JPS6071660A - Thermoplastic forming composition based on polysiloxane/polycarbonate block copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides thermoplastic molding compositions based on A1 polydiorganosiloxane/polycarbonate block copolymers and ABS polymers, and B1 polydiorganosiloxane/polycarbonate block copolymers, elastic polymers and young and, if appropriate, thermoplastic molding compositions based on polyalkylene terephthalates.

A.

Thermoplastic mixtures of polycarbonates and ABS polymers based on aromatic dihydroxy compounds are known in principle (German Patent Application No. 1.1 ?).
0.141 and German Patent Application No. 1.810.
(See No. 993). Aromatic polycarbonate and specific AB
The mixture with the S system is described in German Patent Publication Specification No. 25.
9.565, German Patent Application No. 4329
, No. 548 and German Patent Publication Specification No. 4329
．． It is described in No. 546.

This mechanical mixture must meet very high technical requirements. In particular, excellent toughness, particularly low-temperature toughness, and improvement in combustion behavior (drip properties) are required.

Up to now, this type of property improvement has only been achieved by different rubber selections and the addition of flame retardants.

It is therefore surprising that such overall property improvements can be achieved simply by using modified polycarbonates. It is also surprising that when polycarbonates modified with diorganosiloxine blocks are mixed with ABS polymers, molding compositions with good properties are obtained regardless of the Si-blocks.

European Patent Publication No. 0.073.067 discloses a mixture of an aromatic polyester, a siloxane/polycarbonate copolymer and a thermoplastic styrenic resin or a thermoplastic alkyl acrylate resin; No particular claim is made regarding the technical transition to the addition of an alkyl resin.

The present invention provides aromatic polycarbonate and ABS polymer based materials that, when exposed to impact, particularly low temperature impact,
The present invention relates to thermoplastic molding compositions which exhibit improved toughness (notched impact strength) and, at the same time, excellent combustion behavior characterized by a high oxygen index and improved drip properties.

Thus, the present invention provides (α) a weight average molecular weight Mw of 20 to 80%
00-200. OOO, about 75% to 97% by weight.
5% by weight aromatic carbonate structural units and 25% by weight
~25% by weight of the polydiol contains nosiloxane structural units and a polydiorganosiloxane-polycarbonate block copolymer prepared from a polydiorganosiloxane containing α,ω-bishydroxy-aryloxy end groups and having a degree of polymerization Pn of 5 to 100. (b) 70 to 5 parts by weight of a polymer obtained by grafting an ethylenically unsaturated monomer onto a rubber selected from the diene monomer series; and (C) 5 to 60 parts by weight of a vinyl monomer. The present invention relates to a thermoplastic molding composition containing rubber-free thermoplastic polymers from a rubber-free thermoplastic polymer in an amount of (α) + (1!l) + (C) in a total of 100 parts by weight.

Component (a) is also a mixture of a polydiorganosiloxane/polycarbonate block copolymer and a conventional polysiloxane-free polycarbonate, in which the content of polydiorganosiloxane structural units is 2.5 to 25% by weight in the mixture. You can do certain things.

In the present invention, the polydiorganosiloxane/polycarbonate block copolymer (a) is a diphenol, a reactive end group based on a polydiorganosiloxane oligomer having a reactive end group, or a mixture of the same oligomer, a carbonate ester precursor, or It is a reaction product obtained from these reaction products.

Such polydiorganosiloxane/polycarbonate block copolymers are those which contain aromatic polycarbonate structural units (1) in the polymer chain on the one hand and polydiorganosiloxanes containing polyaryloxy groups (2) on the other hand. It is characterized by being.

11 (11 -O-A r -0-C-0-A r -0-RR1 1l l -0-Ar-0(-51-O-)H(-51-O-)2
i-(-5i -111 RR1 -0-) -Ar-0(2) However, in the formula, Ar is the same or different, is an arylene group obtained from diphenol, and R and R1 are the same or different, and linear alkyl branched alkyl, a/L/ )y = /L/, halogenated helical alkyl, rhodanated branched alkyl, aryl or halogenated alinol, but preferably methyl, and The number of diorganosiloxy units n<=α+b+C) is 5 to
1001 preferably 20-80.

In the above formula (1), alkyl Cto-alkyl; in formula (1), alkenyl is, for example, C2-C6-alkenyl, and in formula +11, aryl is C6-CI4 aryl. In the above formula, no-logenation refers to partial or complete chlorination, bromination or fluorination. Alkylalkenyl, aryl,
Alkyl halides and aryl halides include, for example, methyl, ethyl, propyl, n-butyl, tert.
- bif, vinyl, phenyl, naphthyl, chloromethyl, perfluorobutyl, perfluorooctyl, and chlorophenyl.

Polydiorganosiloxane/polycarbonate block copolymers of this type are described, for example, in U.S. Pat.
No. 9.662, U.S. Pat. No. 3,8'21.325
No. 3,832,419. Their improved low temperature mechanical properties are described in the literature [eg B, M.

Beach, R.p., Kambowr and A.R.

5chultz, J., polytn, Sci., pol.
ym.

Lett, Ed, 12 24? (1974)).

A preferred polydiorganosiloxane/polycarbonate block copolymer has an average weight molecular weight Jfw (measured by ultracentrifugation or light scattering) of 10,000 to 200,0.
00, containing about 75% to 97.5% by weight of aromatic carbonate structural units and 25 to 2.5% by weight of diorganosiloxy units, and having α,ω-bishydroxyaryloxy end groups. Organosiloxanes can be prepared by using interfacial polymerization methods (two-ph, α8
eboundary method) [H, Sr, hn
ell.

Chemistry and physics of
Poly-Carbonates (Chemistry and Physics of Polycarbonates), Polymer Rev, Volume 9,
27 pages and more, Interscience pwblisl
Lers (New York)], by reacting the difunctional phenolic reactants in a ratio selected to provide the aromatic carbonate structural unit and diorganosiloxy unit contents of the present invention, respectively.

Polydiorganosiloxanes containing such α,ω-bishydroxyaryloxy end groups are disclosed, for example, in US Pat. No. 3,419,634.

Polyorganosiloxane and polydiorganosiloxane containing α,ω-bishydroxyaryloxy end groups/
Diphenols used in the production of polycarbonate block copolymers include hydroquinone, resorcinol, dihydroxydiphenyl, bis-(hydroxyphenyl)-alkane, bis(hydroxyphenyl)-cycloalkane, bis-(hydroxyphenyl)-sulfide, Bis-
(hydroxyphenyl) ether, bis-(hydroxyphenyl) sulfoxide, bis-(hydroxyphenyl) sulfone and α,ω-bis-(hydroxyphenyl)
- Diisopropylbenzene and their nuclear alkylated and nuclear halogenated products. These and other suitable aromatic dihydroxy compounds are described in U.S. Pat.
028.365 and 2,999,846, and German Patent Application Nos. 4063.050 and 42
No. 11,957.

Examples of preferred diphenols include 2,2-bis-(4-hydroxyphenyl)-furonon, 1,1-bis-(4
-hydroxyphenyl)-cyclohexane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl fiv
)-propane, 2,2-bis-(3,5-dibromo-4
-hydroxyphenyl)-propane, 2,2-bis-(
3,5-dimethyl-4-hydroxyphenyl)-furonokun, bis-(a,S-dimethyl-4-hydroxyphenyl)-methane and hibis-(4-hydroxyphenyl)
It is a sulfide.

Suitable diphenols, alone and in mixtures, branching agents which can be used are compounds having three or more functional groups, especially those having three or more phenolic hydroxyl groups, and - The customary amounts of 0.05 to 2 mol %, based on the diphenol used together, should be maintained.

The production of branched polycarbonates is described, for example, in DE 1.570.533, DE 1.595.762 and US 3.544.514.

Some examples of compounds that have three or more phenolic hydroxyl groups and can be used include 2゜4-bis-(
4-hydroxyphenyl-isopropyl)-phenol, 2,6-bis-(2'-hydroxy-57-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxy phenyl)
-furopane and 1,4-bis-(4,4'-dihydroxytriphenyl-methyl)-benzene. Other trifunctional compounds include 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, 3,3-bis-(4-hydroxyphenyl)-2-oxo-2,3-dihydroindole, and 3,3-dihydroindole. Bis-(4-hydroxy-3-
(Mef-phenyl)-2-oxo-2,3-dihydroindole.

Compounds which can be used as chain terminators in the preparation by interfacial polymerization methods are aromatic compounds containing one functional group, in particular the conventional phenols, such as p-tert, -
Butylphenol, p,-chlorophenol, 2,4
．． 6-driflomphenol and phenol, the amount of which is used is determined by the molecular weight to be toxic in each block copolymer of the invention. Generally, from 0.5 mol % to 10.0 mol % is used, based on the diphenol used.

The graft polymer (b) of the present invention is a rubber containing monomers from the styrene series, methyl methacrylate, or 95-
50% by weight of styrene, α, methylstyrene, methyl methacrylate or mixtures thereof and 5-50% by weight of acrylonitrile, methyl methacrylate, maleic anhydride,
It is obtained by gelasting a mixture with an N-substituted maleimide or a mixture thereof. In particular, suitable rubber
Polybutadiene, a butadiene/styrene copolymer containing up to 30% by weight of styrene as a copolymer unit, a butadiene-acrylonitrile copolymer containing up to 20% by weight of acrylonitrile, or a lower alkyl of acrylic acid or methacrylic acid up to 20% by weight Esters (e.g. methyl acrylate, ethyl acrylate, methyl methacrylate,
and ethyl methacrylate).

Other suitable rubbers are, for example, polyisoprene or polychloroprene. Acrylic acid alkyl ester rubbers based on C, C8 alkyl esters of acrylic acid, especially ethyl, butyl or ethylhexyl acrylate, are also suitable.

These acrylic acid rubbers may, if appropriate, contain up to 30 weight units as copolymerized units and monomers such as vinyl acetate,
Can include acrylonitrile, styrene, methyl methacrylate or vinyl ether. These acrylic rubbers can further contain relatively small amounts (up to 0.50% by weight) of crosslinkable ethylenically unsaturated monomers. Examples of such compounds include acrylic or methacrylic diesters of alkylene diols, diacrylic or dimethacrylic polyesters, di- and trivinylbenzenes,
Triallyl cyanurate, triallyl acrylic acid or methacrylate, butadiene, isoprene, and others. Such alkyl acrylates are known.

The acrylic acid rubbers used as grafting substrates also contain as core material crosslinked diene rubbers consisting of one or more common dienes, such as polybutadiene, or conjugated dienes, ethylenically unsaturated monomers such as styrene and/or Or it can be a product containing a copolymer with acrylonitrile. Examples of other suitable rubbers include EPDM rubbers, ie, rubbers derived from ethylene, propylene, and non-conjugated diene monomers.

Diene monomer rubber or alkyl acrylate rubber is preferred.

The graft copolymer (b) has a weight of 5 to 80% by weight.
~70% by weight of rubber and 95-20% by weight, especially 80-20% by weight
Contains 30% by weight of graft monomer.

The rubber has an average particle size of 0.09 to 5 μm, in particular 0.1 μm, at least partially crosslinked in these graft copolymers.
It exists in the form of particles of ~1 μm.

Graft copolymers of this type are made by radically grafting monomers selected from the series consisting of styrene, alpha-methylstyrene, acrylonitrile, methyl methacrylate, and maleic anhydride in the presence of the rubber to which they are grafted. They are produced by copolymerization and are all known. Preferably, such graft copolymers are produced by emulsion polymerization, solution polymerization, bulk polymerization, or suspension polymerization.

Particular preference is given to so-called ABS polymers.

Rubber-free polymers (C) of vinyl monomers include graft monomers or similar monomers, in particular styrene, α-methylstyrene, halogenostyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, acetic acid. It can consist of at least one monomer selected from the series consisting of vinyl, and N-substituted maleimide.

The polymer preferably has a weight ratio of 95 to 50%,
It is a copolymer consisting of α-methylstyrene, methyl methacrylate, or a mixture thereof, and 5 to 50% by weight of crylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, or a mixture thereof. Such copolymers are often formed as by-products during graft polymerization, especially when large amounts of monomer are grafted onto small amounts of rubber.

In addition to or instead of the copolymer produced in this way, it is also possible to separately produce this type of copolymer and add and mix it. On the contrary, the non-grafted resin portion present in the graft polymer does not necessarily have to be chemically identical to the thermoplastic vinyl polymer (C) added and mixed.

Separately prepared copolymers of this type are resinous, thermoplastic, and rubber-free.

These are in particular copolymers of styrene and/or α-methylstyrene with acrylonitrile, if appropriate also mixed with methyl methacrylate.

A particularly preferred copolymer consists of 20-40% by weight acrylonitrile and 80-60% by weight styrene or alpha-methylstyrene. Such copolymer materials are known, especially by radical polymerization methods, especially emulsion polymerization methods,
It can be produced by suspension polymerization, solution polymerization, or bulk polymerization.

The copolymer is preferably 15,000 to 2X
It has a molecular weight of 10'.

The molding composition of the invention can be obtained by mixing the individual components. In the production method, preferably, the latex of the graft copolymer (b) is first precipitated and dried. The obtained powder is mixed with a polydiorganosiloxane-polycarbonate block copolymer (α) and a separately produced copolymer (C).

For example, roll mills, screw extruders or mixers are suitable for this purpose.

Any of the individual components of the molding composition of the present invention may be a fill agent,
For example, stabilizers, pigments, free-flow agents
cigent), lubricants, mold release agents, antistatic agents and/or flame retardants, or these additives can be added during mixing of the individual components. Suitable additives are those commonly used for thermoplastic polycarbonates, graft copolymers or thermoplastic vinyl polymers.

The molding composition of the present invention can be used for manufacturing all kinds of shaped articles. In particular, shaped articles can be manufactured by injection molding. Molded products that can be manufactured include:
For example, any housing parts (e.g. household appliances,
Examples include fruit juice extractors, coffee makers and mixers) or architectural coverings and automotive parts. The same molding composition also has very good electrical properties not found in other compositions and is used in the field of electrical technology.

In the following examples, the diorganosiloxane/polycarbonate block copolymers shown below were used.

(a,) Block chain length (Pn) based on bisphenol A and 4.5 MB polydimethylsiloxane
40 and a polycarbonate copolymer with a relative viscosity of 1.39 measured at 25° C. at a concentration of 0.5% by weight in methylene chloride,
(α,) A polycarbonate copolymer based on bisphenol A and 10% by weight polydimethylsiloxane and having a block chain length (Pn) of 40 and a relative viscosity of 1.29.

(αS) bisphenol with relative viscosity 1.29)
Comparative polycarbonate based on Shi A.

((Z4) Polycarbonate copolymer all the same as (al) except with 5 itft% polydimethylsiloxane and a relative viscosity of 1.29.

The determination of the siloxane content, ie the proportion of dimethylsiloxane units in % by weight relative to the total weight of the block copolymer, is carried out gravimetrically and by NMR spectroscopy. The average siloxane block chain length is expressed as the degree of polymerization pn, and can be determined by measuring the end groups of the siloxane prepolymer.

In the examples shown in the table, component (b) and component (C) are A
Used as BS resin.

(b) 40 parts by weight of 35 parts by weight of styrene and 15 parts by weight of acrylonitrile are mixed with 50 parts by weight of coarse-grained polybutadiene (the coarse-grained polybutadiene is described in German Patent Publication No. 1.247.665) and Section 1.26
A graft polymer obtained by emulsion polymerization according to the production data of No. 9,360, and grafted onto a polybutadiene for graft base material in the latex (average particle size of 0.3 to 0.4 μm). (The particle size referred to here and in the text refers to the average particle size (dSO), which is measured by ultracentrifugation measurement (F.

5choltan et al, Co11oids.

Z, potymere, 250 780-796 (19
72)).

(C) 60 parts by weight of a styrene/acrylonitrile copolymer having a styrene/acrylonitrile ratio of 70:30 and an intrinsic viscosity [η]-〇, 79 dll'f/, measured in dimethylformamide at 20°C.

The molding compositions of the following examples were prepared by mixing the individual components in a twin-screw extruder at about 260°C.

Notched impact strength The impact strength is 453/l5O to DIN (German Industrial Standard) 5 (910 to International Standard 63).
Measurements were made using several test pieces. The dripping property during combustion was measured using a test piece with dimensions of 127 x 12.7 mm. In this case, two types of 1
The specimens were ignited using a continuous ignition method lasting 0 seconds and the number of specimens that ignited and dripped were counted. The data in the table is from UL (Underwriters' Labora).
tories.

Inc.) UL94F test method.

B.

Mixtures of polycarbonates and polymers are known (e.g. Japanese Patent Publication No. 1861168 (large quantity, priority date June 30, 1965), U.S. Pat. No. 3.66).
3.471, US Pat. No. 437.631, US Pat. No. 4.299.928 or German Patent Application No. 114,494).

Compared to pure polycarbonate, such mixtures have improved toughness.

Thermoplastic molding compositions based on polydiorganosiloxane/polycarbonate block copolymers and polyalkylene terephthalates are well known. For example, U.S. Pat. No. 4.161.569 and U.S. Pat.
．． See No. 161.498. These are said to have significantly improved impact strength and heat distortion temperature.

European Patent Publication Specification Letter No. 0.073.067 is
Discloses mixtures of aromatic polyesters, siloxane/polycarbonate block copolymers, polyesters from diols and aromatic dicarboxylic acids, and thermoplastic styrenic resins or thermoplastic acrylic alkyl ester resins, which compared to aromatic polyesters. It is stated that the impact strength has been significantly improved.

Although the above-mentioned molding compositions have many advantageous properties, they also meet certain special requirements, for example for equipment parts in automobile engine compartments, such as resistance to thermal deformation, non-deformation, gasoline It does not meet the requirements such as resistance to water and excellent toughness at low temperatures.

Surprisingly, mixtures of polydiorganosiloxane/polycarbonate block copolymers and elastomeric polymers with glass transition temperatures below -20°C have a high resistance to thermal deformation and also have a high resistance to thermal distortion between tough and brittle states. It has now been discovered that the transition temperature of

If particularly high resistance to gasoline is required while keeping other property values unchanged, it is appropriate to add polyalkylene terephthalate.

The present invention comprises: (a) having an average molecular weight of from 10 to 98, preferably from 30 to 90 parts by weight &wto, ooo to 200.000;
Contains 5% to 97.5% by weight of aromatic carbonate structural units and 25% to 2.5% by weight of polydiorganosiloxane structural units, contains α,ω-bishydroxyaryloxy end groups, and has a polymerization degree of Pn5. -100 polydiorganosiloxane/polycarbonate block copolymer prepared from polydiorganosiloxane, (d) 1 to 30, preferably 5 to 20 parts by weight - 20°C
An elastomeric polymer having a glass transition temperature of The present invention relates to a thermoplastic molding composition comprising:

Component (α) also includes a conventional polysiloxane-free thermoplastic polycarbonate, containing polydiorganosiloxane/polycarbonate containing 25 to 25% by weight of polydiorganosiloxane structural units in the mixture, consisting essentially of the following monomers: namely: chloroprene, butadiene, isoprene, isobutyne, styrene, acrylonitrile, ethylene, propylene, vinyl acetate, at least two types of acrylic or methacrylic esters having 1 to 18 carbon atoms in the alcohol component and -carbon oxides. obtained from monomers, i.e. for example “Methoden deγ Organi
schen Ch, emie (methods of organic chemistry) (H
ouben-11'eyl) 14/ Volume 1 (Geo
rg 'Thieme-Verlag, Stuttga
rt published in 1961) pages 393-406, and Buck
"Toughened plasti" by nall
cs”, Appl.

5science publislbers (London)
(on), published in 1977. Preferred polymers have a gel content of 20 or less, preferably 40 or more.

Preferred polymers are 15 to 70% by weight of the components.
of vinyl acetate, DIN 53. '753 Yoshi, 1
When measured at 90°C and under a z16kp load, the melt index is non-flowing to i, o o o, preferably 0. -1~
20, an ethylene-vinyl acetate copolymer. Also preferred are terpolymers obtained from ethylene, alkyl acrylate or vinyl acetate and -carbon oxide.

A preferable polymerization solution for component (d) has, for example, a weight ratio of ethylene groups to propylene groups of 40:60 to 90:
10, preferably in the range 40:60 to 65:35, so-called E p M and E P D Af rubbers.

Moon of non-crosslinked E p M and E p D M rubber
ey viscosity (MLl+4 (10
0℃)) is 25 to 100 MU, preferably 35 to 90 MU
within the range of The gel content of non-crosslinked EpM and E p D Af is less than 1% by weight.

The ethylene/propylene copolymer (EpH) used is substantially free of double bonds. On the other hand, ethylene-propylene/diene terpolymer (EpDM) has a
0 carbon atoms! I can contain from 11 to 20 double bonds. Suitable diene monomers in EPDM include, for example, conjugated dienes such as isoprene and butadiene; non-conjugated dienes with 5 to 25 carbon atoms, such as 1,4-octadiene; cyclic dienes, such as cyclopentadiene. , cyclohexadiene, cyclooctadiene and dicyclopentadiene; alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-
7' tylidene-2-norbornene, 2-methallyl-5-
Mention may be made of norbornene and 2-impropenyl-5-norbornene; sositetricyclodienes, such as 3-methyltridichloro[5,2,1,0,2,6)-3,8-decadiene. Preferable examples include non-conjugated dienes, 1,5-hexadiene, ethylidene norbornene and dicyclopentadiene.

The diene content in E p DM is preferably 0.5 to 1
It is 0% by weight.

EPMs and EpDMs of this type are described, for example, in German Patent Application No. 4808.709.

Preferred polymers for component () are of the X-Y type or x-(x-y
) block copolymers of the r type (here r is 1 to 5) or the Y-(X) type (here 8 is 3 to 5).
The block copolymer may be selectively hydrogenated.

These block copolymers can be produced by known methods.

Generally, the production of suitable X-Y type block copolymers from styrene, α-methylstyrene, vinyltoluene, and conjugated dienes such as butadiene, iso-tableprene, etc. is similar to the production of styrene/diene block copolymers. It is manufactured using the technology used in the “Encyclopedia
of polymer 5science and Tec
hnology” Volume 15 (Interscience
Published by E Company (New York), page 508 et seq. Selective hydrogenation can be carried out in a manner known per se, in which the ethylenic double bonds are substantially completely hydrogenated and the aromatic double bonds remain essentially intact. Selectively hydrogenated block copolymers of this type are described, for example, in German Patent Application No. 3, OOO, 282.

Preferred polymers for component (d') include, for example, butadiene/styrene copolymers, polyacrylic or methacrylic esters, and polyacrylic or methacrylic esters grafted thereon. Copolymers of polybutadiene, for example styrene or alkylstyrene and conjugated dienes (impact polystyrene) (copolymers of this type are described in German Patent Application No. 1,694,173 (=U.S. Pat. 564.077)) and acrylic or methacrylic esters, vinyl acetate, acrylonitrile, styrene and/or
Or an alkylstyrene, for example as described in German Patent Application No. 2.348.377 (=U.S. Patent No. 3)
．． 919.353) grafted butadiene/styrene or butadiene/acrylonitrile copolymers, polyisobutyne, polyisoprene, or polybutadiene.

Particularly preferred copolymers for the component (for example
0-35, in particular 15-25% by weight of at least one acrylic or methacrylic ester and/or 10-3
5. A mixture of preferably 20 to 35% by weight (based on the mixture) of acrylonitrile and 65 to 90, preferably 65 to 80% by weight (based on the mixture) of styrene; 90, preferably 65-90. In particular, it is a graft copolymer obtained by grafting onto a butadiene polymer containing 75 to 85% by weight, at least 70% by weight relative to (1), of butadiene groups as a grafting base material, preferably in the grafting base (2). Gel rate (measured in toluene)
is 70%, the degree of grafting g is 0.15-0.55 and the average diameter d of the graft copolymer.

is a graft copolymer having a diameter of 0.2 to 0.6 μm, preferably 0.3 to 0.5 μm.

Acrylic or methacrylic esters I are esters of acrylic or methacrylic acid and monohydric alcohols having 1 to 18 carbon atoms.

In addition to the butadiene group, the graft base material ■ has 3
0% by weight or less of ethylenically unsaturated monomers, such as styrene, acrylonitrile, and 1 to 4 in the alcohol component.
acrylic or methacrylic esters having 5 carbon atoms, such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. The preferred grafting substrate (1) consists of pure polybutadiene.

In the grafting reaction, the graft monomer I usually does not completely craft onto the grafting substrate (2), so in the present invention, the graft polymers are also used in the same product as those products, in addition to the polymer actually grafted. It is thought that it contains monopolymers and copolymers of graft monomer I. The graft copolymer in the present invention is obtained by graft polymerizing vinyl monomers in the presence of polymer (1).

The average particle diameter "50" is the diameter around which 50% by weight of the particles are distributed.
oltan and H. Lange, Kolloid.

Z, und Z, Polymere 250 (1,9
, 70), 782-786) or particle counting by electron microscopy (G, Kampf and H, 5chuster.

Angew, Macromoleculare
mie 14 (1970), 111-129) or by a light scattering method.

Other examples of particularly preferred polymers for component (i),
As the grafting base material, acrylate rubber having a glass transition point of -20°C or less and 25 to 98% by weight of the component (2) and (2) as the graft monomer, 2 to 75% by weight of the component The graft polymer is composed of at least one polymerizable ethylenically unsaturated monomer whose monopolymer or copolymer formed in the presence of %wt.

The polymeric acrylate rubber for component (2) is preferably obtained from alkyl acrylates or, if appropriate, from other polymerizations thereof, with up to 40% by weight of 1% ethylenically unsaturated monomers. It is a polymer.

If the acrylate comb used as the grafting substrate is a grafted product with an entirely diene rubber core (as described below), this diene rubber stone layer is not taken into account when calculating weight percent. . Preferred polymerizable acrylic esters include 01-C, alkyl esters such as methyl, ethyl, butyl, octylhexyl esters, halogenoalkyl esters, preferably td halo'y'/-C, ~C8- Included are alkyl esters such as chloroethyl acrylate, and aromatic esters such as benzyl acrylate and phenethyl acrylate. These can be used alone or as a mixture.

The acrylate rubber (2) may be non-crosslinked or crosslinked, but is preferably partially crosslinked.

To effect crosslinking, it is possible to copolymerize monomers having one or more polymerizable double bonds.

Preferred monomers for crosslinking include, for example, 3-
an unsaturated monocarboxylic acid having 8 carbon atoms;
Esters of unsaturated monohydric alcohols with 12 carbon atoms or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate, polyunsaturated Heterocyclic compounds such as cyanuric acid and trivinyl incyanurate and triallyl and tris-acryloyl-
8-triazines, especially triallyl cyanurates; polyfunctional vinyl compounds such as di- or trivinylbenzene and triallyl phosphates and diallyl phthalates.

Preferred monomers for crosslinking include allyl methacrylate,
Ethylene glycol dimethacrylate, diallyl phosphate and a heterocyclic compound having at least three ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triaryl isocyanurate, trivinyl cyanurate, triacryloyl-hexahydro-8-triazine and trif'J rubenzene.

The amount of monomer that performs crosslinking is
Preferably it is 0.02 to 5% by weight, especially 0.05 to 2% by weight.

In the case of cyclic monomers which undergo a crosslinking reaction and have at least three ethylenically unsaturated groups, it is advantageous to limit their amount to 1% by weight of the grafting substrate (1).

Preferred polymerizable ethylenically unsaturated monomers which can be used in the preparation of the grafting substrate (2), if appropriate in addition to the acrylic ester, are acrylonitrile, styrene, α
-Methylstyrene, acrylamide, hinyl C0~go.

-alkyl ethers, butadiene and isoprene. The preferred acrylate rubber as grafting substrate is an emulsion polymer with a gel content of 60% by weight.

The gel content of the graft substrate ① is determined in dimethylformamide at 25°C (M, Hoffmann.

E. Kromer and R. Kuhn, polymera.
-nalytik I and L I, Georg T
hiemer-Verlag (Strbttgert)
) Published in 1977).

The acrylate rubber used as the graft base material can also be a crosslinked diene rubber consisting of one or more conjugated dienes, such as polybutadiene, or a conjugated diene and an ethylenically unsaturated monomer, such as styrene and/or acrylonitrile, as core material. The product may include a copolymer of

The proportion of polydiene core material in the graft base material (1) may be from 0.1 to 80 and from 10 to 50% by weight relative to (2). The shell layer and the core can be, independently of each other, uncrosslinked, partially crosslinked or highly crosslinked.

Particularly preferred grafting substrates based on polyacrylic esters of graft polymers according to component (1) can have the following suite: 1. Acrylic ester polymers without diene rubber core and 2. Acrylic acid ester polymers and copolymers containing a diene rubber core.

The grafting yield, that is, the ratio of the amount of monomer (1) used for grafting to the monomer used for grafting, is generally from 20 to 80% by weight. The measurements were performed by M, Hoff-mann, Il, K
Romer and R, Kwhn.

Polymeranalytik, Volume 1, Georg
It is carried out as described in Tieme-Verlyag (1977).

Preferred grafting monomers (1) are α-methylstyrene, styrene, acrylonitrile, methyl methacrylate, or mixtures of these monomers. A preferred graft monomer mixture is 90:10-5 with styrene and crylonitrile.
It is a 0:50 weight ratio mixture.

Graft polymers based on polyacrylic esters are described, for example, in German Patent Publication No. 2.444.584 (-US Patent No. 4).
, 022,748) and German Patent Application No. 2.7 '26.256 (=U.S. Patent Specification No. 4.
OF6,202).

A particularly advantageous graft polymer of this type is
~20 preferably 3 to 15% by weight of monomer (1), of (80 to 98, preferably 85 to 97 M%), completely ground and suspended without lI!5pA agent It can be obtained by grafting it onto latex.

The resulting finely divided graft polymer is then dried and
The average particle size d50 of component (d') in the mixture according to the invention with the other components under the action of shear forces in the desired ratio is 0.05.
The thickness can be made uniform to 3 to 3 μm, preferably 0.1 to 2 μm, particularly 0.2 to 1 μm.

The expression "in the absence of suspending agents" means that there are no substances capable of suspending the graft monomers V in the aqueous phase, depending on their type and amount. This definition does not exclude the presence of substances that acted as suspending agents, for example in the preparation of the grafted graft substrate (1). In such cases, the coagulant or precipitant used to break up the latex must be added in an amount to compensate for the suspending action of the material used in the previous step. In other words, care must be taken that the grafted monomers never form a (stable) emulsion or suspension in the aqueous phase.

The graft polymer produced in this way in the absence of a suspending agent can be used as a component of the molding composition of the invention to form very fine particles suspended in the other resin components. The particle size remains unchanged for a long period of time even at high temperatures.

This expression "very small particle size" means that the number, shape, and size of the graft polymer particles used are such that, even after the homogenization step, the graft polymer particles introduced into the other melted resin components are It means corresponding to the number, shape and size of.

As the grafting substrate (2), the glass transition point of the monopolymer or copolymer thereof, already grafted in an aqueous emulsion in an amount of 1 to 20, preferably 1 to 10% by weight relative to (2), is 0°C.
It is also possible to use aqueous emulsions (latexes) which contain acrylate rubbers with a higher monomer content as emulsified particles.

Preferred grafting monomers of this type are alkyl acrylates, alkyl methacrylates, styrene, acrylodryl, α-methylstyrene/or vinyl acetate.

Graft substrates of this type are produced, for example, by emulsion polymerization or emulsion graft polymerization. However, they can also be prepared by first producing acrylate rubbers by solution or bulk polymerization, then grafting onto graft monomers, and converting these rubbers into aqueous emulsions suitable for the subsequent grafting process. .

Suitable grafting substrates for the acrylate rubber of this particular embodiment therefore include, in addition to the polymers listed on page 19, in an aqueous emulsion or if appropriate a diene rubber core and an ethylenic rubber core. Unsaturated polymerization 1! There are graft polymers made from acrylic ester polymers or copolymers or copolymers containing raw monomers.

In the present invention, component (e) polyalkylene terephthalate is the product of the reaction between an aromatic dicarboxylic acid or its lano-reactive derivative (e.g. dimethyl ester or anhydride) and an aliphatic, alicyclic or aromatic substituted aliphatic dioate. or a mixture of these reaction products.

The preferred polyalkylene terephthalates of component (e) are terephthalic acid (or reactive derivatives thereof) and 2 to 10
(Krbns
tstoff Handbuch (Plastic Handbook) Volume 1, pp. 695 et seq., Cart Han
ser Verlag (Afwni ch) 197
(See 3rd edition).

Preferred polyalkylene terephthalates for component (e) contain at least 80, preferably at least 90, mole % of terephthalic acid groups based on the dicarboxylic acid component and at least 80, preferably less than 80, preferably less, on the diol component. Tomo90
Contains mole % ethylene glycol and/or 1,4-butanediol groups.

The preferred polyalkylene terephthalate (e) is 8 to 14% by mole of terephthalic acid ester, up to 20 mol%.
Other aromatic dicarboxylic acids having 4 to 4 carbon atoms or
Aliphatic dicarboxylic acids having 12 carbon atoms, such as 7-talic acid, isophthalic acid, 7-talene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, cepatic acid, azelaic acid , or cyclohexane diacetic acid groups.

Preferred polyalkylene terephthalates (e) include, in addition to ethylene glycol or 1,4-butanediol, 2
Up to 0 mol % of other aliphatic diols with 3 to 12 carbon atoms, cycloaliphatic diols with 6 to 21 carbon atoms, such as 1,3-propanediol, 2-ethyl-
1,3-propanediol, neopentyl glycol,
1,5-bentanediol, 1,6-hexanediol, cyclohexane-1,4-dimetatool, 3-methyl-2,4-bentanediol, 2-methyl-2,4-bentanediol, 2,2.4- ) riftyl-1,3-bentanediol, 2,2.4-trimethyl-1,6-pentadiol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2 ，
5-hexanediol, 1,4-di(β-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl cyclobutane, 2,2
-bis-(3-β-hydroxyethoxyphenyl)-furopane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane groups (DE-OS 2.407. No. 647, No. 44
071776 and 2,715,932).

The polyalkylene terephthalate for component (e) is
With the addition of relatively small amounts of trihydric or tetrahydric alcohols or tribasic or tetrabasic carboxylic acids, for example DE 1,900,270 and U.S. Pat. It can be branched as described in the issue. Preferred are ethane, and propane and pentaerythritol. It is appropriate to use up to 1 mol % of the branching agent based on the acid component.

Particularly preferred polyalkylene terephthalate (e) is
Terephthalic acid and its reactive derivatives (e.g. dialkyl esters) are prepared singly from ethylene glycol and/or 1,4-butanediol, and are mixtures of these polyalkylene terephthalates.

Other preferred polyalkylene terephthalates (e) are:
A particularly preferred copolyester is poly(ethylene glycol/1,4-butanediol) terephthalate.

The polyalkylene terephthalate preferably used as component (g) is phenol 10-dichlorobenzene (
1:1 parts by weight), and the intrinsic viscosity measured at 25° C. in a mixed solvent is generally 0.4 to 1. s cl l/111 preferably 0.5 to L3dl/El, especially 0.6 to 1.2d
l/g.

The components ((Z), (of and, if appropriate, (e) of the present invention)
) to further improve the gasoline resistance of mixtures containing components (a) + (b) and if appropriate (e)
Up to 5% by weight of ethylene homopolymer or copolymer can be added to the total weight of the ethylene. In this case, the ethylene copolymer contains, in addition to the ethylene group, 3
Polyethylene containing up to 0% by weight of other copolymerizable materials such as acrylic acid or methacrylic acid.

The molding compositions according to the invention based on components C(L), <d) and if appropriate (e) contain additives customary in polycarbonate chemistry, rubber chemistry and polyester chemistry, such as It can include lubricants, mold release agents, crystallization nucleating agents, stabilizers, fillers, reinforcing materials, flame retardants and dyes.

Molding compositions containing fillers and reinforcing agents and based on components (α), (d) and, if appropriate, (e),
Up to 30% by weight of fillers and/or reinforcing substances can be included in the reinforced molding composition. A preferred reinforcing material is glass fiber. Preferred fillers which also have a reinforcing effect are glass peas, mica, silicates, quartz, talc, titanium dioxide and wollastonite.

Molding compositions containing a flame retardant and based on components (α) + () and, if appropriate, (e), generally contain up to 30% by weight of the flame retardant molding composition. It can contain flame retardants in concentrations. All known flame retardants used for polyester molding compositions are suitable, such as polyhalogenodiphenyl, polyhalogen diphenyl ether, polyhalogenophthalic acid and its derivatives and polyhalogenoligo- and -polycarbonates. and the corresponding bromine compounds are particularly effective. Synergistic compounds such as antimony trioxide can also be used simultaneously.

Ingredients (α), (f) and, if appropriate, (6) of the present invention
The molding compositions based on can be prepared in customary mixing equipment, such as mills, kneaders, single-screw sets and multi-screw set extruders. The molding composition based on the components (α), (d) and, if appropriate, (e) of the present invention, can be molded with very little deformation even when subjected to a heat load for a relatively long period of time. It can be processed into products. In many cases, components (α), (d) and (g
), although it is advantageous to mix in a one-step process.
Sometimes it is appropriate to first remove one component and then add and mix only this component.

The polymers used in the examples are listed below.

(dI) A graft polymer consisting of 75% by weight of crosslinked polybutadiene (gel content of 70% or more as measured in toluene) and styrene, the particle size of the latex-like grafting substrate being 03-0.4 μm. .

(d2) 79.2 parts by weight of acrylic acid n crosslinked with 0.4 parts by weight of butylene 1,3-diacrylate and containing 0.4 parts by weight of diallyl maleate in the form of a graft monomer; - a grafting substrate consisting of butyl and a polymer consisting of 20 parts by weight of polymethacrylic acid ester.

The polydiorganosiloxane/polycarbonate block copolymers used in the examples are listed below.

(al) Bisphenol A and 4.5% by weight polydimethylsiloxane with a block chain length (pn) of 40 as base material, at 25°C, CHx (' l in 0.5
Ji' / Relative viscosity measured at 100ml concentration is 1
．． 31 polycarbonate copolymer.

The determination of the siloxane content, ie the proportion by weight of dimethylsiloxy monomer relative to the total weight of the block copolymer, was carried out gravimetrically or by nuclear magnetic resonance spectroscopy. The average siloxane block chain length is expressed by the degree of polymerization pn obtained by measuring the terminal groups in the siloxane prepolymer.

(α3) A polycarbonate homopolymer based on bisphenol A and having a relative viscosity of 1.29 was used as a comparative example.

(C) Phenol 10-dichlorobenzene (
1:1) Intrinsic viscosity x measured in mixed solvent, 18 dtt
/Elf: Polybutylene terephthalate was also used in the examples and is listed in the table.

Optionally, an ethylene copolymer containing 4-% by weight of acrylic acid and 12% by weight of tert,-butyl acrylate, as well as heat stabilizers and pigments in the form of a concentrate in bisphenol A/polycarbonate. It was used again. The preparation of molding compositions based on components (a), (me and, if appropriate, (e)) was carried out by melting and homogenizing in suitable equipment. The molding process was carried out in an injection molding machine. It was carried out in

Mechanical strength measurements in tensile tests are based on DIN 5 tome 455.
/150 Based on R527, 70% proportional test bar (pr
Portion α1 bar).

The notched S impact strength is a rod-shaped test piece with dimensions of 80 guns x 10 max.
, 452/150 R179.

The critical width is AST
Measured according to MD256.

The firing pin entry test according to DIN 53,443 is determined by evaluating the fracture behavior (3=toughness-brittleness, 4=toughness).

Measurement of heat deformation resistance by Vicαt (B) method is DIN
It was carried out according to s3,46o/l5O36o. Gasoline resistance is 0% in 1:1 isooctane/toluene and premium gasoline-like mixtures of isooctane (41L 5%)/toluene ((525%)/methanol (15%)).
．． A selection test method was used in which the sample was stretched by 6% and immersed for 5 minutes.

-0°C 11 -20°C calculation -40°C impact penetration test; rupture behavior damage energy J , 5-6.8 - > 8 > 8 > 3 > 5 10X4 10X4 2X4/8X3 3X4/7X3
75 70 54 50 145 145 146 145 Fracture Increase Crack Crack Crack Crack Fracture Slightly crack critical width - room temperature -0°C - -20°C □.

Impact penetration test at -40°C: Single action failure energy at rupture J Vic, at13 Temperature 0C vs. gasoline vs. 1:1 isooctane/toluene vs. M-is (isooctane/toluene/methanol) 1
) Gray pigment; effective amount 1% by weight 2) iJ,X(3-ethynone-oxetanyl-5,8
- a, 0 < 4 > s > s-, -7,0-
7,24,9-5,1 7X4/3X3 2X4/8X3 10X 4 9X
4/lX365 69 62 69 122 123 122 124 Crack Crack Slight crack Slight crack No crack No crack No crack No crack 3-methyl)
Phosphite, effective amount 01% by weight Critical width - Room temperature 10°C m-20°C @ Impact penetration test at -40°C: Fracture behavior Failure energy Vicat B temperature reduction Gasoline property vs. l:1 isooctane/toluene vs. Af-15 (isooctane/toluene/methanol)
1) Gray pigment: effective amount 1% by weight 2) Toss(3-ethyl-oxetanyl) 5.
6-5.8 > 8 > 8 > 8 order -> 8 < 4
6.5-6.7 mm -5,1-5,4- 10X4 10X4 7X4/3X3 10X4/ 7
0 59 54 62 'CI 25 115 123 123 Crack No crack Slight crack Crack

Claims (1)

[Claims] 1. (a) 20 to 80 parts by weight of an average molecular weight Mw10
．． 000 to 200.000, contains about 75 rigidorganosiloxane structural units, and contains α,ω-bishydroxyaryloxy end groups, and has a degree of polymerization pn of 5 to 1.
(b) a polymer obtained by grafting an ethylenically unsaturated monomer onto 70 to 5 parts by weight of rubber; 1. A thermoplastic molding composition comprising 100 parts by weight of a rubber-free thermoplastic polymer of vinyl monomers, wherein (α) + (b) + (C) is 100 parts by weight. 2. (a) 10 to 98 parts by weight, average molecular weight Afw10
．． 000 to 200.000, and 75% by weight to 97.000.
5% by weight aromatic carbonate structural units and 25% by weight
Contains ~2.5% by weight polydiorganosiloxane units, α. A polydiorganosiloxane/polycarbonate block copolymer produced from a polydiorganosiloxane containing an ω-bishydroxyaryloxy end group and having a degree of polymerization pn of 5 to 100, containing 1 to 30 parts by weight of (glass transition below 20°C) and (e) 0 to 50 parts by weight of thermoplastic polyalkylene terephthalate, characterized in that (a) +(6) is 100 parts by weight. 3. The ethylenically unsaturated monomer of component (b) is styrene, a styrene derivative, methyl methacrylate, or
From 5 to 50% by weight of styrene, α-methylstyrene, methyl methacrylate, or mixtures thereof and from 5 to 10% by weight of acrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleic acid, or mixtures thereof. The composition according to claim 1, characterized in that it is a mixture of the following. 4. The composition according to claim 1 or 3, wherein the rubber of component (b) is based on a diene monomer, an alkyl acrylate, or EPDM. 5. Rubber contains polybutadiene and 30 copolymerized units.
Butadiene/styrene copolymers containing up to 20% by weight of styrene, butadiene copolymers containing up to 20% by weight of acrylic or methacrylic acid lower alkyl esters, polyisoprene, polychloroprene or acrylic acid 01-Ca
5. The composition according to claim 4, which is an alkyl acrylate rubber based on an alkyl ester. 6. The graft copolymer (b) contains 5-80% by weight of rubber and 95-20% by weight of grafted monomer, and the rubber has an average particle size of 0.0% in the graft copolymer.
6. A composition according to claim 1, characterized in that it is present in the form of at least partially crosslinked particles having a diameter of 9 to 5 .mu.m. 7. The vinyl monomer of component (C) is styrene, α-methylstyrene, halogenostyrene, acrylonitrile,
7. The composition according to claim 1, wherein the composition is methacrylonitrile, methyl methacrylate, maleic anhydride, vinyl acetate or N-substituted maleimide. 8 Component (C) is 95 to 50% by weight of styrene, α-
A patent claim characterized in that it is a copolymer consisting of methylstyrene, methyl methacrylate, or a mixture thereof, and 5 to 50% by weight of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, or a mixture thereof. The composition according to item 7. 9. The composition according to claim 8, wherein component (C) is a copolymer consisting of 20 to 40% by weight of acrylonitrile and 80 to 60% by weight of styrene or α-methylstyrene. thing. 10. Precipitating the latex of the graft polymer (b);
The powder thus obtained was dried, and the block copolymer (
The composition according to any one of claims 1 and 3 to 9, characterized in that it is produced by mixing α) and polymer (c). 11. Claim 1 also includes stabilizers, pigments, free-flowing agents, lubricants, mold release agents, antistatic agents, and/or flameproofing agents.
The composition according to any of Items 3 and 3 to 10. 12. Polydiorganosiloxane/polycarbonate block copolymer containing one or more components (α) and 1
A mixture of thermoplastic polycarbonates containing one or more polysiloxane species, the total content of polydiorganosiloxane structural units in the mixture being 25 to 25% by weight.
12. A thermoplastic molding composition according to any one of claims 1 to 11, characterized in that the weight is . 13. Component (α) 30-90 parts and weight (5-2
Claim 2, characterized in that it consists of 0 parts by weight.
Go to the group listed in the section. 14. Ingredients (1) in chloroprene, butadiene, isoprene, isobutyne, styrene, acrylonitrile, ethylene, propylene, vinyl acetate, and alcohol components.
14. Composition according to claim 2 or 13, characterized in that it is a copolymer obtained from at least two acrylic or methacrylic esters having from 18 carbon atoms. 15. The composition according to any one of claims 2, 13 and 14, wherein the component (having a gel content of 20% by weight or more). 16. The composition having a gel content of 20% by weight or more. The composition according to any one of claims 2 and 13 to 15, which is an ethylene-vinyl acetate copolymer containing vinyl acetate and having a melt index of non-flowability to 1,000. 17. Component (EpM or EpD in which the weight ratio of ethylene groups to propylene groups is 40:60 to 90:10)
The composition according to claims 2 and 13 to 15, characterized in that the composition is M. 18. Component (composed of megavinyl aromatic monomer X and conjugated diene Y, X-)' type or X-(Y-X)? . (r=1~5) or Y - (Xs) (s=3~s
) The composition according to any one of items 13 to 15. 19. Component (d') contains 10 to 40% by weight of one kind of acrylic acid or methacrylic ester and/or
or a mixture of 10-35% by weight of acrylonitrile with respect to the mixture and 65-90% by weight of styrene with respect to the mixture; (1) 60-90% by weight with respect to the grafted product; The graft polymer according to claims 2 and 13 to 15, characterized in that it is a graft polymer obtained by grafting onto a butadiene polymer containing at least 70% by weight of butadiene as a grafting base material. A composition according to any of the above. 20, component (d') is ■, as a graft base material, component (25 to 95
(wt%) acrylate rubber having a glass transition point of 20°C or less;
The homopolymer or copolymer formed in the presence of 5% by weight of at least one of (i) is a graft polymer consisting of a polymerizable ethylenically unsaturated monomer having a glass transition point of 25°C or higher; The second claim characterized in that
The composition according to any one of Items 1 and 13 to 15. 21. Claim 2, wherein the graft monomer (2) is α-methylstyrene, styrene, acrylonitrile, methyl methacrylate, or a mixture thereof.
The composition according to item 0. The latex state is completely broken and suspended in water in the absence of a turbidity agent of 80 to 98 weight percent (by weight to the force) of 2z component (force). The composition according to claim 20 or 21, characterized in that it is produced by grafting onto the latex of (1) which becomes cloudy.23. Claims 2 and 3, characterized in that the pre-prene-curic acid group and the diol component contain at least 80 mol% of ethylene glycol and/or 1,4-butanediol groups. The composition according to any one of Items 13 to 22. 24. Component (C), in addition to the terephthalic acid ester,
Claim 3, characterized in that it contains up to 20 mol % of groups of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or of aliphatic dicarboxylic acids having 4 to 12 carbon atoms. The compositions described in Items 1 and 13 to 23. 25. Claims further comprising ethylene copolymers or ethylene copolymers containing not more than 30% by weight of other comonomers relative to the ethylene copolymer in each case The composition according to any one of the ranges 2 and 13 to 24. 26. The ethylene homopolymer or copolymer is (a), (
26. A composition according to claim 25, characterized in that said and (e) are present in an amount of not more than 5% by weight relative to the total weight of said and (e). 27. Claims 2 and 13 to 26 also include lubricants, mold release agents, nucleating agents, stabilizers, fillers, reinforcing agents, dyes and/or flame retardants. Composition of. 28. A thermoplastic molding composition according to claim 1 or 2 substantially as described in claim 1 or 2. 2. A molded article produced from the composition described in any of the claims above.