Flame retardants and orange colorants for use in combination with thermoplastics

Abstract

The present disclosure relates to a novel flame retardant and colorant additive composition for thermoplastic polymers including at least one phosphorus-containing flame retardant and an orange colorant, as described herein. The additive compositions of the present disclosure are useful in a wide range of thermoplastic applications, particularly in thermoplastic polymers processed and / or used at high temperatures. The resulting thermoplastic composition is compared with [Delta] Elt; [Delta] Elt; [Delta] Elt, [Delta] Elt, [Delta] Elt; 20, preferably [Delta] Elt; 10, more preferably [Delta] Elt; 5. The use of the additive composition improves the processing of thermoplastics.

Description

Technical Field

[0001] The present disclosure relates to flame retardant and orange colorant additive compositions for thermoplastic polymers and to compositions combining a flame retardant, a colorant, and one or more thermoplastic polymers. Background Art

[0002] During melt processing of thermoplastics, various additives are often added for various purposes, such as antioxidants, lubricants, stabilizers, flame retardants, and the like. While flame retardant additives are crucial for providing flame retardancy to thermoplastics, they can affect the stability of thermoplastics during melt processing, such as by increasing polymer degradation and / or discoloration. For example, these types of effects have been discussed and reported in the literature for certain phosphorus-containing flame retardants, such as those described for phosphinate flame retardants in U.S. Patent Nos. 7,255,814 and 9,534,109.

[0003] With electric vehicles becoming a dominant industry trend, high-voltage cables and plastic components used in this sector often feature a warning color coding, often orange. Consequently, experts in the flame retardant industry are searching for a halogen-free flame retardant system that would not negatively impact orange dyes or pigments. More importantly, the orange color should not compromise processing stability, flame retardancy, and other ancillary properties, such as mechanical and / or electrical performance. Meeting these goals with commercially available flame retardants has proven difficult.

[0004] US2022 / 0153962 describes a high-voltage component, in particular for an electric vehicle, comprising a thermoplastic polymer composition based on polyamide and 10,10'-oxybis-12H-phthalopyrin-12-one [CAS No. 203576-97-0] for the signal color orange. Although not exemplified, a flame retardant is an optional component of the thermoplastic component, with a preferred flame retardant being aluminum tris(diethylphosphinate) [CAS No. 225789-38-8], such as Aluminum Tris(diethylphosphinate) [CAS No. 225789-38-8] from Clariant International GmbH, Muttenz, Switzerland. OP1230 or OP 1240. However, this application does not disclose an additive composition for addition to thermoplastics, which comprises a combined flame retardant and a colorant before addition to the polyamide.

[0005] When the present inventors added the colorant disclosed in US2022 / 0153962 to Exolit OP 1312 (the preferred phosphorus-containing flame retardant taught), this destabilized the injection molding process in glass-filled PA66. Furthermore, the orange dye imparted a dull reddish-brown color rather than a bright orange. Therefore, there is a need for a phosphorus-containing flame retardant that is compatible with 10,10′-oxybis-12H-phthalopyrin-12-one and other orange colorants in polyamides. There is also a need to combine phosphorus flame retardants and colorants with other thermoplastic additives in a stable additive composition that can be used not only with polyamides but also with a variety of thermoplastic polymers.

[0006] The present disclosure utilizes a newer class of phosphorus-containing flame retardants in additive compositions for thermoplastic polymers that stabilize the injection molding process and will produce bright orange thermoplastics. The phosphorus-containing flame retardants of the present disclosure (also described in the applicant's co-pending patent application numbers PCT / US2019 / 067184, PCT / US2019 / 067221, and PCT / US2019 / 067230) provide the additional benefit of being compounded into thermoplastic polymers (such as high-temperature polyamides and polyterephthalates) at high temperatures without decomposition due to the high thermal stability of these phosphorus-containing flame retardants.

[0007] The inventors' co-pending patent applications PCT / US2021 / 037706, PCT / US2021 / 037716, and PCT / US2022 / 050062 describe such flame retardants with stabilizers and with synergists and stabilizers for thermoplastics, but do not disclose how colorants affect the thermal stability and / or processing properties of such systems. Unexpectedly, the applicants' previously disclosed flame retardant additive compositions are compatible with orange dyes (such as 10,10'-oxybis-12H-phthalpyrin-12-one) and are able to provide orange flame-retardant thermoplastic compositions with enhanced processing properties in extrusion and injection molding processes without negatively affecting flame retardant properties. Furthermore, the additive composition produces a thermoplastic with a bright orange hue.

[0008] Thus, the colorant-containing additive compositions of the present disclosure are useful in a wide range of thermoplastic applications, particularly for thermoplastic polymers used in electric vehicle applications that are processed and / or used at high temperatures. Summary of the Invention

[0009] The present disclosure provides a flame retardant and colorant additive composition for thermoplastic polymers, the composition comprising

[0010] (A) at least one phosphorus-containing flame retardant of the empirical formula (I):

[0011]

[0012] wherein R is an alkyl or aryl group, M is a metal, and y is 2 or 3 such that M (+)y is a metal cation, wherein (+)y represents the charge formally assigned to the cation, a, b and c represent the ratios of their corresponding components relative to each other in the compound and satisfy the charge balance equation 2(a)+c=b(y), and a and c are not zero, and

[0013] (B) Orange colorant.

[0014] In certain preferred embodiments, R is an unsubstituted alkyl group, y is 3, and a and c are not zero. More preferably, a is 1, b is 1, c is 1, and M is Al or Fe. Most preferably, M is Al, and the flame retardant has the empirical formula (II)

[0015] Most preferably wherein R is methyl or ethyl.

[0016] The flame retardant and colorant additive composition may further comprise (C) at least one flame retardant synergist and / or additional flame retardants.The additive composition may additionally comprise (D) one or more stabilizers.

[0017] In some embodiments, (C) at least one flame retardant synergist and / or additional flame retardant comprises a nitrogen-containing flame retardant synergist, such as melam or melamine polyphosphate. In some embodiments, component (C) comprises polydibromostyrene.

[0018] In certain embodiments, the (D) stabilizer is selected from zinc borate or zinc stannate. In some embodiments, the (D) stabilizer comprises a carbodiimide, such as an aromatic polycarbodiimide.

[0019] In some embodiments, the flame retardant and colorant additive composition comprises 20 wt % to 99.95 wt % (such as 40 wt % to 95 wt % or 50 wt % to 90 wt %) of at least one phosphorus-containing flame retardant (A), based on the total weight of the additive composition, 0.01 wt % to 50 wt % (such as 0.05 wt % to 25 wt %, 0.1 wt % to 20 wt % or 0.5 wt % to 10 wt %) of at least one colorant (B), based on the total weight of the additive composition, 0 wt % to 80 wt % (such as 10 wt % to 60 wt % or 20 wt % to 50 wt %) of at least one flame retardant synergist and / or additional flame retardant (C), based on the total weight of the additive composition, and 0 wt % to 35 wt % (such as 0 wt % to 10 wt %) of one or more stabilizers (D), based on the total weight of the additive composition.

[0020] The present disclosure further provides a method for improving the processing of thermoplastics by adding a flame retardant and colorant additive composition comprising or consisting of (A) and (B) to a thermoplastic polymer. The additive composition used in the method may further comprise or consist of (C) and (D) in any combination with (A) and (B).

[0021] The present disclosure further provides a flame retardant thermoplastic composition comprising

[0022] (i) at least one thermoplastic polymer,

[0023] (ii) at least one phosphorus-containing flame retardant of the above empirical formula (I), and

[0024] (iii) Orange colorant.

[0025] In some embodiments, (i) at least one thermoplastic polymer is selected from the group consisting of polyesters and polyamides. In some of those embodiments, (i) the thermoplastic polymer comprises or consists of polyamide 6,6 (PA 66) and / or polyamide-6 (PA 6).

[0026] Preferably, the flame retardant (II) has formula (II), wherein R is methyl or ethyl, and the orange colorant is a perinone, such as Solvent Orange 11 or Solvent Orange 60.

[0027] In some embodiments, at least one thermoplastic polymer (i) is present in the flame retardant thermoplastic composition in an amount of 30 wt % to 95 wt % (such as 40 wt % to 90 wt % or 50 wt % to 90 wt %) based on the total weight of the flame retardant thermoplastic composition. In certain embodiments, the phosphorus-containing flame retardant (ii) is present in an amount of 1 wt % to 30 wt % (such as 3 wt % to 20 wt %) based on the total weight of the flame retardant thermoplastic composition. At least one orange colorant (iii) is present in the flame retardant thermoplastic composition in an amount of 0.01 wt % to 5 wt % (such as 0.05 wt % to 2.5 wt %, 0.1 wt % to 2.0 wt % or 0.2 wt % to 1.0 wt % or 0.2 wt % to 0.5 wt %) based on the total weight of the composition.

[0028] The flame retardant thermoplastic composition may further comprise (iv) at least one inorganic filler (e.g., glass fiber), (v) at least one flame retardant synergist and / or additional flame retardant, and / or (vi) at least one stabilizer, and / or (vii) one or more other additives that enhance the properties of the thermoplastic composition.

[0029] In some embodiments, (v) at least one flame retardant synergist and / or additional flame retardant comprises a nitrogen-containing flame retardant synergist, such as melam or melamine polyphosphate. In some embodiments, component (v) comprises polydibromostyrene.

[0030] In certain embodiments, the (vi) stabilizer is selected from zinc borate or zinc stannate. In some embodiments, the (vi) stabilizer comprises a carbodiimide, such as an aromatic polycarbodiimide.

[0031] The at least one inorganic filler in the flame retardant thermoplastic composition is 1 wt% to 50 wt%, for example, 5 wt% to 50 wt%, 10 wt% to 40 wt%, or 15 wt% to 30 wt%, based on the total weight of the flame retardant thermoplastic composition. The (vi) at least one stabilizer is typically 0.01 wt% to 5 wt%, based on the total weight of the flame retardant thermoplastic composition.

[0032] In some preferred embodiments, the flame retardant thermoplastic composition comprises at least one thermoplastic polymer (i) in an amount of 40 wt% to 90 wt%, at least one phosphorus-containing flame retardant (ii) in an amount of 3 wt% to 20 wt%, an orange colorant (iii) in an amount of 0.01 wt% to 5 wt%, at least one inorganic filler (iv) in an amount of 10 wt% to 40 wt%, at least one flame retardant synergist and / or additional flame retardant (v) in an amount of 5 wt% to 25 wt%, all based on the total weight of the flame retardant thermoplastic composition. In some embodiments, the composition further comprises at least one stabilizer (vi) in an amount of 0.01 wt% to 5 wt%, based on the total weight of the flame retardant thermoplastic composition.

[0033] The foregoing summary of the invention is not intended to limit the scope of the claimed invention in any way. In addition, it should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the claimed invention. DETAILED DESCRIPTION

[0034] Unless otherwise stated, the terms "a" or "an" in this application mean "one or more than one".

[0035] Unless the context requires otherwise, the term "alkyl" as used herein includes "arylalkyl".

[0036] Unless the context dictates otherwise, the term "aryl" as used herein includes "alkylaryl".

[0037] Unless the context dictates otherwise, the term "phosphonic acid" as used herein refers to an alkyl or aryl substituted phosphonic acid.

[0038] Unless the context dictates otherwise, the term "pyrophosphonic acid" as used herein refers to an alkyl or aryl substituted pyrophosphonic acid.

[0039] The present disclosure provides a flame retardant and colorant additive composition for thermoplastic polymers comprising

[0040] (A) at least one phosphorus-containing flame retardant of the empirical formula (I):

[0041]

[0042] wherein R is an alkyl or aryl group, M is a metal, and y is 2 or 3 such that M (+)y is a metal cation, wherein (+)y represents the charge formally assigned to the cation, a, b and c represent the ratios of their corresponding components relative to each other in the compound and satisfy the charge balance equation 2(a)+c=b(y), and a and c are not zero, and

[0043] (B) Orange colorant.

[0044] The at least one phosphorus-containing flame retardant (component (A)) of the present disclosure has the following empirical formula:

[0045]

[0046] wherein R is an alkyl or aryl group, M is a metal, and y is 2 or 3 such that M (+)y is a metal cation, wherein (+)y represents the charge formally assigned to the cation, a, b, and c represent the ratios of their corresponding components relative to each other in the compound, and satisfy the charge balance equation 2(a)+c=b(y), and a and c are not zero. Typically, a is 1 or 2, b is 1 to 4 (e.g., 1 or 2), and c is 1 or 2, and the product is charge balanced. Examples of suitable metals (M) include, but are not limited to, Al, Ga, Sb, Fe, Co, B, Bi, Mg, Ca, and Zn.

[0047] As is common with inorganic coordination compounds, formula (I) is empirical or idealized, such that the compound can be a coordination polymer, a complex salt, a salt sharing certain atomic valences, etc. For example, in many embodiments, the empirical formula (I) represents a monomer unit (i.e., a coordination entity) of a coordination polymer, whereby the extended coordination polymer structure forms the phosphorus-containing flame retardant of the present disclosure.

[0048] In certain embodiments, y in Formula (I) is 2 (ie, M (+)y is a dicationic metal). In certain embodiments, the dicationic metal M is Mg, Ca, or Zn. In other embodiments, y in formula (I) is 3 (i.e., M (+)yis a tricationic metal), a is 1, b is 1, and c is 1. In certain embodiments, the tricationic metal M is selected from Al, Ga, Sb, Fe, Co, B, and Bi. In certain embodiments, the tricationic metal M is Al, Fe, Ga, Sb, or B.

[0049] In one example, M is Al, and y is 3, and the phosphorus-containing flame retardant has the following empirical formula:

[0050]

[0051] As shown herein, the absence of subscripts a, b, and c in the empirical formula indicates that each subscript is 1, indicating that the ratio of di-anionic pyrophosphonate ligand, metal atom, and mono-anionic pyrophosphonate ligand is 1:1:1. In many embodiments, empirical formula (II) represents a repeating monomer unit (i.e., coordination entity) of a coordination polymer, whereby the extended coordination polymer structure forms the phosphorus-containing flame retardant of the present disclosure.

[0052] Typically, R is C 1-12 Alkyl, C 6-10 Aryl, C 7-18 Alkyl aryl or C 7-18 Arylalkyl, wherein the alkyl, aryl, alkylaryl or arylalkyl is unsubstituted or substituted by halogen, hydroxy, amino, C 1-4 Alkylamino, di-C 1-4 Alkylamino, C 1-4 Alkoxy, carboxyl or C 2-5 In some embodiments, the alkyl, aryl, alkylaryl or arylalkyl is an unsubstituted C 1-12 Alkyl, C6 aryl, C 7-10 Alkyl aryl or C 7-10 Arylalkyl, for example, C 1-6 Alkyl, phenyl or C 7-9 In some embodiments, R is a substituted or unsubstituted C 1-6 Alkyl, C6 aryl, C 7-10 Alkyl aryl or C 7-12 Arylalkyl, for example, C 1-4 Alkyl, C6 aryl, C 7-9 Alkyl aryl or C 7-10 In many embodiments, R is an unsubstituted C 1-12 Alkyl groups, such as C 1-6 In many embodiments, lower alkylphosphonic acids are used, for example, methyl-, ethyl-, propyl-, isopropyl-, butyl-, tert-butyl-, etc.

[0053] R as alkyl can be a straight or branched chain alkyl group with a specific carbon number, and includes, for example, unbranched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexylheptyl, octyl, nonyl, decyl, undecyl, dodecyl, and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, ethylhexyl, tert-octyl, etc. For example, R as alkyl can be selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. In many embodiments, R is methyl, ethyl, propyl, or isopropyl, such as methyl or ethyl.

[0054] Typically, when R is an aryl group, it is a phenyl group. Examples of R as an alkylaryl group include phenyl groups substituted with one or more alkyl groups, such as a group selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and the like. Examples of R as an arylalkyl group include, for example, benzyl, phenethyl, styryl, cumyl, phenylpropyl, and the like.

[0055] In many embodiments, R is selected from methyl, ethyl, propyl, isopropyl, butyl, phenyl and benzyl. In certain embodiments, R is methyl, ethyl, propyl, isopropyl or butyl, and M is Al, Fe, Zn or Ca.

[0056] In certain preferred embodiments, R is an unsubstituted alkyl group, y is 3, and a and c are not zero. More preferably, a is 1, b is 1, and c is 1, and M is Al or Fe. Most preferably, M is Al.

[0057] Compared to the phosphorus-containing flame retardants described in the art, the phosphorus-containing flame retardants of the present disclosure have a high phosphorus content (i.e., a higher ratio of phosphorus atoms to metal atoms (P to M)). For example, it is known that tricationic metals (e.g., aluminum) and dicationic metals (e.g., zinc) form trisubstituted and disubstituted charge-balanced compounds, respectively. As seen in the art, aluminum triphosphonates with a phosphorus-aluminum ratio of 3:1 and zinc diphosphonates with a phosphorus-zinc ratio of 2:1 are known as flame retardants. However, according to the formation of pyrophosphonic acid ligands disclosed herein, the ratio of phosphorus to metal in the flame retardant product is higher. For example, as demonstrated in the examples disclosed herein, the ratio of phosphorus to aluminum or phosphorus to iron in the resulting flame retardant product is 4:1.

[0058] The phosphorus-containing flame retardant of the present disclosure may be a mixture of compounds of the empirical formula (I).

[0059] Phosphorus-containing flame retardants of empirical formula (I) and (II) can be prepared by methods as disclosed in WO 2020 / 132075 or WO 2021 / 076169. In addition, the phosphorus-containing flame retardant of empirical formula (I) can be prepared by the following steps: preparing a metal phosphonic acid solution; and reacting a reaction mixture of an alkyl or aryl substituted pyrophosphonic acid and a metal phosphonic acid solution at a reaction temperature of 130°C to 240°C, preferably 190°C to 210°C, more preferably 195°C to 205°C for a time sufficient to produce a phosphorus-containing flame retardant. The method generally includes preparing the alkyl or aryl substituted pyrophosphonic acid before adding the alkyl or aryl substituted pyrophosphonic acid to the reaction mixture with the metal phosphonic acid solution.

[0060] The pyrophosphonic acid prepared and / or used in this method can be represented by the following formula:

[0061]

[0062] wherein R is as described above, and is preferably an unsubstituted alkyl group, such as methyl or ethyl.

[0063] The method for preparing unsubstituted or alkyl or aryl substituted pyrophosphonic acid may comprise adding a catalyst to the unsubstituted or substituted phosphonic acid and heating for a time sufficient to produce the unsubstituted or substituted pyrophosphonic acid. A heating temperature of 105° C. or higher is used. In certain embodiments, when the temperature of heating the unsubstituted or substituted phosphonic acid is about 240° C. or higher and a vacuum or nitrogen purge is employed, a catalyst may not be necessary to produce the pyrophosphonic acid. The nitrogen flow rate is typically about 2 L / min to about 6 L / min, most preferably about 5 L / min. Alternatively, a catalyst may not be necessary when the vacuum is drawn to less than 10 Torr.

[0064] The phosphonic acid used to form pyrophosphonic acid is preferably an unsubstituted C 1-12 Alkyl groups, such as C 1-6 Alkyl group, more preferably methyl or ethyl group.

[0065] The catalyst used to prepare pyrophosphonic acid can be any Lewis acid that promotes dehydration. The catalyst is typically present in the reaction in an amount ranging from about 0.001 mol% to about 0.5 mol%, preferably from about 0.01 mol% to 0.1 mol%, based on the weight of the reactants.

[0066] When preparing a metal phosphonic acid solution, the phosphonic acid used is as described above. The metal phosphonic acid solution can be prepared from a mixture comprising (a) an alkyl or aryl substituted phosphonic acid, (b) a solvent for the phosphonic acid, and (c) a metal or suitable metal compound, the mixture being reacted at a temperature above the melting point of the phosphonic acid but below the boiling point of the phosphonic acid to ensure that the solution remains and that no metal phosphonate is formed. In other words, the metal phosphonic acid should be free of precipitates. Typically, components (a), (b), and (c) are mixed at a temperature ranging from 100° C. to 280° C. Typically, the weight ratio of the phosphonic acid (a) to the solvent (b) is from about 1:3 to 1:50, more preferably from about 1:2.5 to 1:25, and most preferably from about 1:2.75.

[0067] The metal in the metal phosphonic acid solution should be capable of being oxidized and can be converted into its corresponding cationic form by the formula M (+)y Wherein M is a metal, (+)y represents the charge of the metal cation, and y is 3. Suitable metal compounds can be represented by the formula M p (+)y X q denoted by , where M is a metal, (+)y represents the charge of the metal cation, y is 3, X is an anion, and the values ​​of p and q provide a charge-balanced metal compound.

[0068] Suitable solvents may be organic or inorganic.Examples of suitable solvents for phosphonic acids include, but are not limited to, water, sulfones, sulfoxides, halogenated (eg, chlorinated) hydrocarbons, aromatic hydrocarbons, and ethers.

[0069] The reaction mixture is heated or reacted under the reaction temperature for a time amount sufficient to produce the phosphorus-containing flame retardant. Usually, the flame retardant product will precipitate from the reaction mixture so that the reaction is carried out for the time sufficient to realize this precipitation. After the reaction, the product reaction mixture is cooled, ensuring that pyrophosphonic acid keeps a liquid form. Excess pyrophosphonic acid and solvent (if present in the product reaction mixture) can be removed by filtering / washing, and optionally reclaimed. The excessive pyrophosphonic acid and / or solvent reclaimed can be recycled, for example, return to the reactor of metal phosphonic acid solution and pyrophosphonic acid reaction. The flame retardant product is usually separated by filtering, optionally subsequently carries out other aftertreatment (for example washing, drying, screening etc.). The gained crystallized flame retardant product is usually in the form of powder or granule, is easy to process, i.e., need not or need not grind, crush or other such physical processing before use.

[0070] The phosphorus-containing flame retardant of the present disclosure may further comprise a compound of empirical formula (IX) or a mixture of different compounds

[0071]

[0072] wherein R is H, alkyl, aryl, alkylaryl or arylalkyl, a, b, c and d represent the proportions of their corresponding components relative to each other in the compound, and a is typically a number from 0 to 8, such as 0 to 6, 0 to 4 or 0 to 2, c is typically a number from 0 to 10, such as 0 to 8, 0 to 6, 0 to 4 or 0 to 2, d is typically a number from 1 to 6, such as 1 to 4 or 1 to 2, M is a metal, y is a number from 2 to 5, such as 2, 3 or 4, typically 2 or 3, and M (+)y is a metal cation, wherein (+)y represents the charge formally assigned to the cation. The values ​​of a, b, c, d, and y can vary, but will satisfy the charge balance equation 2(a) + c + d = b(y), and only one of a or c can be 0. In many embodiments, c is non-zero. In the case of a dianionic phosphonic acid ligand present in the compound, the charge balance equation becomes 2(a) + c + d + 2(d) = b(y). The value of b is limited to what must satisfy the aforementioned equation, but in many embodiments, b is a number from 1 to 4, such as 1 or 2. In some embodiments, a is 0, 1, or 2 (e.g., 0 or 1), c is 1 or 2, and d is 0, 1, or 2 (e.g., 0 or 1), and the product is charge balanced. Typically, c in the above formula (IX) is non-zero (e.g., c is 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 or 2).

[0073] When a compound of empirical formula (IX) or a mixture of different compounds is present, the compound of formula (I) and / or (II) or the mixture of compounds typically comprises all, substantially all, or at least a majority of the flame retardant product, such as at least 75%, 85%, 90%, 95%, 98% or more, or any range therebetween, by weight of the flame retardant product. In certain embodiments, at least one phosphorus-containing flame retardant (component (A)) of the present disclosure consists of a compound of formula (I) and / or (II) or a mixture of compounds.

[0074] Compounds of formula (IX) can be prepared according to various methods, such as those disclosed in U.S. Patent Nos. 9,534,108; 9,745,449; 9,752,011; 9,758,640; and 9,765,204; and WO 2021 / 132095.

[0075] The composition will further comprise (B) an orange colorant, preferably a solvent dye.

[0076] In the context of the present invention, orange is understood to mean a color in the RAL color system according to https: / / de.wikipedia.org / wiki / RAL-Farbe#Orange which has a color number starting with "2" in the RAL color chart. Specifically, orange chromaticities are distinguished according to Table 1:

[0077] Table 1

[0078]

[0079] Table 1 shows the device-independent CIE L*a*b* color values ​​for each RAL value: L* stands for lightness, a*=D65, and b*=10°. The color model is standardized in EN ISO / CIE 11664-4 "Colorimetry - Part 4: CIE 1976 L*a*b* color space." For the L*a*b* color space (also: CIELAB), see: https: / / de.wikipedia.org / wiki / Lab-Farbraum. Each color in the color space is defined by a color point with Cartesian coordinates {L*, a*, b*}. The a*b* coordinate plane is constructed using the theory of opposite colors. Green and red are located at opposite ends of the a* axis, while the b* axis extends from blue to yellow. Complementary chromaticities are each opposite each other at an angle of 180°; the midpoint between them (the coordinate origin a*=0, b*=0) is gray.

[0080] The L* axis describes the lightness (luminance) of a color, with values ​​ranging from 0 to 100. In the diagram, it is perpendicular to the a*b* plane at the origin. It can also be called the neutral gray axis because all achromatic colors (gray chromaticities) are contained between the endpoints of black (L*=0) and white (L*=100). The a* axis describes the percentage of green or red in a color, with negative values ​​representing green and positive values ​​representing red. The b* axis describes the percentage of blue or yellow in a color, with negative values ​​representing blue and positive values ​​representing yellow.

[0081] The a* values ​​range from approximately -170 to +100, and the b* values ​​range from -100 to +150, with the maximum values ​​only being achieved at medium brightness for some chromaticities. The CIELAB color solids have their maximum extent in the medium brightness region, but this varies in height and size across the color range.

[0082] The present invention encompasses orange-like chromaticities having a color difference ΔE<20, preferably ΔE<10, more preferably ΔE<5, between the L*a*b* coordinates of the polymer composition and the L*a*b* coordinates of a color number starting with "2" in the RAL color chart.

[0083] Suitable orange colorants are perylone-type dyes. Examples of perylone dyes suitable for dyeing plastics are described in US Patent Nos. 5,466,805; 5,530,130; and 5,955,614, the contents of which are incorporated herein.

[0084] In certain embodiments, 10,10'-oxybis-12H-phthalopyrin-12-one of formula (X) [CAS No. 203576-97-0], also known as Solvent Orange 11, meets the desired requirements.

[0085]

[0086] 10,10′-Oxybis-12H-phthalopyrin-12-one can be prepared by the synthetic route specified in Example 3 of EP 1 118 640 A1 or can be obtained from Angene International Limited, UK Office, Churchill House, London, or Lanxess Deutschland GmbH, Cologne. 10,10′-Oxybis-12H-phthalopyrin-12-one can be used directly in powder form or in the form of a masterbatch, compressed cake, or concentrate, preferably a masterbatch, and is particularly preferably used in combination with the flame retardants and other components described herein.

[0087] In a particularly preferred embodiment, the orange colorant is LANXESS Germany GmbH from Cologne. Orange HT.

[0088] In other embodiments, the orange colorant may be 12H-phthalocyanine-12-one [CAS No. 6925-69-5], known as Solvent Orange 60, available, for example, from LANXESS Germany GmbH in Cologne. Orange 3G.

[0089] Most preferably, the orange colorant is LANXESS Germany GmbH from Cologne. Orange HT.

[0090] The thermoplastic containing the additive composition for electric vehicles is preferably orange, particularly preferably a color corresponding to the color numbers RAL2001, RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 and RAL2011 in the RAL color system, and very particularly preferably a color corresponding to the color numbers RAL2003, RAL2008 and RAL2011 in the RAL color system.

[0091] "Similar colorimetry" permitted according to the present invention is a colorimetry whose color difference from a color number starting with "2" in the L*a*b* system is <20, preferably <10, and more preferably <5. For an explanation of the ΔE defined in EN ISO 11664-4, see, for example: https: / / de.wikipedia.org / wiki / Delta_E.

[0092] The flame retardant and colorant additive composition may further comprise at least one flame retardant synergist and / or additional flame retardant (component (C)).

[0093] Examples of suitable flame retardant synergists include condensation products of melamine (e.g., melam, melem, melon), melamine cyanurate, reaction products of melamine with polyphosphoric acid (e.g., dimelamine pyrophosphate, melamine polyphosphate), reaction products of melamine with condensation products of polyphosphoric acid (e.g., melem polyphosphate, melem polyphosphate, melon polyphosphate), melamine-poly(metal phosphates) (e.g., melamine-poly(zinc phosphate)), triazine-based compounds (such as trichlorotriazine, reaction products of piperazine and morpholine, for example, poly-[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine] / piperazine (e.g., PPM Triazine HF), metal phosphinates such as aluminum hypophosphite (e.g. Italmatch IP-A), calcium hypophosphite (e.g., Italmatch IP-C); organic phosphinates such as aluminum dialkylphosphinates, for example aluminum diethylphosphinate (Exolit OP); and aluminum dihydrogen phosphite, other flame retardants such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), di-DOPO or DOPO derivatives, etc. In many embodiments, nitrogen-containing synergists are used. Suitable nitrogen-containing synergists can be selected from, for example, melamine derivatives such as melamine and its condensation products (melamine, melem, melon or similar compounds with a higher degree of condensation), melamine cyanurate, and phosphorus / nitrogen compounds such as dimelamine phosphate, dimelamine phosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate and melem polyphosphate, and mixed polymeric salts thereof. Examples of additional flame retardants suitable for use in the flame retardant and stabilizer additive composition of the present invention include halogenated flame retardants, alkyl or aryl phosphine oxide flame retardants, alkyl or aryl phosphate flame retardants, alkyl or aryl phosphonates, alkyl or aryl phosphinates, and salts of alkyl or aryl phosphinic acids.

[0094] The additive composition may additionally comprise one or more stabilizers (component (D)).

[0095] Examples of suitable stabilizers include carbodiimides, metal hydroxides, oxides, oxide hydrates, borates, molybdates, carbonates, sulfates, phosphates, silicates, siloxanes, stannates, mixed oxide-hydroxides, oxide-hydroxide-carbonates, hydroxide-silicates, hydroxide-borates, preferably wherein the metal is zinc, magnesium, calcium or manganese, typically zinc.

[0096] In many embodiments, the stabilizer is selected from zinc borate, zinc stannate, zinc molybdate complexes (e.g., Kemgard 911B), zinc molybdate / magnesium hydroxide complexes (e.g., Kemgard MZM), zinc molybdate / magnesium silicate complexes (Kemgard 911C), calcium molybdate / zinc complexes (e.g., Kemgard 911A), and zinc phosphate complexes (e.g., Kemgard 981), polysiloxanes, montmorillonite, kaolinite, halloysite, and hydrotalcite.

[0097] In certain embodiments, stabilizer (D) comprises at least one carbodiimide (i.e., a compound comprising the functional group -N=C=N-). In some of those embodiments, at least one carbodiimide is an aromatic carbodiimide. Preferably, the carbodiimide is polymeric, meaning that the compound contains repeated -N=C=N- groups in its chemical structure. Typically, the polymeric carbodiimide contains 2 to 500 groups -N=C=N- per mole, such as 2 to 100 groups -N=C=N- per mole, for example up to 20 such groups or up to 10 groups per mole. In many embodiments, the carbodiimide is a polymeric aromatic carbodiimide. Carbodiimide compounds (including polymeric carbodiimides) are known and can be produced according to known methods.

[0098] Preferably, the carbodiimide has the following general formula (III), (IV) or (V):

[0099]

[0100] where R 1 and R 2 are independently hydrogen or C l -C l0 -alkyl, C6-C 12 -aryl, C7-C 13 -aralkyl, or C7-C 13 -alkylaryl,

[0101] a and b are independently integers from 1 to 5, and

[0102] c and d are independently integers from 0 to 10;

[0103]

[0104] where R 4 It's NCO.

[0105] R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 are independently hydrogen or C1-C 10 -alkyl, C6-C 12 -aryl, C7-C 13 -aralkyl, or C7-C 13 -alkylaryl,

[0106] g is an integer from 0 to 5,

[0107] h is an integer from 1 to 100; or

[0108]

[0109] wherein m is an integer from 1 to 5000, preferably an integer from 2 to 500, such as from 3 to 20 or from 4 to 10,

[0110] R 3 is an arylene group, an alkyl-substituted arylene group, an alkylaryl-substituted arylene group, or an aralkyl-substituted arylene group, for example, R 3 Selected from arylene, C1-C 12 -alkyl-substituted arylene, C7-C 18 -alkylaryl-substituted arylene, C7-C 18 - arylalkyl substituted arylene, and C1-C 12 - alkyl-substituted C1-C8-alkylene-bridged arylene,

[0111] R' is aryl, alkylaryl, aralkyl or R 3 -NCO,

[0112] R" is -N=C=N-aryl, -N=C=N-alkylaryl, -N=C=N-aralkyl or -NCO.

[0113] In certain embodiments, R 3is an arylene group having one or more aliphatic and / or alicyclic substituents having at least 2 carbon atoms, preferably a branched or cyclic aliphatic moiety having at least 3 carbon atoms, in one ortho position, preferably in two ortho positions, relative to the aromatic carbon atom bearing the -N=C=N- group. For example, in some embodiments, R 3 for where R 13 、R 14 and R 15 are independently C1-C3 alkyl, for example, independently methyl, ethyl or isopropyl.

[0114] In many embodiments, the polymeric aromatic carbodiimide has formula (VI):

[0115]

[0116] where R 13 、R 14 and R 15 are independently C1-C3 alkyl, R 16 is -NCO, and

[0117] n is 0 to 200, such as 1 to 100, 1 to 20, or 1 to 10. Typically, R 13 、R 14 and R 15 is independently methyl, ethyl or isopropyl. In many embodiments, R 13 、R 14 and R 15 In other embodiments, each phenyl ring bears only one methyl group.

[0118] Other suitable examples of specific carbodiimides are of formula (VII) and (VIII):

[0119]

[0120] Where R = NCO, and

[0121] n is an integer of 1 to 200, typically 1 to 20.

[0122] The quantitative proportions of components (A), (B), (C), and (D) in the flame retardant and colorant additive composition can vary and generally can depend on, for example, the intended application, processing conditions, and the like. In many embodiments, the flame retardant and colorant additive composition comprises 20 wt% to 99.95 wt% (such as 40 wt% to 95 wt% or 50 wt% to 90 wt%) of at least one phosphorus-containing flame retardant (A), based on the total weight of the additive composition, 0.01 wt% to 50 wt% (such as 0.05 wt% to 25 wt%, 0.1 wt% to 20 wt% or 0.5 wt% to 10 wt% of at least one colorant (B), based on the total weight of the additive composition, 0 wt% to 80 wt% (such as 10 wt% to 60 wt% or 20 wt% to 50 wt%) of at least one flame retardant synergist and / or additional flame retardant (C), based on the total weight of the additive composition, and 0 wt% to 35 wt% (such as 0 wt% to 10 wt%) of one or more stabilizers (D), based on the total weight of the additive composition.

[0123] The present disclosure further provides a flame retardant thermoplastic composition comprising

[0124] (i) at least one thermoplastic polymer,

[0125] (ii) at least one phosphorus-containing flame retardant of the above empirical formula (I), and

[0126] (iii) an orange colorant as described above. The flame retardant thermoplastic composition may further comprise (iv) at least one inorganic filler (e.g., glass fiber), (v) at least one flame retardant synergist and / or additional flame retardant, (vi) one or more stabilizers, and / or (vii) additional additives to enhance the properties of the thermoplastic composition.

[0127] At least one thermoplastic polymer (i) is typically present in the flame retardant thermoplastic composition in an amount of 30 wt % to 95 wt % (such as 40 wt % to 90 wt % or 50 wt % to 90 wt %) based on the total weight of the flame retardant thermoplastic composition. The at least one thermoplastic polymer can be a thermoplastic polyester, polyamide, polystyrene (including high impact polystyrene (HIPS)), polyolefin, polycarbonate, polyurethane, polyphenylene ether or other thermoplastic polymer. In many embodiments, the thermoplastic polymer comprises a polyester (e.g., polyalkylene terephthalate) or a polyamide. In many embodiments, the thermoplastic polymer comprises a polyamide. More than one thermoplastic polymer (thermoplastic polymer blend) can be used, such as a polyphenylene ether / styrene resin blend, polyvinyl chloride / acrylonitrile butadiene styrene (ABS) or other impact-modified polymers, such as ABS containing methacrylonitrile and α-methylstyrene, and polyester / ABS or polycarbonate / ABS. The thermoplastic polymer may be unreinforced or reinforced, for example glass reinforced, such as a glass-filled polyester (eg glass-filled polyalkylene terephthalate) or a glass-filled polyamide.

[0128] Examples of thermoplastic polyesters include homopolyesters and copolyesters obtained by polycondensation of an acid component and a diol component. For example, suitable polyesters may be selected from polybutylene terephthalate and polyethylene terephthalate.

[0129] The diol component may contain one or more of the following diols: ethylene glycol, trimethylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, or neopentyl glycol. The acid component may contain one or more of the following acids: terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, p-hydroxybenzoic acid, sebacic acid, adipic acid, and polyester-forming derivatives thereof.

[0130] In many embodiments, the thermoplastic polyester is selected from poly(ethylene terephthalate), poly(1,3-propylene terephthalate), poly(1,4-butylene terephthalate), and blends thereof. For example, the thermoplastic polyester blend may contain from about 1 to about 99 parts by weight of one polyester and from about 99 to about 1 part by weight of a different polyester, based on 100 parts by weight of the two components combined. The poly(1,4-butylene terephthalate) may be obtained by polymerizing a diol component composed of at least 70 mol%, such as at least 80 mol%, of 1,4-butanediol with an acid component composed of at least 70 mol%, such as at least 80 mol%, of terephthalic acid and / or its polyester-forming derivatives.

[0131] Thermoplastic polyamides include polyamides derived from diamines and dicarboxylic acids, polyamides obtained from aminocarboxylic acids (including combinations with diamines and / or dicarboxylic acids), and polyamides derived from lactams (including combinations with diamines and / or dicarboxylic acids). Examples of suitable polyamides include aliphatic polyamides such as polyamide-4,6, polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-6,12, polyamide-11 and polyamide-12; polyamides obtained from aromatic dicarboxylic acids (such as terephthalic acid and / or isophthalic acid) and aliphatic diamines (such as hexamethylenediamine or nonamethylenediamine); polyamides obtained from aliphatic dicarboxylic acids (such as adipic acid and / or azelaic acid) and aromatic diamines (such as metaxylenediamine); polyamides obtained from aromatic and aliphatic dicarboxylic acids (such as terephthalic acid and adipic acid) and aliphatic diamines (such as hexamethylenediamine); polyamides obtained from adipic acid, azelaic acid and 2,2-bis-(p-aminocyclohexyl)propane; and polyamides obtained from terephthalic acid and 4,4'-diaminodicyclohexylmethane. It is also possible to use mixtures and / or copolymers of two or more of the aforementioned polyamides or their prepolymers, respectively.

[0132] The polyamides can be prepared by any known method, such as by polymerizing a monoaminomonocarboxylic acid having at least two carbon atoms between the amino group and the carboxylic acid group, or a lactam thereof, a diamine having at least two carbon atoms between the amino group and the dicarboxylic acid in substantially equimolar proportions, or a monoaminocarboxylic acid or a lactam thereof as defined above together with a diamine and a dicarboxylic acid in substantially equimolar proportions. The dicarboxylic acids can be used in the form of their functional derivatives, such as salts, esters or acid chlorides.

[0133] Polyamides with a melting point of at least 280°C are widely used for producing molding compositions. These compositions make it possible to produce molded articles with excellent dimensional stability at high temperatures and very good flame retardancy, for example for the electrical and electronics industry. Molding compositions of this type are required in the electronics industry, for example, to produce components for mounting on printed circuit boards using so-called surface mount technology (SMT). In this application, these components must withstand temperatures of up to 270°C for short periods without dimensional changes.

[0134] Such high-temperature polyamides include certain polyamides prepared from alkyl diamines and diacids, such as polyamide 4,6. Additionally, many high-temperature polyamides are aromatic and semi-aromatic polyamides, i.e., homopolymers, copolymers, terpolymers, or higher polymers derived from monomers containing aromatic groups. Aromatic or semi-aromatic polyamides can be used, or blends of aromatic and / or semi-aromatic polyamides can be used. Blends with aliphatic polyamides can also be used.

[0135] Examples of suitable high temperature aromatic or semi-aromatic polyamides include polyamide-4,T, poly(m-xylene adipamide) (polyamide-MXD,6), poly(dodecanediamine terephthalamide) (polyamide-12,T), poly(decanediamine terephthalamide) (polyamide-10,T), poly(nonanediamine terephthalamide) (polyamide-9,T), hexamethylene adipamide / hexamethylene terephthalamide copolyamide (polyamide-6,T / 6,6 ), hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide copolyamide (polyamide-6, T / D, T); hexamethylene adipamide / hexamethylene terephthalamide / isophthalamide copolyamide (polyamide-6, 6 / 6, T / 6, I); poly (caprolactam-hexamethylene terephthalamide) (polyamide-6 / 6, T); hexamethylene terephthalamide / isophthalamide (polyamide-6, T / 6, I) copolymer; etc.

[0136] Thus, certain embodiments of the present invention relate to compositions comprising polyamides that melt at elevated temperatures, such as 280° C. or higher, 300° C. or higher, or 320° C. or higher. In some embodiments, the polyamides have a melting temperature of 280° C. to 340° C., such as polyamides 4, 6, or the aromatic and semi-aromatic polyamides described above.

[0137] Preferred polyamides are polyamide-6, polyamide-6,6, polyamide-11, polyamide-12, polyphthalamides such as polyamide-4,T, polyamide-6,T / 6,6 and polyamide-6,6 / 6,T / 6,I copolymers, glass-filled polyamides thereof, and blends thereof. For example, the thermoplastic polyamide blend may contain about 1 to 99 parts by weight of one polyamide and about 99 to about 1 part by weight of a different polyamide, based on 100 parts by weight of the two components combined.

[0138] In some embodiments, the polymer is a thermoplastic elastomer (eg, a thermoplastic polyolefin or a thermoplastic polyurethane). In some embodiments, the thermoplastic elastomer is a thermoplastic polyurethane.

[0139] At least one phosphorus-containing flame retardant (ii) is as described above and is present in the flame retardant thermoplastic composition in a flame retardant effective amount. Typically, the phosphorus-containing flame retardant disclosed herein is present in an amount of 1 wt % to 30 wt % (such as 3 wt % to 20 wt %) based on the total weight of the flame retardant thermoplastic composition.

[0140] The at least one orange colorant (iii) in the flame retardant thermoplastic composition is as described above and is typically present in the flame retardant thermoplastic composition in an amount of 0.01 wt% to 5 wt%, e.g., 0.05 wt% to 2.5 wt%, 0.1 wt% to 2.0 wt%, or 0.2 wt% to 1.0 wt%, or 0.2 wt% to 0.5 wt%, based on the total weight of the composition.

[0141] At least one inorganic filler (iv) may be present in the flame retardant thermoplastic composition. As known in the art, inorganic fillers can reduce the molded shrinkage coefficient and the linear expansion coefficient of the resulting molded article, and improve high thermal shock and low thermal shock performance. Depending on the desired product, various fillers in fiber or non-fibrous form (for example, powder, sheet) can be used. Some examples of fibrous fillers as the type of inorganic filler can be those such as glass fiber, glass fiber (such as flat fiber) with non-circular cross section, carbon fiber, silica fiber, silica alumina fiber, zirconium oxide fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and other metal fiber material (such as stainless steel, aluminum, titanium, copper and brass). Typical fibrous fillers are glass fiber or carbon fiber. Alternatively, the inorganic filler can be a powdered filler, such as carbon black, graphite, silicon dioxide, quartz powder, glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicate (such as wollastonite), metal oxide (such as iron oxide, titanium oxide, zinc oxide and aluminum oxide), metal hydroxide, metal carbonate (such as calcium carbonate and magnesium carbonate), metal sulfate (such as calcium sulfate and barium sulfate), silicon carbide, silicon nitride, boron nitride and various metal powders. Another example of inorganic filler is a flake filler, such as mica, glass flake and various metal foils. These inorganic fillers can be used alone or in combination of two or more. In use, if necessary, it is desired that the inorganic filler is processed in advance with a sizing agent or a surface treating agent.

[0142] When present, the amount of at least one inorganic filler in the flame retardant thermoplastic composition is typically 1 to 50 wt%, e.g., 5 to 50 wt%, 10 to 40 wt%, or 15 to 30 wt%, based on the total weight of the flame retardant thermoplastic composition.

[0143] The flame retardant thermoplastic composition may further comprise at least one flame retardant synergist and / or additional flame retardant (v). Exemplary flame retardant synergists and additional flame retardants are described above. When present, the amount of at least one flame retardant synergist and / or additional flame retardant (v) is typically 1 wt% to 25 wt%, such as 5 wt% to 25 wt%, based on the total weight of the flame retardant thermoplastic composition.

[0144] The flame retardant thermoplastic composition may further comprise at least one stabilizer (vi). Exemplary additional stabilizers are described above. When present, the at least one stabilizer is typically present in an amount of 0.01 wt% to 5 wt%, based on the total weight of the flame retardant thermoplastic composition.

[0145] Other ingredients or additives (vii) may be present in the flame retardant thermoplastic composition and are typically used in an amount of less than 10% by weight, for example less than 5% by weight, of the flame retardant thermoplastic composition and include non-limiting examples such as antioxidants, UV stabilizers, lubricants, impact modifiers, plasticizers, other stabilizers or acid scavengers, heat stabilizers, pigments, dyes, optical brighteners, antistatic agents, anti-drip agents (e.g., PTFE), and other additives for enhancing resin properties.

[0146] In many embodiments, the flame retardant thermoplastic composition comprises at least one thermoplastic polymer (i) in an amount of 30 wt% to 95 wt%, at least one phosphorus-containing flame retardant (ii) in an amount of 1 wt% to 30 wt%, an orange colorant (iii) in an amount of 0.001 wt% to 5 wt%, at least one inorganic filler (iv) in an amount of 0 wt% to 50 wt%, at least one flame retardant synergist and / or additional flame retardant (v) in an amount of 0 wt% to 25 wt%, all based on the total weight of the flame retardant thermoplastic composition. In many embodiments, the flame retardant thermoplastic composition comprises at least one thermoplastic polymer (i) in an amount of 40 wt% to 90 wt%, at least one phosphorus-containing flame retardant (ii) in an amount of 3 wt% to 20 wt%, an orange colorant (iii) in an amount of 0.01 wt% to 5 wt% (such as 0.05 wt% to 2.5 wt%, 0.1 wt% to 2.0 wt% or 0.2 wt% to 1.0 wt%, or 0.2 wt% to 0.5 wt%), at least one inorganic filler (iv) in an amount of 0 wt% to 50 wt% (such as 10 wt% to 40 wt%), at least one flame retardant synergist in an amount of 0 wt% to 25 wt% (such as 5 wt% to 25 wt%), and / or an additional flame retardant (v), all based on the total weight of the flame retardant thermoplastic composition. In some embodiments, the composition further comprises at least one stabilizer (vi) in an amount of 0 wt% to 5 wt% (such as 0.01 to 5 wt%), based on the total weight of the flame retardant thermoplastic composition.

[0147] Preparation of flame retardant and colorant additive compositions

[0148] The present invention is not limited to any particular method of mixing components (A), (B), (C), and (D) of the flame retardant and colorant additive compositions of the present disclosure. For example, at least one phosphorus-containing flame retardant (A) and orange colorant (B), optionally with at least one flame retardant synergist and / or additional flame retardant (C) and / or one or more stabilizers (D), can be mixed / blended by conventional mixing techniques, such as drum mixing, convection mixing, fluidized bed mixing, high shear mixing, and the like. Conventional processing aids, such as dispersants, antistatic agents, adhesives, coupling agents, and the like, may also be used.

[0149] Preparation of flame retardant thermoplastic compositions

[0150] The present invention is not limited by any particular method for blending the components of the flame retardant thermoplastic composition of the present disclosure. Suitable compounding and blending techniques known in the art can be used. For example, one method includes blending thermoplastic polymers and additives in powder or granular form and melt mixing the blend (for example, using a twin-screw extruder). Thermoplastic polymers, flame retardants, colorants, synergists and other additives are typically pre-dried before melt mixing. The extruded blend can be crushed into granular pellets or other suitable shapes by standard techniques. Other melt mixing process equipment (such as a kneader mixer or a bowl mixer) can be used to compound the flame retardant additive and any additional ingredients with the thermoplastic polymer. In either case, the generally suitable machine temperature can be in the range of about 200°C to 330°C, depending on the specific type of the selected thermoplastic.

[0151] The flame retardant thermoplastic composition can be molded in any equipment suitable for this purpose, such as an injection molding machine. After pelletization, the granulated pellets are typically dried again before being molded in an injection molding machine suitable for this purpose. Typically, the processing temperature is in the range of about 200°C to 330°C, depending on the molding properties of the specific thermoplastic polymer, the loading level of additives and / or reinforcing fillers, and other factors such as the thickness of the mold cavity and the gate size. Those skilled in the art will be able to make appropriate adjustments during the molding process to accommodate differences in the composition or tooling.

[0152] Further non-limiting disclosure is provided in the following examples.

[0153] Example

[0154] Example 1 - Flame Retardant

[0155] Methylphosphonic acid (MPA) (3678.8 g, 38.3 mol, 30 equivalents, 75% aqueous solution) and alumina (130.2 g, 1.28 mol, 1 equivalent) were mixed at room temperature and a limited exotherm (increased by about 2 ° C) was observed. The tank temperature was set to 165 ° C, the agitator was at 200 RPM at atmospheric pressure, and nitrogen was purged (4 L / min). When no distilled water was observed in the condenser, 1.0 g of seed material was optionally added, which was a flame retardant product prepared from MPA and alumina as described herein. The reaction mixture was heated at 165 ° C for 3 hours. The product reaction mixture containing the white slurry product was then cooled to about 130 ° C and poured into 1.5 L of water in a beaker cooled in an ice-water bath. The white slurry was then filtered out, washed with water (500 mL × 3), and dried to produce fine crystals in a 92% yield. According to the following empirical formula, the product has a phosphorus-aluminum ratio of 4: 1 (ICP elemental analysis):

[0156]

[0157] The above product empirical formula represents the repeating monomer units (ie, coordination entities) of the coordination polymer that form the pure crystalline product.

[0158] Example 2 - Flame Retardant

[0159] 800mL dimethylbenzene is loaded into a 1L flask and is provided with a Dean-Stark water trap. The solution is heated to 115°C and methylphosphonic acid (MPA) (33.89g, 0.35mol) is added. The acid is dissolved and the temperature is raised so that the solution begins to reflux. Aluminum oxide (4.01g, 0.039mol) is added in batches over 3 hours. Reflux is maintained at 142°C overnight. The solid product obtained is separated by filtration, washed with DMF (100mL) and Et2O (2 × 50mL), and dried to produce a fine powder (18.86g, 71% yield). According to the following empirical formula, the product has a phosphorus-aluminum ratio of 4:1:

[0160]

[0161] The above product empirical formula represents the repeating monomer units (ie, coordination entities) of the coordination polymer that form the pure crystalline product.

[0162] Example 3 - Flame Retardant

[0163] Methylphosphonic acid (MPA) (2216g, 23.1mol, 15 equivalents, aqueous solution) and aluminum trihydroxide (120g, 1.5mol, 1 equivalent) are mixed at room temperature. The tank temperature is set to 165°C, and the agitator is at 200RPM, nitrogen purging (4L / min) at atmospheric pressure. When no distilled water is observed in the condenser, 1.0g of seed material is optionally added, which is a flame retardant product prepared from MPA and aluminum trihydroxide as described herein. The reaction mixture is heated at 165°C for 3 hours. The product reaction mixture containing the white slurry product is then cooled to about 130°C and poured into 1.5L water in a beaker cooled in an ice-water bath. The white slurry is filtered out, washed with water (500mL×3), and dried to produce fine crystals in about 100% yield. According to the following empirical formula, the product has a phosphorus-aluminum ratio (ICP elemental analysis) of 4: 1:

[0164]

[0165] The above product empirical formula represents the repeating monomer units (ie, coordination entities) of the coordination polymer that form the pure crystalline product.

[0166] Example 4 - Flame Retardant

[0167]

[0168] Methylphosphonic acid (MPA) (1412.6g, 14.7mol, 30 equivalents, 75% aqueous solution) and ferric oxide (78.2g, 0.49mol, 1 equivalent) are mixed at room temperature. The tank temperature is set to 130 DEG C for about 12 hours, and agitator is in 250RPM, nitrogen purge (4L / min) at atmospheric pressure. The reaction mixture is subsequently heated to 165 DEG C for 12 hours. The product reaction mixture containing off-white slurry product is then cooled to about 130 DEG C and poured into 1.5L water in a beaker cooled in an ice-water bath. The off-white slurry is filtered out, washed with water (500mL×3), and dried to produce the fine off-white crystals of 92% yield. According to the following empirical formula, the product has a phosphorus-iron ratio (ICP elemental analysis) of 4:1:

[0169]

[0170] The above product empirical formula represents the repeating monomer units (ie, coordination entities) of the coordination polymer that form the pure crystalline product.

[0171] Example 5 - Flame Retardant

[0172]

[0173] Methylphosphonic acid (MPA) (1727g, 18.4mol, 15 equivalents, 75% aqueous solution) is cooled to 5°C in an ice-water bath under a nitrogen stream (1L / min). Aluminum isopropylate (250g, 1.2mol, 1 equivalent) is added in batches while keeping the tank temperature below 10°C. The tank temperature is then set to 165°C, and the agitator is in 250RPM. At 165°C, 4.5g of seed material of a flame retardant product prepared by MPA and aluminum isopropylate as described herein is optionally added, and the reaction mixture is kept at 165°C for 3 hours. The product reaction mixture containing the white slurry product is then cooled to about 130°C and poured into 1.5L water in a beaker cooled in an ice-water bath. The white slurry is filtered out, washed with water (500mL×3), and dried to produce fine crystals in a 44% yield. According to the following empirical formula, the product has a phosphorus-aluminum ratio (ICP elemental analysis) of 4:1:

[0174]

[0175] The above product empirical formula represents the repeating monomer units (ie, coordination entities) of the coordination polymer that form the pure crystalline product.

[0176] Example 6 - Flame Retardant

[0177]

[0178] Ethylphosphonic acid (EPA) (55.0g, 0.50mol, 30 equivalents) and aluminum oxide (1.70g, 17mmol, 1 equivalent) are mixed with 50mL water at room temperature.The tank temperature is set to 165 ℃, and agitator is in 250RPM, nitrogen purge (4L / min) at atmospheric pressure.The reaction mixture is heated at 165 ℃ for 3 hours.Then the product reaction mixture containing white slurry product is cooled to about 130 ℃ and poured into the 100mL water in the beaker cooled in an ice-water bath.The white slurries are filtered out, washed with water (50mL×3), and dried to produce the fine crystals of 76% productive rate.According to the following empirical formula, product has the phosphorus aluminum ratio (ICP elemental analysis) of 4:1:

[0179]

[0180] The above product empirical formula represents the repeating monomer units (ie, coordination entities) of the coordination polymer that form the pure crystalline product.

[0181] Example 7 - Flame Retardant

[0182]

[0183] 114.6g of methylphosphonic acid was added to a 250mL three-necked flask and then heated. At 105°C, the methylphosphonic acid melted and began to stir vigorously under N2 cover. The methylphosphonic acid was heated to 240°C and 7.78g of aluminum oxide was added as quickly as possible without causing a large amount of heat release. The slurry was cooled until it was just above the melting point (about 110°C) of the excess methylphosphonic acid and then added to 250mL of H2O while ensuring that the addition rate did not cause excessive steam to form. The resulting mixture was stirred to break up any large lumps that may have formed, the product was separated by filtration, washed with another 750mL of H2O, and dried to produce 45.08g of the product in an 87% yield as fine colorless crystals. The above product empirical formula represents the repeating monomer units (i.e., coordination entities) of the coordination polymer forming the pure crystalline product.

[0184] Example 8 - Flame Retardant

[0185]

[0186] Into a 250mL three-necked flask, 149.8g of ethylphosphonic acid was charged and heated to melting (62°C). Under N2, vigorous stirring was started, ethylphosphonic acid was heated to 240°C, and 6.9g of aluminum oxide was added as quickly as possible without causing a large exotherm. The slurry was cooled to approximately 80°C and then added to 250mL of H2O while ensuring that the rate of addition did not result in excessive steam formation. The resulting mixture was stirred to break up any large lumps that may have formed, the product was separated by filtration, washed with another 750mL of H2O, and dried to produce 49.07g of the product in an 84% yield as fine colorless crystals. The above product empirical formula represents the repeating monomer unit (i.e., coordination entity) of the coordination polymer forming the pure crystalline product.

[0187] Example 9 - Flame Retardant

[0188]

[0189] 83g of methylphosphonic acid was charged to a resin kettle and heated to 120°C. An intermediate material prepared from 50g of methylphosphonic acid and 35.4g of tri(isopropoxy)aluminum in the presence of water was added to the resin kettle as a slurry. The resulting solution contained a methylphosphonic acid intermediate in a 5:1 molar ratio of methylphosphonic acid to aluminum, which was heated to 240°C under mechanical stirring. After the solid had formed, stirring was continued at 240°C for about 30min. 500mL of H2O was added, and the mixture was stirred for 16h while forming a uniform slurry. As described above, the product was isolated by filtration, washed with an additional 750mL of H2O, and dried to produce 64.3g of the product in the form of fine colorless crystals in a 93% yield. The above product empirical formula represents the repeating monomer units (i.e., coordination entities) of the coordination polymer that form the pure crystalline product.

[0190] Example 10 - Flame Retardant

[0191]

[0192] 1305g of methylphosphonic acid was added to a 1L three-necked flask and then heated. The methylphosphonic acid melted at 105°C and began to stir vigorously under vacuum. The methylphosphonic acid was heated to 180°C and 61g of alumina was added as quickly as possible without causing a large amount of heat release or excessive foaming. The slurry was cooled until just above the melting point (about 110°C) of the excess methylphosphonic acid and then added to 1L of H2O while ensuring that the addition rate did not result in excessive steam formation. The resulting mixture was stirred to break up any large lumps that may have formed and the product was separated by filtration, washed with another 1.5L of H2O, and dried to produce 408g of the product in an 84% yield of fine colorless crystals. The above product empirical formula represents the repeating monomer units (i.e., coordination entities) of the coordination polymer forming the pure crystalline product.

[0193] The product from each of Examples 7-10 had a P / Al ratio of 4:1 (ICP elemental analysis).

[0194] Example 11 - Flame Retardant

[0195]

[0196] 1412.6g methylphosphonic acid is packed into 1L reaction vessel, then under nitrogen purge (4L / min), under 250RPM stirring, it is heated to 165 ℃.Under the situation that does not cause a large amount of heat release, the ferric oxide of 78.2g is added in batches.Reaction mixture is heated at 165 ℃ for about 24 hours.Then the product reaction mixture containing off-white slurry product is cooled to about 130 ℃ and poured into the 1.5L water in the beaker cooled in ice-water bath.By filtering separation product, with other 500mLx3 water washing, and dry to produce the fine off-white crystals of 83% productive rate.According to following empirical formula, product has the phosphorus-iron ratio (ICP elemental analysis) of 4:1:

[0197]

[0198] The above product empirical formula represents the repeating monomer units (ie, coordination entities) of the coordination polymer that form the pure crystalline product.

[0199] Example 12 Preparation of Methylpyrophosphonic Acid

[0200]

[0201] Methylphosphonic acid (MPA) (1920 g, 15 equivalents, 75% fresh aqueous solution) and AlO (0.8 g, 7.5 mmol, 0.05 mol% based on total MPA) were placed in a 2 L RBF and stirred at room temperature using a magnetic stirrer. Careful heating was performed to remove the aqueous solvent (the tank was set to 200°C), followed by careful vacuuming to remove the generated water. The target endpoint was 33% conversion.

[0202] Hour 1, tank setting @200°C, vacuum start @19.4 Torr, end @14.2 Torr, conversion rate 34.1%

[0203] Example 13 - Aluminum in Methylphosphonic Acid Solution

[0204]

[0205] MPA (1024 g, 8 equiv., 75% fresh aqueous solution) and Al2O3 (50.2 g, 0.50 mol total, 1.0 equiv., in combination with the catalytic amount from Example 2) were mixed in a 3 L reactor at room temperature. The pot temperature was set to 130°C at 100 RPM without nitrogen purging. The pot temperature was stabilized at about 110°C for about 1 hour while the white slurry turned opaque and then turned into a clear, light yellow solution. After the pot temperature stabilized at 130°C, the reaction mixture was kept at 130°C overnight. The next morning, vacuum was carefully applied to remove water while the pot temperature was set to 200°C and the house vacuum was finally stabilized at 57 Torr until no distillate came out.

[0206]

[0207] Example 14 - Flame Retardant

[0208] The methylpyrophosphonic acid product of Example 12 is preheated to 205°C, and seed material (1.9g, 0.5wt% of the theoretical amount of flame retardant) is added thereto. The preheated methylpyrophosphonic acid is then poured into the 200°C solution of Example 13 at 300RPM. After mixing, the reaction is kept at 200°C for 5min. The reaction mixture is then cooled to 130°C and slowly and carefully poured into 2.8L water in a 4L beaker at room temperature and stirred at 250RPM for 10min. The white slurry is filtered out and dried under house vacuum for 4 hours. The solid is then transferred to a beaker and stirred with 700mL water for 10min, and suction dried overnight under house vacuum. The crude yield is 83.0%, and the screening yield of 100 mesh sieve at 99min is 94.0%.

[0209] The resulting material had an acid value <0.1 mg KOH / g sample and a P / Al ratio of 4:1 (ICP elemental analysis).

[0210] Example 15 - Flame Retardant

[0211] MPA (1553 g, 12 equivalents, 75% aqueous solution) was placed in a 3 L resin reactor. Carefully heat to remove water (tank set to 200° C., 150 RPM) and carefully apply vacuum when no distillate comes out. The target endpoint of conversion is 71% (31P NMR measurement, MPA set 100%). Day 2, tank set @ 200° C., vacuum @ 150 Torr, 37.2% conversion; Day 3, tank set @ 200° C., vacuum @ 200 Torr, 54.4% conversion; Day 4, tank set @ 200° C., vacuum @ 120 Torr, 69.1% conversion to pyrophosphonic acid. 1.

[0213]

[0214] Separately, MPA (768 g, 6 eq., 75% fresh aqueous solution) and Al2O3 (51.0 g, 0.50 mol, 1.0 eq.) were mixed at room temperature. The pot temperature was initially set to 130°C at 250 RPM without nitrogen purging. The pot temperature was stabilized at approximately 110°C for approximately 1 hour while the white slurry became opaque and then a clear, light yellow solution. The pot temperature was then set to 200°C. Vacuum was carefully applied to remove the water, with the final vacuum level stabilizing at 140 Torr until no more distillate came out. 2.

[0216]

[0217] Pyrophosphonic acid was preheated to 200°C and then mixed with the Al in the MPA solution at 200°C and 250 RPM. No seed material was required, and the slurry remained unchanged. The reaction mixture was kept at 200°C for 3 hours. The reaction mixture was then slowly and carefully poured into 2.8L of water in a 4L beaker at room temperature and stirred at 250 RPM for 10 minutes. The white slurry was filtered out and dried under house vacuum for 4 hours. The solid was then transferred to a beaker and stirred with 700mL of water for 10 minutes and suction dried overnight under house vacuum. The crude yield was 88.7%. SEM showed that the product was needle-shaped. The material was further dried in a 60°C oven and sieved through a 100 mesh sieve (67.5% @ 99 min; 97.2% @ 198 min). 3.

[0219]

[0220] Example 16 - Polymer composition

[0221] The combined flame retardants and colorants of the present disclosure were evaluated in polyamide-6,6 thermoplastic compositions. The ingredients are listed below and shown in Table 2, including the proportions of the blend components.

[0222] Thermoplastic polymers:

[0223] Polyamide-6,6 (from Nilit P-50 / 2)

[0224] Inorganic fillers:

[0225] Glass fiber (from PPG 3540)

[0226] Phosphorus-containing flame retardant (Phos-FR):

[0227] Phos-FR produced according to Example 7 above

[0228] OP 1312

[0229] Colorants

[0230] from LANXESS Orange HT

[0231] Flame retardant synergist:

[0232] Melam or melamine polyphosphate (MPP)

[0233] Stabilizer:

[0234] zinc borate

[0235] The formulations shown in Table 1 were compounded using a Liestritz 18 mm twin-screw extruder at 265° C. and 200 rpm. 0.8 mm (thickness) specimens were prepared for each formulation using a Vandorn 55 candence injection molding machine at 260-280° C. and a mold temperature of 80° C. The flame retardant activity of each prepared formulation was evaluated under the UL-94 test, and the molecular weight of the polymer was determined by gel permeation chromatography (GPC).

[0236] Table 2

[0237]

[0238] As shown in Table 1, all formulas containing colorant all show V-0 performance under UL-94 test.However, when using contrast flame retardant OP 1312, injection molding process is unstable.When orange colorant is added in contrast flame retardant (formula 3), even narrower process window is observed.By contrast, show more stable injection molding process with formula 1,2,5 and 6 containing flame retardant according to the present disclosure, particularly, formula 1 and 5 demonstrate more stable injection molding process than these counterparts (formula 2 and 6).All of these show that the polymer degradation caused by flame retardant additive and colorant is less.Compared with the formula (2 and 6) that does not contain colorant, in formula 1 and 5, comprising colorant brings less energy consumption, also provides wider process window for injection molding process.

[0239] Example 17 - Polymer composition

[0240] The combined flame retardants and colorants of the present disclosure can be combined in a polyamide-6 thermoplastic composition. The ingredients are listed below and shown in Table 2, including the proportions of the blended components.

[0241] Thermoplastic polymers:

[0242] Polyamide-6 (from LANXESS B30S)

[0243] Inorganic fillers:

[0244] Glass fiber (from PPG 3540)

[0245] Phosphorus-containing flame retardant (Phos-FR):

[0246] Phos-FR produced according to Example 7 above

[0247] Additional flame retardants:

[0248] Polydibromostyrene (from LANXESS PBS-64HW)

[0249] Carbodiimide:

[0250] Aromatic polycarbodiimide of formula (VI) (from LANXESS P100)

[0251] A twin-screw extruder was used to compound the formulations shown in Table 3 at 255-265°C. An injection molding machine was used to prepare 1.6 mm (thickness) samples for each formulation at 245-255°C and at a mold temperature of 80°C.

[0252] Table 3

[0253] Recipe Number 7 8 PA 6wt% 42-47 42-47 Glass wt% 25 25 Phos-FR wt% 6 6 PBS-64HW wt% 22 22 Stabaxol P100wt% - 1 Colorants 0.01-5 0.01-5

[0254] Example 18 - Polymer composition

[0255] An alternative polyamide-6,6 thermoplastic composition is provided below. The ingredients are listed below and shown in Table 4, including the proportions of the blended components.

[0256] Thermoplastic polymers:

[0257] Polyamide-6,6 (from Nilit P-50 / 2)

[0258] Inorganic fillers:

[0259] Glass fiber (from PPG 3540)

[0260] Phosphorus-containing flame retardant (Phos-FR):

[0261] Phos-FR produced according to Example 7 above

[0262] Flame retardant synergist:

[0263] melam

[0264] Heat stabilizer:

[0265] Zinc stannate (Flamtard S from William Blythe)

[0266] Carbodiimide:

[0267] Aromatic polycarbodiimide of formula (VI) (from LANXESS P100)

[0268] A twin-screw extruder was used to compound the formulations shown in Table 4 at 265°C. An injection molding machine was used to prepare 0.8 mm (thickness) samples for each formulation at 260-280°C and a mold temperature of 80°C.

[0269] Table 4

[0270]

[0271] While particular embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various modifications and variations may be made from consideration of the specification and practice of this disclosure without departing from the scope of the invention as claimed. It is therefore intended that the specification and examples be considered exemplary only, with the true scope of the invention being indicated by the following claims and their equivalents.

Claims

1. A flame retardant and colorant additive composition for thermoplastic polymers, comprising: (A) at least one phosphorus-containing flame retardant of the empirical formula (I): in, R is an alkyl or aryl group, M is a metal, and y is 2 or 3, such that M (+)y is a metal cation, wherein (+)y represents the charge formally assigned to the cation, a, b and c represent the ratios of their corresponding components relative to each other in the compound and satisfy the charge balance equation 2(a)+c=b(y), and a and c are not zero, and (B) Orange colorant.

2. The flame retardant and colorant additive composition according to claim 1, wherein In the empirical formula (I), a is 1 or 2, b is 1 to 4, and c is 1 or 2.

3. The flame retardant and colorant additive composition according to claim 1, wherein y is 3, a is 1, b is 1, and c is 1.

4. The flame retardant and colorant additive composition according to claim 3, wherein M is selected from Al, Ga, Sb, Fe, Co, B and Bi.

5. The flame retardant and colorant additive composition according to claim 4, wherein M is Al or Fe.

6. The flame retardant and colorant additive composition according to any one of claims 1 to 5, wherein In the empirical formula (I), R is C 1-12 Alkyl, C 6-10 Aryl, C 7-18 Alkyl aryl or C 7-18 Arylalkyl, wherein the alkyl, aryl, alkylaryl or arylalkyl is unsubstituted or substituted by halogen, hydroxy, amino, C 1-4 Alkylamino, di-C 1-4 Alkylamino, C 1-4 Alkoxy, carboxyl or C 2-5 Alkoxycarbonyl substitution.

7. The flame retardant and colorant additive composition according to claim 6, wherein R is unsubstituted C 1-12 Alkyl, C6 aryl, C 7-10 Alkyl aryl or C 7-10 Arylalkyl.

8. The flame retardant and colorant additive composition according to claim 6, wherein R is unsubstituted C 1-6 alkyl.

9. The flame retardant and colorant additive composition according to claim 8, wherein R is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl and tert-butyl.

10. The flame retardant and colorant additive composition according to any one of claims 1 to 9, wherein M is Al, y is 3, a is 1, b is 1 and c is 1.

11. The flame retardant and colorant additive composition according to claim 10, wherein R is C 1-6 alkyl.

12. The flame retardant and colorant additive composition according to claim 11, wherein R is selected from methyl and ethyl.

13. The flame retardant and colorant additive composition of claim 1 further comprising (C) at least one flame retardant synergist and / or additional flame retardant.

14. The flame retardant and colorant additive composition according to claim 13, wherein Component (C) comprises a nitrogen-containing flame retardant synergist.

15. The flame retardant and colorant additive composition of claim 1 further comprising (D) one or more stabilizers.

16. A flame retardant thermoplastic composition comprising at least one thermoplastic polymer and the flame retardant and colorant additive composition according to any one of claims 1 to 15, wherein: The thermoplastic composition has a ΔE of <20, preferably ΔE <10, compared to a color number starting with "2" in the RAL color chart. More preferably, ΔE<5.

17. The flame retardant thermoplastic composition according to claim 16, wherein The at least one thermoplastic polymer is selected from the group consisting of polyesters and polyamides.

18. The flame retardant thermoplastic composition according to claim 17, wherein The at least one thermoplastic polymer is a polyamide selected from the group consisting of polyamide-4,6, polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-6,12, polyamide-11, polyamide-12, polyamide-4,T, polyamide-MXD,6, polyamide-12,T, polyamide-10,T, polyamide-9,T, polyamide-6,T / 6,6, polyamide-6,T / D,T, polyamide-6,6 / 6,T / 6,I, polyamide-6 / 6,T, polyamide-6,T / 6,I and mixtures thereof.

19. The flame retardant thermoplastic composition of claim 16, further comprising at least one inorganic filler.

20. The flame retardant thermoplastic composition according to claim 19, wherein The inorganic filler includes glass fiber.

21. A method of improving the processing of a thermoplastic polymer comprising adding to the thermoplastic polymer a flame retardant and colorant additive composition according to any one of claims 1 to 15.

22. The method according to claim 21, wherein The thermoplastic polymer is selected from the group consisting of polyesters and polyamides.

23. The method according to claim 21, wherein The thermoplastic polymer is a polyamide selected from the group consisting of polyamide-4,6, polyamide-6, polyamide-6,6, polyamide-6,10, polyamide-6,12, polyamide-11, polyamide-12, polyamide-4,T, polyamide-MXD,6, polyamide-12,T, polyamide-10,T, polyamide-9,T, polyamide-6,T / 6,6, polyamide-6,T / D,T, polyamide-6,6 / 6,T / 6,I, polyamide-6 / 6,T, polyamide-6,T / 6,I and mixtures thereof.

24. The method of claim 21, further comprising adding at least one inorganic filler to the thermoplastic polymer.

25. The method according to claim 24, wherein The inorganic filler includes glass fiber.

26. The method according to claim 21, wherein The processing is an injection molding process.

Images