Title of Invention	"COMPOSITIONS FOR MOULDED ARTICLES"
Abstract	The present invention relates to theremoplastic molding composition comprising a thermoplastic polymer, graft polymer and special additive mixtures.

Full Text

The present invention relates to a thermoplastic molding composition. The subject of the present invention are compositions containing matrix polymer, graft polymer and special additive mixtures, their use for the production of moulded articles, as well as the moulded articles obtainable therefrom. The subject of the invention is also the additive combination. ABS moulding compositions have already been used for many years in large quantities as thermoplastic resins for the production of all types of moulded parts. The property spectrum of these resins ranges from relatively brittle to extremely tough. A special area of use of ABS moulding compositions is the production of moulded parts by injection moulding (e.g. housings, toys, vehicle parts), an important factor being in particular a very good flowability of the polymer material. Also, the moulded parts produced in this way must as a rule have a good notched-bar impact strength as well as a good resistance to thermal stresses. The object therefore exists of achieving, for a given rubber content, a given rubber particle size and given matrix resin molecular weight, toughness values that are as high as possible while retaining the good thermoplastic flowability. In this connection the high toughness values .should as far as possible be obtained independently of the type of matrix resin that is employed, and especially when using the styrene/acrylonitrile copolymers and α-methylstyrene/acrylonitrile copolymers typical of ABS. One possible way of improving the toughness of ABS polymers with a given rubber content, given rubber particle size and given matrix molecular weight is to add special silicone oil compounds (see EP-A 6521); however, disadvantages may arise such as poor paintability, unsatisfactory prmtability or impaired yield stress values (danger of stress whitening). The addition of minor amounts of EPDM rubber (see BP-A 412 370) or AES polymer (see EP-A 412 371) has also been described. Both methods require the use of considerable amounts of relatively expensive additive components however. The use of large amounts of individual low molecular weight additive components may m special cases improve the processability, although this is normally offset by a negative effect on other properties such as for example toughness, modulus of elasticity and thermal stability It has now been found that by using special additive mixtures, ABS products can be obtained having a very good combination of notched-bar impact strength (at room temperature as well as at low temperatures) and excellent processability. The invention provides thermoplastic moulding compounds or compositions containing A) 5 to 95 wt.%, preferably 10 to 90 wt.% and particularly preferably 20 to 75 wt.% of one or more thermoplastic homopolymers, copolymers or terpolymers of styrene, α-methylstyrene, nuclear-substituted styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide or mixtures thereof, B) 5 to 95 wt.%, preferably 10 to 90 wt.% and particularly preferably 25 to 80 wt.% of one or more graft polymers of B.l) 5 to 90 parts by weight, preferably 20 to 80 parts by weight and particularly preferably 25 to 60 parts by weight of styrene, cc-methylstyrene, nuclear-substituted styrene, methyl methacrylate, acrylonitrile, methacrylomtrile, maleic anhydride, N-substituted maleimide or mixtures thereof, on B 2) 95 to 10 parts by weight, preferably 80 to 20 parts by weight and particularly preferably 75 to 40 parts by weight of at least one rubber having a glass transition temperature of ≤10°C and C) 0 05 to 10 parts by weight, preferably 0.1 to 8 parts by weight and particularly preferably 0.5 to 5 parts by weight, in each case per 100 parts by weight of A) + B), of a combination of at least 3 components selected from compounds I), II), III) and IV), wherein I) denotes a compound with at least one structural unit (Structure Removed) where M = metal, preferably Mg, Ca, Zn n = valency of the metal M, preferably 1 or 2 II) denotes a compound with at least one structural unit (Structure Removed) and at least one structural unit III) denotes a compound with at least one structural unit (Structure Removed) IV) denotes a compound with structural units that are different from the specified structural units or combination of structural units contamed in the compounds (I) to (III), 1 e the compound (IV) contains no structural unit from the structural units or combmation of structural units contained m the compounds (I) to (III) Preferably each of the compounds I) to IV) contains at least one terminal aliphatic C6-C32 hydrocarbon radical. According to the mvention suitable thermoplastic polymers A) are those of styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, halogenated styrene, methyl acrylate, methyl methacrylate, acrylonitnle, maleic anhydride, N-substituted maleimide or mixtures thereof The polymers A) are resin-like, thermoplastic and rubber-free Particularly preferred polymers A) are those of styrene, methyl methacrylate, styrene/acrylonitrile mixtures, styrene/acrylonitrile/methyl methacrylate mixtures, styrene/methyl methacrylate mixtures, acrylonitrile/methyl methacrylate mixtures, α-methylstyrene/acrylonitrile mixtures, styrene/α-methylstyrene/acrylonitrile mixtures, α-methylstyrene/methyl methacrylate/acrylomtnle mixtures, styrene/a-methylstyrene/methyl methacrylate mixtures, styrene/α-methylstyrene/methyl methacrylate/acrylomtnle mixtures, styrene/maleic anhydride mixtures, methyl methacrylate/maleic anhydride mixtures, styrene/methyl methacrylate/maleic anhydride mixtures, and styrene/acrylonitrile/N-phenyhnalermide mixtures. The polymers A) are known and can be produced by free-radical polymerisation, m particular by emulsion, suspension, solution or bulk polymerisation. The polymers preferably have molecular weights Mw of 20,000 to 200,000 and mtrinsic viscosities (n) of 20 to 110 ml/g (measured m drmethylformamide at 25°C) Suitable rubbers for the production of the graft polymers B) are in particular polybutadiene, butadiene/styrene copolymers, butadiene/acrylomtnle copolymers, polyisoprene or alkyl acrylate rubbers based on C1-C8 alkyl acrylates, in particular ethyl acrylate, butyl acrylate and ethylhexyl acrylate The acrylate rubbers may optionally contain up to 30 wt % (referred to the rubber weight) of monomers such as vinyl acetate, acrylonitrile, styrene, methyl methacrylate and/or vinyl ether incorporated by copolymerisation. The acrylate rubbers may also contain small amounts, preferably up to 5 wt.% (referred to the weight of rubber) of crosslrnking, ethylenically unsaturated monomers incorporated by polymerisation. Crosslinking agents are for example alkylene diol diacrylates and methacrylates, polyester diacrylates and methacrylates, divinyl benzene, trivinyl benzene, triallyl cyanurate, allyl acrylate and methacrylate, butadiene and isoprene Graft bases may also be acrylate rubbers with a core/shell structure, with a core of crosslinked diene rubber of one or more conjugated dienes such as polybutadiene, or a copolymer of a conjugated diene with an ethylenically unsaturated monomer such as styrene and/or acrylonitrile. Further suitable rubbers are for example the so-called EPDM rubbers (polymers of ethylene, propylene and a non-conjugated diene such as for example dicyclopentadiene), EPM rubbers (ethylene/propylene rubbers) and silicone rubbers that may optionally have a core/shell structure. Preferred rubbers for the production of the graft polymers B) are diene rubbers and alkyl acrylate rubbers as well as EPDM rubbers The rubbers in the graft polymer B) are present in the form of at least partially crosslinked particles having a mean particle diameter (d50) of 0.05 to 20 jam, preferably 0 1 to 2 urn and particularly preferably 0.1 to 0 8 urn The mean particle diameter d50 is determined by ultracentrifuge measurements according to W Scholtan et al, Kolloid-Z u.Z Polymere 250 (1972), 782-796, or by evaluating electron microscope images. The polymers B) may be produced by free-radical graft polymerisation of the monomers B.l) in the presence of the rubbers B 2) to be grafted on. Preferred processes for producing the graft polymers B) are emulsion, solution, bulk or suspension polymerisation and combinations known per se of these processes Particularly preferred graft polymers B) are ABS polymers Most particularly preferred polymers B) are products that have been obtained by free-radical polymerisation of mixtures of styrene and acrylonitnle, preferably in a weight ratio of 10.1 to 1.1, particularly preferably in a weight ratio of 5 1 to 2-1, in the presence of at least one rubber built up predominantly from diene monomers (preferably polybutadiene that may contam up to 30 wt.% of styrene and/or acrylonitnle incorporated as comonomers) and having a mean particle diameter (d50) of 100 to 450 nm, most particularly preferably in the presence of two rubbers built up predominantly from diene monomers (preferably polybutadiene that may contam up to 30 wt.% of styrene and/or acrylonitnle incorporated as comonomers) and having a) a mean particle diameter (d50) of 150 to 300 nm and b) a mean particle diameter (d50) of 350 to 450 nm, in a weight ratio (a) (b) = 10-90 to 90.10, preferably 30:70 to 60.40. The rubber content of the polymers B) is preferably 40 to 95 wt.%, particularly preferably 50 to 90 wt.% and most particularly preferably 55 to 85 wt.%. As individual components of the additive mixture C) the following compounds are for example and preferably suitable As component I)- magnesium stearate, calcium stearate, zinc stearate, magnesium montanate, calcium montanate, zmc montanate, magnesium behenate, calcium behenate, zinc behenate, magnesium oleate, calcium oleate, zmc oleate, magnesium stearate and/or calcium stearate are preferred, magnesium stearate being particularly preferred As component II) esters of p-thiodipropionic acid, such as for example and preferably, lauryl, stearyl, myristyl or tndecyl esters of P-thiodipropionic acid, pentaerythritol-tetrakis-(P-dodecylmercapto)-propionate, compounds of the formula (V) in which (Structure Removed) R, R1 and R2 independently of one another denote C1-C20 alkyl, phenyl radicals that may be substituted by one or two C1-C8 alkyl groups, C7-C12 aralkyl radicals, or C5-C12 cycolalkyl radicals, R3 denotes H or C1-C4 alkyl. The compounds of the formula (V) can be produced according to the procedure given in EP-A 64 020 Preferred are esters of p-thiodipropionic acid, and particularly preferred are lauryl esters or stearyl esters of P-tmodiopropionic acid or mixtures thereof. As component III) ethylenediamme bisstearyl amide, erucic acid amide, oleic acid amide, .stearic acid amide, behemc acid amide, montanic acid amide; ethylenediamine bisstearyl amide and/or erucic acid amide are preferred, ethylenediamme bisstearyl amide being particularly preferred As component IV) paraffin oils, hydrocarbon waxes, low molecular weight polystyrene produced by using C8-C18 alkyl mercaptans as molecular weight regulators with mean molecular weights (M)w between 2,000 and 15,000, preferably between 2,500 and 12,000 and particularly preferably between 3,000 and 10,000, low molecular weight styrene/acrylonitrile copolymer produced by using C8-C18 alkyl mercaptans as molecular weight regulators with mean molecular weights (M)w between 2,000 and 15,000, preferably between 2,500 and 12,000 and particularly preferably between 3,000 and 10,000, low molecular weight α-methylstyrene/acrylonitnle copolymer produced by usmg C8-C18 alkyl mercaptans as molecular weight regulators with mean molecular weights (M)w between 2,000 and 15,000, preferably between 2,500 and 12,000 and particularly preferably between 3,000 and 10,000, low molecular weight polymethyl methacrylate produced by using C8-C18 alkyl mercaptans as molecular weight regulators with mean molecular weights (M)w between 2,000 and 15,000, preferably between 2,500 and 12,000 and particularly preferably between 3,000 and 10,000, C6-C32 alkanols, e g. stearyl alcohol, and C6-C32 alkenols, e g. oleyl alcohol. Preferred are paraffin oils, low molecular weight styrene/acrylonitrile copolymers and α-methylstyrene/acrylomtrile copolymers; particularly preferred are paraffin oils and/or low molecular weight styrene/acrylonitrile copolymers. Preferably all the components I), II), III), and IV) have a molecular weight above 300, preferably above 400 and particularly preferably above 500 The quantitative ratios for the use according 10 the invention of at least three components selected from the components I), II), III), and IV) may be varied within wide ranges The ratios are selected so that the following relationship is observed (Formula Removed) Particularly preferred mixtures contain 15 to 65 wt.% of graft polymer of 25 to 60 parts by weight of styrene, α-methylstyrene, acrylonitnle, N-phenylmaleimide or mixtures thereof on 75 to 40 parts by weight of polybutadiene, 85 to 35 wt % of thermoplastic copolymer of 5 to 40 parts by weight of acrylomtnle and 95 to 60 parts by weight of styrene, α-methylstyrene, N-phenylmaleimide or mixtures thereof, and 0.5 to 5 parts by weight per 100 parts by weight of A+B of a combmation of at least 3 components selected from I) magnesium stearate, II) ß,ß'-thiodipropionic acid dilauryl ester or ß,ß'-thiodipropionic acid distearyl ester, III) ethylenediamrne bisstearyl amide IV) paraffin oil or low molecular weight styrene/acrylonitnle copolymer The mixtures accordmg to the invention containing A), B) and C) and optionally conventional additives such as processing aids, stabilisers, pigments, antistatics and fillers are prepared by mixmg the respective constituents in a manner known per se simultaneously or successively at room temperature or at elevated temperature, following which the resultant mixtures are melt-compounded or melt-extruded at temperatures of 150°C to 300°C in conventional equipment such as internal mixers, extruders or double-shaft screw extruders. The moulding compositions of the present invention may be used to produce moulded articles of all types, in which connection conventional production procedures may be employed, and in particular moulded articles may be produced by injection moulding A further type of processing of the moulding compositions according to the invention is the production of moulded articles by thermoforming from sheets or films previously fabricated by known methods The present invention accordmgly furthermore provides for the production of the compositions according to the invention, as well as moulded articles produced therefrom. The invention also covers the additive combination per se Examples Thermoplastic Resin Al A statistical styrene/acrylonitnle (72 28) copolymer with a Mw of ca. 115,000 determined by GPC (gel permeation chromatography) Thermoplastic Resin A2 A statistical α-methylstyrene/acrylomtrile (72:28) copolymer with a Mw of ca. 75,000 determined by GPC. Graft Polymer Bl Graft product obtained by emulsion polymerisation of 42 wt.% of a styrene/acrylonitrile mixture (weight ratio 73 27) on 58 wt.% of a 1.1 mixture (weight ratio) of two particulate polybutadienes with a) a mean particle diameter (d50) of 290 nm and b) a mean particle diameter (d50) of 420 nm. The product is worked up by coagulating the latex with magnesium sulfate, washing with water, followed by drying in vacuo. Graft Polymer B2 Graft product obtained by emulsion polymerisation of 50 wt.% of a styrene/acrylonitnle mixture (weight ratio 73:27) on 50 wt.% of particulate polybutadiene with a mean particle diameter (d50) of 130 nm. The product is worked up as under B1. Additive C11: magnesium stearate (Barlocher, Munich, Germany) Additive C12: calcium stearate (Barlocher, Munich, Germany) Additive CIII- P,(3'-thiodipropiomc acid dilauryl ester (Irganox PS800®, Ciba Speciality, Basle, Switzerland) Additive CH2 ß,ß'-thiodipropionic acid distearyl ester (Irganox PS802®, Ciba Speciality, Basle, Switzerland) Additive CIII1 ethylenediamine bisstearyl amide (Henkel KG, Dusseldorf, Germany) Additive CIV1: low molecular weight styrene/acrylonitnle copolymer (Mw ≈ 4,200, determined by GPC) produced by free-radical emulsion polymerisation of a mixture of 63.9 parts by weight of styrene, 23.6 parts by weight of acrylonitrile and 12.5 parts by weight of tert.-dodecyl mercaptan. The individual components are compounded in the weight proportions specified in Table 1 m a 1 3 1 capacity internal mixer at temperatures of 160°C to 200°C. The moulded articles are produced m an injection moulding machine at 240°C. The notched-bar impact strength is measured at room temperature (at ) and at -30°C (ak-30°C) according to ISO 180/1A (unit:kJ/m2), and the thermoplastic flowabihty is evaluated by measuring the melt flow index (MVR) according to DIN 53 735 U (umfcm3/10 min). As can also be seen from Table 1, only by usmg the mixtures according to the invention can a very good combination of high toughness even at low temperatures and good processability be obtained. Table 1: Compositions and Test Data of the Moulding Compositions (Table Removed) n b. = not measured WE CLAIM: 1. A thermoplastic molding composition comprising: A) 5 to 95 wt.% of a thermoplastic polymer selected from at least one of the thermoplastic homopolymers, copolymers or terpolymers of styrene, α-methylstyrene, nuclear-substituted styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide or mixtures thereof, B) 5 to 95 wt. % of at least one graft polymer of B.l) 5 to 90 parts by weight of styrene, α-methylstylene, nuclear-substituted styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide or mixtures thereof, on B.2) 95 to 10 parts by weight of at least one rubber having a glass transition temperature of ≤ 10°C and C) 0.05 to 10 parts by weight (per 100 parts by weight of A + B), of a combination of compound II) and at least 2 components selected from compounds I), III) and IV), wherein I) denotes a compound with at least one structural unit (Formula Removed) M - metal, n - valency of the metal M II) denotes a compound with at least one structural unit and at least one structural unit III) denotes a compound with at least one structural unit (Structure Removed) selected from ethylenediamine bisstearyl amine, erucic acid amide, oleic acid amide, strearic acid amide, behenic acid amide or montanic acid amide and IV) denotes a compound with structural units that are different from the specified structural units or combination of structural units contained in the compounds (I) to (III), and selected from: paraffin oils, hydrocarbon waxes, polystyrene produced by using C8-C18 alkyl mercaptans as molecular weight regulators with mean molecular weights (M)W between 2,000 and 15,000, styrene/acrylonitrile copolymer produced by using C8-C18 alkyl mercaptants as molecular weight regulators with mean molecular weights (M)w between 2,000 and 15,000, α-methylstyrene/acrylonrile copolymer produced by using Cs-Cis alkyl mercaptans as molecular weight regulators with mean molecular weights (M)w between 2,000 and 15,000, poly(methyl methacrylate) produced by using C8-C18 alkyl mercaptans as molecular weight regulators with mean molecular weight (M)w between 2,000 to 15,000, C6-C32 alkanols, and C6-C32 alkenols. 2. Compositions as claimed in claim 1, wherein each of the compounds (I) to (IV) contains at least one terminal C6-C32 hydrocarbons radical. 3. Compositions as claimed in claim 1 or 2, wherein compound (I) is selected from magnesium stearate, calcium stearate, zinc stearate, magnesium montanate, calcium montanate, zinc montanate, magnesium behenate, calcium behanate, zinc behenate, magnesium oleate, calcium oleate or zinc oleate. 4. Compositions as claimed in claim 1 or 2, wherein compound (II) is selected from esters of ß-thiodipropionic acid with monohydric alcohols. 5. Compositions as claimed in any one of the preceding claims, wherein the compounds (I) to (IV) are in each case selected from: Compound (I): magnesium stearate, calcium stearate, Compound (II); |auryl ester of ß-thiodiproptonic acid, stearyl ester of ß-thlodipropionic acid, Compound (III): ethylenediamine bisstearyl amide, erucic acid amide, Compound (IV): paraffin oils, tow molecular weight styrene/ acrylonitrile copolymers, α-methyl styrene/acrylo-nitrile copolymers. 6. Compositions as claimed in any one of the preceding claims, wherein the quantitative ratios of at least three components selected from (I), (II), (III) and (IV) have the following relationship (l)≤(IV)≤(ll)≤(|||)or (I)≤(IV)≤(III)≤{II). 7. Compositions as claimed in any one of the preceding claims, containing 0.5 to 5 parts by weight of C) per 100 parts by weight of A + B. 8. Compositions as claimed in any of the preceding claims, wherein component B.2 is selected from diene or alkyl acrylate rubbers or EPDM rubbers. 9. Compositions as claimed in any of the preceding claims, optionally containing processing aids, stabilisers, pigments, antistatics and/or fillers. 10. Thermoplastic molding composition as claimed in any of the preceding claims as and when used for obtaining moulded articles.

Documents:

331-delnp-2003-abstract.pdf

331-DELNP-2003-Assignment-(30-07-2009).pdf

331-delnp-2003-assignment.pdf

331-delnp-2003-claims.pdf

331-delnp-2003-complete specification (as-fiels).pdf

331-delnp-2003-complete specification (granted).pdf

331-DELNP-2003-Correpsondence-Others.pdf

331-delnp-2003-correpsondence-po.pdf

331-delnp-2003-description (complete).pdf

331-delnp-2003-form-1.pdf

331-DELNP-2003-Form-16-(29-07-2009).pdf

331-delnp-2003-form-18.pdf

331-delnp-2003-form-2.pdf

331-DELNP-2003-Form-3.pdf

331-delnp-2003-form-5.pdf

331-delnp-2003-form-6.pdf

331-DELNP-2003-GPA-(29-07-2009).pdf

331-delnp-2003-gpa.pdf

331-delnp-2003-pct-210.pdf

331-delnp-2003-pct-304.pdf

331-delnp-2003-pct-409.pdf

331-delnp-2003-petition-137.pdf