The invention relates to a free-flowing molding composition, in particular for injection molding, and also to a molding produced from this molding composition.
In electrical engineering and in the electronics industry the trend is toward ever smaller components. With this, there is a constant increase in requirements for the flowability of plastics. These requirements are particularly critical when the molding composition comprises fillers or reinforcing materials, with resultant considerable reduction in flowability.
One possible way of improving the flowability of plastics is to reduce the molecular weight. However, there are certain limits here, since if the molecular weight is reduced too drastically there is also impairment of mechanical properties.
When preparing polyester molding compositions it is not practical to start from a specially prepared grade of polyester tailored specifically for this purpose, since cost-related factors would make this type of intervention in the production process unacceptable, especially where a plant operates continuously. Instead, it is desirable to start from a standard grade of polyester and to reduce the molecular weight while compounding.
US-A 4 882 375 uses the sulfonate salt of a mono- or dicarboxylic acid for this purpose. However, its stated reduction in melt viscosity is far from sufficient for the production of injection moldings with small dimensions. The use of sulfonated dicarboxylic acids appears to be more efficient than that of sulfonated monocarboxylic acids.
Starting from this prior art, an object was to develop a polyester molding composition which exhibits a significantly more marked reduction in melt viscosity or improvement in flowability, without any excessive impairment of the mechanical properties of the molding composition.
This object has been achieved by means of a molding composition which comprises the following components:

a) from 95 to 99.5 parts by weight, preferably from 96 to 99 parts by weight, and particularly preferably from 97 to 98.75 parts by weight, of a thermoplastic aromatic polyester,
b) from 5 to 0.5 parts by weight, preferably from 4 to 1 parts by weight, particularly preferably from 3 to 1.25 parts by weight, of a monocarboxylic acid,
where the total of the parts by weight of a) and b) is 100;
c) from 0.5 to 60% by weight, preferably from 2 to 55% by weight, and particularly preferably from 4 to 50% by weight, in each case based on the molding composition, of particulate, lamellar and/or fibrous additives, selected from fillers, pigments, reinforcing materials, additives which give the molding composition antielectrostatic properties or electrical conductivity, nucleating agents, and particulate flame retardants,
d) from 0 to 30% by weight of a non-particulate flame retardant,
e) from 0 to 20% by weight of a synergist, and
f) from 0 to 5% by weight of other additives and/or processing aids,
where the solution viscosity of the resultant polye^^ter, measured as J value
according to DIN 53 728/ISO 1628/Part 5, is in the range from 50 to 80
cm^/g, and preferably from 52 to 70 cm^/g, the melt index of the molding
composition, measured as MVR at 250X/5 kg to DIN EN ISO 1133 is from
12 to 60cm^/10 min, preferably from 15 to 50 cm^/10 min, particularly
preferably from 20 to 40 cm^/10 min, and very particularly preferably from
20 to 35cm3/10min.
The invention also provides moldings which have been produced using this molding composition.
Thermoplastic polyesters are prepared by polycondensing diols with dicarboxylic acids or with their polyester-forming derivatives, such as dimethyl esters. Suitable diols have the fomiula HO-R-OH, where R is a divalent, branched or unbranched aliphatic and/or cycloaliphatic radical having from 2 to 40. preferably from 2 to 12. carbon atoms. Suitable dicarboxylic acids have the formula HOOC-R'-COOH, where R' is a divalent aromatic radical having from 6 to 20 carbon atoms, preferably from 6 to 12 carbon atoms.

Examples which may be mentioned of diols are ethylene glycol, trimethylene glycol, tetramethylene glycol, but-2-ene-1,4-diol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, and the C36 diol dimerdiol. The diols may be used alone or as a diol mixture.
Examples of aromatic dicarboxylic acids which may be used are terephthalic acid, isophthalic acid, 1,4-, 1,5-, 2,6-, and 2,7-naphthalenedicarboxylic acid, bfphenyl-4,4'-dicart50xylic acid, and diphenyl ether 4,4'-dicarboxylic acid. Up to 30 mol% of these dicarboxylic acids may have been replaced by aliphatic or cycloaliphatic dicarboxylic acids having from 3 to 50 carbon atoms, and preferably having from 6 to 40 carbon atoms, e.g. succinic acid, adipic acid, sebacic acid, dodecanedioic acid, or cyclohexane-1,4-dicarboxylic acid.
Examples of suitable polyesters are polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene 2.6-naphtha/ate, polypropylene 2,6-naphthalate, and polybutylene 2,6-naphthalate.
The preparation of these polyesters is prior art (DE-A 24 07 155, 24 07 156; Ullmann's Enzyklopadie der technischen Chemie [Ullmann's Encyclopedia of Technical Chemistry], 4th edition. Volume 19, pp. 65 ef seq., Verlag Chemie, Weinheim, 1980).
In principle, any acid of the formula
R-COOH
may be used as monocarboxylic acid. R is an aliphatic, cycloaliphatic, or aromatic radical; it preferably has at least 5 carbon atoms. Examples of compounds which may be used, either alone or as a mixture, are hexanecarboxylic acid. 2-ethylhexanecarboxylic acid, stearic acid. cyclohexanecarboxylic acid, benzoic acid, o-, m- or p-methylbenzoic acid, tert-butylbenzofc acid, p-phenylbenzoic acid, p-phenoxybenzoic acid, and naphthalene-2-carboxylic acid.
The polyester molding composition may comprise up to 60% by weight, preferably up to 55% by weight, and particularly preferably from 4 to 50%

by weight, of fibrous, lamellar, or particulate fillers or reinforcing agents or mixtures of these materials.
Examples which may be mentioned here of fibrous fillers or fibrous reinforcing materials are glass fibers, carbon fibers, aramid fibers, potassium titanate fibers, and fibrous silicates, such as wollastonite.
Examples of lamellar fillers or lamellar reinforcing materials are mica, talc, and graphite.
Examples of particulate fillers or particulate reinforcing materials which may be mentioned are glass beads, powdered quartz, kaolin, boron nitride, calcium carbonate, barium sulfate, silicates, silicon nitride, titanium dioxide, carbon black, and also oxides or oxide hydrates of magnesium or aluminum.
The polyester molding composition may moreover comprise from 0 to 30% by weight, and preferably from 0.1 to 25% by weight, of non-parliculate flame retardants. Use may be made here of any of the flame retardants which are usually used for polyester molding compositions. Examples of suitable flame retardants, either particulate [component c)] or non-particulate [component d)]. are polyhalobiphenyl, polyhalodiphenyl ether, polyhalophthalic acid and its derivatives, polyhalooligo- and -polycaribonates. and halogenated polystyrenes, the corresponding bromine compounds being particulariy effective; melamine cyanurate. melamine phosphate, melamine pyrophosphate, elemental red phosphorus; organophosphorus compounds, such as phosphonates, phosphinates, phosphinites; phosphine oxides, such as triphenylphosphine oxide; phosphines, phosphites, and phosphates, such as triphenyl phosphate. Other suitable flame retardants are compounds which contain phosphonjs-nitrogen bonds, such as phosphonitrile dichloride, phosphoric ester amides, phosphoramldes, phosphonamides, phosphinamides, tris(aziridinyl)phosphine oxide, or tetrakis(hydroxymethyl)-phosphonium chloride, or else fillers which release water in the event of a fire, for example magnesium hydroxide or aluminum hydroxide.
If a flame retardant is used, concomitant use may be made of up to 20% by weight, preferably from 0.1 to 15% by weight, of a synergist. Examples which may be mentioned of these synergists are compounds of cadmium, of

zinc, of aluminum, of silver, of iron, of copper, of antimony, of tin, of magnesium, of manganese, of vanadium, and of boron. Examples of particularly suitable compounds are oxides of the metals mentioned, and also carbonates or oxycarbonates, hydroxides, and also salts of organic or inorganic acids, for example acetates, phosphates or hydrogenphosphates, or sulfates.
Besides, the molding composition may comprise other additives and/or processing aids, such as antioxidants, heat stabilizers, light stabilizers, dyes, pigments, lubricants, mold-release agents, or flow promoters.
The polyester molding composition may be prepared by known processes, by mixing the starting components in conventional mixers, in particular twin-screw extruders, and then extruding them. The extrudate is cooled, pelletized, and dried.
The solution viscosity of the polyester present in the molding composition is measured according to DIN 53 728/ISO 1628/Part 5, on a 0.5% strength by weight solution of the polyester in a phenol/1,2-dichlorobenzene mixture (ratio 1:1 by weight) at 25oC. An appropriate amount of the molding composition is weighed out to prepare the solution; insoluble constituents are then removed by filtration or centrifuging.
The molding composition of the invention is particularly advantageously used for moldings with small dimensions, in particular injection moldings, for example for relay components, capacitor cups, plug connectors, semiconductor housings, multipoint connectors, or SMD components,
The invention will be illustrated by way of example below.
Comparative Example 1
Standard molding composition
The following materials were fed into the first intake of a Werner & Pfleiderer ZSK 30 M9/1 twin-screw kneader:

83 parts by weight of VESTODUR® 1000, a polybutylene terephthalate from Degussa AG with solution viscosity J = 107cm3/g,
14 parts by weight of antimony oxide (synergist),
0.5 part by weight of a commercially available processing stabilizer, 0.5 part by weight of a commercially available heat stabilizer, and
15 parts by weight of a color concentrate from 15% by weight of
carbon black and 85% by weight of VESTODUR® 1000,
and then
105 parts by weight of glass fibers and
17.5 parts by weight of a commercially available bromine-containing flame retardant
were fed into the second intake. Melt temperature was 280°C and rotation rate was 250 rpm. The product was extruded, pelletized, and dried for 4 hours at 120°C.
The results of testing are given in Table 1.
Comparative Example 2
As comparative example 1, with the sole difference that the 83 parts by weight of VESTODUR® 1000 were replaced by 83 parts by weight of a corresponding low-molecular-weight polybutylene terephthalate (J = 80 cm3/g).
Comparative Example 3
As comparative example 1, with the sole difference that 1.5 parts by weight of terephthalic acid were included in the addition at the first intake.
Comparative Example 4
As comparative example 1, with the sole difference that 2 parts by weight of terephthalic acid were included in the addition at the first intake.
I

Example 1
As comparative example 1, with the sole difference that 1.75 parts by weight of benzoic acid were included in the addition at the first intake.
Example 2
As comparative example 1, with the sole difference that 2.25 parts by weight of benzoic acid were included in the addition at the first intake.
It is seen from Table 1 that the mechanical properties of the molding composition of the invention (Examples 1 and 2) are similar or somewhat better than those of a molding composition in which a low-molecular-weight specialty polyester grade was used (comparative example 2), while flowabifity was comparable, and that moreover the improvement in flowability brought about by addition of a monocarboxylic acid is considerably greater than when a comparable amount of a dicarboxylic acid is added. Despite the considerably improved flowability, which per se would promote dropping, in the fire test according to UL 94 the material is still graded as fire class V-0.

wnat IS ciaimea is:
1. A molding composition which comprises the following components:
a) from 95 to 99.5 parts by weight of a thermoplastic aromatic
polyester,
b) from 5 to 0.5 parts by weight of a monocarboxylic acid,
where the total of the parts by weight of a) and b) is 100;
c) from 0.5 to 60% by weight, based on the molding composition,
of particulate, lamellar and/or fibrous additives, selected from
fillers, pigments, reinforcing materials, additives which give the
molding composition antielectrostatic properties or electrical
conductivity, nucleating agents, and particulate flame retardants,
where the solution viscosity of the resultant polyester, measured as J value according to DIN 53 728/ISO 1628/Part 5, is in the range from 50 to 80 cm3/g, and the melt index of the molding composition, measured as MVR at 250X/5 kg. is from 12 to 60 cm3/10 min.
2. The molding composition as claimed in claim 1.
which
also comprises
d) not more than 30% by weight of a flame retardant. and/or
e) not more than 20% by weight of a synergist, and/or
f) not more than 5% by weight of other additives and/or processing aids.
3. The molding composition as claimed in any of the preceding claims,
wherein
the solution viscosity of the polyester present is in the range from 52 to 70 cm3/g.
4. The molding composition as claimed in any of the preceding claims,
which
has a melt index at 250X/5 kg of from 15 to 50 cm3/10 min.
5. The molding composition as claimed in any of the preceding claims,
which
has a melt index at 250°C/5 kg of from 20 to 40 cm3/10 min.

6. The molding composition as claimed In any of the preceding claims,
which
has a melt index at 250oC/5 kg of from 20 to 35 cm3/10 min.
7. The molding composition as claimed in any of the preceding claims,
wherein
the polyester has been selected from the group of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate, polypropylene 2.6-naphthalate, and polybutylene 2,6-naphthalate.
8. A molding produced from the molding composition as claimed in any of the preceding claims.
9. The molding as claimed in claim 8, produced by injection molding.
10. The molding as claimed in claim 8 or 9, which
is a relay component, a capacitor cup, a plug connector, a semiconductor housing, a multipoint connector, or an SMD component.
11. A molding compositioii substantially as herein described and ex^nplified.