0%, and preferably at least 70.0%. This volume-weighted distribution can be characterized by the following:

[0074] More specifically, the polyamide molding composition of the present invention is - Average length (L p ) is 400 μm to 1800 μm, and - The proportion of GF with a length exceeding 400 μm must be at least 65.0%. It can be characterized by:

[0075] The percentage of GFs with a length exceeding 400 μm is typically between 65.0% and 100%.

[0076] The polyamide molding composition of the present invention, - Average length (L p ) is between 400 μm and 1800 μm. - The proportion of GF having a length exceeding 500 μm is at least 40.0%, preferably at least 50.0%, and preferably at least 55.0%. This volume-weighted distribution can also be characterized by [this method].

[0077] More specifically, the polyamide molding composition of the present invention is - Average length (L p ) is 400 μm to 1800 μm, and - The proportion of GF with a length exceeding 500 μm must be at least 50.0%. It can be characterized by:

[0078] The percentage of GFs with a length exceeding 500 μm is typically between 50.0% and 100%.

[0079] Lp is 400 μm to 1800 μm or 400 μm to 1700 μm.

[0080] Lp is preferably at least 450 μm, and preferably at least 500 μm.

[0081] The number n corresponds to a statistically significant number of observed GFs. Typically, n is at least 200, preferably at least 500, and preferably at least 5000.

[0082] Both the number-weighted and volume-weighted distributions are obtained after separating GF from the polyamide molded composition. This separation can be carried out according to one of the methods specified below.

[0083] Ashing method (a) The separation of GF may be carried out by any one of the ashing methods disclosed herein.

[0084] The separation of GF is (a1) A step of heating a sample of the polyamide molded composition in a furnace, (a2) Process for recovering glass fibers and This can be carried out by ashing (a).

[0085] The temperature at which step (a1) is performed should preferably be such that the polymer components can be decomposed without degrading the glass fibers (GF). It is preferable that the decomposition proceeds smoothly without degrading the GF.

[0086] The temperature at which process (a1) is carried out is typically at least 500°C.

[0087] The duration of step (a1) should be long enough to allow the polymer components to decompose. Step (a1) is typically carried out until the weight of the burned sample no longer changes.

[0088] A muffle furnace can be used for the ashing method (a).

[0089] Method (a) may preferably be one of the following two specific methods:

[0090] [Table 3]

[0091] [Table 4]

[0092] Separation may preferably be carried out by the ashing method disclosed in ISO 22314:2006(E). It should be noted that the ashing method disclosed in ISO 22314:2006(E) may be adapted by varying the heating temperature of the sample.

[0093] chemical method(b) The separation of GF may be carried out by any one of the chemical methods disclosed herein.

[0094] Separation is, (b1) A step of heating the dispersion of the sample in a sulfuric acid solution, (b2) Process for recovering glass fibers and This can also be carried out by a chemical method (b) including the following.

[0095] Step (b1) is carried out until the polyamide molding composition is dissolved in the acidic solution. Preferably, a concentrated solution (e.g., at least 98.0% by weight) is used. The temperature at which step (b1) is carried out is at least 200°C.

[0096] Method (b) could be more specifically as follows: - Place 1.0 g of the sample together with a stirring bar into a 150 mL Erlenmeyer flask. - Place approximately 75-100 mL of H2SO4 (98.5% concentration) into a flask. - Place the flask on a stirring hot plate, cover the flask with a watch glass, and heat while stirring vigorously until the temperature rises (up to approximately 220°C). - After leaving the flask for at least 4 hours, let it cool to a temperature of approximately 50-60°C. - Filter by vacuum filtration using a filter, washing each flask twice with approximately 75 mL of H2SO4 (98.5% concentration), and then filtering each flask at least three times with approximately 100 mL of water. - Dry the glass fiber and filter in an aluminum tray at 105°C until their weight no longer changes (at least 1 hour).

[0097] Glass fibers separated by either ashing or chemical methods can be dispersed in a plastic Petri dish using low-pressure compressed air to promote dispersion. The glass fibers are then imaged using an optical microscope with reverse illumination, adjusting the image magnification according to the fiber length. The glass fibers are then observed, their lengths measured under the microscope, and the fiber length distribution is reported as a histogram.

[0098] According to one embodiment of the present invention, the glass fiber (GF) has a diameter of 5 μm or more, preferably 6 μm or more. In some specific embodiments, the glass fiber (GF) has a diameter of 5 μm to 20 μm. In another specific embodiment, the glass fiber (GF) has a diameter of 6 μm to 15 μm.

[0099] The morphology of glass fibers is not particularly limited. Glass fibers may have a circular cross-section ("circular glass fiber") or a non-circular cross-section ("flat glass fiber"). Suitable examples of flat glass fibers include, but are not limited to, glass fibers having oval, elliptical, and rectangular cross-sections. For glass fibers that do not have a circular cross-section, the diameter referred to herein is the equivalent diameter, which is the diameter of a circle having the same area as the cross-section of a glass fiber with a non-circular cross-section.

[0100] According to a particular embodiment (E*) of the present invention, a polyamide molding composition may be characterized by a set of parameters (S1*) or (S2*) or a set of parameters (S1*) and (S2*), the sets of which are as defined herein.

[0101] [Table 5]

[0102] [Table 6]

[0103] L disclosed herein av , L p All embodiments and specifications relating to the proportion of glass fibers having a length exceeding 400 μm or 500 μm also apply to Embodiment (E*).

[0104] Each parameter L av , L p Furthermore, the proportion of glass fibers having a length exceeding 400 μm or a length exceeding 500 μm from the number-weighted distribution and the volume-weighted distribution can take any value disclosed in this application.

[0105] Damage time (t F ) As described above, polymer molding compositions need to have sufficient resistance to thermal stress caused by thermal runaway. The longer the time they can withstand thermal stress, the more effective they are in suppressing thermal runaway. Polyamide molding compositions have the following failure time parameter (t) disclosed below. F ;t F T1 ;t F T2 Characterized by at least one of the following:

[0106] UL Solutions (https: / / www.ul.com / ) is an accredited certification body that provides standards and regulations. UL Solutions developed the Torch-and-Grit (TaG) test disclosed in UL2596, "Test Method for Thermal and Mechanical Performance of Battery Enclosure Materials." This test addresses the dynamic stresses observed in thermal runaway events in actual automotive batteries.

[0107] The polyamide molded composition has a breakage time of at least 90.0 seconds, preferably at least 100.0 seconds (t F Characterized by, t F This is measured in a sample having a thickness of 3 mm and according to the Torch-and-Grit (TaG) test disclosed in UL2596 2nd edition, published on September 8, 2023. F This is typically up to 190.0 seconds.

[0108] The applicant has also developed a similar test T1 disclosed in the experimental section. This test uses a lower flame temperature than UL2596 2nd edition. The polyamide molded composition is subjected to a break time of at least 5.0 minutes, preferably at least 6.0 minutes, and more preferably at least 10.0 minutes (t F T1 Characterized by, t F T1 This is determined according to protocol T1 defined in the experimental section. F T1 This is typically up to 20.0 minutes. Failure is defined as either a flame being observed on the cooler side due to meltdown, or the plaque sample falling through the hollow ceramic platform under its own weight.

[0109] The applicant also developed a similar test T2 disclosed in the experimental section. This test is identical to UL2596 2nd edition, except that no grit is used and the flame temperature is lower. The polyamide molded composition is subjected to a break time (t) of at least 500.0 seconds, preferably at least 750.0 seconds, more preferably at least 1000.0 seconds, and preferably at least 1400.0 seconds. F T2 Characterized by, t F T2 This is determined according to protocol T2 defined in the experimental section. F T2 This is typically up to 2000.0 seconds.

[0110] The polyamide molding composition of the present invention has a fracture time (t) disclosed herein. F ) can be characterized by:

[0111] The polyamide molding composition of the present invention has a fracture time (t) disclosed herein. F T1 ) can be characterized by:

[0112] The polyamide molding composition of the present invention has a fracture time (t) disclosed herein. F T2 ) can be characterized by:

[0113] Mechanical properties The polyamide molding composition of the present invention typically has a concentration of 10.0 to 25.0 kJ / m³. 2 Preferably 15.0 to 25.0 kJ / m 2 Preferably 20.0~25.0 kJ / m 2 This shows the impact strength (notched Izod test, room temperature, measured according to ISO 180, specimen size: Type 1A rod).

[0114] The polyamide molded compositions of the present invention typically exhibit a breaking tensile strength of at least 180 MPa (speed: 5 mm / min, measured according to ISO 527, specimen size: Type 1A rod).

[0115] Polyamide (PA) The polyamide (PA) present in the polyamide molding composition of the present invention may be any one of the polyamides disclosed herein, particularly the polyamide according to embodiment (E).

[0116] Polyamides (PA) are defined by formulas (I) and / or (II), respectively: [ka] (In the formula, - R1 is C2~C 18 Selected from the group consisting of alkylene groups, - R2 is C2~C 18 Alkylene group, C6~C 18 Cycloalkylene group and C6~C 18 Selected from the group consisting of arylene groups, and - R3 is C4~C18 Alkylene group, C6~C 18 Cycloalkylene group, C8~C 18 (Selected from the group consisting of an arylene group, 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), 1,4-bis(aminomethyl)cyclohexane ("1,4-BAC"), and a divalent radical derived from bis(aminomethyl)cyclohexane selected from the group consisting of combinations thereof) Repeating unit by (R PA ) includes.

[0117] Repeating unit (R PA )teeth, - Amino acid components comprising at least one amino acid of formula (III)NH2-R1-COOH, and / or - At least one lactam, and / or - A dicarboxylic acid component (a) containing at least one dicarboxylic acid of formula (IV) HOOC-R2-COOH and a diamine component (b) containing at least one diamine of formula (V) H2N-R3-NH2 It is formed from the condensation of a reaction mixture (RM) containing [the specified substance].

[0118] The alkylene group may be linear or branched. Preferably, the alkylene group is of the formula -(CH2) n - (wherein n is an integer between 2 and 18 or between 4 and 18)

[0119] The arylene group is preferably a phenylene group.

[0120] According to a preferred embodiment, the polyamide (PA) comprises only the repeating units of formula (II). In this case, the repeating units (R PA ) is formed by the condensation of a dicarboxylic acid component (a) containing at least one dicarboxylic acid of formula (IV) and a diamine component (b) containing at least one diamine of formula (V).

[0121] Repeating units (R) in polyamide (PA) PAThe proportion of ) is preferably at least 95.0 mol%, preferably at least 98.0 mol%, and preferably at least 99.0 mol%, and this proportion is given with respect to the total number of moles of repeating units in the polyamide (PA).

[0122] Non-limiting examples of amino acids suitable for use in the production of polyamides include, in particular, 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 13-aminotridecanoic acid, and combinations thereof.

[0123] Non-limiting examples of lactams suitable for use in the manufacture of polyamides include β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam, lauryllactam, and combinations thereof.

[0124] Non-limiting examples of dicarboxylic acids in dicarboxylic acid component (a) include, in particular, phthalic acid (including isophthalic acid (I) and terephthalic acid (T)), 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, bis(4-carboxyphenyl)methane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)ketone, 4,4'-bis(4-carboxyphenyl)sulfone, 2,2-bis(3-carboxyphenyl)propane, bis(3-carboxyphenyl)methane, 2,2-bis(3-carboxyphenyl) The combination of two or more of the dicarboxylic acids is: (nyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)ketone, bis(3-carboxyphenoxy)benzene, naphthalenedicarboxylic acid (including 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 1,8-naphthalenedicarboxylic acid), oxalic acid, malonic acid, succinic acid, glutaric acid, 2,2-dimethylglutaric acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, 2,4,4-trimethyladipic acid, pimelic acid, suberic acid, sebacic acid, undecanediic acid, dodecanediic acid, and the aforementioned dicarboxylic acids.

[0125] Non-limiting examples of diamines in diamine component (b) include, in particular, 1,2-diaminoethane, 1,2-diaminopropane, propylene-1,3-diamine, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,5-diamino-2-methylpentane, 1,4-diamino-1,1-dimethylbutane, 1,4-diamino-1-ethylbutane, 1,4-diamino-1,2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, and 1,4-diamino-2,3-dimethylbutane. Butane, 1,2-diamino-1-butylethane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2,4-dimethylhexane, 1,6-diamino-3,3-dimethylhexane, 1,6-diamino-2,2-dimethylhexane, 1,9-diaminononane, 1,6-diamino-2,2,4-trimethylhexane, 1,6-diamino-2,4,4-trimethylhexane, 1,7-diamino-2,3-dimethylheptane, 1,7-diamino-2 ,4-dimethylheptane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-2,2-dimethylheptane, 1,10-diaminodecane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino-1,4-dimethyloctane, 1,8-diamino-2,4-dimethyloctane, 1,8-diamino-3,4-dimethyloctane, 1,8-diamino-4,5-dimethyloctane, 1,8-diamino-2,2-dimethyloctane, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,4-dimethyloctane The diamines are 1,6-diamino-2,4-diethylhexane, 1,9-diamino-5-methylnonane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,3-bis(aminomethyl)cyclohexane, para-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), isophoronediamine, meta-phenylenediamine, meta-xylylenediamine, para-xylylenediamine, 1,3-BAC, 1,4-BAC, and two or more combinations of the aforementioned diamines.

[0126] In the present invention, the reaction mixture (RM) may further contain a monoacid and / or monoamine as an end-capping agent. Non-limiting examples of end-capping agents include acetic acid, propanoic acid, benzoic acid, benzylamine, 1-aminohexane, and 1-aminododecane.

[0127] In one embodiment, the polyamide (PA) is polyamide 66, polyamide 6, or a blend thereof.

[0128] Embodiment (E) According to a preferred embodiment (E) of the present invention, the polyamide (PA) is a partially aromatic (also known as semi-aromatic) polyamide.

[0129] According to embodiment (E), the repeating unit (R) of polyamide (PA) PA ) is preferably, - (i) at least one phthalic acid selected from the group consisting of isophthalic acid (I), terephthalic acid (T), and combinations of I and T, and (ii) optionally, formula (IV) (wherein R2 is C2~C 18 Alkylene group, C6~C 18 A dicarboxylic acid component (a) comprising at least one dicarboxylic acid (selected from the group consisting of cycloalkylene groups and combinations thereof), - Formula (V) (in the formula, R3 is C4~C 18 (b) a diamine component comprising at least one diamine (selected from the group consisting of alkylene, 1,3-BAC, 1,4-BAC, and divalent radicals derived from bis(aminomethyl)cyclohexane selected from the group consisting of combinations thereof) It is obtained from the condensation of the following.

[0130] The dicarboxylic acid component (a) is more specifically (i) at least one phthalic acid selected from the group consisting of isophthalic acid (I), terephthalic acid (T), and combinations of I and T, and (ii) optionally, formula (IV) (wherein R2 is C2~C 18 Alkylene group, C6~C 18Essentially consisting of or comprising at least one dicarboxylic acid (selected from the group consisting of cycloalkylene groups and combinations thereof).

[0131] The diamine component (b) is more specifically defined by formula (V) (wherein R3 is C4~C). 18 Essentially comprising or consisting of at least one diamine (selected from the group of divalent radicals derived from bis(aminomethyl)cyclohexane, selected from the group consisting of alkylene, 1,3-BAC, 1,4-BAC, and combinations thereof).

[0132] More specifically, R2 is selected from the group consisting of C4-C8 alkylene groups, cycloalkylene groups, and combinations thereof.

[0133] More specifically, R3 is selected from the group consisting of C4-C8 alkylene groups, divalent radicals derived from bis(aminomethyl)cyclohexane, and combinations thereof.

[0134] More specifically, polyamides (PA) are repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), and are composed of repeating units (R PA ) may consist of, and the diamine component (A) is • 55.0 mol% to 75.0 mol% of one or more C4-C8 aliphatic diamines • 25.0 mol% to 45.0 mol% of an aliphatic diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, and combinations thereof. • 0 mol% to 10.0 mol% of bis(aminomethyl)cyclohexane selected from the group consisting of 1,3-BAC, 1,4-BAC, and combinations thereof. Essentially consisting of or made of • The mol% is relative to the total number of moles of diamine in diamine component (A), and "essentially consisting of" means that diamine component (A) consists of C4-C8 aliphatic diamines, other aliphatic diamines, bis(aminomethyl)cyclohexane, and up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol%, of additional diamines other than C4-C8 aliphatic diamines, other aliphatic diamines, and bis(aminomethyl)cyclohexane. The dicarboxylic acid component (B) is, • 90.0 mol% to 100 mol% terephthalic acid, • 0 mol% to 10.0 mol%, C6 to C 18 A dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, isophthalic acids, and combinations thereof, • 0 mol% to 10.0 mol% of 1,4-cyclohexanedicarboxylic acid and Essentially consisting of or made of • The mol% is relative to the total number of moles of dicarboxylic acid in dicarboxylic acid component (B), and "essentially consisting of" means that dicarboxylic acid component (B) consists of terephthalic acid, other dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, and up to 1.5 mol%, preferably up to 1.0 mol%, and preferably up to 0.5 mol%, of additional dicarboxylic acids other than terephthalic acid, other dicarboxylic acids, and 1,4-cyclohexanedicarboxylic acid. Bis(aminomethyl)cyclohexane or 1,4-cyclohexanedicarboxylic acid, or both, are present in proportions exceeding 0.5 mol% in the diamine component (A) or the dicarboxylic acid component (B), respectively. This polyamide is called polyamide (PA1).

[0135] More specifically, polyamides (PA) are repeating units formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), and are composed of repeating units (R PA ) may consist of, and the diamine component (A) is • 55.0 mol% to 75.0 mol% of one or more C4-C8 aliphatic diamines • 25.0 mol% to 45.0 mol% of an aliphatic diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, and combinations thereof. • 0 mol% to 10.0 mol% of bis(aminomethyl)cyclohexane selected from the group consisting of 1,3-BAC, 1,4-BAC, and combinations thereof. Essentially consisting of or made of • The mol% is relative to the total number of moles of diamine in diamine component (A), and "essentially consisting of" means that diamine component (A) consists of C4-C8 aliphatic diamines, other aliphatic diamines, bis(aminomethyl)cyclohexane, and up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol%, of additional diamines other than C4-C8 aliphatic diamines, other aliphatic diamines, and bis(aminomethyl)cyclohexane. The dicarboxylic acid component (B) is, • 90.0 mol% to 100 mol% terephthalic acid, • 0 mol% to 10.0 mol%, C6 to C 18 A dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, isophthalic acids, and combinations thereof, • 0.5 mol% to 10.0 mol% of 1,4-cyclohexanedicarboxylic acid and Essentially consisting of or made of The molar percentages are relative to the total number of moles of dicarboxylic acid in dicarboxylic acid component (B), and "essentially consisting of" means that dicarboxylic acid component (B) consists of terephthalic acid, other dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, and up to 1.5 mol%, preferably up to 1.0 mol%, and preferably up to 0.5 mol%, of additional dicarboxylic acids other than terephthalic acid, other dicarboxylic acids, and 1,4-cyclohexanedicarboxylic acid. This polyamide is called polyamide (PA2).

[0136] According to one embodiment, in particular with respect to polyamides PA1 and PA2, the C4-C8 aliphatic diamine present in the diamine component (a) is 1,6-diaminohexane (also known as hexamethylenediamine).

[0137] The polyamide (PA) according to embodiment (E) is, more specifically, - 6T / 6I / 66, - 6T / 66, - 6T / 6I, - 6T / 10T, - 6T / 10T / BACT (where BAC is 1,3-BAC and / or 1,4-BAC, preferably 1,3-BAC), - 6T / BACT / 66 / BAC6 (where BAC is 1,3-BAC and / or 1,4-BAC, preferably 1,3-BAC), - 6T / 10T / 6.CHDA / 10.CHDA (where CHDA is 1,4-cyclohexanedicarboxylic acid. This polyamide repeating unit (R PA ) is formed from the condensation of a dicarboxylic acid component consisting of T and 1,4-cyclohexanedicarboxylic acid and a diamine component consisting of 1,6-diaminohexane and 1,10-diaminodecane), and - 6T / 9T / 6.CHDA / 9.CHDA (where CHDA is 1,4-cyclohexanedicarboxylic acid. This polyamide repeating unit (R PA ) is formed by the condensation of a dicarboxylic acid component consisting of T and 1,4-cyclohexanedicarboxylic acid and a diamine component consisting of 1,6-diaminohexane and 1,9-diaminononane), - those combinations It is selected from the group consisting of the following.

[0138] All polyamides referred to herein are prepared by polycondensation. This polymerization technique involves heating a reaction mixture containing all monomers to a temperature sufficient to induce the formation of amide bonds. The temperature at which the reaction mixture is heated is typically at least 200°C, more preferably at least 250°C. Conditions can be followed as shown in the experimental section of European Patent No. 4021959B1.

[0139] Polyamide (PA) and polyamide molding compositions should preferably exhibit excellent heat resistance even under normal conditions.

[0140] Polyamide (PA), particularly the polyamide (PA) according to embodiment (E), is semi-crystalline.

[0141] Polyamide (PA), particularly polyamide (PA) according to embodiment (E), and especially polyamide (PA1) and polyamide (PA2), preferably contain at least 30.0 J / g, preferably at least 35.0 J / g of H m This indicates H m The maximum is typically 60.0 J / g.

[0142] Polyamide (PA), particularly polyamide (PA) according to embodiment (E), and especially polyamide (PA1) and polyamide (PA2), preferably have a melting temperature of at least 295°C, preferably at least 300°C (T m ) indicates T m It is usually below 340°C. m This can be measured by DSC according to ASTM D3418.

[0143] T m The temperature is preferably at least 310°C.

[0144] Polyamide (PA), particularly polyamide (PA) according to embodiment (E), and especially polyamide (PA1) and polyamide (PA2), preferably have a glass transition temperature (T) of at least 90°C, preferably at least 100°C. g ) indicates Tg The temperature is preferably at least 120°C, and preferably at least 130°C. g The temperature is usually below 170°C. g This can be measured by DSC according to ASTM D3418.

[0145] Polyamides suitable for preparing polyamide molding compositions are commercially available from Solvay Specialty Polymers USA, LLC under the trade name AMODEL®.

[0146] The polyamides (PA) disclosed herein, particularly polyamides (PA1), (PA2), or any one of the polyamides disclosed above, are preferably semi-aromatic polyamides exhibiting the following properties: - Melting temperature of at least 300°C (T m ), - Heat of fusion (Hm) of at least 30.0 J / g, - A glass transition temperature (Tg) of at least 100°C.

[0147] The conditions shown in the experimental section are useful for determining the thermal properties of polyamide (PA).

[0148] Glass fiber (GF) The glass fibers used in the preparation of the polyamide molded composition are endless glass fibers, i.e., continuous glass fibers or chopped glass fibers. Two types of glass fibers can be used in the preparation of the polyamide molded composition of the present invention, but it is preferable to use only one type of glass fiber, particularly one type of glass fiber having a uniform diameter.

[0149] An example of glass fiber that can be used in the preparation of the polyamide molded composition of the present invention is Tufrov® 4510 roving from Nippon Electric Glass Co., Ltd. (see https: / / www.neg.co.jp / en / assets / file / product / fiber / e-roving / e-roving_list / TufRov_4510_LFT_roving_210907.pdf). These E glass fibers typically have a fiber diameter of 12-17 μm and a roving tex exceeding 1000 g / km.

[0150] These glass fibers are used in the methods for preparing polyamide molded compositions disclosed herein. Their length is shortened in the methods for preparing pellets (p) and the preparation methods disclosed herein.

[0151] Glass fibers typically contain multiple oxides. The main oxide is silica (SiO2), but other oxides such as calcium oxide (CaO), sodium oxide (Na2O), and alumina (Al2O3) are added to modify desired properties, such as lowering the melting point and suppressing crystallization.

[0152] Flame retardant (FR) The polyamide molding composition also includes at least one FR.

[0153] FR preferably does not contain halogens.

[0154] FR is preferably an organophosphorus compound. In another embodiment, FR comprises an organophosphorus compound and a flame retardant synergist. In relation to the present invention, the organophosphorus compound is, in particular, any one of the organophosphorus compounds disclosed herein.

[0155] In certain embodiments of the present invention, FR is or comprises at least one organophosphorus compound selected from the group consisting of phosphinates, diphosphinates, and combinations thereof.

[0156] In certain embodiments of the present invention, FR is or comprises at least one organic phosphorus compound selected from the group consisting of phosphinates of formula (a), diphosphinates of formula (b), and combinations thereof.

Chemical formula

[0157] m, n and x are typically numbers such that the molecule of formula (a) or (b) is neutral.

[0158] In formulas (a) and (b), M is preferably Ca, Al or Zn, the protonated nitrogen base is preferably ammonia, melamine, triethanolamine, particularly the protonated base of NH4 + , R 7 and R 8 are the same or different, preferably straight-chain or branched C1-C6 alkyl and / or phenyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl. R 9 is preferably methylene, ethylene, n-propylene, isopropylpropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene. In certain embodiments, R 9 is phenylene or naphthylene.

[0159] According to one embodiment of the present invention, - M is Mg, Ca, Al, or Zn. - m is 2 or 3, and - n is 1 or 3, and - x is either 1 or 2.

[0160] More specifically, FR is the organophosphorus of formula (a).

[0161] Phosphinates are preferred as the organophosphorus compounds. Aluminum phosphinate, calcium phosphinate, and zinc phosphinate are particularly preferred. Among aluminum phosphinates, aluminum ethylmethylphosphinate and aluminum diethylphosphinate are preferred. In a particularly preferred embodiment, the organophosphorus compound is aluminum diethylphosphinate.

[0162] The following FRs can be used in the molding composition: a mixture of 80% by weight of aluminum diethylphosphinate salt and 20% by weight of aluminum phosphate, and an aluminum salt of diethylphosphinate.

[0163] In one embodiment of the present invention, FR comprises a (di)phosphinate and a nitrogen-containing synergistic agent.

[0164] The synergistic combination of a specific phosphinate in various polymers with a nitrogen-containing compound that has a more effective effect than the phosphinate alone is also within the scope of the present invention.

[0165] The nitrogen-containing synergistic agent preferably includes benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluryl, melamine, melamine cyanurate, dicyandiamide, guanidine, carbodiimide, and the like.

[0166] The nitrogen-containing synergistic agent preferably contains a melamine condensation product. For example, the melamine condensation product is melem, melam, or melon.

[0167] Phosphorus / nitrogen-containing synergistic agents may include reaction products of melamine with phosphoric acid or condensed phosphoric acid. Examples include dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate, melam polyphosphate, and melam polyphosphate, as well as mixed polysalts.

[0168] The phosphorus / nitrogen-containing synergistic agent may be ammonium hydrogen phosphate, ammonium dihydrogen phosphate, or ammonium polyphosphate.

[0169] The polyamide molding composition according to the present invention may optionally contain other known flame retardant synergens. Examples of such synergens include metal oxides such as silica, iron oxide, titanium oxide, aluminum oxide, and magnesium oxide; metal hydroxides and hydroxide oxides such as aluminum hydroxide, boehmite, and magnesium hydroxide; and metal salts such as zinc borate, zinc carbonate, magnesium carbonate, barium carbonate, and barium metaborate.

[0170] Non-limiting examples of FR include antimony trioxide, antimony pentoxide, antimony-metal compounds, zinc borate, alumina trihydrate, magnesium hydroxide, and basalt fibers.

[0171] In certain embodiments, FR includes basalt fibers.

[0172] Additives The polyamide molding composition may contain a flame retardant (FR) and at least one additive (Add) different from the FR. The proportion of the additive (Add) is typically 0 to 15.0% by weight.

[0173] In one embodiment, the polyamide molding composition contains at least one additive (Add) in an amount of 0% to 10.0% by weight relative to the total weight of the polyamide molding composition.

[0174] Additives are typically selected from the group consisting of impact modifiers, strengtheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants (e.g., calcium stearate, magnesium stearate, or sodium montanoate), heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical foaming agents, nucleating agents, and any combination thereof.

[0175] In preferred embodiments of the present invention, the additive (Add) is selected from the group consisting of impact modifiers, strengtheners, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, antioxidants, and any combination thereof.

[0176] In another preferred embodiment of the present invention, the additive (Add) is selected from the group consisting of plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, antioxidants, and any combination thereof.

[0177] additional filler The polyamide molded composition may further contain at least one additional filler different from glass fibers (GF), the additional filler being selected from the group consisting particularly of inorganic fillers (e.g., talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate) and glass spheres (e.g., hollow glass microspheres).

[0178] In one embodiment, the additional filler is selected from the group consisting of calcium carbonate, magnesium carbonate, graphite, carbon black, carbon fiber, carbon nanofiber, graphene, graphene oxide, fullerene, talc, wollastonite, mica, alumina, silica, titanium dioxide, kaolin, silicon carbide, zirconium tungstate, and boron nitride.

[0179] Preparation of the polyamide molding composition of the present invention Polyamide molding composition, - Step a): A step of introducing pellets (p) prepared from strands consisting of multiple filaments of glass fiber (GF) impregnated with a composition (c) containing all components of a polyamide molding composition except glass fiber (GF) into an extruder. - Step b): A step of molding the composition obtained after step a). It can be easily obtained by including it in the method.

[0180] Composition (C) comprises all components of a polyamide molding composition except for glass fibers (GF) (i.e., polyamide (PA), flame retardant (FR), optional additives (if present in the polyamide molding composition), and optional additional fillers (if present in the polyamide molding composition)).

[0181] The proportions of the components of composition (c) are typically as follows: - Polyamide (PA): 50.0-80.0% by weight - FR:20.0~50.0wt%, - Additives and additional fillers: 0-20.0% by weight. These proportions are relative to the total weight of composition (c).

[0182] In step a), the pellet (p) is introduced into an extruder, particularly a single-screw extruder.

[0183] In step b), the technique used to mold the composition obtained after step a) is typically selected from the group consisting of extrusion molding, injection molding, blow molding, rotational molding, overmolding, compression molding, and pultrusion molding. Step b) may be carried out according to any one of the listed techniques. Extrusion molding and injection molding are simple methods that enable the preparation of the polyamide molded compositions of the present invention. The technique used in step b) is, in particular, injection molding.

[0184] The polyamide molded composition is typically in the form of pellets or molded articles, particularly at the end of step b).

[0185] For the preparation of the polyamide molded composition, the conditions shown in the examples in the experimental section can be followed (see §2 Injection Molding).

[0186] About pellets (p) The pellets (p) are prepared from strands consisting of multiple filaments of glass fiber (GF) impregnated with composition (c), which contains all the components of a polyamide molding composition except for the glass fiber (GF).

[0187] Pellet(p) is typically, - A step of bringing a molten composition (c) into contact with a strand composed of multiple GF filaments, - A step of passing the composite obtained in this way through an impregnation die, - After the die, the composite is cooled and cut into pellets (p). It is prepared by a method that includes [a specific method].

[0188] Examples of usable impregnation dies are disclosed in European Patent No. 0320653, U.S. Patent Publication No. 2013 / 0145986A1, or U.S. Patent No. 5,277,566.

[0189] The viscosity of the molten composition (c) should be low enough to spread and permeate well around the fibers, and in particular, low enough to completely "wet" and envelop the fibers. For this purpose, the temperature of the molten composition (c) needs to be high enough to reduce its viscosity. The temperature of the molten composition (c) should be high enough to reduce its viscosity and below the decomposition temperature of the composition (c).

[0190] The temperature of the molten composition (c) is typically at least Tm + 40°C, preferably at least Tm + 50°C, where Tm represents the melting temperature of the polyamide (PA). In the case of polyamide (PA) combinations, the melting temperature to be considered is the highest Tm, which is typically 350-400°C.

[0191] The speed of the strand during impregnation is typically 1.0–20.0 m / min, more specifically 5.0–15.0 m / min.

[0192] The length of the pellet (p) is typically 4 to 15 mm, more preferably 5 to 12 mm. The longer the length, the L of the polyamide molded composition. av and L p It gets bigger.

[0193] The present invention relates to a method for preparing pellets (p), - A step of bringing a molten composition (c) into contact with a strand composed of multiple GF filaments, - A step of passing the composite obtained in this way through an impregnation die, - After the die, the composite is cooled and cut into pellets (p). The invention also relates to a method comprising, wherein composition (c) comprises a polyamide (PA1) or polyamide (PA2), at least one FR disclosed herein, optionally at least one additive (Add) disclosed herein, and optionally additional fillers (different from GF) disclosed herein.

[0194] The proportions of the components of composition (c) are, in particular, as follows: - Polyamide (PA1) or (PA2): 50.0-80.0% by weight, - FR:20.0~50.0wt%, - Additives and additional fillers: 0-20.0% by weight. These proportions are relative to the total weight of composition (c).

[0195] More specifically, the polyamide (PA1) may be a polyamide selected from the group consisting of 6T / 10T / BACT, 6T / 10T / 6.CHDA / 10.CHDA, 6T / 9T / 6.CHDA / 9.CHDA, and combinations thereof.

[0196] For impregnation, the conditions shown in the examples in the experimental section can be followed (see §1 for kneading).

[0197] According to a preferred embodiment, the polyamide (PA) in the composition (c) is a semi-aromatic polyamide as defined in embodiment (E). The polyamide (PA) is, in particular, any one of the semi-aromatic polyamides defined in embodiment (E).

[0198] Molded article According to one embodiment, the polyamide molding composition is, in particular at the end of step b), in the form of a molded article.

[0199] The article can be any other part of the battery, such as a battery housing or a cover for the battery housing. The function of the battery housing is to house and protect the battery of any electric vehicle (EV) (e.g., hybrid vehicle, plug-in hybrid vehicle, and full EV). An example of a battery housing is disclosed in U.S. Patent Application Publication No. 2010 / 0273034A1.

[0200] The article can be the housing of the battery housing, a wall (e.g., inner wall or outer wall), or a cover. An example of a housing is disclosed in International Publication No. 2013 / 098121 pamphlet. Examples of articles made from polymeric materials are disclosed in European Patent No. 3460870.

[0201] An additional indicator of the electrical properties required for articles for electrical or electronic devices / parts, such as electrical connectors, is the comparative tracking index (CTI). CTI is used to measure the dielectric breakdown properties of insulating materials. Tracking is defined as the current flowing on the surface of an insulator between two electrodes, which can be caused by the degradation of the insulator. In addition, tracking resistance is the ability of an insulator to prevent the formation of such a current. <000​CTI can be measured according to IEC60112. This represents the relative resistance of solid electrical insulating materials to tracking at voltages up to 600V when the surface is exposed to water with contaminants such as ammonium chloride solution under electrical stress. The CTI value refers to the voltage at which no tracking occurs even when 50 drops of the solution are dropped, provided that no tracking occurs even when 100 drops of the solution are dropped at another voltage 25V lower. The larger the value, the higher the resistance of the material.

[0203] In one embodiment, the polyamide molding composition according to the present invention exhibits a CTI of 600V or more corresponding to category (PLC)0 of the highest performance level.

[0204] Use The polyamide molding composition of the present invention can be used to produce at least one part of a battery housing, and this part is particularly selected from the group consisting of the housing, inner wall or cover of the battery housing.

Examples

[0205] Raw materials - Polyamide (PA): Amodel® PPA Bios, commercially available from Solvay Specialty Polymers USA, LLC. Tm is about 315°C; - (GF)(I): TufRov® 4510, which is E-glass fiber with a fiber diameter of 12μm, commercially available from Nippon Electric Glass Co., Ltd.; - (GF)(II): ChopVantage® HP3610, which is E-glass fiber with a nominal cut length of 3.2mm and a nominal fiber diameter of 10μm, commercially available from Nippon Electric Glass; - Flame retardant (FR): Exolit® OP1230, commercially available from Clariant GmbH.

[0206] Thermal properties of polyamide (PA): Tg, Tm and Hm are measured by differential scanning calorimetry ("DSC") according to ASTM D3418 using a heating and cooling rate of 20°C / min.

[0207] The weight percentages of each component of the polyamide molded composition are shown in Table 1 or Table 2 below.

[0208] The polyamide molded composition was prepared by injection molding the pellets obtained after the kneading process disclosed below.

[0209] 1) Mixing Conditions for E1-E3 (Examples): PA was first tumble-blended in a 50-gallon drum for 30 minutes to form a resin premix with additives (ADK Pep-36 and ADK AO-80 as antioxidants, commercially available from ADEKA Corporation) to produce the premix. The premix was then metered and fed into the feed port of a 25 mm Berstorff co-rotating twin-screw extruder with eight barrel sections. The resin mixture was metered and fed at a rate of 78.00 lb / hr using a gravimetric feeder. FR was fed into barrel 7 at a rate of 22.5 lb / hr using a gravimetric feeder. Vacuum venting was performed in barrel section 8 to remove moisture and any other volatile residues from the compound by achieving a vacuum level of 25 in Hg. After heating the extruded material to 370°C, it was added to a continuous strand of GF(I). The polymer-coated continuous glass strand was first cooled and cut into 9 mm long pellets (p).

[0210] These conditions used in the preparation of the pellets (p) are referred to as Condition A.

[0211] CE1-CE2 (Comparative Examples): PA was first tumble-blended in a 50-gallon drum for 30 minutes to form a resin premix with additives (ADK Pep-36 and ADK AO-80 as antioxidants, commercially available from ADEKA Corporation) to produce the premix. The premix was then metered and fed into the feed port of a 25 mm Berstorff co-rotating twin-screw extruder with eight barrel sections. The resin mixture was metered and fed at a rate of 13.00 lb / hr using a gravimetric feeder. GF(II) was similarly fed into barrel section 6 at a rate of 8.25 lb / hr using a gravimetric feeder. FR was fed into barrel 7 at a rate of 3.75 lb / hr using a gravimetric feeder. The total mixing rate was 25 lb / hr. During mixing, the barrel section temperatures were set to 216°C (barrel 2), 306°C (barrel 3), 340°C (barrels 3-4), and 300°C (barrels 5-9, adapter, die). During mixing, the molten material temperature was monitored using a handheld temperature probe and confirmed to be within the range of 330°C to 350°C. Vacuum venting was performed in barrel 8 to achieve a vacuum level of 25 in Hg, removing moisture and other volatile residues from the compound. The extruded material was pulled from the die in strand form, cooled in a water bath, and then cut into cylindrical pellets approximately 3.0 mm in length and 2.7 mm in diameter.

[0212] These conditions used to prepare the pellets in the comparative example are referred to as Condition B.

[0213] 2) Injection molding (IM) The pellets obtained from the kneading process (conditions A or B) described in detail above were initially dried in a dry convection air oven at 82°C for at least 8 hours (overnight) in preparation for injection molding. To maintain the moisture content of the dried pellets, injection molding was performed using an injection molding machine SE180EV-A (commercially available from Sumitomo Heavy Industries, Ltd., equipped with a 50mm diameter screw) with a hopper dryer to produce articles for testing and performance measurement. The cycle time varied from 36.0 to 47.0 seconds, and the peak filling pressure was adjusted to 7000 to 9000 psi. The temperature of the composition during injection was approximately 271°C. The dimensions of the produced plaques were 152mm × 152mm × 2mm and 101mm × 101mm × 2mm. Furthermore, ISO tensile test rods according to ISO 180 were also injection molded.

[0214] Measurement of glass fiber (GF) length The length of the fiberglass (GF) was measured according to ISO 22314:2006, with some modifications made to facilitate optical length tracking. The molded plaque pieces were cut to a size of 10 mm × 10 mm × 2 mm using a handsaw, and the samples were stored in an oven at 525°C for 4.5 hours. After separating the fibers according to the ashing method using a muffle furnace as described herein, the GF was dispersed in a plastic petri dish using low-pressure compressed air to promote dispersion.

[0215] The separated GF was imaged using an optical microscope, and the length of GFs greater than 200 was measured on the image.

[0216] The fiber length distribution (number-weighted distribution) is reported in the fiber length histogram shown in Figure 1.

[0217] Test T1 Test T1 was conducted according to the following protocol, in accordance with the guidance provided by UL Solutions.

[0218] [Table 7]

[0219] Test T2 Test T2 was conducted according to the following protocol in accordance with the guidance prepared by UL Solutions.

[0220]

Table 8

[0221] In Protocol T2, a temperature of 1000 °C is maintained by varying the ratio of methane to oxygen according to UL's internal calibration curve for torch temperature.

[0222] The t F T1 values shown in Table 1 correspond to the arithmetic mean values obtained from five repeated tests for each composition.

[0223]

Table 9

[0224] In Table 1, “>10” corresponds to a very good result, which means that the test was stopped at the 10-minute point without the occurrence of a flame. If it had not stopped, it is considered that the test could have been carried out for a longer time.

[0225] CE1 and CE2 in the presence of FR combined with GF(II) respectively failed the test. As can be seen from the data in Table 1, the polyamide molding composition of the present invention exhibits very excellent combustion resistance under dynamic conditions.

[0226] The polyamide molding composition according to the present invention exhibits an impact strength (notched Izod, room temperature, measured according to ISO 180, test piece size: type 1A bar) of 10.0 to 25.0 kJ / m 2 . The polyamide molding composition according to the present invention exhibits a tensile breaking strength of at least 180 MPa (speed: 5 mm / min, measured according to ISO 527, test piece size: type 1A bar).

[0227] Preparation of additional polyamide molding compositions An additional polyamide molding composition was prepared using the preparation method of the present invention. The pellets (p) obtained from kneading under condition A were initially dried in a dry convection air oven at 82°C for at least 8 hours (overnight) in preparation for injection molding. To maintain the moisture content of the dried pellets, injection molding was performed using an injection molding machine SE250EV-A (commercially available from Sumitomo Heavy Industries, Ltd., equipped with a hopper dryer and a 45 mm diameter screw) to produce articles for testing and performance measurement. The cycle time varied from 36.0 to 47.0 seconds, and the peak filling pressure was adjusted to 7000 to 9000 psi. The temperature of the composition during injection was approximately 271°C. The dimensions of the resulting plaque were 152 mm × 152 mm × 3 mm.

[0228] The injection molding machine settings were changed (see Table 2).

[0229] [Table 10]

Claims

1. - At least one type of polyamide (PA), - Glass fiber (GF), and - At least one type of flame retardant (FR), - At least one additive (Add) other than the flame retardant (FR), optionally selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical blowing agents, nucleating agents, and any combination thereof. A polyamide molding composition comprising, - In a sample having a thickness of 3 mm, a fracture time (t) of at least 90.0 seconds, preferably at least 100.0 seconds, as measured according to the Torch-and-Grit (TaG) test disclosed in UL2596 2nd edition, published on September 8, 2023. Ｆ ), and / or - A corruption time (t) of at least 5.0 minutes, preferably at least 6.0 minutes, and more preferably at least 10.0 minutes, determined according to protocol T1 defined in the experimental section. Ｆ Ｔ１ ), and / or - A corruption time (t) of at least 500.0 seconds, preferably at least 750.0 seconds, more preferably at least 1000.0 seconds, preferably at least 1400.0 seconds, determined according to protocol T2 defined in the experimental section. Ｆ Ｔ２ ) A polyamide molded composition characterized by the following.

2. - t Ｆ is 90.0 seconds to 190.0 seconds, and / or - t Ｆ Ｔ１ This is 5.0 to 20.0 minutes, and / or - t Ｆ Ｔ２ The polyamide molding composition according to claim 1, wherein the time interval is 500.0 seconds to 2000.0 seconds.

3. - At least one type of polyamide (PA), - Glass fiber (GF), and - At least one type of flame retardant (FR), - At least one additive (Add) other than the flame retardant (FR), optionally selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical blowing agents, nucleating agents, and any combination thereof. A polyamide molding composition, particularly according to claim 1 or 2, wherein the length distribution of the GF in the polyamide molding composition is - A set of parameters (S1) or (S2), or a set of parameters (S1) and (S2): 【number】 【number】 or - A set of parameters (S1*) or (S2*), or a set of parameters (S1*) and (S2*): 【number】 【number】 Characterized by, Average length (L ｐ ) is expressed by the following formula: [Math 1] (In the formula, ni is the number of glass fibers of length Li, and n is the number of glass fibers measured.) It is calculated using, The number-weighted distribution and volume-weighted distribution are determined in particular after the separation of the GF from the polyamide molded composition by a ash method (a), particularly by an ash method disclosed in ISO 22314:2006(E) or by a chemical method (b), in a polyamide molded composition.

4. The polyamide molding composition according to claim 3, characterized by a proportion of GF having a length exceeding 400 μm, at least 25% (in numbers), preferably at least 30% (in numbers), preferably at least 35% (in numbers), preferably at least 40% (in numbers), preferably at least 45% (in numbers), preferably at least 50% (in numbers), preferably at least 60% (in numbers), and preferably at least 65% (in numbers).

5. (L ａｖ The polyamide molding composition according to claim 3 or 4, wherein the length of the GF is 300 to 750 μm, and the proportion of the GF having a length exceeding 400 μm is at least 45% (in numbers), preferably at least 50% (in numbers).

6. The proportion of GF having a length exceeding 400 μm is 45% to 90%, and the proportion is obtained from the number-weighted distribution, the polyamide molding composition according to claim 3 in combination with claim 3 or claim 4 or 5.

7. A polyamide molding composition according to claim 3 or in combination with any one of claims 4 to 6, characterized by a proportion of GF having a length exceeding 500 μm, at least 20.0% (in numbers), preferably at least 25.0% (in numbers), preferably at least 30.0% (in numbers), preferably at least 40.0% (in numbers), and preferably at least 50.0% (in numbers).

8. (L ａｖ ) is 300 to 750 μm, and the proportion of the GF having a length exceeding 500 μm is at least 30.0% (in number), the polyamide molding composition according to claim 3 in combination with any one of claims 3 or 4 to 7.

9. The proportion of GF having a length exceeding 500 μm is 30.0% to 80.0% or 30.0% to 75.0%, and the proportion is obtained from the number-weighted distribution, the polyamide molding composition according to claim 3 in combination with any one of claims 3 or 4 to 8.

10. (Lav) is, - 220 μm to 750 μm, or - 220 μm to 700 μm, or - 300 μm to 750 μm, or - 300 μm to 700 μm, or - 270 μm to 550 μm, or -300μm~400μm The polyamide molding composition according to claim 3 in combination with claim 3 or any one of claims 4 to 9.

11. At least 90.0% (in number) of the GF has a length of 3000 μm or less, preferably 2500 μm or less, and the proportion is obtained from the number-weighted distribution, the polyamide molding composition according to claim 3 in combination with any one of claims 4 to 10.

12. The proportion of GF having a length exceeding 400 μm is at least 60.0%, preferably at least 65.0%, preferably at least 70.0%, preferably at least 75.0%, preferably at least 80.0%, preferably at least 85.0%, and preferably at least 90.0%, and the proportion is obtained from the volume weight distribution, the polyamide molding composition according to claim 3 in combination with any one of claims 3 or 4 to 11.

13. The proportion of GF having a length exceeding 400 μm is 65.0% to 100% or 70.0% to 100%, and the proportion is obtained from the volume weight distribution, the polyamide molded composition according to claim 3 in combination with any one of claims 3 to 12.

14. The proportion of GF having a length exceeding 500 μm is at least 50.0%, preferably at least 55.0%, preferably at least 60.0%, preferably at least 65.0%, preferably at least 70.0%, preferably at least 80.0%, preferably at least 85.0%, and preferably at least 90.0%, and the proportion is obtained from the volume weight distribution, the polyamide molded composition according to claim 3 in combination with any one of claims 3 or 4 to 13.

15. The proportion of GF having a length exceeding 500 μm is 55.0% to 100% or 80.0% to 100%, and the proportion is obtained from the volume weight distribution, the polyamide molded composition according to claim 3 in combination with any one of claims 3 or 4 to 14.

16. L ｐ teeth, - 400 μm to 1700 μm, or - 500 μm to 1800 μm, or -700μm~1800μm The polyamide molding composition according to claim 3 in combination with claim 3 or any one of claims 4 to 15.

17. - 35.0 to 65.0% by weight of at least one type of polyamide (PA), - 20.0 to 60.0% by weight of glass fiber (GF), - 10.0 to 30.0% by weight of at least one flame retardant (FR), and - 0 to 15.0% by weight of at least one additive (Add) other than the flame retardant (FR), selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical blowing agents, nucleating agents and any combination thereof, other than the flame retardant (FR), or - 35.0 to 60.0% by weight of at least one type of polyamide (PA), - 30.0 to 55.0% by weight of glass fiber (GF), - 10.0 to 30.0% by weight of at least one flame retardant (FR), and - At least one additive (Add) other than the flame retardant (FR), in an amount of 0 to 15.0% by weight, selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical foaming agents, nucleating agents, and any combination thereof. The polyamide molding composition according to any one of claims 1 to 16, comprising or consisting thereof, wherein the proportion in weight percent is relative to the total weight of the polyamide molding composition.

18. The proportion of GF is, - 30.0 to 55.0% by weight, or - 30.0 to 50.0% by weight The polyamide molding composition according to any one of claims 1 to 17.

19. The polyamide molding composition according to any one of claims 1 to 18, wherein the proportion of FR is 10.0 to 20.0% by weight.

20. The percentage of PA is, - 35.0 to 60.0% by weight, or - 35.0 to 55.0% by weight The polyamide molding composition according to any one of claims 1 to 19.

21. The polyamide molding composition according to any one of claims 1 to 20, wherein the proportion of the additive (Add) is 0 to 10.0% by weight.

22. The composition according to any one of claims 1 to 21, wherein the flame retardant (FR) does not contain halogens and is preferably an organophosphorus compound or contains an organophosphorus compound.

23. The composition according to any one of claims 1 to 22, wherein the flame retardant (FR) is at least one organophosphorus compound selected from the group consisting of phosphinates, diphosphinates, and combinations thereof, or comprises the same.

24. The composition according to any one of claims 1 to 23, wherein the polyamide (PA) is a partially aromatic polyamide.

25. The aforementioned polyamide (PA) is - (i) at least one phthalic acid selected from the group consisting of isophthalic acid (I), terephthalic acid (T), and combinations of I and T, and (ii) optionally, formula (IV) HOOC-R ２ -COOH (in the formula, R ２ C ２ ~C １８ Alkylene group, C ６ ~C １８ A dicarboxylic acid component comprising at least one dicarboxylic acid (selected from the group consisting of cycloalkylene groups and combinations thereof), - Formula (V)H ２ N-R ３ -NH ２ (In the formula, R ３ C ４ ~C １８ A diamine component comprising at least one diamine (selected from the group consisting of alkylene, 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC"), 1,4-bis(aminomethyl)cyclohexane ("1,4-BAC"), and divalent radicals derived from bis(aminomethyl)cyclohexane selected from the group consisting of combinations thereof) The condensation yields at least 95.0 mol%, preferably at least 98.0 mol%, preferably at least 99.0 mol%, of repeating units (R ＰＡ A composition according to any one of claims 1 to 24, comprising )

26. The repeating unit of the polyamide (PA) is formed by polycondensation of a diamine component (A) and a dicarboxylic acid component (B). ＰＡ ) consists of units, and the diamine component (A) is, - 55.0 mol% to 75.0 mol% of one or more C ４ ~C ８ Aliphatic diamines, - 25.0 mol% to 45.0 mol% of an aliphatic diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, and combinations thereof. - 0 mol% to 10.0 mol% of bis(aminomethyl)cyclohexane selected from the group consisting of 1,3-BAC, 1,4-BAC, and combinations thereof. Essentially consisting of or made of - The mol% is relative to the total number of moles of diamine in the diamine component (A), and "essentially consisting of" means that the diamine component (A) is C ４ ~C ８ An aliphatic diamine, the other aliphatic diamine, the bis(aminomethyl)cyclohexane, and a maximum of 1.5 mol%, preferably a maximum of 1.0 mol%, preferably a maximum of 0.5 mol%, of the C ４ ~C ８ This means comprising an aliphatic diamine, the other aliphatic diamines and additional diamines other than bis(aminomethyl)cyclohexane, and The aforementioned dicarboxylic acid component (B) is 90.0 mol% to 100 mol% terephthalic acid, ・0 mol% to 10.0 mol%, C ６ ~C １８ A dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, isophthalic acids, and combinations thereof, - 0 mol% to 10.0 mol% of 1,4-cyclohexanedicarboxylic acid and Essentially consisting of or made of • The mol% refers to the total number of moles of dicarboxylic acid in the dicarboxylic acid component (B), and "essentially consisting of" means that the dicarboxylic acid component (B) consists of terephthalic acid, the other dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and an additional dicarboxylic acid other than terephthalic acid, the other dicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid in amounts of up to 1.5 mol%, preferably up to 1.0 mol%, and preferably up to 0.5 mol%, respectively. The polyamide molding composition according to any one of claims 1 to 25, wherein the bis(aminomethyl)cyclohexane or the 1,4-cyclohexanedicarboxylic acid or both each constitutes more than 0.5 mol% of the diamine component (A) or the dicarboxylic acid component (B).

27. The aforementioned polyamide (PA) is the following polyamide: - 6T / 6I / 66, - 6T / 66, - 6T / 6I, - 6T / 10T, - 6T / 10T / BACT (where BAC is 1,3-BAC and / or 1,4-BAC, preferably 1,3-BAC), - 6T / BACT / 66 / BAC6 (where BAC is 1,3-BAC and / or 1,4-BAC, preferably 1,3-BAC), - 6T / 10T / 6.CHDA / 10.CHDA (where CHDA is 1,4-cyclohexanedicarboxylic acid), - Those combinations A composition according to any one of claims 1 to 26, selected from the group consisting of the following.

28. The polyamide (PA) has a heat of fusion of at least 30.0 J / g, preferably at least 35.0 J / g, as measured by differential scanning calorimetry (DSC) according to ASTM D3418 at a heating rate of 20°C / min. ｍ A composition according to any one of claims 1 to 27, which shows the characteristics of the composition.

29. The polyamide (PA) has a melting temperature (T) of at least 295°C, preferably at least 300°C and / or 340°C or lower, as measured by DSC according to ASTM D3418. ｍ A composition according to any one of claims 1 to 28, which shows )

30. The polyamide (PA) has a glass transition temperature (T) of at least 90°C, preferably at least 100°C, as measured by DSC according to ASTM D3418. ｇ A composition according to any one of claims 1 to 29, which shows )

31. Polyamide (PA), GF, FR, and additives (Add) (if present) are blended together in the polyamide molding according to any one of claims 1 to 30.

32. A polyamide molding composition according to any one of claims 1 to 31, further comprising at least one additional filler selected from the group consisting of calcium carbonate, magnesium carbonate, graphite, carbon black, carbon fiber, carbon nanofiber, graphene, graphene oxide, fullerene, talc, wollastonite, mica, alumina, silica, titanium dioxide, kaolin, silicon carbide, zirconium tungstate, and boron nitride, wherein the additional filler is different from the glass fiber.

33. 10.0~25.0kJ / m ２ Preferably 15.0 to 25.0 kJ / m ２ Preferably 20.0 to 25.0 kJ / m ２ A polyamide molded composition according to any one of claims 1 to 32, exhibiting impact strength (notched Izod, room temperature, measured according to ISO 180, specimen size: type 1A rod).

34. A polyamide molded composition according to any one of claims 1 to 33, exhibiting a breaking tensile strength of at least 180 MPa (speed: 5 mm / min, measured according to ISO 527, specimen size: type 1A rod).

35. - Step a): A step of introducing pellets (p) prepared from strands consisting of multiple filaments of glass fiber (GF) impregnated with a composition (c) containing all the components of the polyamide molding composition except for the glass fiber (GF) into an extruder. - Step b): A step of molding the composition obtained after step a). A polyamide molding composition according to any one of claims 1 to 34, obtained by a method including the following.

36. The polyamide molding composition according to claim 35, wherein in step b), the technique used to mold the composition obtained after step a) is selected from the group consisting of extrusion molding, injection molding, blow molding, rotational molding, overmolding, compression molding, and pultrusion molding.

37. An article comprising or manufactured therefrom the polyamide molding composition described in any one of claims 1 to 36.

38. The article according to claim 37, which is a housing, wall, or cover for a battery enclosure.

39. A method for preparing pellets (p), - A step of bringing a molten composition (c) into contact with a strand composed of multiple glass fiber (GF) filaments, - The process of passing the composite obtained in this way through an impregnation die, - After the die, the composite is cooled and cut into pellets (p). Includes, Composition (c) comprises polyamide (PA1) or polyamide (PA2), at least one FR as described in claim 22 or 23, optionally at least one additive (Add) selected from the group consisting of impact modifiers, reinforcing agents, plasticizers, colorants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, antioxidants, nucleating agents, polymer processing aids, antiblocking agents, lubricants, antifogging agents, chemical blowing agents, nucleating agents and any combination thereof, optionally additional fillers (different from GF), wherein the repeating units of polyamide (PA1) are repeating units (R) formed from the polycondensation of a diamine component (A) and a dicarboxylic acid component (B). ＰＡ ) consists of, and the diamine component (A) is - 55.0 mol% to 75.0 mol% of one or more C ４ ~C ８ Aliphatic diamines, - 25.0 mol% to 45.0 mol% of an aliphatic diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, and combinations thereof. - 0 mol% to 10.0 mol% of bis(aminomethyl)cyclohexane selected from the group consisting of 1,3-BAC, 1,4-BAC, and combinations thereof. Essentially consisting of or made of - The mol% is relative to the total number of moles of diamine in the diamine component (A), and "essentially consisting of" means that the diamine component (A) is C ４ ~C ８ An aliphatic diamine, the other aliphatic diamine, the bis(aminomethyl)cyclohexane, and a maximum of 1.5 mol%, preferably a maximum of 1.0 mol%, preferably a maximum of 0.5 mol%, of the C ４ ~C ８ This means comprising an aliphatic diamine, the other aliphatic diamines and additional diamines other than bis(aminomethyl)cyclohexane, and The aforementioned dicarboxylic acid component (B) is 90.0 mol% to 100 mol% terephthalic acid, ・0 mol% to 10.0 mol%, C ６ ~C １８ A dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, isophthalic acids, and combinations thereof, - 0 mol% to 10.0 mol% of 1,4-cyclohexanedicarboxylic acid and Essentially consisting of or made of • The mol% refers to the total number of moles of dicarboxylic acid in the dicarboxylic acid component (B), and "essentially consisting of" means that the dicarboxylic acid component (B) consists of terephthalic acid, the other dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and an additional dicarboxylic acid other than terephthalic acid, the other dicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid in amounts of up to 1.5 mol%, preferably up to 1.0 mol%, and preferably up to 0.5 mol%, respectively. The bis(aminomethyl)cyclohexane or the 1,4-cyclohexanedicarboxylic acid or both are present in a proportion exceeding 0.5 mol% in the diamine component (A) or the dicarboxylic acid component (B), and The repeating units of polyamide (PA2) are formed by the polycondensation of a diamine component (A) and a dicarboxylic acid component (B), and are called repeating units (R ＰＡ ) consists of, and the diamine component (A) is - 55.0 mol% to 75.0 mol% of one or more C ４ ~C ８ Aliphatic diamines, - 25.0 mol% to 45.0 mol% of an aliphatic diamine selected from the group consisting of 1,9-nonanediamine, 1,10-decanediamine, and combinations thereof. - 0 mol% to 10.0 mol% of bis(aminomethyl)cyclohexane selected from the group consisting of 1,3-BAC, 1,4-BAC, and combinations thereof. Essentially consisting of or made of - The mol% is relative to the total number of moles of diamine in the diamine component (A), and "essentially consisting of" means that the diamine component (A) is C ４ ~C ８ An aliphatic diamine, the other aliphatic diamine, the bis(aminomethyl)cyclohexane, and a maximum of 1.5 mol%, preferably a maximum of 1.0 mol%, preferably a maximum of 0.5 mol%, of the C ４ ~C ８ This means comprising an aliphatic diamine, the other aliphatic diamines and additional diamines other than bis(aminomethyl)cyclohexane, and The aforementioned dicarboxylic acid component (B) is 90.0 mol% to 100 mol% terephthalic acid, ・0 mol% to 10.0 mol%, C ６ ~C １８ A dicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, isophthalic acids, and combinations thereof, - 0.5 mol% to 10.0 mol% of 1,4-cyclohexanedicarboxylic acid and Essentially consisting of or made of The mol% is relative to the total number of moles of dicarboxylic acid in the dicarboxylic acid component (B), and "essentially consisting of" means that the dicarboxylic acid component (B) consists of terephthalic acid, the other dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and an additional dicarboxylic acid other than terephthalic acid, the other dicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid in an amount of up to 1.5 mol%, preferably up to 1.0 mol%, preferably up to 0.5 mol%, of terephthalic acid, the other dicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

40. The proportion of the components in composition (c) is - Polyamide (PA1) or (PA2): 50.0 to 80.0% by weight, - FR: 20.0 to 50.0% by weight, - Additives and additional fillers: 0-20.0% by weight The method according to claim 39, wherein the proportion is relative to the total weight of composition (c).

41. A pellet (p) that can be obtained by the method of claim 39 or 40, wherein the pellet (p) has a length of preferably 4 to 15 mm, preferably 5 to 12 mm.

42. Use of pellets (p) for producing a polyamide molding composition according to any one of claims 1 to 36 or an article according to claim 37 or 38, wherein the pellets (p) are prepared from strands consisting of a plurality of filaments of glass fiber (GF) impregnated with composition (c) containing all of the components of the polyamide molding composition except the glass fiber (GF), or as described in claim 41.

43. The use according to claim 42, wherein the length of the pellet (p) is 4 to 15 mm, preferably 5 to 12 mm.

44. A method for producing a polyamide molding composition according to any one of claims 1 to 36 or an article according to claim 37 or 38, - Step a): A step of introducing the pellet (p) described in claim 41 into an extruder, - Step b): A step of molding the composition obtained after step a). A method comprising, wherein the pellet (p) is prepared from a strand consisting of a plurality of filaments of glass fiber (GF) impregnated with composition (c) which contains all the components of the polyamide molding composition except the glass fiber (GF), or the method according to claim 41.

45. Use of a polyamide molding composition according to any one of claims 1 to 36 or an article according to claim 37 or 38 for producing at least one component of a battery housing, wherein the component is selected in particular from the group consisting of a housing, an inner wall or a cover of the battery housing.

Images