Patent Application
20190136053
The present invention refers to a polyamide moulding composition consisting of the following components:
whereby the entirety of components (A) to (F) add up to 100% by weight.
Moreover, the present invention refers to a moulded article producible from this polyamide moulding composition by extrusion, extrusion blow moulding or injection moulding, especially by gas or liquid assisted injection moulding processes.
The assisted injection moulding technologies include the injection of an inert gas (e.g. nitrogen, carbon dioxide) or a liquid such as water at high pressure into plastic in an injection mould. This cores out sections of the part, leaving hollow areas. These allows to mould hollow or partly hollow parts, reduce part weight and can provide much better distribution of packing pressure and eliminate sink marks. Gas can also be applied to the surface of a plastic part to replace moulding machine packing pressure with a uniform gas packing pressure, eliminating sink marks and reducing clamping force and often leading to lower part weight and cycle time.
With the water assist injection moulding process, water is used to core out the hollow sections, then flows through the part to cool the plastic. Unlike the gas injection process, cooling is provided from the exterior of the part by the tooling and from the interior channel by the water. Direct cooling inside the part is a big advantage of this moulding method because, the thermal conductivity of water is 40 times greater than gas and the heat capacity is four times greater—so cooling cycle times can be reduced to up to 50% that of traditional gas assist.
Polyamide moulded articles are broadly used in the engineering field, in particular for electronic components as well as components in the automotive field. Due to the demand for moulded articles with a reduced weight but a high mechanical strength these articles are in general reinforced by fillers, in particular fibrous fillers and optionally have hollow areas.
Such polyamides moulded articles are also used for articles like housings or covers with integrated connectors, pipes, fittings, intakes or outlets. These can be used in particular in the automotive field e.g. for parts of the air intake system inclusive charger system or for the automotive coolant circuit. For such articles it is important that they show a excellent heat resistance at temperatures above 200° C. and/or high hydrolytic resistance at temperatures of 130° C. and more which can occur in the surrounding of the engine or the turbo charger.
EP 0 052 944 refers to aliphatic polyamide moulding resins that contain carbon black and nigrosine. The carbon black acts to block or absorb ultraviolet rays and therefore can be used to improve weathering resistance. However, impact resistance and elongation are adversely affected by incorporation of carbon black. It was found that when nigrosine is employed with carbon black in a blend with a polyamide moulding resin, the resulting moulding blend produces moulded articles having better impact resistance and greater elongation than a resin comprising carbon black and polyamide alone.
EP 1 265 962 describes a use of thermoplastic moulding compositions consisting of preferably aliphatic polyamide, glass fibers and of mica or other lamellar mineral reinforcing materials as antinucleating additives for the production of mouldings for the automotive coolant circuit by means of a gas-assisted injection moulding process, wherein the standard GAIM process (melt inflation method) or the melt expulsion method or a combination of inflation and expulsion methods is used.
U.S. Pat. No. 6,265,081 propose the use of nigrosine to improve the weld line strength of integrally moulded articles, manufactured by glass fiber reinforced aliphatic resins, like PA 6 or PA 6/66.
However, a still not-solved drawback of the fiber reinforced polyamide moulding compositions mentioned above is, that the surface moulded articles, formed from these compositions, is not fully smooth. This is mainly due to the fact that the fibers, being present in the polyamide moulding composition, are not fully covered with the polyamide at the surface so that fibers are not completely incorporated into the moulded compound. Accordingly, in use of the moulded compounds, e.g. under mechanical stress or when in contact with fluids such as e.g. fuel compositions, fibers can release from the surface of the moulded compound and spread in the surrounding, e.g. can wash out into a fuel composition. This phenomenon is not only deterious as far as the remaining mechanical strength of the polyamide moulding compound is concerned, but also unwanted, especially where the fiber reinforced moulded article is in contact with fluids, such as e.g. fuel compositions or coolants.
In addition, the above mentioned polyamide moulding compositions cannot provide the required heat and hydrolytic resistance in order to resist the demanding environments near the engine or in contact with hot coolant medium and the proposed lamellar mineral as antinucleating agent provokes a significant void formation using the assist injection moulding processes.
It was therefore the object of the present invention to provide polyamide moulding compositions with excellent heat resistance, good hydrolytic resistance, in particular in contact to coolant medium and excellant mechanical and thermal properties, in particular with a high tensile strength and a high deflection temperature under load and having excellent processability in gas or liquid (e.g. water) assist injection moulding. The moulded articles produced from these compositions should exhibit a smooth surface, in particular a smooth inner surface in case the articles are hollow. Furthermore articles produced by gas or liquid assist injection moulding processes show a significantly reduced void formation, improving the performance of such articles or enables a reduced wall thickness.
This problem is solved by the polyamide moulding composition according to claim 1 a method of producing a moulded article according to claim 16 as well as the moulded article with the features of claim 17. The dependent claims show preferred embodiments.
The present invention provides a polyamide moulding composition which consists of the following components:
whereby the entirety of components a) to f) add up to 100% by weight.
According to a preferred embodiment of the the invention, the polyamide moulding composition is free of the following nucleating agents (part of component (F)): PA22, minerals, clay minerals, talc, in particular magnesium silicate, kaolin or kaolinite.
The term particulate filler (or non-fibrous inorganic filler) refers to silicates, wollastonite, zeolite, sericite, kaolin, mica, clay minerals, pyrophyllite, bentonite, asbestos, talc, aluminosilicate, aluminium oxide, silicon oxide, metal carboxylate, such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate and, magnesium hydroxide, calcium hydroxide, and aluminium hydroxide, glass beads, ceramic beads, boron nitride or silicon carbide. These particulate fillers are also a part of componente (F).
According to a further preferred embodiment, the polyamide moulding compositions according to the present invention are completely free of nucleating agents and particulate fillers.
According to the present invention the term “nucleating agents” refers to compounds which accelerate the crystallization and reduce the size of spherulites of the polyamide compounds due to more crystallization sites. Nucleating agents are described and defined in Becker/Braun, Kunststoff-Handbuch 3/4 Polyamide 1998, p. 181 and in Kohan, Nylon Plastics Handbook 1995, p. 444-446. For the purpose of the present invention, the definition of the aforementioned text book is adopted and incorporated by reference.
According to a further preferred embodiment the polyamide moulding compositions are free from particulate fillers. A particulat filler, as being understood in the present invention, may be described as a non-fibrous solid, usually in finely divided form, whereby single particles have a length-to-diameter ratio of not more than 10:1. Particulate fillers are described and defined in S. T. Peters, Handbook of Composites, Sec. Ed. 1998, Chapter 11. For the purpose of the present invention, the definition of the aforementioned text book is adopted and incorporated by reference.
Azine dyes are commercial products and e.g. described in H. Bernetz, Azine Dyes, Ullmann's Encyclopedia of Industrial Chemistry (DOI 10.1002/14356007. a03_213.pub3). Preferred azine dyes are e.g. nigrosines and indulines, wherein nigrosines are especially preferred. For the purposes of the present invention as far as azine dyes are concerned reference is made to the aforementioned textbook.
Surprisingly it was established by the inventors that the polyamide moulding compositions according to the invention allow the production of high heat and/or hydrolytic resistant hollow or partly hollow parts by using the composition of the present invention showing an improved inner surface quality and none or reduced void formation in the wall of the part. Improved inner surface means that the inner surface, which is formed by direct contact of the gas or liquid (e.g. water) injected during the assist injection moulding process, is smoother and has a reduced roughness and the incorporated fibers are covered by the polyamide matrix, so that glass fiber debonding is significantly reduced or prevented.
Surface roughness, often shortened to roughness, is a measure of the texture of a surface. It is quantified by the vertical deviations of a real surface from its ideal form. If these deviations are large, the surface is rough; if they are small the surface is smooth. Most common parameters to characterize the mean roughness are the values Ra and Rz. Ra is the arithmetic average of the roughness profile (line) and describes the roughness or finish of a technical surface. To determine Ra the surface of a defined measured section is scanned and each difference in height and depth of the rough surface is recorded. After calculating the definite integral of the roughness profile the result is divided by the length of the measured section. The roughness value Ra spreads from 25 μm for very rough surfaces with noticeable grooves (scratches) to the point of 0.1 μm for surfaces without an observable unevenness. The mean roughness depth Rz is calculated by measuring the vertical distance from the highest peak to the lowest valley within five sampling lengths (Rzi), then averaging these distances. Rz averages only the five highest peaks and the five deepest valleys therefore extremes have a much greater influence on the final value. The roughness measurement was performed on samples according to DIN EN ISO 4287 (2010 July) by using a Mahrsurf XR1 Surface Measuring Station.
In a preferred embodiment, the moulding composition has
In the following preferred embodiments of the essential components of the polyamide moulding composition according to the invention will be discussed in greater detail.
Polyamide (A)
In a preferred embodiment, the moulding composition comprises the partially crystalline polyamide (A) in an amount of 30.0 to 73.6% by weight, preferably 32.5 to 72.5% by weight, more preferably 41.5 to 68.4% by weight, more preferably 43.0 to 66.75% by weight.
The partially crystalline polyamide (A) preferably has a melting point of at least 280° C., preferred of 285 to 335° C., more preferred of 290 to 330° C., most preferred of 295 to 325° C., measured according to DIN EN ISO 11357-3 (2013 April) with a heating rate of 20 K/min.
Preferred semiaromatic, semicrystalline polyamides are prepared from
a) 30-100 mol %, especially 50-100 mol % terephthalic acid and/or naphthalene dicarboxylic acid, and 0-70 mol %, especially 0-50 mol %, of at least one aliphatic dicarboxylic acid having 6-12 carbon atoms, and/or 0-70 mol %, especially 0-50 mol % of at least one cycloaliphatic dicarboxylic acid having 8-20 carbon atoms, and/or 0-50 mol % isophthalic acid, with respect to the total amount of the dicarboxylic acids
b) 80-100 mol % of at least one linear or branched aliphatic diamine having 4-20 carbon atoms, preferably 6-12 carbon atoms, and 0-20 mol % of at least one cycloaliphatic diamine, preferably one having 6-20 carbon atoms, such as PACM (4,4′-bis(aminodicyclo-hexyl)methane), MACM (3,3′-dimethyl-4,4′-bis(aminodicyclohexyl)methane), BAC (1,3-bis(aminomethyl)-cyclohexan) and/or IPDA (3-aminomethyl-3,5,5-trimethylcyclohexylamine) and/or 0-20 mol % of at least one araliphatic diamine such as MXDA (meta-Xylylendiamine), and PXDA (para-Xylylendiamine), with respect to the total amount of the diamines, and optionally
c) aminocarboxylic acids and/or lactams, each having 6-12 carbon atoms.
According to a preferred embodiment the at least one semiaromatic polyamide (A) is formed on the basis of at least 30 mol %, especially at least 50 mol % terephthalic acid and at least 80 mol % aliphatic diamines, preferably linear aliphatic diamines, having 4-20 carbon atoms, preferably 6-12 carbon atoms, and optionally other aliphatic, cycloaliphatic and aromatic dicarboxylic acids as well as lactams and/or aminocarboxylic acids. Isophthalic acid and naphthalenedicarboxylic acid can be used besides the terephthalic acid as other aromatic dicarboxylic acids. Suitable aliphatic and cycloaliphatic dicarboxylic acids other than terephthalic acid that can be used have 6-36 carbon atoms and are used in a maximum amount of 70 mol %, especially a maximum of 50 mol %, with respect to the total amount of the dicarboxylic acids.
Moreover, it is preferable that the said aromatic dicarboxylic acids of the semiaromatic polyamide of component (A) be chosen from the group: terephthalic acid, isophthalic acid, and mixtures thereof.
According to another preferred embodiment said, e.g., aliphatic dicarboxylic acids of the semiaromatic polyamide of component (A) that can be used besides terephthalic acid are chosen from the group: adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid and dimeric fatty acid (C36). Among the dicarboxylic acids, adipic acid, sebacic acid, dodecanedioic acid, isophthalic acid or a mixture of such dicarboxylic acids, especially adipic acid and isophthalic acid, and especially adipic acid alone are preferred.
According to another preferred embodiment, said aliphatic diamines of the semiaromatic polyamide of component (A) are chosen from the group: 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, methyl-1,8-octanediamine, 1,10-decandiamine, 1,11-undecanediamine, 1,12-dodecanediamine, or a mixture of such diamines, where 1,6-hexanediamine, 1,10-decanediamine, 1,12-dodecanediamine, where a mixture of such diamines is preferred, where 1,6-hexanediamine and 1,10-decanediamine are especially preferred. In addition to said diamines, cycloaliphatic and/or araliphatic diamines can be used in a concentration of 0-20 mol % with respect to the total amount of diamines.
Especially preferably, the high-melting polyamides are formed from the following components:
(Aa) Dicarboxylic acids:
50-100 mol-% aromatic terephthalic acid and/or naphthalene dicarboxylic acid, with respect to the total content of dicarboxylic acids that are present, 0-50 mol % of an aliphatic dicarboxylic acid, preferably having 6-12 carbon atoms, and/or a cycloaliphatic dicarboxylic acid having preferably 8-20 carbon atoms, and/or isophthalic acid;
(Ab) Diamines:
80-100 mol % of at least one linear or branched aliphatic diamine having 4-20 carbon atoms, preferably 6-12 carbon atoms with respect to the total content of diamines that are present, 0-20 mol % cycloaliphatic diamines, preferably having 6-20 carbon atoms, most preferred are PACM, MACM and IPDA, and/or araliphatic diamines such as MXDA and PXDA,
whereby the molar percentage of dicarboxylic acids in the high melting polyamides is 100% and the molar percentage of diamines makes up 100%, and optionally of
(Ac) Aminocarboxylic acids and/or lactams, containing lactams having preferably 6-12 carbon atoms and/or aminocarboxylic acids having preferably 6-12 carbon atoms.
While the components (Aa) and (Ab) are largely used in equimolar amounts, the concentration of (Ac) is a maximum of 20 wt.-%, preferably a maximum of 15 wt.-%, especially a maximum of 12 wt.-%, in each case with respect to the sum of (Aa) to (Ac). In a most preferred embodiment component (A) is free of any aminocarboxylic acids and/or lactams.
In addition to the components (Aa) and (Ab), which are used in largely equimolar amounts, dicarboxylic acids (Aa) or diamines (Ab) can be used to regulate the molecular weight or to compensate monomer losses in production of the polyamide, so that the concentration of one component (Aa) or (Ab) can predominate in its totality.
Suitable cycloaliphatic dicarboxylic acids are the cis- and/or trans-cyclohexane-1,4-dicarboxylic acid and/or cis- and/or trans-cyclohexane-1,3-dicarboxylic acid (CHDA).
The obligatorily used aliphatic diamines indicated above can be replaced by other diamines in a lesser amount of no more than 20 mol %, preferably no more than 15 mol %, and especially no more than 10 mol %, with respect to the total amount of diamines. For example, cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane (BAC), isophoronediamine (IPDA), norbornanedimethylamine, 4,4′-diaminodicyclohexylmethane (PACM), 2,2′-(4,4′-diaminodicyclohexyl)propane (PACP) and 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane (MACM) can be used as cycloaliphatic diamines. As araliphatic diamines, m-xylylenediamine (MXDA) and p-xylylenediamine (PXDA) may be mentioned. In a most preferred embodiment component (A) is free of any cycloaliphatic or any araliphatic diamines.
In addition to the described dicarboxylic acids and diamines, lactams and/or aminocarboxylic acids can also be used as polyamide-forming components (component (Ac)). Suitable compounds are, for example, caprolactam (CL), α,ω-aminocaproic acid, α,ω-aminononanoic acid, α,ω-aminoundecanoic acid (AUA), lauryllactam (LL) and α,ω-aminododecanoic acid (ADA). The concentration of the aminocarboxylic acids and/or lactams that are used together with the components (Aa) and (Ab) amount to a maximum of 20 wt.-%, preferably a maximum of 15 wt.-%, and especially preferably a maximum of 12 wt.-%, with respect to the sum of the components (Aa) through (Ac). Especially preferred are lactams or α,ω-amino acids having 4, 6, 7, 8, 11 or 12 C atoms. These are the lactams pyrrolidin-2-one (4 C atoms), ε-caprolactam (6C atoms), enanthlactam (7C atoms), capryllactam (8C atoms), lauryllactam (12C atoms) or the α,ω-amino acids 1,4-aminobutanoic acid, 1,6-aminohexanoic acid, 1,7-aminoheptanoic acid, 1,8-aminooctanoic acid, 1,11-aminoundecanoic acid, and 1,12-aminododecanoic acid.
In an especially preferred embodiment, component A is free of a lactam or aminocarboxylic acid and additionally free of a cycloaliphatic or an araliphatic diamines.
Regulators to control the molecular weight, relative viscosity or flowability or MVR (melt volume flow rate) in the form of monocarboxylic acids or monoamines can be added to the batch and/or the precondensate (before the postcondensation). Aliphatic, cycloaliphatic or aromatic monocarboxylic acids or monoamines that are suitable as regulators are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3-(3-tett-butyl-4-hydroxy-5-methylphenyl)propanoic acid, 2-(3,5-di-tert-butyl-4-hydroxybenzylthio)acetic acid, 3,3-bis(3-tert-butyl-4-hydroxyphenyl)butanoic acid, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, 3-(cyclohexylamino)propylamine, methylcyclohexylamine, dimethylcyclohexylamine, benzylamine, 2-phenylethylamine, 2,2,6,6-tetramethylpiperidin-4-amine, 1,2,2,6,6-pentamethylpiperidin-4-amine, 4-amino-2,6-di-tett-butylphenol, among others. Especially preferred are acetic acid, benzoic acid and stearic acid. The concentration of the monofunctional regulators is 0.5 to 0.5 mol-%, preferably 1.0 to 2.5 mol-%, related to the total content of all diamines in case the regulator is a monocarboxylic acids and is 0.5 to 0 5 mol-%, preferably 1.0 to 2.5 mol-%, related to the total content of all dicarboxylic acids in case the regulator is a monoamine.
The regulators can be used individually or in a combination. Other monofunctional compounds that can react with an amino or acid group such as anhydrides, isocyanates, acid halides or esters, can also be used as regulators. The usual amount of regulators is between 10 and 200 mmol per kg of polymer.
The semiaromatic copolyamides (A) can be prepared by substantially known methods. Suitable methods have been described elsewhere, and some of the possible methods that have been discussed in the patent literature will be given below. The disclosure contents of the following documents are expressly incorporated into the disclosure content of this application with regard to the method for preparation of the copolyamide of component (A): DE-A-195 13 940, EP-A-0 976 774, EP-A-0 129 195, EP-A-0 129 196, EP-A-0 299 444, U.S. Pat. No. 4,831,106, U.S. Pat. No. 4,607,073, DE-A-14 95 393 and U.S. Pat. No. 3,454,536.
Specific representatives of the polyamides (A) in accordance with the invention are: PA 4T/4I, PA 4T/6I, PA 5T/5I, PA 6T/6, PA 6T/6I, PA 6T/6I/6, PA 6T/6I/66, PA 6T/6I/610, PA 6T/6I/612, PA 6T/66, 6T/610, 6T/612, PA 6T/10T, PA 6T/10I, PA 9T, PA 9MT (M=Methyloctanediamine), PA 10T, PA 12T, PA 10T/10I, PA 10T/106, PA 10T/12, PA 10T/11, PA 6T/9T, PA 6T/12T, PA 6T/10T/6I, PA 6T/6I/6, PA 6T/6I/12, and mixtures thereof; especially preferably, the semiaromatic polyamide of component (A) is chosen from the group: PA 6T/6I, PA 6T/6I/66, PA 6T/6I/610, PA 6T/6I/612, or PA 6T/6I/X whereby X can be an aliphatic unit selected from the group consisting of 66, 610 or 612 or a combination thereof, and mixtures thereof. Regarding the polyamides PA 6T/6I/X the ones are especially preferred, which have a content of the aliphatic polyamide units X in the range of 5 to 20 mol-% and a content of the unit polyamide 6I in the range of 20 to 35 mol-%.
Therefore in accordance with the invention the following semiaromatic copolyamides are especially preferred as high-melting polyamides (A):
The semiaromatic, semicrystalline polyamide (A) has a solution viscosity ηrel measured according to DIN EN ISO 307:2013-08 on solutions of 0.5 g polymer in 100 mL m-cresol at a temperature of 20° C., of a maximum of 2.60, preferably a maximum of 2.3, especially a maximum of 2.0. Polyamides (A) having a solution viscosity ηrel in the range from 1.4-2.3, further preferred in the range from 1.45-2.00, further preferred in the range from 1.50-1.90 and especially from 1.55 to 1.85.
The polyamides (A) in accordance with the invention can be prepared in conventional polycondensation equipment via the process sequence precondensate and postcondensation. The described chain length regulators are preferably used for the polycondensation to regulate the viscosity. In addition, the viscosity can be established through the use of an excess of diamine or diacid.
Especially the partially crystalline polyamide 6T/6I (70:30) is made from hexamethylenediamine as the only diamine, terephthalic acid and isophthalic acid in a molar ratio of 70:30. The melting point of this partially crystalline polyamide is 325° C.
The partially crystalline polyamide 10T/6T is made from decanediamine, hexamethylenediamine and terephthalic acid whereby the a molar ratio of decanediamine to hexamethylenediamine is in the range of 95-40:5-60, in particular 90-75:10-25.
The partially crystalline polyamide 10T/6T/10I/6I, is made from decanediamine, hexamethylenediamine, terephthalic acid and isophthalic acid with an amount of decanediamine of 7.5 to 20 mol-%, an amount of hexamethylenediamine of 30 to 42.5 mol-%, an amount of terephthalic acid of 36 to 49.15 mol-% and an amount of isophthalic acid of 0.85 to 14 mol-%, whereas the amounts of the four monomers add up to 100 mol-% and the amounts of the diamines add up to 50 mol-% and the amounts of the dicarboxylic acids add up to 50 mol-%.
The partially crystalline polyamide 6T/6I/612 is made from 60-75 wt.-% 6T-units, composed by 1,6-hexanediamine and terephthalic acid, 20-35 wt.-% 6I-units, composed by 1,6-Hexandiamin and isophthalic acid, and 3-15 wt.-% 612-units, composed by 1,6-hexanediamine and dodecandioic acid.
It is to be noted that the term “polyamide” is a generic term, which comprises both homopolyamides and copolyamides. The abbreviated polyamide nomenclature conforms to the norm ISO 16396-1 (2015 April). The diamine 2-methyl-1,5-pentanediamine is abbreviated as MPMD. The diamine 2-methyl-1,8-octanediamine is abbreviated as MOD.
Component (B)—Second Polyamide
The inventive moulding compositions comprise, as component (B), from 0 to 10% by weight, preferably 1.0 to 10% by weight, more preferably from 2.0 to 10% by weight, more preferably from 2.0 to 7.0% by weight, more preferably from 2.0 to 6.0% by weight, and in particular from 2.5 to 6.0% by weight, of a polyamide different from component (A).
Polyamide (B) preferably is selected from the group consisting of partially crystalline polyamides (B1), based on aliphatic or araliphatic diamines and aliphatic dicarboxylic acids, and amorphous polyamides (B2), based on cycloaliphatic or aromatic dicarboxylic acids or on cycloaliphatic or aromatic diamines.
Polyamide (B1) is preferably selected from the group consisting of PA 46, PA 56, PA 6, PA 66, PA 6/66, PA 69, PA 610, PA 612, PA 614, PA 1010, PA 1012, PA 1014, PA 1212, PA 11, PA 12, PA 6/12, PA MXD6, PA MXD10 and also copolymers and mixtures thereof. In particular polyamide (B1) is PA 6, PA 66 or PA 6/12 and also copolymers and mixtures thereof. Polyamides of component (B1) are characterized in that the melting enthalpy determined according to DIN EN ISO 11357-3 (2013) with a heating rate of 20 K/min is at least 20 J/g, perferably in the range of 20 to 70 J/g.
Polyamide (B2) is preferably selected from the group consisting of PA 51, PA 6I, PA DI (D=2-methyl-1,5-pentandiamine), PA 5I/5T, PA DI/DT, PA 6T/6I, PA5I/5T/6I/6T, PA 5I/5T/DI/DT, PA6I/6T/DI/DT, PA 6I/101, PA 10I/10T, PA MXDI, MXD6/MXDI, PA MACM10, PA MACM12, PA MACM14 and also copolymers and mixtures thereof. In particular PA 5I/5T, PA DI/DT or PA 6T/6I are preferably used as polyamide (B2). In case that the polyamide (B) is derived from isophthalic and terephthalic acid, it is preferred that the molar ratio of isophthalic acid:terephthalic acid is 51 to 100:49 to 0 (mol-%), most preferred 60 to 80:40 to 20 (mol-%), whereby a ratio of 1/(I+T)=100 mol-% means, that in the considered polyamide (B2) exclusively isophthalic acid is used. Polyamides (B2) are characterized in that the melting enthalpy determined according to DIN EN ISO 11357-3 (2013) with a heating rate of 20 K/min is less than 8 J/g, perferably less than 5 J/g.
Polyamide (B) preferably has a solution viscosity ηrel measured according to DIN EN ISO 307:2013-08 on solutions of 0.5 g polymer in 100 mL m-cresol at a temperature of 20° C., of a maximum of 2.7, preferably a maximum of 2.3, especially a maximum of 2.0. Polyamides (B) having a solution viscosity ηrel in the range from 1.5 to 2.3, especially in the range from 1.6-2.0 are preferably preferred.
Component (C)—Fibers
The fiber reinforcing agent (component (C)) is preferably comprised in an amount of 25 to 50% by weight, more preferably in an amount of 30 to 45% by weight.
According to another preferred embodiment of the proposed polyamide moulding compound, reinforcing agents of component (C) are fibers, in particular glass and/or carbon fibers, where short fibers, preferably with a length in the range of 2-50 mm and/or endless fibers (rovings), each with a diameter of 5-40 microns, are preferably used and where in particular fibers having a circular and/or noncircular cross section are used, where in the latter case the cross-sectional aspect ratio (long axis of cross section to secondary axis) is in particular >2.
Glass fibers having a noncircular cross section and a cross-sectional aspect ratio greater than 2, preferably 3-8, especially 3-5, are preferably used. These so-called flat glass fibers have an oval, elliptical, elliptical with constrictions (so-called “cocoon” [or “peanut”] fiber), rectangular, or nearly rectangular cross-sectional area.
The flat glass fibers in accordance with the invention that have a noncircular cross-sectional area are preferably used as short glass fibers (chopped strands; cut glass with a length of 0.1-50 mm, preferably 0.2-20 mm, more preferably 2-12 mm).
Another preferred characteristic of the flat glass fibers that are used is that the length of the main (long) cross-sectional axis lies preferably in the range of 6-40 microns, especially in the range of 15-30 microns, and the length of the secondary cross-sectional axis lies in the range of 3-20 microns, especially in the range of 4-10 microns. Mixtures of glass fibers with circular and noncircular cross sections can also be used to strengthen the moulding compounds in accordance with the invention, where the amount of flat glass fibers as defined above is preferably predominant, i.e., more than 50 wt.-% of the total weight of the fibers.
Especially preferred are the so-called flat glass fibers with a cross-sectional aspect ratio of 3-5. In particular, E glass fibers are used in accordance with the invention. However, all other types of glass fibers such as A, C, D, M, S and R glass fibers or any mixtures thereof or mixtures with E glass fibers can be used.
In the case of moulding compounds reinforced with endless fibers having circular cross-section (rovings), higher toughness result and thus properties that are still more metal-like properties result if, instead of the conventional endless glass fibers having diameters of 15-19 microns, ones with diameters of 10-14 microns, especially ones with diameters of 10-12 microns are used.
The polyamide moulding compounds in accordance with the invention can be prepared by the known methods for preparation of long fiber-reinforced rod-shaped pellets, in particular by pultrusion processes, in which the endless fiberstrand (roving) is thoroughly soaked with the polymer melt and then chilled and chopped.
The long fiber-reinforced rod-shaped pellets obtained in this way, which preferably have a pellet length of 3-25 mm, especially 4-12 mm, can be further processed into moulded objects using the conventional processing methods such as injection moulding or pressing.
The endless carbon fibers used in the pultrusion process have a diameter of 5-10 microns, preferably 6-8 microns. To improve matrix binding and fiber handling, the fibers can be coated with chemically different layers, as are known in the prior art for glass and carbon fibers.
The glass fibers themselves, independent of the shape of the cross-sectional surface and length of the fibers, can be chosen from the group consisting of E glass fibers, A glass fibers, C glass fibers, D glass fibers, M glass fibers, S glass fibers, and/or R glass fibers, where E glass fibers are preferred.
Component (D)—Azine Dye
The inventive moulding compositions comprise, as component (D), from 0.2 to 2.0% by weight, preferably from 0.3 to 2.0% by weight, preferably from 0.3 to 1.5% by weight, preferably from 0.3 to 1.0% by weight, and in particular from 0.35 to 1.0% by weight, of an azine dye, especially nigrosine.
Nigrosines are generally a group of blue, black or gray phenazine dyes (azine dyes) related to the indulines and taking various forms (water-soluble, oleo-soluble, spirit-soluble), used in wool dyeing and wool printing, in black dyeing of silks, and in the coloring of leather, of shoe creams, of varnishes, of plastics, of stoving lacquers, of inks, and the like, and also as microscopy dyes.
Synthesis of the nigrosine dye can be achieved by, for example, oxidizing and dehydrate-condensing aniline, aniline hydrochloride and nitrobenzene by heating them in the presence of metallic iron or copper and metal salts like iron chloride (FeCl3) at a reaction temperature of 160 to 180° C. (the name being derived from the Latin niger=black). Nigrosine is produced as a mixture of various different compounds depending on reaction conditions, raw materials charged, charge ratio and the like; for example, it is postulated that nigrosine may be a mixture of various triphenazineoxazines and phenazineazine compounds.
Component (D) can be used in the form of free base or else in the form of salt (e.g. hydrochloride).
As the nigrosine (component (D)) of the present invention, the black azine-series mixture described as C.I. Acid Black 2, C.I. SOLVENT BLACK 5, C.I. SOLVENT BLACK 5:1, C.I. SOLVENT BLACK 5:2 and C.I. SOLVENT BLACK 7 in the COLOR INDEX can be suitably used (in this specification, C.I. Generic Names are described according to the third edition of the COLOUR INDEX).
Examples of commercially available nigrosine dyes include Spirit Black SB, Spirit Black SSBB, Spirit Black AB (all are categorized under C.I. SOLVENT BLACK 5); Nigrosine Base SA, Nigrosine Base SAP, Nigrosine Base SAP-L, Nigrosine Base EE, Nigrosine Base EE-L, Nigrosine Base EX, Nigrosine Base EX-BP (all are categorized under C.I. SOLVENT BLACK 7) and the like [all are products by Orient Chemical Industries, Ltd.].
It is preferably used C. I. SOLVENT BLACK 7 (CAS No 8005-02-5).
A volume average particle size Dv50 (or X50) according to ISO 13320:2009 of nigrosine as component (D) is preferably ranging from 5 to 20 microns, and it is furthermore preferably ranging from 5 to 15 microns. When the above nigrosine is used in the present invention, the assist injection moulding procedure is easily performed and hollow articles with reduced roughness of the inner surface are prepared.
In particular nigrosine can be introduced into the inventive moulding composition as masterbatch or concentrate, preferably on base of polyamides (B), preferably polyamides (B1) whereby the content of nigrosine is preferably in the range of 20 to 40 wt.-%. As base of these masterbatches the aliphatic polyamides PA6, PA66, PA6/12 or mixtures thereof are preferred.
Concentration of iron in nigrosine is for example less than 1 weight %, preferably less than 0.5 weight %, furthermore preferably less than 0.4 weight %. This improves dispersibility or compatibility of nigrosine as color for the resin and therefore the quality of assisted injection moulded articles made from the resin.
Concentration of aniline in nigrosine is for example less than 1 weight %, preferably less than 0.5 weight %, furthermore preferably not more than 0.4 weight %.
Component (E)—Heat Stabilizer
The thermoplastic moulding compounds in accordance with the invention contain as component (E), 0.1-3.0 wt.-%, preferably 0.2-2.0 wt.-%, especially preferably 0.2-1.5 wt.-%, especially preferred 0.3 to 1.0 wt.-% of at least one heat stabilizer or thermostabilizer which preferably is selected from the group consisting of compounds of mono- or divalent copper, stabilizers based on secondary aromatic amines, stabilizers based on sterically hindered phenols, phosphites, phosphonites, metal salts or metal oxides, whereby in particular the metal is copper and mixtures of the above-mentioned stabilizers.
In a preferred embodiment the thermal stabilizers (component (E)) are chosen from the group consisting of
Especially preferred examples of stabilizers based on secondary aromatic amines that can be used in accordance with the invention are adducts of phenylenediamine with acetone (Naugard A), adducts of phenylenediamine with linolene, Naugard 445, N,N′-dinaphthyl-p-phenylenediamine, N-phenyl-N′-cyclohexyl-p-phenylenediamine or mixtures of two or more thereof.
Preferred examples of stabilizers based on sterically hindered phenols that can be used in accordance with the invention are N,N′-hexamethylenebis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, bis(3,3-bis(4′-hydroxy-3′-tert-butylphenyl)butanoic acid) glycol ester, 2,1′-thioethylbis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, or mixtures of two or more of these stabilizers.
Preferred phosphites and phosphonites are triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl))pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. Especially preferred are tris[2-tert-butyl-4-thio-(2′-methyl-4′-hydroxy-5′-tertbutyl)phenyl-5-methyl) phenyl phosphite and tris(2,4-di-tert-butylphenyl)phosphite (Hostanox® PAR24, commercial product of Clariant, Basel).
An especially preferred embodiment of the thermostabilizer consists of the combination of organic heat stabilizers (in particular, Hostanox PAR 24 and Irganox 1010), a bisphenol A-based epoxide (in particular, Epikote 1001), and a copper stabilizer based on CuI (copper iodide) and KI (potassium iodide). Thermal stabilization exclusively on the basis of CuI and KI is especially preferred.
Besides the addition of organic heat stabilizers and/or copper or copper compounds, the use of other transition metal compounds, especially metal salts or metal oxides of groups VB, VIIB, VIIB or VIIIB of the periodic table, is preferably excluded. Moreover, preferably no transition metals of the groups VB, VIIB, VIIB or VIIIB of the periodic table such as iron or steel powders, are added to the moulding compound in accordance with the invention.
Component (F)—(Additives, Different from Components A to E)
It is further preferred that the moulding composition comprises 0-10% by weight of at least one additive, different to any of the components A to E, which is selected from the group consisting of UV- and light-stabilisers, lubricants, coloring- and marking materials, inorganic pigments, organic pigments, IR absorbers, antistatic agents, antiblocking agents, crystal-growth inhibitors, condensation catalysts, chain extenders, defoamers, chain-lengthening additives, conductivity additives, carbon black, graphite, carbon nanotubes, mould-release agents, separating agents, flame retardants, non-halogen-containing flame retardants, anti-dripping-agents, impact modifiers, optical brighteners, photochromic additives, metallic pigments, nucleating agents, like PA22, minerals, clay minerals, talc, in particular magnesium silicate, kaolin or kaolinite and particulate fillers like silicates, wollastonite, zeolite, sericite, kaolin, mica, clay minerals, pyrophyllite, bentonite, asbestos, talc, aluminosilicate, aluminium oxide, silicon oxide, metal carboxylate, such as calcium carbonate, magnesium carbonate, dolomite, calcium sulfate and, magnesium hydroxide, calcium hydroxide, and aluminium hydroxide, glass beads, ceramic beads, boron nitride or silicon carbide.
The at least one additive is preferably comprised in an amount of 0 to 7.0% by weight, more preferably 0.1 to 4.0% by weight.
In particular preferred is a polyamide moulding composition which is free of carbon black.
Most preferred is a polyamide moulding composition which consists of the following components:
Moreover, the present invention provides a method for the production of a moulded article as well as a moulded article which is producible from the above-described moulding composition. Such moulded article is manufactured by extrusion, extrusion blow moulding or injection moulding, preferably by an assisted injection moulding process, especially gas or liquid assisted injection moulding process, and is preferably partially hollow or hollow. The present invention also relates to moulded articles which are producible or produced from the polyamide moulding compositions according to the invention. Preferably, these moulded articles are produced by the method according to the invention as described above.
In particular the moulded articles of the present invention includes tubes or tube sections, connectors, fittings, intakes or outlets, housings or covers with integrated connectors, pipes, fittings, intakes or outlets, or pellets. These can be used in particular in the automotive field e.g. for parts of the air intake system, the charger system or for the automotive coolant circuit.
According to a especially preferred embodiment the surface of the moulded articles is very smooth. That is, at least a part of the surface has a roughness measured according to DIN EN ISO 4287 (2010 July) with Ra values of less than 4.2 μm, preferably less than 4 μm, especially preferred less than 4.0 μm and/or Rz values of less than 25 μm, preferably less than 20 μm, especially preferred of less than 18 μm. A part of the surface of the moulded article especially includes the inner surface of a hollow article, e.g. the inner surface of an article which has been produced by means of assisted injection moulding methods.
Surprisingly it could be demonstrated that the articles according to the invention have
Furthermore the inventive moulding compositions show a very good processability and high flow ability, especially regarding to assist injection moulding processes, allowing to produce moulded articles with thinner walls (reduced thickness) and/or a higher aspect ratio (longer parts). Due to the improved inner surface quality hollow moulded articles according to the invention have a reduced friction regarding the medium (fluid) flowing through such an article and show none or a reduced glass fiber debonding from the inner surface during the use.
To produce the polyamide moulding composition the components (A) to (F) were compounded on typical compounding machines, e.g. single- or twin-screw extruders or screw kneaders. The dried component (A), (B), (D), (E) and (F) will be preferably metered via a gravimetric metering scale into the intake. Component (C) can be metered via a gravimetric metering scale into the in-take or via a side feeder into the molten component (A). Components (C) and if necessary (D) can be metered separately into the intake or via a side feeder into the molten component (A). Components (A), (B), (D) and (F) can also be metered into the intake in form of dry blends. (D) can also be used in form of a concentrate (masterbatch), preferably on base of polyamides (B), more preferably on base of polyamides (B1).
The compounding is performed at set cylinder temperatures of preferably 70 to 100° C. for the first cylinder and depending on the nature of component (A) 300 to 370° C. for the remaining cylinders. Vacuum can be applied or degassing can be performed to the atmosphere before the nozzle. The melt is extruded in strand form, cooled down in a water bath at 10 to 90° C. and subsequently pelletized. The pellets are dried for 12 to 24 hours at 80 to 120° C. under nitrogen or in vacuum to a water content of less than 0.1 wt.-%.
The present invention is described in more detail by the following examples.
The following measuring specifications were used to analyse the polyamides and test the polyamide moulding compounds. If not noted elsewhere the test pieces were analysed dry as moulded.
Relative Viscosity (RV or ηrel, both terms are interchangeably used):
ISO 307:2013-08
Pellets
0.5 g in 100 ml m-cresol
Temperature 20° C.
Calculation of the relative viscosity according to RV=t/t0
Melting Point, Melting Enthalpy (Heat of Fusion):
ISO 11357-3:2013-04
Pellets
Differential scanning calometry (DSC) was performed at a heating rate of 20 K/min. For the melting point, the temperature was specified at the peak maximum.
HDT (Heat Deflection Temperature):
ISO 75-1:2013-04, ISO 75-2:2013-04
ISO test bar, standard: ISO/CD 3167, type B1, 80×10×4 mm (flatwise)
HDT A load 1.80 MPa
Tensile Modulus, Tensile Strength, Elongation at Break:
ISO 527
ISO tension bar, standard: ISO/CD 3167, type A1, 170×20/10×4 mm
Testing speed 1 mm/min for Tensile Modulus, 5 mm/min for Tensile Strength and Elongation at Break
Temperature 23° C.
Charpy Impact Strength:
ISO 179/eU
ISO test rod, standard: ISO/CD 3167, type BI, 80×10×4 mm, temperature 23° C.
Charpy Notched Impact Strength:
ISO 179/eA
ISO test rod, standard: ISO/CD 3167, type BI, 80×10×4 mm, temperature 23° C.
Izod Impact Strength
ISO 180 (Method 180/A)
ISO test rod, standard: ISO/CD 3167, type BI, 80×10×4 mm, temperature −40° C.
Hydrolytic Resistance
Before testing, the test pieces were stored at a temperature of (+23±5) ° C. for at least 8 h and shall be free from strain during this period. The tests on unaged test pieces (Stress at Break ISO 527-1, Strain at Break ISO 527-1 and Charpy Impact Strength at +23° C. ISO 179-1/1 eU) were performed on dry as moulded test specimen.
The other test pieces were stored in a mixture of glycol (LLC) and water (1:1) in an autoclav for 504/1008 hours (test time) at 140° C. (test temperature). As glycol VW coolant G13 pursuant to VW TL 774 J was used. After test time the test specimens were cooled down in the test medium to (+23±5) ° C. Then the test specimens were removed from the test medium, rinsed with water and wiped dry with a cotton cloth. After cleaning the test specimen were stored in a desiccator. Within 7 days (maximum) after the storage in the autoclav the properties Stress at Break ISO 527-1, Strain at Break ISO 527-1 and Charpy Impact Strength at +23° C. ISO 179-1/1 eU were determined.
Surface Roughness
The roughness measurement was performed on samples manufactured by assisted injection moulding processes according to DIN EN ISO 4287 (2010 July) by using a Mahrsurf XR1 Surface Measuring Station. Before determining the roughness profil of the inner surface along injection direction, the hollow test samples (tubes) were cut into halves in longitudinal direction of the tubes. The mean roughness depth Rz was calculated by measuring the vertical distance from the highest peak to the lowest valley within five sampling lengths (Rzi), then averaging these distances.
Production of Moulding Compositions
The moulding compositions having the compositions in Tables 2 and 3 were produced on a twin-screw extruder from Toshiba Machine Co., Ltd. Modell TEM-37BS. The components A, B and D to F were metered into the feed zone. The glass fibres (C) were metered into the polymer melt by means of a side feeder 3 barrel units upstream of the die. The barrel temperature was set as rising profile up to 340° C. for the examples E1-E8 and comparison examples CE4-CE8 and up to 300° C. for the comparison tests CE1-CE3. A throughput of 10 kg/h was achieved at a revolution speed of 120 to 200 rpm. Degassing was performed to the atmosphere before the nozzle. The compounded materials were discharged as strand from a die of diameter 3 mm and pelletized after water cooling. After pelletizing and drying for 24 h at 110° C. in vacuum (30 mbar) to a water content of less than 0.1 wt.-%, the properties of the pellets were measured and the test samples were produced.
Production of Test Pieces
The test pieces for the tensile test and HDT test were produced on an injection moulding machine by the Arburg Company, Modell Allrounder 420 C 1000-250. For polyamide 6T/6I compounds or polyamide 6T/66 compounds increasing cylinder temperatures from 310° C. to 340° C. were thereby used. The moulding temperature was 130 to 150° C. For polyamide 66 compounds or polyamide 6 compounds increasing cylinder temperatures from 260° C. to 290° C. were thereby used. The moulding temperature was 70 to 90° C.
The test bodies were used in a dry state, they were stored for this purpose after the injection moulding for at least 48 h at room temperature in a dry environment, i.e. over silica gel.
The hollow test pieces (25×3×200 mm tube) were produced on an gas or water assisted injection moulding machine Maximator WD/300/1.5/2/U. For polyamide 6T/6I compounds or polyamide 6T/66 compounds increasing cylinder temperatures from 310° C. to 340° C. were thereby used. The melt resin temperature was 330° C. and moulding tool temperature was 95° C. or 130° C. Gas assist: Speed 50 cm3/s at a pressure of 30 bar. Water assist: Speed 100 ml/s at a pressure of 350 bar.
For the preparation of the polyamide moulding compositions the following materials were used (s. Table 1):
Table 2 and 3 show the analytical results of the inventive and comparative examples.
1)0: none voids are observed, 1: few, small voids, 2: serveral large voids are observed
2)504 h storage in a mixture of LLC (Long Life Coolant) and water (1:1) at 140° C.
1)0: none voids are observed, 1: few, small voids, 2: serveral large voids are observed
2)504 h storage in a mixture of LLC (Long Life Coolant) and water (1:1) at 140° C.
1)0: none voids are observed, 1: few, small voids, 2: serveral large voids are observed
2)504 h storage in a mixture of LLC (Long Life Coolant) and water (1:1) at 140° C.
3)Reproduction of Example 21 (table 5B) of US2013/0338261A1
4)Reproduction of example 47 (table 11) of US2013/0338261A1
For the comparative examples 9-12 the following compounds were used:
The effect of the invention further is demonstrated in the following figures.
As can be seen from the figure, virtually no glas fibers at all are present at the surface. The surface is fully covered by the polyamide matrix material. Therefore, a high surface smoothness can be realized.
In contrast,
As can be seen, a numerous isolated glass fibers, which are not fully integrated into the polyamide matrix are present at the surface. These more or less exposed glass fibers contribute to the reduced surface smoothness, furthermore, these exposed glass fibers are subject to abrasion or extraction (glass fiber debonding).
In comparison to the inventive examples CEx.9 and 10 are cearly inferior with respect to heat deflection temperature, hydrolytic resistance and quality of the inner surface.
| Number | Date | Country | Kind |
|---|---|---|---|
| 16168402.2 | May 2016 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/060679 | 5/4/2017 | WO | 00 |
