GB1583966A

GB1583966A - Polyesters and use thereof in dyeing

Info

Publication number: GB1583966A
Application number: GB3509777A
Authority: GB
Original assignee: Cassella AG
Current assignee: Sanofi Aventis Deutschland GmbH
Priority date: 1976-08-23
Filing date: 1977-08-22
Publication date: 1981-02-04
Also published as: BE858005A; IT1125792B; JPS5326894A; FR2362880A1; NL7709154A; DE2637926A1

Description

(54) POLYESTERS AND USE THEREOF IN DYEING (71) We, CASSELLA AKTIENGESELLSCHAFT,- formerly Cassella Farbwerke Mainkur Aktiengesellschaft, of 526, Hanauer Landstrasse, 6 Frankfurt(Main)-Fechenheim, Germany, a body corporate organised under the laws of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The manufacture of water-soluble polyesters which are branched via polycarboxylic acids is known in principle (compare U.S. Patent 3,053,782 and U.S.

Patent 3,067,158).

They are obtained by polycondensing dihydric alcohols (glycols)..and/or polyhydric alcohols (polyols) with a mixture of dicarboxylic and polycarboxylic acids or their esters, anhydrides or acid chlorides. These branched polyesters can be dispersible or soluble in the form of their alkali metal or ammonium salts.

Polyesters of this type which are soluble or dispersible in water have various possible industrial uses, for example as modifying agents for melamine resins or as a constituent of lacquers and paints. In various respects, however, the technological properties of the products known hitherto leave much to be desired.

The present invention relates to branched .copolyesters which are soluble or dispersible in water and which have a considerably extended field of industrial application by virtue of their particularly advantageous properties.

The copolyesters according to the invention are characterised in that they have an apparent molecular weight of 600 to 5,000 preferably 600 to 3,000, and contain, relative to the molar quantity of the dicarboxylic and polycarboxylic acid units involved in the structure of the polyester, 5-50 mol /O of COOM groups and e5 mol ( of S03M groups, M denoting the cation of an alkali metal, in particular the sodium cation, ammonium or the cationic radical of an organic amine.

Preferred copolyesters according to the invention contain 10 to 30 mol V0 of COOM groups.

The polyester according to the invention is built up from radicals of the following formulae

and optionally

with t'he -reservation that an equivalentamount of (A+B) can be replaced by

and an equivalent amount of (Al+B1) can be replaced by

wherein R1 denotes a direct bond or a divalent aliphatic, cycloaliphatic, araliphatic or aromatic radical, m denotes the number, 0, 1 or 2, R,' denotes an aliphatic, cycloaliphatic or aromatic radical which is trivalent if m=0, tetravalent if ml and pentavalent if m=2, R2 denotes a divalent radical which, as a statistical average, is composed to the extent of 4095 mol /" of the radicals -CM2CH2-O-CH2- CH2- and/or -CH2-CH2-O-CH2CH2-O-CH2ClI2-, to the extent of 5-20 mol V of radicals of the formula ClI2CH2OC2H4)u having an average molecular weight of 30-2,000 and to the extent of 050 mol % of aliphatic, cycloaliphatic or araliphatic radicals, n is the number 0, 1 or 2 and R2, denotes an aliphatic or cycloaliphatic radical which is trivalent if n=0, tetravalent if n=l and pentavalent if n=2, R3 is a divalent aliphatic, cycloaliphatic or araliphatic radical, R3, is a hydrocarbon radical, and p and q are the same or different and each has a value of 0, 1, 2 or 3 provided that the sum of q plus p is 1, 2 or 3.

The polyester according to the invention can contain eS mol V of SO3M groups, relative to the molar ratio of the dicarboxylic and polycarboxylic acid units involved in the structure of the polyester. The reference to the molar ratio of the dicarboxylic and polycarboxylic acid component does not mean, however, that the SO3M group can only be linked to R1 or R2 units. In the event that a polyester according to the invention is built up from X mols of dicarboxylic and polycarboxylic acid units of the formula A and A, and Y mols of diol and polyol units of the formula B and B,, it can contain 5X 100 mols of --SO3M groups which can, however, be statistically distributed either over dicarboxylic and/or polycarboxylic acid components A and/or A, or over the diol and/or polyol components B and/or B1 or over all the components A, A1, B and B,.

The polyester according to the invention is predominantly branched via the radicals A, and optionally also to some extent via B, and/or C,. Polyesters having only one branching or only two branchings in the radicals A, or B1 are preferred.

That is to say m and n preferably denote the number 0 or 1.

The COOM groups are introduced into the polyester through terminal dicarboxylic acid units which are incorporated into the polyester only by means of one carboxyl group, or through polycarboxylic acid units which are not incorporated into the polyester by means of all their carboxyl groups.

In the polyester according to the invention there may for example be 80 to 140 mol V of radicals (A+A,), relative to 100 mol V of the radicals (B+B,).

The radicals A1 may for example form a proportion of 5-60 mol %, preferably l040 mol V of the sum of the radicals A+A,.

The radicals B, may for example form up to 10 mol % of the sum of the radicals B and B,. Preferred radicals B, are those which do not contain more than 2-CH2-O- groups.

It is advantageous if at least 40 mol -V preferably 60 mol /O, of the radicals A consist of radicals of the formula A3.

Copolymers according to the invention which are particularly preferred are those in which at least 40 mol V of the radicals A consist of radicals of the formula

It is advantageous if at least 50 mol %, preferably at least 80 mol V of the radicals (B+Bt) are present as radicals of the formula -O-CH2CH2-O-CH2CH2-O- and/or -O-CH2CH2-O-CH2CH2-O-CH2CH2-O- As already indicated, some of the radicals A and B can be replaced by an equivalent proportion of radicals of the formula

wherein R3 is a divalent, aliphatic, cycloaliphatic or araliphatic radical.

Some of the radicals (A,+B,) can also be replaced by an equivalent proportion of radicals of the formula

wherein q denotes 0, 1, 2 or 3, p denotes 0, 1, 2 or 3 and p and q are so chosen that (q+p) is 1, 2 or 3, and R3, denotes a hydrocarbon radical, especially an aliphatic radical.

As can be seen, R3, is a trivalent radical if (q+p)=l, a tetravalent radical if (q+p)=2 and a pentavalent radical if (q+p)=3. Accordingly, one, two or three branchings are incorporated into the polyester through the radical C,. C, radicals which have one branching or two branchings, that is to say those in which (q+p) is I or 2, are preferred.

Polyesters according to the invention which are preferred are those in which divalent, aliphatic radicals represented by R2 contain 2 to 10 carbon atoms, divalent, cycloaliphatic radicals contain 6 to 10 carbon atoms and divalent, araliphatic radicals contain 8 to 14 carbon atoms, those in which divalent, aliphatic radicals represented by R, contain 2 to 8 carbon atoms, divalent, cycloaliphatic radicals contain 6 to 8 carbon atoms and divalent, aromatic radicals contain 6 to 12 carbon atoms, and also those in which divalent, aliphatic radicals represented by R3 contain l to 10 carbon atoms, divalent, cycloaliphatic radicals contain 6 to 11 carbon atoms and divalent, araliphatic radicals contain 8 to 12 carbon atoms.

The copolyesters according to the invention can be manufactured in a manner which is in itself known by a condensation reaction of a dicarboxylic acid component of the formula

and a polycarboxylic acid of the formula

with a diol component of the formula (B') HO-R2-OH and, optionally, with a polyol component of the formula

with the reservation that an equivalent amount of (A'+B') can be replaced by a hydroxy-carboxy acid component of the formula

(or ester thereof) and an equivalent amount of (A,'+B,') can be replaced by a compound of the formula

(or ester, anhydride or acid chloride thereof).

The ratio of dicarboxylic and polycarboxylic acids A' and A,' to diol or polyol components B' and B,', respectively, can be varied between 80 mol V: 100 mol V and 140 mol V: 100 mol V. In addition the components are so chosen that a quantity of COOH groups which is more than equivalent to the OH groups is present in the intial mixtures of the components and, in particular, such a quantity of dicarboxylic and polycarboxylic acid is employed that COOH groups are present in an excess of S to 50 mol V and preferably 10 to 30 mol V relative to the total quantity of the dicarboxylic and polycarboxylic acids (A'+A,'). The proportion of branching polycarboxylic acids A,' may for example be selected so as to be in the range of from 5 to 60, preferably 10-40 mol V of the sum of the cpmpounds of formulae A' and A,', and the proportion of branching polyols B,' may for example be selected so as to be in the range from 0 to 10 mol V of the sum of the compounds of formulae B' and B1'. It is preferable to employ branching components A,' and B,' in which m or n denote 0 or 1, that is to say components which cause only one or, at most, two branchings.

The diol component B', as already indicated, is composed of different individual substances. Diol components B' in which R2 is composed, as a statistical average, of 4(w95 mol V of the radicals -CH2-CH2-O-CH2-CH2- and/or -CH2-CH2-O-CH2-CH2-O-CH2-CH2- 5-20 mol V of radicals of the formula -CH2CH2-(O-C2H4-)u- having an average molecular weight of 300-2,000 and 0-50 mol V of aliphatic, cycloaliphatic or araliphatic radicals, are employed for the manufacture of the copolyesters according to the invention.

It is preferable to employ diol components B' in which divalent, aliphatic radicals represented by R2 contain 2 to 10 carbon atoms and divalent, araliphatic radicals contain 8 to 14 carbon atoms.

If the number of moles of the dicarboxylic and polycarboxylic acids A' and A,' employed is made equal to 100 mol V, up to 5 mol V of all the reactants can contain an SO3M group.

For the case where, a polyester according to the invention is made by a condensation reaction from X mols of dicarboxylic and polycarboxylic acids A' and A,' and Y mols of diols and polyols B' and B,' a total of 5X 100 mols of the initial compounds A', A,', B' and B,' can contain a SO3M group. The distribution of this total quantity of 5X 100 mols of components containing sulpho S03M over the individual categories of compounds A', A,', B' and B,' can be selected at will.

Instead of the carboxylic acids, it is also possible to employ their esters, especially those with readily volatile lower alcohols of 1 to 4 carbon atoms, and also anhydrides -or acid halides thereof. The condensation reaction is carried out as usual at an elevated temperature of 100--280"C, especially 130--2500C, e.g. 150- 230"C, preferably under an atmosphere of an inert gas, such as, for example, nitrogen or carbon dioxide, and the volatile products of the condensation reaction (water and/or alcohols), as well as, where appropriate, excess starting products, usually a diol, are distilled off. It can be- appropriate to apply a vacuum of, for example, 10 to 15 mm Hg or, if appropriate, even lower (0.5 mm Hg) towards the end of the condensation reaction, in order largely to remove the volatile products.

The condensation reaction normally lasts 3 to 15 hours and is carried on until the desired molecular weight has been reached. Care must always be taken to ensure that crosslinking of the copolyester does not take place as the result of a condensation reaction having been carried too far, since otherwise the products become water-insoluble and unsuitable for the purpose according to the invention.

In the condensation reaction it is possible for all the components used to be subjected to the polycondensation reaction from the start, that is to say they can be initially charged. They can also, however, be added at intervals of time in any desired sequence, so that the fractions which are first added can already form precondensates. In particular, it is advisable not to add components which cause branching until later. Particularly components which cause considerable branching, such as, for example, pentaerythritol, are appropriately added only at a relatively late point in the reaction.

The polycondensation reaction can be carried out both with the customary esterification or trans-esterification catalysts (e.g. alkali metal alcoholates, titanium alcoholates, manganese acetate and zinc acetate and also entirely in the absence of such catalysts. Both courses can have their particular advantages in an individual case and, depending on the choice, products of a different kind, above all, of course, in respect of molecular weight and solubility, are obtained when the reaction is in other respects carried out identically.

Examples of trans-esterification catalysts which can be used are alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, or alkali metal alcoholates, such as sodium methylate or ethylate, alkaline earth metal oxides or hydroxides, such as, for example, the corresponding calcium or magnesium compounds, and, furthermore, also zinc oxide or cadmium oxide, salts of organic carboxylic acids, such as sodium acetate or formate, calcium acetate or formate, or zinc acetate or formate, and organic titanium compounds, especially the titanium alcoholates, for example, titanium isopropylate or titanium butylate. The quantities to be used depend, above all, on the activity of the particular catalyst. The quantity of catalyst is normally kept as small as possible.

In the manufacture of the copolyesters, a fraction of the components (A'+B') can-be replaced by an equivalent fraction of one or more hydroxycarboxylic acids of the formula (C')

A fraction of the branching components (A,'+B,') can be replaced by an equivalent fraction of one or more branching components of the formula C,'

Herein, R3, R3,, q and p have the meanings already mentioned.

The apparent average molecular weight is determined in a vapour pressure osmometer, using dimethylformamide as the solvent. Owing to the dissociation of the acid groups or their salts, the actual average of the molecular weight is higher than the average value thus measured. The value measured is, however, an adequately precise criterion for the characterisation of the degree of condensation of the copolyesters according to the invention and for the determination of the end point of the condensation reaction.

If, in carrying out the copolycondensation reaction, components are employed in which the fraction of the components indicated above contains a SO3M group, the copolyesters according to the invention which contain SO3M groups are obtained direct. It is, however, also possible subsequently to introduce, by reaction with bisulphite, SO3M groups into an existing branched and unsaturated polyester which contains a quantity of aliphatic C-C double bonds equivalent to the number of SOsM groups to be introduced. For this purpose a branched and unsaturated polyester is first prepared, SO3M-free components being used and the components being selected in such a way that, relative to the molar ratio of the dicarboxylic and polycarboxylic acids employed, up to a total of 5 z mol V of the starting compounds A', A1,, B' and B1, contain z olefinic double bonds. It is preferable to select components in which z is 1, which therefore contain one olefinic double bond.

Suitable compounds having unsaturated C-C bonds are, in particular, maleic acid, fumaric acid and itaconic acid as well as their lower esters and anhydrides. A quantity of a HSO3M solution, especially a HSO3Na solution, which is equivalent to the unsaturated C-C bonds present in the polyester is now added, at an elevated temperature of 50 to 1000C, preferably 90 to 1000C, to the branched and unsaturated polyester thus prepared. Copolyesters according to the invention which contain -SO3M groups are obtained as a result of the addition reaction of H7SO3M the unsaturated C-C bonds which takes place.

Dicarboxylic acidcomponents which can be used for the preparation of the copolyesters according to the invention are, above all, all the dicarboxylic acids A':

or the corresponding acid halides, anhydrides or esters thereof which are suitable for the preparation of polyesters and which incorporate into the final polyester the radical

wherein R, represents a direct bond or a divalent, aliphatic, cycloaliphatic or aromatic radical and some of these radicals can additionally, within the scope of the above specifications, carry a SO3M group. R1 preferably denotes a divalent, aliphatic radical having 2 to 8 carbon atoms, a divalent, cycloaliphatic radical having 6 to 8 carbon atoms or a divalent, aromatic radical having 6 to 12 carbon atoms. Examples of suitable aliphatic, cycloaliphatic and aromatic dicarboxylic acids are: oxalic acid, malonic acid, succinic acid, methylmalonic acid, glutaric acid, dimethylmalonic acid, adipic acid, pimelic acid, suberic acid, 2,2-dimethylglutaric acid, azelaic acid, trimethyladipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,2 - cyclohexane - dicarboxylic acid, 1,3 - cyclohexane dicarboxylic acid, 1,4 - cyclohexane - dicarboxylic acid, norbornanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4- naphthalene dicarboxylic acid, 2,5 - naphthalene - dicarboxylic acid and diphenic acid. The carbon skeleton of the suitable dicarboxylic acids can also be interrupted by hetero-atoms, such as oxygen or sulphur, or hetero-groups, such as SO2.

Examples of these are diglycollic acid, thiodipropionic acid, 4,4'-oxydibenzoic acid or 4,4'-sulphonyldibenzoic acid.

As already mentioned, the said dicarboxylic acids can also be employed in the form of their esters, anhydrides or acid halides. The acid chlorides are preferred as acid halides. Suitable esters are those with mono-alcohols which can readily be distilled off, that is to say, preferably, those with 1 to 4 carbon atoms. On the other hand, esters with diols which have yet to be mentioned are also suitable. The following are examples of esters, anhydrides and acid chlorides which are suitable for the component A' or for the incorporation of A; terephthalic acid dimethyl ester, terephthalic acid diethyl ester, terephthalic acid dipropyl ester, terephthalic acid di-isopropyl ester, terephthalic acid dibutyl ester, isophthalic acid dimethyl ester, isophthalic acid diethyl ester, isophthalic acid dipropyl ester, isophthalic acid dibutyl ester, isophthalic acid diisobutyl ester, phthalic acid dimethyl ester, phthalic acid diethyl ester, phthalic acid dipropyl ester, phthalic acid di-isopropyl ester, phthalic acid dibutyl ester, malonic acid dimethyl, diethyl, dipropyl or dibutyl ester, succinic acid dimethyl or dibutyl ester, glutaric acid diethyl or diisopropyl ester, adipic acid diethyl or di-isobutyl ester, pimelic acid dimethyl, diisopropyl or dibutyl ester, suberic acid dimethyl, diethyl, dipropyl or dibutyl ester, 1,4-cyclohexane-dicarboxylic acid dimethyl, diethyl, dipropyl or dibutyl ester, 1,2 cyclohexane - dicarboxylic acid dimethyl, diethyl, dipropyl or dibutyl ester, 1,,3 cyclohexane - dicarboxylic acid dimethyl, diethyl, dipropyl or dibutyl ester, phthalic anhydride, maleic anhydride, succinic anhydride or phthalyl chloride.

The copolyester according to the invention preferably contains at least 40 mol V of radicals of the formula

relative to the radicals A1 present. This means that it is appropriate, when preparing the copolyester, to employ at least 40 mol 0/,, relative to the component A', of a benzenedicarboxylic acid of the formula

that is to say phthalic acid, isophthalic acid or terephthalic acid or esters thereof, anhydrides, in so far as they exist, or acid chlorides thereof. Particularly good results are obtained if at least 40 mol V, relative to the component A', of radicals of the formula

are incorporated into the copolyester. It is therefore particularly appropriate, when preparing the copolyester, to employ at least 40 mol V relative to the component A', of isophthalic acid of the formula

or an ester thereof, in particular isophthalic acid dimethyl ester, or mixtures of two or three benzenedicarboxylic acids which predominantly contain isophthalic acid or esters thereof.

Diol components which can be used for the preparation of the copolyesters according to the invention are, above all, all the diols B': (B') HO-R2-OH which are suitable for polyester manufacture and which incorporate into the final polyester the radical (B) -O-R2-O- wherein R2 is a divalent aliphatic, cycloaliphatic or araliphatic radical as specified earlier which, within the scope of the limitation indicated above, can also carry an additional SO3M group. As a statistical average, R2 is composed of from 40 to 95 mol V of radicals of the formula -CH2CH2--O-CH2CH2- and/or radicals of the formula -CH2CH2-O-CH2CH2-O-CH2CH2-, from 5 to 20 mol V of radicals of the formula CH2CH2(OC2H4)u, wherein u is a number such that said radicals of the formula CH2CH2(OC2H4)u have an average molecular weight of from 300 to 2,000 and from 0 to 50 mol V of aliphatic, cycloaliphatic or araliphatic radicals, in particular cycloaliphatic radicals having 6 to 10 carbon atoms or araliphatic radicals having 8 to 14 carbon atoms.

The following are examples of suitable diols B' which supply the radical B: ethylene glycol, propane- 1 ,2-diol and propane- 1 ,3-diol, butanediols, especially butane- 1 ,4-diol, pentanediols, such as pentane-1,5-diol, hexane-diols, especially hexane- 1 ,6-diol, decane-1,10-diol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycol of molecular weight 300--2,000, bis - (4 - hydroxybutyl)- ether, 2methylenepropane - 1,3 - diol, 2,4 - dimethyl - 2 - ethyl - hexane - 1,3 - diol, 2 ethyl - 2 - butyl - propane - 1,3 - diol, 2,2 - dimethyl - propane - 1,3 - diol, 2 ethyl - 2 - isobutyl - propane - 1,3 - diol, 2,2,4 - trimethyl - hexane - 1,6 - diol, 1,3 - dihydroxy - cyclohexane, 1,4 - dihydroxy - cyclohexane (quinitol), 1,4 bis - (hydroxymethyl) - cyclohexane, 1,3 - bis - (hydroxymethyl) - cyclohexane, 1,2 - bis - (hydroxymethyl) - cyclohexane, 1,4 - bis - (hydroxymethyl) - benzene, 1,3 - bis - (hydroxymethyl)- benzene and 2,6 - bis - (hydroxymethyl)naphthalene.

Further examples of suitable components B' are araliphatic bishydroxy compounds which have been obtained by reacting diphenols with 2 s mols of ethylene oxide and to which, for example, the general formula B2,

wherein r is 0 or 1 and s is l, 2, 3 or 4, can be assigned.

By means of this compound the radical B2

wherein r and s have the meaning mentioned, is incorporated into the copolyester molecule. In calculating the mol percentages, B2 is included with the radicals B, and B2, is included with the components B', respectively. The following are examples of suitable components B2,:

and also other products which are polyoxyethylated on both sides.

As already indicated, the dicarboxylic acids A! and the diols B' can be replaced by equivalent amounts of hydroxycarboxylic acids C', or esters thereof, which incorporate into the final copolyester the radical

wherein R3 denotes a divalent, aliphatic, cycloaliphatic or araliphatic radical, one fraction of which can, within the scope of the above specifications, also contain an additional S03M group. In particular, R2 denotes a divalent, aliphatic radical having 1 to 10 carbon atoms, a divalent, cycloaliphatic radical having 6 to 11 carbon atoms or a divalent, araliphatic radical having 8 to 12 carbon atoms, and in the araliphatic radical the aliphatic part can also be separated from the aromatic part by a hetero-atom or the aliphatic part can also be interrupted by a hetero-atom. A suitable hetero-atom is, in particular, oxygen. The following are examples of suitable hydroxycarboxylic acids C' which supply the radical C: glycollic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5 - hydroxy - penten - 3 -. oic acid, mandelic acid, 3.- hydroxymethyl cyclohexane - carboxylic acid, 4 hydroxymethyl- cyclohexane - carboxylic acid, 6 - hydroxymethyl - decalin - 2 - carboxylic acid,

The following should be mentioned as examples of suitable esters of hydroxycarboxylic acids C': lactic acid methyl ester, lactic acid ethyl ester, 4hydroxybutyric acid methyl ester, mandelic acid ethvl ester,

Within the scope of the limitation indicated above, the radicals A2, A3 and B2 can also contain a SO3M group. Both aliphatic, cycloaliphatic, aromatic or araliphatic compounds can be employed as compounds A', B' or C' which contain SO3M groups.

The following are examples of suitable compounds A', A2, and A3,, or esters, anhydrides or acid chlorides thereof, which carry SO3M: sodium sulphosuccinic acid, potassium sulphosuccinic acid, ammonium sulphosuccinic acid, 4 - sodium sulphophthalic acid, 4 sodium - sulphophthalic an hydride, 4- potassium sulphophthalic acid, 2- sodium - sulphoterephthalic acid, 2- sodium sulphoterephthalic acid dichloride, 5 - sodium - sulphoisophthalic acid, 5 sodium - sulphopropoxy - isophthalic acid, 5 - sodium - sulphoethoxy isophthalic acid, sodium sulphosuccinic acid dimethyl ester, sodium sulphosuccinic acid diethyl ester, 4 - sodium - sulphophthalic acid diethyl ester, 4 - sodium sulphophthalic acid dimethyl ester, 4 - ammonium - sulphophthalic acid dimethyl ester, 2- sodium - sulphoterephthalic acid diethyl ester, 5- sodium sulphoisophthalic acid dimethyl ester, 5 - sodium - sulphopropoxy - isophthalic acid dimethyl ester, 5 - sodium - sulphoethoxy - isophthalic acid diethyl ester, 5 sodium - sulphoethoxy - isophthalic acid diisopropyl ester, 5- potassium sulphoethoxy - isophthalic acid di-n-propyl ester,

The following should be mentioned as examples of hydroxycarboxylic acids C', or esters thereof, which carry S03M groups:

The following are examples of compounds B' which carry S03M groups:

It is apparent from the examples mentioned that the SO3M group can be linked either directly or indirectly, for example via radicals such as -OCH2CH2-, -O-CH2CH2CH2- or

to the real carbon skeleton of the molecule of the compounds A', A,', A2,, A3,, C', C,' and B'.

The copolyesters according to the invention are branched. It is therefore also necessary, for the manufacture of the copolyesters, additionally to utilise components by means of which a branching is incorporated into the copolyester, in addition to the components A' and B' which have already been mentioned, and optionally A2,, A3, and/or C'.

Branching components of this type are: a) The polycarboxylic acids A,' which have 3, 4 or 5, preferably 3, carboxyl groups, or esters thereof, especially those with lower alcohols having 1 to 4 C atoms, anhydrides thereof or acid chlorides thereof: and optionally b) the polyhydroxy compounds B1, which have 3, 4 or 5, preferably 3, hydroxyl groups; and optionally c) the hydroxycarboxylic acids C,' which have up to 3 further hydroxyl or carboxylic acid groups.

The polycarboxylic acids A,' mentioned under a) which have 3, 4 or 5, preferably 3 or 4, carboxyl groups can also, within the scope of the above limitation, carry a SO3M group. Compounds of the formula A,' introduce the radical A, into the copolyester molecule, the number of the branchings ZA which are incorporated into the copolyester molecule by means of a radical A, or a compound A,' being ZA=m+l.

The following are examples of suitable compounds A,' which incorporate the group A, into the copolyester molecule: trimellitic acid, trimesic acid, hemimellitic acid, mellophanic acid, prehnitic acid, pyromellitic acid, aconitic acid, tricarballylic acid and ethanetetracarboxylic acid.

Anhydrides are also suitable, such as, for example: trimellitic anhydride, pyromellitic dianhydride, hemimellitic anhydride, mellophanic dianhydride and prehnitic anhydride.

Esters are also suitable, especially those with alcohols having 1 to 4 C atoms, such as, for example: trimellitic acid trimethyl ester, trimellitic acid triethyl ester, trimesic acid trimethyl ester, hemimellitic acid trimethyl ester, mellophanic acid tetramethyl ester, prehnitic acid tetramethyl ester, pyromellitic acid tetramethyl ester and pyromellitic acid tetraethyl ester.

The following are also suitable, for example: 1,2,3 - cyclohexanetricarboxylic acid, 1,2,4 - cyclohexanetricarboxylic acid, 1,3,5 - cyclohexanetricarboxylic acid and naphthalenetricarboxylic acids.

The polyhydroxy compounds B,' mentioned in the preceding text under b) which have 3, 4 or 5, preferably 3 or 4, hydroxyl groups, can also, within the scope of the limitation indicated above, contain a SO3M group. the number of the branchings Za which are incorporated into the copolyester molecule by means of a radical B, or a compound B,', is ZB=n+l.

The following are examples of suitable compounds B,': glycerol, erythritol, pentaerythritol, trimethylolpropane and trimethylolethane.

Compounds B,' in which n is 0 or 1 and which, accordingly, contain three or four hydroxyl groups in the molecule are particularly suitable. With these compounds there is less risk of an overdosage during the manufacture of the copolyester which would produce crosslinking to give insoluble products, A quantity which is permissible within the scope of the limitation mentioned above, of the hydroxycarboxylic acids C,' mentioned under c) which have up to 3 further hydroxyl or carboxylic acid groups, can contain a SO3M group. The number of the branchings Zc which are incorporated into the copolyester molecule by means of a radical C, or a compound C,', is Zc=q+p.

Examples of suitable compounds C,' are: citric acid, malic acid and tartaric acid.

Instead of the free hydroxycarboxylic acids of the formula C,', it is also possible to employ corresponding derivatives, in particular the corresponding esters with lower alcohols, that is to say with 1 to 4 C atoms, for example: citric acid trimethyl ester, malic acid dimethyl ester and tartaric acid dimethyl ester.

Unless products are being manufactured for particular end uses, in the case of the compounds A,' and C,', as also in the case of the compounds B,', those compounds are normally preferred which incorporate only one branching or only two branchings into the copolyester molecule, that is to say those in which m or n is 0 or 1 and q+p is 1 or 2, since with them there is the least risk of an overdosage which leads to crosslinking.

For the manufacture of the copolyesters, 80140 mol V of the polycarboxylic acid component consisting of the compounds A' and A,' are commonly employed, relative to 100 mol V of the polyol component consisting of the compounds B' and B,' (any compounds B2, present are included with the compounds B'), and the components are so chosen that, relative to 100 mol V of the polycarboxylic acid component (A'+A,'), up to 5 mol V of SO3M groups are present, or, if the SO3M groups are introduced by an addition reaction with a finished S03M free copolyester, up to 5 mol V of unsaturated C-C bonds are present. Normally, 1 to 40 mol V preferably 5 to 40 mol V of branching components (A,'+B,') are employed, relative to 100 mol V of a polycarboxylic acid component (A'+A,'). At least 40 mol V of the compounds A' advantageously consist of benzenedicarboxylic acids A2, and, in particular, of isophthalic acid A3,. It is furthermore advantageous if the compounds of the polyol component consisting of the components B'+B,' are so chosen that at least 40 mol V of diethylene glycol and/or triethylene glycol are employed, relative to 100 mol V of (B'+B,').

If hydroxycarboxylic acids C' or C,' are employed in the manufacture of the copolyester, these compounds must be distributed arithmetically over the polycarboxylic acid and polyol component or over the branching component (A,'+B,'), in accordance with the number of hydroxyl and carboxyl groups present, when establishing the mol percentages. For example, when calculating the mol percentages, a hydroxy-carboxylic acid of the general formula C' is thus included as to one half with the component A' and as to the other half with the component B'. One representative or several representatives of each of the components A', A,', A2,, A3,, B',-B 1" B2,, C' and C,' can be employed for the manufacture of the copolyesters. The radicals A, A1, A2, A2, B, B,, B2 C and C, are incorporated statistically during the manufacture of the copolyesters. For this reason and because of the branchings present, it is no longer possible to specify a simple formula for the copolyester according to the invention. If, for example, the number of branchings was indicated in the preceding text as 1, this means that 1 to 40 mol V preferably 50 to 40 mol V of radicals A, having m=0 and optionally of B, having n=0 and optionally of C, having (q+p)=l are present, distributed statistically, relative to 100 mol V of the radicals (A+A,).

The copolyesters according to the invention are suitable for many kinds of applications and, in particular, are outstandingly suitable as levelling auxiliaries in polyester dyeing, above all for rapid dyeing processes. They are also suitable as hair setting lotions, as sizes, as water-soluble adhesives and as an additive for adhesives and as a modifying agent for melamine resins or other aminoplast resins with the manifold end uses associated therewith.

Wide possibilities of variation exist, depending on the choice of the individual components. Thus aliphatically linked SO3M groups, especially SO3Na groups, effect a significantly stronger improvement on the solubility in water of the products than does an aromatically linked SO2M group. Moreover, isophthalic acid or aliphatic dicarboxylic acids have a favourable effect on the solubility in water, but terephthalic acid has an unfavourable effect. Bisalcohols containing ether groups also have a favourable effect on the solubility in water, but simple bisalcohols, on the other hand, have an unfavourable effect. Every desired property can be adjusted by varying the quantity and the nature of the individual components.

The copolyesters according to the invention have a real or colloidal solubility in water or can at least be dispersed easily without the use of special dispersing agents. When using the copolyesters according to the invention, application in other solvents can be carried out; it can be appropriate, above all to effect, a partial addition of other solvents, preferably alcohols, such as methanol or ethanol, or dipolar, aprotic solvents, such as dimethylformamide or dimethylsulphoxide.

Products with a low degree of branching act, above all, as sizing agents or, in particular, as levelling auxiliaries for polyester dyeing. Products with a greater degree of branching are particularly suitable as modifying agents for melamine resins if they are branched partially via polyalcohols, that is to say partially via the radical B,; if they are wholly branched via polycarboxylic acids, that is to say via the radical A1, they are the particularly suitable for the manufacture of hair setting lotions. Products which contain very high additions of polyalcohol or polycarboxylic acid tend to cross-link to give insoluble resins during the condensation reaction.

The copolyesters are generally produced during manufacture with a pH value of 2 to 5, so that it is frequently appropriate to increase the pH value to pH 6 to 7 by stirring in an aqueous solution of a base, whereby acid groups COOH are converted into salts COOM wherein M denotes the cation of an alkali metal or of an organic amine or the ammonium ion.

When used as levelling auxiliaries in polyester dyeing, the water-soluble copolyesters according to the invention display a certain partial carrier action.

Probably, a reversible addition reaction takes place between the disperse dyestuff and the molecules of the auxiliary, and this reaction is outweighed in favour of the final absorption of the dyestuff onto the fibre. As a result the dyestuff is brought up very uniformly and with a certain degree of delay to the fibre and thus produces extremely level dyeings. It is surprising in this mode of action that there is no retention of the dyestuff on the auxiliary and that full depths of colour are obtained. It is not necessary to prolong the dyeing time. A further surprising mode of action of the copolymers according to the invention makes it possible to employ even insoluble dyestuffs which have been inadequately finished. In the course thereof the optimum fine distribution which is necessary for dyeing is produced even in dyeing liquor which has been heated to over 1000 hand simultaneously an extremely high stability of the dyeing liquors is achieved. The harmful tendency to crystallisation which is often observed with disperse dyestuffs is also reduced or eliminated, so that it is possible to prevent deposition of the dyestuff and deposits on the material to be dyed.

All these factors together lead to an increase in the tinctorial yield which could not have been foreseen. When using the copolyesters according to the invention as levelling auxiliaries it has become possible even for dyestuffs which, by virtue of their individual properties, could not have been employed, for example, for dyeing wound packages, to be used for these purposes. The use of cheaper products is thus possible in many cases.

A further considerable advantage arises for the rapid dyeing processes which are universally desirable.

The effect of the copolyesters according to the invention is to match to one another the absorption curves of the disperse dyestuffs employed. This means that, with combinations of three or even four dyestuffs, it is not necessary to make allowances in respect of the individual absorption phases. Although a retarding effect cannot be established with high temperature dyeings and also with dyeings at 100"C, the absorption rate of the dyestuffs in the rapid dyeing technique is certairily lowered. In these processes large quantities of dyestuff are suddenly presented to the polyester fibres at 1300C at specific places in the dyeing vessel, which can produce unevenness. In this case a reduced dyestuff absorption rate is advantageous, since it produces even dyeings.

For dyeing, the dyebaths are made up at 5(600C in the customary manner, adjusted to pH 56 by means of substances which regulate the pH and prepared by adding the appropriate copolyester in quantities of 0.1-5 g/l. After the predispersed, water-insoluble disperse dyestuff has been added, the bath is heated up to the required dyeing temperature and dyeing is carried out for the customary dyeing time. The dyeings are finished in the customary manner, for example by means of a reductive after-scouring. A subsequent dry heat treatment or other measures for the removal of residual "quantities of carrier" are superfluous, since none of these remains on the goods and thus the fastness to light of the dyeing also cannot be harmfully affected.

In the rapid dyeing processes, the dyeing liquors are also brought to the required dyeing temperature of 120--1300C, with the addition of the quantities of auxiliary according to the invention separately from the material to be dyed. They are then allowed to flow very rapidly into the dyeing apparatus containing the material to be dyed and are thus brought into rapid contact.with the fibre. In the course thereof the dyestuff is fixed in an absolutely level manner. Different dyestuff absorption properties are assimilated to one another by means of the copolyesters according to the invention. When dyeing by the injection technique, it is, of course, readily possible to add the copolyesters according to the invention to the dyebath before the addition of the dyestuff dispersion.

It is to be noted that the invention additionally includes a method of dyeing a polyester in an aqueous medium using a copolyester as described herein as a levelling agent, and an aqueous dyeing liquor for dyeing a polyester, which liquor comprises a dyestuff and a polyester as described herein, with the proviso, in each case, that the copolyester concerned can have radicals R2 comprising 0 to 20 mol V (i.e. not necessarily 5 to 20 mol V) of the radicals of the formula -CH2CH2-(O- C2H4)U The following abbreviations are used in the examples: IPA=isophthalic acid DMI=isophthalic acid dimethyl ester DMT=terephthalic acid dimethyl ester SIM=5-sodium-sulphonato-isophthalic acid dimethyl ester K-SIM=5-potassium-sulphonato-isophthalic acid dimethyl ester SPO=5-sodium-sulphonatopropoxy-isophthalic acid dimethyl ester TPA=terephthalic acid TMA=trimellitic anhydride MA=maleic anhydride DEG=diethylene glycol TEG=triethylene glycol TMP=trimethylolpropane TME=trimethylolethane PEG=polyethylene glycol MW=average apparent molecular weight SA=succinic anhydride PDA=pyromellitic dianhydride The temperatures are quoted in "centigrade; unless otherwise specified, the percentages quoted are percentages by weight.

Example 1 80 mol V of IPA; 20 mol V of-TMA; 90 mol V of DEG; 10 mol V of PEG 600; MW 1,420.

238.5 g (2.25 mols) of diethylene glycol, 150 g (0.25 mol) of polyethylene glycol 600 and 332 g (2 mols) of isophthalic acid of a purity of at least 99V strength are heated to 1600 in the course of one hour, under nitrogen and without the addition of a catalyst, -in a 4-litre four-necked flask with ground joints, equipped with a stirrer, a thermometer, a gas inlet tube for nitrogen and a descending condenser.

The temperature in the flask is then raised, in the course of 3 hours, by a further 20 per hour, up to 2200. Heating is then continued for 2 hours at 22-2250, after which a total of about 52-55 g of water are distilled off. The internal temperature is now reduced to 1500 and .96 g (0.5 mol) of trimellitic anhydride are stirred in in portions in the course of half an hour (while continuing to pass nitrogen over the surface, of course). Tke contents of the flask are then heated first to 2000 in the course of one hour, to 2100 in the course of a further hour and to 2200 in the course of a third hour. Finally, heating is continued for a further 2 hours at 22O2.250 and lastly, a waterpump vacuum is applied at this temperature. As soon as a vacuum of 1015 mm has been reached, the condensation reaction is completed in the course of a further half hour. Approximately 15 ml of water are again collected in the receiver in the course of the second condensation phase. 732 g of an ambercoloured residue are obtained, which can readily be made up to 3,660 g with water and approximately 140 ml of 27V strength sodium hydroxide solution to give a pale, virtually clear 20V strength solution of pH 7. The molecular weight of the melt is 2,130; the apparent molecular weight of the sodium salt (on account of the dissociation effects which occur) is only 1,420, however. The COONa mole percentage was 48.53.

If heating is carried out for a shorter time in vacuo at 220225 , a product with a lower molecular weight is obtained; on longer heating, however, a product with a higher molecular weight is obtained.

Example 2 If an aliquot quantity of hemimellitic acid is used instead of TMA in Example 1, a product with correspondingly good properties is obtained, its apparent molecular weight being 1,510.

Example 3 If an equivalent quantity of polyethylene glycol 300, 400, 1,000 or 2,000 is used instead of polyethylene glycol 600 in Example 1, products of somewhat modified properties are obtained, all of which are also, however, very suitable for use as levelling auxiliaries. Their apparent molecular weights were 1,480, 1,460, 1,560 and 1,630 for PEG 300, PEG 400, PEG 1,000 and PEG 2,000 respectively.

Example 4 Correspondingly good products are obtained from the following components a to e, their respective apparent molecular weights being 1,380, 1,290, 1,420, 1,430 and 1,480: a. 50 mol V of IPA; 30 mol V of SA; 20 mol O/, V of TMA; 90 mol V of DEG; 10 mol V of PEG 600.

b.50 mol % of IPA; 30 mol % of SA, 20 mol % of TMA; 50 mol /n of DEG; 30 mol V of 1,2-propylene glycol; 20 mol V of PEG 400.

c. 50 mol V of IPA; 30 mol V of SA; 20 mol % of TMA; 50 mol O/, V of TEG; 30 mol V of ethylene glycol; 20 mol V of PEG 300.

d. 60 mol V of IPA; 20 mol V of phthalic anhydride; 95 mol V of DEG; 20 mol V of TMA; 5 mol V of PEG 2,000.

e. 70 mol % of IPA; l0molVofMA;20molV0fTMA;80molVofDEG; 10 mol V of hexane-1,6-diol; 10 mol V of PEG 600.

It is to be understood that the products of Examples 2 had COOM mole percentages of 5 to 50.

Example 5 90 mol V of IPA; 10 mol V of PDA; 90 mol V of DEG; 10 mol V of PEG 600.

238.5 g of diethylene glycol, 150 g of polyethylene glycol 600 and 373.5 g of isophthalic acid of a purity of at least 99V strength are heated to 1600, under nitrogen and without the addition of a catalyst, in the course of one hour in a 4-litre four-necked flask with ground glass joints, equipped with a stirrer, a thermometer, a gas inlet tube for nitrogen and a descending condenser. The temperature in the flask is then raised in the course of 3 hours by a further 20 per hour up to 2200.

Heating is then continued for 2 hours at 22e2250, after which a total of about 80 g of water has distilled off. The internal temperature is now reduced to 1500 and 63 g of pyromellitic dianhydride are stirred in in portions in the course of half an hour (while continuing to pass nitrogen over the surface, of course). The contents of the flask are then heated first to 2000 in the course of one hour, to 2f0a in the course of a further hour and to 2200 in the course of a third hour. Finally, heating iscontinued for a further 2 hours at 220225 and, lastly, a waterpump vacuum is applied at this temperature. As soon as a vacuum of 1015 mm has been reached, the condensation reaction is completed in the course of a further half hour.

Approximately 10 ml of water are again collected in the receiver in the course of the second condensation phase. 732 g of an amber-coloured residue are obtained, which can be readily made up to 3,690 g with water and approximately 74 ml of 27V strength sodium hydroxide solution to give a pale, virtually clear 20V strength solution of pH 6.3. The molecular weight of the melt is 2,070; the apparent molecular weight of the sodium salt (on account of the dissociation effects which occur) is only 1,460, however. The COONa mole percentage was 25.65.

If potassium hydroxide solution, ammonia, monoethanolamine, diethanolamine or triethanolamine are used for neutralisation instead of sodium hydroxide solution, products of correspondingly good technical properties are obtained, which differ greatly, however, in the viscosity of their 20V strength aqueous solutions.

Example 6 80 mol V of IPA; 20 mol V of citric acid; 90 mol V of DEG; 10 mol V of PEG 600; MW=1,710.

238.5 g (2.25 mols) of diethylene glycol, 150 g (0.25 mol) of polyethylene glycol 600 and 332 g (2.0 mols) of isophthalic acid of a purity of at least 99V strength are heated to 1600 under nitrogen and without the addition of a catalyst in the course of one hour in a 4 litre four-necked flask with ground glass joints, equipped with a stirrer, a thermometer, a gas inlet tube for nitrogen and a descending condenser.

The temperature in the flask is then raised in the course of 3 hours by a further 20 per hour up to 2200. Heating is then continued for 2 hours at 220225 , after which a total of about 70 g of water has distilled off. The internal temperature is now reduced to 1500 and 96.1 g (0.5 mol) of citric acid are stirred in in portions in the course of half an hour (while continuing to pass nitrogen over the surface, of course). The contents of the flask are then heated first to 2000 in the course of one hour, to 2100 in the course of a further hour and to 2200 in the course of a third hour. Finally, heating is continued for a further 2 hours at 220225 and, lastly, a waterpump vacuum is applied at this temperature. As soon as a vacuum of 115 mm has been reached, the condensation reaction is completed in the course of a further hour and 15 minutes. Approximately 40 ml of water are again collected in the receiver in the course of the second condensation phase. 700 g of an ambercoloured residue are obtained, which can be readily made up to 3,500 g with water and approximately 60 ml of 27V strength sodium hydroxide solution to give an amber-coloured, virtually clear 20V strength solution of pH 7.5. The apparent molecular weight of this solution is 1,710. The COONa mole percentage was 20.8.

A slight turbidity can, if necessary, be completely removed by stirring the 20V strength solution for half an hour with 35 g of kieselguhr (lV) and forcing the product through a filter press.

If an equivalent quantity of tartaric acid or malic acid is employed instead of citric acid, a similar product is obtained, which is also very suitable for use as a levelling auxiliary in polyester dyeing.

Example 7 -4 mol V of SIM; 76 mol V of IPA; 20 mol V of TMA; 100 mol V of DEG; MW=l ,360.

159 g (1.5 mols) of diethylene glycol, 189.24 g (1.14 mols) of isophthalic acid of a purity of at least 99V strength and 17.76 g (0.06 mol) of 5-sodium-sulphoiosphthalic acid dimethyl ester are heated to 1600 in the course of one hour under nitrogen and without the addition of a catalyst in a 2 1 four-necked flask with ground glass joints, equipped with a stirrer, a thermometer, a gas inlet tube for nitrogen and a descending condenser. A wash bottle, which permits a convenient check on the rate of flow of the nitrogen, is placed downstream of the receiver. The temperature in the flask is then raised in the course of-3 hours by a further 20 per hour up to 2200. Heating is then continued for 2 hours at 22-2250, after which a total of about 43 g of water and methanol has distilled off. The internal temperature is now reduced to 1500 and 57.6 g of trimellitic anhydride are stirred in in portions in the course of half an hour (while continuing to pass nitrogen over the surface, of course). The contents of the flask are then heated first to 2000 in the course of one hour and to 2100 in the course of a further hour. Finally, heating is continued for a further 2 hours at 21--2150 and, lastly, a waterpump vacuum is applied at this temperature. As soon as a vacuum of 115 mm has been reached, the condensation reaction is completed in the course of a further half hour. 8-10 ml of water are again collected in the receiver in the course of the second condensation phase. 365 g of an amber-coloured residue are obtained, which can be readily made up to 1,820 g with water and approximately 50 ml of 27V strength sodium hydroxide solution to give a pale, virtually clear 20V strength solution of pH 6.85.

The apparent molecular weight of this sodium salt is 1,360. The COONa mole percentage was 28.9.

a. By varying the duration of heating at the waterpump, the degree of condensation (=the average apparent molecular weight) of the water-soluble polyester can be modified upwards or downwards.

b. If the sodium salt of 5-sulphoisophthalic acid dimethyl ester is replaced by an equivalent quantity'of 5 - potassium - sulpho - isophthalic acid, 5 - sodium sulphopropoxy - isophthalic acid dimethyl ester, 4 - sodium - sulphophthalic acid diethyl ester, 2 - sodium - sulpho - terephthalic acid dipropyl ester, sodium sulphosuccinic acid dimethyl ester or one of the following two sodium salts of sulphonic acids:

products of-qualifications which are similar from a technical point of mm has been reached, the condensation reaction -is completed in the course of a further half hour. Approximately 10 ml of water are again collected in the receiver in the course of the second condensation phase. 730 g of an amber-coloured residue are obtained. which can be readily made up to 3,650 g with water and approximately 85 ml of 27V strength sodium hydroxide solution to give a pale, virtually clear 20V strength solution of pH 7.9. The molecular weight of the melt is 2,760; the apparent molecular weight of the sodium salt (on account of the dissociation effects which occur) is only 1,600, however. The COONa mole percentage was 29.5.

Example 8a If in Example 8 the isophthalic acid dimethyl ester is replaced by an equivalent quantity of terephthalic acid dimethyl ester, a water-soluble polyester is obtained which is particularly suitable for use as a levelling auxiliary for dyeing polyester fibres.

Example 9 If in Example 8 the isophthalic acid dimethyl ester is replaced by an equivalent quantity of phthalic acid dimethyl ester, succinic acid dimethyl ester or adipic acid dimethyl ester, 20V strength aqueous solutions which can be used extensively in industry are also obtained. It is to be understood that the products of Example 9 had COOM mole percentages of 5 to 50.

Example 10 80 mol V of IPA; 20 mol V of TMA; 100 mol V of DEG; MW=1,340.

265 g (2. 5 mols) of diethylene glycol and 332 g (2 mols) of isophthalic acid of a purity of at least 99V strength and 96 g (0.5 mol) of trimellitic anhydride are heated to 1600 in the course of one hour under nitrogen and without the addition of a catalyst in a 4 litre four-necked flask with ground glass joints, equipped with a stirrer, a thermometer, a gas inlet tube for nitrogen and a descending condenser.

The temperature in the flask is then raised in the course of 6 hours by a further 10 per hour up to 2200. Heating is then continued for a further hour at 220--2250, after which a total of about 80 g of water has distilled off and, lastly, a waterpump vacuum is applied at this temperature. As soon as a vacuum of 1015 mm has been reached, the condensation reaction is completed in the course of a further half hour. 650 g of an amber-coloured residue are obtained, which can be readily made up to 3,300 g with water and approximately 60 ml of concentrated aqueous ammonia to give a pale, but very viscous, 20V strength solution of pH 7. Its (apparent) molecular weight is approximately 1,340. The COONH4 mole percentage was 31.8.

Example 11 A liquor which has been prepared from soft water with a pH of 4.5 (adjusted with acetic acid) and 0.5 g of a branched, water-soluble copolyester according to Example 1 is allowed to flow, at 1300C-and at a liquor ratio of 1:10 through wound packages (muffs) composed of texturised polyester yarns in a HT dyeing apparatus.

To -this liquor is added rapidly by means of an injection apparatus a mixture, predispersed with water at 400 C, of the following disperse dyestuffs in a commercially available form: 0.46V of the dyestuff of the formula I

0.52V of the dyestuff of the formula II

and 0.lav of the dyestuff of the formula III (composed of equal parts)

The quantity which flows through the muff is 20 l/kg per minute. After 30 minutes' treatment at 1300C the batch is cooled, the liquor is discharged and the goods are cleared by reduction.

A completely level brown dyeing is obtained at a full tinctorial yield.

If the same dyeing is carried out with the same dyestuffs and under the same conditions, but without adding the water-soluble, branched copolyester and using commercially available dispersing auxiliaries (based on a naphthalene-sulphonic acid/formaldehyde condensate) and levelling auxiliaries (consisting of a fatty acid polyglycol ester, polyglycol and oxethylated alkylphenols), an uneven dyeing is obtained which has great differences in the depth of colour and in the colour shade of the individual wound packages.

Example 12 The procedure followed is as in Example 11, but another branched, watersoluble polyester, according to Example 2, is used. Dyeing is carried out for 30 minutes at 1300C and a completely level brown dyeing is obtained.

If in this dyeing the water-soluble, branched polyester is replaced by customary dispersing agents (based on a naphthalenesulphonic acid/formaldehyde condensate) and levelling agents (based on a fatty acid polyglycol ester, polyglycol and oxethylated alkylphenols), an uneven dyeing is obtained.

Example 13 The dyeing is carried out by following the procedure described in Example 11, but using 0.4V of the disperse dyestuff of the formula IV

0.32V of the disperse dyestuff of the formula V

and 0.26V of the dyestuff of the formula-VI

Dyeing is carried out for 25 mins. at 1300C, a reductive after-treatment is carried out and a level brown dyeing is obtained. If in this dyeing the branched, watersoluble copolyester is replaced by commercially available dispersing and levelling auxiliaries, an uneven dyeing which has great differences in depth of colour and colour shade is obtained.

Example 14 a) Comparison A dyeing liquor which consists of soft water adjusted to pH 5 with acetic acid and 0.5 g/l of-sodium 2,2' - dinaphthylmethane - 6,6' - disulphonate is allowed to flow, at 80"C and at a liquor ratio of 1:12, through wound packages (muffs) composed of texturised polyester threads in a HT dyeing apparatus.

I .5V, based on the weight of the goods, of the disperse dyestuff of the formula VII

in its commercially available preparation for use as a liquid, are added- to this liquor. The dyebath is heated-to 1300C in the course of40 minutes and-.dyeing is carried out at this temperature for 30 minutes. The goods are then given a hot rinse and a reductive after-treatment.

b) Example If in the dyeing described above the sodium 2,2' - dinaphthylmethane - 6,6' disulphonate is replaced by 0.3 g/l of the water-soluble, branched polyester according to Example 8a and the procedure followed is exactly as described above, a level, golden-yellow dyeing is obtained, which is fast to rubbing and does not have deposits on the packages.

The dyestuff, which has hitherto not been usable for dyeing wound packages, can be employed without difficulties.

Example 15 The procedure followed is as described in Example 14 under b), but using 2V of the red disperse dyestuff of the formula VIII

in a liquid state and a form which has hitherto not been suitable for dyeing wound packages, and using 0.7 g/l of the water-soluble polyester mentioned in Example 5.

A level, brilliant scarlet dyeing which is fast to rubbing is obtained.

If the same dyeing is carried out with the water-soluble, branched polyester replaced by a commercially available dispersing agent, for example based on the condensation product of formaldehyde and cresol, and unusable, uneven, flat dyeing is obtained, which is not fast to rubbing owing to deposited dyestuff.

Example 16 The dyeing is carried out by following the procedure of Example 11, but using the dyestuff of the formula VIII. A vivid, level scarlet dyeing is obtained which is fast to rubbing.

If the water-soluble, branched copolyester mentioned in Example 11 is replaced by the commercially available dispersing agent mentioned in Example 11, an uneven dyeing is obtained, which is not fast to rubbing and is contaminated by dyestuff which has been filtered off on it.

WHAT WE CLAIM IS:- 1. A branched copolyester which is soluble or dispersible in water, has an apparent molecular weight of from 600 to 5,000, contains, relative to the dicarboxylic and polycarboxylic acids utilised for the manufacture of the polyester, from 5 to 50 mol V of COOM groups and 0 to 5 mol V of SO2M groups wherein M denotes the cation of an alkali metal, the ammonium ion or the cationic radical of an organic amine, and which copolyester is built up from the radicals of the following formulae:

0 II C o 0 II 0 II -C-R1-C- ii 011 (A) -C-Ra-C- ; (Al) ( > /m 0 (B) - O- R2-0- and optionallY (B1) OR\O with the reservation that an equivalent amount of (A+B) can be replaced by

and an equivalent amount of (A,+B,) can be replaced by

wherein R, denotes a direct bond or a divalent, aliphatic, cycloaliphatic or aromatic radical, m denotes the number 0, 1 or 2, R1, denotes an aliphatic cycloaliphatic or aromatic radical which is trivalent when m is 0, tetravalent when m is 1 and pentavalent when m is 2, R2 denotes a divalent radical which, as a statistical average, is composed of from 40 to 95 mol V of radicals of the formula -CH2-CH2-O-CH2-CH2- and/or radicals of the formula -CH-CH2-O- CH2CH2-O-CH2CH2-, from 5 to 20 mol V of radicals of the formula -CH2- CH2(OC2H4)U wherein u is a number such that said radicals of the formula CH2CH2HOC2H4)Uhave an average molecular weight of from 300 to 2,000 and from 0 to 50 mol V of aliphatic, cycloaliphatic or araliphatic radicals, n denotes the number 0, 1 or 2, R2, denotes an aliphatic or cycloaliphatic radical which is trivalent when n is 0, tetravalent when n is 1 and pentavalent when n is 2, R3 is a divalent, aliphatic, cycloaliphatic or araliphatic radical, R2, is a hydrocarbon radical and p and q are the same or different and each has a value of 0, 1, 2 or 3 provided that the sum of q+p is 1, 2 or 3.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. condensation product of formaldehyde and cresol, and unusable, uneven, flat dyeing is obtained, which is not fast to rubbing owing to deposited dyestuff. Example 16 The dyeing is carried out by following the procedure of Example 11, but using the dyestuff of the formula VIII. A vivid, level scarlet dyeing is obtained which is fast to rubbing. If the water-soluble, branched copolyester mentioned in Example 11 is replaced by the commercially available dispersing agent mentioned in Example 11, an uneven dyeing is obtained, which is not fast to rubbing and is contaminated by dyestuff which has been filtered off on it. WHAT WE CLAIM IS:-

1. A branched copolyester which is soluble or dispersible in water, has an apparent molecular weight of from 600 to 5,000, contains, relative to the dicarboxylic and polycarboxylic acids utilised for the manufacture of the polyester, from 5 to 50 mol V of COOM groups and 0 to 5 mol V of SO2M groups wherein M denotes the cation of an alkali metal, the ammonium ion or the cationic radical of an organic amine, and which copolyester is built up from the radicals of the following formulae:

and an equivalent amount of (A,+B,) can be replaced by

2. A copolyester as claimed in claim I, wherein from 80 to 140 mol V of

radicals of the formulae A and A, as defined hereinbefore are present, relative to 100 mol V of radicals of the formulae B and B, as defined hereinbefore.

3. A copolyester as claimed in claim 1 or 2, wherein M is the sodium cation.

4. A copolyester as claimed in any of claims I to 3, wherein m denotes the number 0 or 1.

5. A copolyester as claimed in any of claims I to 4, wherein n denotes the number 0'to 1.

6. A copolyester as claimed in any of claims I to 5, wherein from 5 to 60 mol V of branching radicals of the formula A, as defined hereinbefore are present, relative to 100 mol V of the radicals of the formulae A and A, as defined hereinbefore.

7. A copolyester as claimed in claim 6, wherein from 10 to 40 mol V of radicals of the formula A, as defined hereinbefore are present, relative to 100 mol V of the radicals of the formulae A and A, as defined hereinbefore.

8. A copolyester as claimed in any of claims I to 7, wherein up to 10 mol V of radicals of the formula B, as defined hereinbefore are present, relative to 100 mol V of the radicals of the formulae B and B, as defined hereinbefore.

9. A copolyester as claimed in any of claims 1 to 8, wherein at least 40 mol V of the radicals of the formula A are radicals of the formula A3

10. A copolyester as claimed in claim 9, wherein at least 40 mol V of the radicals of the formula A are radicals of the formula

11. A copolyester as claimed in any of claims 1 to 10, wherein at least 50 mol V of radicals of the formula -O-CH2CH2-O-CH2CH2-O- and/or radicals of the formula -O-CH2CH2-O-CH2CH2-O-CH2CH2-O- are present, based on in the radicals of the formulae B and B, as defined hereinbefore.

12. A copolyester as claimed in any of claims 1 to 11, wherein p and q are so chosen that the sum of q+p is 1 or 2.

13. A copolyester as claimed in any of claims 1 to 12, wherein R2 is-a divalent, aliphatic radical having from 2 to 10 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 10 carbon atoms or a divalent, araliphatic radical having from 8 to 14 carbon atoms.

14. A copolyester as claimed in any of claims 1 to 13, wherein R, is a divalent, aliphatic radical having from 2 to 8 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 8 carbon atoms or a divalent, aromatic radical having from 6 to 12 carbon atoms.

15. A copolyester according to claims I to 14,.wherein R3 is a divalenjt, aliphatic radical having from 1 to 10 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 11 carbon atoms or a divalent, araliphatic radical having from 8 to 12 carbon atoms.

16. A process for the manufacture of a copolyester according to claim I comprising condensation of a polycarboxylic acid component comprising compounds of the formulae A' and A,' HOOC-R1-COOH (kl), and

wherein m, R, and R,' have the same meaning as defined hereinbefore in formulae A and A2 or esters, anhydrides or acid chlorides thereof, with a polyol component of the formula B' HO-R2OH (B'), wherein R2 has the same meaning as defined hereinbefore in formula B, and optionally with a polyol component of formula B,'

wherein R2, and n have the same meaning as defined hereinbefore in formula B,, with the reservation that an equivalent amount of (A'+B') can be replaced by a hydroxy-carboxylic acid component of formula C'

or esters thereof, wherein R2 has the same meaning as defined hereinbefore in formula C, and an equivalent amount of (A,'+B,') can be replaced by C,'

or esters, anhydrides or acid chlorides thereof, wherein R2,, p and q have the same meaning as defined hereinbefore in formula C1, the compounds being so chosen that there is an excess of from 5 to 50 mol V of the --COOH groups and up to a total of 5 mol V relative to the molar amount of the dicarboxylic and polycarboxylic acid employed, of said starting compounds of formulae A', A,', B' and B,' containing a SO2M group, at a temperature of from 130 to 2500C until the apparent average molecular weight of the condensation product, measured in a vapour pressure osmometer with dimethylformamide as the solvent, has a value of from 600 to 5,000 and the acid groups COOH are converted into the salts COOM wherein M denotes the cation of an alkali metal or of an organic amine or the ammonium ion. .

17. A process for the manufacture of a copolyester according to claim I, which copolyester contains up to 5 mol V of SO3M groups, wherein M has the same meaning as defined hereinbefore relative to the dicarboxylic and polycarboxylic acids utilised for the manufacture of the polyester, said .process comprising condensation of a polycarboxylic acid component comprising compounds of the formulae A' and A,' HOOC-R1-COOH (A'), and

wherein m, R, and R,' have the same meaning as defined hereinbefore in formulae A and A2 or esters, anhydrides or acid chlorides thereof, with a polyol component of the formula B' HO-R2-OH (B'), wherein R2 has the same meaning as defined hereinbefore in formula B, and optionally with a polyol component of the formula B,'

wherein R2, and n have the same meaning as defined hereinbefore in formula B,, with the reservation that an equivalent amount of (A'+B') can be replaced by a hydroxy-carboxylic acid component of the formula C'

or esters thereof, wherein R3 has the same meaning as defined hereinbefore in formula C, and an equivalent amount of (A,'+B,') can be replaced by C1,

or esters, anhydrides or acid chlorides thereof, wherein R3,, p and q have the same meaning as defined hereinbefore in formula C1, the compounds being so chosen that there is an excess of from 5 to 50 mol V of COOH groups and up to a total of 5 mol V relative to the molar amount of the dicarboxylic and polycarboxylic acids employed, of said starting compounds of formulae A', A,', B' and B,' containing an olefinic double bond, at a temperature of from 130 to 2500C until the apparent average molecular weight of the condensation product, measured in a vapour pressure osmometer with dimethylformamide as the solvent, has a value of from 600 to 5,000, and the copolyester thus obtained is subsequently reacted with a compound HSO3M wherein M has the same-meaning as defined hereinbefore and the acid groups COOH are converted into the salts COOM wherein M denotes the cation of an alkali metal or of an organic amine or the ammonium ion.

18. A process as claimed in claim 17, wherein from 80 to 140 mol V of the polycarboxylic acid component is condensed with 100 mol V of the polyol component.

19. A process as claimed in claim 17 or 18, wherein M denotes the sodium cation.

20. A process as claimed in any of claims 17 to 19, wherein, in the compounds of formula A,', m has the value 0 or 1.

21. A process as claimed in any of claims 17 to 20, wherein, in the compounds of formula B,', n has the value 0 to 1.

22. A process as claimed in any of claims 17 to 21, wherein from 5 to 60 mol V of the-compound of formula A,' as defined hereinbefore, is used relative to 100 mol V of the compounds of formulae A' and A,' as defined hereinbefore.

23. A process as claimed in claim 22, wherein from 10 to 40 mol V of the compound of the formula A2, as defined hereinbefore is used.

24. A process as claimed in any of claims 17 to 23, wherein up to 10 mol V of the compound of formula B,' is used, relative to 100 mol V of the compounds of formulae B' and B,' as defined hereinbefore.

25. A process as claimed in any of claims 17 to 24, wherein at least 40 mol V of the compound of formula A' comprises benzenedicarboxylic acid or an ester or anhydride thereof.

26. A process as claimed in claim 25, wherein the benzenedicarboxylic acid is isophthalic acid.

27. A process as claimed in any of claims 17 to 26, wherein at least 50 mol V of the compound of formula B' comprises diethylene glycol and/or triethylene glycol.

28. A process as claimed in any of claims 17 to 27, wherein the esters of the carboxyl groups of the compounds of formulae A', A,', C' and C,' as defined hereinbefore, are formed with alcohols having from 1 to 4 carbon atoms.

29. A process as claimed in any of claims 17 to 28, wherein in the compounds of formula C1,, q and p have values such that the sum of p+q is 1 or 2.

30 A process as claimed in any of claims 17 to 29, wherein in the compounds of formula B' as defined hereinbefore, R2 denotes a divalent, aliphatic radical having from 2 to 10 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 10 carbon atoms or a divalent, araliphatic radical having from 8 to 14 carbon atoms.

31. A process as claimed in any of claims 17 to 30, wherein in the compounds of formula A' as defined hereinbefore R, denotes a divalent, aliphatic radical -having from 2 to 8 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 8 carbon atoms or a divalent, aromatic radical having from 6 to 12 carbon atoms.

32. A process as claimed in any of claims 17 to 31, wherein in the compound of formula C' as defined hereinbefore, R3 denotes a divalent, aliphatic radical having from 1 to 10 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 11 carbon atoms or a divalent, araliphatic radical having from 8 to 12 carbon atoms.

33. A copolyester according to claim 1 substantially as described hereinbefore with particular reference to any of the specific embodiments of Examples 1 to 6, 8, 8a and 9.

34. A process for the manufacture of a copolyester according to claim 16 or 17 substantially as described hereinbefore with particular reference to any of the specific embodiments of Examples 1 to 6, 8, 8a and 9.

35. A copolyester when prepared by a process as claimed in any of claims 17 to 32 and 34.

36. A method of dyeing a polyester in an aqueous medium wherein a copolyester is used as a levelling agent, and said copolyester is a branched copolyester which is soluble or dispersible in water, has an apparent molecular weight of from 600 to 5,000, contains, relative to the dicarboxylic and polycarboxylic acids utilised for the manufacture of the polyester, from 5 to 50 mol V of COOM groups and 0 to 5 mol V of SO3M groups wherein M denotes the cation of an alkali metal, the ammonium ion or the cationic radical of an organic amine, and which copolyester is built up from the radicals of the following formulae:

0 II C 0 0 0 (A) (A1) -C-Rt-C- ; (A1) -C-R < (R) II ) 0 (B) - O- R2-O- and optionally (B1) ~ ~ R2 whereby an equivalent amount of (A+B) can be replaced by

and an equivalent amount of (A,+B,) can be replaced by

wherein R, denotes a direct bond or a divalent, aliphatic cycloaliphatic or aromatic radical, m denotes the number 0, 1 or 2, R,' denotes an aliphatic, cycloaliphatic or aromatic radical which is trivalent when m is 0, tetravalent when m is 1 and pentavalent when m is 2, R2 denotes a divalent radical which, as a statistical average, is composed of from 40 to 100 mol V of radicals of the formula -CH2 CH2-O-CH2-CH2- and/or radicals of the formula -CH2-CH2-O- CH2CH2-O-CH2CH2-, from 0 to 20 mol V of radicals of the formula -CH2- CH2.(OC2H4)u wherein u is a number such that said radicals of the formula CH2CH2HOC2H4)Uhav an average molecular weight of from 300 to 2,000 and from 0 to 50 mol V of aliphatic, cycloaliphatic or araliphatic radicals, n denotes the number 0, 1 or 2, R2, denotes an aliphatic or cycloaliphatic radical which is trivalent when n is 0, tetravalent when n is 1 and pentavalent when n is 2, R3 is a divalent, aliphatic, cycloaliphatic or araliphatic radical R3, is a hydrocarbon radical and p and q are the same or different and each has a value of 0, 1, 2 or 3 provided that the sum of q+p is 1, 2 or 3.

37. A method as claimed in claim 36, wherein from 80 to 140 mol V of radicals of the formulae A and A, as defined hereinbefore are present, relative to 100 mol V of radicals of the formulae B and B, as defined hereinbefore.

38. A method as claimed in claim 36 or 37, wherein M is the sodium cation.

39. A method as claimed in any of claims 36 or 37, wherein the divalent radical R2 is composed, as a statistical average, of from 40 to 100 mol V of radicals of the formula -CH2-CH2-O-CH2-CH2- and/or radicals of the formula -CH2 CH2-O-CH2CH2-O-CH2CH2-, from 5 to 20 mol V of radicals of the formula CH2CH2(OC2H4)u wherein u is a number such that said radicals of the formula CH2CH2OC2H4)u have an average molecular weight of from 300 to 2,000 and from 0 to 50 mol V of aliphatic, cycloaliphatic or araliphatic radicals.

40. A method as claimed in any of claims 36 to 39, wherein m denotes the number 0 or 1 and wherein n denotes the number 0 or 1.

41. A method as claimed in any of claims 36 to 40, wherein from 5 to 60 mol V of branching radicals of the formula A1 as defined hereinbefore are present, relative to 100 mol V of the radicals of the formulae A and A1 as defined hereinbefore.

42. A method as claimed in claim 41, wherein from 10 to 40 mol V of radicals of the formula A, as defined hereinbefore are present, relative to 100 mol V of the radicals of the formulae A and A, as defined hereinbefore.

43. A method as claimed in any of claims 36 to 42, whereby at least 40 mol V of the radicals of the formula A are radical of the formula A3.

44. A method as claimed in claim 42, wherein at least 40 mol V of the radicals of the formula A are radicals of the formula

45. A method as claimed in any of claims 36 to 44, wherein at least 50 mol V of radicals of the formula -O-CH2CH2-O-CH2CH2-O- and/or radicals of the formula -O-CH2CH2-O-CH2CH2-O-CH2CH2-O- are present in the radicals of the formulae B and B, as defined hereinbefore.

46. A method as claimed in any of claims 36 to 45, wherein p and q are so chosen that the sum of q+p is 1 or 2.

47. A method claimed in any of claims 36 to 44, wherein R2 is a divalent, aliphatic radical having from 2 to 10 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 10 carbon atoms or a divalent, araliphatic radical having from 8 to 14 carbon atoms and wherein R1 is a divalent, aliphatic radical having from 2 to 8 carbon atoms, a divalent, cycloaliphatic radical having. from 6 to 8 carbon atoms or a divalent, aromatic radical having from 6 to 12 carbon atoms and wherein R3 is a divalent, aliphatic radical having from I to 10 carbon atoms, a divalent, cycloaliphatic radical having from 6 to 11 carbon atoms or a divalent, araliphatic radical having from 8 to 12 carbon- atoms.

48. A aqueous dyeing liquor for use in the dyeing of a polyester with liquor comprises a dyestuff and a copolyester, effective as a levelling agent, this copolyester comprising a branched copolyester which is soluble or dispersible in water, has an apparent molecular weight of from 600 to 5,000, contains, relative to the dicarboxylic and polycarboxylic acids utilised for the manufacture of the polyester, from 5 to 50 mol V of COOM groups and 0 to 5 mol V of SO3M groups wherein M denotes the cation of an alkali metal, the ammonium ion or the cationic radical of an organic amine, and which copolyester is built up from the radicals of the following formulae:

0 II C 0 II II - 0 0 (A) -C-Rt-C- ; (A1) -C-R 1c /0 (B) -0-R2-0-and optionally ( -0- \O whereby an equivalent amount of (A+B) can be replaced by

and an equivalent amount of (A1+B1) can be replaced by

wherein R1 denotes a direct bond or a divalent, aliphatic cycloaliphatic or aromatic radical, m denotes the number 0, 1 or 2, R,' denotes an aliphatic, cycloaliphatic or aromatic radical which is trivalent when m is 0, tetravalent when m is I and pentavalent when m is 2, R2 denotes a divalent radical which, as a statistical average, is composed of from 40 to 100 mol V of radicals of the formula -CH2- CH2-O-CH2-CH2- and/or radicals of the formula -CH2-CH2-O- CH2CH2-O-CH2CH2-, from 0 to 20 mol V of radicals of the formula -CH2- CH2(OC2H4)u wherein u is a number such that said radicals of the'formula -CH2-CH2-(O-C2H4)u-have an average molecular weight of from 300 to 2,000 and from 0 to 50 mol V of aliphatic; cycloaliphatic or araliphatic radicals, n denotes the number 0, 1 or 2, R2, denotes an aliphatic or cycloaliphatic radical which is trivalent when n is 0, tetravalent when n is 1 and pentavalent when n is 2, R3 is a divalent, aliphatic, cycloaliphatic or araliphatic radical, R3' is a hydrocarbon radical and p and q are the same or different and each has a value of 0, 1, 2 or 3 provided that the sum of q+p is 1,2 or 3.

49. A method of dyeing according to claim 36 substantially as described hereinbefore with particular reference to any of the specific embodiments of any of Examples 11 two 16.