CA2006203A1 - Polyester resin filled with low-adhesive glass fibre - Google Patents

Abstract

TITLE

POLYESTER RESIN FILLED WITH LOW-ADHESIVE GLASS FIBRE

ABSTRACT OF THE DISCLOSURE

A glass or mineral fibre-filled polyester resin comprising a polyetherester or poly(etherimide ester) or a blend of one or both of a polyetherester or a poly(etherimide ester) with poly(butylene terephthalate) or poly(ethylene terephthalate). The composition must not have a matrix phase of poly(butylene terephthalate) or poly(ethylene terephthalate). The fibre has substantially no adhesion for the polyester base resin. The glass or mineral fibres effectively control the coefficient of linear thermal expansion of the polymer blend. The low adhesive fibre does not result in the reduction in toughness associated with conventional reinforcing adhesive fibre (which is coated with a coupling agent for the resin).

Description

POI"YESTER RESI~I FILLED WITH LOW-ADHESIVE GI~ASS FIBRE

S BACX~i:ROUND QF q'HE INVENTION

The present invention relates to glass fibre-filled polyester resins and, more particularly, to the use in polyester resins o~ glass Pibres with low adheFion for the resin to reduce the coefficient of linear thermal expansion of the polyester resin.
It is known to make exterior ~utomotive parts, for example side cladding and rocker panels, out of moulded, glass fibre-reinforced thermoplastic polymer. Thermoplastic polyesters such as poly(butylene terephthalate~(PBT~ or poly(ethylene terephthalate)(PET), for example, are stiff enough to be used as the thermoplastic polymer in such applications but are not 6ufficiently tough at low temperatures. Addition of thermoplastic elastomeric polyesters, for example a polyetherester (PEE), increases toughness. Poly(etherimide)ester6 are known to have properties very similar to polyetheresters and may be used in place of some or all of the polyetherester toughener.
The polymer blend itself has a coefficient of linear thermal expansion (CLTE) which is too high for the demanding requirements of exterior automotive parts and glass fibre is incorporated in the resin to reduce CLTE.
One such fibre-reinforced polyester resin is a thermoplastic polyester composition of wh~ch the basic components are a crystalline segmented block copolymer with elastomer~c soft 6egments and high melting cry6talline polyester hard segments (a thermoplastic elastomeric polyester) and a thermoplastic, h$gh ~odulus, high melting crystalline polyester. The thermoplastic elastomeric polyester used is 3 polyetherester containing poly (butylene terephthalate) (PBT) hard segments and polytetramethyleneetherglycol (PTMEG) soft segments. The high modulus, high melting crystalline polyester is PBT.

It is well known that the fibre ln polyester blends must act as ~ reinforcament by the use of ~n ~ppropriate coupling agent on the glass f~bre to fitrongly adhere the fibre to the polyester. However, adeguate reinforcement, while it reduces CLTE, results in a significant reduction in toughness ~s measured by elongation at brea~, Rheometrics impact 6trength or the falling dart impact test. The notched Izod impact tect 18 ~ons~dered to be not of great ~ensitivity in studies on fibre-filled resins, particularly because most of the fibres are aligned perpendicular to the impact pendulum.
Also commercially important is the surface quality of polyester compositions used in exterior automotive applications and the ability to paint exterior parts efficiently~ The surface appearance of the exterior parts must be maintained over time. 'IPaintability'' requires heat sag resistance whereby less support of the parts is needed durins painting. Surface guality requires that fibre-related surface defects should be avoided; examples of such defects are weld lines, waviness and warpage. Pibre-related surface defect~ are exacerbated by increasing glass fibre level.
The present invention aims to provide fibre filled resins which have a reduced CLTE as compared with the unfilled resin but do not have the reduction in toughness associated with previous f~bre-filled resins.

SUMMARY OF ~HE INVENrICN

The present invention i5 based on the unexpected finding that the replacement of reinforcing fibres in certain polyester resins with non-reinforcing fibres does not result in a significant loss of reduction in CLTE and yet does significantly ameliorate the loss in toughness attendant upon use of reinforeing fibres.
The invention provides a fibre-filled polyester resin, comprising:

~ polyetherester, a poly(etherimide)ester or a blend of both, or a blend of one or both of a polyetherester or a poly(etheri~ide)e6ter with a poly(butylene terephthalate) or poly(ethylene terephthalate) other than a blend having a matrix phase of poly(butylene ter~phthalate), poly(ethylene terephthalate) or both; and glass or mineral f$bres that do not subfitantially adhere to the resin, the fibre-filled resin having an elongat$on at break when injection moulded substanti~lly greater than that of the same resin when filled with reinforcing glass or mineral fibre that adhere to the resin.

DESCRIPTION OF PREFERRED EMBODIMENT
The base polymer of the invention is a polyetherester (PEE) or a poly(etherimide)ester (PEI). PEI is known to have similar properties to PEE and i8 often u~ed ~s an alternatîve to PEE; PEI ~ay therefore be referred to as a "PEE equivalentn. PEE and PEI share the feature of comprising elastomeric soft segments (polyether or polyetherimide segments) and crystalline hard segments (polyester segments). A blend of PEE and PEI may be used as the base polymer of the invention.
The PEE, PEI or PEE/PEI blend ~ay be blended with poly(butylene terephthalate). Some or all of the PBT may be replaced with PET.
The base resin may, of course, include other components, for example additives, such as carbon black or antioxidant, or glass flakes to reduce fibre anisotropy.
The nature and quantity of the other components will be selected so as not to alter the properties of the fibre-filled resin to make it unsuitable for the proposed application.
The fibre u~ed in the base resin i~ at least in part non-reinf~rcinq. Reinforcing fibre is coated with coupling agent to strongly adhere to the base resin and is a term of art which will require no explanation to the reader.

Reinforcing fibre increa6es the tensile ~trength ~nd flex modulus of the base reain. As ueed herein, "non-reinforcing" fibre refers to fibre which does not ~dhere to the resin 6ufficiently to obtain substantially full reinforcement. Thus, the fibre i8 subst~ntially non-adhesive for the resin. The fibre is usually, ~nd preferably, glass but mineral fibres can also be u~ed in place of some or all of the glacs ~ibre.
The use of non-reinforcing fibre reduces the tensile strength of the resin, at lea~t as compared with reinforced resin. We have found non-adhesive fibre to reduce the tensile strength to below that of the unfilled resin. The tensile strength may be improved by increasing the adhesiveness of the fibre and/or by incorporating reinforcing as well as non-reinforcing fibre in the resin, albeit at the expense of reduced toughness. The tensile strength of the fibre-~illed composition i8 therefore a measure of reinforcement. However, tensile ~trength is also increased by increasing the resin hardnes6 or decreasing the amount of non-adhesive filler. As explained below, a critical degree of adhesion csnnot be specified. However, experiments indicate that the use of non-adhesive or low adhesive fibres in accordance with the invention reduces tensile strength by at least 15 or 20% in the flow direction of a moulded sample, as compared with a corresponding reinforced resin. The compositions we have prepared for automotive parts usually have an absolute tensile strength of no more than about 25 MPa and often of no greater than about 22 ~Pa in the rlow direction of a moulded sample;
given the different factors which affect tensile ~trength, the importance of these figures should not be over-emphasised.
It has ~een found by transmission electron microscopy that the desired improvement in toughness is not obtained if the resin has a matrix phase of PBT or PET. Thus such resins are excluded from the invention. As the ~killed person will know, which polymer forms the matrix depends on the relative volumes and viscosities of the polymers.

s The critical property of the flbre-filled resin of the invention iB that, when in~ection moulded, lt has significantly greater elongation at break than the same base resin when filled exclusively with reinforcing fibre.
Elongation at break is widely recogni6ed as a good indirect measure of toughness. A number of different toughnQss tests are known and a feel for overall toughness ~ay be determined by ascertaining the results of different te~t~. ~owever, we regard elongation ~t break ~fi a particularly useful measure of toughness and, for example, ~utomobile manufacturers do ~pecify minimum elongations at break for exterior automotive parts. Other important tests for toughness include the CEAST impact test and rheometrics impact test.
The degree of elongation is determined by a complex interaction of different factors or parameters. TWo important factors are the proportion of fibre ~the less the amount of fibre, the greater is the elongation~ and the hardness of ther PEE or PEI ~the harder the polymer, the less is the elongation). Of course, an increased degree of fibre adhesion or proportion of reinforcing fibres reduces elongation. In a blend with P~T and/or PE~, the relative viscosities and proportions of, on the one hand, the PBT/PET
and, on the other hand, the PEE/PEI also play a role in determining elongation. Thus, an increase in the vi~cosity or amount of PBT and/or PET increases the elongation at break.
The increase in elongation achieved by the invention as compared with the corresponding reinforced resin cannot be fipecified precisely. The aim of the invention i5 to provide a significant increase in elongation and the skilled person will be able to determine whether an increase in elongation is functional or useful for any particular application. As a guide, however, the present invention can readily achieve an elongation at break twice that of a comparative reinforced resin, and an increase of five, eight or even ten times is often achieved.
An absolute elongation at break of 70% or more is commonly obtained in the flow direction of a moulded composition of the invention but it i8 more preferred to have an elongation of at least 250% or 300%. For BOme applications, an elongation of 60% might be ~atisfactory.
In view of the combination of ~actors which determine elongation at break, a unique set of parameters required to achieve any specific elongation or comparative increase in elongation cannot be given. Nevertheless, experiments indicate tbat when the Shore D hardness of the PEE or PEI
exceeds 70 or 75 it is difficult to achieve a large increase in elongation vis-a-vis the reinforced comparison; for many applications a hardness of no more than 60 to 65 D will probably be appropriate. For optimum results a hardness from in the order of 40 D up to 55 D te.g. 35 to 45 D) is preferred. Shore D hardness may be measured in accordance with DIN 53505 or ISO 868.
We have obtained useful results using fibre contents of up to 25% based on the weight of the whole ~ibre filled composition. It is preferred not to use a higher proportion of fibre. The most preferred amount of fibre is from 15 to 20 wt % and generally no less than about 10 wt % will be used. These fibre contents are not critical and, for example, will depend of the hardness of the PEE or PEI or the PBT/PET:PEE/PEI ratio. In a PBT or PET containing blend, less than 10% could be used 80 long as more PBT/PEI
was included to counteract the loss in stiffness (assuminq that the same stiffness was required).
In the case of a blend with PBT or PET, it ha~ been found that useful results tend not to be obtained if the PBT/PET:PEE/PEI ratio exceeds 60:40 or 65:35.
30The nature of the components and their relative proportions for any application may be optimised by trial and error experiment and using the guidance herein in conjunction with the knowledge of the skilled person. For any given application, an appropriate balance of properties i8 required and improving one property may involve reducing another. Thus, improving fibre ~dhesion increases tensile ~trength but reduces toughness.

The present invention i8 further described by way of example only with reference to the accompanying drawings, ln which:
Figure 1 is a Scanning Electron Microscope (SEN) picture of a prior art resin filled with reinforcing glass fibre;
Figure 2 is an SEM picture of a resin of the invention filled with a substantially non-adhesive fibre;
Fiqure 3 is a graph showinq the variation of elongation at break with PBT:PEE ratio of a 6ubstantially non-adhesive fibre-filled PEEIPBT blend of the invention and an adhesive fibre-filled PEE/PBT blend;
Figure 4 is a graph showing the variation of tensile strength with polymer hardness of unfilled PEE, PEE filled with reinforcing fibre and PEE filled with non-reinforcing fibre;
Figure 5 is a graph showing the variation of elongation at break with polymer hardness of unfilled PEE, PEE filled with reinforcing fibre and PEE filled with non-reinforcing fibre;
Figure 6 is a graph showing the variation of flex modulus with polymer hardness of unfilled PEE, PEE filled with reinforcing fibre and PEE filled with non- reinforcing fibre;
Figure 7 is a graph showing the variation of tear strength with polymer hardness of unfilled PEE, PEE filled with reinforcing fibre and PEE filled with non-reinforcing fibre;
Figure 8 is a graph showing the variation at 23C of rheometrics impact energy with polymer hardness of PEE
filled with reinforcing fibre and PEE filled with non-reinforcing fibre; and Figure 9 is a graph showing the variation of rheometrics impact energy with temperature of PEE filled respectively with reinforcing and non-reinforcing fibre and of PBT ~illed respectively with reinforcing and non reinforcing fibre.

The oomponents of the fibre-filled polyester re~in of the invention will now be de6cribed by way of non-limiting example.
The polyetherester generally compri6es a multiplicity of recurring intralinear long chain and short chain ester units connected head-to-tail through ester linkages.
The long chain ester units are represented by the structure:
O O
-OGO-CRC- (~) and the short chain ester units are represented by the structure:
O O
-ODO-CRC- (b) wherein:
G is a divalent radical remaining after removal of terminal hydroxy groups from a long chain polymeric glycol, i.e. a glycol having a molecular weight of aboveabout 400 and preferably of no more than about 6,000, the long chain glycol generally being a poly(alkylene oxide) glycol;
R is a divalent radical remaining ~fter removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than about 300; and D is a divalent radical remaining after removal of hydroxyl groups from a low ~olecular weight diol, i.e. a dial having a molecular weight of less than about 250.
If desired, the polyetherester may comprise a plurality of different long chain glycol re~idues, dicarboxylic acid residues and/or low molecular weight diol residues. The polyetherester consists essentially of the long and short chain ester units. It will be understood, therefore, that it may contain other units in an amount 6mall enough not to significantly detract from the properties of the polymer.
The long chain ester units (a) are the reaction product of a long-cha~n glycol with a dicarboxylic acid.
The long-chain glycols are polytalkylene oxide)glycols having terminal (or as nearly terminal as possible) hydroxy groups and a molecular weight of from about 400 to, preferably, 6,000.
Representative long-chain glycol~ are poly(ethylene oxide)glycol, poly (1,2-and 1,3-propylene oxide) glycol, 5 poly(tetramethylene oxide) glycol, random or block copolymers of ethylene oxide and 1,2-propylene oxide, and random or block copolvmer6 of tetrahydrofuran with minor amounts of a second monomer such as 3-methyltetrahydrofuran.
Poly(tetramethylene oxide)glycol i8 mo~t preferred.
The short-chain ester unit~ (b) are low molecular weight compounds or polymer chain units having molecular weights of less than about 550. They are made by reacting a low molecular weight diol (below about 250) with a dicarboxylic acid to form ester units represented by formula (b) above.
Included among the low molecular weight diols which react to form short-chain ester units are aliphatic, cycloaliphatic, and aromatic dihydroxy compounds. Preferred are diol6 with 2-15 carbon atoms ~uch as ethylene, propylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene and decamethylene glycols, dihydroxy cyclohexane, cyclohexane dimethanol, resorcinol, hydroquinone, 1,5-dihydroxy naphthalene etc.
Especially preferred are aliphatic diols containing 2-8 carbon atoms. Included among the bis-phenols which can be usedarebis(p-hydroxy)diphenyl,bi~(p-hydroxyphenyl)methane and bis(p-hydroxyphenyl) propane. Equivalent ester-forming derivatives of diols are alsp useful (e.g. ethylene oxide or ethylene carbonate can be used in place of ethylene glycol).
The term "low molecular weight diol~ used herein ~hould be construed to $nclude such equivalent ester-forming derivatives; provided, however, that the molecular weight requirement pertains to the diol only and not to $ts derivatives. 1,4-butanediol i8 most preferred, although 1,4- butenediol may also be used. If a mixture of diols is used, then 1,4-butanediol preferably predominates, i.e.
forms more than 50 mol ~ of the mixture.

The dicarboxylic acids are generally aliphatic, cycloaliphatic, or aromatic dicarboxyll¢ acids having a molecular weight of less than about 300. Th- term "dicarboxylic acids", as used herein, lncludes eguivalents of dicarboxylic acids having two functional carboxyl groups which perform substantially li~e dicarboxylic acids in reaction with glycols and diols in forming copolye~ter polymers. These eguivalents include e6ters and ester-forming derivatives, such as acid halides and anhydrides.
The molecular weight requirement pertains to the acid and not to its equivalent ester or ester-forming derivative.
Thus, an ester of a dicarboxylic acid having 2 molecular weight of greater than 300 or an acid equivalent of a dicarboxylic acid having a molecular weight of greater than 300 are included provided the acid has a molecular weight of below about 300. The dicarboxylic acids can contain any substituent groups or combinations which do not substantially interfere with the copolyester polymer formation and use of the polymer of this invention.
Aliphatic dicarboxylic acids, as the term iB u6ed herein, refers to carboxylic acids having two carboxyl groups each attached to a saturated carbon atom. If the carbon atom to which the carboxyl qroup is attached is 6aturated and i8 in a ring, the acid is cycloaliphatic.
Aliphatic or cycloaliphatic acids having conjugated unsaturation often cannot be used because of homopolymerization. However, some unsaturated acids, such as maleic acid, can be used.
Aromatic dicarboxylic acids, as the term is used herein, are dicarboxylic acids having two carboxyl qroups attached to a carbon atom in an isolated or fused benzene ring. It is not necessary that both functional carboxyl groups be attached to the same aromatic ring and, where mor~
than one ring is present, they can be joined by aliphatic or aromatic divalent radicals or divalent radicals such as -0-or -S02-.
Representative aliphatic and cycloaliphatic acids which can be used for this invention are sebacic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric acid, ~uccunic acid, carbonic acid, oxalic acid, azelalc acid, diethylmalonio acid, allylmalonic acid, 4-cyclohexene-1,2-dicarboxylic acld, 2-ethyl6uberic acid, 2,2,3,3-tetramethyl~ucclnic acid, cyclopentanedicarboxylic acid, decahydro-1,5-naphthalenedicarboxylicacid,4,~'-bicyclohexyldicarboxylic acid, decahydro-2,6-naphthalene dicarboxylic acid, 4,4'-methylenebis(cyclohexane carboxylic acid), 3,4-furan dicarboxylic acid, and l,l-cyclobutane dicarboxylic acid.
Preferred aliphatic acids are cyclohexane-dicarboxylic acids and adipic acid.
Representative aromatic dicarboxylic acids which can be used include terephthalic, phthalic and isophthalic acids, bi-benzoic acid, substituted dicarboxy compounds with two benzene nuclei such as bis(p-carboxyphenyl) methane, p-oxy(p-carboxyphenyl)benzoic acid, etbylene-bis (p-oxybenzoic acid), 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid, and Cl-C12 alkyl and ring substitution derivatives thereof, 6uch as halo, alkoxy, and aryl derivatives. ~ydroxyl acids such as p(~-hydroxyethoxy)benzoic acid can also be u6ed providing an aromatic dicarboxylic acid is also present.
Aromatic dicarboxylic acids are an especially preferred class for preparing the copolyetherester polymers of this invention. Among the aromatic acids, those with 8-16 carbon atoms are preferred, particularly the phenylene dicarboxylic acids, i.e., phthalic, terephthalic and isophthalic ~cids and their derivatives, especially their dimethyl esters.
It is preferred that at least 50% of the 6hort segments are identical and that the identical segments form a homopolymer in the fiber-forming molecular weight range (molecular weight >5000) having a melting point of at least 150C and preferably greater than 200~C. Copolyetheresters meeting these requirements exhibit properties such as tensile strength and tear strength at a useful level.
Polymer melting points are conveniently determlned by a differential ~canning calorimetry.
The copolyetheresters may be made by a conventional s ester interchange reaction. A preferred procedure lnvolves heating the dicarboxylic acid, e.g. dimethyl ester of terephthal~c acid, with a long chain glycol, e.g., polyttetramethylene oxide)glycol having a ~olecular weight of absut 600-2,000, and a ~olar excess of diol, e.g. 1,4-butanediol, in the presence of a catalyst at about 150-260C and a pressure of 0.5 to S atmospheres, preferably ambient pressure, whilst distilling off methanol formed by the ester interchange. Depending on temperature, catalyst, glycol excess, and equipment, this reaction can bz completed within a few minutes e.g. 2 minutes to a few hours, e.g. 2 hours.
At least about 1.1 mole of diol should be present for each mole of acid, preferably at least about 1.25 mole of diol for each mole of acid. The long chain glycol should be present in an amount of about 0.0025 to 0.85 mole per mole of dicarboxylic acid, preferably 0.01 to 0.6 ~ole per mole of acid.
This procedure results in the preparation of a low molecular weight prepolymer which can be carried to the high molecular weight copolyetherester of thifi invention by the procedure described below. Such prepoly~ers can also be prepared by a number of alternative Qsterification or ester interchange processes.
The prepolymer i8 then carried to high molecular weight by distillation of the excess of short chain diol.
This process is known as "polycondensation~.
Additional ester interchange occurs during this polycondensation which serves to increase the molecular weight and to randomize the arrangement o~ the copolyetherester units. Best results are usually obtained when this final distillation or polycondensation is run at less than about 5 ~mHg (6.67 kPa) pressure and about 200-270C for less than about two hours e.q. 0.5 to ~.5 hours.

Most practical polymerizatlon technigues rely upon ester interchange to complete the polymerization reaction.
In order to ~void excessive hold time ~t high temperatures wi~h possible irreversible thermal degradation, ~ catalyst for the ester interchange reaction ~hould be employed.
While a wide variety of catalysts can be employed, organic titanates such as tetrabutyl titanate used alone or in combination with magnesium or calcium acetates are preferred. Complex t$tanates, such as ~g[HTi(OR)6~2, lo derived from alkali or alkaline earth ~etal alkoxides and titanate esters are also very effective. Inorganic titanates, such as lanthanum titanate, calcium acetate/antimony trioxide mixtures and lithium and magnesium alkoxides are representative of other catalysts which can be used.
The catalyst should be present in an amount of 0.005 to 0.2% by weight based on total reactants.
Ester intexchange polymerizations are generally run in the melt without added solvent, but inert ~olvents can be used to facilitate removal of volatile component~ from the mass at low temperatures. This technigue i8 especially valuable during prepolymer preparation, for example, by direct esterification. However, certain low molecular weight diols, for example, butane diol in terphenyl, are conveniently removed during high polymerization by azeotropic distillation.
The dicarboxylic acids or their derivatives and the polymeric glycol are incorporated ~nto the final product in the same molar proportions as are present in the ester interchange reaction mixture. The amount of low molecular weight diol actually incorporated corresponds to the difference between the moles of diacid and polymer1c qlycol present in the reaction mixture. When mixtures of low molecular weight diols are employed, the amounts of each diol incorporated are largely a function of the amounts of the diols present, their boiling points, and relative reactivities. The total amount of diol incorporated is still the difference between moles of diacid and polymeric glycol ~
Polyetheresters o~ the aforegoing type and their preparation nre described ln U.S. Patent No. 3907926 Polyes~ of the aforegoLng type are also d~
m U.S. Patent No. 3766146. A parti ~ ar ~xd~t of such polyes~ is d~x~x~ in U.s. Patent No. 3651014.
Th~ polymer of U.s. Patent No. 3651014, which may be used in the pr~t invention, o~prises lonq cham ester units of at least one of the followLng struch~x~:

O O O O
-OGO-CRlC- and OGO-CR2C-(c) (d) and ~hort chain ester units represented by at least two of the following structures:
O O O O O O O O
Il ~I 11 11 11 lî
-OD10-CRlC-, OD10-CR2C-, OD20-CRlC- and -OD20-C22C-, wherein G is as defined above, and Rl and R2, and Dl and D2 are, respectively, different groups falling within the above definitions of R and D.
These polyesters are prepared by polymerizing ~ith each other (a) one or more dicarboxylic acids or their eguivalents (their esters, or ester-form~nq derivatives, ~0 e.g. acid chlorides or anhydrides), (b) one or more long chain glycols and (c) one or ~ore low molecular weight diols, provided that two or more dicarboxylic acids or their equivalents are used when only one low molecular weight diol i6 used and that two or more low molecular weight diol~ are used when only one dicarboxylic acid or its equivalent is present.
The poly(etherimide)ester comprises the reaction product of one or more diols, one or more dicarboxylic acids and one or more poly(oxyalkylene imlde)diacids.
The poly(etherimide)esters used in the present invention may be prepared by conventional proces~es ~rom (A) one or more diols, (b) one or more dicarboxylic acids and S ~c) one or more poly(oxyalkylene imlde)diacids. Preferred poly~etherimide)esters can be prepared when the d$ol (a) ~s one or more C2-C15 aliphatic and/or cycloaliphatic diols, when the dicarboxylic acid (b) i~ one or ~ore ~4-C16 alip~atic, cycloaliphatic and/or aromatic dicarboxylic acids or ester derivatives thereof and when the poly(oxyalkylene imide) diacid (c) is derived from one or more polyoxyalkylene diamines and one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group.
Suitable diols (a) for use in preparing the poly(etherimide)ester elastomers include ~aturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds. These diols pre~erably have low molecular weights, i.e. have a molecular weight of about 250 or less. When used herein, the terms "diols" and "low molecular weight diols" should be construed to include eguivalent ester forming derivatives thereof, provided, however, that the molecular weight requirement pertains to the diol only and not to it8 derivatives.
Exemplary ester forming derivatives are the acetates of the diols as well as, for example, ethylene oxide or ethylene carbonate for ethylene glycol.
Preferred diols include those discussed above in connection with group D.
Where more than one diol i8 employed, it is preferred that at least about 60 mole %, based on the total diol contentt be the ~ame diol, most preferably at lea~t 80 mole ~. The preferred compositions ~re those in which 1,4-butanediol is present in a predominant amount, most preferably when 1,4-butanediol is the only diol used.
Dicarboxylic acids (b) which are used to make the poly(etherimide)ester elastomer~ are aliphatic, cycloaliphatic, andlor aromatic dicarboxylic acids.

Preferably, thase acids have low molecular weight, i.e. have a molecular weiqht of les~ than about 300; however, higher molecular weight dicarboxylic acids, especially dimer acids, may be used.
Representative and preferred dicarboxylic acids are described above in connection with group R.
Where mixtures of d$carboxylic acids are employed, it is preferred that at least about 60 mole %, preferably at least about 80 mole %, based on 100 mole % of dicarboxylic acid (b) be the 6ame dicarboxylic acid or ester derivative thereof. The preferred compositions are those in which dimethyl terephthalate is the predominant dicarboxylic acid, most preferably when dimethyl terephthalate is the only dicarboxylic acid.
Poly(oxyalkylene imide)diacids (c) suitable for use herein include high molecular weight imide diacids wherein the number average molecular weight is greater than about 900, most preferably greater than about 1,200. They may be prepared by the imidization reaction of one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group which must be esterifiable and preferably is nonimidizable with a high molecular weight polyoxyalkylene diamine. The high molecular weight polyoxyalkylene diamines used to prepare the poly(oxyalkylene imide)diacids generally have the formula H2N-G-NH2 where G i~ a divalent radical remaining after removal of hydroxyl groups of a long chain ether glycol having a molecular weight of from about 600-6,0~0, usually 900-4,000. The polyalkylene diamines are those usually having 2-5 carbon atoms in the alkylene group.
Reprecentativ~ polyoxyalkylene diamines include polyoxyethylene dia~ine, polyoxypropylene diamine, polyoxybutylene diamine and the like.
A special class of poly(oxyalkylene imide)diacids i6 prepared by imidization of ~ hiqh molecular weight poly(oxyalkylene)diamine with one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride qroup and an additional carboxyl group in the presence of pyromellitic anhydride. The number of eguivalents of anhydride or vicinal carboxylic acid functions provided by the tricarboxylic acid compounds and pyromellitic anhydride should be the same as the total number of amine ~unctions. Generally, the molar ratio of pyromellitic anhydride to the tricarboxylic acid compounds containing two vicinal carboxylic acid groups or an anhydride group and an acid group ranges from 0.33 to 1.5. This modification with pyromellitic anhydride increases the molecular weight of the poly(oxyalkylene imide)diacids and increases the hydrophilic nature of the resulting poly(etherimide)ester elastomer.
In general, preferred poly(oxyalkylene imide)diacids useful herein can be characterized by the following formula:

R'OOC-R ~N-G-(X-G)~3-N\ ~ -COOR' wherein each R is independently a trivalent organic radical, preferably a C2 to C20 aliphatic aromatic or cycloaliphatic trivalent organic radical; each R' is independently hydrogen or a monovalent aliphatic or cycloaliphatic radical containing 1-6 carbon atoms or an aromatic radical containing 6-12 carbon atoms, e.g., benzyl, most preferably R' is hydrogen; and G is the radical remaining after the removal of the terminal (or nearly terminal as possible) hydroxy groups of a long chain alkylene ether glycol having an average molecular weight of from about 600 to, preferably, about 6,000, and X is 8S follOW6:

~ ~ ~

~0062(~3 Briefly, the poly(oxyalkylene lmide)diacid~ may be prepared by known imidization reactions lncludlng melt synthesis or by synthesising in n solvent ~y~tem. Such reactions will generally occur at temperatures of from 100C
to 300C, preferably at from about 150C to about 250C
while drawing off water or ~n a ~olvent 6ystem at the reflux temperature of the solvent or azeotropic (solvent) mixture.
For preparation of the poly(etherimide)ester elastomers, it i6 preferred that the diol be present in ~t least a molar equivalent amount, preferably a molar excess, most preferably 150 ~ole %, based on the mole~ of dicarboxylic acid (b) and poly(oxyalkylene imide) diacid (c) combined. Such molar excess of diol will have a beneficial effect on the polymerization kinetics and ensure complete reaction of the acid components.
Poly(etherimide)esterelastomersandtheirpreparation are well known and more fully described in United States Patents Nos. 4556688, 4556705 and 4769273.

It is preferred that a polyetherester be used in the composition of the invent$ve; rather than a poly(etherimide)ester. Most preferred are polyetheresters in which the dicarboxylic acid is terephthalic acid, optionally with a minor proportion (less than 50 mol % of the amount of terephthalic acid) of another phenylene dicarboxylic acid, e~g. isophthalic acid, the long chain glycol is poly(tetramethylene oxide)glycol having a molecular weight of from 600 to 2,000 and the 6hort chain glycol is 1,4-butanediol. Poly(ethylene oxide)glycol having a molecular wei~ht of from 600 to 1,500 is another preferred long chain glycol and optionally up to about 30 mole percent, preferably 5-20 ~ole percent, of the terephthalate in the polymer may be replaced by phthalate or isophthalate.
Particularly preferred are copolyetheresters containing 30-50~ by weight of ~hort chain ester units derived fro~terephthalate of which a ~inor proportion ~ay optionally be replaced ffl isophthalate ~nd 1,4-butanediol.

The PBT or PET preferably has a we~ght average molecular weight of from 30,000 to 70,000, more preferably from 40,000 to 60,000. As the molecular weight or visco~ity of tbe P~T or PET iB increased, o the toughness of the composition increases. When large parts, for example rocXer panels, are to be in~ection moulded, the P~T or PET should be chosen to have a low viscosity, otherwise diff~culties might arise in filling the mould.
The glass or mineral fibre $6 non-reinforcing and i8 therefore not coated with coupling agent for the resin at a reinforcing level. PEE and PEI are polar polymers and the fibre may therefore be coated with an incompatible, non-polar polymer to prevent or reduce adhesion ~unless the base resin contains a PBT or PET matrix phase). Suitable non-polar coating polymers are polyolefins grafted to maleicanhydride or an organosilane. The degree of adhesion may be modified by altering the amount of the coverinq resin; if 6ufficient polymer is used only to obtain partial coating of the fibre then improved adhesion will result, as the base resin can adhere to the exposed areas of ~ibre.
An exemplary substantially non-adhe61ve fibre for PEE
or PEI is that sold under the designation ~OCF RO8FXl~ by European Owens-Corning Fiberglass, Route de Charneux, B-4651 Battice, Belgium. Samples of the fibre are also available from Du Pont (U.K.) Limited, of Maylands Avenue, Bemel Hempstead, Hertfordshire, HP2 7DT, United Xingdom. Fibre RO8FXl i5 coated with a polyolefin re~ln grafted to a coupling agent to anchor the resin to the glass. More particularly, the coating on RO8FXl iB a silane-grafted or 30 maleic anhydride- grafted blend of polyethylene (PE) or other polyolefin and polyethylene/polypropylene (PE/PP) copolymer, in accordance with United States Patent No.
4,6S9,752 (see Column 2 lines 57-61 and Column 6 line6 39-42). The preparation of the silane graft is described in U.S. Patent No. 3,505,279. The on~osilane or maleic anhydride ~es to attach the polyolefin to the surfaoe of the glass fibres.

~ ccordinq to U.S. Patent No. 3,505,279, the coatlng polymer comprises ~ backbone of polyolefin with a molecular weight of from nbout 500 to about 50,000 w~tb an organosilane coupled to each end of the backbone polymer.
The grafted polymer is made by reacting a polyolefin with terminal unsaturated groups with an organosilane whose organic portion has a functional group reactive with the unsaturated group. The functional group ~ay be an alpha-beta double bond, an oxirane, an lmine or an amine group.
Specifically, the polyolefin ls heated to a temperature above 240F (about 115C) ~nd preferably above 350F (about 175C), but below a temperature at which decomposition occurs. In a separate vessel, a free radical catalyst is mixed with an organosilane and an organic solvent at room temperature. The organosilane may be of any type in which the organic portion has a functional group reactive with the unsaturated radical of the polyolefin. A
preferred material is an amino silane, for example gamma aminopropyltrialkoxy silane. Af~er the catalyst and the organosilane are thoroughly mixed and dissol~ed in the solvent, this mixture while at room temper~ture i8 ~lowly blended into the hot resin.
The coating can be applied directly under the bushing or off line, the latter being preferred. The coatinq may be applied using a continuous sized bundle with a conventional aqueous size. The coating can be applied by any known method, e.g. through dispers$on in water or another liguid, solution, hot ~elt coating or ~pray$ng, or el~ctrostatic powder coating, hot melt coating being preferred.
Reference is also made to V.S. Patent No. 3,644,141, which describes a method for making organosilane-grafted polyolefins dispersible in water by incorporating such a polyolefin in ~ water dispersible polyester resin. This U.S. Patent also includes a d~iption of coupling of 35 organosilane with polyolefin.
A m~re of the amcunt of organic coating on a fibre is "Lsss of Ignition" (LOI). LDI is the p~x~ntage weight loss which results when fibres are heated to burn o~f organic materi~l. Typically, the fibres are heated to 600-700C, e.g. 650C. An ~OI of, for example, from 0.4 to 0.8%, preferably 0.5 to 0.7S i~ suitable for fibres coated with substantially non-~dhesive, organos11ane grafted or maleic anhydride grafted polyolefin. The preferred R08FXl fibre has an LOI of between 0.5 and 0.7t.
~ he length of the fibre used i~ ~ further factor which affects the properties of the fibre filled res~n. Thus, as fibre length iB increased the degree of an~otropy and stiffness in the flow direction of a moulded article is increased but the CLTE and toughness are decreased in the flow direction. With very small fibres (those described as "milled"), the stiffness and CLTE of the resin are unsuitable for exterior automotive parts.
A critical range of fibre size cannot be 6tipulated because of the complex interaction of different parameters and the different physical properties desired for different applications. Fibre ~ze i8 not, of course, relevant to the gist of the invention which resides in the non-reinforcing adhesion of the fibres to the resin. However, for good results we prefer that chopped 6trand fibres be used. More particularly, a lenqth of from 3 to 6 mm, e~pecially 4 to 5 mm, e.g. 4.5 mm, is preferred. Thi8 length is the manufacturer's nominal length and a small proportion of longer and shorter fibres will be present.
Fibre length may ~lso be judged by the aspect ratio (length: diameter ratio) of the fibres. We have found ~n aspect ratio of about 320 (based on the manufacturer's nominal dimensions) to be 6atisfactory for exterior automotive parts and it is therefore preferred that the fibres have an aspect ratio of from 200 to 400. R08FXl has a nominal length of 4.5 mm and diAmeter of 14 ~m.
The fibres are broken during compounding and moulding of the resin, the degree of breakage bein~ determined by the degree of shear. Typically, the nominal or average fibre length in the moulded resin is fro~ 0.3 to 0.7 m~, especially in the order of 0.5 ~m. For exterior automotive parts, the fibre generally needs to be side fed if a twin screw extruder i6 used, in order to avoid excessive fibre breakage.
The degree of anisotropy is a further factor which affects physical properties of the fibre-filled blend. A
high degree of anisotropy reduces CLTE in the flow direction of the moulded resin and decreases elongation at break, and has the converse effect on properties in the cro6s flow direction. In the case of elongate articles, for example automotive rocker panels, a relatively high degree of anisotropy is desirable, in order that CLTE along the article may be adequately controlled. The degree of anisotropy may be increased by increasing fibre length and reduced by incorporating particles such as glass flakes, for example. Anisotropy is also increased by increasing the speed of injection moulding. The degree of anisotropy for any application can be selected by trial and error. A
measure of isotropy is crossflow: flow direction flex modulus ratio.
Typically, the co~position of the invention contains the PBT/PET and the PEE/PEI in a weight ratio (PBT/PET:PEE/PEI of no more than 60:40, e.g. from 20:80 to 50:50 or 60:40. In principle, the precise ratio used is not critical to the invention, but is determined by the desired properties for any particular application.
The total proportion of fibre is typically from 10 to 25% by weight based on the weight of the whole composition.
If more than 25% fibre i~ used, undesirable fibre-related surface defects tend to arise, as well as a reduction in maximum elongation at break and CEAST (falling dart) lmpact strength. If less than 10% is used, the reduction in CLTE
may be too small. Preferably the proportion of fibre is no more than 20% and, most preferably about 15%.
Although the following Examples demonstrate the use of glass fibre that do not substantially adhere to the resin, it is contemplated that appropriate mineral fibres could also be used.

The composition of the invention may ~urther include additive6, for example carbon black, ant1Oxidants, UV-stabilizers, lubricants, plasticizers or other types of fillers. The total proportion of such additives typically amounts to no more than 5S by weight of the matrix of the composition (the matrix compri6es the polymer and the additives). The composition generally contains an antioxidant, for example, 4,4-bis(~,~-dimethylbenzyl) diphenylamine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy hydrocinnamoyl)hexahydro-6-triazine or 1,6-bis t3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]hexane.
As a stabilizer, the composition may include a compound containing an amide linkage, e.g. a copolymer of polycaprolactam and polyhexamethylene adipamide, or a terpolymer of these two and polyhexamethylane sebacamide.
The antioxidant, stabilizer and any other additive may be incorporated at any stage. When the composition comprises a polyetherester, it ~6 preferred that an antioxidant be present during the polycondensation stage of its preparation; it i~ also preferred that an antioxidant be present at any point in the process where poly(alkylene oxide)glycol is exposed to elevated temperatures, e.g. above about 100C.
The composition may also contain glass flake in an amount of up to about 5~ by weight of the whole composition, e.g. 2-3 wt%.
The compositions of the invention may be ~ade by first mixing the base polymers, if more than one type i8 used, to form a preblend. The preblend or, as the case m~y be, cingle unmixed polymer (PEE or PEI) is then blended with the glass or mineral fibre that does not substantially adhere to the resin, and any other components, for example carbon black, antioxidant or glass flakes. The resultant blend may then be fed into an extruder. Alternatively, the ~5 ingredients may be fed separately into an extruder.
Preferably, a single screw extruder should be used or if a twin screw extruder is ~hosen, the fibre should preferably be ~ide fed because the higher shear in a twin 6crew extruder tends to break the fibre lnto excess$vely ~mall pieces.
The temperature ~nd res$dence time of the extruder must be chosen ln the usual way to ~void harmful degradatlon of the polymer. Generally, th~ melt temperature ic of ~rom about 220C to about 270C. In a single screw extruder a temperature of from about 225C to 245C, especially 230C
to 240C, is preferred; usually the temperature does not exceed 240C. A higher temperature, e.g. up to 270C and generally of at ~east 245C i~ often unavoidable in ~ twin screw extruder, because the h$gher shear makes it difficult to control the temperature.
After extrusion, the fibre-filled resin i~ usually quenched in water and cut into pellets for injection moulding into its final form. The injection moulding may be performed using a screw injection moulding machine. A melt temperature of between about 240C and about 260C (e.g.
245-255C) is customarily used and a mould temperature of from about 40C to 80C, for example 50C-70C. Other important moulding parameters such a~ in~ect$on and hold pressures and times, and cooling time, may be ad~usted for opt$mum appearance of the specimen, in the usual way.
The above temperatures especially mould temperature, would be somewhat higher if a PEE or PEI blend with PET were used.
Customarily, the moisture content of the polymer~ is controlled to avoid excessive polymer degradation, and we prefer to use polymers containing no more than about 0.25~
water by weight, ~ore preferably no more than 0.~5% by weight based on the total weight of the resin. It is also the general practice to remove surface water from the guenched compounded material by compressed air; likewise the dried material is generally further dried in a vacuum oven if its moisture content is too h$gh, e.g. above about 0.1 or 0.15 wt %.
The invention includes both the moulded and the extruded composit$on.

~X~MPLES

1. PREPARATION AND TESTING OF FIBRE-FILLED BLENDS

The Resins The polymers used to prepare the compound~ of present inventionwerethermoplasticpolybutyleneterephthalate (PBT) and polyetherester thermopla~tic el~stomer~ (PEE).
The PBT utilized for the pre6ent invention has a 10 weight average molecular weight of 50,000 and an intrinsic viscosity of 0.70 dl/g (0.lg/lOOml m-cresol, at 30C).
PEE A is a segmented copolyetherester containing 38 wt % 1,4-butylene terephthalate and 11 wt ~ 1,4-isophthalate short chain ester units derived from poly(tetramethylene ether)glycol having a number average molecular weight of about 1,000. PEE A has a Shore D hardness of 40 D.
PEE B is a segmented copolyetherester co~taining 35 wt % 1,4-butylene terephthalate short chain ester units derived from poly(tetramethylene ether)glycol having a number average molecular weight of about 2,000. PEE B also has a Shore D hardness of 40 D.
PEE C is substantially the same as PEE B except that it contain~ a minor amount of branching agent.
CB is a concentrate of carbon black in a base polyester similar to PEE A.

THE GLASS FIBR~S
The glas6 fibre referred to as 'standard' glass fibre was OCF R17BXl from Owens Corning Fiberglass (OCF), Belgium.
This glass fibre is recommended by OCF for reinforcement of PBT a6 well as of other engineering polymers ~uch a6 PET and Nylon. The glass fibre referred to as 'non-adhesive' glass fibre was OCF R08FXl from Owens Corn$ng Fiberglsss, Belgium.
That glass fibre i8 recommended by OCF for polycarbonate and PVC for improved toughness with fibre levels of up to 10%.
OCF's literature indicates that OCF R08FXl does not ~mprove elongation ~n ~traight PBT, nor ~n PET. The di~ferentiation in fibre/matrix adhesion between OCF R17BX1 and OCF R08FXl 2006;~03 is baæed on Scanning Electron Microscopy ~SEM) pictures which indicate good adhesion of polyester blend to OCF
R17BXl and no polymer adhesion o~ polyester blend to OCF
R08FX1.
In the following Tables gla68 fibres OCF R17BXl and OCF ~08FXl are identified as follows:

Glass Fibre 1 - OCF R17BXl Glass Fibre 2 - OCF R08FX1 PREPARATION

General Procedure To avoid excessive polymer degradation only PBT and polyetherester (PEE) that had a moisture content below 0.15%
were used. The ingredients were then mixed in their proper proportions in a suitable vessel such as 2 drum or a plastic bag. The mixture was then melt blended in a 2.5" (6.35 cm) ~ingle screw extruder from EAGAN at a ~elt temperature at the exit of the die of 230 to 240C, using a standard screw designed for melt blending glass filled polymers. Melt temperatures above 240C may be used for other reasons such as ~or adjustment of extrusion rate and melt viscosity of the blend. Some compounds of this invention have al60 been prepared on a 25mm twin screw extruder from Berstorff at a measured melt temperature of 250 to 265C. In this case the glass fibres were side fed downstream to avoid excessive fibre breakage, whereas all remaining ingredients were fed into the rear of the extruder. The compounded material exiting the die was guenched in water, surface water removed by compressed air and cut into pellets. In cases where the remaining moisture content was higher than 0.1% the material was dried in a vacuum oven. The dried material was then molded into test specimens using a DEMAG D60-182 standard screw injection molding machine. Preferably a melt temperature of 245 to 255C and a mould temperature of 50 to 70C was used. Other important moulding parameters such as injection and hold pressure and times and cooling time were ad~usted for optimum appearance of the ~pecimen.
In some of the Example~, the moulded 8pecimens are annealed in order to ~im~late the paint oven cyclo.
Annealing relieve~ internal ~tres~es and help~ obtain full crystalli6ation.
~EST METHODS
If not otherwise $ndicated dry-as-molded (DAM) test specimens were used for te~ting phy~ical propertie~. MELT
VISCOSITY was determined on a Rayeness vi~cometer ~t 250~C
and 5 different shear rates. Only pellets dried to a moisture content below 0.15S were used.
SHRINKAGE was determined on 3" (7.6 cm) x 4" (10.2 cm) x 2 or 3mm plaques and measured parallel as well as perpendicular to the flow direction. All plaques were endgated on the 3" (7.6 mm) 6ide with a film gate 2.75"
(6.99 cm) wide and lmm thick.
The COEFFICIENT OF LINEAR THERMAL EXPANSION (CLTE) was analysed by Thermo-Mechanical-Analysis (TMA). A Thermo Mechanical Analyzer 943 from Du Pont Instruments was used, attached to a Computer/Thermal Analyzer 9900 from Du Pont Instrument6. The test specimens normally had a height of ca.5mm. They were cut either from the midsection of a dumbbell tensile bar (according to DIN 53455) or from thecentre of a 3" (7.6 cm) x 4" (10.2 cm) x 3mm plaque.
CLTE both parallel and perpendicular to the flow direction were measured, to assess the isotropy of the in~ection moulded specimen. Before testing, all specimen6 were annealed for lh at 90 or 120C. As indicated in the Tables, the single measurements of CLTE parallel and perpendicular to the flow direction were determined either on two separate samples or both CLTEs were measured on the same sample, first in parallel then in cross flow direction.
TENSILE PROPERTIES such ~8 tensile ~trength and elongation were determined on in~ection moulded dumbbell bars according to DIN 53455 and/or on dumbbell bars (type B, according to ASTM D412) which were die-cut from 3" (~.6 cm) x 4" (10.2 cm) x 2 or 3mm plaques, parallel nnd perpendicular to the flow directi~n. A test speed of 25 mm/min was used.
FLEX MODULUS was determined accordlng to ASTM D790 on test specimens 1" (2.5 cm) wide, die-cut from 3~ (7.6 cm) x 4" (10.2 cm) x 2 or 3mm plaque~ parallel and perpendicular to the flow direction. Th~ ratio of ~lex ~odulus in parallel ver6us cross flow direction multiplied by 100 can be taken as an indicator for isotropy of the specimen which i~ known to be affected by the degree o~ gla~s fibre orientation.
TEAR STRENGTH was determined according to ASTM D624 or DIN 53515 using die B type test bar and a crosshead speed of 25mm/min. Test specimen were die cut from 3" (7.6 cm) x 4" (10.2 cm) x 2 or 3mm plaques parallel and perpendicular to the flow direction, measuring tear strength across and in flow direction, respectively.
DYNSTAT IMPACT STRENGTH according to DIN S3435 was determined on both unnotched and notched 16 x 10 x 2 or 3mm test 6pecimens which were die-cut from 3~ (7.6 cm) x 4"
(10.2 cm) x 3mm plaques parallel and perpendicular to the flow direction. A 2 Joule hammer was used.
CEAST I~PACT STRENGTH was determined with an Advanced Fractoscope System "AFS/MK3~ CEAST Modular Falling ~eight cod.6557/000 at a test temperature of +23 and -25C. A test load of 11.5kg at a fallinq height of 1.27m resulted in an impact ~peed of 5m/sec. Only 3" (7.6 cm) x 4" (10.2 cm) x 2" or 3mm plaques were used. Before the impact test the plagues were stored in the temperature chamber at the test temperature for at lea~t 1.5 h.
NOTCHED IZOD IMPACT STRENGTH was determined for resins 24 to 34 of Example 5 according to ASTM D256. ~est bars the size of a Charpy bar (DIN 53453) were die-cut from 3"
(7.6 cm) x 4" (10.2 cm) x 3mm plaques parallel to the flow direction, notched and then tested.

TEST RESULTS AND TABLES
Where not otherwise specified in thi6 ~pecification and clalms, temperatures are given ~n degrees centigrade, and all parts, prop~rtions and percentages are by weight.

~)06203 EX~NPLE_1 trefer to re8ins 1 and 2 in Table 1) A mix*ure of dry 50% poly(butyleneterephthalate), 30%
PEE A and 2~ carbon black concentrate was blended uniformly in a polyethylene bag. The ~ixture was then fed lnto the rear of a 25mm Berstorff twin screw extruder with 82% of the total feed rate. The remaining 18% gl~ss fibres OCF R17BX1 or 18% OCF R08FXl of the composition were side fed with 18%
of the total feed rate of 7kg/hr at barrel 1 to die temperature settings of 250/240/245/245~245/245/245C and RPM of 200. During the extrusion the melt temperature was between 250 and 265C; vacuum was used.
The extrudate exiting the die was quenched in water, the surface water on the strands removed by compressed air lS and cut into pellets. The pellets were then dried in a vacuum oven at 80 to 100C overnight. Those pellets were then molded into 3" (7.6 cm) x 4" (10.2 cm3 x 2mm plaques.
From those DAM plaques type B dumbbell tensile bars and 1"
(2.5 cm) wide flex bars were die-cut parallel and perpendicular to the flow direction and tested in accordance with ASTM D412 and ASTM D7g0, respectively. For Tear strength, Dynstat impact strength, CEAST impact strength and shrinkage 3" (7.6 cm) x 4" (10.2 cm) x 2 or 3mm plaques were utilized. Melt visc06ity and % ash were determined from 2S dried pellets.
The test results in Table 1 ~how that resin 2 with non-adhe~ive glass fibre OCF R08FXl had ~ lower tensile 6trength, but at the s~me time ~ surpricingly higher elongation at break in flow direction as well as cross flow directlon compared to resin 1, reinforced with standard glass fibre OCF R17BXl.
SEM pictures of resins 1 and 2 are ~hown respectively in Eigures 1 ~nd 2. OCF R17BX1 clearly adheres to the resin, whilst OCF RO8FXl ~hows no adhesion.
EXAMP~E 2 (refer to resins 3 to 13 in Table 2) These resins are glass fibre and glass flake filled 2006;~03 PBT/PEE compounds which were prepared on a 2.5" ~6.4 cm) EAGAN single Qcrew extruder. To these and subsequent reslns described in Example~ 3, 4, 5 and 6, 0.3% antloxidant Irganox 1010 ~tetrakis~methylene(3,5-ditertiarybutyl-4-bydroxy cinnamate)lmethane) was added to ~llow ln~ectionmolding at higher melt temperatures o~ up to 265~C without excessive polymer degradation. Some of the resins included a lubricant, Radia 7176, which i8 a pentaerythrytoltetra-stearate. To make up these blends only dry poly~er was~0 used. The mixtures of ~11 ingredients were uniformly blended in a polyethylene bag. These mixtures were then fed into the rear of the extruder and compounded at barrel temperature settings of 230C, RPM of 30 and an average feed rate of ca.2Or.
The extrudates exiting the die were quenched in water, the surface water removed by compressed air and cut into pellets. The pellets were then dried in a vacuum oven at 80 to 100C overnight. Those pellets were then molded into dumbbell bars according to DIN 53455 and 3"(7.6 cm) x 4"~10.2 cm) x 2 and 3 ~m plaques. From the DAM plagues, type B dumbbell bars and 1" (2.5 cm) wide flex bars were die-cut parallel and perpendicular to the flow direction and tested in accordance with ASTM D412 and ASTM D790, respectively. Other properties were tested in the 6ame way as described for Example 1.
The data in Table 2 show that flex modulus of this type of blend can be adjusted by both PBT/PEE ratio and the glass fibre level and that elongation at brea~ of resins 3 to 12, all containing OCF R08FX1, i8 larger than 300%, significantly higher than usually found for glass reinforced polymers. Resin 13, which is a control to resin 9 but contains 6tandard glass fibre OCF R17BXl, exhibits elongation of less than 20%. The elongation of only 4%
determined on injection molded tensile bars of resin 9 is believed to be an anomaly and could partially have resulted from the presence of 2% glass flakes. ~owever the tensile bar6 die-cut from plaques do also ~how for resin 9 elongations of larger than 300%. Comparing the CEAST impact strength of resins 9 and 11 does also show increased toughness at both +23C and -25C for resin 9, containing OCF R08FX1. Another important finding i6 that CLTE
especially in flow direction i6 as effectively reduced with OCF R08FXl as with ~17~Xl.

EXAMPLE 3 (refer to resins 14 to 18 in Table 3) Resins $4 to 18 were prepared in the ~ame manner as described fox resins 3 to 13 in Example 2.
All 5 resins contain a total level of glass fibres of 15%, resins 14, 15 and 16 contain OCF R08FXl and resins 17 and 18 contain OCF R17BXl.
As the ratio of PBT to the total of PEE A and PEE B
increases from 28/72 to 40/60 to 52/48 for resin 14 to 15 to 16, the flex modulus increases from 887 to 1030 to 1903 MPa on die-cut test specimen. The 1030 MPa found for resin 15 is unusually low and should be as high as the 1425 HPa measured for the control resin 5. The comparison of the flex moduli of resins 16, filled with OCF R08FXl and resin 18, reinforced with OCF R17BXl does confirm almost identical stiffness independent of the degree of glass fibre adhesion.
The data confirm dramatically improved elongation at break and CEAST impact strength for resins 14, 15 and 16 compared to resins 17 and 18. Resins 14, 15 and 16 further show that toughness decreases as the level of PBT increases.
The opposite trend, that of an increasing level of toughness with an increased proportion of PEE, ~mplies that with a higher level of PEE the level of qlass fibres OCF R08FXl can be increased to more than 15% before elongation ~nd CEAST
impact strength is adversely affected (see Example 5 and 6).
Other properties such as tear strength, Dynstat toughness and CLTE are also listed for comparison.

EXAMPLE 4 (refer to resins 19 to 23 in Table 4~

Resins 19 to 23 were prepared in the same manner as described for resins 3 to 13 in Example 2.

Resins 19 to 23 contain only one grade of PEE. In resins 19 to 23 the total level of glass fibres was 15%. To evaluate the effect of decreasing fibre adhesion, the ratio of the mixture of OCF R08FX1 to OCF R17BXl was changed from 0/15 to 7.5/7.5 to 10/5 to 12.5/2.5 to 15/0 in resins 19 to 23.
The flex moduli of all 5 resins i8 virtually the same.
As with decreasing glass fibre adhesion the tensile strength decreases, the elongation at brea~ and the CEAST impact strength increase significantly. The elonqation in the flow direction of resin 20 appears to be anomalously low, probably as a result of surface defects or fibre agglomeration.
The absolute toughness of the resins in Example 4 is however not quite as high as for the equivalent resins in Example 3. Resin 15 has for example both a higher elongation at break and requires a higher total CEAST impact energy at -25C than resin 23, indicating that the partial or total replacement of PEE B by PEE A can result in tougher compounds.
However the lower melting PEE A does diminish heat sag performance of these glass filled PBT/PEE compounds more than the higher melting PEE B does and the selection of the type of PEE and the ratio of the mixture of different types of PEE will therefore depend on the required balance of mechanical and thermal properties.
The resins containing both RO8FXl and R17BXl ~ay be considered a rough model of resin filled with low adhesive fibre having an adhesion intermediate that of non-adhesive and reinforcing fibre.

EXAMPLE S (refer to resins 24 to 34 in Table 5) Resins 24 to 34 were prepared in the same manner as described for resins 3 to 13 in Example 2.
Resins 24, 25 and 26 are equivalent to resins 14, 15 and 16 in Example 3, but PEE B was repla~ed by PEE C and glass fiber OCF R08FX1 with a lower level of coating tloss of ignition (LOI) of 0.55%~ was used. Resin 27 does contain PEE B as a second type of PEE as does resin 15, but low LOI
OCF R08FX1 was used as well. The average level of coatinq (LOI) on glass fiber OCF R08FX1 used in all other resins, including re6ins 28 to 34 of Example 5 was 0.65%.
In resins 28, 29 and 30 only the type of toughening PEE was varied at a constant PBT/PEE ratio of 40/60 and 15%
OCF R08FX1. In resins 31 and 32 the PBT/PEE A ratio was 28/72 with an increased level of OCF R08FX1 of 20 and 25%, respectively. Resins 33 and 34 are equivalent to resins 31 and 32 but contain standard glass fiber OCF R17BXl.
All those resins filled with OCF R08FXl do exhibit higher elongation at break and CEAST impact strength at -25C at virtually the same Dynstat and Notched Izod impact strength.

EXAMPLE 6 (refer to resins 35 to 40 in Table 6) Resins 35 to 40 were prepared in the same manner as described for resins 3 to 13 in Example 2.
All 6 resins in Example 6 are based on various ratios of PBT and PEE A. ~he use of only PEE A a~ toughening polymer was chosen because resins in the previous Examples had indicated an increase in toughness even at low test temperatures as PEE B was replaced by PEE A. Further adjustments were made in terms of PBT/PEE ratio (resin 35) and glass fiber level (resins 37 to 40~ to explore the toughness limits of these compounds. Resin 36 i6 equivalent to resin 35, but 15% OCF R08FX1 was replaced by 15~ OCF
R17BX1.
The resins 35, 37, 38, 39 and 40, containing non-adhesive OCF R08FXl do all exhibit a drastically increased elongation at break of larger than 300% in flow direction compared to only 10% for resin 36, reinforced with ~tandard glass fiber OCF R17BX1. Resin 36, containing standard OCF
R17BX1, does al60 have a significantly lower CEAST impact strength at -25C compared to resin 35, containing OCF
R08FX1.

~- Z~)06Z03 -- 34 _ TA~LE 1 I EXAMPL~ 1 s = ~
,_.___ ______ _....... ~._____ R~SI~ ~to . ~. 2 __. . . _ .... _ _ _ _ . .. ... _. .. , __ ~ed lnto re~r of ~xtrudor _ ._...,~..._ _ PEE B 3a 30 Fed Into ldo of extru~-r _____..~..~_ Glass ~ibre 1 ~8 Glass Fibre 2 ~ 18 _____,.~.,..._________...._._...
P~ PEE <-62 . 5/37 . 5->
~atlo (~xcludlng carbon black concentrate) ________...... ,.. ,.... _________ h (~ t~) 16.9 15.8 Propetle~ ~f ~pcc~mon dle-cut ~m 3"x4"x2 mm pl~
Fl-x Modulu~ MP~
ln ~low 2351 1961 c~o-~ ~low lOS0 976 Ten~ Stron~eh MP~
In flow ~3.9 21.2 cro~ flow 26.9 19.2 ~long-tlon ~t bro~k !~
ln~low 7.0 25.0 cro-~ ~low 9,3 70,7 _.. ,..... _ _ _ _ ... __ ....

~A9LE 21 ~XAMPLE 2 ~ o ~
_______._____________.... ____________.... ,,,.______________ RES~N NO. 3 4 5 6 7 8 9 10 11 12 13 .. ,....... ________.. ______._.__.. ___________________._... _._ ~8~ 34.~ 34.8 34.0 33.2 23.2 ~3.8 23.2 28.2 33.2 32.9 33.2 PEE A - 26.125.5 24.929.9 30.529.9 27.424.924.6 24.9 PEE B ~2.2 26.125.5 24.929.9 30.629.9 27-4 24-924-6 2~-9 CB 1.7 1.7 1.7 1.7 1-7 1-7 ~.7 1.7 1.71.7 1.7 Glass ~ibre 111-011-0 ~3-0~5.0 1~-013.0 13.0 13-0 13.0 13-0 Glass Fibre2 - ~ - 13.0 Glass Flake , _ , _ _ - 2.0 2.0 2.02.0 2.0 R~dl~7176 - - - ~ - 0.~ -SrganoxlO10 0.3 0.3 0-3 0-3 0.3 0.3 0.3 0-3 0-3 0-3 0-3 ._.. _~_._~_______________.......... ______________________.
~S/PEE ~ iO/60 ~ > <- 28/72 -~ 34/66 ~- 40/60 -~Ratlo ~exclud~n~ CB) .. _____________.__.. _._... _._~.. __________________~._.. _.. O.
K~yoneos Molt v~-co-lty t ~50C Pa~ ~Folloto) 55 /~ 453 437 46a 5~1 SO9 51~ ~S5 486 la~ - ~71 g7 /~ 351 349 371 400 ~17 395 403 37~1 3?5 331 362 555 /~ 231 229 240 2S1 253 245 237 240 239 22~ 234 1000/~ 192 187 196 201 202 l9~ 196 196 194 192 191 2777/~ 119 116 123 120 120 123 118 117 1~6 lll 116 ~h ~ ~1.0 11.2 ~2.5 1~.2 1~.7 1~.9 14.8 lC.5 ~5.4 15.0 15.8 Shrln~ 3"x4"x2mm ~la~uen ln ~low 0.30 0.29 0.27 0.20 0.20 0.25 0.20 0.20 0-25 0.20 0.20 croco flow 0.60 0.60 0.60 0.53 0.57 0.47 0.47 O.S3 0.47 O.S3 0.47 Flex Mo~ulu~ M~ ~a~ ~lo-~ut ~rom 3"x4"x2mm pl~u~
1~ flow 1002 lOB~ 8 1350 941 760 884 1055 ~226 ~20~ ~267 oro~ flow 460 S20 551 569 368 342 345 ~19 520 S24 S26 ~n~llo Pro~ext~o~ T-~ar~
Y-Str M~- 23.3 ~.4 23.3 23.~ 21.0 22.3 21.1 20.1 20.9 20.3 36.9 ~Eb ~ 3S1 3~2 359 365 372 422 405 366 4 19 16 $onolle ~rop-rtl-~ bar~ dlo-cut from 3"x4"x2mm ~l~guo~
Ylold Stronoth MPA
ln flow 22.2 23.~ 21.7 21.7 21.4 22.1 20.8 20.3 19.9 21.3 32.1 c~or~ ~low 19.5 19.~ 19.0 17.7 lB.3 19.6 17.9 17.1 17.7 17.4 19.5 Elongatlon ~e ~r~
ln flow 352 231 33- 332 41~ UR .l ~ ~7 ~n~ ~31 cro~n flow 392 392 3~5 33~ ~77 524 468 390 336 330 16 Teas ~tr~gth N/mm b~r~ dlo-cut from 3"x4"x2mm pl~o-~n ~low ~ - - 123 106 - ~ - 125 - 146 cross ~low - - - 163 137 - - - 161 - l9a ______,~,.,..,,__.,,__,.. _.,_._.,__ .,_ ___ __ ___ _ _ _ _ _ _ _ ~ Eb = Extension at break _ 36 --TA~ 2: -~or~t . -....___.,..__,...___..__ ....__...___..__..--_...,__..__~.... _..

R~S~N No. 3 ~ 5 6 7 ~ 9 10 11 12 13 P9T34.8 34.3 34.0 33.2 23.2 23.~ 23.2 2~.2 33.2 32.~ 33.2 PEE A- 26.1 25.5 24-9 29-9 30-6 29-9 27.4 24.~ 24-6 24.9 PEE B52.2 26.1 25.5 24.9 29.9 30.6 29.9 27.~ 24.~ 2~.6 2q.9 CB1-7 1.7 ~-7 1-7 1-7 1-7 1.7 1.7 1.7 1.~ 1.7 Glass Fibre 2 11-0 11.0 13.0 15-0 lS-0 13-0 ~3-0 13-0 13.0 13.0 Glass Fibre 1 - - - ~ 13.0 Glass Flake ~ ?-0 2.02.0 2.0 2.0 ~-dl~7176 ~ . o . ~ -lr~anoxlO10 0.3 0,3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0 3 0 3 ___.. _ _.. _ .... __ .. ~ ___. .... _ _.. _ __.. _ ~.. ___... ___ ~3T/PEE <--- 40/60 --~ - 2a/72 -~ 3~/66 ~- ~0/60 ->
2~tlo (3xclud~nç~ CB) .._____~_______..___....~.___..___....___...____...___.,..___...
CEAST Sm~act ~n~rgy J 3"x~"x2r~n pl~qu~ 11.5kçl~1.27m~Sm/6~c at 23C
19 ~9 17 14 1~ 17 as 12 16 ~9 13 tot~l 21 21 ~ 16 16 19 16 15 ~,8 21 17 modo ~ d ~ d d d d ~ ~ d d at-2SC
~r~X 24 23 22 20 22 2~ 22 19 20 17 9 tot~l 2~ 27 26 23 26 27 25 23 23 22 16 modc t d d ~ d ~ d d ~ d Dyn~tat notct~-d/ln ~low/KJ/m2/~ -cYt f~om 3"x4"x3mm pl.
~t ~23C n~ nb n~ nb nb nb nb n~ nb n~ nb ~t -25C n~ pb27 pb26 pb22 fl~nb ~2a pb22 p~23 Dynct~t notch-d/c~o~ flow/1W/m2/b~ lo-cut ~rom 3`'x4"x3mm pl.
~t ~23C nb nb rlb nb n~ n~ r,b Jlb nb nb nb ~t -2SC nb ~ n~ p~2~ ab n~ ~b ~24 pb~2 pD26 CLT~ / x 10-6 mm/mmC by rMA / ~p~clm-n ~r~ bar~
~n ~
-as-~2sc 36 36 31 32 26 16 35 35 30 35 29 ~2S-~ l 120~ S6 49 41 35 39 2~ 3B S3 ~4 26 30 c~o~ ~low~
-2~ 2SC ~65 132 ~20 1~ ~34 153 1~2 29 1~2 108 91 ~5-~120C al4 162 17S ;52 169 101 161 33 139 149 136 ___._.__~_.. __,.. ____.,_ _.. ___.. ,~__.~.. __.... ____.. ______.
d ~ ductllo J b - ~rlttl~ no bro~ p~rt~ roak valu-s ~ dot~m1n-~ on two dl~ ont ~amplo~ b-for- to~t~n~
the ~-mpl~ WOEO nn~alo~ ~or lh~ at 90C

~;)0~;203 TA~L~ 3: ~XAM~ 3 _~ . __. ~ ... ___.. ~. __.. __.... __,.. _,.~.. ~ .... __.. _ .. ~.. ._.

RESI~ No~ 14 ~5 ~6 17 ~
__~___ .. _. __~.__ ..... __._.. _ .,_ _... _.. ~_.~.__..... ___ P~T 23.233.2 43.2 33.2 43.2 P~:E A 2~.9 24-9 19-9 ~4-~ 19-9 PE:2 B 29-9 24.~ I9.Q 2~.9 19.9 CB 1.7 ~ .7 1-7 1.7 Glass Fibre 215-015.0 15-0 Glass Fibre 1 ~ ~ ~ lS.O 15.0 lrg~noxlO10 0.3 0.3 0.3 0.3 0,3 ___.._ _.. __. __....__.._~,._._..,_ ..._ ...~.__.~._ _ _.__ ~T/PE~ 2~2 ~0/60 ;2/48 40/C0 52~4e R-tlo ~-xclu~ing CB) _ .._ _ __ .. _ _ ... .__ . . .. _.. .. . _ _ . . . _. . . . _ _ . . __, . . _ _ . . . __ . _ . __ .. _ t~-y~n~-~ M~lt ~ co~1~cy t 2SOC PaJ ~v-llot~) SS ~ - 3-3 44~ 82 34S
97 /- ~3~9 ~62 360 35~
55S /~ -2~0 2~0 23~ 232 ~000/~ 2 193 ~93 1~
~7~7/~ -115 119 1~9 ~17 ~-h ~ -14.3 15.0 ~.9 lS.O
Shrln~ e ~ 3"x4"x3mm plaguor ln ~low 0.25 0-27 0-30 0.30 0.32 ~ro6s ~low 0.60 0.63 0.~3 0.70 0.90 Fl-x Modulu- MPa bar- dle-out ~rom 3"x4"x3mm ~laqu~
~n tlow 8~7 1030? 1903 1425 1~3 oY ~low/n-~r ~50 ~23 lOC3 81? 9S3 cr ~low/~ar 393 ~73 1027 650 9~,7 ~t~
Ten~ ro~-rt~a~ bas- dl~-cut trom 3"x4"x3mm pl~qu-~
Y1-ld str~ngth MP~
ln ~low 20 2~ 2S ~ 36 cro~- ~low ~ - 20 - 26 Ten~ Ctr-r,gth ~a ln ~low - - 21 2- 3 cro~ ~low 1~ ~ 20 19 23 ~lon~tlon ~t b~
~n 210w 300 a300 72 23 16 c~o~ ~low 300 ~300 80 1~ ~2 ~r ~tr~n~t~ N/nu~ ~r- ~lo-out ~om 3"x~nx3mm pl~que~
~n ~low 141 14~ 1~9 ~36 ~S
crw~ 3 153 1~ ~73 193 _ _ . ... _ _ . . . . . .. . _ .

S~ 3 l -cont. ~
,... ____ . _.. __.. __. ._.. ,_ .. _... _______ _ ___ RSSIt~ No. 14 15 16 ~,7 18 ~... ,.~........... _~.................. ~.__.. _____ ~BS 23~2 33.2 ~3.2 33.2 43.2 PE~: A 29.9 2409 19.9 2~.9 19-9 PEE B 29.~ 24.~ 19.9 24.9 1~.9 CB 1-7 1.7 1.~ 1.7 1.
Glass ~ibre 2 15.0 15.0 15-0 Glass Fibre 1 - - - l S . 0 15 . 0 ~rgar,oxlO10 0 . 3 ~ . 30, 3 O. 3 0 . 3 PBT/PEE 2~/72 ~0/60 52/~840/60 52/48 Ratlo ~ ~x~lu~lng CB) _________________________.___,... ,,,.. _."."______._ C~AST Imp~ct ~ne~y at -2SC - J 3~'x4"x3mm pla~ue~
~r--~c 38 39 25 10 5 total ~O 43 29 19 13 mod- d d b b b Dyn-t-t - notch~d ~t -25C - ~J/m2 3"x~"x3~ ~la~ue~
ln f lo~ nb ~24 c~7 ~b22 ~bl3 cror~ ~low nb ~b20 ob6 ~b23 cbl2 Dynrt~t - unnotc~ at -2~C - KJ/m2 ln f low n~ ~ pbl ~ pb2 ~ ~b2 1 c~o~ ~low nb nb nb nb nb CLSE xlC-~ mm/n~nC ~y ~ to ~lOOC - 3"x~"x3mm ~laqu~
ln ~low~ 10 29 19 sa c~o~ ow~ 57 64 ~6 ~6 5 _.. ,.. _.. ,....... _........ _................ ~_ d ~ duotll~ b~ltt~ J ~ ~ no ~a~ artl-1 br-~k - cb - co~ te bre~
both v~lu-~ w~ d-to~mln~d on tho r~ mpl~ or- t-~t$ng tho ~ ?10 wa~ nneal~ ~or lhr ~t 120C

_ 39 _ ~BLE 4 I EX~ E ~

J~ES2'R NO. 19 20 2l 22 23 .__.__.,..__.__.~___,_.._..._..._..__.__,,__,__.______.__.
P~3~ 33.233.2 33-2 33.2 33.2 PEE B J9.~49.11 49.~ 49.8 CB 1-7 1-7 1-7 1.7 1.7 Glass Fibre2 ~ 7.5 10.0 i2-5 lS.0 Glass ~ibre115 . 0 7 5 S . 0 2 . 5 Ir~noxlO10 0.3 0.3 0.3 0,3 0.3 PB~ 'PE~ 40/C0 ------~-~~>
~atio t~xclut~g CB) . . _ _ . __ . .. _ .. ~ _ . ._ . _ _. _ .. .. _ . ~_ . O . _ . .. _.. ._.. . ~
K~yen~ M~lt ~l~co~ty at 250C ~ Ipa~lot~
55 /~ 559 ~96 5~5 S55 565 97 /~ 621 ~20 42~ 424 410 555 /~ a52 260 256 2S6 25~
1000/~ 202 20S ~03 .203 201 2777/~ 127 12~ 126 12~ 121 ~Ch ~ 1~.2 lS.2 15.3 15.~ 15~7 Shr~n~qe ~ 3"x4"x3mm ~la~u~r ln flow 0.27 0.33 0.30 0.30 0.30 c~o~ ~low 0.73 0.73 0.76 0.6~ O.CO
Fl~x Modulu- MP~ ~ar~ d1o-cut ~rom 3"x4"x3mm ~la~u~s ln flow 12i7 1150 1223 ~2~3 1267 cr ~low/ne~r 623 597 5~7 573 643 cr flow~f~r 673 627 ~40 613 620 ga~-T-nG~lo Propertlo~ le-c~t ~rom 3"x4"x3mm ~la~ue~
Yl~ trsncth M~
~n ~low - - 22 22 c~o~ flow Tonr~1~ 6tr-nsth ~P~
~n f~ow ~1 2S 20 l9 ~o~ ow 22 1~ 19 l ~lon~atlon ~t ~r~k b In ~low 21 13 t~ ~3 2-7 cro~ ~low 12 ~3~ 269 2a4 280 T~ str~ th N/mm ~ar~ cut from 3"x~"x3~n ~ u-~ln ~low ~37 13S 13~ 0 cro~ ~low l~a 16~ 164 ~6a ~5~
,_.. _~_ . ~.. _.. _~_.0~ ... _.. __.. _ . .. ... ,,_.. ... _ Z00~i203 _ 40 --oont. -2~_ ~=~--_s--=~s~
_.. ,.... ~.___... _._______________.. .. ______________ ~ESSN No. 19 20 2~ 22 23 ___ ~ ...~.~.. ,.. _.~ _ _ _ ... _.. ~.. _. _ PB'r 33.2 33.2 33.2 33.2 33.2 PEE B 49.6 49.a 49.B ~9.~ 49.B
CB 1.7 1.7 1.7 1.7 1.7 Glass Fibre 2~ 7.S 10.0 ~2.5 15.0 Glass Fibre 1 lS.O 7.5 S.O ~.5 Ir~anoxl910 0.30.3 0,3 0,3 0,3 _ ......., .. ~.... _ _ _ _ _ . ... .. _ ..... _ P~T~ PEE c - ~ 0 ~ ~ 0 ~ - - 9 F~a~lo (~x~ludln~ CB) ,_____________... _.. ,.. ,_______________.____.. _, CEASI~ Im~ct ~nergy ~t -~5C - ,~ 3"x4"x3mm ~ ue~
bre~ ~ 8 9 10 ~7 total 20 . 19 20 23 25 modo ~ b b ~ b Dyn~t~t - notch~d ~t -25C - KJ/m2 3"x~"x3mTn pl~uoc ln ~low ~o'D23 ~b20 pb20 pbl6 pbl9 cro~r tlow pb27 pb20 ~bl6 ~bl~ pbl8 Dyn~tat - unnotcho~ ~ -25C ~ ~tJ~m2 ln ~low ~29 pb2~ pb21 ~23 pb2 cro~ ~lownb nb nh nb n~
CLTE x10-6 ~ mmC by ~MA ~ ~T to ~lOOC - 3"x4"x3nrn pl~u2s ~A flow~14 21 63 43 SS
cro~- ~low~ 35 36 39 S2 40 _______,_...... _~_____________............. ___.__ ~rlttl- t nb - no ~ros~ rtl~l b~a)c * ~oth v-lu-~ wo~o d~termlnod on th- o~ lo~ or~ t-~tlng th~ wa~ ~nn-al-d ~or lhr ~t 120C

TA~ Sa ~~XAMPS,E 5 ~--~ss . ~ _ _ ...... _ _ _ .. _ ... _ ... .,, ...... _ , ... ... ...

P~ESIN NO. 2~ 25 26 27 28 29 30 ._ .. ____... __ .. ~, _ ., .. ,.. ___.. _ _.. ~,__.. ,____,~. _ _,.. ~__ ...
P~T 23.2 33.2 ~3.2 33.233.2 33.2 33.2 PEE A 29.9 2-.9 19.9 2~-9 PEE B ' ' ~ 2~.9 - ~9.~ -, PEE C 29.~ 24.9 19.~ - ~ ~ 49.
CB 1.7 ~.-7 ~.. 7 1-~ 1.7 1.7 1.7 Glass Fibre 2 15,0b lS.0~ 15-0~15.0~15.0 ~5-0 ~5.0 ~r~noxlO100.3 0,3 0.3 0,30.3 0,3 0.3 __ ..~___....~.__....,___..~.__..~.. __.. _.__..__~ _,.__ ...__ ...
PE~T/PEE 28/72 ~0/60 ~2/48 C-~ 40/60 ~-t~o ~ex~ludln~ CB) ~ay-nos~ M-lt Vlwo-~ty ~lt 2~0C / ~ la~t~3 5S /- 532 527 ~76 549 4~ ~68 ~99 97 /~ ~25 411 ~06 3B8 377 36~ 396 555. ~ 258 2~1 2~1 245 237 228 2~4 7 000/~ l99 195 193 1 93 192 185 195 2777/- 119 119 117 ~19 lla 111 116 ach ~ 12.613.8 14.1 14.812.7 1-.6 14.
Shr ln~go ~n tlow 0.250~30 0.32 0.2S0.25 0.30 0.30 cro~ tlow 0.530.60 0.69 0.600.53 0.69 0.72 T-~t ~-clmen ~lo-cut ~rom 3"x-"x3m~ ~lagu~
~1~X Mod~llus M~a ln ~low 766117~ 1~19 13591204 1139 1108 C~06~ ~low ~3S 61~ ~27 ~S5 602 575 5 ~l~ld Str~ngth M~
ln ~low ~7. 19 ~7 a7 16 16 16 cro~r ~low - - 13 ~on~llo Str-ngth b~a ln ~low 19 lg 16 18 21 18 ~a o~o~ ow 1~ ~8 ~8 ~6 19 16 17 Elongatlon ~t b~o~k ln ~low 390 32~ 2~0 278 3~4 29~
cro~ ~low 440 320 300 292 3~ 292 292 ~r ~t~-~gth N/n~n 101109 1 18 106 cro~ w 108 120 129 122 124 109 110 dlg~rant lot o~ OCF ROaFXl with ~.O.~. o~ 5~.55 ro~ of OCF P0~FX~ u-~ h~d ~.O.X. o~ 0.6S ~
.. .. . . . _ _ . . . .

200~;Z03 T)~;8L~ 511 -cont . -___ ___,._.,.. _... ____ __ __............. ,_ _______ P~SIN t~O. 2~ 25 2~ 27 2~ 2g 30 _________..... ~.,._____ ___ _.___.__..... ,.. __.__ . _ _ __ ~BT 23.2 33.2 63.2 33.2 33.'2 33.2 33.2 PEE A 29.9 24-~ 19-~2~,.9 ~9.8 - -PEE 8 - - - 2~.9 ~ 49-~ ' PEE C 29-9 24.9 19.9 ~ . ~ 69.3 (~B ~ .7 1.7 ~,.7 1.7 1.7 ~ .7 1.7 Glass Fibre 2 15.0~ lS.O~15.0~~.5.0~ 15.0 lS.0 15.0 noxlO10 0.3 0,3 0.3 0.3 0.3 0.3 0 3 7B~P~E 2~72 40/60 52/48 ~ 60 ---~~>
Ratlo ~XCludlnc~ CB) ~ _ . _ _ _ _ _ __ _ _ . _ . _ _ .. . .., . _ . , . .. . . . ., . . ,. , __ __ __ _ ___ _ .. .. . ._ . . . ._ _ __ _ __ __ C~AS~ ~mpact Enorgy ~t -25C - ~ 3"x-"x3mm pl~.gu-e ~roa~c 42 ~1 43 3a ~ 23 tot~ ~4 ~ 6 ~2 ~7 44 30 ~o~- ~ d t d d d b ttot~h-d 2~od J/m of p~clmen ~1--cut ~rom 3"x4"x3Nn pla~
~t ~23 C ~Op 307p 278~ 260p 39Bp 308p 292~
at -~0 C - 37~ 267p 318p 428p 336p 300p t -25 C 5~9p 272p 149p 271~ 184p 237p 213p Dyn-t-t - notch~d ~t -25C - X,J/m2 3"x~1"x3n~ u~-ln f low ~b pb26 pbl9 ~26 pb26 Db28 ~b26 oro~ tlow n~ pb2~ ~lS pb2~ pb21 pb23 ~b22 ~rn6t~t - unnotch~ ~t -25C - 1W/m~ 3"x4"x3mm placue~
ln ~low n~ ~b36 ~26 pb30 ~b ~b2~ ~b23 cro~r ~low nb nb nb n~ n~ nb nb CL~E x10-6 mmtmmC by ~ - ~ to ~lOOC - 3"x~"x3mm ~aqu~-ln ~low x a2 ~o 34 38 113 60 64 cso~- flow x 1~ ~5 61 . 42 51 57 42 ... __.___________.___.. ~...... ________~_.. _..... __________ ~ffor~nt lot of OCF ~OB~Xl wlth L.O.~. o~ O.S5 ro~t o~ OC~ ~08FXl u~ h~ .S. of 0.65 ~
d ~ ductll- J ~ ~ ~rlttl~ ~ ~ s no b~kt ~, ~b - p~st~l br--k x ~oth v~ w-r- doto~mlnod on th~ s~ o~ tln~
th~ lo w~ ~nn~lo~ ~o~ lhr ~t 120C

TAa~E S~ ~ ~x~lo 5 ~e~ 5---__~.._...,__~,___,___.____..__",,__.,__..,._...-__..__--.___..__..._ RESIN No. 31 32 33 34 .. .~ ~... .. _.. _.___ ._~. _. ... .. ... _ .. .. _.. .
P~'r 21.~ 20-~ 21.~ 20.4 P~:E A S6.2 S2.6 5~-2 52-6 CE~ 1.7 1.7 1.7 1.7 Glass ~ibre 2 ~0-0 25.0 - - -Glass Fibrel ' ~ 20.0 25.0 ~rg~noxlO10O . 30 . 3 0 . 30 . 3 ~8T/PE~ ~o~ 2~/~2 ~ >
R~tlo ~exolud~n~ CB) _,..__..~..~_--._--.__-__.__~__..,_..._1--~.__..__..__O~..__..__ 1t~yen~o Melt Vl~co~lty at 2SOC ~ P~ t~) S5 /~ 752 110 751 97 /~ ~95 S76 5~2 ~40 55S /~ 2~0 298 2~6 302 1000/~ 217 227 22~ 23~
2777/- ~25 133 ~32 138 ~h ~ 1~.7 23.0 20.t 22.
Sh~lnk~e ~
ln ~low 0.20 0.~5 0.15 0.13 cro-~ ~low 0.47 0.45 0.47 0.51 S--t ~ocl~on d~e-ou~ from 3"x4"x3mm plaqu Fl-x Mo~ulu~
ln flow I~B~ 15~1 1385 1411 c~o~ ~low 54~ 5~9 55~ 595 Yl~l~ Stren~th M~
ln flow 16 16 28 29 oro~- ~low 11 11 1- 19 ~on~lo Stron~th M~
ln ~low l~ 16 10 12 oro~ flow 16 lS 12 12 ~long~lon ~t br~
ln ~ow 412 374 33 ~a crs~ ~low ~00 390 72 62 ~e~ ~tron~th ~/mm low 100 98 96 97 cro~- flo~ ~06 105 126 121 ._.,..._...,._.,,_...._..._..___.._...._.,__,,,_..,_. __ _~.._._.____._ , .. . . ...

Z006z03 ~A~ 5~: ~Gont . -_._~.... ~.. ~._~.~.. __,____._._~.. _.. ___ _ O.. _ _.. .. __ .__ ~:SIN ~to, 31 32 33 3~
.... _.~________________~,,,.. ,.~.~__________0__.. ,.... _,.. _,_____ ~T a~.8 20.~ 21-0 20.~
P~ A 5~-2 52-6 56.2 52.6 CB 1.7 1-7 1.7 1.7 Glass Fibre 2 20.a 25.0 - -Glass Fibre I ~ - 20-0 25.0 ~rg~n~xl 010 0 3 0 3 0 ~ 3 ~ 3 ._.. _.________,_,~.,,,,,,,_,_,_,____________,",,_~,,_,_________ ~B~/PEE <.._-- 28/72 ~~~
~tlo ~exc1~d1ng CB) ________ ,_...... -.__.-_________O--"__--_ _ _~_______ CEAS~ Imp-ct En-rgy At -2~C - J 3~X4"X31~1 p1 br~ak 39 a7 l~ 15 tot~1 41 35 23 21 modo d m b ~otch~ o~ J/m o~ ~oc~m~n dl~-cut t~om 3"x4"x3mm plaque6 at ~23 C 296~ 256p 398~ 3~2p ~t -10 C 357-p 235~ 339p 333p ~t -25 C 359p 222p 30,~ 292p ~no~t ~ notcho~ ~t -25C - KJ/m2 3"x~"x3r~
1n ~low nb pb27 pb23 pb2 cros~ flow pb2~ pb23 p~23 p~2 Dynot~t - unnotcho~ ~t -25C - KJ/m2 3"x~"x3mm~ ,ue~
ln ~low pb27 ~2~ p~35 pb33 c~o~t f low r.b nb n~ n~
CL~E xlO-C mm/mmC by rMA - R~ to ~lOOC ~ 3"x~"x3mm pla~
In ~low x 40 20 31 26 cro~ ~low x 42 28 34 33 ______,,,_,,,,,,,,__________~_,,_,,,,,,,,,,_,,,.,,,,,,~,__________ d ~ duotll~ br~ttl- a m ~ mlx-4 t nb ~ no brea~cJ ~, ~b ~ tl~ ak x ~oth valu~o woro ~-t-rmlnod on th~ ~amo ~mplol b~for~ te~tlnsJ
tho -mpl- w~,~ anno~lod for lhr ~t 120C

2006~03 -_ 45 --'rABLE 61 ~XAM~L~ 6 ... __________,.. _.. _____--_.... ___________... ,._______.~.

PESIN No. 3S 36 37 3~ 39 ~
. .._ , ___ _ , _ _ , -- . . . ..~ _ _ _ _ _ __ _ .--, .. . ... ~__ ____ __ . .- . _ _ _ _ _ _ . . . . ..
~I~T 37 37 19.5 23.~ 27.3 31.2 PE:~: A 46 ~1; S8.5 54.6 50-7 46-1~
CB ~.7 1.7 1.7 1.7 1.7 1.7 Glass Fibre 215 - 20 20 20 20 Glass ~ibre 1 ~ 15 nox~010 0.3 0,3 0.3 0.3 0.3 0.3 ~BT/PEE 45~SS ~5/~5 25/75 30/10 35/65 40/60 R~t lo ~ ~xo lu~lng CB ) _____,~... ~________._._.. _._______.. __,______... _____ ___ ~y~ M~lt Yl~co~lty ~t 250C / ~A ~ t~) 55 /~ 517 535 607 61~ 617 ~03 97 /~ 3~0 393 ~72 ~72 ~7 ~45 SS5 ~ 240 244 ~0 268 273 269 1000/~ 191 197 20B 210 21~ 205 2777/~ 119 120 118 ~ 2'~ 122 127 ~h ~ 14.1 14.2 17.7 18.9 19.1 lg.2 ShrlnX6g~ ~ 3"x4"x3mm p1aqu~
ln ~low 0.30 0.30 0.20 0.20 0.20 0.20 cro~c flow 0.73 0.67 0.53 O.S3 0.53 0.60 ~e~t ~clm~ out from 3"x4"x3~Nn pla~u-~
Flox ~o~u1u~ M~a ~n flow 1424 ~6~3 1298 1436 16~ 40 oro~ flow C36 ~03 4~2 S86 5~0 703 ~n~ Str~ngth ~
~n ~low 21 34 1~ 20 19 19 cro~s ~low 17 19 16 15 15 1 ~1Or.s~tlon ~t ~ k %
~ f~ow 326 10 463 4~7 3~0 319 c~ low 2~ 8 427 376 339 2~7 5t~-n~th N/r~
~n ~low ~25 145 91 95 ~C0 108 oro~ flow ~53 188 10~ 106 122 130 . . .
TA~LE 6 ~ -cont . -~........... ~.
__________ _____.. ____.. ",______._,_.,.___ ____ ___________ __ P~ES~1 No. 35 36 37 3~ 39 40 _______________________O__~.. ~.. ~........ ______________ _.__ P~T 37 37 l9.S 23.4 ~7.3 31.2 P~E A 46 46 58.5 5~.6 SO.7 ~6.8 CB 1~7 1~7 ~o? 1~7 ~L.7 ~7 Glass Fibre 215 - 20 20 20 20 Glass Fibre 1 - 15 - ~ - -Srg-noxlO10 0.3 0.3 0.3 0.3 0.3 0~3 ._._,...._~.__.___ ___ ~ _ _ __ __ ____ __ _ ___ __ P~/pEE 45/55 45/S5 25/75 30/70 35/6S ~0/60 Ratlo ~excludln~ CB) _____._._____.__.. ___.___._____.__.______.,.__.,_,.~.______~_._ C~AS~ lmp~ot Er~-rgy t -2iC - ~ 3"x4"x3mm pla~uo~
~o~c 38 13 36 36 3~ 33 eo~al 43 16 39 40 38 3t mot- d b d d d 0, Dyn~tat - notch-d at -25C - K~/m2 3"x~"x3mm pl~qu~
ln flow pbl2 pbl7 hc29 pb27 hc28 pb24 o~o~ ~low pbl5 pb21 hc25 hc22 hc22 pbl7 Dyn6tat - unno~ched Bt -25C - KH/m2 3"x4"x3mm pl~ue~
ln f low pb26 pb26 hc40 hc34 pb27 pb29 oros8 f low nb pb35 nb nb nb nb C~E x10-6 mm~mmC ~y SMA - R~ to lOOC - 3"x4"x3mm gla~uc~
ln ~low~ 29 12 5~ 26 42 ~7 cro~ flow~ S9 S9 38 5~ ~1 3S
_____________________________.. _~_.... ______________________ ___ d ductllo J ~ ~ brlttl~ J
* ~oth value~ w~r~ rml~od on tho ~uma ~um~lo~ ~fore tectlng th~ ~umpl- wa~ anneal-4 for lhr ~t 120C

Resins were compounded which contained 15% gla~s fibre R08FXl or, respectively, 15% gla~s fibre R17BXl ~nd base resins comprising, respectively:

wt % PEE A wt ~ PBT
100% o%
72% 28%
10 60% ~0 55% 45~
48~ 52%
% 100%

The resins were ~oulded and their elongation at break measured, and the results are graphically displayed in Figure 3. The area defined by the lines for the R08FXl-filled and R17BXl-filled resins may be said to represent where the invention lies, in this particular embodiment.
Figure 3 and the data shown in Tables 1 to 6 indicate that PEE (or PEI) resins with a hardness of 40 D, containing 15-20% glass fibre and combined with PBT and R08FXl have a critical PBT/PEE ratio of between 45:55 and 50:50 above which overall toughness, especially elongation ~t break, drops rapidly to the very low level of the corresponding R17BX1 resin. As the amount of glass fibre i8 reduced, so the critical PBT/PEE ratio shifts to higher PBT levels.

~XAMP~ 8 Neat PBT, PEE A and PEE's with a hardness of 55 D, 63 D, 72 D and 82 D were single screw-compounded with 20%
non-adhesive glass fibre R08FXl and 20% reinforcing glass fibre R17BXl. The resins were moulded and annealed for lh at 120~C. The resins also all contain 1.7 wt % CB and 0.3%
Irganox 1010. Some of the physical properties of the PEE
resins were plotted versus Shore D hardness and the results are ~hown in Figures 4 to 9. The data points in these graphs are connected with curves ~ust for easier comparability of the result6.
Figures 4 to 9 show the following graphs:

Figure 4: tensile 6trength ~ersus polymer hardne6s Figure 5: elongation at break versus polymer hardness Figure 6: flex modulus ver6us polymer hardness Figure 7: tear strength versus polymer hardne~s Fiqure 8: rheometrics impact ~nergy at 23C ~ersus polymer hardness Figure 9: rheometrics impact energy versus temperature.
Tensile strength and elongation at break were determined using injection moulded 1/8 inch ~3.175 mm) T-bars. Tear strength was determined using 3 inch x 5 inch x3 mm (7.6 cm x 10.2 cm x 3 mm) plaques, as was rheometrics impact strength. ~nless otherwise indicated, all tests were performed at 23C.
The following conclusions can be drawn from Figures 4 to 9:
1. Tensile strength is approximately twice AS great for glass fibre R17BXl filled resins as for glass fibre R08FXl filled resins, and increases with increasing hardness.
2. Elongation at break of R08FXl-filled resins is increasingly superior with decreasing resin hardness.

3. Flex modulus of the two types of filled resins does i not differ ~ignificantly.

4. Tear strength of the two types of resin i6 similar, except that the R08FXl-filled 63 D resin i6 significantly higher compared to the R17BXl-filled 63 D resin and the other R08FXl-filled resins.

5. Rheometrics impact 6trength at 5 mph (8 km/h) and 23C
is superior for all R08FXl-filled resins. The 63 D resin requires the highest impact energy, correlating with the maximum tear strength. Further experiments (results not shown) demonstrated that the maximum shifts from 55 D to 40 D, respectively, as the temperature is reduced from -10C
to -30~C.

200~Z03 The heat 6ag resi~tance ~nd CLTE of the re~ins of Example 8 were tested and the results obtained are shown in Tables 7a-7c. The results ~how that the CLTEs of the glass fibre R08FX1 filled resins are generally superior or at least comparable to those of the R17BXl-filled resin6. Heat ~ag of the R08FXl-filled resins is excellent up to the measured 160DC for all resins except tho6e based on PEE A.

_ ~ CD 1` O
,~ ~ o r7 .~ I` ,~ ~ o o o~ ,~ o ~
_ ,~ o ~ CO ~ o . -~ ~ o tD CO 1` 0 ~
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O I` ~i ~ O
u~ ~O CD 1~ 0 ~
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u~ ~ ~ O r~
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~ p~ w It) M N N 1~ 0 ~
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200~Z03 ~ N O O ~

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.
R .~ ~ _ 3 ~ _ , .3 0 ~ ~
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~; ~ ~ ~ ~ o o o O ~D U~ O ~ ~ U~ I~
u~ ~ ~D . . .
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a~ ~ ~D ~ ~ ~
~ ~ _ ,1 ~ ~ ,~ ~ ~ r7 OD O U~
a ~ . ~,o ~` ~ ~ ~ ~ l l l C~ O _ ~
O o s~ ~ ~ ~ In ~,SS ~ I ~n, ~V ooo _l. C.~
c2. ~ -- P- ~ O O O
E~ 13 ~3 ~a ~ ~ ~ o o 0 ~J D ~ ~ 0 N
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Claims (13)

1. A fibre-filled polyester resin, compri6ing:
a polyetherester, a poly(etherimide)ester or n blend of both, or a blend of one or both of a polyetherester or a poly(etherimide)ester with a poly(butylene terephthalate) or poly(ethylene terephthalate) other than a blend having a DatriX phase of poly(butylene terephthalate), poly(ethylene terephthalate) or both; and glass or mineral fibres that do not 6ubstantially adhere to the resin, the fibre-filled resin having an elongation at break when injection moulded substantially greater than that of the same resin when filled with reinforcing glass or mineral fibre that adhere to the resin.

2. A fibre-filled polyester resin of claim 1, wherein the percentage elongation at break is at least twice that of the same resin when filled only with reinforcing glass or mineral fibre that adhere to the resin.

3. A fibre-filled resin of claim 2, which has been injection moulded and has a flow direction and a cross flow direction and which has an elongation at break in the flow direction of at least 70%.

4. A fibre-filled polyester resin of claim 1, wherein the fibres are glass fibres.

5. A fibre-filled polyester resin of claim 1, wherein the polyetherester or poly(etherimide)ester has a Shore D
hardness of substantially no more than 75.

6. A fibre-filled resin of claim 1 where1n the resin comprises a blend containing poly(butylene terephthalate) and the weight ratio of poly(butylene terephthalate) and the weight ratio of poly(butylene terephthalate): polyetherester or poly(etherimide)ester is substantially no greater than 60:40.

7. A fibre-filled polyester resin of claim 1 wherein the glass or mineral fibre i8 present in an amount of from 10 to 25% by weight of the fibre-filled resin composition.

8. A fibre filled polyester resin of claim 1 wherein the polyetherester comprises a multiplicity of recurring intralinear long chain and short chain ester units interconnected head-to-tail through ester linkages, the long chain ester units being represented by at least one of the following structures:
and and the short chain ester units being represented by at least one of the following structures:
and wherein:
G is a divalent radical remaining after removal of terminal hydroxy groups from a long chain polymeric glycol having a molecular weight of above 400;
R1 and R2 are different divalent radicals remaining after removal of carboxyl groups from a dicarboxylic acid having a molecular weight of less than 300; and D, and D2 are different divalent radicals remaining after removal of hydroxyl groups from a low molecular weight diol having a molecular weight of less than 250.

9. A fibre-filled polyester resin of claim 8, wherein G
is a divalent radical remaining after removal of terminal hydroxy groups from a poly(alkylene oxide)glycol having a molecular weight of no more than 6,000.

10. A fibre-filled polyester resin of claim 9, wherein the poly(alkylene oxide)glycol is poly(tetramethylene oxide)glycol, the dicarboxylic acid is terephthalic acid and optionally isophthalic acid or ester thereof in a proportion of less than 50 mol % of the amount of terephthalic acid, and the low molecular weight diol in 1, 4-butanediol.

11. A fibre-filled polyester resin of claim 8, wherein the fibres are glass fibres.

12. A fibre-filled polyester resin of claim 11, wherein the glass fibre is present in an amount of from about 15 to 20% by weight of the fibre-filled resin composition.

13. A fibre-filled polyester resin of claim 12, wherein the polyetherester has a Shore D hardness not more than 55.