CA1249272A - Process for sizing paper with anionic hydrophobic sizing agents and cationic retention aids - Google Patents

Abstract

A process for sizing paper with anionic hydrophobic sizing agents and cationic retention aids Abstract Sizing agents of which some are novel and which have at least one anionic or acidic group which is optionally in the form of a salt and at least two hydrophobic substituents which each have at least 5 carbon atoms, at least two of the most adjacent hydrophobic substituents being bonded to each other with a linking member which has at least 2 hetero atoms, are particularly suitable for use, together with commercially available polymeric, cationic retention aids, in a process for sizing paper or cardboard.

Description

~2~ 2 Case 1-13939~ 2/ ~

A process for fiizing paper with anionic hydrophobic sizing agents and cationic retention aids _ __ It is an object of the present invention to make available to the paper manufacturer easily accessible and simply prepared sizing agents which, combined with conventional, eationic retention aids, are suitable for effeeting effieient sizing in the produetion of paper from the dispersions of the fibres.

This object is achieved in a novel manner by using in the production of paper in the presence of polymeric eationie retention aids sizing agents which have at least two long-ehain hydrophobie substituents and at least one anionic or acidic group whieh can be in the form of a salt.

The present invention thus relates to a process for sizing paper or cardboard, which comprises adding to aqueous dispersions of the fibres, which can, if desired, also contain filler, in any order or simultaneously, at least (A) a sizing agent which contains at least one anionie or acidic group which can be in the form of a salt and at least two hydro-phobie substituents whieh eaeh have at least S earbon atoms, at least one of the hydrophobie substituents having at least 8 earbon atoms or preferably every hydrophobie group has at least 8 earbon atoms, and at least two of the most adjaeent hydrophobie substi-tuents being bonded to eaeh other with a linking member whieh has at least 2 hetero atoms and preferably at least l earbon atom , and ~$

7~

(B) a polymeric cationic retention aid.

The invention further relates to - the aqueous compositions for carrying out the paper-sizing process which, if the sizing agent (A) and the retention aid (B) are added to the dispersion of the fibres separately in any order, contain, in addition to optional customary additives, the sizing agent (A) alone, which is at least partly in the form of salts, or, if the sizing agent (A) and the retention aid (B) are added to the fibre-bearing liquid simultaneously, contain not only the sizing agent (A) which can be at least partly in the form of a salt but also the retention aid (B) in addition to optional custornary additives, - the paper or cardboard sized in the process of the invention and - the use of a sizing agent (A) of the specified type for sizing paper or cardboard.

Some of the representatives of the specified sizing agents (A) are known compounds, while others are novel compounds.
The use of the compounds known per se is novel. Where the sizing agents are novel compounds they, together with the process for their preparation, also form part of the subject matter of the present invention.

The sizing agents (A) used in the invention have as an essential feature 1 to 6, above all 1 to 4 preferably 1 or 2, in particular one anionic or acidic group which each generally contain one or two negative charges. For example, acid phosphates -P~ O ~ or -P~ OH
O ~ OH

as acidic groups have 2 negative charges, while acid sulfates, -S03 Q or S03H, or carboxyl groups, -COO ~ or -COOH,only have one negative charge. In a further embodiment, the sizing agents (A)have preferably 1 or 2 potential anionic, acidic methylene or methine groups. The capacity of anionic or acidic groups to have or be able to form anions in an aqueous medium is a further significant characteristic of the sizing agent. The formation of anions takes place at the pH
values of the dispersion of the fibres which are customary in the pro-duction of paper. Under said conditions the cationic retention aid (B) form cations. The capacity of the sizing agents and of the retention aids to form anions or cations under paper production con-ditions can also be referred to as anion-active or cation-active.
The anionic sizing agents and the cationic retention aids can also be called anion-active sizing agents and cation-active retention aids respectively.

The sizing agents (A) have as a further characterising feature 2 to 10, preferably 2 to 6, in particular 2 or 3 hydrophobic substi-tuents which only contain the carbon and hydrogen atoms and have at least 5, preferably 8 to 22, in particular 16 to 20, carbon atoms, for example C5-C12-cycloalkyl, C6-C10-aryl, alkaryl or aralkyl radicals. Preferred substituents, however, are open-chain alkyl or alkenyl radicals which generally derive from unsaturated or preferably saturated fatty alcohols, amines or acids having 8 to 22 carbon atoms. The way these hydrophobic substituents are bonded to one another is a Eurther characteristic of the sizing agents (A).
The linking members which link at least two of the hydrophobic substituents namely have in a particular embodiment of the sizing agents (A) preferably 4 to 15 carbon atoms and at least

2 hetero atoms, preferably at least two oxygen, and/or nitrogen atoms.

For example, in possible carboxyl or amide radicals O H O
Il 1 11 (-C-O or -N-C-) an oxygen sr a nitrogen atom as hetero atoms are part of a linking member.

Depending on the number of hydrophobic substituents, the sizing agents contain 1 to 5, preferably 1 to 3, linking members of the specified type.

Preferred linking members generally have one of the formulae (1) ~Ql~()n-l~Al~()m-l Q2 or (2) -0-A2-0- , in ~hich n and m each are 1 or 2, Al is a divalent aliphatic or cycloaliphatic radical, A2 is a divalent aromatic radical and Ql and Q2 are different from or, preferably, identical to each other and, if n and m are 1, they are -NH-, o -N/ , or - ~ , or, if n and m are 2, in particular -C- , n and m preferably being 2.

In formula (1), the radical A1 forms part of an aro-matic, preferably aliphatic or cycloaliphatic, bridging member wh;ch preferably has 1 or 2, in particular one anionic or acidic group and can have 1 to 5, preferably 1, 2 or 3, nitrou-gen atoms~ Examples of bridging members are those of the formulae _ 5 ~ 2

(3) o e C - O - CH2 - ICH -CH2 - (CH2) t-l OX
I

(o=o ( ~ ) ~H 2 - C - O - Cl:l ~ C - CH - O - C -OX
~0~

OX
( 6 ) - C - O - A3 f ~ A4 1 N 3 A~3 13 11=o OX
_ q-l (7) N~A3--X~() t-l X~ ~(0)-~-~0-(9) ~0-1~`~

. .

6 ~ 2 ( 1 0 ) 1c 3 ~ o3 A -OX
('Il) 3 OH ~ OH
~NH-CH2---CH-CH2-~/ ~ CH2 CH 2 CH -CH-CH2-N~
OH X

OH C OH
( 12 ) -Q3-CH2-CH-CH2-~/ ~-CH2 CH 2 Q3 OX
( 13 ) OH ~OH X

OH OX
(1 4) ;n wh;ch ~ ;s 1 or 2, q is an integer from 1 to 5, preferably 1 to 3, A3 and A4 each are propylene, ;sopropylene or ethyl-ene, A5 is branched or unbranched alkylene having 1 to 6 carbon atoms, X ;s an an;on;c or ac;d;c group and Q3 is CO ~
- N~ o r -0-~- .
o Of particular importance for use as sizing agent (A) are those ;2Jr7~P~

which can be obtained by chemical reaction of (a) an aliphatic alcohol which has 3 to 26 carbon atoms and 2 to 6, preferably 2 to 4, hydroxyl or hydroxy-C1-C4~alkYl groups and which can have 1 to 5, preferably 1, 2 or 3, nitro-aen atoms and~ in the presence of 2 hydroxyl groups, can have a C6-C22 ~ preferably C8-C2z-, in particular C16-C20-, fatty amine radicaL, a he~erocyclic alcohol or a glycide which pre-ferably has 3 nitrogen atoms in the hetero ring and 3 hydroxy-C1-C4-alkyl or glycide groups, an alkanedioldiglycide having 2 to 6 carbon atoms in the alkane radical or a diphenol or tri-phenol or a dihydroxynaphthalene, with (b) a saturated or unsaturated fatty acid or its halides or a primary or secondary fatty amine having 6 to 22, preferably 8 to 22, ;n particular 16 to 20, carbon atoms in the fatty radical and (c) a polybasic inorganic or organic acid having 2 to 18, preferably 4 to 9, carbon atoms or its anhydrides.
Examples of specific representatives of component (a), from which the sizing agents (A) can be obtained, are as dihydroxy-naphthalenes and diphenols or triphenols 1,5-, 1,8-, 2,3 and 2,7-dihydronaphthalene, pyrogallol, hydroxyhydroquinone, phloroglucine, hydroquinone and especially pyrocatechol and resorcinol, as heterocyclic alcohols or glycides especially tris(hydroxyethyl) isocyanurate and isocyanuric acid triglycide as alkanedioldiglycides especially butane-1,4-dioldiglycide, as aliphatic alcohols sorbitol, sorbitan (i.e. cyclic anhydro-sorbites obtained from sorbitol by elimination of water), especially butane-1,2,4-triol, glyGerol, pentaerythritol, tris(hydroxymethyl)-aminomethane, trialkanolamines, for example triethanolamine, C8-C22-fatty amine dialkoxylates, for example laurylamine diethoxylate, and polyhydroxyalkylpolyaLkylene-polyamines, for example N,N,N',N'-tetrakis(2-hydroxypropyl)-ethylenediamine~
Aliphatic alcohols are preferred for use as component (a) to dihydroxynaphthalenes, diphenols, triphenols, hetero-cyclic alcohols or glycides or alkanedioldiglycides.
Sizing agents (A) having a bridging member of the formula (3) can be obtained from butane-1,2,4-triol or glycerol, having a bridging member of the formula (4) from pentaerythritol, having a bridging member of the formula (5) from tris(hydroxy-methyl)-aminomethane, having a bridging member of the formula (6) from a fatty amine dialkoxyiate or polyhydroxyalk.ylpoiy-alkylenepolyamine, having a bridging member of the formula (7) from a trialkanolamine, having a bridging member of the formula ~8) from a diphenol or triphenol, having a bridging member of the formula (9) from a dihydroxynaphthalene, having a bridging member of the formula (10) from a tris(hydroxy-alkyl) isocyanurate, having a bridging member of the formula (11) or (12)from isocyanuric acid triglicide and having a bridging member of the formuLa (13) or (14) from an alkane-dioldiglycide, for use as component (a).
Espec;ally suitable for use as component (b), from which the sizing agents (A) can be obtained, are saturated or unsatu-rated fatty acids having 6 to 22, preferably ~ to 22, in par-ticular 16 to Z0, carbon atoms, halides thereof or, as second-ary and especially primary fatty amines, monoalkytamines or dialkylamines or monoalkenylamines or dialkenylamines each having 6 to 22, preferably 8 to Z2, in particular 16 to 20, carbon atoms in the alkyl or alkenyl radical. An unsaturated or saturated C6-C22-, preferably C~-C22-, in particular C16-C20-, fatty acid for use as component (b) is, for example caproic, preferably caprylic, capric or arachidic acid, in particular lauric, myristic, palmitic, stearic or behen;c acid or myr;stoleic, palmitoleic, elaeostearic, clupan~
odonic acid, in particular oleic, elaidic, erucic, linoleic or linolenic acid. Of these, lauric, palmit;c, stearic, oleic and behenic acid are of particular importance, stearic acid being to the fore in interest. Technical, readily accessible mixtures of the acids just mentioned are also suitable. The unsaturated or preferably saturated fatty acid halides, for example alkyl or alkenyl halides, the monoalkylamines or di-alkylamines or monoalkenylamines or dialkenylamines structurally derive from the fatty acids just mentioned. Suitable alkyl or alkenyl halides are especiaLly the chLorides or, in particular, the bromides. Dioctadecylamine, especially octa-decylamine and octadecyl bromide, are specifically mentioned as representatives of monoalkylamines or dialkylamines having C16-C20-alkyl rad;cals or of alkyl halides because they are ,eadily accessible. Technical mixtures of fatty amincs or alky! halides of the specified type are also suitable~
Specific representatives of component (c) are in par-ticular sulfur trioxide, sul-furic acid, phosphoric acid, tri-mellitic anhydride, phthalic anhydride, glutaric anhydride and especially chlorosulfonic acid, phosphorus pentoxide, succinic anhydride and maleic anhydride. X in the formulae (3) to (14) is thus preferably one of the acidic groups -CO-C6H4-COOH, -CO-(CH2)2-COOH, -CO-CH=CH-COOH, -P~OH or -SO3H .
OH
The reaction products from the components (a) and (b) are intermediates from which the sizing agents (A) can be obtained by reaction with component (c~. A skilled worker will know from the type of component (a) used whether a fatty acid, a fatty amine, a fatty acid anhydride or an alkyl halide or alkenyl halide needs to be used as component (b). If a diphenol, triphenol or a dihydroxynaphthalene is used as component (a), an alkyl halide or alkenyl halide is used as component (b), while if an aliphatic or heterocyclic alcohol ;s used as component (a), a fatty ac;d ;s generally used as component (b). If, however, a heterocyclic glycide or an alkanedioldiglycide is used as component (a), it is possible to use not only fatty amines but also fatty acids.
If a diphenol, a triphenol or a dihydroxynaphthalene is used as component (a), preferably Ch~ mols of alkyl hal;de or alkenyl halide are used as component (b) per mol of com-ponent (a), Ch~ denoting the number of hydroxyl groups of component (a). It ;s thus possible in this case to obtain hydroxyl-free aromatic di- or tri-ethers as intermediates, from which the sizes (A) can be obtained by using 1 to 2, preferably 1 to 1.5, in particular 1, mol(s) of component - lo ~ 2~

(c) per mol of starting component (a). Since the reaction with component tc) takes place at the aromatic nucleus of the fatty acid di- or tri-ether, it is advisable to use as component (c) sulfuric acid, sulfur trioxide or, in particular, chlorosulfonic acidu The sizes (A) can accordingly be ob~ained in one of their preferred embodiments by reacting at least (a) 1 mol of a diphenol, a triphenol or a dihydroxynaphthalene with ~b) Ch] mols of an alkyl halide or alkenyl halide having 6 to 22, preferably 8 to 22, in particular 16 to 20 carbon atoms, Ch] denoting the number of hydroxyl groups of component (a), and (c) 1 to 2, preferably 1 to 1.5, in particular 1, mol(s) of chlorosulfonic acid, component (c) being added last.
If a heterocyclic glycide or an alkanedioldiglycide is used as component (a), preferably Ch'] mol(s of a fatty acid and/or of a primary or secondary fatty amine are used, Ch'] denoting the number of glycide groups of component (a).
In this case it is thus possible to obtain as intermediates heterocyclic compounds or alkanes which have ~-hydroxy-y-(fatty acid)-propyl groups, primary or secondary )~-hydroxy-y-(fatty amino)-propyl groups orl3-hydroxy-y-bis(fatty arnino)-propyl groups or secondary ~-hydroxy-~-(fatty carboxamide)-propyl groups~ ~leterocyclic compounds as intermediates preferably have 3 such groups and alkanes as intermediates preferably have 2 such groups, which are contained, for example, in the bridging members of the formulae (11) to (1~). The sizing agents (A) can be obtained from such intermediates by using 1 to 2, pre-ferably 1 to 1.5, in particular 1, mol(s) of component (c) per mol of starting component (a), any abovementioned, spe-c;fic representat;ves of polybasic ;norganic or organic ac;ds having 2 to 8 carbon atoms, or anhydrides thereof being possible for use as component (c).
If the intermed;ate is obtained from component (a) together w;th a pr;mary fatty amine as component (b), and therefore has primary ~-hydroxy-~ fatty amino)-propyl groups, 7~i:

the reaction with component (c) generally takes place at the hydrogen atom of the -NH- radical of such groups. However, if tne intermediate is obtained from component (a~ by means of a fatty acid or a secondary -fatty amine, i.e. by means of a dialkylamine or dialkenylamine h2ving 6 to 22 sarbon atoms, or by means of a primary -fatty amine~ i.e. by means of C6-C22-alkylamine or -alkenylamine, and has secondary ~-hydroxy-~'-(fatty acid ester)-propyl groups, ¦~hydroxy-~-bis-(fa~ty amino)-propyl groups or ~-hydroxy-d--(fatty carboxamido)-propyl groups, the reaction with component tc) generally takes place at the hydrogen atom of the l~-hydroxyl radical of such groups.
Sizi~g agents (A) in a further preferred embodiment can thus be obtained by reacting at least (a) 1 mol of a heterocyrlic glycide having preferably 3 n;trogen atoms in the hetero ring and 3 glycide groups, in particular isocyanur;c acid triglycide, or an alkanedioldi-glycide having preferably 2 to 6 carbon atoms in the alkane radical, in particular butane-1,4-dioldiglycide, with (b) Ch'~ m'ol(s) of a fatty acid or of a primary or secondary fatty amine each having 6 to 22~ preferably ~ to 22, in par-ticular 16 to 20, carbon atoms in the fatty radical, Lh']
denoting the number of glycide groups of component (a), and then with tc) 1 to 2, preferably 1 to 1.5, in particular 1, mol(s) of a polybasic inorganic or organic acid having 2 to ~ carbon atoms or anhydrides thereof, component (c) being added last.
If, as preferred, a heterocyclic or aliphatic alcohol is used as component (a), preFerably Ch-1] mol(s) of a fatty acid are used, ~h~ denoting the number of hydroxyl groups of component (a). If, for example, an aliphatic alcohol having 2 hydroxyl groups and a fatty amine radical is used as com-ponent (a), 1 mol of fatty acid is used as component (b) per mol of component (a). However, if a heterocyclic alcohol having 3 hetero atoms is used as component (a), 2 mols of fatty acid are used as component (b) per mol of component (a). If aliphatic alcohols having preferably 3 or ~ hydroxyl groups are used as component (a), 2 or 3 mols of fatty acid are used as component (b) per mol of component (a). The intermediates obtained from component (a) and (b) if alcohols of the specified type are used as ccmponent (a) are partially esterified compounds, i.e~ partial esters which still contain a free hydroxyl group. The si~ing a~ents (A) can be obtained :~rom these çompounds by us;ng 1 to 2 mols, preferably 1 to 1.5 mols, in particular 1 mol, of component (c) per mol of starting component (a), the component (c) forming an ac;d ester with the hydroxyl group of the intermediates from (a) and (b) and any abovementioned specific representative of polybasic inorganic or organic acids having 2 to 8 carbon atoms or anhydrides thereof can be used as component (c).

Sizing agents (A) can thus be obtained in their particlllarly preferred form by reacting at least (a) 1 mol of an aliphatic alcohol which has 3 to 26 carbon atoms, 2 to 6, preferably 2 to 4, hydroxyl groups and can have 1 to 5, preferably 1, 2 or 3, nitrogen atoms and, in the presence of 2 hydroxyl groups, can have a C6-Cz2-, prefer-ably C8-C22-, in par~icular C16-C20-, fatty amine radical, w;th (b) Ch-1] mol(s) of an unsaturated or preferably saturated fatty acid having 6 to 22, preferably 8 to 22, in particular 16 to 20, carbon atoms or mixtures thereof, Ch] denoting the number of hydroxyl groups of component (a), and then with (c) 1 to 2, preferably 1 to 1.5, in particular 1, mol(s) of a polybasic inorganic or organic acid having 2 to18 carbon atoms or anhydrides thereof, the polybasic acid being used as component (c) being added last and forming acid esters with the hydroxyl groups present in the intermediates formed from components (a) and ~b).

Those acid esters which are intended for use as sizes (A) and which can be obtained by reacting intermediates from 1 mol of laurylamine diethoxyla~e and 1 mol of behenic acid, from 1 mol of glycerol, triethanolamine or tris(hydroxymethyl)-aminomethane and 2 mols of stearic acid or an equimolar mixture of stearic acid and palmitic acid or from 1 mol of pentaeryth-ritol or N,N,N',N'-tetra~is(2-hydroxypropyl)ethylenediamine and 3 mols of stearic acid, with 1 to 1.5 mols each of chloro-sulfonic acid, phosphorus pentoxide or maleic anhydride, are of oarticular importance.
To the fore of interest are sizing agents (A) which can be obtained by reactin~
(a3 1 mol of triethanolamine or, in part;cular, 1 mol of glycerol with (b) 2 mols of stearic acid and then with (c~ 1 mol of phosphorus pentoxide, or, in particular, (a) 1 mol of tris(hydroxymethyl)aminomethane with (b) 2 mols of stearic acid and then with (c) 1 to 1.5 mols ot maleic anhydride.

Further sizing agents of interest can be obtained by reacting tensides which are derived from sulfosuccinic acid, e.g. sulfosuccinic isooctyl ester, with a fatty alcohol.
Preferred sizing agents (A) can be obtained from components (a), (b) and (c) or from the tensides of the specified type and have molecular weights of about 400 to about 3,000, preferably of about 600 to 1,500, and an acid value (mg of KOH/g oE substance) of about 15 to about 150, preferably 35 to about 125.
As mentioned above, some of the compounds used in the invention as sizing agents and some of the intermediates from which these sizing agents can be obtained are known.

German Patent 733,689, for example, discloses inter-mediates from eriethanolamine and stearic acid which still have at least one free hydroxyl group, which can be esteri-fied with phthalic anhydride. However, this publication dis-closes no intermediates prepared from two fatty acids which differ from each other. The publication mentions as poly-basic acids or anhydrides ~hereof for preparin~ the acid - 14 ~

esters apart from aromatic acids such as phthalic acid, and its isomers, and naphthalic acid, only tartaric acid and suc-cinic acid.
German Patent 193,189, for example, discloses further inte,-mediates from glycerol and stearic acid which have a ,ree hydroxyl group~ which can be esterified with phosphorus pentoxide~ Apart from phosphorus pentoxide, this publication mentions no other polybasic acid or anhydride thereof for preparing the acidic esters.
Nor do the German patents mentioned contain any in-formation about using the disclosed compounds as sizing agents for paper.
U.S. ?aten. 2,504,951, moreover, describes how 2-heptadecyl-bist4-stearyloxymethyl)-2-oxazoline i~ prepared from 1 mol of tris(hydroxymethyl)aminomethane and 3 mols of stearic acid. However, this patent contains no information about 2-heptadecyl-4-hydroxymethyl-4-stearoyloxymethyl-Z-oxa-zoline from 1 mol of tris~hydroxymethyl)aminomethane and 2 mols (instead of 3 mols) of stearic acid, nor about using the oxazoline described as a sizing agent for paper.
Reference is finally made to U.S. Patent 2,~67,960, which discloses C12-C14-alkyl diethers of hydroquinone, resor-cinol or pyrocatechol, but does not contain any information about reaction products of such ethers with polybasic inor-ganic or C2-C8 organ;c acids or their anhydrides or about their use as sizing agents for paper.

Furthermore, the German "Offen1egungsschrift" 2,162,620 discloses the final products which can be obtained from tensides which are clerived from sulfo-succinic acid. This reference contains, however, no information about the utility of such products, e.g. as sizing agents for paper.

The invention thus also relates to novel intermediates, from which the sizing agents (A) to be used in the invention can be obtained and which have one of the formulae - 15 ~L~4~

R 1 j - - CH

(15) [R - ~_ - - CH2 [~1-]

Rl - C _ o 2 ~

(16) R - ll - O - CH _ C CH2 OH
R - C - O - CH

(17) Rl - C CH2 o N--C - CH - O - C - R

(18) l1 ] O O

[ -H ] L R=30 R=2 N~A3 - OH o (19) 1 \ 11 >~O-Rl ( 20) i +1 0-R2 o R
.~,~-\./-~
(21) !~ ; O-(Z2) O \~

o OH C OH
(23) 4 2 CH CH2 ~ - CH2 - CH - CH2 Q4 or CH2 - ICH - CH2 ~4 OH
OH OH
(24) Q4 - CH2 - CH - CH2 - O - A5 - O - CH2 - CH - C~i2 - Q4 in which q is an integer from 1 ~o 5, preferably 1 to 3, in particular 1, ~ is 1 or 2, A3 and A~ each are propylene, iso-propylene or ethylene~ As is branched or unbranched alkylene having 1 to 6 carbon atoms, Q4 is ~ CO-R1 R1 or -O-~-R1 and R1, R2 and R3 are different from or, preferably, identical to one another and each is alkyl or alkenyl hav;ng 6 to 22, preferably 8 to 22, in particular 16 to 20, carbon atoms, R1 and R2 being d;fferent from each other in the formula ~15) and (18) ;f q and t are 1.
The method of preparing the intermediates of the for-mulae (15) to ~24) ;s also part of the subject matter of the invention, and comprises reacting with one another (a) 1 mol of butane-1,2,4-~r;ol, pentaerythritol, tris(hydroxy-methyl)aminomethane or a compound of the formula 7~:

(25) HO - A3 - [ ~3 A4 ]q-l ~ 3 ~3 A13 OH OH
in which q, A3 and A4 are as defined above, ;n part;cular N~N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine or a com-pound of the formula ~ -OH

(26) Rl - N' in which R1 and R3 are as defined above, in particular a C8-C22-fatty amine diethoxylate, or a compound of the formula o (27) HO-A3-N ~ -A30H
,N&
I

in which A3 is as defined above, in part;cular tris(hydroxy-ethyl) isocyanurate, with (b) [h-1] mol(s3 of an unsaturated or preferably saturated fatty acid of the formula (28) R1 ~ COOH, (29) R2 ~ COOH and/or (30) R3 ~ COOH, in which R1, R2 and R3 are as defined above and ~h] is the number of hydroxyl groups of component (a) or (a) 1 mol of pyrogallol, hydroxyhydroquinone, phloroglucine or a dihydroxynaphthalene with (b3 [h-1~ mol(s3 o-F an alkenyl halide or preferably alkyl halide of the formula (31) R1 ~ Z1' (32) R2 ~ Z2 and/or (33) R3 ~ Z3~

in which R1, R2, R3 and h are as defined above and Z1~ Z2 and Z3 each are a halogen, preferably chlorine, in part;cular brom;ne, or ~a) 1 mol of isocyanuric acid triglycide or 1 mol of ~he com-pound of the formula CH/-\CH - CH2 - 0 - A5 - C~l2 2 in which A5 is as defined above, in particular butanediol-diglycide, with (b) Ch'] mol(s) of a fatty ac;d of the formula (26), a pr;-mary fatty amine of the forMula (35) R1 ~ NH2 o~ a secondary fatty amine of the formula (36) R1 ~ , in which R1 and R2 are as defined above, or Ch'] mol(s) of a pr;mary fatty amine of the formula (33) and then Ch'] mol(s) of a fatty acid of the formula (26) in which [h'] is the num-ber of glycide groups of component (a)~
The invent;on also relates to novel compounds and their salts, wh;ch can be obtained from the novel intermediates prepared from components (a) and (b) of the formulae (15) to (24) or from dialkyl ethers or dialkenyl ethers of hydro-quinone, resorcinol or pyrocatechol each having 6 to 22, pre-ferably 8 to 22, in particular 16 to 20, carbon atoms in the alkyl or alkenyl radical and from a polybasic inor~anic or crganlc acid having Z to 18 carbon atoms aS component (c) and which can be used as si~ing agent (A) in the invention and have one of the formulae 1l ~ ~ - O - ~,H 2 [R C '¦ l - - C~12 oXl-]

Rl - C - O - CH2 (38) R - 1~ - O - CH --- C - CH2 - OX
R - C - O - CH

(39) R - C CH2 1l 40) R1 - C -! ~ 3 1 4 q'-1 1 A3 [X2-] c=o l=o R3 2 .
A - OX
(41) R- N R
A - O - C - C-R
~O-Rl (42) HS03 --~(0 R3) t-1 . OR
i ~ 1 S ~3) ~ 0/ \ 0~; 503~1 t44)Rl - C - O - A3 ~ ~ 3 _ O - C - R2 13-ox OH R OH
(45) Rl - NH - CH2 - CH - CH2 - N N - CH2 - CH - CH2 - NH - R2 O=C~ C=O

CH2 - ICH - CH2 - ~ - R3 OH X
OH ~ OH
(46) Q5 - CH2 - CH - CH2 - N/"\N - CH2 - CH - CH2 - Q
=C~N~C=

OX
IOH IOH lX
NH - CH - CH - CH2 - O - A5 ~ CH2 2 or IOH lOX
(48) Q - C~ - CH - CH2 - O - A5 - O - CH2 C 2 6 in which q is an integer from 1 to 5, t is 1 or 2, Q5, Q~ and Q7 each are _N& 1 , -NiRl _o - C ~ Rl, X is the radical of a polybasic inorganic or oryanic acid having 2 to 18, preferably 4 to 9, carbon atoms, X1 ;s de-fined in the same way as X or, if t is 1, is -CO-C6H4-COOH,-Co-(CH2)2-COOH, -CO-CH=CH~COOH, or S03H, X2 is defined in the same way as X or, if q is 1, is -CO-CH=CH-COOH, / or -P-OH
OH

03H~ and A3~ A4~ A5~ R1, R2 and R3 are each as def-ined above.
The method of preparing the novel compounds of one of the formulae (37) to (48) or ~heir salts is part of the subject matter of the invention. This method comprises reacting 1 mol of an intermediate of the formulae (16), (17), (19), (22), ~23) and (24) or 1 mol of an intermediate of the formula (15) in which t is 2 or 1 mol of an intermediate of the formula (1B) in which q is 2, 3, 4 or 5, with 1 to 2, preferably 1 to 1.5, in particular 1, mol(s) of a polybasic acid, as com-ponent (c), of the formula (49) ~l - X, in which X is defined as above, or 1 mol of the ;ntermediate of the formula (15) in which t is 1, with 1 to 2, preferably 1 to 1.5, in particular 1, mol(s) of a polybasic acid, as com-ponent (c), of the formula (50) H - X1 in which X1 is -CO~C6H4-COOH, -CO-(CH2)2-COOH, -CO-CH=CH-COOH or -503U, or 1 mol of the intermediate of formula (18) in which q is 1 and R1 and R2 are different from or, preferably, iden~ical to each other, with 1 to 2, preferably 1 to I.5, in par~icular 1, mol(s) of a polybasic acid, as component (c)~
of the formula (51) H X2 ~
in which X2 is -CO-CH=CH-COOH, ~H or -S03H or 1 m~l of an intermedia~e of the formula (20) or (21) or of the compound of the formula O-R
(52) .~ ~
! I!

;n which R1 and R2 are each as defined above, with 1 to 2, pre-ferably 1 to 1.5, in particular 1, mol(s) of chlorosulfonic acid as component (c), and, if desired, converting the reaction products obtained into the corresponding salts.
In the course of the reaction of aliphatic or hetero-cyclic compounds of ~he formulae (15) to (19) or (22) to ~24) as intermediates, with the acids of the formula (49), (50) or (51) as component (c), the free hydroxyl group of the com-pounds (15) to (19) or (22) or at least one of the Eree hydroxyl groups present in the compounds of the formula (23) or (24) reacts w;th the compound of the formula (49), (50) or (51) in such a way that acidic esters are formed. However, if aro-matic compounds of the formula (20) or (21) are used as inter-mediates or compounds of the formula (52) are used as starting materials, the reaction with chlorosulfonic acid as component (c) takes place at the aromat;c nucleus of said intermediates or starting materials~

The processes for preparing intermediates from the components (a) and (b) and acidic esters by further re-action with component (c) are preferably carried out in the presence of solvents which need to be inert not only to every s~arting component (a), (b) and (c) but also to the inter-mediate and end products, ;.eO the reaction products of (a) and (b) and of (a), (b) and (c). Suitable solvents are in particular halogenated or unhalogenated hydrocarbons which have a boiling point of at most 140C. For the reaction be-tween components (a) and (b) hydrocarbons which boil between about 110C and about 140C are preferred, for example tol-uene, chlorobenzene, o-, m- or p-xylene, a technical xylene mixture or even mixtures of the hydrocarbons ment;oned. If the further reaction of the intermediates from components (a) and (b) with component (c), not only the specified hydro-carbons but also preferably halogenated hydrocarbons which boil at a lower boiling point, for example at about 40C to about 80C, for example dichloroethane or carbon tetra-chloride~ are sui~able. Particularly suitable elevated tem-peratures in the reaction of components Sa) and (b) are temperatures of 100C to 140C and in the further reaction with component (c) room temperature (15 to 25C) to elevated temperatures of about 40 to 80C.
It is furthermore advantageous to carry out the re-action of components ta) and (b), especially, in the presence of a catalyst which will accelerate the esterification re-action if need be.
Examples of suitable catalysts are inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid, and especially organic acids such as organic sulfonic acids and, in particular, p-toluenesulfonic acid. It is advantageous to use, for example, 1 to 4~ of these catalysts per mol of component (a).
To prevent polymerisation in the course of the pre-paration of acidic esters having a reactive C=C double bond, - 2~ -the esterification with component (c) can advantageously be carried out in an inert nitrogen atmosphere. This is partic-ularly relevant when par~icularly reactive components, for example maleic acid, are used. In this case or when an un-sacurated (b) component, for example ole;c acid, is used, i~ is advantageous to use a polymerisation inhibitor, especially a~ elevated temperatures. Examples of such inhibitors are methylene blue, benzothia~ine and, in particular~hydroquinone.
It is advantageous to use, for example, 0.1 to 0~3% of these ;nh;b;tors per mol of unsaturated components (b) or (c).

In another preferred embodiment the sizing agents (A) used in the invention preferably contain besides acidic phosphate or sulfate or carboxyl groups as anionic or acid group and preferably 2 to S, in parti-cular 2 hydrophobic substituents of the specified type divalent linking members with which at least two of the most adjacent hydrophobic substi-tuents are bonded to each other, which have preferably 1 to 15, pre-ferably 2 to ~, carbon atoms and at least 2 hetero atoms, preferably 2 to 6, in particular 2, nitrogen atoms. Depending on the number of hydrophobic substituents, such sizing agents contain 1 to 5, preferably 1 to 3, in particular 1, linking member of the specified type.

In their simplest embod;ment preferred link;ng mem-bers have the formula t53) -Q1 - N - A1 ~ N ~ Q2-, in which Ql ;s ethylene, propylene or butylene and Ql and Q2 each are a direct bond, -C0 or -C0-NH-.
Linking members of the formula (53) are parts of ;ng members wh;ch have at least one an;onic or acidic group bonded to a nitrogen atom and the formula I Q

in which A1, A2 and A3 each are ethylene, propylene or butyl-ene, at least one of the radicals ~3, ~4 and ~5 is -X', at least two of the radicaLs Q3, Q4 and Q5 are -C0-, -C0-NH- or a direct bond, X' is an anionic or acid;c group or a radical carrying SUC~l a group, and y' is an integer from 1 to 5.
In ~he formula (54), y' is preferably 2, andespecially 1. Moreover, A1, A2 and A3 are preferably def;ned in chesame way and are ;n particular propylene and, especially, ethylene.
~ ridging members to the fore of interest thus have the formula (55) - N - A3 - ~ - A3 - N -in which the A3 radicals are ethylene or propylene and two of the Q6 ' Q7 and Q8 radicals are -C0- or -C0-NH- and one of the radicals `6' Q7 and Q8 is -X', -X' being as defined above.

Those sizing agents (A) are of particular importance which can be ob-tained by reacting (a') a polyalkylenepolyamine which is unsubstituted or mono-substituted by N-C6-C22-alkyL or -alkenyl and has 3 co 6 nitrogen atoms and 4 to 4û carbon atoms with ~b~) a fatty acid or a fatty alcohol, an alkyl or alkenyl halide or an alkyl or alkenyl isocyanate having at least ~pre-ferably 6 to 22, especially 16 to 20, carbon atoms in the alkyl or alkenyl radical and then with (c') the anhydride of a polybasic, preferably tribasic, ;n particular dibasic, inorganic or organic acid having 2 to 18, preferably 2 to 8, carbon atoms or an ~- ori~_halogenocar-boxylic acid having 2 to 6 carbon atoms, the component (c') being added last.
Examples of specific representatives of ' from which the sizing agent can be obtained are N,N'~bis(3-aminopropyl)-1,4-diaminobutane, N-(3-aminopropyl)-1,4-diaminobutane, 1,2-?d~2~

bist3-aminopropylamino~ethane, pentaethylenehexamine, especially tetraethylenepentamine, triethylenetetramine and in particular dipropylenetriamine and diethylenetriamine, the last being to the fore of ;nterest.
A component (b') from which the sizirAg agent (A) can be ob~
I:ained i5 in particular a saturated or unsatura~ed fatty acid, an alkenyl, preferably alkyl isocyanate having 6 to Z2, pre-ferably 8 to 22, in particular 16 to 20 carbon atoms in the alkyl or alkenyl rad;cal. An unsaturated or saturated C6-C22-, preferably C8-C22-, ;n particular C16-C20-, fatty acid for use as component (b') is e.g. caproic, preferably caprylic, capric, lauric, myristic or arachidic acid, in particular palm;tic, stear;c or behen;c acid or myristoleic, palmitoleic, elaeostearic, clupanodonic acid, in particular ole;c, elaidic, eruc;c, linoleic or linolenic acid. Of these, palmit;c, stearic, oleic and behenic acid are all of particular importance, palm-itic and especially stearic acid being to the fore of interest.
Technical, read;ly accessible, m;xtures of the ac;ds just mentioned are also suitable. Because it is readily accessible, octadecyl isocyanate is mentioned as a C16-C20- alkyl isocyanate.
Anhydrides of organ;c polybasic acids are preferred to those of inorganic polybasic acids for use as component (c'). Examples of specif;c representatives of the anhydrides of ;norgan;c polybas;c acids are sulfur trioxide, especially phosphorus pentoxide and in particular chlorosulfonic acid.
An organ;c polybas;c ac;d anhydr;de is, for example, the anhydride o-f benzophenone tetracarboxyl;c acid, 1,8-naphthalic ac;d, tr;mell;t;c ac;d, pyromell;t;c ac;d, b;cyclo~2,2,1)hept-S-ene-2,3-dicarboxylic acid (also called norbornene dicar-boxylic acid or nadic acid), hexahydrophthalic acid, tetra-hydrophthalic acid, phthalic acid, succinic acid, glutaric acid, dimethylmale;c acid, citraconic acid, itaconic acid, and in particular maleic acid. The halogenocarboxyl;c acid is, for example, 2-chlorobutyric acid, 2- and 3-chloropro-p;onic acid, bromoacet;c ac;d or chloroacet;c acid and the;r alkali metal salts. The sultone used is especially propane-sultone. To the fore of interest are glutaric anhydride, succinic anhydride, sodium chloroacetate, citraconic anhydride, itaconic anhydride, phthalic anhydride, pyromellitic anhydride an~ in particular trimelli~ic anhydride and maleic anhydridef from which particularly effect;ve sizing agents can be obtained~
The reaction p~oducts of co.~ponents (a') and (b') are intermediates fro~ which the sizing agents (A) can be obtained by reacting these intermediates with component (c').
As mentioned above, so~e of the si~ing agents (A) used in the invention are compounds known per se. This is also true of intermediates from components (a') and (b') -from which the sizing agents (A) can be obtained.
For ;nstance, French Patent 1,388,523, inter alia, describes intermediates prepared from fatty acids, for example oleic acid or stearic acid, and polyalkylenepolyamines, for example triethylenetetramine, which are reacted with poly-basic acids. As polybasic acids, however, this pa~ent speci-fication explicitly only mentions hexahydrophthalic, tetra-hydrophthalic, phthalic, terephthalic, trimellitic, succinic, adipic and maleic acid and the corresponding anhydrides~

U~S. Patent 4,332,737 also describes intermediates prepared from fatty acids and polyalkylenepolyarnines, which are reacted with polybas;c acids, but as polybasic acids it explicitly mentions naphthalene dicarboxylic acids, phthalic, terephthalic, malonic~ succinic, ~lutaric, rnaleic and c;tra-conic acid and the corresponding anhydrides.
Japanese Patent Appl;cation 74/137,917, f;nally, dis-closes intermediates prepared from fatty acids and polyalkyl-enepolyamines, wh;ch are only reacted w;th sodium chloro-acetate as acid.
Intermediates prepared from polyalkylenepolyamines and fatty alcohols or alkyl or alkenyl halides are known and are commercially available. Intermediates prepared from poly-~2~,7;~

alkylenepolyamines or N-alkyl or -alkenylpolyalkylenepolyamines and alkyl or alkenyl isocyanates, however, are novel. This is also true of the reaction products of such intermediates with any desired polybasic acid. Reaction products prepared from polyalkylenepoly-amines and fatty acids and reacted with polybasic acids are also novel provided the polybasic acid anhydride used was that of pyromellitic acid, norbornene dicarboxylic acid, di-rnethylmaleic acid or citraconic acid. Reaction products reacted with 2-chlorobutyric acid, 2- or 3-chloropropionic acid, bromoacetic acid or propanesulcone are also novel.
The invention accordingly also relates to - intermediates which can be obtained by reacting (al) 1 mol of a polyalkylenepolyamine wh;ch is unsubstituted or monosubstituted by C6-C22-alkyl or -alkenyl and has 3 to 6 nitrogen atoms and 4 to 40 carbon atoms with (b1) 1 to ~h"-1] mol(s) of an alkenyl isocyanate or preferably alkyl isocyanate having at least 5, preferably 6 to 22, especially 8 to 22, in particular 16 to 20, carbon atoms in the alkyl or alkenyl radical,[h'] denoting the number of nitrogen atoms of component (a1) - compounds which can be obtained by reacting intermediates prepared from components (a1) and (bl) with (cl) 1 to [h'l] mol(s) of the anhydride of a polybasic, pre-ferably dibasic, inorganic or, in particular organic acid having 2 to 18 carbon atoms, a 2- or 3-halogenocarboxylic acid having 2 to 6 carbon atoms or a sultone, [hl] denoting the number of free nitrogen atoms present in the intermediate from (al) and (bl) which are not reacted ~ith component (bl), - compounds which can be obtained by reacting (al) 1 mol of a polyalkylenepolyamine having 3 to 6 nitrogen atoms and ~ to 20 carbon a-coms with (b2) 1 to ~h"-1] mol(s) of an unsaturated or pre-ferably saturated fatty acid havin~ at least 5, preferably 6 to 22, especially 8 to 22, in particular 17 to 20, carbon atoms, ~h"] being as defined above, and then with (c1) 1 to ~h2'~ mol(s) of pyromellitic, norbornene dicarboxylic, dimethylmaleic or citraconic anhydride, 2-chloro-butyric acid, 2- or 3-chloropropionic acid, bromoacetic acid or propanesultone, [h2'~ denoting the number of free nitrogen atoms present in the intermediate product ~rom (al) and (b2) wnich are not reacted with component tb2).
The reactions of components (a'~ and (b') are generally carried out at about 120 to about 250C, preferably up to 200C, in the melt. If high temperatures o-f about 200 to 250C are used, the resulting products can be purified with active charcoal if necessary. However, especially if alkenyl or alkyl isocyanates are used as component (b') or in the reaction with component (c') it is also possible to carry out the re-actions in the presence of at least one solvent which needs to be inert to the starting, intermediate and end products.
If such solvents are used, the reactions can also be carried out at lower temperatures, for example 30 to 120C. Examples of poss;ble solvents are acetone, d;oxane and halogenated or unhalogenated hydrocarbons, for example dichloroethane, carbon tetrachloride, benzene, toluene, chlorobenzene, o-, m- and p-xylene, a technical xylene mixture or mixtures of the hydrocarbons mentioned. If halogenated carboxylic acids, for example chloroacetic acid, are reacted as component (c') it is advisable to prevent the formation of by-products by using an approx;mately equ;molar amount (based on the halogen-ated ac;d) of a weak nitrogen-containing base, for example pyr;d;ne, ;soquinoline, quinoline or preferably triethyl-amine, as an acid acceptor. If unsaturated (c') or especially (b') components are used, it is furthermore advantageous to carry out ~he reaction in an inert nitrogen a-tmosphere and/or especially at elevated temperatures in the presence of a poly-merisation inhibitor, For example methylene blue, benzothi-azine or preferably hydroquinone.

7~

Preferred sizing agents (A) of the type specified from the components ~a'), (b') and (c') in particular have molecular weights of about 400 to about 3,000, preferably about 500 to about 3,000~ ;n particular about 600 to about 1,500, and, owing to the fact that they contain at least one acidic group, for example an -S03H or -COOH group, an acid value (mg of KO~Vg of substance) of about 15 to 150, preEerably about 50 to about 120.

In a further preferrecl embodiment the sizing agents (A) used in the invention contain besides 1 or 2 potential anionic, acidic methylene or methine groups and 2 or 3 h~dro?hobic substituents of the specified type divalent linking members with which at least two of the most adjacent hydrophobic substituents are bonded to each other which have 1 to 15, preferably 3 to 8, carbon atoms and each have at least 2 hetero atoms, preferably 2 to 4 nitrogen and/or oxygen atoms or in particular 4 nitrogen atoms or 2 oxygen atoms. The linking members which each have 3 to 5 carbon and 2 oxygen atoms are parti-cularly preferred.Depending on the number of hydrophobic substituents, the sizing ager.ts prefercably contain 1 or 2 lir.kir.g ~.e~lbe~s of the speci-fied type.

Preferred l;nking members generally have one of the formulae (56) -~ - ~ - t-CH2 ~ ~)ff,1 CH - ~ - 0-or (57) ~ H-~-NH-ali-Nl~ H-~-N\

;n which n"and m"each are 1 or 2 and A1 1s branched or espec-;ally stra;ght-cha;n alkylene hav;ng 4 to 12, ;n particular 6 to 10, carbon atoms, cycloalkylene hav;ng 6 to 1~ carbon - 31 ~ 7~

atoms or arylene having 6 to 1~, in particular 6 to ~, carbon atoms. If m in the formuLa t56) is 1, the linking member has a methine group at the corresponding site. However~ if m"
is 2, the linking member has a methylene group at the corres-ponding site.
In linking members of the formula (56~ or (57) the methylene or methine groups are part of a divalent or tri-valent -CO-C~l2CO- or -CO-CH-CO radical where the acidic properties of the methylene or methine groups is due to each methylene group being linked between two CO groups or the meth-;ne group being linked between 3 CO groups or 2 CO groups and one CN group.
If n in the formula (56) is Z, m is generally 2.
m is generally only defined as 1 if n is also 1. However, the linking member particularly preferably has the formula (56) in which n is 1 and m is 2.
Those sizing agents (A) are of particular importance which can be obtained by reacting ta'1) malonic acid, a malonyl dihalide, acetone dicar-boxylic acid or a C1-C4-alkyl malonate, acetone or methane tricarboxylate with (b'1) a fatty alcohol or (a'2) cyanoacetic acid or its C1-C4-alkyl ester with (b'2) a fatty amine and then with (c") a C4-C12-alkylene, C6-C14-cycloalkylene or C6-C~4 arylene diisocyanate.
A suitable component (al'), from which the sizing agent (A) can be obtained, is in partic~llar a dihalide, for example the di-bromide and in particular the dichlor;de, of malon;c acid and its methyl or in particular ethyl esters. Malonyl dichlor-ide is particularly preferred because of its high reactivity.

The dimethyl and especially the diethyl ester of acetone di-carboxylic acid and the trimethyl and especially triethyl ester of methanetricarboxylic acid are also suitable because ~hey are readily accessible.
Component (a2) is in particular methyl cyanoacetate and especially e~hyl cyanoacetate.
Malonyl dichloride and ethyl cyanoacetate are to the fore of interest for use as components (a1) and (a2) Suitable for use as component (bl) , fronn which the sizing agent (A) can be obtained~ are in particular saturated or unsaturated aliphatic alcohols having 6 to 22, preferably 8 to 22, in particular 16 to 20 carbon atoms and for use as component (b'2) in particular monoalkylamines, dialkyl-amines, monoalkenylamines or dialkenylamines which each have 6 to 22, preferably 8 to 22, in particular 16 to 20, carbon atoms in the alkyl or alkenyl radical. Saturated fatty alco-hols and alkylamines or dialkylamines are preferred to un-saturated fatty alcohols and alkenylamines or dialkenylamines.
Primary amines are also preferred to secondary amines. Spe-c;f;c C16-C20 fatty alcohols and C16-C20-alkyl radical monoalkylamine or dialkylamine representatives mentioned be-cause they are readily accessible are hexadecanol, octadecanol, oleyl alcohol, octadecylamine and dioctadecylamine. Tech-nical mixtures of fatty alcohols or fatty amines of the speci-fied type are also suitable.
An aliphatic diisocyanate as component (c") has branched or preferably straight-chain alkylene radicals having about 4 to 12, in particular 6 to 10, carbon atoms. Specific representatives of such diisocyanates are butylene diiso-cyanate, dodecylene diisocyanate, especially decylene 1,10-diisocyanate and in particular hexylene 1,6-diisocyanate.
A cycloaliphatic diisocyanate ~enerally has 6 to 14 carbon atoms in the cycloalkylene radical. Examples are cyclohexyl 3L~d~

and dicyclohexyl diisocyanate. The aromatic diisocyanates generally have 6 to 14, preferably 6 to ~, carbon atoms in the arylene rad;cal. Examples of specific representatives are naphthylene 1,5-diisocyanate, diphenylmethane 4,4'-diiso cyanate, phenylene 1,4-diisocyanate and toluylene 2,4- and 2,6 diisocyanate. Hexane 1,6-diisocyanate and toluylene ~,4-or 2,6-diisocyanate and especially technical toluylene 2,4-and 2,6-diisocyanate mixtures are mentioned because they are readily accessible.
About 1 mol of fatty alcohol as component (b'1) is generally used per functional group of the component (a'1) used~ For instance, about 2 mols of fatty alcohol are gener-ally used per mol of component (al) if component (a1) is malonic acid or acetone dicarboxylic acid or halides or esters thereof, and about 3 mols of fatty alcohol are used per mol of component (a'l) if the component (al) is methyl or ethyl methanetricarboxylate.
If components (a'2) and ~b2) are used, they are gen-erally reacted with each other, in about equimolar ratios.
The resulting cyanoacetic acid fatty amide is an intermediate which is reacted with component (c"), about 0.5 mol of alkylene, cycloalkylene or arylene diisocyanate of the specified type being used as component (c"~ per mol of the intermediate from about equimolar amounts of the components (a2) and (b2).
Sizing agents (A) of the speciEied type from the components (a'l) and (b'l) orfrom the components (a2), (b'2) and (c") which are pre-ferably used have molecular weights of about ~00 to about3,000, preferably of about 600 to about1,500.
The reactions of the (a'l), (a2), (bl), (b2) and (c") components specified above are generally carried out by methods known per se. For example, the reactions of components (al) with (b'l) or (a2)with (b2) are carried out at about 30 to about 250C, preferably at about 40 to 140C,in ~he melt9 as the case may be. If high temperatures of about 200 to 250C
are used, the resulting products can be purified with active charcoal if necessary. However, on use of acid hal;des as component (a'1) in particular and on reac-ting intermediates pre?ared from componentâ (a2) and (b2) with component (cl') in general it is advantageous to carry out the reactions in the presence of at least one solvent which needs to be inert to every starting, intermediate and end product. If such solvents are used, the reactions can also be carried out at lower temperatures, for example at 30 to 120C, preferably 30 to 50C. Examples of possible solvents are acetone, dioxane and halogenated or unhalogenated hydrocarbons such as d;chloroethane, carbon tetrachlor;de, benzene, toluene, chlorobenzene, o-, m- and p-xylene, a technical xylene mixture or even m;xtures of the hydrocarbons ment;oned, which are particularly suitable for use as reaction med;um when ac;d hal;des as component (al) are reacted w;th fatty alcohols as component (b1). If ;ntermediates prepared from (a2~ and (b'2) are reacted with component (c"), in particular dimethyl-formamide or dimethylsulfoxide are particularly suitable for use as further solvent. If free acids are reacted as com-ponents (a'1) or (a2) with fatty alcohols or fatty amines as components (b'1) or (b'2), the use of a catalyst, for example hydrochloric acid, sulfuric acid, phosphor;c acid or organic sul-fonic ac;ds, preferably p-toluenesulfon;c ac;d, can be advantageous to accelerate the esterification or trans-esterificat;on reactions ;f need be. If unsaturated (b1) and (b2) components are used 1t is furthermore advantageous to carry out the reaction in an inert nitro~en atmosphere and/
or, especially at high temperatures, for example above 90C, in the presence of a polymerisation inhibitor~ for example methylene blue, benzothiazine or preferably hydroquinone.
~ s mentioned above, some of the sizing agents (A) are compounds known per se. For example, the article by Staudinger et al.
in the journal"Makromolekulare Chemie,' Volume 3, pages 251 to 2~û (1949), describes fatty alkyl diesters of malonic acid, - 35 ~ 2 i.e. compounds which have a linking member of the formula (56) in which n is 1 and m is 2. The article by Staudinger et al. says nothing, however, about the possible use of the disclosed compounds. Furthermore, British Patent 737,528 for example, discLoses fatty alkyl diesters of acetone di-carboxylic acid, i.e. compounds which have a linking member of the formula (56) ;n which m and n are 2. However, this patent specification has nothing to say about using the d;s-closed compounds as sizing agents for paper.
On the other hand, compounds which have a linking member of the formula (56) in which n and m are 1, or a link-ing member of the formula (57) are novel compounds. The intermediates prepared from components (a2) and (b2') are also novel.
The invention thus also relates to compounds which can be used as intermediates and have the formula (58) /Ri' NC-CH -CO-N
i 2 (R2)p-1( )2-p in which p" is 2 or preferably 1, R1" and R2" are different from or preferably identical to each other and each is alkenyl or preferably alkyl having 6 to 22, but preferably 8 to 22, ;n particular 16 to 20, carbon atoms, and to their salts.
The invent;on also relates to a process for prepar;ng the compounds of the formula (5~), which comprises reacting 1 mol of cyanoacetic ac;d or ;ts C1-C4-alkyl ester w;th about 1 r,lol of a secondary or primary amine of the formula HN
( 2 p-l 2-p Novel compounds wh;ch are part of the subject matter of the invention and can be used as sizing agents (A) have the formula (60) i \ 3 R2'-0~ or t61) R C C C
cH-~-NH--All-N~ H- -~
(li) Z_~ 2) p" 1 1 (R'4) qll 1 (ia) 2-q'' in wh;ch p" and q" are different from or preferably identical co each other and each is 2 or preferably 1, R1", R2", R3" and R4" are different from or preferably identical to one another and each is alkenyl or preferably alkyl having 6 to 22, pre-ferably 8 to 22, in particular 16 to 20, carbon atoms and A1"
is cycloalkylene having c6 to 14 carbon atoms, especially alkylene having 4 to 12, preferably 6 to 10, carbon atoms or arylene having 6 to 14, preferably 6 to 8, carbon atoms.
The process for preparing compounds of the formula t60) or (61) comprises reacting 1 mol of C1-C4-alkyl methanetr;carboxylate, in particular ethyl methanetr;carboxylate, with about 3 mols o~
a fatty alcohol of one of the formulae ~62) R1"-OH, (63) R2"-OH or t64) R3" OH, in which R1", R2" and R3" are as defined above, or reacting 1 mol of d;isocyanate of the formula (65) 0 = C = N - A1" - N = C = O, in which A1 is as defined above, with about 2 mols of the intermediate oF the formula (5~) or of the formula ,R"
t66) NC- c~a - co - N 3 2 \(R" ) - (H) ,1 in which R3", R4" and q" are as defined above.

?~

In a further also preferred embodiment, the sizing agents (A) as inventively used contain besides 1 to 6, preferably 1 to 4, in parti-cular l or 2, -COO ~ or -COOH groups as anionic or acidic groups and 2 to 10, preferably 2 to 6, hydrophobic substituents of the specified type divalenL linking members wi.th which at least two of the most adjacent hydrophobic substituents are bonded to each other which pre-ferably have 4 to 15 carbon atoms and at least 2 hetero atoms each, preferably one nitrogen and one oxygen atom or in particular 2 nitrogen atoms or 2 oxygen atoms. Linking members which each have 4 to 10 carbon and two oxygen atoms are particularly preferred. Depending on the number of hydrophobic substituents, the sizing agents contain 1 to 5, preferably 1 to 3, linking members of the specified type.

Preferred linking members generally have one of the formulae O O
(67)11 11 -Ql -C-Al -C -Q'2 ~ or O O
Il 11 (68) -C-O-A'2'-0-C-in which A1"' and A2"' each are a divalent aliphatic or aroma-tic radical, Q1"' and Q2"' are different from or preferably /

identical to each other and are -O-, -NH- or -N ~ , In the formulae (67) and (68), the radicals A1'and A2"' form part of an aliphatic or aromatic bridging member which has 1 to 6, preferably 1 to 4, in particular 1 or 2, anion;c or acid;c groups and can have 1 n;trogen atom.
Specific examples of preferred bridging members are those of the formulae - 38 - ~2 o o Il . Il -Ql -C i li Q2 ( ) (Yl )p~l O O ' --Q " ~--C--i ~ C ~ IJ I--C-- 2 (70) X"~>~(Y"' "' ( "' ~ \(X"') ) q -1 Yl ) q~ ~ -1 n" ' -1 O X"' o (71) -Ql -C-cH2-c-cH2-c-Q2 - 9 Z"~

O O
Il 11 (72) -Ql -C-C-CH2-C-Q2 -CH
X"' O O
Il 11 73) _Q'l'-C-(C~12)n''l-Cll2-N-cil2 (CH2)n-1 Q2 (C~2)m~ ~ 1 X"' (74) ll I li X"' O O
Il 11 -X"' O O
Il 11 -C-O-CH-(CH ) "' -CH-O-C-(76) 1 2 n-l I
CH3 X"
O or Il 11 (77) ( 2)2 ~ 2 2 1 2n~

in which Q1 and Q2 each are -O-, -NH- or -N , X"' is -COOH, ~ r~
or -COO~J, Y"' is -COOH, -COO~ or O
-C-Q1 " ' Zll7 is hydrogen, methyl or preferably hydroxyl, n"' and m"' each are 1 or 2, p"' ;s an integer from 1 to 4 and q"' and q"" each are 1, 2 or 3.

7~
~,o In par~icular those sizing agents (A) are of special impor-tance which can be obtained by reacting at least (a"') an alipha~ic or aromatic carboxylic acid having at least 3 carboxyl groups, a polyalkylenepolyaminopolyacetic acid having 4 to 6 carboxyl groups or an aliphatic monocar-boxylic acid or aminocarboxylic acid having 2 hydroxyl groups with (b"') a fatty alcohol and/or a fatty am;ne or a fatty acid, fatty alcohols and/or fatty amines being used as component (b"') when carboxylic acids having at least 3 or 4 ~o 6 carboxyl groups are used as component (a"') and fatty acids being used as component (b"') when monocarboxylic acids are used as component (a"').
The sizing agents which can be obtained in this way are, as a rule, aliphatic or aromatic fatty acid esters or fatty acid amides. Preferred esters or amides of this type have bridging members of one of the formulae- (69) to (73) in which Q1"' and Q2"' are ident;cal~ Other sizes, however, are in the form of amide-esters which can be obtained not only from fatty alcohols but also from fatty amines and from aliphatic or aromatic acids having at least 3 carboxyl groups or 4 to 6 carboxyl groups. Preferred amide-esters of this type have bridging members of one of the formulae (69) to (73) in which Q1"' and Q2"' differ from each other. If mono-carboxylic acids having 2 hydroxyl groups are used as com-ponent (a"') , only fatty acids are suitable for use as com-ponent (b"') , to give fatty acid es~ers which, in their pre-ferred embodiment, have bridging members of one OT the formulae ~74) to (77).
Sizing agents (A) of the specified type from the components (a"') and (b"') which are preferably used have molecular weights of about ~00 to about 3,000,preferably of about 600 to about 1~500.Sizes having a bridging member of one of the formulae (69) or (71) are particularly preferred.
In particular those sizing agents are to the fore of interest which can be obtained by reacting at least ~2~ 2 (a"') an aromatic acid which has 9 to 20 carbon atoms and 3 to 6 carboxyl groups, an aliphatic acid which has 3 car-boxyl groups and can have a nitrogen atom, a polyalkylene-polyam;nopolyacetic ac;d which has 4 to 6 carboxyl groups and 2 to 4 nitrogen atoms~ an aliphatic dihydroxymonocar-boxylic acid or bis(hydroxyalkyl)aminomonocarboxylic acid which has 3 to 6 carbon atoms, their halides or anhydrides, with (b"') a fatty alcohol and/or a primary or secondary -fatty amine or, if a monocarboxylic acid of the specified type is used as component (a"'), from a fatty acid, the fatty radicals of the fatty alcohols, fatty amines and fatty acids being unsaturated or preferably saturated and having 6 to 22, preferably ~ to 22~ in particular 16 to 20, carbon atoms~
For the si~ing agents,as mentioned earlier, to have at least one -COO ~ or -COOH group as anionic or acidic substituents and the linking member with which the hydrophobic substituents are directly bonded to each other to contain at least 2 hetero atoms, the sizing agents, in their preferred embodiment, can be obtained from 1 mol of component (a"') and 2 to (h"'-l) mol(s~ of component (b"'),h"' denoting the number of carboxyl groups of component (a"'), if carboxylic acids having at least 3 or 4 to 6 car-boxyl groups are used as component (a"') and fatty alcohols and/or fatty amines as component (b"'). If 1 mol of mono-carboxylic acid having 2 hydroxyl groups is used as component (a"l), 2 mols of fatty acid are generally used, however.
Owing to the presence of at least one -COO ~ or -COOH
group in the sizing agents, they have an acid value (mg of KOH/g of substance) of about 15 to about 150, preferably of about 40 to about 100.

Carboxylic acids having at least 3 carboxyl groups :Eor use as component (a"'), from which the si~ing agents (A) can be - 42 ~ 2~2 obtained, are in particular aromatic mononuclear polycar-boxylic acids, for example hemimellitic, trimellit;c, trimesic, prehnitic, mellophanic, pyromellitic or mellitic acid~benzene pentacarboxylic acid~ aromatic binuclear polycarboxylic acids, for example kenzophenonetricarboxylic to benzophenonehexa-caiboxylic acid or anhydrides of said aromatic carboxylic acids, aliphatic tr1carboxyl;c ac;ds, for exarnple ~ricarb-allylic, aconitic or citric acid, aliphatic tricarboxylic acids which have a nitrogen atom, for example bis(2-carboxy-ethyl)carboxymethylamine, nitrilotr;propionic acid and nitrilotriacetic acid, and polyalkyleneaminopolyacetic acids, for example triethylenetetraaminehexaacet;c acid,diethylenetri-aminepentaacetic acid, dipropylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N'-bis(2-carboxyethyl)-N,N'-bis(carboxymethyl)ethylenediamine~ trisC2-bis(carboxy-methylamino)ethyl]amine, bisC2-bis(carboxymethylamino)ethyl]-methylamine or N,N'-bisC2-bis(carboxymethylamino)ethyl]-N,N'-dimethylethylenediamine. Of these, because they are easily accessible, trimellitic anhydride, pyromellitic dianhydride, hemimellitic acid, benzophenonetetracarboxylic dianhydride, tricarballylic acid, trans-aconitic acid, citric acid and nitrilotriacetic acid are particularly preferred. Aliphatic monocarboxylic acids suitable for use as component ~a"') are, for example, glyceric acid, 1,2-dihydroxybutyric acid, 1,3- and 2,3-dihydroxyvaleric acid, 2,2-bis(hydroxymethyl)-propionic acid, N,N-bis(hydroxyethyl)-~-alanin and N~N-bis-(hydroxyethyl)glycine, of which 2,2-bis(hydroxymethyl)pro-pionic acid and N,N-bis(hydroxyethyl)glycine are preferred~
Trimellit;c anhydr;de, pyromell;t;c d;anhydr;de and c;tr;c acid are to the fore in interest~

If polyalkylenepolyaminopolyacetic acids are used as component (a"'), oligomeric sizing agents can be obtained thereErom. However, if the other acids are used as component (a"'), monomeric sizing agents can be obtained and are preferred to the oligomeric sizing agents.
Sizing agents (A) having a bridging member of the formula (69) can be obtained from, for example, said aromatic mono-nuclear polycarboxylic acids, having a bridging member of formula (70~ from benzophenonetricarboxylic tO benzophenone-hexacarboxylic acid, having a bridging member of the formula (71) from tricarballylic or citric acid, having a bridging member of the formu-a (72j from aconitic acid, hav,ng a bridging member of the formula (73) from aliphatic tricar-boxylic acids ~hich have a nitrogen atom, having a bridging member of the formula (74) from 2,2-bis(hydroxymethyl)pro-pionic acid, having a bridg-ing member of the formula (75~
from glyceric acid, having a bridging member of the formula (76) from 1,3-dihydroxyvaleric acid or 1,2-dihydroxybutyric acid, and having a bridging member of the formula (77) from N,N-bis(hydroxyethyl)-J~-alanin or N,N~bis(hydroxyethyl)-glyc;ne as component (a"!).
Component (b"'~, from which the sizing agent (A) can be obta;ned, ;s ;n particular a saturated or unsaturated ali-phat;c fatty ac;d or alcohol having 6 to 22, preferably 8 to 22, in particular 16 to 20, carbon atoms or a monoalkyl-am;ne, d;alkylam;ne, monoalkenylam;ne or dialkenylamine each hav;ng 6 to 22, preferably 8 to 22, in particular 16 to 20, carbon atoms in the alkyl or alkenyl radical. A component (b"') unsaturated or saturated C6-C22-, preferably C8-C22~, in particular C16~C20-, fatty acid is, for example caproic, preferably capryl;c, capr;c, laur;c, myr;st;c or arach;d;c ac;d, ;n part;cular palmitic, stearic and behenic acid or myristole;c, palmitoleic, elaeostearic, clupanodonic acid, in particular oleic, elaidic, erucic, linoleic and lino-lenic acid. Of these palmitic, stearic, oleic and behenic acid are of particular importance, palmitic and especially stearic acid being to the fore of interest. Technical, read;ly access;ble m;xtures of the acids just ment;oned are also su;table. The unsaturated or saturated fatty alcohols and the unsaturated or preferably saturated monoalkylamines or dialkylamines or monoalkenylamines or dialkenylamines structurally derive from the fatty acids just mentioned.
eecauSe they are readily accessible, hexadecanol, octadecanol~
oleyl alcohol, octadecylamine and dioctadecylamine are mentioned as specific representatives of C16-C20 fatty alcohols and of monoalkylamines or dialkylamines hav;ng C16-C20 alkyl radicals. Technical mixtures of fatty alcohols or ~atty amines of the specified type are also suitable.
The followin~ compounds which can be used as size as component (A) of the process of the invention and their preparation from components (a"') and (b"'~ are known per se~
- diesters and diamides of aromatic carboxylic acids having a~ least 3 carboxyl groups and bridging members of the for-mula (69) in which Q1"' and Q2"' are identical, and described in for example, German'~ffenlegungsschrif~"2,417,556, British Patent 1,025,433 and U.S. Patent 3,981,838;
- diamides of aromatic carboxylic acids having at least 3 carboxyl groups and bridging members of the formula (70) in which Q1"' and Q2"' are identical and are -~IH- or -N~
and described in, for example, U.S. Patent 3,275,651;
- diesters and diamides of aliphatic carboxylic acids having 3 carboxyl groups and bridging members of the formula (71) in which Q1"' and Q2"' are identical and are -O-, -NH- or -N/

and Z"' is -OH and described in, for example, U.S. Patents 3,929,712 and 4,021,377; and - diesters of 2,2-bis(hydroxymethyl)propionic acid which have bridging members of the formula (74) and are described in, for example, British Patent 1,257,928 and U.S. Patent 3,441,953.
On the other hand, novel compounds which can be used as sizing agents in the invention have ~he ~ormula (78) ;~I-C-All-C-Q4~ or (79) 0 0 Il 11 C-O-~"-O-C-R"' in wh;ch m"' and n"' each are 1 or 2, Q3"' and Q~,"' each are -O-or -~H- or, if n"' and/or m"' are 2, Q3"' and/or Q4"' are -~\

ànd R1"'~ R1""~ R2"' and Rc."" each are alkyl or alkenyl having at least 5 carbon atoms, ai least one of the rad;cals R"1, ~1', R2' and R2"" having at least 8, preferably 8 ~o 22, in particular 16 to 20, carbon atoms,A1' is a divalent radical of one of ~he formulae X"' (80) X"' t81) (82) ll or CH
X"' - (CH2)s-l ~1-CH2-N (CH2) (CH2) s" ' -1 (83) CIH2 (CH2) X"' or, if Q3"' and Q4"' in the formula ~78) are different from each other, one of the formulae (84) -i ll- or (ylll )~ xll ~

~ 46 -t85) OH
ory if Q3"' and Q~t'~l in the formula ~78) are idelltical and are -O-- or Q3"~ and Qlt"' are differen-t from each other, the formula o (86) ~ ~ - C -~ and X (Y2 ~ ) q~ ~ -1 (Y2 ) qll~

A2"' is a d;valent radical of one of the formulae (87) -CH -CH- 9 X~

CH ( 2)n~1 (88) 1 1 or CH3 X"' -(CH ) -N-(CH2)2-(89) 2 2 1 (CH2) X" ' in which X"' is -COOH or -COO ~ , Y2' is Y2'-CO-Q3'\

p"' is an integer from 1 to 4, q"' and qll11 each are 1, 2 or 3 and m"', n"', s"' and t"' each are 1 or 2 and Q3', Rl' and Rl"

~2~27~:

are as defined above.
Preferred novel compounds which can be used as sizes have one of the formulae O O
R~ ' 11 11 /R" ' ( 9 3 ~Q$ C--C--CI{2 -C--Q~' l 3 (R3')n"' 1 11 (R3")n~,_ X"' O O
R" ' ll ll ~R" ' (91 ) 3 /Qll5-c-cH2-N-cH2-c-Ql5~\ 3 X" ' X" ' O
3 l l l l R3' ~N C CH2-C-CH2-C-O R" ' OH

O O O
(93)R3~'-O-C-i~ il-C-II ~T-C-O-R3~ or X"'~
,~

O O
Il 11 (94) R3~-C-O~C~12)2-N--tCH2)2-O-C-R3"
CH

(C~lZ ) X"' ~ 2~

in which n"' and s"' are 1 or 2, Q5"' is -O- or, if n"' is 2, -N / , X"' is -COOH or -COO~ and R3"' is alkenyl or preferably alkyl. having 16 .o 20 carbon atoms.
The novel compnunds are generally prepared bY reacting mol of a polycarboxylic acid c.f the formula O O
Il 11 (95) HO-C-A'1' -C-OH

with Z to (h"'-1) mol(s) of a fatty alcohol of the formula (96) R1"'-OH or ~97) R2"'~OH

and/or with 2 to ~h"'-1) mol(s) of a primary or secondary fa~ty amine of the formc.la R"' (98) ~(~)2- ",-H or R~

~2 9 ~ ~ ""~N (H)2_n""-H
(R2 or 1 mol of a diol of the formula (100) HO-A2"'-OH

with Z mols of a fatty acid of the formula (101) R1"'-COOH or (102) R2"'-COOH

7~

by methods known per se, A1 , A2 , R1 , R1 , R2 , R2 and n"' being as defined above and h"' being the number of car-boxyl groups of the carboxylic acid of the formula (95).
The reactions are generally carried out at about 120 to about 250~C, preferably up o 200C, in the melt~ If high ~emperatures of about 200 to 250C are used, the resulting produccs can be purified with active charcoal ;f need be. Es-pecially if acid anhydrides are used, however, it is also pos-sible to carry out the reactions in the presence of at least one solvent which needs to be inert to every starting and end product. If such solvents are used, the reactions can also be carr;ed out at lower temperatures, for example 30 to 120C.
Examples of possible solvents are acetone, dioxane or halo-genated or unhalogenated hydrocarbons such as dichloroethane, carbon tetrachloride, benzene, toluene, chlorobenzene, o-, m- and p-xylene, a technical xylene mixture and mixtures of the hydrocarbons ment;oned. If, for example, diols of the formula (100) are reacted with fatty acids of the for-mulae ~101) or ~102), it can be advantageous to use a cata-lyst, for example hydrochloric acid, sulfuric acid, phos-phoric acid or organic sulfonic acids~ preferably p-toluene-sulfonic acid, to accelerate the ester;f;cation reactions if necessary~ If polycarboxylic acids of the formula (95) are reacted with primary fatty amines of the formula ~98) or t99) in which n'" is 1, it is advisable to prevent the formation of by-products by using an approximately equimolar amount (based on the primary fatty am;ne) of a weak n;troCJen-containing base, for example pyridine, tr;ethylamine, iso-quinoline or preferably qu;noline. If R1"', R1"", R2"' and R2"t' in the formulae (96) to (99), ~101) and (10Z) are an alkenyl radical of the spec;fied type, orA1' in -the formula (95) is the formula (82), it ;s furthermore advantageous to carry out the reaction in an inert nitrogen atmosphere and/or in the presence of a polymerisat;on ;nhibitor, for example methylene blue, benzothiazine or preferably hydroquinone.
The reactions are generally carried out in one step.
However, it is also possible to react in a first stage, for 7~

example, the polycarboxylic acid of the formula (95) with a secondary fatty amine of the formula (98) in which n"' is 2 and then, in a second stage, with a primary fatty amine of the formula (99) in which n"' is 1.

Before they are used as component (A) in the paper-sizing process of the invention, the sizing agents need &~nerally not be purified or re-crystallised after they have been prepared from (a), (b) and (c), from (a'), (b') and (c'), from (a'l) and (b'l), from (a'2), (b'2) and ~c") or from (a"') and (c"') components, and are thus, as a rule, directly used.
This also applies to the intermediates from (a) and (b), (a') and (b') or (a'2) and (b2) components which thus are, as a rule, not purified or recrystallized before they are further reacted with (c), (c') or (c") components to obtain the sizing agents (A).

Especially if the sizing agent (A) and the retention aid (B) are added separately (in any order) to the dispersion of the fibres in the process of the invention for sizing paper or cardboard it is ad-vantageous to use the sizing agent at least partly in salt formO
If desired, such salts can be obtained after the reaction of components (a), (b) and (c); (a'), (b') and (c'); (al) and (bi'); (a2),(b2) and (c") or (a"') and (b"') has ended by converting the resulting reaction products into the corresponding salts, at least partly if desired, by adding e.g. an alkylamine or alkanolamine having a total of at most 6 carbon atoms, for example trimethylamins, triethylamine, ethanolamine, diethanolamine, especially by adding ammonia or an alkali metal hydroxide, for example potassium hydroxide or especially sodium hydroxide, generally in arl aqueous medium at room temperature (about 15 to about 25C). An alkali metal hydroxide, for example potassium hydroxide or especially sodium hydroxide, or in particular ammonia is advantageously used in the form of its dilute approximately 1 to approximately 10 per cent by weight aqueous solution. It is generally advantageous to use at most 2 mols, especially at most 1 mol, preferably 0.1 to 0.9, in parti-cular 0.2 to 0.7, mol of ammonia or alkali metal hydroxide per negative charge present in the anionic sizing agent. The sizing agents in the form of salts thus have e.g. -CH2-, -¢H, -S03H or -COOH groups which are least partly converted into the -CH ~ M ~ -¢l ~ M ~ -S03 ~ M ~ or -C00 ~ M ~ groups in which is the corresponding amine, ammonium or alkali metal cation.

Examples of compounds which are partly in the form of a salt and which are suitable for use as sizing agents (A) are especially those which can be obtained by reacting (a) 1 mol of triethanolamine or gLycerol with (b) 2 mols of stearic acid, then with (c) 1 to 1.5 mols of chlorosulfonic acid or phosphorus pentoxide and finally with (d) 0.1 to 0.9 equivalent oE an aqueous potassium or sodium hydroxide solution, based on the acidic protons of the acidic substituents of the sizing agent, i.e. in the present case of the mixture of acidic esters of (a), (b) and (c).

In addition to the monomeric to oligomeric anionic sizing agent (A) described above, the paper-sizing process of the invention always makes use of a polymeric cationic retention aid (B) which, as a rule, has a molecular weight of about 1,000, preferably about 5,000 to about 2,000,000. Retention aids having molecular weights within the range from 10,000 to 100,000 are particularly preferred. In principle, any commercially available re-tention aid can be used in the process of the invention.
E~amples of conventional retention aids (B) which are particularly suitable for use in the paper-sizing process of the invention together with the sizing agent (A) are polyalkyleneimines, epi-halogenohydrin adducts of reaction products of polyalkylenepolyamines and aliphatic dicarboxylic acids or of reaction products of poly-alkylenepolyamines,dicyanodiamide and free or alkanol-esterified organic dicarboxylic acids, reaction products of dicyanodiamide, formaldehyde, ammon;um salts, strong organ;~ ac;ds and of alkylened;amines or polyalkylenepolyam;nes, cat;onically modif;ed starches or carbohydrates from carob bean or guar bean flour, copolymers based on polyam;de-am;nes and react;on products of ep;halogenohydr;ns and polymer;sed diallylam;nes.

- 52 - ~ 7~

Preferred epichlorohydrin adducts of reaction products of polyalkylenepoLyamines and aliphatic dicarboxylic acids have been described, for example, in British Patent 865,727, epi-chlorohydrin adducts of reaction products of diethylenetri-amine and dicyanodiam;de, for example, in German"Offenlegungs-schrift"2,710,061 and British Patent 1,125,4~6, epichloro-hydrin adducts of reaction products of diethylenetriamine, dicyanodiam;de and free or preferably lower alkanol-esterified dicarboxyl;c acids, ;n part;cular dimethyl ad;pate, for example in 3ritish Patent 1,125,4~6, and reaction products of dicyanodiamide, formaldehyde, ammonium salts, strong ;n-organic ac;ds and of ethylenediamine or triethylenetetra-amine, for example, in U.S. Patent 3,491,064. Preferred cat;on;cally modified starches or carbohydrates from carob bean or guar bean flour are alkylene oxide adducts of these starches or carbohydra~es, the alkylene oxide used having 2 or 3 carbon atoms in the alkylene radical and qua~ernary ammonium groups. Copolymers based on polyamide-am;nes have molecular weights of 103 to 105, preferably 103 to 104 and can be obtained from, for example, aliphatic saturated di-carboxylic acids having 2 to 10, preferably 3 to 6, carbon atoms,in particular adipic acid, and polyalkylenepolyamines, for example polypropylenepolyamine or polyethylenepolyamine, in particular di-methylaminohydroxypropyl diethylenetriamine.
They are described in, for example, the CTFA Cosmetic Ingre-dient D;ctionary, 3rd edition, 19~2, of the Cosmet~c, Toiletry and Fragrance Association. Reaction products of epihalogeno-hydrins and polymerised diallylarnines preferably have mol-ecular weights of 1,000 to 2,000, and are described in, for example, U.S. Patents 3,700,623 and 4,279,794.
A retention aid (a) which is to the fore of interest for use together with sizing agents (A) in the paper-sizing process of the invent;on is a corn or potato starch which con~
tains quaternary ammonium groups, has been modified with ?J~

1,2-propylene oxide and whose 25% suspension in distilled water at 20C has pH 4.2 to 4.6, a polyethyleneimine which has a molecular weight of 10,000 to 100,000, an epichlorohydrin adduct of a reaction product of triethylenetetraamine and dicyanodiamide, an epichlorhydrin adduct of a reaction product of diethylene triamine, dicyanodiamide and di-methyladipate,a reaction product of dicyanodiamide, formaldehyde~ ammonium chloride and ethylenediamine, an epichlorohydrin adduct of a puly-N-methyldiallylamine and a copolymer of adipic acid and dimethylamino hydroxypropyl diethylenetriamine.

The process is carried out with, as a rule, 0.02 to 3, preferably 0.1 to 3, in particular 0.2 to 0.8, % by weight of sizing agent (A) and 0.02 to 3, preferably 0.1 to 3, in particular 0.2 to 0.4, % by weight, of retention aid (B), each based on the dry matter in (A) and (~) and on the solids content of the dispersion of the fibres. 0.02 to less than 0.1%
by weight of sizing agent (A) and of retention aid (B) are only sufficient for size press control, which is not detectable with conventional sizing tests (cf~ for example the article "Control and understanding of size press pickup" by D.R.
Dill in the journal TAPPI (Proceedings of the TechnicaL
Association of the Pulp and Paper Industry), Volume 57~ No.
1, of January 1974, pages 97-10~).

The dispersion of the fibres to which the sizing agents (~) and retention aids (B) are added has, as a rule, a solids content of 0.1 to S, pre-ferably 0.3 to 3, in particular 0.3 to 1% by weight and a Schopper-Riegler freeness of about 10 to about 90, especially 20 to 60, pre-ferably 20 to 45, in particular 25 to 35. It contains as a rule cellulose, i.e. pulp, in particular from softwood, for examp:Le pine-wood, or from hardwood, i.e. deciduous wood, for example beech wood, the pulp being prepared by conventional processes, for example the sulEite or especially the sulfate process. The dispersion of the fibres can also contain mechanical woodpulp. The dispersion of the fibres can even contain alum-containing waste paper. Suspensions of cellulose which are prepared by the CMP or CTMP process (Chemi-_echanical and chemithermomechanical pulping processes, cf. for example the article "Developments in refiner mechanical pulping" by S.A. Collicutt and co-workers in TAPPI, Volume 64, No. 6, of June 1981, pages 57 to 61) are also suitable.

The dispersions of the fibres can also contain organic or mineral filLers. Suitable organic fillers are inter alia synthetic pigments, for example polycondensation products of urea or melamine and formaldehyde which have large specific surface areas, are in a highly disperse form and have been described in, inter alia, British Patents 1,043,437 and 1,318,24~, and suitable mineral fillers are, inter alia, montmorillonite, titanium dio~ide~ calcium sulfate and especially talc, kaolin and/or chalk (calcium carbonate).
The dispersion of the fibres generally contains 0 to 40, preferably 5 to 25, in particular 15 to 20, % by weight, based on the solids content of the dispersions of the fibres, in dry matter of fillers of the specified type.

The pH of the dispersion of the fibres can vary within a wide range, for example between about 3.5 and about 10.

Adding calcium carbonate, for example, gives alkaline dispersions of the fibres with a pH of about 7 to about 9, preferably 7.5 to 8.5. Acid dispersions of the fibres with a pH of 3.5 to 7, preferably 5 to 7, in particular 5 to 6, can be obtained in the absence of calcium carbonate by adding acids, for example sulfuric or formic acid, or especially, for example, latent acidic sulfates, such as aluminium sulfate (alum).

Dispersions of the fibres which do not contain filler can exist within a broad pH range from, for example, 3.5 to lO. Those dispersions of the fibres are preferred which have a pH of about 7 to 9, possibly due to added chalk, and the reason they are advantageous is that corrosion on the sensitive paper machines is prevented.

.

- 55 - ~ 7~

The dispersions of the fibres can also contain additives which increase~he fibre/fibre or fibre/filler bond, for example starch or its break-dowm products.

High molecular weight polymers of the acrylic acid class, for example polyacrylamides, which have molecu]ar weights above l,000,000 can also be added to the dispersions of the fibres as auxiliaries for retaining very fine pulp fibre particles, very small amounts of about 0.005 to 0.02% by weight, based on the dry matter in the polymer and the solids content of the dispersions of the fibres being sufficient.

In the process of the invention the dispersion of the fibres is processed in a manner kno~m per se into paper or cardboard on sheet formers or preferably in a continuous operation on paper machines of conventional design. Drying at about 100 to 140C for about 0.5 to 10 minutes can give, for example, papers of variable weight per unit area, for example from 50 to 200 g/m2.

As mentioned above, the aqueous composition for carrying out the paper-sizing process of the invention contains the sizing agent (A) in addition to optional customary additives if the sizing agent and the retention aid (B) are added separately to the fibre-bearing liquid.
In this case the preparation generally contains the sizing agent, as a rule, at least partly in the form of its salts (obtained by using e.g. ammonia, an alkylamine, an alkanolamine or an alkali metal hydroxide of the specified ~ype in the above ratios). Such compositions generally contain 5 to 30, preferably 5 to 20, per cent by weight in dry matter of the sizing agent, which is at least partly in form of the salt, based on the weight of the aqueous composition.

However, if the sizing agent (A) and the retention aid (B) are added simultaneously to the fibre-bearing liquid, the aqueous composition, in addition to optional customary additives, contains (A) 2 to ~0, preferably 5 to 30, ir~ particular 5 to 10,~er cent by weight of size (expressed as solids), based on the weight of the aqueous composition~ where the size ~an be in the form of a salt, and (B) 0.1 ~o 20, preferably 0.5 to 10, in particular 3 to 8, per cent by weight o~ retention agent (expressed as solids), based on the aqueous composition.
Aqueous compositions of the spec;fied type can con-tain as customary additives surface-active compounds, for example dispersants or emuls;fiers and/or water-soluble organic solvents. Examples of suitable dispersants and emulsifiers are conventional lignin sulfonates, ethylene oxide adducts of alkylphenols, fatty am;nes, fa~ty alcohols or fatty acids, fatty acid esters of polyhydric alcohols~
subst;tuted benzimidazoles or condensation products of aro-matic sulfonic acids and formaldehyde. Other surfaGe-active compounds preferably are an;on;c surfactants, in particular sulfate surfactants, for example diethanolaminelauryl sulfate or ethoxylated lauryl sulfates. Poss;ble water-soluble organic solvents are aliphatic ethers having 1 to 10 carbon atoms, for example d;oxane, methylene glycol n-butyl ether or d;ethylene ~lycol monobutyl ether or alcohols having 1 to ~ carbon atoms, for example isopropanol, ethanol or methanol.
The compositions are prepared in a customary manner by stirring the sizing agent (A) together with the retention aid ~B) or the si~e (A) generally partly ;n the form of a salt on its own either in the molten state or preferably in the solid state, ;n part;cular ;n pulverulent form~ as a rule ;n the presence of glass beads and ;f necessary emuls;f;ers (in the case of sizing agents in the molten state) or dispersants (;n the case of sizing agents in pulverulent :~orm~ at most 90C, preferably about 50 to about 85C in the case of emulsions, in part;cular at about 15 to about 25C in the case of dispersions, to give long-shelflife homogeneous emulsions or pre~erably dispersions. Since the sizing agents together with the retention aids or the sizing agents which are partly in salt form are, as a rule self-dispersing or self-emulsifying, the use of the dispersants or emulsifiers is generally not absolutely necessary. This also applies to the optional addition of solvents and/or surfactants which are only uzed if the dispersions or emulsions have an inadequate shelf life.

The advantage of the process of the invention is that widely differing dispersions of the fibres can be processed in a simple manner using relatively sma]l amounts of sizing agent and retention aid into paper which has good size properties (ink flotation period and especially Cobb water absorption). The paper which is sized according to the present process has good mechanical properties, i.e. good strengths, in particular a good tear strength. In particular, dispersions of the fibres containing mechanical woodpulp or waste paper can be processed.
Another advantage is that the sizing agents used in the invention are compatible with a wide variety of fillers, and also additives thereof, in particular kaolin and alum, in acid dispersions of the fibres.
The sizing agents also have advantageous compatibility with fluorescent brightening agents. The whiteness of sized paper is hardly affected by the size, and can, in certain circumstances, even be increased. The generally surprisingly long shelf life of the dispersion of the sizing agents of the specified type, in particular, is of great advantage.

The parts and percentages given in the following methods and working examples are by weight.

Methods for the manufacture of known compotmds for use as intermediates _ Method A:

149 parts of triethanolamine (1 mol), 56~ parts of stearic acid (2 mols) and 3.5 parts of p-toluenesulfonic acid as a catal.yst are d;ssolved in 510 parts of p-xylene.
This solution is heated to the reflux temperature of about ?~

140C and is held at this temperature until the theoretical amount of water formed by the esterification reaction (2 mols) has been azeotropically removed by means of a water separator. The xylene is then distilled off. LeEt behind as residue are 680 parts of a waxy ester mixt~re which in addition to homologous monoesters and triesters, contains as main constituent the diester of the formula (10~ -(CH2)2-0-C-(cH2)16 CH3]2 (CH2) 2-OH

Melt;ng point : 40-44C.
Method B:
22 parts of pyrocatechol (0.2 mol) are dissolved in Z00 parts o~ dimethyl sulfoxide, and then admixed with 44.8 parts of a 50% aqueous potass;um hydroxide solution (0.4 mol). The reaction mixture is stirred at 20C for 30 minutes. 133.2 parts of octadecyl bromide (0.4 mol) are then added to the reaction mixture. The reaction mixture is heated to 50C, is held at this temperature for 6 hours, is then diluted ~ith 1,000 parts of water and, ~ith an aqueous acetic acid solution is brought to a pH of 4-S, and the reaction product precipitates. The product is filtered off, washed with water and recryctallised from acetone. This gives 98.6 parts of the diether of the formula ~104) j~ \.-0-(CH2)l7-CH3 .~ ~--o-(C~12)17-CH3 Melting point: 58-61C.

_ 59 ~ 7~

Method c:
Method B is followed, except that 22 parts of resor-cinol ~in place of pyrocatechol) are used, affording 97 parts of the diether of the formula 0- (CH2) 17-CH3 (105) ~ \
-O-(CH2) 17-CH3 Melt;ng po;nt: 71-73C.

Method D-1,136 parts of stearic acid (4.0 mols) are melted at 100C. 227 parts of diethylenetriamine (2.2 mols) are added in the course of 1 hour, during which the temperature cf the reaction m;xture rises to 110C of its own accord.
The reaction m;xture is then heated to 160C in the course of 2 hours and held at this temperature for 2 hours, dur;ng which a slow stream of nitrogen is used to help d;still out of the reaction mixture the theoretical amount of water ~4 mols) liberated by the reaction together w;th excess of di-ethylenetriamine. The reaction mixture is then cooled down to room temperature (15 to 25C) This gives 1,232 parts of an am;de m;xture which is in the form of a yellow;sh wax and contains as main constituent the diamide of the formula (CH2)2 [- H ~

(106) (CH2) 2 [~ ~ - (CH2)16 3] 2 Melting point: 100-105C.

~4~27~:

Method E:
Method D is followed, except that 287 parts of di propylenetriamine (2.2 mols) are used (;n place of 277 parts of diethylenetr;am;ne3, afford;ng 1,288 parts of an amide mixture which is in the form of a whitish wax and contains as main constituen~ the diamide of the formula NH [-H]

(107) (CH2)3 L-~ ~ (CH2)16-CH3]
NH-Melting point: 101-104C.

Method F:
Method D ;s followed, except that 1,128 parts of oleic acid (4.0 mols) (in place of 1,136 parts of stearic acid~ and 1 part of hydroquinone as a polymer;sat;on ;nhibi-lor are used and the reaction m;xture is held a~ 160C for 3 hours (not 2 hours)~ affording 1,Z25 parts of a am;de mix-ture-which is in the form of an amber-coloured oil and con-tains as main constituent the diamide of the formula ~ (CH2) 2~ [ H i (108) I- C
(CH2) 2 l- - (CH2) 7-CH=CH- (CH2) 7 3~ 2 NH--Methods for the manufacture of known compounds for use as a sizing agent Method G-624 parts of a technical mixture which~ in addit;on to 'nomologous monoes~ers and triesters~ contains as main constituent 1~3- and 1,2 glycerol distearate (1 mol) are dissolved in 2,000 parts of carbon tetrachloride. Elsewhere, 142 parts of phosphorus pentox;de ~1 mol) are dispersed ;n 500 parts of carbon tetrachlor;de. The solut;on of glycerol d;stearate is then added to the phosphorus pentoxide dis-persion in the course of 20 minutes. Thne reaction mixture is then heated to the reflux tempera~ure of about 76C and held at this temperature for 1Z hours. The reaction solut;on is then clarif;ed from impurities. The solvent is removed, and the crude product is recrystallised from methyl ethyl ketone. This gives 650 parts of an ester mixture which is in the form of a beige-coloured powder and contains as main constituent the acidic diester of the formula (109) L I H - ~~ ~ \OH ¦
2 [ ( 2)16 3] 2 Melting point: 57-59C. Acid value: 112.

Method H:
320 parts of the am;de mixture obtained by Method D ~0.5 mol) are suspended at 20C in 1,500 parts of chloro-form. A solution of 7~ parts of phthalic anhydride (O.S
mol) in 80U parts o-f acetone ;s adaed at 20C ;n the course of 35 m;nutes~ The temperature of the reaction mix~ure rises to Z5C of its own accord and is held at th;s tempera-ture for one hour. The reaction mixture is then heated to the reflux temperature of about 57C and held at this tempera-ture for one~ r during which a clear solution forms. .The solvent is then distilled out of the reaction m;xture under reduced pressure. This gives 390 parts of a crude product wh;ch is in the form of a yellowish powder, can be recrystal lised from acetone and contains as main constituent ~he re-action produc~ of the formula ¦(NIH-2)2l [-~-(CH2)16-CH3]

(110) L'l 2)2~ 0 ._.
NH- L_C_~

COOH
l~elting point (recrystallised product): 77-78C.
Acid value (recrystallised product): 73 Method I:
Method H is repeated, except that 50 parts of succinic anhydride (0.5 mol~ are used (in place of 74 parts of phthalic anhydride), affording 366 parts of a crude product which is in the form of an ochre-coloured powder, can be recrystal-lised from ethanol and contains as main constituent a reaction product of the formula ~ (CH2)2 ~ [ C-(CH2)16-CH

(111) (CH ) r R

l~elting point (recrystallised product): 108-112C
Acid value (recrystallised product): 68.

Method J:
Method H is repeated, except that 77 parts of hexa-hydrophthalic anhydride (0.5 mol) are used, affording 391 parts of a crude product wh;ch is in the form of an c,chre-c--loured powder~ can be recrystallised from acetone and con--tains as main constituent the reaction product of the formula (CH2) 2 ~ j -C~CH2) 16-CH3 ¦
(1 1 Z ) ~ ~- ~-C-CH/ 2 \CII

COOH
Melt;ng point (recrystallised product~: 66-69C
Acid value (recrystallised product): 66.
Method K:
Method H ;s repeated, except that 49 parts of maleic anhydride (0.5 mol) are used, affording 350 parts of a crude product which is in the form of a yellowish powder, can be recrystallised from acetone and contains as main constituent the reaction product of the formula (CH2) 2 L ' 2 16 3 1 ( 1 1 3 ) N- 2 L NH- ¦ [ -C-CH=CH~COOH ~

Meltin~ point (recrystallised product): ~2-~7C
Acid value (recrystallised product): 88.
Method L:
Method H is repeated~ except that. 56 parts of citra-conic anhydride (û.S mol) are used, afford;ng 360 parts of a crude product which is in the form of an ochre-coloured powder, can be recrystallised from acetone and contains as main constituent the reaction product of the formula (Cu2)2 ~ [-C-(CH2)16 3 ~IIL) l IH2 2 ~ [_C_cH=cl-cOOH

Melting po;nt (recrystallised product): 71~75C
Ac;d value (recrystallised product): 82.
Method M:
Method H is repeated, except that 232 parts of the am;de m;xture obta;ned by Method B (0.5 mol) and 49 parts of maleic anhydride (0.5 mol) are used (in place of 320 parts of the amide mixture obtained by Method A and of 74 parts of phthalic anhydr;de), affording 370 parts of a crude pro-duct which is in the form of a whitish powder, can be re-crystallised from acetone and contains as main consti~uent the reaction product of the formula ~ C-(CH ) 6-CH ]

( 1 1 s L ~u ¦ [-C-CH=CH-COOH ¦

Melting po;nt (recrystall;sed product): 89-100C
Acid value (recrystallised product): 72 Method N:
Method H is repeated, except that 313 parts of the amide mixture ob-tained by Method C (0.5 mol) and 49 parts of maleic anhydr;de (0.5 mol) are used, afford;ng 350 parts of a brown oil which contains as main constituent the reaction product of the formula (116) ¦ 2)2 C-(CH2) 7-CH=CH-(CH2)7-CH

~H- -C-CH=CH-COOU

Acid value : 57.
Method 0:
320 parts of the amide mixture obtained by Method D (0.5 mol) are melted and heated to 110C. 96 parts of trimellitic anhydride (0.5 mol) in freshly powdered form are added to th;s melt. The react;on m;xture, wh;ch is ;n the form of a suspension, is heated to 160C. At 120 to 125C an exothermic reaction sets in and the suspended trimellitic anhydride goes into solution. The react;on m;x-ture is then held at 160C for 30 minutes and is then cooled down to room temperature (15-25C). This gives 410 parts of a pale brown wax which contains as main constituent the reaction product of the formula (CH2)2 l i C (CH2)16 3 ]
(117) L (C~12)2 ~ [ -C-.~ ~--COOH ]

COOII
Melt;ng po;nt: 67-70C, ac;d value: 115.
Method P
Method 0 is repeated, except that 48 parts (;n place of 96 parts) of tr;mell;t;c anhydr;de (0.25 mol) are used, afford;ng 350 parts of a pale brown wax which contains as main constituent the reaction product of the formula - 66 - ~ 7~

~ 2 1~ -C-(c~2)l6-cll3 ~ ~ -C--~ ~--C- j Melt ng point: 68-71C, acid value: 57.
Method Q-_ .
635 parts of the amide mixture obtained by MethodD t1 mol) are suspended in 150 parts of chloroform. 116 parts of sodium chloroacetate (1 mol) and 102 parts of tri-ethylamine (1 mol), as an acceptor for hydrochlor;c acid, are added. The react;on mixture is stirred at room tempera-ture t15-25C~ for 1 hour, is then heated to the reflux temperature of about 62C and is held at this temperature for 1 hour. The solvent is then distilled out of the re-action mixture. The distillation residue ;s worked up by dissolving it in 500 parts of water, stirring the solution for 15 minutes and then filtering it. This gives 670 parts of a crude product which is in the form of a slightly yellow powder, can be recrystallised from dioxane and contains as main constituent the reaction product of the formula NH- [-C-(CH2)16-CH3 (ll9) L _ ECH2_COO ~ Na ~ ]

Melting point (recrystallised product): 103-107C.

~ 67 -Method R:
52.3 parts of a technical mixture of 2/3 hexadecanol and 1t3 octadecanol (0.2 mol) are dissolved in 250 parts of toluene at 35C. 13.9 parts of malonyl dichloride (0~1 mol) are added in the course of 30 minutes, during which the temperature of the reaction mixture rises to 40C of its own accord and hydrogen chloride gas is liberated. The reaction rnixture is then heated to 40C, is held at this temperature for Z4 hours and is then cooled down to-10C, and the reaction product precipitates. The crude product is filtered off and recrystallised from acetone. This gives 49 parts of colourless crystals of the reaction product of the formula t120) Ro~O~~~CH2~C~O~~ R = 67 % -(CH2)15-CH3 33 % -(CH2)17-CH3 Melting point: 54-59C
Method S:
19 parts of diethyl acetone dicarboxylate ~û.1 mol) and 54.1 parts of octadecanol (0.2 mol) are heated to 100C
and held at this temperature for 24 hours, dur;ng which the theoretical amoun~ of ethanol liberated by the trans-esteri-fication react;on (0.2 mol) is distilled out of the reaction mixture. The reaction mixture is then cooled down to 20C, and the crude product is recrystallised from acetone. This g;ves 39 parts of a colourless powder of the react~on product of the formula (121) CH3-(cH2)l7~o-c-c~2-c-cH2-c-o-(cH2)l7 cH3 Melting point: 58-60C.

- 68 - ~2~ ~2~

Method T:
12 parts of trimellitic anhydride (1 mol) and 540 parts of octadecanol (2 mols) are heated to 160C and are held at this temperature for 60 minutes. The reaction mix-tu e is cooled ~own to 15 to 25C to give 690 parts of a colourless waxy ester mixture which contains as main con-sti~uent the diester of the formula r . -(122) -OOC T~ '- coo [-H]
~ -C00-- j [ ( 2 17 3 2 Melting point: 52-60C
Acid value: 90 Method U:
Method T is repeated, except that 218 parts of pyro-mellitic dianhydride (1 mol) are used (in place of 192 parts of trimellitic anhydride), affording 748 parts of a likewise colourless waxy ester mixture which contains as main con-stituent the diester of ~he formula r_ooc-i -coo- 1 [-H]'2 (123) L-C-~ _coo- ~ [ t 2 17 3]2 Melt;ng point: 81-90C
Acid value: 135.
Method V:
Method T is repeated, except that 213 parts of pyro-mellitic dianhydride (1 mol) and 484 parts of hexadecanol (2 mols) are used, affording 683 parts of a likewise colour-69 ~2~

less waxy ester mixture which contains as main cons~ituent the diester of the formula r _ooc- ~ `^ co l [-H]2 (124! ¦ -ooc-!~ /I! coo ~ I-(cH2)l5 C~l3]2 Melting point: 35-46C
Ac;d value: 132.

Method W:
_ Method T is repeated, except that 218 parts of pyro-mellitic dianhydride (1 mol) and 810 parts (in ~lace of 540 parts) of octadecanol (3 mols) are used, affording 1,011 parts of a likewise colourless waxy ester mixture which con-tains as main constituent the triester of the formula (125) ~ [-(CH2)17~CH3]3 Melting point: 74-82C
Ac;d value: 51 Method X:
218 parts of pyromellitic dianhydr;de (1 mol) and 536 parts of oleyl alcohol ~2 mols) are heated to 160C
in an inert nitrogen atmosphere in the presence of Z parts oF hydroquinone as a polymer;sat;on ;nh;bitor and are held - 70 - ~ 27~

at this temperature for one hour. The reaction mixture is cooled down to 15 to 25C to give 743 parts of a pale brown l;qu;d creamy ester m;xture wh;ch conta;ns as ma;n constit-uent the diester of the formula (126) L-~C~ ol-COO- l [-H]2 OOC-~ --COO [-(CH2)8-C~ScH' (CH2~7 C~13~'2 Acid value: 145.
Method Y:
109 parts of pyromellitic dianhydride (0.5 mol) and 521 parts of dioctadecylam;ne (1 mol) are heated to 160C
and held at this temperature for 5 hours. The reaction mix-ture is cooled down to 15 to 25~C to give 627 parts of an ochre-coloured waxy amide mixture which contains as main constituent the diamide of the formula _ _ (127) L ~ r o ] 2 L (CH2)l7 CH3 ¦ 2 Melting point: 45-55C
Ac;d value: 94.
Method Z:
A solution of 53.8 parts of octadecylam;ne (0.2 mol) and 25.8 parts of quinoline (0.2 mol) in 300 parts of acetone is admixed w;th a solut;on of 21.8 parts of pyromell;t;c d;anhydr;de (0.1 mol) in 300 parts of acetone in the course of 30 minutes, during which the temperature of the reaction mixture rises to 40 to 50C of its own accord and a white precipitate settles out. The reaction mixture is then stirred for 3 hours, dur;ng which the temperature falls from initially 40 to 50C to 15 to 35C after 3 hours. The reaction mixture is then admixed with 35 parts of an aqueous 38% hydrochloric ac;d solution and 100 parts of wa~er, and then held at 15 to 25C for 30 m;nutes~ The wh;te precipitate formed ;s filtered off and washed w;th water unt;l the wash water has pH 6Ø The product ;s dried at 50C under reduced pressure to g;ve 71 parts of an am;de mixture which is in the form of a white powdèr and contains as main constituent the di-amide of the formula _ _ ~ ~ [ -OH ~ 2 ( 1 2 8 ) ~-OC~ -CO- I [-NH- ( CH2) 17 CH 3 ] 2 Melting point: 175-180C
Acid value: 150.

Method AA:
-Method Y is repeated, except that 161 parts of benzo-phenonetetracarboxylic dianhydride (0.5 mol) are used (in place of 109 parts of pyromellitic dianhydr;de), afford;ng 664 parts of a likewise ochre-coloured semisolid waxy amide mixture which contains as main constituent the diamide of the formula O
(129) l-OC-I ~il g 11 CO ~ r, CH2)l7-CH3 ~
(C~l2)17 Cll3 2 Acid value: 88 Method BB:
A solution of 315 parts of the amide mixture obtained by Method Y (0~25 mol) and 46 parts of dodecylamine t0.25 mol) in 1,5C0 parts of toluene is heated to the reflux tem-perature of about 111C and is held at this temperature for 10 hours, during which the water liberated by the reaction is removed by means of a water separator. The toluene is then distilled off under reduced pressure and the product obtained as residue is dried. This gives 343 parts of an ochre-coloured waxy amide mixture which contains as main constituent the triamide of the formula ~ ¦ [~ CH2)17-CH3~

(130) (CH2)17 CH3 2 [ ~ (CH2)11-cH3]

Melting point: 81-85C
Acid value: 41.
Method CC:
Method Y ;s repeated, except that 105 parts of hemi-mell;tic acid (0.5 mol) are used (in place of 109 parts ofpyromellitic dianhydride), affording 580 parts of a pale brown waxy amide mixture which contains as main constituent the diamide of the formula CO- l [-OH]
t131) T~ il_co-l E~ 2)17 3 ~

Melting point: 46-50C
Acid value: 44.
Method DD:
Method T is repeated, except that 210 parts of citric acid rnonohydrate (1 mol) are used (in place of 192 parts of trimellitic anhydride) and the length of reaction at 160C
is 90 minutes (not 60 minutes), affording 672 parts of a colourless waxy ester mixture which contains as main con-stituent the diester of the formula CH2-COO- [-H]

(132) CH -COO [-(CH2)17 C 3]2 Melting point: 48-50C
Acid value: 83 Method EE:
Method T is repeated, except that 210 parts of citric acid monohydrate ~1 mol) (in place of 192 parts of trimellitic anhydride) and 507 parts of a technical mixture of 2/3 hexa-decanol and 1/3 octadecanol (2 mols) (in place of 540 parts of octadecanol) are used and the length of reaction at 160C
is 90 minutes (not 60 minutes), affording 635 parts of a yellowish waxy ester mixture which contains as main constituent the diester of the formula CH -CO0-l [-R ] R ~ 67~ -(CH ) -CH
(133~ h0-~-C0U- I [-~I] 33~ -(c~2)l7 C 3 (;~l2-coo-J

~ 74 -Melting point: 44-46C
Acid value: 87.
Method FF:
Method T is repeated~ except that 210 parts of cit-ric acid monohydrate (1 mol) (in place of 192 parts of tri-mellitic anhydride) and 1,042 parts of dioctadecylamine (2 mols) (in pLace of 540 parts of octadecanol) are used and the length of reaction at 160C is 70 minutes (not 60 minutes), affording 1,150 parts of a yellowish waxy arnide mixture which contains as main constituent the diamide of the formula _ _ l CH -CO- [-OH]
(134) HO-C-CO- l ~ (CH2)17-CH3 Melting point: 49-56C
Acid value: 45.
Method GG:
284 parts of stearic acid ~1 mol), 67 parts of 2,2-bis(hydroxymethyl)propionic acid (0.5 mol) and 2.5 partsof p-toluenesulfonic acid as a catalyst are dissolved in 200 parts of p-xylene. Th;s solution ;s heated to the reflux temperature of about 140C and is held at this temperature until the theoretical amount of water (1 mol) formed by the esterification reaction has been azeotropically rernoved by means of a water separator. The p-xylene is then distilled off under reduced pressure, and the product obtained as the residue is dried. This gives 306 parts of a yellowish waxy ester mixture which contains as main constituent the diester of the formula 327~

o CH3 0 Il 1 11 (135) CH3-(cH2)l6-c-o-cH2-c-cH2-o-c-(cH2)l6-cH3 Melting point: 39-~i2C
Acid value: 92.

Method HH:
222.3 parts (0.5 mol) of the sodium salt of bis-2-ethyl-hexyl sulfosuccinate and 270 parts (1.0 mol) of stearyl alcohol are heated to 165-170C together with 2.2 parts (0.04 mol) of sodium methylate. The resulting melt is stirred at this temperature for 3 hours and then allowed to cool down to 90-95C, and the 2-ethylhexyl alcohol formed is distilled off under reduced pressure.

This gives as residue of the distillation 360 parts of the sodium saltof bis-octadecyl sulfosuccinate of the formula (136) ~ -C0-0-C ~ 7 ~;ào3s-cl;-co-o-cl8~37 in the form of a yellow waxy product.

Examples for the ~anufacture of novel compounds for use as inter-mediates Example 1:
Method A is repeated, except that 284 parts of stearic acid (1 mol) and 256 parts of palmitic acid (1 mol) are used (in place of 568 parts of stearic acid), affording 650 parts of a waxy ester mixture which, in addition to homologous monoesters and triesters, contains as main constituent the diester mixture of the formula ~L I~ d 7 2 N/[ (CH2)2 0 C Ro]2 Ro = 50% -(CH2)16-CH3 (CH2) 2-OH (C 2)14 CH3 Melting point: 38-42C.
Example 2:
Method A is repeated, except that 136 parts of penta-erythr;tol (1 mol), 852 parts of stearic acid (3 mols), 5 parts of p-toluenesulfonic acid and 1,000 parts o-f p-xylene are used and 3 mols of water are azeotropically removed, affording 930 parts of a waxy ester mixture which, in addition to homologous monoesters, diesters and tetraesters, contains as main const;tuent the triester of the formula ~[CH2- o-c- (CH2) l6-CH3] 3 ~ 13 8 ~ CH 20H

Melting point: 54-58C.
Example 3:
Method A is repeated, except that 121 parts of tris-(hydroxymethyl)aminomethane (1 mol), 568 parts of stearic acid (2 mols), 3.4 parts of p-toluenesulfonic acid and 600 parts of p-xylene are used and the theoretical amount oF
3 mols of water formed by the esterification reaction under ring closure is azeotropically removed, affording 630 parts of a waxy mixture which, in addition to homologous ring-shaped monoesters and triesters, contains as main constituent the diester of the formula t 139 ) CH3-(CH2)16 ~CH -O-C-(CH2)16-CH3 Melt;ng po;nt: 75-7~C~

Example 4:
Method A is repeated, except that 273 parts of lauryl-am;ne diethoxylate t1 mol) (prepared from 1 mol of lauryl-am;ne and 2 mols of ethylene ox;de), 340 parts of behen;c ac;d (1 mol), 2~3 parts of p-toluenesulfon;c acid and 625 parts of p-xylene are used and 1 mol of water is azeotropically removed, affording 593 parts of a pale yellow waxy ester mixture which, ;n add;t;on to the homologous d;ester, con~
tains as main constituent the monoester of the formula (CH2~2-0-~-(cH2)20 3 (140 ) CH3 (CH2)11 N~(CH ) -~

Melt;ng point; 35-37C A
Example 5:
Method A is repeated, except that 292 parts of N,N,N',N'-tetrak;st?-hydroxypropyl)ethylened;amine t1 mol), 852 parts of stear;c ac;d t3 mols), 6 parts of p-toluene-sulfon;c acid and 933 parts of p-xylene are used and 3 mols of water are azeotropically removed~ afford;ng 1,0~5 parts of a waxy ester m;xture wh;ch, ;n addition to the homologous monoesters, d;esters and tetraesters, conta;ns as ma;n con-st;tuent the tr;ester of the formula ~2~7~

CH3 I ~ ( 2)16 3 (141) ~,HCH2 I H [-H3 kC~I 2-CH-O-~ 3 ~
Melting point: 35-40C.
Example 6:
Method A ;s repeated, except that 42.4 parts of 1,2,4-butanetriol (0.4 mol), 227.Z parts of stearic acid tO.8 mol), 1.3 parts of p-toluenesulfonic acid and 270 parts of p-xylene are used and 0.~ mol of water ;s azeotrop;cally removed, affording 240 parts of a waxy ester m;xture which contains as ma;n const;tuent the diester of the formula ~ CHI~~ 1 [-H]

(142) ~ ~ 2 ¦ I _C_(CH2)16_CH ¦

Melt;ng po;nt: 46-48C.
Example 7:
Method A is repeated, except that 65.25 parts of tris(hydroxyethyl) ;socyanurate (0.25 moL), 142 parts of stear;c acid (0.5 mol), 1,2 parts of p-toluenesulfonic acid and 170 parts of p-xylene are used, 0.5 mol of water is azeo-tropically removed and the result;ng crude product is re-crystall;sed from acetone, affording 150 parts of an ester m;xture wh;ch is in the form of a wh;te powder and conta;ns as main constituent the d;ester of the formula _ 79 _ ~ 2 (Cl H2) 2-OH
o o=C~N~C=o o ) 3 ~)16 o (CH2)2 N\ / -(CH2)2-o-c-(cH2)l6-cH3 o Melting point: 67-69C.
Example 8:
Z01.8 parts of stearylam;ne tO.75 mol~ are dissolved at 50C in 700 parts of isopropanol. 74.3 parts of iso-cyanuric acid triglycide (0.25 mol) (prepared from 1 mol of ;socyanuric acid and 3 mols of epichlorohydrin) are intro-duced into this solution. The reaction mixture is heated to 80C and is stirred at this temperature for 5 hours, during which a slightly turbid solution forms. This solution is filtered at 80C. The reaction product precipitates as the filtrate cools down. The product is filtered off, washed with 200 parts of isopropanol a little at a time and is dried at 35C under reduced pressure. This gives 223 parts of a compound of the formula ~ C OH
(144) ( ) CH CH CH N/ \N CH CH CH NH (CH ) -CH
O=C~N/C=O
CH 2-CH-CH2-NH- ( CH 2) 1 7-CH 3 OH
Melting point: 78-83C.

Examp~e 9:
167 parts of isocyanuric acid triglycide t0.5 mol) 4Z7 parts of stearic acid t1.5 mols) and 1.5 parts of sodium stearate as a catalyst are heated to 135C. The heating bath is removed at this temperature. The temperature of the reaction mixture then increases to 160C of its own accord. ~Jhen the exothermic reaction has died down the reaction mixture is st;rred at 150C for 3 hours. The melt is then allowed to cool down and sol;d;f;es. Th;s g;ves 594 parts o-f the compound of the formula O OH ll OH O

(145) CH -(CH ) -C-O-CH -CH-CH -~ ~-CH2-CH-CH2-O-C-(CH2)16-CH3 \`N/
CH -CH-CH -O-C-(CH ) 6-CH3 OH

wh;ch ;s ;n the form of a pale be;ge crude product. A sample of the crude product ;s recrystall;sed from methanol. The recrystallised product ;s colourless.
Melt;ng po;nt: 58-62C.
Example 10:
139 parts of stearylam;ne tO.5 mol) are d;ssolved at 75C ;n 400 parts of ;sopropanol. 50.5 parts tO.25 mol) of butaned;ol d;glyc;de tprepared from 1 mol of 1 4-butanediol and 2 mols of ep;chlorohydr;n) are added. The react;on solut;on ;s heated to 80C and ;s st;rred at 80C
for 4 hours. The solvent ;s d;st;lled out of the clear solution under reduced pressure. The distillation residue is recrystallised from methanol. This gives 163 parts of a compound of the formula - 81 - '~2~

OH OH
(146) CH3-(cH2)l7-Nu-cH2-cH-cH2-o-(cll2)4-o-c~2-cH-cH2-~H-(cu2)l7-cu3 Melting point: 85-88C.
Example 11:
76.02 parts of the formula (146) compound obtained in Example 10 (0.1 mol) are d;ssolved in 200 parts of o~
xylene at 60C. 56~9 parts of stear;c acid t0.2 mol~ are addedR This solut;on is heated to the reflux temperature of about 145C and ;s held at th;s temperature for about 8 hours until the theoretical amount of water (0.2 mol) formed by the ester;fication reaction has been azeotropically removed by means of a water separator. The solvent is d;stilled out of the clear solution under reduced pressure. This gives as distillation residue 128 parts of the compound of the formula o o (147) ~_CH2_cu_cH2~o-(cH2)4-o-cH2-cH-cH2-~\ 1 3 Melting point: 82-8~C.
Example 12:
A solution of 10.~ parts of diethylenetriamine (0.1 mol) in 80 parts of toluene is admixed at room temperature (15 to 25C) w;th a solut;on of 59 parts of octadecyl ;so-cyanate (0.2 mol) in 2~0 parts of toluene in the course of 20 minutes. The temperature of the reaction mixture r;ses to 50C of its own accord. The reaction mixture is then heated to the reflux temperature of abou~ 111C~ is held at this temperature for 15 minutes, is then cooled down to 60C and is split into two equal parts. The toluene is distilled out of one half of the reaction mixture at 60C
under reduced pressure. This gives as distillation residue 34 parts of an amide mixture which is in the form of a beige powder and which contains as main constituent the reaction product of the forrnula ~ (I 2)2 l (148) ¦ (C~2)Z ¦ [-C-NH-(CH2)17 CH3~ 2 l~elting po;nt: 138-141C.
Example 13:
106.7 parts of a technical commercially available m;xture which conta;ns as ma;n const;tuent N1-stearyld;ethyl-enetetraamine (0.3 mol) are dissolved at room temperature (15-25C) ;n 300 parts of toluene. A solution of 88~8 parts of octadecyl isocyanate (0.3 mol) in 200 parts of tolu-ene is added the resulting mixture needing to be cooled to 25C and be;ng held at th;s temperature for 6 hours.
The reaction mixture is then heated to 50C and is held at this temperature for 2 hours. The toluene is then dis-tilled out of the reaction mixture at 50C under reduced pressure and the reaction residue is recrystallised from methanol. This gives 163 parts of a product rnixture which is in the form of a colourless powder and which contains as main constituent the reaction product of the formula (149) ~ /)2 l~elting point: ~6-92C.

Example 14:
177.9 parts of the mixture used in Example 13, which contains as main const;tuent l~1-stearyldiethylenetetraamine tO~5 mol), are melted at 60C together with 199.3 parts of ne1:hyl stearate (OAS mol)~ This meit is heated to 190C
and held at this temperature until the theoretical amount o-f methanol liberated by the reaction (0.5 mol) has been distilled out of the reaction mixture. The resulting crude product is recrystallised from ethyl acetate. This gives 296 parts of a product mixture which is in the form of a pale yellow wax and which contains as main constituent the reaction product of the formula _CH2_(CH2)17_N_ ~ -H]2 (cH2, 2 r 1l (150) N _ ~ ( 2)16 3 (CH2)2 NH
_ _ Melting point: 66-70C.
Example 15:
53 parts of octadecylamine (0.2 mol) are melted at 35C. 22~6 parts of ethyl cyanoacetate (0.2 mol) are added at 40C. The reaction mixture is then held at 40C
for 2 hours and is then cooled down to room temperature (15-25C), and the reaction product precipitates~ The crude product is filtered off, washed with ethanol and recrystal-l;sed from toluene. This gives 65 parts of a reaction pro-duct which is in the form of a wh;te powder and has the formula (151) I~C CH2-co-~H-(cH2)17 C~l3 Melting point: 79-~0C.

- 84 ~
Examples for the manufactu~e of novel compounds for use as si~ing agents Example 16:

681 parts of the ester mixture prepared by Method A (1 mol) are dissolved in 1,C00 parts of dichloromethane.
?28 parts of chlorosulfonic acid '1.1 mols) are added in ~he course of 45 minutes, during which the tempera~ure is held be~ween 25 and 35C by cooling and escaping hydrogen chloride gas is driven off with nitrogcn. ~hen all of the chlorosulfonic acid has been added, the reaction mixture is held at 35C for 1 hour. The dichloromethane is then distilled off. The crude product obtained as a residue is recrystallised from methyl ethyl ketone. This gives 620 parts of an ester mixture which is in the form o-f white pow-der and which contains as main constituent the acid ester of the formula o [-(CH2)2-O-c-(cH2)16 CH3]2 (152) (CH2) 2-OS03}1 , Melting po;nt: ~0~83C, acid value: 122.
Example 17:
Example 16 ;s repeated, except that 653 parts of the ester mixture prepared as in Example 1 (1 mol) are used in place of 6~1 parts of the ester mixture prepared by Method A (1 mol~, affording 613 parts of a mixture likewise re-crystallised from methyl ethyl ketone, in the form of a white powder and containing as main constituent the acid ester of the formula 153 [_(cH2)2_o_c_RO]2 R = 50% -(CH2)16-CH3 (CH2)2 3 50% (C 2)14 3 Melting point: 70-75C~ acid value: 105.

- 85 - ~ 27~

Example 18:
Method D is repeated, except that 6~1 parts of the ester mixture prepared by Method A (1 mol) are used in place of 624 parts of the ester mixture which contains ~lycerol distearate as the main component ~1 mol), and ,he crude pIO
dutt is recrystaliised from methyl e~hyl Icetone~ affording 600 parts of an es~er m;xture wh;ch ;s ;n the form of a wh;te powder and wh;ch contains as ma;n cons-tituent the acid es-ter of the formula o ~[-(CH2)-0-C-(C~I2)16 3]2 (154) (CH2)2-o-Y\oH

Melting point: 78-83C, ac;d value: 95.
Example 19:
681 parts of the ester m;xture prepared by Method A (1 mol), 147 parts of male;c anhydr;de (1.5 mols), 4 parts of p-toluenesulfonic ac;d as a catalyst and 0.33 part of hydroqu;none as a polymerisat;on ;nhibitor are dissolved in 1,000 parts of toluene. This solution ;s heated to the reflux temperature of about 110~ and ;s held at this tempera-ture for 12 hours. The reaction solution ;s then clar;f;ed from ;mpur;t;es. The solvent ;s d;st;lled off, and the crude product ;s recrystallised from acetone. Th;s gives 662 parts of an ester mixture which is in the form of a white powder and wh;ch conta;ns as ma;n const;tuent the acid ester of the formula [-(CH2)2-O-c-(cH2)16 CH3]2 (155) (CH2) 2-OOC-CH=CH-COOH

Melting po;nt: 53-55C, acid value: 69.

Example 20:
Example 16 is repeated, except that 934 parts of the ester mixture prepared in Example 2 (1 mol), 126.8 parts of chlorosulfonic acid (1.088 mol) and 1,555 parts of di-chloromethane are used, -the chloîosulforlic acic is added in the course of 30 minutes and the reaction mixture is then held at the reflux temperature of 35C for 4 hours, affording 867 parts of an ester mixture Likewise recrystallised from methyl ethyl ketone, in the form of a pale be;ge powder and containing as main constituent the acid ester of the formula (156) /[CH2-0-C-(CH2)16-CH3]3 \CH -OSO H

Melting point: 60-64C, acid value: 49.5.
Example 21:
Example 16 is repeated, except that 635 parts of the ester mixture prepared in Example 3 (1 mol), 128 parts of chlorosulfonic acid (1.1 mol) and 1,500 parts of dichloro methane are used, the chlorosulfon;c ac;d is added in the course of 30 minutes and the crude product is recrystallised from acetone, affording 622 parts of an ester mixture which is in the form of a white powder and which conta;ns as main constituent the acid ester of the formula o (157) CH3-(CH2)16 C CH2 0 11 ¦&H O C (CH ) -CH
\CH 2-OSO3H

Melting point: 66-71C, acid value: 75.
Example 2Z
.

Example 19 is repeated, except that 635 parts of the ester mixture prepared in Example 3 (1 mol), 98 parts of maleic anhydride (1 mol), 18 parts of p-toluenesulfonic - 87 ~ ~ 2J~

acid, 1 Dart of hydroquinone and 1,500 parts of p-xylene are used and the react;on mixture is held at 110C for 8 hours, affording 681 parts of an ester mixture likewise recrystallised from acetone, and containing as main con-stituent the acid ester of the formula (158) CH3-(C~l2)l6 ~ 2-o-c-(cH2)l6-cH3 CH2-OOC-CH=CH-COOH

Melt;ng point: 53-55C~ ac;d value: 53.
Example 23:
Example 16 is repeated, except that 624 parts o-f the 1,3- and 1,2-glycerol distearate mixture used ;n Method D (1 mol), 128 parts of chlorosulfonic acid (1.1 mol) and 666 parts of d;chloromethane are used, the chlorosulfon;c acid is added in the course o~ 3û minutes and the crude pro-duct ;s recrystall;sed from acetone, affording 616 parts of an ester mixture which conta;ns as ma;n constituent the acid ester of the formula ICH2 [-S03H]
(159) CH -0- [ 8 ( 2)16 3 Melting point: 54-56C~ acid value: 71.
Example 24:
Example 16 is repeated, except that 595 parts of the ester mixture prepared ;n Example 4 (1 mol), 128 parts of chLorosulfon;c ac;d (1.1 mol) and 8ûO parts of dichloro-methane are used, the chlorosulfonic acid is added in the course of 30 minutes and the crude product is recrystallised from acetone, affording 618 parts of an ester mixture which - 88 ~ 7~

is in the form of a white powder and which contains as main constituent the acid ester of the formula (CH2)2-0-C-(cu2)20 3 (1~0) CH3 (C 2)11 ~(C~I ) OSO H

!~elt;ng po;nt: 65-70C, acid value: 79.
_xample 25:
Example 19 ;s repeated, except that 1,090 parts of the ester mixture prepared in Example 5 (1 mol), 98 parts of male;c anhydride ~1 mol), 20 parts of p-toluenesulfonic ac;d and 2.2 parts of hydroqu;none are used ;n 3,333 parts of toluene, affording 1,027 parts of a waxy ester mlxture l;kewise recrystallised from acetone and containing as main constituent the acid ester of the formula ¦ ~CH2-CH-0- ~ ( 2 16 3j (161) ~ 3 [ OC-CH=C~-COOY~
\CH2-CH-O-Melt;ng point: 37-38C, acid value: 35.6.
Example 26:
Example 16 ;s repeated, except that 1,090 parts of the ester m;xture prepared ;n Example 5 (1 mol), 116 parts of chlorosulfonic acid (1 mol), and 2,500 par~s of dichloro-methane are used and the crude product is recrystallised from acetone, affording 1,006 parts of an ester mixture which ;s ;n the form of a wh;te powder and wh;ch conta;ns as ma;n const;tuent the ac;d ester of the formula - 89 - ~ 2~

¦ 1 3 1 ~
N/ 2 -C- (CH2) 16 3 (162) ~ [ S03U ]

\CH -CH-0-Melt;ng point: 65-70C, acid value: 55.
Example 27:
Example 16 is repeated, except that 92~1 parts of the diether obtained by Method B (0.15 mol), 17.5 parts of chlorosulfon;c acid (0.15 mol) and 350 parts of dichloro-methane are used and the crude product is recrystallised from ethyl acetate, affording 85.3 parts of a sulfonated compound of the formula ~ o-(CH2)17 C 3 (163) 1 ._o-(CH2) 17 CH3 Melting point~ 78-82C, acid value: 90.
Example 28:
Example 16 is repeated, except that 61.4 parts of the d;ether obtained by Method C (0.1 mol), 11.56 parts of chlorosulfon;c ac;d (0.1 mol) and 300 parts of d;chloro-methane are used and the crude product ;s recrystall;sed from ethyl acetate, afford;ng 61.8 parts of a sul-fonated compound of the formula o-(C~I2)17 C 3 (164) ~ ~!_o-(cH2)l7-cH3 Melt;ng point 71-73C, acid value: 106.

Example 29:
95.9 parts of the ester mixture obtained in Example 6 (0.15 mol) and 21.3 parts of phosphorus pentoxide (û.15 mol) are dissolved in 380 parts of toluene. This solution is heated up to 85C and stirred at this temperature for o hours~ The turb;d react;on solution is then f;ltered.
~he solvent ;s d;st;lled out of the f;ltrate under reducecl pressure. The crude product obta;ned as distillation residue ;s recrystallised from acetone. Th;s gives 103 parts o-f an ester mixture which is in the form of a beige powder and which contains as main constituent the acid ester of the formula (165) l CH2-- j ~ -C- (CH2) 16-CH3~

Melting po;nt: ~t8-5ûC, acid value: 65.
Example 30:
Example 19 is repeated, except that 158~6 parts of the ester mixture prepared in Example 7 (0.2 mol), 19.6 parts of maleic anhydride (0~2 mol), 1.5 parts of p-toluenesulfonic ac;d and 0.5 part of hydroquinone are used in 150 parts of p-xylene, affording 109 parts of an ester mixture likewise recrystallised from acetone, in the form of a white powder and containing as main constituent the acid diester of the formula (CH2)2-0-1C~-CH=CH-C-OH
O O

(166) CH3-(CU2)l6-C-0-(CH2)2-~\ ~ (c~l2)2-~-c-(cH2)l6-cH3 Melt;ng point: 65-67C, acid value: 53.

Example 31O
332 par~s of the formula (144) compound obtained in Example 8 (0.3 mol) are dissolved in 1,000 parts of iso-propanol at 60C. A solution of 29.~ parts of male;.c an-h~fdride (0.3 mol) in 500 parts o~ rnethyl ethyl ketone is added while the temperature o-f the reaction mixture is held at 60C~ The react;on mixture is then held at this tempera-ture for 3 hours and ;s then cooled down to 15C, and the react;on product precipitates. The product is filtered off with suction and dried at 35C in vacuo. This gives 319 parts of a colourless ester rnixture which contains as main constituent the acid ester of the formula H C OH -(167) CH3-~CII2)17-NH-CH2-CH-CH2-~ ~ _CH2_CH_CH2_NH_(CH2)17 CH3 o=c\ /c=o CH2-CH-cH -N/ oH2 17 CH3 1H \C-CH=CH-COOH

Melting point: 62-65C, acid value: 47.
Example 32:
Method D is repeated, except that 229.5 parts of the formula (145) compound obtained in ~xample 9 (0.2 mol) dissolved in 1,8aO parts of carbon tetrachloride and a sus-pens;on of 19 parts of phosphorus pentoxide (0.13 mol) in 500 parts of carbon tetrachlor;de are used and the reaction is carried out at 50C for 3 hours, affording 179 parts o4 a pale beige ester mixeure likew;se recrystallised from rnethyl ethyl ketone and containing as ma;n const;tuent the acid ester of the -formula O OH ll OH O
Il I ~C~ I 11 (168) 3 2 l 2 2 ~ ~ 2 2 2 1~ 3 o= \ /c=o N O
CH2 fH o2 2 ( 2)16 3 O-P-OH
Melting point: 48-55~C, acid value: 91. \OH

d~7~

Example 33:
153.8 parts of the formula tl47) compound (0~1 mol) obtained in Example 11 are mixed with 10 parts of succinic anhydride (0.1 mol), and the m;xture is melted at 130C
and he!d at th;s temperature for 6 hours. Tne resul~ing ciude product is recrystallised from ethyl acetate and dried at 45C under reduced pressure~ -rhis gives 121.1 parts of a colourless ester mixture ~Ihich contains as main con-stituent the acid ester of the formula O O
o 11 11 0 (169) CH -(CH ~ 6-C O-c-cH2-cH2-c-oH OH / ( 2)16 3 3 2 l \N-cH2-cH-cH2-o-(cH2)ll-o-cH2-cH-cH2-N\

Melting point: 62-65C, acid value: 41 Example 34:
Method H is repeated, except ~hat 63 parts of dimethyl~
maleic anhydride tO.5 mol) are used, affording 360 parts of a crude product which is in the form of a whit;sh powder, can be recrystallised from ethyl acetate and contains as main constituent the ac;d arn;de of the formula (170) ~ (CIU~)2 ~ [ -C-(CI12)16-CH
~ 1 2 2 ~ ~ -8-C=g-CooH j Melting point trecrystall;sed product): 66-72C
Ac;d value (recrystall;sed product): 67.

4~

Example 35:
Method H is repeated, except that 56 parts of ita-conic anhydride (0.5 mol) are used, affording 360 parts of a crude produc~ wh-ich is in the form of a cream-coloured powder, can be recrystalLised from acetone and contains as main cons.ituent the reaction product of the formula (CH2) 2 l [ -C- (CH2) 16-C~13 ( 1 71 ) ~ 2) 2 ~ [ -C-CH2-C-COOH

Melting po;nt (recrystallised product): 79-83C
Acid value (recrystallised product): 87 Example 36:
Method H is repeated, except that 55 parts of pyro-mellitic anhydride (0.25 mol) are used, affording 360 parts of a crude product which is in the form of a white powder~
can be recrystallised from ethyl acetate and contains as ma;n const;tuent the react;on product of the formula ~ ~ (CH2~ 2 1 ~ l ~ 8 ~ Nl~ C-(C~12)16-CH3 ¦ ~ ¦-C- \ / _ ¦

Melting point (recrystall;sed product): 124-130C
Acid value: (recrystallised product): 80.

Example 37:
Method H is repeated, except that 41 parts of pro-panesultone (0.5 mol~ are used, affording 260 parts of a crude product which is in the form of an ochre-coloured powder, can be recrystall;sed from ethanol and contains as main con-sti~uent the reaction product of the formula C- (CH2) 16-CH3 ]
t173~ U2)2 ~ [ -(CH ) -S0 H I

Melting po;nt (recrystallised product~: 96-99C
Acid value (recrystallised product~: 49.
Example 38:
320 parts of the am;de mixture obtained by Method D (0.5 mol3 are melted at 100C. 32 parts of bicyclo(2,2,1~~
hept-5-ene-2,3-d;carboxyl;c anhydr;de (0.5 mol~ are added.
The reaction mixture is st;rred, the anhydride goes into solut;on after 2 to 3 minutes, and the temperature of the reaction mixture rises in the course of about 10 minutes to 115 to 120C of its own accord. The reaction mixture is held at 120C for 30 minutes and is then cooled down to room temperature (15-25C~. This gives 380 parts of a pale brown wax wh;ch contains as main constituent the reaction product of the formula ,, , ~ 32'~

~ (I 2)2 l ~ ( 2~16 C~l3~

(CH2) ~ ~ -R`-Ci~

Mel-t;ng point: 63-64C, ac;d value: 61 Example 39:
A solut;on of 49 parts of male;c anhydride ~0.5 mol) ;n 40 parts of toluene is added to 347 parts of the reaction product obta;ned ;n Example 12 (0~5 mol), wh;ch ;s in the form of a solut;on ;n 160 parts of toluene at 60C, ;n the course of 15 minutes, during which the temperature o-f the reaction mixture rises to 70C of its own accord. The reaction mixture is then heated to the reflux temperature of about 111C, ;s held at th;s temperature for 2 hours and is then cooled down to 60C. The solvent is then dis-tilled out of the reaction mixture under reduced pressure.
The distillation residue constitutes 384 parts of a crude product which is in the form of a beige powder~ can be re-crystallised from dioxane and contains as main constituent the ac;d amide of the formula (CH 2) 2 ~ NH- ~CH7 ) l 7-cH3 I ~ -C--CH=CH-COOil Melting point (recrystall;sed product): 112-130C
Acid value (recrystallised product): 64 Example 40:
195 parts of the product mixture obta;ned ;n Example 13 (0.3 mol) are d;ssolved ;n 900 parts of toluene. A sol-ution of 30 parts (0.3 mol) of succ;nic anhydride ;n 300 parts of methyl ethyl ketone ;s added a~ 50C. The reaction mixture is then heated to 65C and held at this temperature for 3 hours. The solvent is then distilled out of the re-act;on mixture under reduced pressure. The crude product resultins as distillation residue s recrystallised from echyl acetate. This gives 175 par~s of an amide mixture which is in the form of a beige powder and which contains as main constituent the reaction product of the formula CH3- ( CH 2 ) 1 7-N~ ~ -H~
(CH2) 2 ( 17 6 ) L (CH2) 2 ¦- -C-NH- (CH2) 17-CH3 ]

NH~ l C CH2 CH2 C0011¦

Melting point: 55-58C, acid value: 74.
Example 41:
Example 40 is repeated, except that 444 parts of phthalic anhydride ~0.3 mol) are used tin p~ace of 30 parts of succinic anhydride), affording 192 parts of an amide mix-ture which is in the form of a beige powder and which con-tains as main constituent the reaction product of the formula CH3-(CH2)17-N- [ -H~

(177~ I C ~ (cu~l7-cu3 CGOH
Melting point 65-70, acid value: 70 .
Example 42-.

Example 40 is repeated, except that 34.2 parts oFglutaric anhydride t0.3 mol) are used, affording 166 parts of an amide m;xture wh;ch ;s ;n the form of a beige powder and wh;ch contains as main constituent the reaction product of the formula - g7 - ~2 -CH3-(CH2)17-N- [ -H ]

~178) ~ ~H- - L~ -C-NH-(CH2~17-CH3¦

C (CH2) 3-cOOH i Melting point: 53-56C, acid value: 73.
Example43:
Example 40 is repeated, except that 186.6 parts of the product mixture obtained in Example 3 tO.3 mol) and 29.4 parts of maleic anhydride (0~3 mol) are used and the maleic anhydride is dissolved in 300 parts of toluene (in place of methyl ethyl ketone), affording 182 parts of an amide m;xture which is in the form of a beige powder and which conta;ns as main constituent the reaction product of the formula -CH3-(CH2)17-l- - I C -H ~

~179) ~ _(CH ) -CH

NH- [ -C-CH=CH-COOH¦

Melt;ng po;nt: 6Z-67C, ac;d value: 78.
Example 44:
116 parts of tr;ethyl methanetr;carboxylate (0.5 mol) and 406 parts of octadecanol (1.5 mols) are heated to 140C and held at this temperature -for 17 hours, during which the theoret;cal amount of ethanol l;berated by the trans-esterif;cation reaction ~1.5 mols) is distilled out of the react;on mixture. The reaction mixture is then cooled down to 20C, and the crude produc~ is recrys-tallised from acetone. This gives 300 parts of a react;on product which is in the form of a colourless ~ ~g~ 7~2 powder and which has the formula C~3-~CH2)17--Q\ /Q ( 2 17 3 ~1$0) / \
3 ( 2)i7 8 H

Melt;ng po;nt: 50-54C.
Example 45:
67.2 parts of the ;ntermed;ate obtained in Example 15(0.2 mol) are d;ssolved at room temperature (15~25C) ;n 300 parts of dimethylformamide, and the solution is ad-m;xed w;th 16 parts of a 50~ sod;um hydrox;de solution (0.2 mol) to give a solution of the corresponding sodium salt. 16.8 parts of 1,6-n-hexane d;;socyanate ~0.1 mol) are then added at 30C ;n the course of 15 m;nutes.
The reaction mixture is then held at 30C for 4 hours, is d;luted w;th 1,000 parts of water and ;s adjusted to pH
.5 by means of aqueous acet;c acid solution, and the re-action product prec;p;tates in the form of a free ac;d.
The crude product is filtered off and recrystallised from ethyl acetate. Th;s gives 61.3 parts of a react;on product wh;ch ;s ;n the form of a wh;te powder and wh;ch has the formula \CH-!~-NH- (CH ) -NH-Q-C/~ 2)17 3 ( 1 ~1 ) CH3- (CH2) 17-NH-~ 2 6 CN

Melt;ng po;nt: 116-120C.
Example 46:
Example ~5 ;s repeated, except that the intermediate obta;ned ;n Example 15 ;s d;ssolved ;n Z00 parts of d;methyl sulfoxide (in place of 300 parts of dimethylformam;de) and 17.4 parts of toluylene di;socyanate (0.1 mol) are used ;n the form of a technical mixture of about 80/o of 1-toluylene 2~4-diisocyanate and about 20X of 1-toluylene 2,6-diisocyan-ate (in place of 16.8 parts of 1,6-n-hexane diisocyanate), affording 68 parts of a reaction product mixture which is in the form of a pale yellow powder and which contains abou 80% of the reaction produc~ of the formula CH-~- NH-( 1 8 2 ) CH3 (CH2) 17 NH o \NH-RC-C~
~-NH- (CH2) 17-CH3 and about 20% of reaction product of the formula CN
CH3~ RC C~
NC~ Rc ! .~ ~-NH(CHZ) 17 CH3 ( 1 8 3 ) CH- -NH~
=.
CH3- (CH2) 17-NH-~

Melting point: 116-120C.
Example 47:
-Method T is repeated, except that 322 parts of benzo-phenonetetracarboxylic dianhydride (1 mol) are used (in place of 192 parts of trimellitic anhydride), affording 823 parts of a likewise colourless waxy ester mixture which contains as main constituent the d;ester of the formula (184) -OOC ~ \ / \ sS \ COO ¦ I-(CH2~17-CH3]2 Melting po;n-t: ~6-47C
Acid value: 110 ~L~ L~

Example 48:
Method T is repeated, except that 176 parts of tri-carballylic acid (1 mol) are used (in place of 192 parts of trimellitic anhydride), affording 650 parts of a colour-iess waxy ester mixture which contains as main sonstituent che diester of the formula r CH2-COO~ H]
(185) CH-CGO- [-(CH2)17 CH3]2 CH - COO-Melting point: 43-45C
Acid value: 85 Example 49:
Method T is repeated, except that 210 parts of citric acid monohydrate (1 mol) (in place of 192 parts of trimellitic anhydride), 270 parts of octadecanol (1 mol) and 521 parts of dioctadecylamine (1 mol) (in place of 540 parts of octa-decanol) are used, affording 909 parts of a yellowish waxy amide and ester m;xture which contains as main constituent the amide-ester of the formula . CH2-cO-l ~-OH]
IO-C-CO- ¦ ~-o-(cH2)l7-CH3]
(~86) CH -co-¦ ~ ~(CH2)17 CH31 l (CH2)17 C ¦

Melting po;nt: 54-67C
Acid value: 63 Example 50:
Method T is repeated, except that 174 parts of trans-aconit;c ac;d (1 mol) are used (;n place of 192 parts of tr;mellitic anhydr;de), the reaction is carried out in the - lol ~2~72 presence of 1 part of hydroquinone as a polymerisat;on in-hibitor and the length of reaction at 160C is 30 m;nutes tnot 60 minutes)~ affording 650 parts of a colourless waxy ester m;xture which contains as main constituent the diester of the formula (187) ~-OOC-C-CH2-C00-¦ [-H]
HC-COO- [ 2 17 3]2 Melting point: 42-43C
Ac;d value: 83 Example 51:
Method T is repeated, except that 87 parts of trans-aconitic acid (0.5 mol) (in place of 192 parts of trimellitic anhydride) and 521 parts of dioctadecylamine (1 mol) (in place of 540 parts of octadecanol) are used and the reaction is carried out in the presence of 1 part of hydroquinone as a polymerisation inhibitor, affording 56D parts (98%
of theory) of a yellowish waxy amide mixture which contains as main constituent the diamide of the formula r -OC-C-CH 2-CO-~ [ -OH ]
(188) L HC-CO- N~(CH2) 17-CH3 ( 2 17 3 1 2 Melting point: 52-57C
Acid value: 47.
Example 52:
Method GG ;s repeated, except that 170.4 parts (in place of 284 parts) of stearic acid (0.6 mol), 48.9 parts of N,N-bis(2-hydroxyethyl)glycine (0.3 mol) (in place of 67 parts of 2,Z-bis(hydroxymethyl)propionic acid), 1.2 parts (in place of 2~5 parts) of p toluenesulfonic acid and 170 7~

parts (in place of 200 parts) of p-xylene are used and 0.6 mol tin place of 1 mol) of water ;s azeotrop;cally removed, affording 208 parts of a yellowish waxy ester mixture which conta;ns as ma;n constituent the diester of the for~ula O O
Il 11 (189) 3 2 16 ~ CH2 CH2-N-C~l2-CH2-0-C-(CH ) CH

COOH
Melting point: 64-6~C
Acid value: 106.
Example 53:
95.6 parts of nitrilotriacetic acid (0.5 mol) and 522 parts of dioctadecylamine (1 mol) are heated to 160C
and held at this temperature for 6 hours. The reaction mix-ture is cooled down to 15 to 25C to give 565 parts of an ochre-coloured waxy amide mixture which contains as main constituent the diamide of the formula CH3-(CH2)17 11 1l ~CH ) -CH
~N-C-CH2-N-CH2-C N 2 17 3 (190) CH3-(CH2)17 lH2 (CH2)17-CH3 C~O~I

Mel~ing point: 44-51C
Acid value: 49.
Application Examples Examples 5~i to 75:
A dispersion of fibres containing bleached birch sulEate pulp and pine sulfate pulp in a weight ratio of 1:1 in 10 (German degrees of hardness) hard water and having a Schopper-Riegler freeness of 35 and a solids content of 0.5% can be mixed with 20% of the filler given in Table I below and then is mixed with 0.01% of PERCOL 292 ~ (cationic high molecular weight (molecular weight > 1-10 ) polyacrylamide) as an auxiliary for retaining very fine pulp fibre particles, and pH

: '.

of the dispersion of the fibres which is likewise given in Table I
becomes established. The percentages are based on the dry matter i auxiliary and filler and in turn on the solids content of the dis-persion of the fibres.

The sizing agent formulations likewise given in Table I below are prepared by stirring the specified sizing agents in powder form or in the form of reaction mixtures as obtained after their manufacture, in the presence of deionised water and of glass beads having a diameter of 2 mm at room temperature (15 to 25C), together with the particular retention aid described below. The resulting dispersions are pourable and homogeneous and have a long shelf life. The per-centages in the formulations are based on the dry matter in sizing agent and retention aid and in turn on the total weight of the formulation. Retention aid No. 1 is POLYMIN P ~ (a polyethyleneimine with a molecular weight of 10,000 to 100,000). Retention aid No. 2 is CATO 110 ~ (a cationically modified starch which has been modified with a propylene oxide containing quaternary ammonium groups and whose pH of 25% suspension in distilled water at 20C is 4.2 to 4.6). Retention aid No. 3 is a condensation product of dicyano-diamide and triethylenetetraamine, which has been reacted with epi-chlorohydrin and is prepared as in Example 2 of German "Offenlegungs-schrift" 2,710,061.

The aqueous formulation of the sizing agent and the retention aid is then added to the dispersion of the fibres in such a way that the result is an amount of the sizing agent of 0.5% in dry matter, based on the solids content of the dispersion of the fibres. The dispersion of the fibres is then processed in a Formette Dynamique Laboratory sheet former supplied by Allimand? Grenoble, France, into sheets of paper which on drying at 130C for 3 minutes have a weight per unit area of 80 g/m2. The sheet of paper thus obtained is subjected to an additional heat treatment, at 140C, for 3 minutes.

7;~
- 104 ~
The two surfaces of the sheets of paper obtained, i.e. the surface obtained against the sieve face of the sheet former and the opposite surface, are tested for their size properties. For this purpose, the Cobb water absorption after a 30 second treatment (WA Cobb30) is measured in accordance ~ith DIN 53,132. The results of the WA Cobb30 measurements on the sieve side (SS) and the opposite side (OS) before and after the heat treatment at 140C and before and after one day storage at 20C are given in g/m in Table I below.
The lower the water absorption, the better the sizing of the paper.
WA Cobb30 values above 100 correspond to a completely unsatisfactory sizing of the paper.

. , .

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~ CL ~ ___ _ D ~ E O ~ ~ I~ ~ L~ O

- 107 - ~ 72 _~ ~ 0 -O ~ ~ r 1~
~ ~n rn r~J ~ r~l r~l ~A rl) r~J O 11~ r~ Il~ `O _ _ r~J r~ rn u~ r~o _ ~
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_ _ O _ r~l r ~S> , (V rr) rv rv _ rv r-~ rJ) ~ ~Z ~Z ~Z Z~Z
r-O rd O rdO rd ~rl O rd ~rV . td Ctd c a td td c , a~ ~, a ~'~a ~" a c a ~"

O ~ O ~o ~ o o c Ln ~,~ u~ a~ u~
O ;~ . ~! 'a~ ' ~t ~ ~ ' L
~ ~ ~) ~ r)I~ r,~J ~J I~ rl~
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- 108 ~ ~2 Examples 76 to 79:
The method of Examples 54 to 75 is repeated, except that a formulation of 7% fsizing agent of Method G and 3.5% of retention aid No. 1 is used. In addition, there is used, besides a dispersion of the fibres which is free of mechanical wood pulp, also a dispersion of the fibres which contains bleached birch sulfate pulp, bleached pine sulfate pulp and bleached mechanical wood pulp in a weight ratio of 1:1:2. The sizing results are shown in Table II below.

Table II

_ _ _ pH of WA Cobb30 (g/m ) Example Mechanical Filler the dis- Aftl after after No. pulp of theimmediately 1 day 1 week * fibres storage storage _SS 05 SS OS SS
76 _ chalk 7.5 15 1~ 15 12 16 77 _ kaolin 6 17 13 18 13 31 78 _ ** 5.6 17 17 18 13 20 79 ** 6.616 1 14 12 10 10 * - dispersions of the fibres which are free of mechanical wood pulp -~ disperion of the fibres containing mechanical wood pulp ** no filler Examples 80 to 83:
The method of Examples 54 to 75 is repeated, except that only 0.3%
(not 0.5%) of dry matter of the sizing agent is used, based on the solids content of the dispersion of the fibres. The sizing results are summarised in Table III beLow.

- log - ~%~7~

3 c~ >~ 0 O` U~ ~ ~
E _ _ _ E c~7 ~ ~ O N
~0 .,.1 - _ _ 4~ ~ C CJ t~l ~1 ~ O
0'~ 00 oo oO ~
~ V ~ V
_ ~ -.
~ O
~0 ~0 ~0 ~
c x z ~ æ ~ z ~ z;
., 41 ~rJ ~1 ~rl ~1 ~,1 41 ~rl ~ O td O td O ~ O td b .~ b ~ bO ~, ~ o N L N bO ~' bO
~0 0 ~o U~ ~0 m ~0 O ~ O ~: O ;?~: O
;~ . a~ ~ ~ ~ ~: ~
1~ I~IV') 1~ 1~1~
_ ~ __ _ - ~z oo oo oo ~
LL _ _ - 110 ~ 92~72 Examples 84 and 85:
The method of Examples 54 to 75 is repeated, except that the following formulations of the sizing agent, which is in each case emulsified in the molten state at 80C in the presence of water, are used:
Formulation made up in Example 84:
7% of si~ing agent of Example 16 3,5% of retention aid No. 1 0.7% of sorbitan monostearate (oil-in-water 0.7% of an adduct of ethylene oxide and sorbitan monostearate (water-in~oil emulsifier).
Formulation made up in Example 85:
30% of sizing agent of Example 23 15% of retention aid No. 1 The two formulations are homo~eneous and have a long shelf life.
The sizing results are shown in Table IV below.

~2~2~2 L

,.~ oooo 2~2 Examples 86 to 93:
The method of Examples 5~ to 75 is repeated, except that the sizing agent and the retention aid are added separately to the dispersion of the fibres, the sizing agent in the form of a powder being stirred with an aqueous 5% sodium hydroxide or potassium hydroxide solution in the presence of water and of glass beads to give self-emulsifying likewise homogeneous and long-shelf-life sizing agent formulations as given in Table V below. The Val~ indicated denote the number of equivalents of sodium hydroxide or potassium hydroxide for 100 equivalents based on the number of negative charges of acid groups of the particular acid ester used as si~ing agent. 10 seconds before or after the sizing agent has been added, the dispersion oE fibres is admixed in either case with 0.25% in dry matter of retention aid No. I., based on the solids content of the dispersion of the fibres. The sizing results are also shown in Table V.

%
-- 113 ~
_ r . ~ O ~ ~ ~ ~ r N I~J a~
o .~ a ~ f~ _ ~ ~ ~ ~
Q 7:~ ~ ~ ~ O ~ ~ ~ ~ `O ~_ 3 aJ a o u~ u~u~ oo ~ ~ ~J ~
~ '~ _ _ _ ~
E ~ ~o I~Il~ ~ ~ O co O`t~
_ _ _ _ _ _ a o :~
~ h ~ ~_ r~J~J ~) ~ O O
4~ a~ ~ oo ~o co oo oo oo ~o 1~ a ~ a _ ~ ~ aJ
_ . _ _"_ ,s:~ ~
~Q ,~J~o a~ v ~ v v v v ~ o c _ _ _ _ _ _ _ ~ ao a~

_ ~ J~ ~~ a a ~ a~ a~D a~9 ao a ~ o C O~ ,0 0 ~
c X OX O X OX O ~ w s X ~w s 'J o Wo ~Wo ~Wo ~ Wo ~Wo ~ v,~V E~ ~ E d ~

E v Ea ~ a ~a~ ~rd ~~ r~d ro~ 1 r~ a CD
bO u) oo u) oo u~~0 v)~0 v) 1:: Q d Q d Q e~ a;
a~ 3 ~od ~0N o~d, ~0d~ ~Or~l ~0I o 1 0 ~ 3 v~ ' ;;~ ~a ~0 ~,1 ~ , ~ ~ ~0 ~ 0 ;~
~ ro~ r~~ ro ~ ro~_ raO raO ra O ra d O~O~ 0~ 0~ O> ~ ~ ~
a~ o~ o ~ o~ o ~ ou~ Ou~ Ou~ O ~1 _ I~ ~ I~ ~ ~ O` r- o~ ~ o~ ~ r- ~ ~ ~ I~ ~ ~
1 . .
~0 ~rl ~,1 bObO d bO d bO b~ bO ~ ra .~ .~d N. ~ N d~ N dl dl " a d 0 . ,1N ~ rl N ~a N N N U ,~
,~-, a~to a~ o~ a~ u~ ~a ~ O
d ~ ~ u~ u ~ u~ u ~ uh .u ~ u4 U a~
a a a ~ ad~ u ad) 4~ ~a) a)~ ad~a~ d ~ ad~ J- a~ O
O S~ ~d~ rd¢ bOa bO¢ rda) bl)¢ bO~ rbdO ~ bO ' '~ a~
_____ _ ~
a a~ C4 ra aJ E 0 ~o ~ r~ 0~ O ~ ~ ~ ;~_ _ ~ z oO ro ro co 0~ 0~ O~ O~ O s ~

~ . _ _. _ c ~ ra Examples 94 to 111:
The method of Examples 54 to 75 is repeated, except that the sizing agent and retention aid are added separately to the dispersion of the fibres, the sizing agent being added 10 seconds after the filler provided a filler has been added. The retention aid is added 10 seconds after the sizing agent and PERCOL 292 ~ is added 10 seconds after the retention aid. The dispersion of the fibres used contains 0.3% of alum (calculated as dry A12(S04)3), based on the solids content of the dispersion, and 1.5 g of sodium sulfate per litre of dispersion. In addition, there is used besides dispersicns of the fibres which are free of mechanical wood pulp also dispersion of the fibres which contain bleached birch sulfate pulp, bleached pine sulfate pulp and bleached mechanical wood pulp in a weight ratio of 1:1:2. Some of these dispersions of the fibres are admixed with the amounts of sulfuric acid or sodium hydroxide specified in Tables VI and VII below (as pure substance, based on the solids content of the dispersion of the fibres), the sulfuric acid and the sodium hydroxide being added in the form of dilute aqueous solutions. The sizing agent used 1s a 15.3% dilutable, homogeneous and stable formulation of a powder of the ester mixture obtained in Example 22 which is dispersed with 65 val% of ammonia in the presence of water and glass beads. Based on the solids content of the dispersions of the fibres, the amounts used are 0.5% of the specified sizing agent (expressed as solids) and 0.25% of retention aid No. 1 (also expressed as solids). The sizing results can be seen from Tables VI and VII.

~Z~3~

L ~ __ _ _co v~ ~ (~ _ _ N , ~~ O _ N _ ~ ~) .- N ~-- ~ N

Nt_ :~ ~ O `i ~_ ~ ~ ~ ~ N N O
L ~ O _ __ . __ _ ~1~) L ~ J __ Ir~ _ ~-- 1-- ~ ~ ~ ~ 1_ 3 ~ tll 0 '... U~ In O `J U~ ~ Il~ ~J

,E ~J o~ I~ oo I~ m oo `J r~ `O

~~
~rO ~ O 0~ O ~ ~O I~ U~

~ _ _ _ __ E 1) ;~ ~1 r~l ~o~ l l ~ ~ l l l O. O, E3 _ __ _ ~ ,, ;~: ~
~ o l ! l l l l l ! i ~ _ r D ID V
~ ~1) _ _ ____ __ .. Q ' ~ Lf~ `O I~ CO O` O ~_ r~l ~ E~z O` O` O` O` O` O` O O C~
~ . ~ ~ __ _ _ , ~2~

O V) ~ N ~ `:t Il~ _ - IrJ N I ' _ _ _ _ E~ CSI L :~, ~) O ~ ~-- O N O 0` 0` O O
~ .,_ ;' V L __ _ _ _ ._ ¦ _ __ D 1~ __ V: 1/'~ ~ N ~ N __ ~ ~ N
L ~ _ O ~ N ~ ~ ~ N ~ N ~

~J V~ N~) 0` 0` ~ ~ 1~ O `O
._ _ _ N ~ N ~ r~) N N ~

O N ~ ~O ,_ `O U~ `O CO .-S:: ~ IJ~ 1_ O 00 `O ` 1--~ I ~ lt -LL~

d _ V L -O ~t .~ ~D I~ _ _ __ ~ _ _ O _I I I I v J L _ a _ _ H E 0 O O O O O O O O ~
~ _ _ .-Examples 112_to 116:
The method of Examples 54 to 75 is repeated, except that sizing agent and retention aid are added separately to the disperion of the fibres and the dispersion of the fibres used contains pine sulfate pulp and bleached mechanical wood pulp in a weight ratio of 1:4. 30%
of chalk is added as a filler to the disperion oL the fibres. The sizing agent is added lO seconds aEter the chalk, the retention aid 10 seconds after the sizing agent and PERCOL 292 ~ 10 seconds after the retention aid. The sizing agent used is a 35% dilutable? horno-geneous and stable formulation of a melt of the ester mixture ob-tained in Example 22 which is emulsified at 80C with 18 val% of sodium hydroxide in the presence of water. Retention aid No. 4 or No. 5 is used in place of retention aids Nos. 1 to 3. Retention aid No. 4 is a reaction product of dicyanodiamide, formaldehyde, ammonium chloride and ethylenediamine, which is prepare~ as in Example 1 of U.S. ~atent 3,491,064. Retention aid No. 5 is RETAMINOL K ~
(a polyethyleneimine with a molecular weight of 20,000 to 40,000).
The amounts of sizing agent and retention aid used are given in Table VIII below, these amounts and the amount of filler (30% of chalk) being based on the dry matter in sizing agent9 retention aid and filler and on the solids content of the dispersion of the fibres. The sizing results can also be seen from Table VIII below.

- 118 ~ 2~
- o~ o o~ o~ 0 ~ ~ _ .,~ ~ .- CO , E ( I ) ~_ >~ O Ll~ ~ O O O
D W _ .~ L ~ ~ ~ = ~ ~
. rl ~ O` O ~ r~J
~ ~ O 1- O O O
1 _ ~ _ r ~ O ~ O O

o Z ZLn L ~ Z
~ _ .C V Lr~ ~

9 N o ~ ~ o ~-~ J _ _ CL . r~l r~ ~t L~ ~O
~) E O ~ ~_ D Ll~ . ~ ~_ Examples 117 to 136:
The method of Examples 54 to 75 is repeated, in which 20% of chalk is added as a filler, except that formulations of 7% of the sizing agents which are specified in the Table IX below and 3.5% of re-tention aid ~o. 1 are added, likewise pourable, homogeneous and long-shelf-life disper~ions being obtained and the dispersions of the sizing agents and retention aids being added to the dispersions of the fibres in such a way, that the result is an amount of the sizing agent of 0.5 or 1.0% in dry matter, based on the so].ids content of the dispersion of the fibres. The sizing results can be seen from Table IX below.

o rl~ -- ---- M ~ ~ --M _ ~ cO ~ ~ C~J _ _~ O O ~O ~ ~ ~ ~ ~ ~ ~O ~O ~ ~ ~ .

r~l ~.n CO 1-- O O M ~o I N rr) O ~-- O O `O
E L (/~ 1~ I I~J M ~1 o~J ~ ~ O~J l CO ~J O~J ~
. 11:1 D _ _ _ __ _ __ _ ~J C O ~O M t~l I~J ~ ~0 ~~J Ir~ C ~0 M ~ 1 3 .~ .
~ _ _ _ _ _ _ L
i~ CO 0~ N U~ I_ 0~ 0~ ~ 0~ N ~ M O
3 v~ ~ ~O ~ ~ ~ r~J ~ n ~ u~ I_ ~ ~ O~
_ _ _ a ~
~J O ~J O N I~ ~-- ( \J I~J ~ r~J ~1 t~J r~J (~J r~J ~
h rl O` O` co O` O` O` O` O` O` O` O` O` O` O`
~i . __ _ __ _ _ _ ~b~ U~ O U~ U~ O U~ U~ U~ O O Ln O U~ U~
3 ~ o ~ o o o o o ~ ~ o ~ o o I I V _ _J ~ ---- a ~ u ~ c ~:S I~ ~ ~ ~ ~ ~ ~5 _ _ _ O O O O r O r O r S E E E E
.y ~ ~ ~ ~ ~ ~ ~ V
S S S S~ S S ~ ~ S X LL LLJ LLJ LL
~_ ~ `.' `~' ~ ~+_ ~ ~ ~ ~ ~ `~' `.' O O O O O O O O O O O O O O
.IJ ~ ~ ~ ~' ~ ~ ~ ~ ~ ~
.) ~ ~ ~ U ~ ~ ~ ~ ~ ~ ~ ~ ~1 ~ ~ _o ~ _o _o ~ o ~ _o o o o o O O O O O O O O O O O O O O
Q Q L L Q L Q Q L Q L L L L
~ ,~, ,C, ,C~ ,C, ,C, ,C, ,C, ., ., ., ,C~ ,~, ,C, ,0 00 . ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
G
~1 ~Y CY ~ C~ ~ Cl: ry t~:: C~ ~ ~ C~ C~ ~
_ _ _ _ . . __ X E O r-- co O O ~ N M ~ Ir~ O r-- CO

_U; ~ ~ L N N N N N N N N N M

_~ o ~ ~r ~ _ r~ ~
_ _ _ ~_ E
, ~ t~7 U~ .- l ~ .~ ~o E v ~n ~ ~o ~ ro ~1 ~__ X
. ~ _ _ _ `~
~0 __ _ _~ o ~ C~ O ~O O~ m ~O I~ ~ O
3 ., 2 ~ . O
~ ~ U~ U~ O` ~ 1 O
n~ ~1-- `O ~--~) I~J N H
. ~0 . _ R s o~ C~ o~ ~ o~ ~
~ . . . . . . o w a) ~ a~o~ oo o~~o a~ oo 0~ ~

~ O O O O O O E
~!~ ~
_ _ . _ `.' O o o o o o C
J ~ ~ v ~ ~
~0 ~0 ~0 ~0 ~0 O ~0 r~ d Q :~ L Q C Q ~,L ~1 L ~ aJ
(Ll td O ~J C O ~J O Q~O (LlO (I) L
~ J .~ J .~ J '~ J.~ J .~ J '~:1 ., ~1)~ Q ~ Q +' Q~ Q ~ Q V n u~ c~
. ~ E E u E (.) E E E
C NCJ Xa~ X~) XaJ XCJ X ~ X _ O '~n~ 111 ~ ILJC~ 111~1: LIJ ~Y llJ t2~ LIJ ~ U~
_ _ _ _ _ ¦ L

- '~ J L
aJ EQ O ~ ~J ~1 ~Ir~ `O ~ L
_ X ~ ~ ~ ~ .- ~ ~ O
~ __ _ _ _ .,~

7;2 Examples 137 to 141:
The method of Examples 54 to 75 is repeated in which 20% of chalk is added as a filler, except that formulations of 7% of the sizing agents which are specified in the Table X below and 3.5% of retention aid NoO 1 or No. 2 are added,likewise pourab]e, homo-geneous and long-shelf-life dispersions being obtained and the dispersions of the sizing agents and retention aids being added to the dispersions of the fibres in 5uch a way, that the result is an amount of the sizing agent of 0.4 or 0.5% in dry matter, based on the solids content of the dispersion of the fibres. The sizing results can be seen from Table X below.

- 1~3 --~ ~o o _~ ~ ~ ~
~ u) ~n u~ O~ oo u~ _~
.~ _ _ _ ~_ _ (n ~ f~ ~ u~ u~

E ~ E O __ ~O .~ .--c~ E (/~ ~ ~-- OJ
0~ ~ _ _

5~ c ~ ~ 1~ ~ r~
v F >~ ~o O ~ ~ ~ ~ ~--~5 ~ ~0 _ ~ _ _ ~ U~ t~ l_ O` O ~ I~
~ ~ r~- ~ ~ ~ ~
~ ~ _ ~: Q~ ~ O ~ ~ ~ ~
a, ~ o ~ ~ ~ r~l ~
O '~ _ _ _ a: E ~n ~ N O` ~o `O
~_ ~' O ~ ~ O O` O`
~ o ~ ~ r- oo oO
~ rl ''I rC ~rl U~
'~è
~ ~ a JJ u~ u~ ~ ~ ~
o.L'-,~ ~
~0 ~ ~
~ C`l ~ ~ ~ ~
~1 ~ O o O O o ~ '~ Z Z; Z Z Z
o o 'o o o .,~
I~
~J L LO o o o d Q ~ c c Q ~ Q~;
~ '~lo~ '~.~o o o o ~ ~ ~ L~ ~- L~ E ~ E ~ E
.,_1 ~ ~ ~ ~ ~ f~ ~ ~ ~ ~u u~ c~ s c~ s aJ x a~ x ~ x ~q aJ Q ~ I~_ oo O` O ~
_ E O ~ ~-- ~ ~ ~t ~ llJ
~ , _ Examples 142 to 167:
The method of Examples 5~ to 75 is repeated in which 20% of chalk is added as a Eiller, except that formulations of 7% of the sizing agents which are specified in the Table XI below and 3.5%
of retention aid No. 1 are added, likewise pourable, homogeneous and long-shelf-life dis~ersions being obtained and the dispersions of the sizing agents and retention aids being added to the dis-persions of the fibres in such a way, that the result is an amount of the sizing agent of 0.25, 0.35, 0.5 or 1.0% in dry matter, based on the solids content of the dispersion o:E the fibres. The sizing results can be seen from Table XI below.

- 125 - ~
-~A ~ ~ ~ ~l ~ ~ U~ O` ~ I
C V) _ _ ~o o , r~ ~ ~ O ~ ~J

N 11:1 _ _ _ r~) ~ ~ 00 O ~ L~ U~ U~
'1:
3 . _ _ _ C O r~J ~1 1~ ~ ~ ~ ~ ~ 1_ CJ _ _ ~ 0~ ~-- OJ ~O ~o ~O 0~ 11~ N 1--V) ~I ~1 1~ ~_ ~_ ~_ 1_ Il~ 00 O _ _ _ _ __ _ _ . O
e- O` ~ ~ ~ L
~rC CO 00 00 00 00 ,00 CO 00 CO
, _ _ ,_ J- Lr~ U~ U~ ~ U) U~ U~ O Vl ~6~ O O O O O O O ~ O
~ ~ ~ ~- - - ~ ~ ~
o o o o o o o o o J ~V L L L L L L L
a~ v ~ v .~-.,u ~ ~ ~ ~
00 E x X' 'E 3, XE X , XE ~ , ,XE ~ X X
~o -a ~ -a -a ~ -a ~a -o -a ~ ~o ~o ~o ~oa,o aJo Q~O ~O ~O
." ~ s ~ ~ a~ sa) s-a s -a s -o s-~ s ~ s N ~) ~ ~ v ~ ~.~- +JE C~E C~ E ~E ~ E O
U~ ~ E u~s ~ LUS ~: _~ C~ ~ CS
C) 1~
_ E O N ~ ~ ~ ~ i~ ~:t O` O
-C0) LLI
.~ _ _ .

~2~

1~1 _ ~I I~ N __ ¦ I __ .-- ~ IA ~O , C3V) v) I~J ~ ~ ~J ~ ~_ ~J 1`0 ~1 ~ ~\J
01 _ _ _ _ __ _ _ ~E Cl O r) O ~' N O` ~ ~J ~ ~_ 1~1 c_ .
:n ~ _ . _ _O L C~) O O` ~ ~ ~0 N X ~1 CO C~
~ '-: _ _ _ .___ _ o ~ r~l r~J r~ ~o ~ ~ In In r~
_ _ _ ___ __~
_ _ r~ ~ U~ N U~ O N ~0 ~ ~

O
u ~.a In u~ u~ ~ ~ v~ In ~O o~ ~ o~
0~1 ~0 00 00 00 00 : 00 CO 0~ 0~ 00 ~ U
.-- - - - - . - -~ o~ o ~o o o ~o ~ o ~o ~o ~o3 _ _ ~ _ _ _ _ o ~o o o o ~o ~o ~o ~o o ~o ~ ~ m ~: ~ ~ ; ~ C~ ~ ~ ~ ~ ~ ; ~ ~ ~

H j E O N U~ ~ 1/~ S 1~ ~/~ S ¦ O `O
- I ILI _ i _ - 127 ~ t7Z

-- _ O V) N .- (~I ~ ~ ~ O ~

L _ O ,.
,_ O Vo> ~ I~J I~J ~ I 1~1 O

E ~ _ _ t O L V) 11~ IV ) I~ i~J `O ~ t V~
8 ~ C~) ~ ~ N~J ~J ~J O ~J
~ 'S _ U~ ~ O r~) U~ ,_,~
C O ~ ~- N ~J ~-- ~-- -O (~
c, _ '~ a O
~ V~ O O O` ~ ~ `O ~J Q ~
_ L ", f~l ~ ~ `:t ~7 ~,.cC
,~a) ~0~
t~ ~ ~ 00 O` oO O` ~ 1~ ~ E
O~ oo oo 00 00 00 oO t~ a~

a, ~, o o ~ a O ~ ~ ~ ~ ~ ~ ~
,~ ~ 2~ o o o o o .d ~ 3 aJ a E ~ L L L L L 1`0 a ~-- E ~ E aJ E al E a~ E a~ ~ C) c O ~ ,~ aJ E Q~ E ~ E ~ E ~ E ~ E ~
t~ .~ ~ ~I~ V (~ ~, ~ ~, ~ ~ ~ ~, ~ Q
U~ E x tn x E x E X v~ x E x E E a, 'J: LLI llJ llJ ~ UJ Cl ~lJ UJ LL ~ LLJ X X ~ Q) ~C I\~ ~ U~ ~O ~ X ~
~ L ~O ~O ~ ~ L~ ~ lc - 128 - ~ 72 Examples 168 to 172:
The method in Examples 54 to 75 is repeated, except that sizing agent and retention aid are added separately to the dispersion of the fibres, 7% of sizing agent in the liquid or molten state being stirred at 80C together with an aqueous 5% ammonia solution in the presence of water to give a self-emulsifying, likewise pourable, homogeneous and long-shelf-life emulsion and the sizing agent formulations given in Table XII below being formed. The val% shown denote the number of equivalents of ammonia for 100 equivalents based on the number of -COOH groups present in the particular ester or amide mixture used as sizing agent. 10 seconds after 0.5% or 1%
in dry matter of sizing agent have been added, the dispersion of the fibres is admixed with respectively half the amount, i.e.
0.25% or 0.5%, in dry matter of retention aid No. 1, the amounts of sizing agent and retention aid being based on the solids content of the dispersion of the fibres. The sizing results can also be seen from Table XII.

2t~

_ ~3~ ~n 00 ~ ~1 0~ o~
~I _ _ L ~ 00 ~ ~ ~o E ~ r ~ ~ _ _ O L ~ CO O I~ O~ O~
~0 ~ V~ U~ ~ ~ .~ _ 3 _ _ L O I~ ~o ~ ~ ~o L _ _ aJ .
~ V) 00 O~ CO O~ ~

'0~ 00 00 00 ~ CO
~ 0 ~0 ,C ~;~
U ,1 U~ O U~ U~ U~
O ~ O O O
~ .
_~ X~ X`~ CClu C~
C ~ C ~ ~ ~ C ~ C ~) C
O O O O O L
L r EL ~ E ~ ~ E r ~ a~ ~ E
v ~ . Q~ ~ q~ ., n~ a~ S
L~ O ~0 O C O ~ o C ~
o., a~e ~, ~ Q) ~ ~ ~: C~ ~
~., ~ :~ 5 L _ L _ L 11~ _ L
N_ ~ o ~ E ~ E '~ E ~
V) ~ ' ~ O X O ~ ' ~ O X O ~ ~ O
~x j_~
~o oo ~O lo r-X
~ .

Examples 173 to 180:
The method of Examples 54 to 75 is repeated, except that the filler specified in Table XIII below is used and the sizing agent and the retention aid are added separately to the dispersion of the fibres, 15% of sizing agent in powder form being stirred together with an aqueous 5% ammonia solution in the presence of water and glass beads to give self-emulsifying, likewise homogeneous and long-shelf-life sizing agent formulations given in Table XIII below.
The val% shown denote the number of equivalents of ammonia for 100 equivalents based on the number of -COOH groups present in the parti-cular ester or amide mixture used as sizing agent. lO seconds after 0.4% in dry matter of sizing agent has been added, the fibre-bearing liquid is admixed with 0.2% in dry matter of retention aid No. 1. The filler, sizing agent and retention aid amounts are based on the solids content of the dispersion of the fibres.
This also holds for the alum amount. The sizing results are also shown in Table XIII.

. __ c v a ~ ~ ~ ~ o~ o~
~3Co _ _ C ~ U~ l_ ~ ~:t ~) O ~
,~ ~ ~n u) ~ `J ~ r~J O O
~ __ ------1-------- --`_ ~ ~`~ ~- ~ ~ ~
_~ ~ O ~ ~ ~_ ~_ ~_ I`J
r ~o _ _ _.
n c~ - ~ v~ oo ~ o ~o o~ u~
n ~ ~ r~ r~
~J _ _ _ 3 ~_~) Vo) 1~1 ~ ~ `:t 00 O
~-C~ ._ _ _ _ C~) N N N ___ `r o .C ~
U
U~ U~ O O U~ U~
U~ ~ ~0 00 00 0~ U~ U~
~- ~-r~
~ _ , 0~ CO~ So ~0 ~ 1 ~ ~ ~1 ~ U~ `o '' ~ ~0 ~ ~
J ~ _ ~ ~IJ V ~ v ~-_~ 1~ O ~ O ;~J O ~ O r~ ~ ~
_ c,~ ~_ c~ a~- c~ a~^ c~ Jo Jo 1~_ ~0 ~ 0~~0 ~ 0~ ~ O ~0 ~ ~ v v ~> f~ ~ a> ~ ~ ~ ~ :~
O C CQZ O C_ J ~O C J O O~
_ __ a~ ~~ c ~ o a~ ~ c) o c~ c ~ e~ o ~ E ~ O ~ E ~ O
d I~ e~ E ~ E x E .~. E x E
~ ., ., ~u ., ., ro ., ~
0~ E 3 ~ E ~E 3 ~ E ~ E 3 ~ E ~
c~ L ~ a~ ~ o c ~ C~ ~ O C ~ ~ ~ O
o~ ~ o ~ ~ o~ o ~ ~ o a) o a~ ~ o ~3 n ~ r~ .,~ r _ E ~ _ ~ , _ E ~ _ N a ~ s ~ ~ IU ~ :. s H U~ ~~ O ~~ Il~ ~ Lf~ ~O C~ ~ o 11~ ~ O ~, a~ ~O 111Pq _ _ __ alE O r~ ~ u~ ~o ~ oO
n.0 z r~ 1-- ~ 1~ ~ ~

~2~

N ~ C

o g 4 ~ ~0 ~o c~ E
41 q~ ,C d ~ ~ ~
O ~ Ll t~ d d ~ ~1, o Q .~, d QJ ~
_ ~ ~ ,~
'LL ~0 d Q g a) ~ 3 ~

(~ .~J a~LI

A d E 3 ~ X a , ~ ~
~d ~-D ~-O O P~
o d ~ o ~ ~ o . a~
_~ N u~ ~ O Ir~ ~ O _ X~ ~ ~0~ ~ W

7;~

Examples 181 to 184:
The method of Examples 54 to 75 is repeated, except that the sizing agent and the retention aid are added separately to the dispersion of the fibres and that no PERCOL 292 ~ is used as an auxiliary. As the filler, there is added 20% of chaLk to the dispersion of the fibres. The addition of the sizing agent is carried out 10 seconds after the addition of the chalk and the addition of the retention aid 10 seconds after the addition of the sizing agent. As the sizing agents, there are used the emulsions and dispersions which are indicated in the following Table XIV.
Retention aid No. 6 or No. 7 is used instead of one of the retention aids Nos. 1 to 3. Retention aid No. 6 is an epichlorohydrin adduct of a reaction product of dicyanodiamide, diethylene triamine and dimethyl adipate which is prepared as in Example 7 of British Patent 1,125,486. Retention aid No. 7 is a copolymer of adipic acid and di-methylamino hydroxypropyl diethylene triamine, this copolymer having a molecular weight of 1,000 to 10,000. The sizing agents and re-tention aids are used in the amounts which are indicated in the following Table XIV, these amounts and the amount of filler (20% of chalk) being based on dry matter of sizing agent, retention aid and filler and on the solids content of the dispersion of the fibres.
sizing results can also be seen from the following ~able XIV.

- - l34 -D

r~ a~ a) ~ V
S J V~ O r-l r-~1 rl ~ rl a V C r-~ r-~ r~ r-l r~
r r r-l _ ~ d d d ' ' ~1 ~ ~ ~ V~ 00 O ~ ~D
--~ d ~d v~ ~ ~1 ~ ~1 ,c O ~ rC O ~C O C
~1 0 00 ~ 0 O
,0 , ~
V ~r~ $ ~ ~

~d u~ ~) f~ ~`I u~ v d Q' d r O ~1 ~ r_l ~1 t~
JJ _ ~0 0 b~ O d~ ~
r N ~ N ~) N r-l a) r~ d r~
.~ V ~t C5~ r-l O a.) aJ ~ o a) d _ C h C ,~ ,r~
r- 4-1 al 4-1 C~ 4~
a) ~ O ,C O C O v > V ~ ~ 1 ~;t U) U) ~ rl(r~rlrdl rl ~1 1:4 0 ~ 0 4-1 00 CO CO ~ r ~ r ~ r ~

rl _~ _ 4-1 ~ ~ 1:1 4-1 8 d d ~-- u~ o o o ,1 ~ rl ~ rl (IJ
El aJ rl ~ ~ ~ ~ r-l ~ r-l r-~ C
r~ O r-l r Ir-l ~1 ~ 4-1 ~ 4-1 V
r-l Or-l Or-l d rl U~ W3 ~ 3 d ~o ~D ~ ~ d ~ d r~ Z Z Z Z r~ r~ r-l r~l _ __ . U~
4~ r~ ~ r~
v ~d d ~ d v d 00 dl rl d u~ u~ n u~ ~ 3 ~0 3 ~4 ~
N O O O O O V O V O V
~ rC ~d rCI J rC
d o v # o x o x ~ d ,~

oo oo ~.~ oo ~ ~o ~ oo ~ ~ a) ~ a) ~ o t~l rl dl Q rl Q) d, Cl ~J r-l V r-l .LI
00 ~ ~ r~ 1 ~ r-l ~r-~ :~ Q ~ Q ~ 4 d 11 0 h O 1~ ~ ~1 Q~ r~ ~ r-l 13 r-l N ~) C~ rC O ~ O ~ rl r~ r~
r~ ~ (I) ~ ~ ~ ~ ~ rC O
V~ rJ X ~ td 1:1t~ P:l ~rJIJ ~ ~ 111 ~1 . ~ d u~ d u~ d C) nl rl~d rlr~ rl r~) r4 O r ~I ~1 ~ C K
~1 Z; r I _ r-l r~ r-~ # # K

7~

Example 185 and comparative test I
The method of Examples 54 to 75 is repeated, except that the sizing agent and the retention aid are added separately to the dispersion of the fibres and that no PERCOL 292 ~ is used as anaUxiliary~ As the filler, there is added 20% of chalk to the dispersion of the fibres.
The addition of the sizing agent is carried out 10 seconds after the addition of the chalk and the addition of the retention aid 10 seconds after the addition of the sizing agent. As the sizing agents, there is used a 35% dilutable, homogeneous and long-shelf-life formulation of the ester mixture in the molten state obtained according to Method T which is emulsified with 58 val% of sodium hydroxide in the presence of water at 80C. Retention aid No. 8 is used instead of the retention aids Nos. 1 to 3. Retention aid No. 8 is an epichlorohydrin adduct of a poly-N-methyldiallylamine which is prepared as in Example 1 of US Patent 4,279,794. The sizing agents and retention aids are used in the amounts which are indicated in the following Table XV, these amounts and the amount of filler (20% of chalk) being based on dry matter of sizing agent, retention aid and filler and on the solids content of the dispersion of the fibres. The sizing results can be seen from the following Table XV.

In addition, the whitness is assessed by measurement of the re-flectance values according to the standard test T 452 of TAPPI
(Technical Association of the Pulp and Paper Industry). The higher the reflectance values, the better the whitness of the paper.

2~72 __ _~__ E~ ~ r~ ,_ a), u:, ~D
a) _ ~ o ,~ ~
~n ~ ~n __ r~ ~ V~ r~
d __ a~ o ~ .~ U~ ~
_ .,~ 4~ oo ~ oo r~
o~ o o~
d d-- O o _ ~o O N ~\ U~
~ O O

æ .~ c~
~i ~ ~ æ ' DI ~1 0 C~ ~1 ~4 E~

Examples_186 to 188 and comparative test II
The method of Examples 54 to 75 is repeated, except that the sizing agent and the retention aid are added separately to the dispersion of the fibres and that there is additionally used as a fluorescent brightening agent 0.075% of the diethanolamine salt of the 4,4'-bis[2-(di-~-hydroxyethylamino)-4-(p-sulfophenylamino)-1,3,5-triazin(6)-yl-amino]-stilbene-2,2'-disulfonic acid. As the filler, there is added 20% of chalk to the dispersion of the fibres. The addition of the chalk is carried out 1 minute after the addition of the fluorescent brightening agent, the addition of the sizing agent 10 seconds after the addition of the chalk , the addition of the retention aid 10 seconds after the addition of the sizing agent and the addition of PERCOL 292 ~ 10 seconds after the addition of the retention aid. As the sizing agents, there are used the emulsions and dispersions which are indicated in the following Table XVI.
Retention aid No. 8 is used instead of one of the retention aids Nos. 1 to 3. The sizing agents and retention aids are used in the amounts which are indicated in the following Table XVI, these amounts, the amount of fluorescent brightening agent (0.075%) and the amount of filler (20% of chalk) being based on dry matter of fluorescent brightening agent, sizing agent, retention aid and filler and on the solids content of the dispersion of the fibres. The sizing results can also be seen from the following Table XVI.

The whitness is assessed by measurement of the reflectance values according to the standard test T 452 of TAPPI.

- 138 - ~2~ 7~
. _ o U~ ~ ~ C~
a~ ~ ~q ~ ~ ~ ~ O O
~ ~ ~ ~ ,~ ,~ , oo co8 ~ ~ ~ ~ 5 ~1 _ ,n ~
.
. o~o ,~ ~ a~
,_ ~ ~d u~c~l ~ ~ ~ rC ~
~J~ ~ O ~
~0 ~0 ~ ~ ~ O
_, "Q~ U~ ~ ~ O
O ~ ~, ~ ~O O ~1 ~1 ~1 ~1 O ~/ ~0 h bO
.Q~ a~ ~d h L~ ~1 ~ O t~O O ~0 O ~0 h C~ n~ C"~1 ~t 00 I N N N
~ 4J ~ ~ ~
v~ ~ ~ C~l u~ a) o a) a~ aJ o O_I ~1~i ~1 .~
~ ~ g ~ o ~ 3 u~~ ~ ~ O ~ o ~ o a u~ ~ ~ ~ l ~ ~ g~
~ . ~
aJ ~1 ~0 ~ ~0 SJ O O O ~o ~ ~ ~n O ,~
,U~ ~ . o . l ~ .~ ~ 4~ 4 .~ ~ ~ ~ o o o ~ 0 ~ al 1 ~ g ~o~ ~
~e u~ n u~ ~
:~ ~ c~ c~lc~J cn O J~ ~ ~ . O I ~\ I J I ~r~
~ O O O oo ~ 0 ~,1 oO
<~ g 3 g æ g oo . .. _ ,~
#
O oo ~ tn ~
d JJ ~-x~ :c o 'n ota o æ
OO bO -X 1~0 ~ o4 ~1 a) d a) d ~ G
~d d E-l d ~1 d d o.) d O d ,1 ,1~ ,I CJ a)J~ o ~ ~ ~ ~d ~ ~oO r~ CO r~l ~0 d~ o ~ o ~o ~ l ~ ~ E~~ ~
N ~) ~ t.) J ~.) O O O C~
,1 t~ O C.) a) v ~ ~ o ~ a~
,4 ~ x~ ~ .c ~ æ
, _._ JJ 1)0 r ~ r-ld ~
d d ~ u~ u~ u~ ~ dai :1 rl d O OO O r l r r~l rl r a.) C~l . _ t~r~ t~ U~
. C) ~D I~tX~ ~ tnE~ ta E~ tn ~,1 r~~
H O ~ tx) t~tx) . ,1 t~ aJ t~ aJ t~ ~ '' t~) t~ o a) a) O t~ H
r-l ~ z r~l r-lr-l )-I H
~ ~ ~ ~ ~ t~l ~
E~ X ~ o t~ :~ ~ ~q o tl~ # #
~ O t'~ J~ ~1 ~ k~ _ ~ ~ * ~ #

- 139 - ~ 7~

Comparative tests III to V
The method of Examples 112 to 116 is repeated, except that Comparative test III is carried out with 0.5% of retention aid No. S without sizi.ng agent, Comparative IV with 0.5% of the specified sizing agent without retention aid and Comparative test V without sizing agent or retention aid, affcrding only poGr sizing of the paper, as is evident from the WA Cobb values above 100 given in Table 2VII below.

Table XVII

Comparative pH-value WA Cobb30 (g/m2) after drying Test No. of the dis-persion of immediately after 1 day storage _ _ III 8.1 191 154 162 148 .
IV 8 U I73 146 150 124 .

V _ 8.1 240 196 197 176

Claims (34)

What is claimed is:

1. A process for sizing paper or cardboard, which comprises adding to aqueous cellulose-containing dispersions of fibres which optionally contain fillers, in any order or simultaneously, at least (A) a sizing agent which contains at least one anionic or acidic group which is optionally in the form of a salt and at least two hydrophobic substituents which each have at least 5 carbon atoms, at least one of the hydrophobic substituents having at least 8 carbon atoms, and at least two of the most adjacent hydrophobic substituents being bonded to each other with a linking member which has at least 1 carbon atom and 2 hetero atoms, and (B) a polymeric cationic retention aid.

2. A process according to claim 1, in which the component (A) used is a sizing agent which contains at least one anionic or acidic group which is optionally in the form of a salt and at least two hydrophobic substituents which each have at least 8 carbon atoms, at least two of the most adjacent hydrophobic substituents being bonded to each other with a linking member which contains at least 2 hetero atoms.

3. A process according to claim 1, in which the component (A) is a monomeric to oligomeric sizing agent which has at least one anionic or acid group which is optionally in the form of a salt and at least two hydrophobic substituents which each have at least 8 carbon atoms, at least two of the hydrophobic substituents being bonded to each other with a linking member which contains at least 2 hetero atoms.

4. A process to claim 1, in which the component (A) used is a sizing agent whose hydrophobic substituents each have 8 to 22 carbon atoms.

5. A process according to claim 1, in which the component (A) used is a sizing agent which contains 1 to 6 anionic groups which each have one or two negative charges and 2 to 10 hydrophobic substituents, at least two of the most adjacent hydrophobic substi-tuents being bonded to each other with 1 to 5 linking members which each have 4 to 15 carbon atoms and at least two oxygen and/or nitrogen atoms.

6. A process according to claim 1, in which the component (A) used is a a sizing agent which is obtainable by reacting at least (a) an aliphatic alcohol having 3 to 26 carbon atoms and 2 to 6 hydroxyl or hydroxy-C1-C4-alkyl groups optionally 1 to 5 nitrogen atoms and in the presence of 2 hydroxyl groups op-tionally a C6-C22 fatty amine radical, a heterocyclic alcohol or glycide having 3 nitrogen atoms in the hetero ring and 3 hydroxy-C1-C4-alkyl or glycide groups, an alkanediol di-glycide having 2 to 6 carbon atoms in the alkane radical or a diphenol or triphenol or a dihydroxynaphthalene with (b) a fatty acid, the halides thereof or a primary or second-ary fatty amine having 6 to 22 carbon atoms in the fatty radi-cal, and then with (c) a polybasic inorganic or organic acid having 2 to 18 carbon atoms or anhydrides thereof.

7. A process according to claim 1, in which the component (A) used is a sizing agent which is obtainable by reacting at least (a) 1,5-, 1,8-, 2,3- or 2,7-dihydroxynaphthalene, pyrogallol, hydroxy-hydroquinone, phloroglucine, hydroquinone, pyrocatechol, resorcinol, tris(hydroxyethyl) isocyanurate, butane-1,4-dioldiglycide, glycerol, butane-1,2,4-triol, pentaerythritol, sorbitol, sorbitan, triethanol-amine, a C8-C22 fatty amine diethoxylate, N,N,N',N'-tetrakis(2-hydroxy-propyl)ethylemediamine or tris(hydroxymethyl)aminomethane with (b) a fatty acid having 16 to 20 carbon atoms or an alkyl halide or alkenyl halide or a monoalkylamine, dialkylamine, monoalkenylamine or dialkenylamine which has 16 to 20 carbon atoms in the alkyl or alkenyl radical and then with (c) sulfur trioxide, sulfuric acid, chlorosulfonic acid, phosphoric acid, phosphorus pentoxide, phthalic anhydride, succinic anhydride or maleic anhydride.

8. A process according to claim 1, in which the component (A) used is a sizing agent which contains 1 to 4 anionic or acidic groups which each have one or two charges and 2 to 5 hydro-phobic substituents, at least two of the most adjacent hydrophobic substituents being bonded to each other with 1 to 5 linking members which each have 1 to 15 carbon atoms and 2 to 6 nitrogen atoms.

9. A process according to claim 1, in which the component (A) is a sizing agent which is obtainable by reacting at least (a') a polyalkylenepolyamine which is unsubstituted or monosubstituted by N-C6-C22-alkenyl or -alkyl and has 3 to 6 nitrogen atoms and 4 to 40 carbon atoms with (b') a fatty acid or an alkyl isocyanate or alkenyl isocyanate having 6 to 22 carbon atoms, and then with (c') the anhydride of a polybasic inorganic or organic acid having 2 to 18 carbon atoms, a halogenocarboxylic acid or a sultone.

10. A process according to claim 1, in which the component (A) used is a sizing agent which is obtainable by reaction at least (a') N,N'-bis(3-aminopropyl)-4-diaminobutane, N-(3-aminopropyl)-1,4-diaminobutane, 1,2-bis(3-aminopropylamino)ethane, pentaethylenehexamine, tetraethylenepentamine, triethylenetetraamine, dipropylenetriamine or diethylenetriamine with (b') palmitic, stearic, oleic or behenic acid or octadecyl isocyanate and then with (c') 2-chlorobutyric acid, 3- or 2-chloropropionic acid, bromoacetic acid, chloroacetic acid or alkali metal salts thereof, propanesultone, benzophenonetetracarboxylic acid, 1,8-naphthalic acid, trimellitic acid, pyromellitic acid, norbornenedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid or phthalic, succinic, glutaric, maleic, dimethylmaleic, citraconic or itaconic anhydride.

11. A process according to claim 1, in which the com-ponent (A) used is a sizing agent which contains 1 or 2 potential anionic, acidic methylene or methine groups and 2 or 3 hydrophobic substituents, at least two of the most adjacent hydrophobic substi-tuents being bonded to each other with 1 or 2 linking members which each have 1 to 15 carbon atoms and 2 to 4 nitrogen and/or oxygen atoms and the potential anionic, acidic methylene or methine groups being in the form of divalent or trivalent -CH-CO2-CO- or -CO-CH-CO-radicals.

12. A process according to claim 1, in which the component (A) used is a sizing agent which is obtainable by reacting (a") malonic acid, a malonyl dihalide,acetonedicarboxylic acid or a C1-C4-alkyl ester of malonic acid, acetonedicarboxylic acid or methane-tricarboxylic acid with (b1") a fatty alcohol or reacting (a2") cyanoacetic acid or a C1-C4-alkyl ester thereof with (b2") a fatty amine and then with (c") a C4-C12-alkylene, C6-C14-cycloalkylene or C6-C14-arylene diisocyanate.

13. A process according to claim 1, in which the component (A) used is a sizing agent which is obtainable by reacting (a1") malonyl dichloride, the dimethyl or diethyl ester of malonic acid or of acetonedicarboxylic acid or the trimethyl or triethyl ester of methanetricarboxylic acid with (b1") at least one saturated or unsaturated aliphatic alcohol having 8 to 22 carbon atoms.

14. A process according to claim 1, in which the component (A) used is a sizing agent which is obtainable by reacting (a2") methyl or ethyl cyanoacetate with (b2") a monoalkylamine,dialkylamine, monoalkenylamine or dialkenylamine which has 8 to 22 carbon atoms in the alkyl or alkenyl radical and then with (c") butylene diisocyanate, dodecylene diisocyanate, decylene 1,10-di-isocyanate, hexylene 1,6-diisocyanate, cyclohexyl diisocyanate, di-cyclohexyl diisocyanate, naphthylene 1,5-diisocyanate, diphenylmethane 4,4'-diisocyanate, phenylene 1,4-diisocyanate or toluylene 2,4- or 2,6-diisocyanate.

15. A process according to claim 1, in which the com-ponent (A) used is a sizing agent which contains 1 to 6 -COO? or -COOH
groups as anionic or acidic substituents and 2 to 10 hydrophobic sub-stituents, at least two of the most adjacent hydrophobic substituents being bonded to each other with 1 to 5 linking members which each have 4 to 15 carbon atoms and 1 oxygen and 1 nitrogen atom or 2 oxygen or 2 nitrogen atoms.

16. A process according to claim 1, in which the component (A) used is a sizing agent which is obtainable by reacting at least (a"') an aliphatic or aromatic carboxylic acid having at least 3 carboxyl groups, a polyalkylenepolyaminopolyacetic acid having 4 to 6 carboxyl groups or an aliphatic monocarboxylic acid or aminomono-carboxylic acid having 2 hydroxyl groups and (b"') fatty alcohols and/or fatty amines, or, if a monocarboxylic acid is used, fatty acids.

17. A process according to claim 1, in which the component (A) used is a sizing agent which is obtainable by reacting at least (a"') hemimellitic, trimellitic, trimesic, prehnitic, mellophanic, pyromellitic or mellitic acid, benzenepentacarboxylic acid, benzo-phenonetriaarboxylic to benzophenonehexacarboxylic acid or anhydrides thereof, tricarballylic, aconitic or citric acid, bis(2-carboxyethyl)-carboxymethylamine, nitrilotripropionic acid, nitrilotriacetic acid, glyceric acid, 1,2-dihydroxybutyric acid, 1,3- and 2,3-dihydroxyvaleric acid, 2,2-bis(hydroxymethyl)propionic acid, N,N-bis(hydroxyethyl)-.beta.-alanin or N,N-bis(hydroxyethyl)-glycine with (b"') at least one saturated or unsaturated aliphatic alcohol having 8 to 22 carbon atoms and/or a monoalkylamine, dialkylamine, monoalkenyl-amine or dialkenylamine which has 8 to 22 carbon atoms in the alkyl or alkenyl radical or, if a monocarboxylic acid is used as component (a"'), a fatty acid having 8 to 22 carbon atoms.

18. A process according to claim 1, in which the component (A) used is a sizing agent which has a molecular weight of 400 to 3,000.

19. A process according to claim 1, in which the component (A) used is a sizing agent which is at least partly in salt form and is obtainable by additionally reacting with an alkali metal hydroxide, ammonia or an alkylamine, or alkanolamine having a total of at most 6 carbon atoms.

20. A process according to claim 1, in which the com-ponent (B) used is a retention aid which has a molecular weight of 1,000 to 2,000,000.

21. A process according to claim 1, in which the retention aid (B) used is a polyalkyleneimine, an epihalogenohydrin adduct of reaction products of polyalkylenepolyamines and aliphatic dicarboxylic acids or of reaction products of polyalkylenepolyamines, dicyanodiamide and free or alkanol-esterified organic dicarboxylic acids, reaction pro-ducts of dicyanodiamide, forrnaldehyde, ammonium salts of strong in-organic acids and alkylenediamines or polyalkylenepolyamines, cationic-ally modified starches or carbohydrates from carob bean or guar bean flour, reaction products of epihalogenohydrins and polymerised diallyl-amines or copolymers based on polyamide-amines.

22. A process according to claim 1, in which 0.02 to 3 %
by weight of sizing agent (A) and 0.02 to 3 % by weight of retention aid (B) are used, each based on dry matter in (A) and (B) and on the solids content of the dispersion of the fibres.

23. A process according to claim 1, in which the optional fillers used are condensation products of formaldehyde and urea, titanium dioxide, calcium sulfate, talc, kaolin, montolorillonite or chalk.

24. An aqueous composition for carrying out the process according to claim 1, where sizing agent (A) and retention aid (B) are added separately in any order to the dispersion of the fibres, which contains the sizing agent (A) at least partly in the form of salts and optionally customary additives.

25. An aqueous composition for carrying out the process according to claim 1, where sizing agent (A) and retention aid (B) are added simultaneously to the dispersion of the fibres which contains (A) 2 to 40 % by weight of sizing agent, (B) 0.1 to 20 % by weight of retention aid each based on dry matter of (A) and (B) and on the weight of the aque-ous composition, and optionally customary additives.

26. Paper or cardboard which is sized by the process according to claim 1.

27. A compound, or its salts, which can be used as a sizing agent in the process according to claim 1 and is obtainable from an intermediate which has one of the formulae , in which q is an integer from 1 to 5, t is 1 or 2, A3 and A4 each are propylene, isopropylene or ethylene, A5 is branched or unbranched alkyl-ene having 1 to 6 carbon atoms, and R3 each are alkyl or alkenyl having 6 to 22 carbon atoms, R1 and R2 being different from each other if q or t is 7, or which is obtainable by reacting dialkyl ethers or dialkenyl ethers of hydroquinone, resorcinol or pyrocatechol which each have 6 to 22 carbon atoms in the alkyl or alkenyl radical with a polybasic inorganic or or-ganic acid having 2 to 18 carbon atoms, which has one of the formulae in which q is an integer from 1 to 5, t is 1 or 2, Q5, Q6 and Q7 each are or and X is the radical of a polybasic inorganic or organic acid having 2 to 18 carbon atoms, X1 is defined in the same way as X, or, if t ;s 1, is -C0-C6H4-COOH, -CO-(CH2)2-COOH or -CO-CH=CH-COOH, X2 is defined in the same way as X or, if q is 1, ;s -CO-CH=CH-COOH

SO3H, and A3, A4, A5, R1, R2 and R3 are as defined above.

28. A compound which can be used as a sizing agent and is obtainable by reacting the intermediate which is formed by reacting (a1') and (b1'), where (a1') is 1 mol of a poly-alkylenepolyamine which is unsubstituted or monosubstituted by N-C6-C22-alkyl or alkenyl and has 3 to 6 nitrogen atoms and 4 to 40 carbon atoms, and (b1') is 1 to [h"-1] mol(3) of an alkenyl isocyanate or alkyl isocynate having 6 to 22 carbon atoms, [h"] denoting the number of nitrogen atoms of component(a1'), with (c') 1 to [h1"] mol(s) of the anhydride of a polybasic inorganic or organic acid having 2 to 18 carbon atoms, a 2-or 3-halogenocarboxylic acid having 2 to 6 carbon atoms or with a sultone, [h1"] denoting the number of free nitrogen atoms present in the intermediate from (a1') and (b1') which have not been reacted with component (b1').

29. A compound which can be used as a sizing agent in the process ac-cording to claim 1 and is obtainable by reacting (al') 1 mol of a polyalkylenepolyamine having 3 to 6 nitrogen atoms and4 to 20 carbon atoms with (b2') 1 to [h"-1] mol(s) of a fatty acid having 6 to 22 carbon atoms, [h"] denoting the number of nitrogen atoms of component (a'), and then with (c1') 1 to [h2"] mol(s) of pyromellitic, norbornene dicarboxylic, di-methylmaleic or citraconic anhydride, 2-chlorobutyric acid, 2- or 3-chloropropionic acid, bromoacetic acid or propanesultone, [h2"] de-noting the number of free nitrogen atoms present in the intermediate product from (al') and (b2') which are not reacted with component (b2').

30. A compound which can be used as a sizing agent in the process ac-cording to claim 1, which has the formula or in which p" and q" each are 1 or 2, R1", R2", R3" and R4" each are alkyl or alkenyl having 6 to 22 carbon atoms and A1" is cycloalkylene having 6 to 14 carbon atoms, alkylene having 4 to 12 carbon atoms or arylene having 6 to 14 carbon atoms.

31. A compound which can be used as sizing agent in the process ac-cording to claim 1 which has the formula in which m''' and n''' each are 1 or 2, Q3''' and Q4''' each are -O-or -NH- or, if n''' and/or m''' are 2, Q3" and/or Q4''' are , R1''', R1''', R2''' and R2'''' each are alkyl or alkenyl having at least 5 carbon atoms, at least one of the radicals Rl''', R1'''', R2''' and R2''' having 8 to 22 carbon atoms, A1''' is a divalent radical of one of the formulae or, if Q3''' and Q4''' are different from each other, one of the formulae or or, if Q3''' and Q4''' are identical and are -O-or Q3''' and Q4''' are dif-ferent from each other, of the formula and A2''' is a divalent radical of one of the formulae in which X''' is -COOH or -COO? , p''' is an integer from 1 to 4, q''' and q''' each are 1, 2 or 3 and m''', n''', s''' and t''' each are 1 or 2 and Q3''', R11''' and R11'''' are as defined above.

32. A process for the manufacture of the compound of claim 27 or its salts, which comprises reacting l mol of an intermediate of the formulae in which A3, A5, R1, R2, R3 and Q4 are as defined in claim 27 or 1 mol of the intermediate of the formula in which q is 2, 3, 4 or 5 and A3, R1, R2 and R3 are as de-fined in claim 27 or 1 mol of butane-1,2,4-triol with 1 to 2 mols of a polybasic acid of the formula H - X
in which X is as defined in claim 32, or reacting 1 mol of glycerol with 1 to 2 mols of the polybasic acid of the formula H - X1, in which X1 is -CO-C6H4-COOH, -CO-(CH2)2-COOH, -CO-CH=CH-COOH or -SO3H, or reacting 1 mol of the intermediate of the formula in which A3, R1 and R2 are as defined in claim 27, with 1 to 2 mols of the polybasic acid of the formula in which X2 is -CO CH-CH=COOH, SO3H, or reacting 1 mol of the intermediate of the formula or or of the compound of the formula in which R1, R2 and R3 are as defined in claim 27, with 1 to 1.5 mols of chlorosulfonic acid and, optionally converting the reaction product obtained into the correspondings salts.

33. A process for the manufacture of the compound of claim 30;
which comprises reacting 1 mol of a C1-C4-trialkyl methanetricarboxylate with 3 mols of a fatty alcohol of one of the formulae R1" -OH, R2"-OH or R3"-OH, in which R1", R2" and R3" are as defined in claim 30, or reacting 1 mol of the diisocyanate of the formula O=C=N-A1"-N=C-O, in which A1" is as defined in claim 30, with 2 mols of the intermediate of the formula or in which R1", R2", R3", R4", p" and q" are as defined in claim 30.

34. A process for the manufacture of the compound of claim 3l, which comprises reacting 1 mol of a polycarboxylic acid of the formula with 2 to (h'''-OH) mol(s) of a fatty alcohol of the formula R1''' -OH or R2'''-OH
and/or with 2 to (h'''-1) mol(s) of a primary or secondary fatty amine of the formula or or reacting 1 mol of a diol of the formula HO-A2''' -OH

with 2 mols of a fatty acid of the formula R1'''-COOH or R2'''-COOH, in which A1''', A2''', R1''',R1'''', R2''', R2'''' and n are as defined in clairn 31 and h''' is the number of carboxyl groups of the carboxylic acid which is used as starting component.