FI79579B - FOERFARANDE FOER LIMNING AV PAPPER MED ANJONISKA HYDROFOBA LIM OCH MED KATJONISKA RETENTIONSMEDEL. - Google Patents

Description

79579

Method for sizing paper with anionic, hydrophobic sizing and cationic retention aids For sizing paper with anionic hydro-fobal liming and cationic retention media

It is an object of the present invention to provide sizing agents which are readily available to the papermaker and which can be prepared in a simple manner and which, when conventional cationic retention aids are used, are suitable for providing good sizing in the manufacture of paper from fiber suspensions.

According to the invention, this object is achieved by using polymeric, cationic retention agents in the papermaking process with sizing agents having at least two long-chain, hydrophobic substituents and at least one anionic or acidic group, optionally present as a salt.

The present invention therefore relates to a process for gluing paper or board, characterized in that at least A) one sizing agent containing at least one anionic or acidic, optionally salt-containing group and at least two hydrophobic, in each case, is added to the aqueous, optionally filler-containing fiber suspensions. a substituent having at least 5 carbon atoms, wherein the at least one hydrophobic substituent has at least 8 carbon atoms or preferably all hydrophobic groups each have at least 8 carbon atoms, and at least two of the adjacent hydrophobic substituents are linked together by a linker containing at least 1 heteroatom carbon atom, and 2,79579 (B) one polymeric cationic retention agent in any order or simultaneously.

Other objects of the invention are - aqueous compositions for carrying out the paper sizing process, which, if the sizing agent (A) and the retention agent (B) are arbitrarily added separately to the fiber suspension, with optional conventional additives, the sizing agent (A) alone present at least in part in the form of salts, or (A) and the retention aid (B) are added to the fiber suspension at the same time as the sizing agent (A), which may be present at least in part in salt form, and the optional conventional additives for the retention agent (B), - paper or board glued according to the process of the invention, and ) for gluing paper or paperboard.

Representatives of the disclosed sizing agents (A) are partly known compounds, partly new compounds. The use of compounds known per se is new. If the sizing agents are new compounds, they together with the process for their preparation form other objects of the above invention.

The essential feature of the sizing agents (A) used according to the invention is 1 to 6, in particular 1 to 4, preferably 1 or 2, in particular one anionic or acidic group, which generally contain one or two negative charges in each case. For example, in decomposed phosphates there are / ° 0e or _ / _ oh \) θ resp. > oh as acidic groups 2 negative charges, while in acid- (Z? \ which sulphates -SO 2 'or -SO 2 H or in carboxyl groups -COC 2 or COOH there is only one negative charge. In another embodiment, the sizing agent ( A) preferably 1 or 2 potentially anionic, acidic methylene or methine groups The ability of anionic or acidic groups to contain or form an anionic acid in an aqueous medium and is another essential characteristic of an adhesive The formation of anions occurs in the papermaking of fiber suspensions. Under said conditions, the cationic retention aids (B) may likewise form cations. a cationic-siks i detention.

Another characteristic feature of the sizing agents (A) is 2-10, preferably 2-6, especially 2 or 3 hydrophobic substituents containing only carbon and hydrogen atoms and having at least 5, preferably 8-22, especially 16-20 carbon atoms, e.g. C 1 -C 6 cycloalkyl, C 8 -C 10 aryl, further alkaryl or aralkyl radicals. Preferred substituents are open-chain alkyl or alkenyl radicals, which are generally due to unsaturated or, above all, saturated fatty alcohols, fatty amines or fatty acids having from 8 to 22 carbon atoms. The manner in which these hydrophobic substituents are joined together constitutes a further feature of the sizing agents (A). Namely, in a particular embodiment of the sizing agents (A), the linking members through which the at least two hydrophobic substituents are combined preferably have 4 to 15 carbon atoms and at least 2 heteroatoms, preferably at least two oxygen and / or nitrogen atoms.

In any carboxyl or amide residues

0 HO

1 i I

(-C-O- or -N-C-) as heteroatoms is, for example, one oxygen atom or one nitrogen atom part of the linking member.

4 79579 π

Depending on the amount of hydrophobic substituents, the sizing agents contain 1 to 5, preferably 1 to 3 such linking members.

The preferred linkers generally correspond to one of the formulas (1) -Qr <°> n-rAr <o) m-r02- _.

(2) -O-A2-O-, wherein n and m in each case denote 1 or 2, denote a divalent, aliphatic or cycloaliphatic residue, A2 denotes a divalent aromatic residue and Q1 and Q2 are different or preferably similar and denote by CQ_ / /, if n and m are 1, the group -NH-, -N or -N, or if n and m are 2, especially the group -Cr, where n and m preferably denote the number 2.

In formula (1), residue A 1 forms part of an aromatic, preferably aliphatic or cycloaliphatic bridging member containing preferably 1 or 2, in particular one anionic or acidic group and optionally 1-5, preferably

1, 2 or 3 nitrogen atoms. Examples are the 0 O of the formulas

li I

(3) - C - O - CH2 - CH - CH2 - (CH2) t_1 - O - c -, 4x c = o 0 0 CH- 0 TI 2 i (4) - C - 0 - CH2 - C - CH2 - 0 - C -,

CH0 I 1 OX

0 / \ -C CH- 0 i: l 2 n (5) N - C - CH- - 0 - C -, i * 9H2

OX

5 79579 o o f -I li (6) - C - O - A3 - - N - A4 - -N - A3 - O - C -, A-, A,

I J I J

0 ox c = o

I I

q-1 / A3- ° -

(7) -N

na3-o- (O) r ·,

./V

(8) Xt— —it ~ ·

'vV

, 9> (Äo- 'o il c (10) -C-O-A, -N // XN-A.-O-C-i 3 I i 3 il O 0 = C C = 0 o ν'

i3-OX

0

OH Ji OH

I / \ I

(11) -NH-CH2-CH-CH2-N N-CH2-CH-CH2 "NH-, 0 => 0 CH0-CH-CH0-N- 2 l 2 i

OH X

* 79579 o 1]

OH C OH

(12) -Q ^ -CH.-CH-CH »- / VcH, -CH-CH.-Q, -, 3 2 2 ·, | 2 2 3 'O = C C = O' n 'CH2-CH-CH2-Q3- ox

OH. OH X

(13) -HN - CH2 - CH - CH2 - O - A5 - O - CH2 - CH - CH2 "N - or

OH OX

(14) Bridge members according to Q3 - CH2 - CH - CH2 - O - A5 - O - CH2 - Ah - CH2 - Q3, where t is 1 or 2, q is 1-5, preferably 1-3, A ^ and A 1 each represents propylene, isopropylene or ethylene, A 1. represents an optionally branched alkylene having 1 to 6 carbon atoms, X is an anionic or acidic group and / CO- / Q3 represents a group -N, -N or -O-C 1-4;

Very significant sizing agents (A) are those which can be prepared by a) aliphatic alcohol having 3 to 26 carbon atoms and 2 to 6, preferably 2 to 4 hydroxyl or hydroxy-C 1 -C 4 alkyl groups and having optionally 1-5, preferably 1,2 or 3 nitrogen atoms and in the presence of 2 hydroxyl groups optionally one C8-C22- 'preferred C8-C22-' especially 6-C22 fatty amine residue, heterocyclic alcohol or glycide preferably having 3 nitrogen atoms in the hetero- in the ring and three hydroxy-C 1 -C 4 -alkyl or glycidyl groups, an alkanediol diglycide having 2 to 6 carbon atoms in the alkane residue or a di- or triphenol or dihydroxynaphthalene to react.

7 79579 (b) with an optionally unsaturated fatty acid or its halides or a primary or secondary fatty amine having from 6 to 22, preferably from 8 to 22, in particular from 16 to 20 carbon atoms in the fatty residue, and (c) from a polybasic, inorganic or organic, 2 - 18, preferably with an acid having 4 to 9 carbon atoms or its anhydrides.

Examples of specific representatives of the components (a) from which the sizing agent (A) can be prepared include 1,5-, 1,8-, 2,3- and 2,7-dihydronaphthalene, pyrogallol, hydroxyhydroquinone, phloroglucin, dihydroxynaphthalenes and di- or triphenols. hydroquinone and especially pyrocatechol and resorcinol, as heterocyclic alcohols or glycides especially tris (hydroxyethyl) isocyanurate and isocyanuric acid triglycide; water), especially butane-1,2,4-triol, glycerin, pentraerythritol, tri (hydroxymethyl) aminomethane, trialkanolamines such as triethanolamine,

C 8 -C 18 fatty amine dialkylates such as laurylamine diethoxylate and polyhydroxyalkyl polyalkylene polyamines such as N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine.

Aliphatic alcohols are considered to be the preferred component (a) over dihydroxynaphthalenes, di- or tridenols, heterocyclic alcohols or glycides or alkanediol diglycides.

Adhesives (A) having a bridge member of formula (3) may be prepared from butane-1,2,4-triols or glycerin, pentaerythritol containing a bridge member of formula (4), tris- (hydroxymethyl) containing bridges of formula (5) aminomethane, a bridged amine diacalkoxy containing a bridging member of formula (6) or a polyhydroxyalkyl polyalkylene polyamine, a bridging member of formula (7) containing a trialkanolamine, a bridging member of formula (8) containing a di- or trigenol 9) containing a bridging member of dihydroxynaphthalene, a bridging member of formula (10) containing tris- (hydroxyalkyl) isocyanurate, a bridging member of formula (11) or (12) containing an isocyanuric acid triglycide, and a bridging member of formula (13) or (14) containing an alkane alkane.

Suitable components (b) from which the sizing agent (A) can be prepared are, in particular, optionally unsaturated fatty acids having 6 to 22, preferably 8 to 22, in particular 16 to 20 carbon atoms, their halides or, as secondary fatty amines, mono- or dialkyl amines or mono- or dialkenylamines in each case with 6 to 22, preferably 8 to 22, in particular 16 to 20 carbon atoms in the alkyl or alkenyl residue. Suitable unsaturated or saturated C6-C22 fatty acids, in particular c8-C22 fatty acids, are suitable as component (b), e.g. caproic acid, preferably caprylic, capric and arachic acid, in particular lauric, myristicin -, palmitic stearic and behenic acid or myristoleic, palmitoleic, eleostearic, clupanodonic acid, especially oleic, elaidic, erucic, linoleic and linolenic acid. In this case, lauric, palmitic, stearic, oleic and behenic acids are very important, with stearic acid being preferred. Technical, easily available mixtures of the just mentioned acids are also possible. Unsaturated or preferably saturated fatty acid halides, i. alkyl or alkenyl halides, mono- or dialkylamines or mono- or dialkenylamines are structurally derived from the above-mentioned fatty acids. Suitable alkyl or alkenyl halides are, in particular, chlorides or, in particular, bromides. Specific representatives of mono- or dialkylamines or alkyl halides containing 6-C20-alkyl radicals include, due to their good availability, dioctadecylamine, in particular octadecylamine and octadecyl bromide. Technical mixtures of the corresponding alkyl halides of such fatty amines are also possible.

Examples of specific representatives of component (c) include, in particular, sulfur trioxide, sulfuric acid, phosphoric acid, trimellitic anhydride, phthalic anhydride, gluric anhydride and especially chlorosulfonic acid, phosphorus pentoxide, succinic anhydride and leucic anhydride. Thus, as the future substituent X in the formulas (3) to (14), the acidic groups -CO-C6H4-COOH, -CO- (CH2) 2-cooh, -co-ch = ch-cooh, o

-P-OH or -SO, H

\ 3 OH

The reaction products obtained from components (a) and (b) are intermediates from which sizing agents (A) can be prepared by using component (c) together. Whether a fatty acid, a fatty amine, a fatty acid anhydride or an alkyl or alkenyl halide is to be used as component (b) will be apparent to one skilled in the art as to the nature of component (a) used. When di- or triphenol or dihydroxynaphthalene is used as component (a), an alkyl or alkenyl halide is used as component (b), while when an aliphatic or heterocyclic alcohol is used as component (a), a fatty acid is generally used as component (b). In contrast, when a heterocyclic glycide or an alkane diol diglycide is used as component (a), it is possible to use both fatty amines and fatty acids.

When di- or triphenol or dihydroxynaphthalene is used as component (a), it is preferable to use (h) moles of alkyl or alkenyl halide as component (b) per mole of component (a), wherein (h) denotes the number of hydroxyl groups of component (a). Thus, in this case, hydroxyl-free aromatic di- or triethers are obtained as intermediates, from which 1-2, 10 79579, preferably 1 to 1.5, in particular 1 mole of component (c) per mole of starting component (a), are obtained as sizing agents (A). Since the reaction of component (c) takes place in the aromatic nucleus of a fatty acid or triether, it is preferable to use sulfuric acid, sulfur trioxide or especially chlorosulfonic acid as component (c). Thus, in one of their preferred embodiments, sizing agents (A) are obtained by reacting at least (a) 1 mole of di- or triphenol or dihydroxynaphthalene with (b) (h) moles of alkyl having from 6 to 22, preferably from 8 to 22, especially from 16 to 20 carbon atoms. or an alkenyl halide, wherein (h) represents the number of hydroxyl groups of component (a) and (c) 1-2, preferably 1 to 1.5, especially 1 mole of chlorosulfonic acid, with component (c) being added last.

When a heterocyclic glycide or an alkanediol diglycide is used as component (a), (h ') moles of fatty acid and / or primary or secondary fatty amine are preferably used, wherein (h1) denotes the number of glycine groups of component (a). Thus, in this case, heterocyclic compounds or alkanes can be prepared as intermediates with β-hydroxy-γ-fatty acid propyl groups, primary or secondary β-hydroxy-γ-fatty amino-propyl groups or β-hydroxy-γ-bis (fatty amino) -propyl groups or secondary β-hydroxy-γ-fatty acid amido-propyl groups. Heterocyclic compounds preferably have 3 such groups as intermediates and alkanes as intermediates 2 such groups contained in e.g. bridging members of formulas (11) to (14). From such intermediates, sizing agents (A) are obtained using 1-2, preferably 1 to 1.5, in particular 1 mole of component (c) per mole of starting component (a), in which case all the above-mentioned polybasic, inorganic or organic, 2- Special representatives of acids containing 8 carbon atoms or their anhydrides.

n 79579

If the intermediate is prepared from component (a) using a primary fatty amine as component (b) and therefore has primary β-hydroxy-γ-fatty aminopropyl groups, the reaction of component (c) generally occurs with the hydrogen atom of the NH residue of such groups. If, on the other hand, the intermediate is prepared from component (a) a fatty acid or a secondary fatty amine, i.

With a dialkyl or dialkenylamine containing 6 to 22 carbon atoms, or a primary fatty amine, i.e. C6-C22-alkyl-ta * -alkylamine and having β-hydroxy-γ-fatty acid ester propyl groups, β-hydroxy-γ-bis (fatty amino) propyl groups or β-hydroxy-γ-fatty acid amido-propyl groups, the reaction of component (c) generally takes place with the hydrogen atom of the B-hydroxyl residue of such groups.

In another preferred embodiment, the sizing agents (A) are thus prepared by introducing at least (a) 1 mole of a heterocyclic, preferably 3 nitrogen atoms in the heterocycle and 3 glycide group glycides, especially isocyanuric acid triglyceride or preferably 2-6 carbon atoms in the alkane residue, 4-diol di-glycide to react with a mole of (b) (h) a primary or secondary fatty amine having in each case a fatty acid having 6-22, preferably 8-22, in particular 16-22 carbon atoms in the fatty residue, where fh ') denotes component (a) ) the number of glycide groups, and then (c) 1-2, preferably 1-1.5 especially with 1 mole of a polybasic, inorganic or organic acid having 2 to 8 carbon atoms or its anhydride, with component (c) being added last.

When a heterocyclic or aliphatic alcohol is preferably used as component (a), (h-1) mole of fatty acid is preferably used, wherein (h) denotes the number of hydroxyl groups of component (a). For example, if 2 hydroxyl groups and an aliphatic alcohol containing 79279 of one fatty amine residue are used, then 1 mole of fatty acid is used as component (b) per mole of component (a).

If, on the other hand, a heterocyclic alcohol containing 3 heteroatoms is used as component (a), then 2 moles of fatty acid are used as component (b) per mole of component (a). When aliphatic alcohols containing 3 or 4 hydroxyl groups are preferably used as component (a), 2 or 3 moles of fatty acid are used as component (b) per mole of component (a). The intermediates obtained from components (a) and (b) are, if alcohols of the type shown are used as component (a), partially esterified compounds, i.e. partial esters with another non-esterified hydroxyl group. These products can be obtained by using 1 to 2 moles, preferably 1 to 1.5 moles, especially 1 mole of component (c) per mole of the starting component (a) of sizing agents (A), wherein component (c) constitutes components (a) and (b) acidic esters with the hydroxyl group of the intermediates prepared and all the above-mentioned representatives of polybasic, inorganic or organic acids having 2 to 8 carbon atoms or their anhydrides can be used as component (c).

In a highly preferred embodiment, the sizing agents (A) can thus be prepared by introducing at least (a) 1 mole of an aliphatic alcohol having 3 to 26 carbon atoms, 2-6, preferably 2-4 hydroxyl groups and optionally 1-5, preferably 1, 2 or 3 a nitrogen atom and, in the presence of 2 hydroxyl groups, optionally a C 1 -C 22 ~ 'preferably C 8 -C 22 ~', preferably a C 8 -C 20 fatty amine residue, to react with (b) (h-1) moles of unsaturated or preferably saturated, 6-22 , preferably a fatty acid having 8 to 22, especially 16 to 20 carbon atoms, or a mixture thereof, wherein (h) represents the number of hydroxyl groups of component (a), and then 13,79579 (c) 1 to 2, preferably 1 to 1.5, especially with 1 mole of a polybasic, inorganic or organic acid having 2 to 18 carbon atoms or an anhydride, the polybasic acid being used as component (c) last and forming acids with the hydroxyl groups present in the intermediates prepared from components (a) and (b) esters.

Of particular importance are acid esters as sizing agents (A) obtained by reacting intermediates obtained from 1 mole of laurylamine diethoxylate and 1 mole of Behen's acid, 1 mole of glycerin, triethanolamine or tris- (hydroxymethyl) aminomethane and 2 moles of stearic acid. and an equimolar mixture of palmitic acid or 1 mole of pentaorythritol, or N, N, N ', Ν'-tetrakis (2-hydroxypropyl) -ethylenediamine and 3 moles of stearic acid, respectively reacting chlorosulfonic acid, phosphorus pentoxide or maleic acid with.

Preference is given to sizing agents (A) obtained by reacting (a) 1 mole of triethanolamine or in particular 1 mole of glycerin with (b) 2 moles of stearic acid and then (c) reacting with 1 mole of phosphorus pentoxide or, above all, by (a) 1 mole of tris ( hydroxymethyl) aminomethane to react with (b) 2 moles of stearic acid and then (c) with 1-1.5 moles of maleic anhydride.

Other sizing agents of interest can be prepared by transesterification of sulfosuccinic acid-based surfactants, e.g., sulfosuccinic acid isooctyl ester, with a fatty alcohol.

Preferred sizing agents (A) from components (a), (b) and (c) or surfactants of the type shown have molecular weights of from about 400 to about 3000, preferably from 14 to 79579 from about 600 to 1500 and an acid number (mg KOH / g substance) about 15 - n.

150, preferably about 35 to about 125.

As mentioned above, the compounds used as sizing agents according to the invention as well as the intermediates from which these sizing agents can be obtained are partly known.

Thus, for example, German Pat. No. 733,689 discloses intermediates made from triethanolamine and stearic acid which still have at least one free hydroxyl group, this hydroxyl group being optionally esterified with phthalic anhydride. However, this publication does not disclose any intermediates prepared from two different fatty acids. As polybasic acids or their anhydrides for the preparation of acidic esters, in addition to aromatic acids such as phthalic acid and their isomers and naphthalic acid, only tartaric and succinic acid are mentioned.

Other intermediates made from glycerol and stearic acid are disclosed, for example, in German Patent Publication 193,189, which has one free hydroxyl group, this hydroxyl group being optionally esterified with phosphorus pentoxide. In addition to phosphorus pentoxide for the preparation of acidic esters, no other polybasic acids or their anhydrides are mentioned in this publication.

The two German patents mentioned also do not contain any information on the use of the published compounds as paper sizing agents.

In addition, U.S. Patent 2,504,951 discloses 2-heptadecyl-bis- (4-stearyloxymethyl) -2-oxazoline prepared from 1 mole of tris (hydroxymethyl) aminomethane and 3 moles of stearic acid. However, there is no information in this patent publication about 2 moles of tris (hydroxymethyl) aminomethane and 2 moles (instead of 3 moles) of stearic acid prepared from 2-heptadecyl-4-hydroxymethyl-4-stearoyloxymethyl-2-oxazoline or the intended use of the disclosed oxazoline.

is 79579

Finally, reference is made to U.S. Patent 2,067,960, which discloses 2- to 1-4 alkyl diethers of hydroquinone, resorcinol or pyrocatechol. However, it does not disclose any information on the reaction products of such ethers with polybasic inorganic or C 2 -C 8 organic acids or their anhydrides or their use as a paper sizing agent.

German patent application 2,162,620 further discloses end products made from sulfosuccinic acid-based ten-binders, but makes no mention of their use as adhesives.

The invention therefore also relates to new intermediates from which the sizing agents (A) used according to the invention can be prepared and which correspond to one of the formulas? 1 Γ- 0 - CH2

Λ - * j- O - CH

(15) r o "(ch2) J

r2 - c -j o-CH2 j l> -j o il R1 - C - O - CH2

° X

(16) li \ '' R2 - c - O - CH2-C - CH2-oh, 0 / r3 - i - O - CH2 ^

(17) R, - 6 CH 'O

1 il I 1 h N_C - CH- - O - C - R „, (!: H2oh, 6 79579

0 '- O - A3 - (- - N - Ä4 - N - A3 - O

(1S) R - έ - * 3 Α3 1 0 0 I- Η | · c = 0 C = 0 __ R3 R2 / A3 "0H 0 (19) R] _ N \ a3 - o - <ϋ - R2 .. 0-R ..

X 1 (20) 1 H> -0_r xx 2

n0-R3 '' \ / N

<21) \ 4 — Xo-R,

\ ./ \. X

o-R2 o

II

o c o (22) R-1 - C - O- A3 - / SN - A3 - O - ci - R2,

o = c C = 0 N

Ä3-oh o

(23) OH * OH

Q4 ~ CH2 ~ CH ~ CH2 - - CH2 - CH - CH2 - Q4 or 0 = C C = 0 'n' <^ H2 - CH - CH2 -Q4

OH

17 79579

OH OH

l) (24) Q4 - CH2 - CH - CH2 - O - Ag - O - CH2 - CH ~ CH2 - Q4 wherein q is an integer from 1 to 5, preferably from 1 to 3, especially 1, t is 1 or 2, and A4 in each case denote propylene, isopropylene or ethylene, Ag represents an optionally branched alkylene having 1 to 6 carbon atoms, q4 denotes the group H CO-R, R "/ / 1/1 Q" -N, -N, -N or -OCR. and R 1, R 2, R 2, R 2, R 2 and R 2 are different or preferably similar and each represents 6 to 22, preferably 8 to 22, especially alkyl or alkenyl having 16 to 20 carbon atoms, wherein in the formula (15 ) and (18) R 1 and R 2 are different if q and t are 1.

The process for the preparation of intermediates of formulas (15) to (24) is likewise the subject of the invention and is characterized in that (1) 1 mole of butane-1,2,4-triol, pentaerythritol, tris (hydroxymethyl) aminomethane or of formula

(25) HO - A3 - (N3 - A4) q-1 -N - A3 - OH

a3 a3

6h OH

wherein Q, A3 and A4 have the meanings given, in particular Ν, Ν, Ν ', Ν'-tetrakis (2-hydroxypropyl) -ethylenediamine or

^ A3 ° H

(26) A compound according to R - N 'a3-oh, 8 79579 · / in which the substituents R1 and A3 have the meanings given, in particular a C8-C22 fatty amine diethoxylate, or a compound of formula 0i

ΗΟ-Α, -Ν N-A, OH

(Z /) 3 j i 3 o = c c = o XN /

A3-OH

wherein the substituent A3 has the meanings given, in particular tris (hydroxyethyl) isocyanurate is reacted with a mole of (b) (h1) of formula (28) R1 to COOH, (29) R2 to COOH and / or (30) R3 to COOH , wherein the substituents R 1, R 2 and R 3 have the meanings given for the substituents R 1, R 2 and R 3 and (h) denotes the number of hydroxyl groups of component (a) or (a) 1 mol of pyrigallol, hydroxyhydroquinone, phlogoglucin or dihydroxynaphthalene is reacted ) (h1) an alkenyl or, preferably, an alkyl halide of the formulas (31) Rx to Z1, (32) R2 to Z2 and / or (33) R3 to Z3, wherein R1, R2, R3 and h have the meanings given and Z and Z3 in each case denote halogen, preferably chlorine, in particular bromine, or is 79579 8A9 1 mol of isocyanuric acid triglyceride or 1 mol of the formula 0 0 '' s \ (34) CH2 ~ CH - CH2 - 0 -A5 - 0 - CH2-CH - CH 2, wherein the substituent A 1 represents me butanediol diglycide is reacted with a mole of (b) (h1) a fatty acid of formula (26) or a primary fatty amine of formula (35) R1 to NH2 or

R1, (36) 'NH,

S

A secondary fatty amine of formula R2 wherein the substituents 1a and R2 have the meanings given, or (h1) a mole of a primary fatty amine of formula (33) followed by (h ') a mole of a fatty acid of formula (26) wherein ( h ') denotes the number of glycide groups of component (a).

The invention also relates to novel compounds or their salts which can be prepared from intermediates of the formulas (15) to (24) to be prepared from components (a) and (b) or from dialkyl ethers or dialkenyl ethers of hydroquinone, resorcinol or pyrocatechol having in each case 6 to 22, preferably 8 to 22, especially 16 to 20 carbon atoms in an alkyl or alkenyl residue, and a polybasic, inorganic or organic acid having 2 to 18 carbon atoms as component (c) and which can be used according to the invention as sizing agents (A) and corresponding to one of formulas 2o 79579 Γ 0 - O - CH »

(37) LR1 'C J - O - CH

0 Ί (CH2 ^ t-1 'r2 - c - - O - CH2 (Xf) o

K

R1 - C - O - CH2 Q \ H \ (38) R2 - C - O - ch2-c - ch2 - OX, 9 r3 - & - O - CH2 o (39) S v

R - C CH »O

ii I 2 II

N - C - CH2 - O - C - R2, i: H2 - ox 0 -O - A »- (N - A.), - N - A» - O - RC- 3 '4 q -1 \ 3 ( 40) 1 A »A, ij I -5 (x2 -)? ? Λ c = o c = o R3 R2

A, - OX

/ 3 o (41) R - N „N a3 - O - C - r2 O-Rj ^ ΙΙΕ.Λ ^ (0-RoL n, (42) HS03-f —fj- 3 t-1 \ .x 0- R2 2i 79579 (43)., OR, y \ M / 2 / - * - j ~ SO3H,

\ .ax

XoR2 0 0 6 0 -Ί ^ v il (44) R. - C - 0 - A- - N N-Aq-0-CR „, 1 3 o = c fc = o 3 2" ν '"λ3-οχ o I /

OH C OH

i / \ 1 (45) R1 - NH - CH2- CH - CH2 ~ N N - CH2 ~ CH - CH2 ~ NH - R2 0 = C C = 0 '/

OF

CH- - CH - CH- - N - R, 2 6h 2 k 3 0/1

OH C OH

I X \ I

(46) Q_ - CH- - CH - CH- - N N - CH- - CH - CH- - Q

j 2 έ j j 2. A

o = c c = o \ /

OF

CH - CH-CH - Q7 2 t 2

OX

(47)

OH OH X

i L I

R1 - NH - CH2 - CH - CH2 - 0 - A5 - 0 - CH2 - CH - CH2 - N-R2

or OH OX

(48) q5 - ch2 - ίη - ch2 - 0 - a5 - 0 - ch2 - ch - ch2- q6 where q is an integer from 1 to 5, t is 1 or 2, Q5, Qg and each denote a group 22 79579 CO-R1 R 1/1 / '-N, -N or -O to C - R 1 R 0 ^ R- w' 2 2 0

X is a basic residue of an inorganic or organic acid having 2 to 18, preferably 4 to 9 carbon atoms, the substituent has the meanings given for the substituent X or, if t is 1, it represents the group -CO-C 9 H 4 -COOH, -CO-tCl -COOH, -CO-CH = CH-C00H or -SO2H, the substituent X2 has the meanings given for the substituent X, if q is 1, it denotes the groups -CO-CH = CH-C00H, -P-OH

H) or -SO 2 H, and the substituents A 1, A 2, A 2, R 2, R 2 and R 2 have the meanings given in each case.

The process for the preparation of the novel compounds of the formulas (37) to (48) and their salts also forms part of the invention. This process is characterized in that 1 mole of an intermediate of formulas (16), (17), (19), (22), (23), (24) or 1 mole of an intermediate of formula (15) wherein q is 2, 3, 4 or 5, is reacted with a formula

(49) H - X

with a polybasic acid 1-2, preferably 1 to 1.5, especially 1 mole of the polybasic acid used as component (c), wherein in this formula the substituent X has the meanings given, or 1 mole of the intermediate of formula (15) in which t is 1, to react with an acid of formula (50) H to X1 used as component (c) 1-2, preferably 1 to 1.5, especially 1 mole, wherein in this formula X 1 represents a group -CO-C 6 H 4 -COOH, -CO- ( CH 2) 2, -CO-CH = CH-C 10 H or -SO 2 H, or 1 mole of an intermediate of formula (18) wherein q is 1 and R 1 and R 2 are different or · preferably the same are reacted with 23,79579 H - X2 of formula (51)

with a polybasic acid used as component (c) according to the formula 1-2, preferably 1 to 1.5, especially 1 mole, wherein in this formula X_ represents a group - CO-CH = CH-COOH, yO

-P-OH or -SO-.H, or 1 mole of formula (20) or (21 = - '' OH

An intermediate or a compound of the formula O-R1 (52) 2 -R 2 in which the substituents R 1 and R 2 in each case have the meanings given in each case is reacted with 1-2 moles of the chlorosulfonic acid used as component (c), preferably 1 to 1.5, especially with 1 mole, and the reaction products obtained are optionally converted into the corresponding salts.

When reacting aliphatic or heterocyclic compounds of formulas (15) to (19) or (22) to (24) as intermediates with acids of formulas (49), (50) or (51) used as component (c), reacts with compounds of formulas (15) - a free hydroxyl group of the compounds of formula (19) or (22) or at least one of the free hydroxyl groups of the compounds of formula (23) or (24) present with a compound of formula (49, (50) or (51) so as to form acidic esters In contrast, if aromatic compounds of formula (20) or (21) are used as intermediates or compounds of formula (52) as starting materials, the reaction with the chlorosulfonic acid used as component (c) takes place in the aromatic nucleus of said intermediates or starting materials.

Preferably, a process for the preparation of intermediates and acidic esters consisting of components (a) 24 79579 and (b) is carried out by further reacting with component (c) in the presence of solvents, which must be present in both each starting component (a), (b) or (c) and each. intermediate or final product, i.e. inert to the reaction products consisting of components (a) and (b) and (a), (b) and (c). Suitable solvents are, in particular, possibly halogenated hydrocarbons having a boiling point of not more than 140 ° C. When reacting components (a) and (b), hydrocarbons having a boiling point of about 110 ° C to about 140 ° C, such as toluene, chlorobenzene, o-, m- and p-xylene, a technical mixture of xylene or also a mixture of said xylenes, are preferably used. mixtures of hydrocarbons. When further reacting the intermediates of components (a) and (b) with component (c), in addition to hydrocarbons of the type in question, hydrocarbons boiling at low temperature, e.g. about 40 to about 80 ° C, preferably halogenated, e.g. ethane or carbon tetrachloride. As elevated temperatures for reacting components (a) and (b), temperatures of 100 to 140 ° C are suitable, and for further reacting with component (c), the temperatures are room temperature (15 to 25 ° C) to about 40 to 80 ° C. C very good.

It is further preferred to carry out above all the reaction of components (a) and (b) in the presence of a catalyst which, if necessary, accelerates the esterification reaction.

Suitable catalysts are inorganic acids, such as, for example, hydrochloric acid, sulfuric acid, phosphoric acid, in particular organic acids, such as, for example, organic sulfonic acids and, in particular, p-toluenesulfonic acid. Suitably, e.g. 1 to 4% of this catalyst per mole of component (a) is used.

To prevent polymerization in the preparation of acidic esters containing a reactive C = C double bond, the esterification with component (c) can be preferably carried out under an inert nitrogen atmosphere. This applies in particular to the use of highly reactive components, such as, for example, maleic acid. In this case, or also when using unsaturated components (b), such as, for example, oleic acid, it is preferable to use, in particular at higher temperatures, a polymer inhibitor. Examples of such inhibitors are methylene blue, benzthiazine or especially hydroquinone. Suitably 0.1 to 0.3% of this inhibitor is used per mole of unsaturated components (b) or (c).

In another preferred embodiment, the sizing agents used according to the invention (a) e.g. contain, in addition to acidic phosphates or sulphates or carboxyl groups, as anionic or acidic groups and preferably 2-5, in particular 2 hydrophobic substituents of the type shown, divalent linkers through which at least two adjacent hydrophobic substituents are joined together and preferably have 1 to 15, especially 2 to 4 carbon atoms and at least 2 heteroatoms, preferably 2 to 6, especially 2 nitrogen atoms. Depending on the number of hydrophobic substituents, such sizing agents contain 1 to 5, preferably 1 to 3, especially one linking member of the type shown.

The preferred connecting members correspond in their simplest embodiment to formula I)

(53) -Qj_ - N - A £ - N - QJ

wherein ethylene, propylene or butylene and Q | and each represents a direct bond, -CO- or -CH-NH-.

The linking members of formula (53) are moieties of bridging members having at least one nitrogen-bonded, anionic or acidic group and corresponding to formula 26 79 579 (54) -N - A '- (N - A'), - N - A'-

I i Y I

? 3? Wherein A 1 and A 1, and A 2 each represent ethylene, propylene or butylene, at least one of the radicals Q 1, Q 1 and represents a group -CO-, -CO-NH- or a direct bond, X ' represents an anionic or acidic group or a residue containing such a group and Y 'is an integer from 1 to 5.

In the formula (54), the figure 2 and above all the figure 1 are preferred as the meanings of the symbol y '. In addition, the substituents A 1 and F 2 and Ag preferably have the same meanings and mean, above all, propylene and in particular ethylene.

The preferred bridge members thus correspond to the formula (55) -N - A '- N - Ai - N -

i 3 i J I

Q'e Q7 Q8 wherein Ag represents ethylene or propylene and two of Qg, Qlj and Qg represent -CO- or -CO-NH- and one of Qg, Q1 and Qg represents -X ', wherein the substituent -X' have the meanings given.

Very significant sizing agents (A) are those prepared by chemically (a ') reacting a polyalkyleneamine having 3 to 6 nitrogen atoms and 4 to 4 carbon atoms, optionally monosubstituted with N-C 1 -C 4 alkyl or alkenyl (b') with a fatty acid or fatty alcohol, an alkyl or alkenyl halide or an alkyl or alkenyl isocyanate having at least 5, preferably 6 to 22, in particular 16 to 20 carbon atoms in the alkyl or alkenyl residue, and then (c ') a polybasic , preferably three-basic, especially two-? 79579 with a basic, inorganic anhydride having 2 to 18, preferably 2 to 8 carbon atoms, or an α- or 8-halocarboxylic acid or 2 to 6 carbon atoms, with component (c ') being added last.

Examples of specific representatives of component (a ') from which the sizing agent is prepared include Ν, Ν'-bis- (3-aminopropyl) -1,5-diaminobutane, N- (3-aminopropyl) -1,4-diaminobutane , 1,2-bis (3-aminopropylamino) ethane, pentaethylenehexamine, especially tetraethylenepentamine, triethylenetetramine and especially dipropylene triamine and diethylenetriamine, with diethylenetriamine being preferred.

Suitable components (b ') from which the sizing agent (A) can be prepared are, in particular, optionally unsaturated fatty acids, alkenyl or, above all, alkyl isocyanates having 6 to 22, preferably 8 to 22, in particular 16 to 20, carbon atoms. - or an alkenyl residue. As the unsaturated or saturated C16-C22 fatty acids used preferably as component (b), e.g., caproic, preferably caryl, capric, lauric, are used as the C16-C20 fatty acids used as component (b). -, myristic or arachic acid, in particular palmitic, stearic and behenic acid or myristoleic, palmitoleic, eleostearic, clupanodonic acid, in particular oleic, elaidic, erucic, linoleic or linolenic acid. In this case, palmitic, stearic, oleic and behenic acids are very important, with palmitic and, above all, stearic acid being preferred. Technical, well-obtained mixtures of the acids just mentioned are also possible. Due to its good availability, octadecyl isocyanate is mentioned as a g-C20 alkyl isocyanate.

As component (c '), anhydrides of organic polybasic acids are preferred over anhydrides of inorganic polybasic acids. Examples of specific representatives of anhydrides of inorganic polybasic acids are sulfur trioxide, in particular phosphorus pentoxide and especially chlorosulfonic acid.

28 79579

Examples of organic polybasic acid anhydrides are benzophenone tetracarboxylic acid, 1,8-naphthalic acid, tri- and pyromellitic acid, bicyclo- (2,2,1) -hept-5-ene-2,3-dicarboxylic acid (including norborne dicarboxylic acid) anhydrides of hexanoic, tetrahydrophthalic acid and phthalic acid, succinic and glutalic acid, dimethylmaleic acid, citraconic and itaconic acid, and in particular maleic acid. Suitable halogen carboxylic acids are, for example, 2-chlorobutyric acid, 2- and 3-chloropropionic acid, bromoacetic acid or chloroacetic acid and their alkali metal salts. The sultone used is primarily propane-sultone. Preference is given to glutaric and succinic anhydride, sodium chloroacetate, citraconic and itaconic anhydride, phthalic acid and pyromellitic anhydride, and especially trimellitic anhydride and maleic anhydride, from which an acid anhydride can be prepared.

The reaction products of components (a ') and (b') form intermediates from which sizing agents (A) can be prepared by further reacting these intermediates with component (c ').

As mentioned above, the sizing agents (A) used according to the invention are in part compounds known per se. This also applies to intermediates consisting of components (a ') and (b1), from which sizing agents (A) can be prepared.

Thus, e.g. French Patent 1,388,523 discloses intermediates made from fatty acids, e.g. oleic acid or stearic acid, and polyalkylene polyamines, e.g. triethylenetetramine, which are further reacted with polybasic acids. However, only hexanoic and tetrahydrophthalic, phthalic, terephthalic, trimellitic, succinic, adipic and maleic acids and the corresponding anhydrides are explicitly mentioned in this patent as polybasic acids.

U.S. Patent No. 4,792,737, U.S. Pat. glutaric, maleic and citraconic acid and corresponding anhydrides.

Finally, Japanese Patent Application 74 / 137,917 discloses intermediates made from fatty acids and polyalkylene polyamines which are further reacted with chlorine sodium acetate used exclusively as an acid.

Intermediates consisting of polyalkylene polyamines and fatty alcohols or alkyl or alkenyl halides are known and commercially available. In contrast, intermediates made from polyalkylene polyamines or N-alkyl or N-alkenyl polyalkylene polyamines and alkyl or alkenyl isocyanates are new. This also applies to the reaction products of such intermediates with arbitrary polybasic acids. Furthermore, the reaction products of polyalkylene polyamines and fatty acids which have been further reacted with polybasic acids are also new if pyromellitic acid, norbornene dicarboxylic acid, dimethylmaleic acid or citraconic acid anhydrides are used as anhydrides of the polybasic acids. Likewise, there are novel reaction products which are further reacted with 2-chlorobutyric acid, 2- or 3-chloropropionic acid, bromoacetic acid or propane sultone.

Other objects of the invention are then - intermediates obtained by reacting (ap 1 mole of a polyalkylene polyamine having 3 to 6 nitrogen atoms and 4 to 40 carbon atoms, monosubstituted with C8-C22 alkyl or alkenyl).

with (m 2) 1 - (h "-1) moles of at least 5, preferably 6-22 30 7 9 5 7 9 in particular an alkenyl or preferably an alkyl isocyanate containing from 8 to 22, in particular from 16 to 20 carbon atoms in the alkyl or alkenyl residue , where (h ") denotes the number of nitrogen atoms in component (a).

- Compounds which can be prepared by reacting the intermediates consisting of components (a *) and (h) with a mole of (c 1) 1 - (h 1) of a polybasic, preferably dibasic, inorganic or especially organic acid having 2 to 18 carbon atoms anhydride, 2- or 3-halocarboxylic acid having 2 to 6 carbon atoms or a sultone, where (h1) denotes the number of free nitrogen atoms present in the intermediate consisting of components (a *) and (b ') which have not reacted with component (b). *) with.

- Compounds which can be prepared by reacting (a ^ j) 1 mole of a polyalkylene polyamine having 3 to 6 nitrogen atoms and 4 to 20 carbon atoms with a mole of (b1) 1 - (h "-1) unsaturated or preferably saturated, at least 5, preferably 6 -22, in particular a fatty acid having from 8 to 22, in particular from 17 to 20 carbon atoms, the symbol in which (h ") has the meaning given, and then (c 1) 1 to (h 2) mole of pyromellitic acid, norborne dicarboxylic acid, dimethylmaleic acid or citraconic anhydride, 2-chlorobutyric acid, 2- or 3-chloropropionic acid, bromoacetic acid or propane sultone, where (h ^ denotes the free nitrogen atoms present in the intermediate consisting of components (a *) and (b ^) which are not reacted with component (b ^).

The reactions of components (a ^) and (b ') are generally carried out in the molten at a temperature of about 120 to about 250 ° C, preferably up to 200 ° C. If high temperatures of approx. 200 - 250 ° C are used, the products obtained can be purified with activated carbon, if necessary. However, in particular when using alkenyl or alkyl isocyanates as component (b ') or reacting with component (c1), it is also possible to carry out the reactions in the presence of at least one solvent / which must be inert to each of the starting, intermediate and final products. . When using such solvents, the reactions can also be carried out at lower temperatures, e.g. 30 to 120 ° C. Examples of possible solvents are acetone, dioxane or optionally halogenated hydrocarbons, such as, for example, dichloroethane, carbon tetrachloride, benzene, toluene, chlorobenzene, o-, m- and p-xylene, a mixture of technical xylenes or also mixtures of said hydrocarbons. If halogenated carboxylic acids, e.g. chloroacetic acid, are reacted as component (c '), it is advisable to use an approximately equimolar amount (relative to the halogenated acid) of a weak, nitrogenous base, e.g. pyridine, isoquinoline, quinoline, to prevent the formation of by-products. preferably triethylamine as an acid acceptor. If unsaturated components (c1) or, above all (b ') are used, it is furthermore preferred to carry out the reaction under an inert nitrogen atmosphere and / or above all at elevated temperatures, in the presence of a polymerization inhibitor, e.g. methylene blue, benzthiazine or, preferably, hydroquinone.

Preferred sizing agents (A) consisting of components (a1), (b ') and (c') of the type shown are of molecular weights of about 400 to about 3000, more preferably about 500 to about 3000, especially about 600 to about 1500 and because they contain at least one an acidic group, e.g. -SO 3 H or -C00H, has an acid number (mg KOH / g substance) of about 15 to about 150, preferably about 50 to about 120.

According to another preferred embodiment, the sizing agents (A) used according to the invention contain, in addition to 1 or 2 potentially anionic, acidic methylene or methylene groups and 2 or 3 hydrophobic substituents of the type shown, divalent linkers through which at least two predominantly adjacent hydrophobic substituents have joined. and containing from 1 to 15, preferably from 32 to 79579 min from 3 to 8 carbon atoms and at least 2 heteroatoms in each case, preferably from 2 to 4 nitrogen and / or oxygen atoms or in particular from 4 nitrogen atoms or 2 oxygen atoms. Very preferred are connecting members having in each case 3-5 carbon atoms and 2 oxygen atoms. Depending on the number of hydrophobic substituents, such sizing agents preferably contain 1 to 2 such linking members.

The preferred linking members generally correspond to one of the formulas 0 0 (H) m "-1 ° (56) -0 - £ - (-CH2 - ^„ _ 1 - CH C - 0- or 0 0 0 0 \ n i n il il ^

(57)). N-C-CH-C-NH-A "-NH-C-CH-C-NX

wherein n "and m" are in each case 1 or 2 and A 1 j represents a branched or, in particular, straight-chain alkylene having 4 to 12, in particular 6 to 10 carbon atoms, cycloalkylene having 6 to 14 carbon atoms or 6 to 14, in particular 6 to 8 carbon atoms. If m "is in formula (56) 1, the linking member has a methine group at the corresponding position. However, if m "is 2, then the linking member has a methylene group at the corresponding position.

The linking members of formulas (56) or (57) have a methylene or methine group as part of the divalent, trivalent residue -C0-CH2-CO- or -CO-CH-CO-, wherein the direct attachment of the methylene group to each of the two CO- between a group or a direct attachment of a methine group between a 3 CO group or 2 CO group and one CN group requires the acidic properties of these methylene or methine groups.

If n denotes the number 2 in the formula (56), then m "denotes the number 2. The meaning of the symbol m" generally applies only if n "is also 1. However, a connecting member of the formula (56) is very preferred, in which n "denotes the number 1 and m" denotes the number 2.

Particularly important sizing agents (A) are, in particular, those which can be prepared by reacting (α 1) malonic acid, malonic acid dihalide, acetonecarboxylic acid or a C 1-4 alkyl ester of malonic acid, acetonedicarboxylic acid or methane tricarboxylic acid or (alcohol). a! J) cyanoacetic acid or a C 1 -C 4 alkyl ester thereof to react (bp with a fatty amine and then (c ") C 1 -C 4 alkylene, C 1 -C 4 cycloalkylene or C 1 -C 4 alkylene with arylene diisocyanate.

Suitable components (a!) From which the sizing agent (A) can be prepared are, above all, dihalides, e.g. malonic acid dibromide and in particular dichloride, and their methyl or especially ethyl esters. Due to its high reactivity, malonic acid dichloride is highly preferred. Due to their good availability, dimethyl and above all diethyl ester of acetone dicarboxylic acid or trimethyl and above all triethyl ester of methanetricarboxylic acid are also possible.

The component (αE) is above all methyl cyanoacetic acid and in particular ethyl cyanoacetic acid.

As components (a'j) and (a '), preference is given to malonic acid dichloride and cyanoacetic acid ethyl ester.

Suitable components (b ^ 1) from which the sizing agent (A) can be prepared are, in particular, optionally unsaturated aliphatic alcohols having from 6 to 22, preferably from 8 to 22, in particular from 16 to 20 carbon atoms, and as component (b) from in particular mono- or dialkylamines or mono- or dialkenylamines in each case from 6 to 22, preferably from 8 to 22, in particular from 16 to 20 carbon atoms in the alkyl or 34 7 9 5 7 9 alkenyl residue. Saturated fatty alcohols and alkyl or dialkylamines are more preferred compared to unsaturated fatty alcohols or alkenyl or dialkenylamines. Primary amines are also superior to secondary amines. Due to their good availability, hexadecanol, octadecanol, oleyl alcohol, octadecylamine and dioctadecylamine may be mentioned as special representatives of g-C20 fatty alcohols and mono- or dialkylamines containing C1-8-C20-alkyl residues. Technical mixtures of such fatty alcohols or fatty amines are also possible.

Suitable aliphatic diisocyanates for use as component (c ") are those having branched or, preferably, straight-chain alkylene radicals having from about 4 to about 12, in particular from 6 to 10, carbon atoms. Particular representatives of such diisocyanates are butylene diisocyanate, butylene diisocyanate. isocyanate, in particular decylene 1,1O-diisocyanate and in particular hexylene-1,6-diisocyanate Suitable cycloaliphatic diisocyanates are those which generally have from 6 to 14 carbon atoms in the cycloalkylene residue. Aromatic diisocyanates generally have from 6 to 14, preferably from 6 to 8 carbon atoms in the arylene residue, examples of which are, in particular, naphthylene 1,5-diisocyanate, diphenylmethane-4,4'-diisocyanate. phenyl, 1,4-diisocyanate and toluene-2,4- and -2,6-diisocyanate, due to their good availability, hexane-1,6-diisocyanate. and toluene-2,4- or -2,6-diisocyanate or, above all, technical mixtures of toluene-2,4- and -2,6-diisocyanate.

Generally, one mole of fatty alcohol is used as the functional group of the component (alf) used as the component (blj). Thus, about 2 moles of fatty alcohol are generally used per mole of component (a! J) if component (a ”) is malonic acid or acetonedicarboxylic acid or its halide or ester, and about 3 moles of fatty alcohol per mole of component (a") , if component (alj) is methane tricarboxylic acid methyl or ethyl ester.

If components (ap or (b 2)) are used, they are generally reacted with each other in approximately equimolar ratios. The resulting cyanoacetic acid fatty amide is an intermediate that can be further reacted with component (c ") using about 0.5 moles of the indicated type alkylene, cycloalkylene or arylene diisocyanate as component (c ") per mole of intermediate consisting of approximately equimolar amounts of components (alj) and (b ^).

Preferably, the molecular weights (A) of the type shown, made from components (aip and (b ^ j) or from components (a ^), (bp and (c ”) 5, have a molecular weight of about 400 to about 3000, preferably about 600 to about. 1500.

The reactions of the above components (a! J), (a ^) / (b! P, (b £) and (c ") are generally carried out according to methods known per se. Thus, for example, the reactions of the components (a! J ') are carried out according to the methods ( blj *) or the reactions of component (a ^) with components (b ^) optionally in melt at a temperature of about 30 to about 250 ° C, preferably about 40 to 140 ° C. When high, about 200 to 250 However, in particular when using acid halides as component (a!) And generally reacting intermediates formed from components (ap and (b)) with component (cH), it is preferable to carry out these reactions for at least one hour. In the presence of a solvent which must be inert to each of the starting, intermediate and final products, such solvents can also be used at lower temperatures, e.g. 30 to 120 ° C, preferably 30 to 50 ° C. is acetone, dioxane or optionally halogenated hydrocarbons, such as, for example, dichloroethane, carbon tetrachloride, benzene, toluene, chlorobenzene, o-, m-36 79579 and p-xylene, a mixture of technical xylenes or also mixtures of said hydrocarbons which are particularly suitable for use as a reaction medium for reacting the acid halides as component (b1.j) with the fatty alcohols as component (b'.j). When reacting the intermediates formed from components (aIJ) and (bJ) with component (c "), dimethylformamide or dimethyl sulfoxide is particularly well suited as a further solvent. In the case of reacting the free acids as components (a? P or (aJJ) as components (b! | ) or (b! J) fatty alcohols or fatty amines, it may be advantageous to use a catalyst, e.g. hydrochloric acid, sulfuric acid, phosphoric acid or organic sulfonic acids, preferably p-toluenesulfonic acid, to accelerate the esterification or conversion esterification reactions if necessary. (bp and (b ”), it is further preferred to carry out the reaction under an inert nitrogen atmosphere and / or above all at high temperatures, e.g. above 90 ° C, in the presence of a polymerization inhibitor, e.g. methylene blue, benzthiazine or preferably hydroquinone.

As mentioned at the beginning, some of the sizing agents (A) are compounds known per se. Thus, for example, fatty alkyl diesters of malonic acid are disclosed in Zeitschrift Makromolekulare Chemie, Volume 3, pages 251-280 (1949) (authors Staudinger et al.), I.e. compounds having a linker of formula (56) wherein n is 1 and m is 2. However, this article does not provide any information on the intended use of the disclosed compounds. Further, for example, GB Patent Publication No. 737,528 discloses fatty alkyl diesters of acetone dicarboxylic acid, i. compounds having a linker of formula (56) wherein m and n are 2. However, this patent does not disclose the use of these compounds as a paper sizing agent.

37 79579

In contrast, compounds having a linker of formula (56) wherein n and m are 1 or a linker of formula (57) are novel compounds.

The intermediates consisting of components (aij) and (b ^) are also new.

Thus, an object of the invention is the formula R "/ 1

(58) NC-CH2-CO-N

Intermediate compounds or salts thereof according to (R2) p1-1 (H) 2-p ", in which p" denotes the number 2 or preferably 1, R1 and R2 are different or preferably similar and in each case denote 6-22 , preferably alkenyl having 8 to 22, especially 16 to 20 carbon atoms, or more preferably alkyl.

The invention also relates to a process for the preparation of compounds of formula (58) which is characterized in that 1 mole of cyanoacetic acid or its -C 1-4 alkyl ester is reacted with about one mole of the formula p "/ 1

(59) HN

\ κ2 »ρ" -1 <Η> 2-ρ "secondary or primary amine.

The novel compounds of the invention which can be used as sizing agents (A) correspond to the formula 38 79579 o o (60) R "-O- (f <? - 0-R"

1 \ / J

O C it

Il x \

R 2 -O-C H

(61) R "O CN O O CN O R" 1 'il 1 li „i 1 ti ./ 0

N-C-CH-C-NH-A "-NH-C-CH-C-N

2-p "p" '1 ^ R4 ^ q "-1 ^ 2-q" wherein p "and q" are different or preferably similar and in each case denote the number 2 or preferably 1, R1, R ", R3 and R4 are different or preferably similar and each represents 6 to 22, preferably 8 to 22, especially alkenyl of 16 to 20 carbon atoms or more preferably alkyl, and A 1 represents a cycloalkylene having 6 to 14 carbon atoms, in particular 4 to 12, preferably 6 to 12 carbon atoms. Alkylene of 10 carbon atoms or arylene of 6 to 14, preferably 6 to 8 carbon atoms.

A process for the preparation of compounds of formula (60) and (61) is characterized by reacting 1 mole of methane tricarboxylic acid C 1 -C 4 alkyl ester, especially methanetricarboxylic acid ethyl ester, with approximately 3 moles of formulas (62) R 11 -OH, (63) R f -OH or a fatty alcohol of (64) R 1 -OH, wherein the substituents R 1, R 8 and R 2 in the above formulas have the meanings given, or 1 mol of formula 39 79579 (65) 0 = C = N - A! J '- N = C = 0, a diisocyanate having the meanings given for the substituent A! J to react with approximately 2 moles of formula (58) or formula R "κ 3

(66) NC - CH2 - CO - N

V <R4> q "-1 (H> 2-q), wherein in the above formula the symbols R1, Rjj and q" have the meanings given.

In another equally preferred embodiment, the sizing agents (A) used according to the invention comprise 1-6,

A

preferably in addition to 1 to 4, in particular 1 or 2 -C00 or -C00H groups, as anionic or acidic groups and 2 to 10, preferably 2 to 6, in addition to the hydrophobic substituent of the type shown, divalent linkers through which at least two of the substantially adjacent hydrophobic substituents are attached, and having in particular 4 to 15 carbon atoms and in each case at least 2 heteroatoms, preferably a nitrogen and oxygen atom or in particular 2 nitrogen atoms or 2 oxygen atoms. Joiner members with 4 to 10 carbon and 2 oxygen atoms are preferred. Depending on the number of hydrophobic substituents, such sizing agents contain 1 to 5, preferably 1 to 3 such linking members.

The preferred linking members generally correspond to one of the formulas 0 (67) -Qjj'-i-Aj'-C-Qj 'or (68) -C-O-A'j-O-C- wherein A "^ and A" 2 denote in each case a divalent, aliphatic or aromatic residue, Q ".j and Q" 2 are different or preferably identical and denote the group -O-, -NH- or -N-.

In formulas (67) and (68), the residues A "1 and A" 2 form part of an aliphatic or aromatic bridging member containing 1-6, preferably 1-4, especially 1 or 2 anionic or acidic groups and optionally 1 nitrogen atom.

Specific examples of preferred bridge members include the formulas 0 0 (69) -V-C-Q "'- 1 i u 1

I II

Iv »I | / Λ U1 V-l o (70) -QV '-C -. ^ \ - ^, -L I M II | * V * · * IV "1 1 '1 \ x,„ ^' g »'-! <Y' * i> q».-1 n "'- l O X'" o (71) -Q ^, -C-CH2-C-CH2-CQ ^ '-, and (72) -Q "' - CC-CH - CQ" '- 4h X "'

II

41 79579 o (73) -Qj'-ä- (CH2) n „1_i-CH2-N-CH2- (CH2) n ...- i-c-Q2 'CH2' -1 X" '

o CH- »O

il I II

(74) -C-O-CH2-C-CH2-O-C-, i X "'

O O

I) a (75) -C-O-CH2 "CH-O-C-, i X" ·

o O

11 (76) -C-O-CH- (CH2) n ", _1-CH-O-C- or I 1 CH3 X" 1 oo '1 J! (77) -CO- (CH2) 2-N - (CH2) 2-O-C2-ch2 (CH2) n, M_i l X ».

wherein Q "'and Q ~' in each case denote the group * · ^ a -O-, -NH- or -N s *, X" 'denotes the group -COOH, -COO,

Y "'represents -COOH, -COO® or O

(I

C-QJ 'Z "' denotes hydrogen, methyl or preferably hydroxyl, n" 'and m "' in each case the number 1 or 2, p" 1 denotes a total number of 42 79579 female numbers 1 to 4 and q "1 and q" "in each case denote Chapter 1, 2 or 3.

Particularly significant sizing agents (A) are, in particular, those which can be prepared by reacting at least one (a "') one aliphatic or aromatic carboxylic acid having at least 3 carboxyl groups, a polyalkylene polyamino polyacetic acid having 4 to 6 carboxyl groups or a hydroxyl group having 2 hydroxyl groups. an aliphatic monocarboxylic acid or aminocarboxylic acid to react (b "1) with a fatty alcohol and / or a fatty amine or fatty acid, using fatty alcohols and / or fatty amines as component (b" ') using at least 3 resp.

Carboxylic acids containing 4-6 carboxyl groups as component (a "') and fatty acids as component (b"') when monocarboxylic acids are used as component (a "') ·

In general, the sizing agents thus obtained are aliphatic or aromatic fatty acid esters or fatty acid amides. Preferred esters or amides of this type have one of the bridge members of formulas (69) to (73) wherein Q1 and Q1 are similar. However, other sizing agents also exist as amide esters, which can be prepared from both fatty alcohols and fatty amines and aliphatic or aromatic, at least 3 carboxyl groups, resp. Acids containing 4-6 carboxyl groups. Preferred amide esters of this type have one of the bridging members of formulas (69) to (73) wherein Q '* and' are different. If monocarboxylic acids containing 2 hydroxyl groups are used as component (a "'), only fatty acids are suitable as component (b"') to give fatty acid esters having, in their most preferred embodiment, one of the bridging members of formulas (74) to (77).

Preferably, the molecular weights (A) of components (a "') and (b"') of the type shown are of molecular weights of about 400 to about 3000, more preferably about 600 to 43 79579 of about 1500. Highly preferred are sizing agents. , having a bridge member of formula (69) or (71).

In particular, sizing agents which are preferred can be prepared by reacting at least (a "') one aromatic acid containing 9 to 20 carbon atoms and 3 to 6 carboxyl groups, an aliphatic acid having 3 carboxyl groups and optionally 1 nitrogen atom, polyalkylene polyamino polyacetic acid, having 4 to 6 carboxyl groups and 2 to 4 nitrogen atoms, an aliphatic dihydroxymonocarboxylic acid or a bis (hydroxylalkyl) amino monocarboxylic acid having 3 to 6 carbon atoms, or their halides or anhydrides for reacting with a (b '') fatty alcohol and / or with a primary or secondary fatty amine or, if a monocarboxylic acid of the type shown is used as component (a "'), with a fatty acid, the fatty residues of the fatty alcohols, fatty amines and fatty acids being unsaturated or preferably saturated and containing 6-22, preferably 8-22, especially 16-20 carbon atoms.

In order, as mentioned at the beginning, the sizing agents contain at least one -C00 or -COOH group as anionic or acidic substituents and the connecting member through which the hydrophobic substituents are attached directly to each other contains at least 2 heteroatoms, the sizing agents can be prepared in 1 mole component in the preferred embodiment. a "') and 2 - (h"' -) molar component (b "')> wherein h"' denotes the number of carboxyl groups of component (a "') if at least 3 is used as component (a" 1), resp. Carboxylic acids having 4 to 6 carboxyl groups and fatty alcohols and / or fatty amines as component (b "'). In contrast, when 1 mole of monocarboxylic acid containing 2 hydroxy groups is used as component (a"'), 2 moles of fatty acid are generally used.

Due to the presence of at least one -COOO or -COOH group, the acid number of the sizing agents (mg KOH / g substance) is 44,79579 from about 15 to about 150, preferably from about 40 to about 100.

Suitable carboxylic acids containing at least 3 carboxyl groups for use as component (a "') from which the sizing agent (A) j can be prepared are, in particular, aromatic mononuclear polycarboxylic acids, e.g. hemimellitic, trimellitic, trimesic, prehnitic, cellophane, pyromellitic or mellitic acid, benzenepentacarboxylic acid, aromatic, dibasic polycarboxylic acids, e.g. a nitrogen atom, e.g. bis (2-carboxyethyl) -carboxymethylamine, nitrilotripropionic acid and nitrilotriacetic acid, and polyalkyleneamino-polyacetic acids, e.g. bis (2karboksiet yl) -N, N'-bis (carboxymethyl) ethylenediamine, tris (2-bis (carboxymethylamino) ethyl) amine, bis (2-bis (carboxymethylamino) ethyl) methylamine or N, N N'-bis (2-bis-carboxymethyl-amino) ethyl) -N, N'-dimethyl-ethylene diamine. Due to their easy availability, they include trimellitic anhydride, pyromellitic anhydride, hemimellitic acid, benzophenone intetracarboxylic acid dianhydride, tricarballyl acid, trans-aconitic acid, citric acid and highly nitric acid. Suitable aliphatic monocarboxylic acids 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, Ν, Ν'-bis - (hydroxyethyl) -β-alanine and N, N'-bis (hydroxyethyl) -glycine, with 2,2-bis (hydroxymethyl-propionic acid and N, N1-bis-hydroxy-ethyl) -glycine being preferred, with trimellitic anhydride being preferred. , pyromellitic dianhydride and citric acid.

45 79579

If polyalkylene polyamino-polyacetic acids are used as component (a "'), these give oligomeric sizing agents. In contrast, the use of other acids as component (a" 1) gives monomeric sizing agents, which are also preferred over oligomeric sizing agents.

Adhesives (A) containing a bridge member of formula (69) may be prepared using as component (a "') e.g. from said aromatic mononuclear polycarboxylic acids, a benzophenone tri-bis-hexacarboxylic acid containing a bridge member of formula (70), a bridge member of formula (71) containing tricarballyl or citric acid, bridging member of formula (72) containing aconitic acid, bridging member of formula (73) containing aliphatic tricarboxylic acids having one nitrogen atom, bridging member of formula (74) containing 2,2-bis (hydroxymethyl) propionic acid 75) a bridging member of formula (76), a bridging member of formula (76) containing 1,3-dihydroxyvivaleric acid or 1,2-dihydroxybutyric acid and a bridging member of formula (77) containing N, N-bis (hydroxyethyl) -glycerol or N, N-bis (hydroxyethyl) -β-alamiinista.

Suitable components (b "') which can be used to prepare the sizing agent (A) are, in particular, possibly unsaturated aliphatic fatty acids and alcohols having from 6 to 22, preferably from 8 to 22, in particular from 16 to 20 carbon atoms or in each case from 6 to 22, preferably mono- or dialkylamines or mono- or dialkenylamines having from 8 to 22, in particular from 16 to 20 carbon atoms in the alkyl or alkenyl residue. When unsaturated or saturated, when used as component (b "') C6-C22-', preferably cq" C22- ' Suitable g-C2O fatty acids are, for example, caproic acid, preferably caprylic, capric, lauric, myristic and arachic acid, in particular palmitic, stearic and behenic acid, or myristoleic, palmitoleic, eleostearic, clupanodonic acid, especially oleic, elaidic, erucic, linoleic and 46olic acid. In this case, palmitic, stearic, oleic and behenic acids are of particular importance, with palmitic and, above all, stearic acid being preferred.

Technical, well-obtained mixtures of the acids just mentioned are also possible. Unsaturated or saturated fatty alcohols and unsaturated or preferably saturated mono- and dialkylamines or mono- or dialkenylamines are structurally due to the aforementioned fatty acids. Due to their good availability, hexadecanol, octadecanol, oleyl alcohol, octadecylamine and dioctadecylamine are particularly representative of C 1 -C 20 fatty alcohols and mono- or dialkylamines containing C 1 -C 20 C α-1 -yl residues. Technical mixtures of such fatty alcohols or fatty amines are also possible.

The following compounds used as component (Δ) as a sizing agent in the process according to the invention and their preparation from components (a "') and (b"') are known per se: - QLeSesters and diamides prepared from aromatic carboxylic acids having at least 3 carboxyl groups. having bridge members of formula (69) wherein Q1 'and Q2' are similar; these are disclosed, for example, in German Patent Application 2,417,556, GB Patent 1,025,433 and U.S. Patent 3,981,838.

- Diamides prepared from aromatic carboxylic acids having at least 3 carboxyl groups and having bridging members of the formula (70) in which Q 1 'and Q 1' are similar and represent a group -NH- or -Nv,; these are disclosed, for example, in U.S. Patent No. 3,275,651.

- Diesters and diamides prepared from aliphatic carboxylic acids having 3 carboxyl groups and having bridging members of the formula (71) in which Q 1 and Q 2 are similar and denote -O-, -NH- or -N and Z "'represents -OH; these are disclosed, for example, in U.S. Patent Nos. 4,779,712 and 4,021,377 to U.S. Patent Nos.

- Diesters prepared from 2,2-bis (hydroxymethyl) -propionic acid and having bridging members of formula (74); these are disclosed in GB Patent 1,257,928 and U.S. Patent 3,441,953.

In contrast, the novel compounds which can be used as sizing agents according to the invention correspond to the formula

O O

nf H o · I »\ ii a / 2 (78) D '" - C-A' "- C-Ql" or <R1 n '"“ I (R2 "', n · '· -! O o II il (79) R ^ "- C - O - A" '- O - C - R £ "where m"' and n "'denote the number 1 or 2 in each case, Q3' and Q4 'denote in each case the group -O- or -NH- or, if n "'and / or m"' denotes the number 2, Q ^ 'denotes the group -N ^ and R 1 j', R e ", R e '' and R 1 'denote in each case an alkyl having at least 5 carbon atoms or alkenyl, in which at least one of the radicals R 1 ', R 1', R 1 and R 2 'is at least 8, preferably 8 to 22, in particular 16 to 20 carbon atoms, A 1' represents one of the formulas X '"/ (80) -CH2-CH-CH2-, 48 79579 X '"ί (81) -CH2-C-CH2-CH3 (82) -C-CH- or

II

CH

a divalent residue according to X '"(83) - (CH2) s, i1_1-CH2-N- (CH2) - (CH2) s, 11_1-CH2 (CH2) ,,,,, X"', or, if 1 and Q "^ in formula (78) are different, the formula (84) - / 'X, i, 1 / or> XX, n / v ·" l ^ Λ ll2} p' "- 1 X" 'i ( 85) -CH2-C-CH2-

OH

or, if Q 1 'and Q "' in formula (78) are the same and represent the group -o- or Q 3 'and' are different, the formula 49 79579 is / \ (86) - / \ _ C _ · · "And / '2' α '" -! (ν '") χ,., z q2 j. \ i2 denotes a divalent residue, A £' denotes the formula (87) -CH0-CH- i X '" (88) CH- (CH2) -CH- or i ^ nx

A divalent radical according to Ah3 χ "'(89) (CH2) 2-N- (CH2) 2- CH_12 (Ch2) s., Where X"' represents -COOH or -C00, Y2 'denotes Ό ”/ 1 Y ^" - CO-Q ^ "; f Χ (κΓ» η' · -1 50 79579 p "'denotes the number 1-4, q"' and q "“ denote the number 1, 2 or 3 and m "', s'" and t "' each denote the number 1 or 2 and the substituents Qij *, R £ 1 3a Ri [" have the meanings given.

The preferred compounds to be used as sizing agents correspond to the formula

Ri "O O RV '\ n w / (90) O ^ -C-C-CH ^ C-O” 1 ^ ^ 3 ^ - 1 I «κ3β,) η · --1

CH

X * 11 pm o 9 RV '3 \ il II / 3 (91) n ^ c,' "C-CHo-N-CH_-O-Q;" / 5 2 I \ (R3 ^ '"- 1 CH2 ^ 3 ^^ - 1 χ., R3"' 0 X '"(92) N-C-CH2-C-CH2-C-OR3" 1

R3 "'OH

000 (93) "-O-1-—-C-j / * \ jC-O-R3" y Λ-X '"oo. Li 1 (94) R1" - C-O- (CH2) 2- N- (CH2) 2-0-CR ^ '' <[η2 (CR2) s "'- l X'" si 79579 • where n "'and s"' denote the number 1 or 2, Q "'denotes the group - O- or, if n "'is 2, a group, X"' represents a group -COOH or -CCK4 and 'alkenyl having 16 to 20 carbon atoms or, preferably, alkyl.

The process for the preparation of new associations is generally such that 1 mole of the formula O O

I! I

(95) HO-C-AV'-C-OH

The polycarboxylic acid of formula (96) is reacted with 2 to (m "'- 1) moles of formula (96) R"

(97) R '"- OH

fatty alcohol and / or 2 - (h "'- 1) moles of formula n I» »R2

OF

XN (h) i, -H

Z Γ1 (R2 ") n ·" -! primary or secondary fatty amine or 1 mole of the formula

(100) HO-A '' - OH

The diol of formula (101) is reacted with 2 moles of the formula (101) R '' - COOH or

(102) R '' - COOH

52 79579 according to methods known per se, wherein the substituents Al 1 ', A 2', R 1 '', R 1, R 1 'and R 2' and the symbol n '' have the meanings given and h "'denotes the formula (95). ) number of carboxylic acid carboxylic acid groups.

The reactions are generally carried out in the molten at a temperature of about 120 to 250 ° C, preferably up to 200 ° C. When using high temperatures of about 200-250 ° C, the resulting product can be purified with activated carbon, if necessary. Above all, however, when acid anhydrides are used, it is also possible to carry out the reactions in the presence of at least one solvent, which must be inert to each of the starting and final products. When using such solvents, the reactions can also be carried out at lower temperatures, e.g. 30 to 120 ° C. Examples of possible solvents are acetone, dioxane and optionally halogenated hydrocarbons, such as, for example, dichloroethane, carbon tetrachloride, benzene, toluene, chlorobenzene, o-, m- and p-xylene, a technical mixture of xylene or also mixtures of said hydrocarbons. For example, when reacting diols of formula (100) with fatty acids of formula (101) or (102), it may be advantageous to use a catalyst, e.g. hydrochloric acid, sulfuric acid, phosphoric acid or organic sulfonic acids, preferably p-toluenesulfonic acid, if necessary to accelerate the esterification reactions. If the polycarboxylic acids of formula (95) are reacted with primary fatty amines of formulas (98) or (99) where n "'is 1, it is recommended to use a weakly approximately equimolar amount (relative to the primary fatty amine) to prevent the formation of by-products. a nitrogen-containing base, e.g. pyridine, triethylamine, isoquinoline or, preferably, quinoline. , R 1 ', R 11' and R 8 'in formulas (96) to (99), (101) and (102) represent an alkylene residue of the type shown, or A 1' in formula (95) represents formula (82) is further preferably 53 79579 is carried out in an inert nitrogen atmosphere and / or in the presence of a polymerization inhibitor e.g. methylene blue, benzthiazine or preferably hydroquinone.

In general, the reactions are performed in a single step. However, it is also possible, for example, to react a polycarboxylic acid of formula (95) with a secondary fatty amine of formula (95) wherein n "'is 2, in a first step and thereafter with a primary fatty amine of formula (99) wherein n" 'is 1, in the second stage.

Prior to the use of sizing agents (A) in the paper sizing process of the invention, sizing agents generally do not need to be purified or recrystallized when prepared from components (a), (b) and (c), components (a1) »(b1) and (e1)» components (a). ) and (b ”), components (a ^), (b ^) and (c £) or components (a" ') and (b "') and can thus generally be used directly. This also applies to intermediates prepared from components (a) and (b), (a1) and (b ') and (a £) and (b'), which therefore do not normally need to be purified or recrystallized before further processing of component (c). , (c ') or (c ") as sizing agents (A).

In particular, when the sizing agent (A) and the retaining agent (B) are added separately (in any order) to the fiber suspension in the method according to the invention for gluing paper or board, it is expedient to use the sizing agent at least in part in salt form. Such salts may, if necessary, be prepared by reacting components (a), (b) and (c), (a '), (b') and (c *), (a · 1) and (b "), (a £ ), (b ^) and (c ") or (a" ') and (b "') after completion of the reaction, the reaction products obtained are converted into the corresponding salts, possibly at least in part by adding e.g. alkylamine or alkanolamine having a total of up to 6 carbon atoms, e.g. trimethylamine, polyethylamine, diethanolamine, in particular by adding ammonia or alkali metal hydroxide, for example potassium or especially sodium hydroxide, usually in an aqueous medium at room temperature. 25 ° C). Suitably alkali metal hydroxide, e.g. potassium and above all sodium hydroxide or in particular ammonia, is generally used in the form of dilute aqueous solutions of about 1 to about 10% by weight. Suitably, at most 2 moles, in particular at most 1 mole, preferably 0.1 to 0.9, in particular 0.2 to 0.7 moles of ammonia or alkali hydroxide per charge of the anionic sizing agent are used. The sizing agent in the form of salts thus has, for example, acidic -CH-, -CH, -SO-, Η or -COOH groups, * I ^ | 0 0 which can be converted at least in part to the groups -CM M, -CÖM®, -SO 2 M® or -COO®M®, in which M0 denotes the corresponding amine or alkali metal cations.

Partially saline compounds which may be used as sizing agents (A) are, for example, those obtained by reacting (a) 1 mole of triethanolamine or glycerin with (b) 2 moles of stearic acid, followed by 1-1.5 moles of (c) chlorosulphonic acid or phosphoric acid and finally 0.1 to 0.9 equivalents of aqueous potassium or sodium hydroxide in this case a mixture of acidic esters with acidic protons of acidic substituents obtained from components (a), (b) and (c).

In addition to the monomeric-bis-oligomeric anionic sizing agent (A) described above, the paper sizing process according to the invention always uses a polymeric cationic retention agent (b), which generally has a molecular weight of at least about 1000, preferably about 2000 to about 2,000,000. having a molecular weight of 10,000 to 100,000 are very suitable. In principle, all retention aids on the market can be used in the process according to the invention. Examples of conventional retention aids (B) which are suitable for use with the sizing agent (A) in the paper sizing process according to the invention are polyalkyleneimines, polyalkylene polyamines and reaction products of aliphatic dicarboxylic acid esterside polyol from or prepared from dicarboxylic acids esterified organic alkanols epihalohydrin-additiotuot-making, dicyandiamide, formaldehyde, ammonium salts of strong organic acids and alkylene diamines or polyalkylene polyamines prepared from the reaction products, cationically modified starches or carob or guar flour made of carbohydrates, based on polyamide-amines of copolymers and epihalogeenihyd-riineistä and polymerized reaction products made from diallylamines.

Polyalkylene polyamines and aliphatic dicarboxylic acids preferred epikloorihydriiniaddiotiotuotteita the reaction products produced is shown e.g. in British Patent No. 865 727, diethylenetriamine and dicyandiamide produced from the reaction products formed from epichlorohydrin adducts are presented e.g. German Offenlegungsschrift 2 710 061 and GB-A-1 125 486, diethylenetriamine, diäyaanidi-Midi and epichlorohydrin addition products of reaction products made from non-esterified or preferably lower alkanols esterified with dicarboxylic acids, especially dimethyl adipate are disclosed e.g. in GB 1,125,486 and U.S. Patent 3,491,064. Preferred cationically modified starches or Joha Carbohydrates derived from wholemeal bread or guar flour are alkylene oxide adducts of these starches or carbohydrates, the alkylene oxide used having 2 or 3 carbon atoms in the alkylene residue and quaternary ammonium groups.

56 7957S

the amine-based copolymers have molecular weights of 3 to 5 3 4, preferably 10 to 10, and can be prepared, for example, from aliphatic, saturated dicarboxylic acids having 2 to 10, preferably 3 to 6 carbon atoms, in particular adipic acids, and polyalkylene polyamines, e.g. polypropylene and polyethylene polyamine, especially dimethylaminohydroxypropyl-diethylenetriamine. They are described, for example, in CTFA Cosmetic Ingredient Dictionary, 3rd edition, 1982, (Cosmetic, Toiletry and Fragrance Association). Reaction products made from epihalohydrins and polymerized diallylamines preferably have molecular weights of 1,000 to 2,000 and are disclosed, for example, in U.S. Patent Nos. 3,700,623 and 4,279,794.

As retention aids (B), which are preferred for use together with sizing agents (A) in the paper sizing process according to the invention, mention may be made of maize or potato starch modified with 1,2-propylene oxide containing quaternary ammonium groups and having a slurry of 25% in distilled water at 20 ° C. value 4.2 to 4.6, polyethylimine with a molecular weight of 10,000 to 100,000, epichlorohydrin adduct of the reaction product of triethylenetetramine and dicyandiamide, reaction product of diethylene triamine, dicyandiamide, dicyandiamide and dimethyladiphide an epichlorohydrin adduct of a reaction product prepared from ethylenediamine, an epichlorohydrin adduct of poly-N-methyldiallylamine, and a copolymer of adipic acid and dimethylamine hydroxypropyldiethylenetriamine.

According to the method, 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 -0.4% by weight of retention aid (B) in each case relative to the dry matter of substances (A) and (B) and the solids content of the fiber suspension. 0.02 to less than 0.1% by weight of adhesive (A) and retention agent (B) are sufficient only for so-called "size press control", which cannot be determined by conventional gluing tests (cf. e.g., article "Control and understanding of size press pickup ". DR Dill in TAPPI (Proceedings of the Technical Association of the Pulp and Paper Industry), Volume 57, No. 1, January 1974, pages 97-100).

The fiber suspension to which the sizing agent (A) and the retaining agent (B) is added generally has a solids content of 0.1 to 5, preferably 0.3 to 3, especially 0.3 to 1% by weight, and has a Schopper-Riegler grinding agent of about 10% by weight. ° - about 90 °, especially 20 ° - 60 °, preferably 20 ° - 45 °, especially 25 ° - 35 °. It generally contains cellulose, especially softwood, e.g. pine, or hardwood, i. cellulose from hardwood, e.g. beech, produced according to conventional methods, e.g. sulphite or, above all, sulphate. In addition, the fiber suspension may contain wood chips. Alum-containing waste paper may also be included in the fiber suspension. Also contemplated are cellulose suspensions prepared according to the so-called CMP or CTMP method (see, e.g., "Developments in refiner mechanical Pulping", SA Collicutt et al., TAPPI, Volume 64, no. 6, June 1981, pp. 57-61).

The fiber suspensions may further contain organic or mineral fillers. As organic fillers, e.g. synthetic dyes, e.g. polycondensation products made of urea or melamine and formaldehyde, which have large specific surfaces in a highly dispersed form and are shown e.g. GB patent publications 1,043,437 and 1,318,244, and as mineral fillers, e.g. montmorillonite, titanium dioxide, calcium sulphate and in particular talc, kaolin and / or chalk (Calcium carbonate). In general, the fiber suspension contains 0-40, preferably 5-25, especially 15-20% by weight of the dry matter of such fillers relative to the solids content of the fiber suspension.

The pH range of the fiber suspension can be in a wide range, in which case values of about 3.5 to about 10 can occur, for example.

For example, the addition of calcium carbonate gives temporary fiber suspensions having a pH of about 7 to about 9, preferably 7.5 to 8.5. Acidic fiber suspensions having a pH of 3.5 to 7, preferably 5 to 7, especially 5 to 6, can be obtained without calcium carbonate by adding acids, e.g. sulfuric or formic acid or, above all, e.g. latent acid sulphates, such as aluminum sulphate (alum ).

Fiber suspensions which do not contain a filler can be present in a wide pH range, e.g. in the range 3.5 to 10. Fiber suspensions which have a pH of about 7 to about 9, possibly due to the addition of chalk, are suitable and are preferred in that thus avoiding possible corrosion phenomena in sensitive paper machines.

Fiber suspensions may also contain additives such as, for example, starch or its degradation products which improve fiber / fiber or fiber / filler bonding.

High molecular weight polymers of the acrylic acid group, e.g. polyacrylamides with molecular weights greater than 1,000,000, can also be added to fiber suspensions as excipients to retain very fine cellulose fiber particles, with minimum application rates of about 0.005 to 0.02 weight percent solids to dry matter of the polymer. sufficient.

In the process according to the invention, the fiber suspension is further processed into paper or paperboard in a manner known per se by means of sheet-forming devices or, preferably, by means of paper machines of conventional construction.

After drying at about 100 to 140 ° C for about 0.5 to 10 minutes, it is possible to obtain, for example, papers with

The bed has, for example, 50 to 200 g / m 2.

As mentioned at the outset, the aqueous composition for carrying out the paper sizing process according to the invention contains the sizing agent (A) in addition to the optional conventional additives, if the sizing agent and the retention agent (B) are added separately to the fiber suspension. In this case, the preparation generally contains the sizing agent in part in the form of its salts (obtained by using e.g. ammonia, an alkyl or alkanolamine of the type shown or an alkali metal hydroxide in the proportions given above). In general, such compositions contain from 5 to 30%, preferably from 5 to 20% by weight of dry matter in the form of a partially salted form relative to the weight of the aqueous composition.

In contrast, the aqueous composition contains, in addition to the optional conventional additives, if the sizing agent (A) and the retaining agent (B) are added simultaneously to the fiber suspension, (A) 2-40, preferably 5-30, especially 5-10% by weight of sizing agent (as dry matter). calculated) relative to the weight of the aqueous composition, the adhesive optionally being in the form of a salt, and (B) 0.1 to 20, preferably 0.5 to 10, especially 3 to 8% by weight of a retention aid (calculated as dry matter) relative to the aqueous composition.

Aqueous compositions of the type described optionally contain, as customary additives, surfactants, e.g. dispersants or further emulsifiers and / or water-soluble organic solvents. Suitable dispersants and emulsifiers are, for example, the customary lignin sulfonates, ethylene oxide adducts of alkylphenols, fatty amines, fatty alcohols or fatty acids. fatty acid esters of polyhydric alcohols, substituted benzimidazoles or condensation products made from aromatic sulphonic acids and formaldehyde. Other surfactants are preferably anionic surfactants, especially sulphate surfactants, e.g. diethanolamine lauryl sulphate or ethoxylated lauryl sulphate. Possible water-soluble organic solvents are aliphatic ethers containing 1 to 10 carbon atoms, e.g. dioxane, methylene glycol n-butyl ether or diethylene glycol monobutyl ether, or alcohols having 1 to 4 carbon atoms, e.g. isopropanol, ethanol or methanol.

The compositions are prepared in a conventional manner by mixing the sizing agent (A) together with the retaining agent (B) or the sizing agent (A) in part in its salt form alone, either in a molten state or preferably in a solid state, especially in powdered form, usually with glass beads and emulsifiers. in the molten state), or in the presence of dispersants (in the form of a sizing agent in powder form) at a temperature of up to 90 ° C, preferably at about 50 to about 85 ° C in the case of emulsions, especially at about 15 to about 25 ° C in the case of dispersions, to obtain storage-stable, homogeneous, further dilutable emulsions or, preferably, dispersions. Since sizing agents together with retention agents or sizing agents which are partly in the form of salts are generally self-dispersing or self-emulsifying, it is generally not necessary to use dispersants or emulsifiers. This also applies to the optional addition of solvents and / or surfactants which are used only when the storage stability of the dispersions or emulsions is insufficient.

An advantage of the method according to the invention is that a wide variety of fiber suspensions can be treated with relatively small amounts of sizing and retaining agents in a simple manner into paper with good sizing properties (ink buoyancy time according to Tintenschwimmdauer and above all water absorption according to Cobb1). The paper glued according to the method has good mechanical properties, i.e. good strengths, especially good tear strength. Good reproducibility of the method is guaranteed. In particular, fibrous suspensions containing wood chips or extension paper can be treated. The compatibility of the sizing agent used according to the invention with a wide variety of fillers, and also with their additives such as, for example, kaolin and alum, in the acidic range of the fiber suspensions is also advantageous. The sizing agents also have a favorable compatibility with optical brighteners. In addition, gluing does not substantially affect the whiteness of the glued paper, but may even improve depending on the conditions. Above all, the generally surprisingly high storage stability of sizing agent dispersions of the type shown is a great advantage.

The parts and percentages shown in the following manufacturing instructions and working examples relate to weight.

Instructions for the preparation of known compounds used as intermediates

Help A; 149 parts of triethanolamine (1 mol), 568 parts of stearic acid (2 mol) and 3.5 parts of p-toluenesulfonic acid used as catalyst are dissolved in 510 parts of p-xylene. This solution is heated to reflux at about 140 ° C and maintained at this temperature until the theoretical amount of water (2 moles) formed as a result of the esterification reaction is removed with a water separator. The xylene is then distilled off. As a residue, 680 parts of a waxy ester mixture are obtained, which, in addition to homologous monoesters and triesters, contain as the main component the formula O / - (CH ~) j -O-C- (CH) -CH2), (103) VT ^ ^ 2 Ib J 2

Nch2) 2-oh diester. Melting point: 40-44 ° C.

Guideline B: 22 parts of pyrocatechol (0.2 mol) are dissolved in 200 parts of dimethyl sulfoxide and then 44.8 parts of 50% aqueous potassium hydroxide solution (0.4 mol) are added.

62 7 9 5 79

The reaction mixture is kept at 20 ° C for 30 minutes with stirring. 133.2 parts of octadecyl bromide (0.4 mol) are then added to the reaction mixture. The reaction mixture is heated to 50 ° C and maintained at this temperature for 6 hours, then diluted with 1000 parts of water and adjusted to pH 4-5 with aqueous acetic acid solution, whereupon the reaction product precipitates. The product is filtered off, washed with water and recrystallized from acetone. 98.6 parts of the formula (104) ./V-O- (CH_) n-CH- are obtained.

I II 2 1 3 diether according to o- (ch2) 17-ch3. Melting point: 58-61 ° C.

Guide C:

Proceed as described in Guide B, but using 22 parts of resorcinol (instead of pyrocatechol). 97 parts of the formula o- (ch2) 17-ch3 are obtained

(105) J

k 'J-ο- (CH9) 1 _-CH

Diether according to V 2 17 3. Melting point: 71-73 ° C.

Guideline D: 1136 parts of stearic acid (4.0 moles) are melted at 100 ° C. To this melt is added 227 parts of diethylenetriamine (2.2 moles) over one hour, at which point the temperature of the reaction mixture automatically rises to 110 ° C. The reaction mixture is now heated to 160 [deg.] C. for 2 hours and kept at this temperature for 2 hours, at which point the theoretical amount of water (4 moles) of 63.79579 released by the reaction in a low stream of nitrogen is distilled off from the reaction mixture with excess diethylenetriamine. The reaction mixture is then cooled to room temperature (15-25 ° C). 1232 amide mixtures in the form of a yellowish wax are obtained, containing NH-r as the main component

(CH) 0 "H

(106) ^ _ <ch2) 2 - <3 - (ch2) 16-ch3 NH-L J2. Melting point: 100-105 ° C.

Guide E:

Proceed as in Guide D, but using 287 parts of dipropylene triamine (2.2 moles) (instead of 277 parts of diethylenetriamine). 1288 parts of an amide mixture in the form of a white wax are obtained, containing NH- |

! (CH) 3 "H

(107) Im ~ 9 -t - (CH_). , -CH, j (CH2) 3 L 2 16 3J 2

‘NH

diamide according to Melting point: 101-104 ° C.

Guide F:

Proceed as described in Guide D, but using 1128 parts of oleic acid (4.0 moles) (instead of 1136 parts of stearic acid) and 1 part of hydroquinone as polymerization inhibitor, keeping the reaction mixture at 160 ° C for 3 hours (instead of 2 hours). 1225 parts of an amide mixture in the form of an amber oil are obtained, containing as main component the formula 64 79579 ~ NH- "r 1 (108) (CH2) 2 I- ~ H -Ϊ N- - O (CH2) I - (! - (CH2) 7- CH = CH- (CH2) 7 "CH3 NH-2 diamide.

Instructions for the preparation of known compounds used as adhesives

Guideline G: 624 parts of a technical mixture containing, in addition to homologous mono- and triesters, as the main component 1,3- and 1,2-glycerol distearate (1 mol), are dissolved in 2000 parts of carbon tetrachloride. On the other hand, 142 parts of phosphorus pentoxide (1 mole) are dispersed in 500 parts of carbon tetrachloride. The glycerol distearate solution is now added to the phosphorus pentoxide dispersion within 20 minutes. The reaction mixture is then heated to reflux at about 76 ° C and maintained at this temperature for 12 hours. The reaction solution is then clarified of impurities. After removal of the solvent, the crude product is recrystallized from methyl ethyl ketone. 650 parts of an ester mixture containing beige powder are obtained, containing as main component the formula r * "i 'o: CH2 - O - f *

(109) CH - O - -P-OH

CH, - O - ..

Acidic diester according to -4-o -c- (ch2) 16-ch3 j 2.

Melting point: 57-59 ° C. Acid number: 112.

65 79579

Guideline H: 320 parts of the amide mixture prepared according to guideline D (0.5 mol) are suspended in 1500 parts of chloroform at 20 ° C. To this suspension is added a solution of 74 parts of phthalic anhydride (0.5 mol) in 800 parts of acetone over a period of 35 minutes at 20 ° C. The temperature of the reaction mixture automatically rises to 25 ° C and is maintained at this temperature for one hour. The reaction mixture is then heated to reflux at about 57 ° C and maintained at this temperature for one hour to form a clear solution. The solvent is distilled off under reduced pressure from the reaction mixture. 390 parts of a crude product in the form of a yellowish powder are obtained, which can be recrystallized from acetone and which contains, as the main component, the formula -NR- "o (^ H2) 2 -C- (CH0) N-216 3 2 (110) 7 U 1 * (ch2) 2 "No

NH- h3 - / '"X

~ (i: OOH -! reaction product.

Melting point (recrystallized product): 77-78 ° C.

Acid number: (recrystallized product): 73

Help I;

Proceed as in Guide H, but using 50 parts of succinic anhydride (0,5 mol) instead of 74 parts of phthalic anhydride). 366 parts of crude product in the form of an ocher-colored powder are obtained, which can be recrystallized from ethanol and contains, as the main component, the formula 6 6 79579 Γ 10 NH-I -C- (CH,) 1fi-CH, (CH,) - L 2 16 3J 2 (111) A- and O- (CH 2), i

-C-CHo-CHo-C00H

Reaction product according to NH-2 2.

Melting point (recrystallized product): 108-112 ° C. Acid number (recrystallized product): 68

Help J:

Proceed as in Guide H, but using 77 parts of hexahydrophthalic anhydride (0.5 mol). 391 parts of crude product in the form of an ocher-colored powder are obtained, which can be recrystallized from acetone and contains NH-° (CH3), -O (CH2) 16 -CH3 (112) 'Z L -7-O CH, -CH as the main constituent.

(f2> 2 -i-C <VCH

NH 2 -CH 2 CH 2 COOH.

Melting point (recrystallized product): 66-69 ° C.

Acid number (recrystallized product): 66

Help Q:

Proceed as described in Guide H, but using 49 parts of maleic anhydride (0.5 mol). 350 parts of a crude product in the form of a yellowish powder are obtained, which can be recrystallized from acetone and contains, as the main component, the formula 67 79579 'MH-]' ° (CH3), -ä- (CH2) 16-CH3 (113) N- (ch2) 2 0

NH- -i-CH = CH-COOH

reaction product according to

Melting point (recrystallized product): 82-87 ° C.

Acid number (recrystallized product): 88

Guide L:

Proceed as described in Guide H, but using 56 parts of citraconic anhydride (0.5 mol). 360 parts of crude product in the form of an ocher-colored powder are obtained, which can be recrystallized and which contains, as the main ingredient, the formula -f r o (114) '' t "2'2 ^ - 'ch2» 16-CH3 N "2

^ H2 ^ 2 U

^ H_ -C-CH = C-COOH

^ J u ch3.

reaction product according to

Melting point (recrystallized product): 71-75 ° C.

Acid number (recrystallized product): 82

Help M:

Proceed as described in Guide H, but using 232 parts of the amide mixture prepared according to Guide B (0.5 mol) and 49 parts of maleic anhydride (0.5 mol) (instead of 320 parts of the amide mixture prepared according to Guide A and 74 parts of phthalic anhydride). 370 parts of a crude product in the form of a white powder are obtained, which can be recrystallized from acetone and contains, as the main ingredient, the formula 68 79579 j ·} «- 1? 1 «W -t- (CH2) 16-CH3 i i z J _: 2 (115) 1” ": (CH ~)., 0

I 2 3 II

NH--C-CH = CH-COOH

l_ _ compliant product.

Melting point (recrystallized product): 89-100 ° C Acid number (recrystallized product): 72

Help N:

Proceed as described in Guide H, but using 313 parts of the amide mixture prepared according to Guide C (0.5 mol) and 49 parts of maleic anhydride (0.5 mol). 350 parts of a brownish oil are obtained which contain the formula as the main ingredient

! -NH- O

i «(CH2) 2 -C- (CH2) 7-CH = CH- (CH2) 7-CH3 (116) N- - n -f“ 2 (ΓΗ 1 Ϊ

'1 2'2 -C-CH = CH-COOH

NH-L -1 compliant product. Acid number: 57 Guideline O: 320 parts of the amide mixture prepared according to guideline D (0.5 mol) are melted and heated to 110 ° C. To this melt is added 96 parts of trimellitic anhydride (0.5 moles) in freshly ground form. The reaction mixture in suspension is heated to 160 ° C.

An exothermic reaction occurs at 120-125 ° C, whereby the suspended trimellitic anhydride dissolves. The reaction mixture is then kept at 160 ° C for 30 minutes and then cooled to room temperature (15-25 ° C). 410 parts of a light brown wax containing 69 69579 NH-? (άΗ,), (CH2) 16_CH3 i Δ Δ - _ 2

(117) (<fH2> 2 Xr “\ .- COOH

NH-

COOH

reaction product according to Melting point: 67-70 ° C, acid number: 115.

Help P:

Proceed as described in Guide 0, but using 48 parts (instead of 96 parts) of trimellitic anhydride (0.25 mol). 350 parts of a light brown wax containing the formula / - \) r r - · (- i

(118) i (? H2 * 2 O i O O

N- n \ ji «- ^ n \ I -C- (CH0) ,, - CH, / -t-y \ .- c- \ ICH,), _ 2 16 31 i \ __ /

) Jk-] L ioo »J

\ A 2 reaction product. Melting point: 68-71 ° C, acid number: 57.

Guideline Q: 635 parts of the amide mixture prepared according to guideline D (1 mole) are suspended in 150 parts of chloroform. To this suspension are added 116 parts of sodium chloroacetate (1 mole) and 102 parts of triethyleneamine (1 mole) as acid acceptor. The reaction mixture is kept for one hour at room temperature (15-25 ° C) with stirring, then heated to reflux at about 62 ° C and kept at this temperature for one hour. The solvent is then distilled off from the reaction mixture. For finishing, the distillation residue is dissolved in 500 parts of water, kept under stirring for 15 minutes and filtered off. 670 parts of a crude product in the form of a slightly yellow-colored powder are obtained, which can be recrystallized from dioxane and contains the formula ~ f Ί? (, 2) 2 -C- (CH9) 9 (119) b- 2 16 3 2 i 2 2 -ch9-coo θ Na ® N- 2.

Melting point (recrystallized product): 103-107 ° C.

Guideline R: 52.3 parts of a technical mixture of 2/3 hexadecanol and 1/3 octadecanol (0.2 mol) are dissolved in 250 parts of toluene at 35 ° C. To this solution is added 13.9 parts of malonic acid dichloride (0.1 mol) over 30 minutes, at which point the temperature of the reaction mixture automatically rises to 40 ° and hydrochloric acid gas is released. The reaction mixture is then heated to 40 ° C, kept at this temperature for 24 hours and then cooled to 10 °, whereupon the reaction mixture precipitates. The filtered crude product is recrystallized from acetone. 49 parts of the formula in the form of colorless crystals are obtained

O O

(120) R-O-i-CH 0-i-O-R R = 67% - (CHO) .c-CHO o 2 o o 2153 33% - (CH 2) 17 -CH 3 reaction product.

Melting point: 54-59 ° C.

Guideline S: 19 parts of acetonedicarboxylic acid diethyl ester (0.1 mol) and 54.1 parts of octadecanol (0.2 mol) are heated to 100 ° C and kept at this temperature for 24 hours, whereby the theoretical amount of ethanol released by the transesterification reaction (0.2 moles) is distilled off from the reaction mixture. The reaction mixture is then cooled to 20 ° C and the crude product is recrystallized from acetone. 39 parts of the formula in the form of a colorless powder are obtained

OQO

(121) Reaction product according to CH3- (CH2) 17-O-CH2-i-CH2-C-O- (CH2> 17 "CH3).

Melting point: 58-60 ° C.

Note T: 192 parts of trimellitic anhydride (1 mole) and 540 parts of octadecanol (2 moles) are heated to 160 ° C and kept at this temperature for 60 minutes. After cooling the reaction mixture to 15-25 ° C, 690 parts of a colorless, waxy ester mixture are obtained, containing as main component the formula (122) / X (~ H) 1'-OOC- / N-COO- (- (CH2) 17-CH3 ) 2 ester.

Melting point: 52-60 ° C.

Acid number: 90

Guideline U: Proceed as in Guideline T, but use 218 parts of pyromellitic anhydride (1 mole) (instead of 192 parts of trimellitic anhydride). 748 parts of a similarly colorless waxy ester mixture are obtained, containing as main component the formula 72 79579 ”('H) 2 (123) -ooc-y \ -C00-. , -OOC-1 ^ β-COO-I, CH2'17 CH3 ^ 2 -. Melting point: 81-90 ° C. Acid number: 135 Note V:

Proceed as described in Guide T, but using 218 parts of pyromellitic acid dianhydride (1 mol) and 484 parts of hexadecanol (2 mol). 683 parts of a similarly colorless, waxy ester mixture are obtained, containing 2 '' -OOC-.x N-COO- as the main component. λ -OOC ls diester according to J-COO- * 'CH2'15 CH3'2. Melting point: 35-46 ° C. Acid number: 132 Help W:

Proceed as in T, but using 218 parts of pyromellitic acid dianhydride (1 mol) and 810 parts (instead of 540 parts) of octadecanol (3 mol). 1011 parts of a similarly colorless, waxy ester mixture containing the main constituent of formula are obtained. '(' H) - OOC- f "·. -COO-.

(125) a triester according to -OOC-11H--COO-CH217CH313. Melting point: 74-82 ° C, acid number: 51. Instruction X: 218 parts of pyromellitic acid dianhydride (1 mol) and 536 parts of oleyl alcohol (2 mol) are heated in the presence of 2 parts of hydroquinone used as polymerization inhibitor under an inert nitrogen atmosphere and maintained at 160 ° C: for 73 79579 hours at this temperature. After cooling the reaction mixture to 15-25 ° C, 743 parts of a light brown, liquid, oily ester mixture are obtained, containing as main component the formula (-H) 2 '126> (Ycool (- <CH 2> 8-CH = CH-, CH 2> 7-Cl , 3) 2 K / diester Acid number: 145 Guideline Y: 109 parts of pyromellitic acid dianhydride (0.5 mol) and 521 parts of dioctadecylamine (1 mol) are heated to 160 [deg.] C. and kept at this temperature for 5 hours. At 25 [deg.] C., 627 parts of an ocher-colored, waxy amide mixture are obtained which contain, as the main component, the formula (127) .alpha.-OC-(. ch2) a diamide according to 17-ch3 N (CH2) 17-CH3 2. Melting point: 45-55 ° C, acid number: 94. Note Z:

To a solution of 53.8 parts of octadecylamine (0.2 mol) and 25.8 parts of quinoline (0.2 mol) in 300 parts of acetone is added over 30 minutes a solution of 21.8 parts of pyromellitic acid dianhydride (0.1 mol) 300 parts of acetone, whereby the temperature of the reaction mixture automatically rises to 40-50 ° C, and a white precipitate precipitates from the reaction mixture. The reaction mixture is then kept under stirring for 3 hours, at which point the temperature initially drops from 40-50 ° C after 3 hours to 15-35 ° C. At the end of this post-reaction time, 79 parts of aqueous 38% hydrochloric acid solution and 100 parts of water are added to the reaction mixture, after which the reaction mixture is kept at 15-25 ° C for 30 minutes. The precipitated white precipitate is filtered off and washed with water until the pH of the wash water is 6.0. After drying the product at 50 ° C under reduced pressure, 71 parts of an amide mixture in the form of a white powder are obtained, which contain the main component of the formula (128) -OC - // \ -CO- (_ i -OC-i. Is —CO— l OYi> Diamide according to 2 - [(-NH- (CH2) 17-CH3) 2 Melting point: 175-180 ° C, acid number 150. Instruction AA:

Proceed as described in Guide Y, but using 161 parts of benzophenone tetracarboxylic acid dianhydride (0.5 mol) instead of 109 parts of pyromellitic acid dianhydride). 664 parts of an ocher-colored, semi-solid, waxy amide mixture containing the formula

O

✓ β, -v f-OH) 9 (129) -OC- / N / γΧ-CO-, 2; -OC- ί 2 1 l-CO- '^ CH2 17 CH3 V /' Y -n "

NcH2) 17-CH3 2 diamide. Acid number: 88.

Help BB:

A solution of 315 parts of the amide mixture prepared according to Guide Y (0.25 mol) and 46 parts of dodecylamine (0.25 mol) of 1500 parts of toluene is heated to reflux at about 111 ° C and kept at 75 79579 for 10 hours. , the water released in the reaction is removed by means of a water separator. The toluene is then distilled off under reduced pressure and the product obtained as a residue is dried. 343 parts of an ocher-colored, waxy amide mixture are obtained, containing as a major component the formula, 130); h ») -OC-l Ϊ-CO- '/ * CH 2) 17_CH 3 L N · / J - <.

: Triamide according to Nch2) -cb3 2, __i {-m- {ch2) u-ch3). Melting point: 81-85 ° C, acid number: 41. Guideline CC:

Proceed as described in Guide Y, but using 105 parts of hemimellitic acid (0.5 mol) instead of 109 parts of pyromelic acid dianhydride). 580 parts of a light brown, waxy amide mixture are obtained, containing N-co- as the main component of the formula CO-A (-oh) (131). - J »-CO- / (CH2) 17 CH3

N / -N

NcH2) 17-CH3 2 diamide. Melting point: 46-50 ° C, acid number: 44.

Help DD:

Proceed as described in Guide T, but using 210 parts of citric acid monohydrate (1 mole) (instead of 192 parts of trimetellic anhydride), the reaction time being 76 79579 at 160 ° C for 90 minutes (instead of 60 minutes). 672 parts of a colorless, waxy ester mixture are obtained, containing as the main component a diester of the formula CH2-COO- (1321 HO-i-COO- (-, CH2) 17-CHJ3 ch2-coo Melting point: 48-50 ° C, oxygen number: 83 .

Help EE:

Proceed as described in Guide T, but using 210 parts of citric acid monohydrate (1 mole) (instead of 192 parts of trimetellitic anhydride) and 507 parts of a technical mixture containing 2/3 of hexadecanol and 1/3 of octade cananol (2 moles) (part 540 of octadecanol). instead) the reaction time at 160 ° C is 90 minutes (instead of 60 minutes). 635 parts of a yellowish, waxy ester mixture are obtained, containing as main component CH - COO- fR) „R = 67% - (CH0) .c-CH0, · £ 'oJ io Zibi (133) HO-C-COO- (-h) 33% - (CH7) 17-CH.

ch2-coo- / I / J

diester. Melting point: 44-46 ° C, acid number: 87.

Help FF:

Proceed as in T, but use 210 parts of citric acid monohydrate (1 mol) instead of 192 parts of trimetellic anhydride) and 1042 parts of di-octadecylamine (2 mol) instead of 540 parts of octadecanol). 1150 parts of a yellowish, waxy amide mixture are obtained, containing as main component the formula 77 79579 ch2-c ° -1 (-OH1 (134) HO-C-CO -> (CH2) 17-CH3-CH2-CO - (CH2) Diamide according to 17-CH3 Melting point: 49-56 ° C, acid number: 45.

Guideline GG: 248 parts of stearic acid (1 mol), 67 parts of 2,2-bis (hydroxymethyl) -propionic acid (0.5 mol) and 2.5 parts of p-toluenesulfonic acid used as a catalyst are dissolved in 200 parts of p-xylene. This solution is heated to reflux at about 140 ° C and maintained at this temperature until the theoretical amount of water (1 mole) formed in the esterification reaction is removed azeotropically by means of a water separator. The p-xylene is then distilled off under reduced pressure and the product obtained as a residue is dried. 306 parts of a yellowish, waxy ester mixture are obtained which contain, as the main component, a diester of the formula O 9H3 (135) ch3- (ch2) 16- <i-o-cH2- <i: -cH2-o-c- (ch2) 16-ch3 ch3. Melting point: 39-42 ° C, acid number: 92.

Guideline HH: 222.3 parts (0.5 moles) of the sodium salt of bis-2-ethylhexylhexyl ester and 270 parts (1.0 mole) of stearyl alcohol are heated together with 2.2 parts (0.04 moles) of sodium methylate 165- To a temperature of 170 ° C. The melt obtained is kept at this temperature for 3 hours and cooled to 90 ° C. The 2-ethylhexyl alcohol formed is distilled off under reduced pressure.

78 79579

As a distillation residue, 360 parts of the sulfosuccinic acid bis-octadecyl ester sodium salt of the formula ch2-co-o-c18h37 (136) NaO3S-CH-CO-O-C18H37 are obtained in the form of a yellow waxy product.

Examples of the valence of the new compounds used as intermediates

Example 1:

Proceed as described in Guide A, but using 284 parts (1 mol) of stearic acid and 256 parts of palmitic acid (1 mol) (instead of 568 parts of stearic acid). 650 waxy ester mixtures are obtained which, in addition to homologous mono- and triesters, contain the

O

/ - (cr2) 2 (Å-c-r0) 2 r · = 50% - (CH-) (137) ° 2 16 3 ^ (CH2) 2-OH 50% - (CH2) 14-CH3 diester mixture. Melting point: 38-42 ° C.

Example 2:

Proceed as described in Guide A, but using 136 parts of pentaerythritol (1 mole), 852 parts of stearic acid (3 moles), 5 parts of p-toluenesulphonic acid and 1000 parts of p-xylene to azeotropically remove 3 parts of water. 930 parts of a waxy ester mixture are obtained which, in addition to the homologous mono-, di- and tetraesters, contain

O

(CH-j-O-d - - (CH-). Fi-CH-.) (138) c / 2 2 16 3 3

^ CH2OH

79 79579 triester. Melting point: 54-58 ° C.

Example 3:

Proceed as described in Guide A, but using 121 parts of tris (hydroxymethyl) aminomethane (1 mole), 568 parts of stearic acid (2 moles), 3.4 parts of p-toluenesulphonic acid and 600 parts of p-xylene, whereby the theoretical ring formation in the esterification reaction An amount of 3 moles of water is removed azeotropically. 630 parts of a waxy mixture are obtained which, in addition to the homologous, cyclic mono- and triesters, contain

O

(139) CH3- (CH2) 16- / NCH25_2H2- ° -c- (cH2,16-CH3

'vCH2OH

diester. Melting point: 75-78 ° C.

Example 4:

Proceed as described in Guide A, but using 273 parts of laurylamine diethoxylate (1 mole) (prepared from 1 mole of laurylamine and 2 moles of ethylene oxide), 340 parts of behenic acid (1 mole), 2.3 parts of p-toluenesulphonic acid and 625 parts of p-xylene, wherein 1 mole of water is removed azeotropically. 593 parts of a pale yellow, waxy ester mixture are obtained which, in addition to the homologous diester, contains as a main ingredient the formula

O

(ch2) 2-o - <? - (ch2) 20-ch3 (140) CH, - (0Η9) ιη — Nx v (ch2) 2-oh monoester. Melting point: 35-37 ° C.

80 79579

Example 5;

Proceed as in Guide A, but using 292 parts of N, N, N ', N1-tetrakis (2-hydroxypropyl) -ethylenediamine (1 mol), 852 parts of stearic acid (3 mol), 6 parts of p-toluenesulphonic acid and 933 parts of p- xylene, with 3 moles of water being removed azeotropically. 1085 parts of a waxy ester mixture are obtained which, in addition to the homologous mono-, di- and tetraesters, contain as a major component the formula _ 9h3 ° ^ Hj-άΗ-Ο-Ic- (ch2) 16-ch3 N i J3 (141) I i ^ CH2-CH- 0- I f 2 ώ3 (~ h)

IC «2 CHS

| i / CH - CH-O-! x: h „-ch-o-2 t ch3 according to triester. Melting point: 35-40 ° C.

Example 6:

Proceed as described in Guide A, but using 42.4 parts of 1,2,4-butanetriol (0.4 mol), 227.2 parts of stearic acid (0.8 mol), 1.3 parts of p-toluenesulphonic acid and 270 parts of p -xylene, with 0.8 moles of water being removed azeotropically. 240 parts of a waxy ester mixture containing the formula e, 79579! CH2-O- (-h) (142) CH-O- "0

H 2 -i- (CH 9) 1 -H

0H2- ° - L J2 diester. Melting point: 46-48 ° C.

Example 7:

Proceed as described in Guide A, but using 65.25 parts of tris (hydroxyethyl) isocyanurate (0.25 mol), 142 parts of stearic acid (0.5 mol), 2.1 parts of p-toluenesulphonic acid and 170 parts of p-xylene, whereby 0.5 mol of water is azeotroped and the crude product obtained is recrystallized from acetone. 150 parts of an ester mixture containing the formula as the main ingredient are obtained as a white powder

(CH 2) -OH

(143) A *

O 0 = C C = 0 O

CH3- tCH2 »16 - ^ - ° ~ <CH2> 2 - ^ A- (CH2) 2-O- (CH2) 16-CH3 8

O

diester: Melting point: 67-69 ° C.

Example 8: 201.8 parts of stearylamine (0.75 mol) are dissolved in 700 parts of isopropanol at 50 ° C. To this solution is added 74.3 parts of isocyanuric acid triglyceride (0.25 moles) (1 mole of isocyanuric acid and 3 moles of epichlorohydrin). The reaction mixture is heated to 80 ° C and kept at this temperature for 5 hours with stirring to form a slightly turbid solution. At 80 ° C, this solution is filtered. As the filtrate cools, the reaction product precipitates. The product is filtered, washed with 200 parts of isopropanol portionwise and dried at 35 ° C under reduced pressure. 223 parts of formula 82 79579 (144) 9 are obtained

OH C OH

ch3- (ch2) 1 7-nh-ch2 - (!: h-ch2-n // xn-ch2 - (: h-ch2-nh- (ch2) 1 7-ch3 0 = 4: ό = ο

V

(Jh2-CH-CH2-NH- (CH2) 17 'CH3 i) H

compound. Melting point: 78-83 ° C.

Example 9: 167 parts of isocyanuric acid triglyceride (0.5 mol), 427 parts of stearic acid (1.5 mol) and 1.5 parts of sodium stearic acid salt acting as a catalyst are heated to 135 ° C. At this temperature, the heating bath is removed. The temperature of the reaction mixture then automatically rises to 160 °. After completion of the exothermic reaction, the reaction mixture is kept at 150 ° C for 3 hours with stirring. The melt is then allowed to cool and solidify. 594 parts of the formula Π45) 5 are obtained? 0 OH C OH 0 CH3- (CH2), 6-i-CK3I2 - !: H-Cl ^ -N VcHj-CH-CHj-Oi- (CH2) g-CH3, o = ic = o N / o (! : h2-ch-ch2-oc- (ch2) 1 6-ch3

J) H

which appears as a pale beige crude product. A sample of the crude product is recrystallized from methanol. The recrystallized product is colorless. Melting point: 58-62 ° C.

Example 10: 139 parts of stearylamine (0.5 mol) are dissolved at 75 ° C in 400 parts of isopropanol. To this solution is added 50.5 parts (0.25 moles) of butanediol diglycide (prepared from 1 mole of 1,4-butanediol and 2 moles of epichlorohydrin). The reaction solution is heated to 80 ° C and kept at 80 ° C for 4 hours with stirring. The solvent is distilled off from the clear solution under reduced pressure. The residue is recrystallized from methanol. 163 parts of the formula are obtained

Π46) 0H 0H

a compound according to CH3- (CH2) 17-NH-CH2-CH-CH2-O- (ch2) 4-o-ch2-ch-ch2-nh- (ch2) 17-ch3. Melting point: 85-88 ° C.

Example 11: 76.02 parts (0.1 mol) of the compound of formula 146 prepared according to Example 10 are dissolved in 200 parts of o-xylene at 60 ° C. To this solution is added 56.9 g of stearic acid (0.2 mol). This solution is heated to approx.

145 ° C to reflux and maintained at this temperature for about 8 hours until the theoretical amount of water (0.2 moles) formed in the esterification reaction is azeotroped with a water separator. The solvent is distilled off from the clear solution under reduced pressure. 128 parts of formula (147) are obtained as a distillation residue? ? CH3 "CB2» 16- \ ° h ° h / - (CH2) 16'CH3

^ N-CH2-CH-CH2-O- (ch2) 4-O-CH2-CH-CH2-N

CH3- (CH2) 17 ^ (CH2) 17-CH3. Melting point: 82-84 ° C.

Example 12:

To a solution of 10.4 parts of diethylenetriamine (0.1 mol) in 80 parts of toluene is added, at room temperature (15-25 ° C), a solution of 59 parts of octadecyl isocyanate (0.2 mol) in 240 parts of toluene for 20 minutes. . The temperature of the reaction mixture rises automatically to 50 ° C. The reaction mixture is then heated to reflux at about 111 ° C, maintained at this temperature for 15 minutes, then cooled to 60 ° C and divided into two portions. Toluene is distilled off from half of the reaction mixture at 60 ° C under reduced pressure. As a distillation residue, 34 parts of an amide mixture in the form of a beige-colored powder containing the formula -NH- as the main component are obtained.

liv, HO

<148> A- -o η 1 5 (CH2) 2 -C-NH- (CH2) 17-CH3 NH- L _ 2

L

reaction product according to Melting point: 138-141 ° C.

Example 13: 106.7 parts of a technical commercial mixture containing stearyl-diethylenetetramine (0.3 mol) as the main ingredient are dissolved in 300 parts of toluene at room temperature (15-25 ° C). To this solution is added a solution of 88.8 parts of octadecyl isocyanate (0.3 mol) in 200 parts of toluene, the reaction mixture being cooled to 25 ° C and kept at this temperature for 6 hours. The reaction mixture is then heated to 50 ° C: n temperature and maintained at this temperature for 2 hours. The toluene is then distilled off from the reaction mixture under reduced pressure at 50 ° C, and the reaction residue is recrystallized from methanol. 163 parts of a product mixture in the form of a colorless powder are obtained, containing as principal 85 - 79 - 79 CH -, - (CH-) 1 -, - N- (149) Vh2) 2 N2 I 2 2 N-O (1H2) 2 -C- Reaction product according to NH- (CH2) 17-CH3. Melting point 86-92 ° C.

Example 14; 177.9 parts of the mixture used in Example 13, containing stearyl-diethylenetetramine (0.5 mol) as the main ingredient, are melted together with 199.3 (0.5 mol) of stearic acid methyl ester at 60 ° C. This melt is heated to 190 ° C and maintained at this temperature until the theoretical amount of methanol (0.5 mol) released by the reaction is distilled off from the reaction mixture. 296 parts of a product mixture in the form of a pale yellow wax containing the formula -ch2- (ch2) 17-n- (_h, (CH,), _

(150) N O

(CH2) 2 -c- (CH2) 16-CH3 NH - '. Melting point: 66-70 ° C.

Example 15: 53 parts of octadecylamine (0.2 mol) are melted at 35 ° C. To this melt is added 22.6 parts of cyanoacetic acid ethyl ester (0.2 moles) at 40 ° C. The reaction mixture is then kept at 40 ° C for 2 hours and then cooled to room temperature (15-25 ° C), whereupon the reaction product precipitates. The crude product is filtered off, washed with water and recrystallized from toluene. 65 parts of the reaction product of the formula 86 7 9 5 7 9 (151) NC-CH2-CO-NH- (CH2) 17-CH3 in the form of a white powder are obtained. Melting point: 79-80 ° C.

Examples of the preparation of new compounds for use as adhesives

Example 16: 681 parts of an ester mixture prepared according to step A (1 mol) are dissolved in 1000 parts of dichloromethane. To this solution is added 128 parts of chlorosulfonic acid (1.1 moles) over a period of 45 minutes, keeping the temperature at 25-35 ° C under cooling and the volatile hydrochloric acid gas being evacuated with nitrogen. After the addition of chlorosulfonic acid is complete, the reaction mixture is kept at 35 ° C for one hour.

The dichloromethane is then distilled off. The crude product obtained as a residue is recrystallized from methyl ethyl ketone. 620 parts of an ester mixture in the form of a white powder containing the formula as the main ingredient are obtained

O

(- <CH2> 2-o-4- <CH2> 16-CH 3) 2

(152> N

Nch2) 2-0SO3H

acid ester according to Melting point: 80-83 ° C, acid number: 122.

Example 17:

Proceed as in Example 16, but use 653 parts of the ester mixture (1 mol) prepared according to Example 1 instead of 681 parts (1 mol) of the ester mixture prepared according to Example A. 613 parts of a recrystallized mixture of methyl ethyl ketone in the form of a white powder containing 87 79579 o (153) / t '(CH2'2-0-C-Ro) 2 Ro = 504 - (CH2 »16'CH3 \ 50%) are obtained as the main constituent. - (CH 2), .- CH 2 x (CH 2) 2 -OSO 3 H * * Melting point: 70-75 ° C, acid number: 105.

Example 18:

Proceed as in D, but use 681 parts of the ester mixture prepared according to A instead of 624 parts of the ester mixture containing the main ingredient glycerol stearate (1 mole) and recrystallize the crude product from methyl ethyl ketone. 600 parts of an ester mixture in the form of a white powder are obtained, containing as main constituent the formula / (- (O½) -O-i- <CH2) 16-CH3) z (154) \.

'' (CH-)) -, -O-P-OH 2 2 \ 0H

acid ester according to Melting point: 78-83 ° C, acid number: 95.

Example 19: 681 parts of an ester mixture prepared according to instruction A (1 mole), 147 parts of maleic anhydride (1.5 moles), 4 parts of p-toluenesulfonic acid used as a catalyst and 0.33 parts of hydroquinone used as a polymerization inhibitor, dissolved in 1000 parts of toluene. This solution is heated to reflux at about 110 ° C and maintained at this temperature for 12 hours. The reaction solution is then clarified of impurities. After distilling off the solvent, the crude product is recrystallized from acetone. 662 parts of an ester mixture in the form of a white powder are obtained, containing as main component 88 79579 of the formula / (- Ich2) 2-o -? - (ch2) 16-ch3) 2 (155) N'v

v (CH 2) 2 OOC-CH = CH-COOH,

acid ester according to Melting point: 53-55 ° C, acid temperature 69.

Example 20:

Proceed as in Example 16, but using 934 parts of the ester mixture prepared according to Example 2 (1 mol), 126.8 parts of chlorosulfonic acid (1.088 mol) and 1555 parts of dichloromethane, add chlorosulfonic acid over 30 minutes and keep the reaction mixture for 4 hours. for 35 hours at reflux temperature. 867 parts of the same methyl ethyl ketone recrystallized ester mixture are obtained in the form of a pale powder containing, as the main ingredient, the formula

(156) C

\: h2-oso3h. Melting point: 60-64 ° C, acid number 49.5. Example 21:

Proceed as in Example 16, but using 635 parts of the ester mixture prepared in Example 3 (1 mol), 128 parts of chlorosulfonic acid (1.1 mol) and 1500 parts of dichloromethane, add chlorosulfonic acid over 30 minutes and recrystallize the crude product from acetone. 622 parts of an ester mixture in the form of a white powder are obtained, containing as main component 89 79579 (157) CH3-'CH2 »16-c / V2 0 I CH2-O-C- (CHO) 1, -CH, N-C 2 2 16 3

XCH2-0S03H

acid ester according to Melting point: 66-71 ° C, acid content: 75.

Example 22:

Proceed as in Example 19, but using 635 parts of the ester mixture prepared according to Example 3 (1 mol), 98 parts of maleic anhydride (1 mol), 18 parts of p-toluenesulfonic acid, 1 part of hydroquinone and 1500 parts of p-xylene and keep the reaction mixture for 8 hours. 110 ° C. 681 parts of an acetone-reconstituted ester mixture containing the formula

- O

/ \

(158) CH3- (CH2) 16-C CH2 O

I an acidic ester according to CH.-O-C- (CH9), -CH-, N __ <2 2 16 3 ch2-ooc-ch = ch-cooh. Melting point: 53-55 ° C, acid content: 53.

Example 23:

Proceed as in Example 16, but using 624 parts of the mixture described in Guide D, consisting of 1,3- and 1,2-glycerol distearate (1 mol), 128 parts of chlorosulphonic acid (1.1 mol) and 666 parts of dichloromethane, add chlorosulphonic acid Within 30 minutes and recrystallize the crude product from acetone. 616 parts of an ester mixture are obtained which contain, as the main constituent, an acidic ester of the formula 90 7 9 5 7 9 CH2-O- (-so3h) (159) CH-O-%} . Melting point: 54-56 ° Cf acid number: 71.

Example 24:

Proceed as in Example 16, but using 595 parts of the ester mixture prepared according to Example 4 (1 mole), 128 parts of chlorosulfonic acid (1.1 moles) and 800 parts of dichloromethane, add chlorosulfonic acid over 30 minutes and recrystallize the crude product from acetone. 681 parts of an ester mixture containing the formula as the main component are obtained as a white powder

O

/ • ch2) 2-Ä-c- (ch2) 20-ch3 (160) CH -.- (CH K.-N.

j z ri \ (CH2) 2-0SO3H

acid ester according to Melting point: 65-70 ° C, acid content: 79.

Example 25:

Proceed as in Example 19, but using 1090 parts of the ester mixture prepared according to Example 5 (1 mol), 98 parts of maleic anhydride (1 mol), 20 parts of p-toluenesulfonic acid and 2.2 parts of hydroquinone in 3333 parts of toluene. 1027 parts of a similarly recrystallized, waxy ester mixture from acetone are obtained, containing as main component CH3 ~ “ch2-ch-o- 9 N -C- (ch2) 16-CH3 (161) iΝϋΗ, -ΟΗ-Ο ^ ~ 3

CH2 L

i J

CH, ch3 - LCH, -iH-O! _- ° c-ch = ch-cooh

\ I

xCH, -CH-O- i-3 acid ester. Melting point: 37-38 ° C, acid number: 35.6.

Example 26:

Proceed as in Example 16, but use 1090 parts of the ester mixture prepared according to Example 5 (1 mol), 116 parts of chlorosulfonic acid (1 mol) and 2500 parts of dichloromethane and recrystallize the crude product from acetone. 1006 parts of an ester mixture in the form of a white powder are obtained, containing CH3 as the main ingredient.

CH - CH-O- O

(162) N'v -ί- (ch2) 16 "ch3 lW-CH-0- 2 16 3 CH2 iH3 3 CH- CH, _

, I J

CH - CH-O- -SO, H

V - CH, -CH-O- 1H acidic ester. Melting point: 65-70 ° C, acid content: 55.

77 ”92 7 9 5 7 9

Example 27:

Proceed as in Example 16, but using 92.1 parts of the diethyl ether prepared in accordance with Guide B (0.15 mol), 17.5 parts of chlorosulfonic acid (0.15 mol) and 350 parts of dichloromethane and recrystallize the crude product from ethyl acetate. . 85.3 parts of a sulfonated compound of the formula (CH2) 17-CH2 <163) L J-o- (ch2) 17-ch, SO3HX · are obtained. Melting point: 78-82 ° C, acid path: 90.

Example 28:

Proceed as in Example 16, but using 61.4 parts of the diether prepared according to Example C (0.1 mol), 11.56 parts of chlorosulfonic acid (0.1 mol) and 300 parts of dichloromethane and recrystallize the crude product from ethyl acetate. 61.8 parts of the formula o- (ch2) 17-ch3 / • \ are obtained.

(164); J

a sulfonated compound according to i -o- (ch2) 17-ch3 so3 ^ ·. Melting point: 71-73 ° C, acid path: 106.

Example 29: 95.9 parts of the ester mixture prepared according to Example 6 (0.15 mol) and 21.3 parts of phosphorus pentoxide (0.15 mol) are dissolved in 380 parts of toluene. This solution is heated to 93 79579 at 85 ° C and kept at this temperature for 6 hours with stirring. The reaction mixture is then filtered. The solvent is distilled off from the filtration under reduced pressure. The crude product as distillation waste is recrystallized from acetone. 103 parts of an ester mixture in the form of a beige powder containing the formula as the main ingredient are obtained

CH2-O-, p ^ H

(165)? H ~ ° ~ \> H

f 2 - O

an acidic ester according to 1H2-O-j -i- (CH2) 16-CH3 J2. Melting point: 48-50 ° C, acid number: 65.

Example 30:

Proceed as in Example 19, but using 158.6 parts of the ester mixture prepared according to Example 7 (0.2 mol), 19.6 parts of maleic anhydride (0.2 mol), 1.5 parts of p-toluenesulfonic acid and 0.5 part hydroquinone in 150 parts of p-xylene. 109 parts of an ester mixture recrystallized from acetone in the form of a white powder are also obtained, containing as main component the formula (CH_) ~ -O-C-CH = CH-C-OH 2 2 [mu] l (0). o = cr Nc = o _ y il u acid diester according to CH 2 - (CH 2 I 16 -C-O- (CH 2) 2 -Νχ 1 - (CH 2) 2 -O-C- (CH 2) 16 -CH 3 I. Melting point: 65-67 ° C, acid number: 53.

Example 31: 332 parts of the compound of formula 144 prepared according to Example 8 (0.3 mol) are dissolved in 1000 parts of isopropanol at 60 ° C. To this solution is added a solution of 29.4 parts of maleic anhydride (0.3 mol) in 500 parts of methyl ethyl ketone, keeping the temperature of the reaction mixture at 60 ° C. The reaction mixture is then kept at this temperature for 3 hours and then cooled to 15 ° C, whereupon the reaction product precipitates. The product is filtered off with suction and dried in vacuo at 35 ° C. 319 parts of a colorless ester mixture are obtained which contains the formula as the main ingredient

O

OH OH

(/ \ 'CH3- (CH2) 17-NH-CH2-CH-CH2-N N-CH2-CH-CH2-NH- (CH2) 17-CH3 o = cc = o (167) XN ^ jCH2) 17- CH3 CH2-CH-CH2 "N" oh 0h \> ch = ch-cooh

A

acid ester according to Melting point: 62-65 ° C, acid content: 47.

Example 32:

Proceed as described in Guide D, but using 229.5 parts of the compound of formula (145) prepared according to Example 9 (0.2 mol) dissolved in 1800 parts of carbon tetrachloride and a suspension prepared from 19 parts of phosphorus pentoxide (0.13 mol). moles) in 500 parts of carbon tetrachloride, and the reaction is carried out for 3 hours at 50 ° C. 179 parts of a pale beige ester mixture, similarly crystallized from methyl ethyl ketone, are obtained, containing as formula 0

II

0 OH t OH O

Il \ / \ i il, CH3- (CH2) 1-C-O-CH2-CH-CH2-N N-CH2-CH-CH2-O-C- (CH2) 16-CH3 o = c t = 0

(168) V O

ch2-ch-ch2-o -! *: - (ch2) 1 6-ch3 1 f

O-P-OH

NDH

95 79579. Melting point: 48-55 ° C, acid content: 91.

Example 33: 153.8 parts of the compound of formula (147) prepared according to Example 11 (0.1 mol) are mixed with 10 parts of succinic anhydride (0.1 mol), melted at 180 ° C and kept at this temperature for 6 hours. The crude product obtained is recrystallized from ethyl acetate and dried at 45 ° C under reduced pressure. 121.1 parts of a colorless ester mixture containing the formula (169) as a major component are obtained.

O

, 4 S? ? c- (ch2) 16-ch3 CH3 "<CH2 16 * .0-fi-CH2-CH2-t-OH OH * / ..

n-ch2-i: an acidic ester according to h-ch2-o- (ch2) 4-o-ch2-ch-ch2-n- (CH3) (CH2) n (ICH2) 17-CH3. Melting point: 62-65 ° C, acid content: 41.

Example 34:

Proceed as described in Guide H, but using 63 parts of dimethylmaleic anhydride (0.5 mol). 360 parts of crude product in the form of a heavy powder are obtained, which can be recrystallized from ethyl acetate and containing as the main ingredient the formula

(170) VH "O

(^ H2) 2 -f- (CH2) 16'CH3 (L2) 2 'a 0

/ 1H- -i-C * C-COOH

The acid amide of J cltjCHj 96 79579.

Melting point (recrystallized product); 66-72 ° C.

Acid number (recrystallized product): 67

Example 35:

Proceed as described in Guide H, but using 56 parts of itaconic anhydride (0.5 mol). 360 parts of a crude product in the form of a cream powder are obtained, which can be recrystallized from acetone and which contains NH-O! (171). h. (* H2) 2 i -e- (CH2) 16-CH3

N- [. _L

! (<u) f o i It

iH- -C-CH2-C-COOH

reaction product according to

Melting point (recrystallized product): 79-83 ° C Acid number (recrystallized product): 87

Example 36:

Proceed as described in Guide H, but using 55 parts of pyromellitic anhydride (0.25 mol). 360 parts of crude product in the form of a white powder are obtained, which can be crystallized from ethyl acetate and containing, as the main constituent, the formula (r 1 x (172) \ NH-I / _ _ I (CH0) 0 already I 0 0 / i 2 2 ii \ v 4 '—V Ί / N- -C- (CH,) 1fi-CH, V ~ CVV “C“ \ 1 2 16 3? Χ / I (CH ~), - -2 |

ÄH- - i00H J

97 79579.

Melting point (recrystallized product): 124-130 ° C Acid number (recrystallized product): 80

Example 37:

Proceed as described in Guide H, but using 41 parts of propane sultone (0.5 mol). 260 parts of crude product in the form of an ocher-colored powder are obtained, which can be recrystallized from acetone and contains NH-O (173) i (CH2) 2 as the main ingredient; -i- (CH2i 16-CH3 N 'r

^ 2 ^ 2 - (CH-) -, - SO 2 H

NH reaction product.

Melting point (recrystallized product): 96-99 ° C Acid number (recrystallized product): 49

Example 38: 320 parts of the amide mixture prepared according to step D (0.5 mol) are melted at 100 ° C. To this melt is added '82 parts of bicyclo (2,2,1) -hept-5-ene-2,3-dicarboxylic acid anhydride (0.5 mol). The reaction mixture is kept under stirring, after which the anhydride dissolves after 2-3 minutes and the temperature of the reaction mixture automatically rises to 115-120 ° C in about 10 minutes. The reaction mixture is kept at 120 ° C for 30 minutes and then cooled to room temperature (15-25 ° C). 380 parts of a light brown wax are obtained, containing 98 79579 as the main ingredient.

NH-! O

I j li (174) (^ H2) 2i -C- <ch2) 16 ~ CH3 NH-! _ 2 | ^ 2 ^ 2 ί Γ O CH-CH, 'NH' j -K-CH / XCH2 ^

XCH ^ CH ^

I 2 COOH

reaction product according to Melting point: 63-64 ° C, acid content: 61.

Example 39: 347 parts of the reaction product prepared according to Example 12 (0.5 moles) present as a solution in 160 parts of toluene at 60 ° C are added over 15 minutes a solution of 49 parts of maleic anhydride (0.5 moles) in 40 parts toluene, whereupon the temperature of the reaction mixture rises to 70 ° C by itself. The reaction mixture is then heated to a reflux temperature of about 111 ° C, kept at this temperature for 2 hours and then cooled to 60 ° C. The solvent is then distilled off from the reaction mixture under reduced pressure. The distillation residue gives 384 parts of a crude product in the form of a beige powder which can be recrystallized from dioxane and which contains, as a major component, the formula j? »- Γ o (175) 'ί" 2'2_-C-NH- (CH2) 17-CH3 N- _ 2

(CH 2), O

i 2 2 li

NH- [_-C-CH = CH-COOH

acid amide according to

Melting point (recrystallized product): 112-130 ° C acid number (recrystallized product): 64 99 79 579

Example 40; 195 parts of the product mixture prepared according to Example 13 (0.3 mol) are dissolved in 900 parts of toluene. To this is added a solution of 30 parts (0.3 moles) of succinic anhydride in 300 parts of methyl ethyl ketone at 50 ° C. The reaction mixture is then heated to 65 ° C and maintained at this temperature for 3 hours. The solvent is then distilled off from the reaction mixture under reduced pressure. The crude product as a distillation residue is recrystallized from ethyl acetate. 175 parts of a mixture of amides in the form of a beige powder are obtained, containing as main component the formula ch3- <ch2> 17-N- [-h] H2) 2 "o -> —— — CH4) 17-CH2- (176) (9H2) 2 - - ^ "H" Ϊ u -ö-ch2-ch2-cooh. Melting point: 55-58 ° C, acid content: 74.

Example 41:

Proceed as described in Example 40, but using 444 parts of phthalic anhydride (0.3 moles) (instead of 30 parts of marine succinic anhydride). 192 parts of a mixture of amides in the form of a beige-colored powder are obtained, containing as main constituent the formula, 00 79579 CH3- <CH2 »17-f- Ί C-h] 'fa12 o (177)

(‘^ H2) 2 L 2-) 7 3J

Λη-

COOH

reaction product according to Melting point: 65-70 ° C / acid state: 70.

Example 4 2:

The procedure is as described in Example 40, but using 34.2 parts of glutaric anhydride (0.3 mol). 166 parts of an amide mixture in the form of a beige-colored powder are obtained, which contains the formula ch3- <ch2) 17-n-L-h] (ch> r Ί Π78) · _2 as the main component. ? -C-NH- (CH 2) 17 -CH- • w 2 o ~ I |

NH ”J -C- (CH2) 3-COOH

reaction product according to Melting point: 53-56 ° C, acid content: 73.

Example 43:

The procedure is as in Example 40, but using 186.6 parts of the product mixture obtained according to Example 3 (0.3 mol) and 29.4 parts of maleic anhydride (0.3 mol), whereby the maleic anhydride is dissolved in 300 parts of toluene (instead of methyl ethyl ketone). 182 parts of an amide mixture in the form of a beige-colored powder are obtained, containing as the main component the formula, 0,79579 CH3- (CH2> 17 -? - 1 Μ

-? b2> 2 O I

(179) A- II

(K), [- ^ - <CH2> 16-C «3_

Ah- - ° Ί

I J | -C-CH = CH-COOHJ

reaction product according to Melting point: 62-67 ° C, acid content: 7 8.

Example 44: 116 parts of methanetricarboxylic acid triethyl ester (0.5 mol) and 406 parts of octadecanol (1.5 mol) are heated to 140 ° C and kept at this temperature for 17 hours, the theoretical amount of ethanol released as a result of the transesterification reaction (1, 4 moles) is distilled off from the reaction mixture. The reaction mixture is then cooled to 20 ° C and the crude product is recrystallized from acetone. 300 parts of a colorless powder of the formula are obtained

W ".J

(180) Nc / / \

CH, - (CH0), .- Ο-C H

3 2.7 {reaction product. Melting point: 50-54 ° C.

Example 45: 67.2 parts of the intermediate prepared according to Example 15 (0.2 mol) are dissolved in 300 parts of dimethylformamide at room temperature (15-25 ° C) and 16 parts of 50% sodium hydroxide solution (0.2 mol) are added, whereby a solution of the corresponding sodium salt is formed. 16.8 parts of 1,6-n-hexanediisocyanate (0.1 mol) are now added to this solution over 15 minutes at 30 ° C. The reaction mixture is then kept at 30 [deg.] C. for 4 hours, diluted with 1000 parts of 102,79579 water and adjusted to pH 4.5 with aqueous acetic acid solution, whereupon the reaction mixture precipitates free. The crude product is filtered and recrystallized from acetic acid ethyl ester. 61.3 parts of the white powder of the formula (181) ° NC OO C-NH- (CH2) 1 - CH2.1, 1/2 17 3, CH-O-NH- (CH--), NH-C-CH 2 ^ 6 \

CHq- (CHO), -, - NH-C CH

j l 1 / li

O

reaction product according to Melting point: 116-120 ° C.

Example 46:

Proceed as in Example 45, but dissolve the intermediate prepared according to Example 15 in 200 parts of dimethyl sulfoxide (instead of 300 parts of dimethylformamide) and use 17.4 parts of toluene-2,4-diisocyanate and about 20% of 1-toluene-2, 6-diisocyanate (instead of 16.8 parts of 1,6-n-hexane diisocyanate). 68 parts of a mixture of reaction products in the form of a pale yellow powder containing about 80% of the formula NC ™ 3 (182) \ 9 '.CH-O-NH-. / X _ / \ _ / 9 / »are obtained.

CH, (CH,). -, - NH-C NH-C-CH

ä c-nh- (ch2) 17-ch3 and about 20% of the formula

II

103 79579 (183)

“O CN

NC 9 ^ 3 /

X O XnH-C-CH

X il J — ζ \ CH-C-NH-./ y. C-NH (CH2) 17-CH3 CH., - (CHO) .., - NH-C 0 3 2 17 Ä reaction product. Melting point: 116-120 ° C.

Example 47:

Proceed as described in Guide T, but using 322 parts of benzophenone tetracarboxylic acid dianhydride (1 mole) (instead of 192 parts of trimellitic anhydride). 823 parts of a colorless, waxy barrier mixture containing the formula

O

(184) l · (OJ

-ooc-X 1 / V N.-coo--° 0C- ^ I ^ J-COO- (- <ch2) 17-ch3) 2 diester. Melting point: 46-47 ° C, acid number: 110 Example 48:

Proceed as described in Guide T, but using 176 parts of tricarballyl acid (1 mole) (instead of 192 parts of trimellitic anhydride). 650 parts of a colorless, waxy ester mixture are obtained, containing as a major component a diester of the formula (185) f2-C0-O- (-H1, °° “(- (CH2) -CH) CH2-COO-104 79579). 45 ° C, acid number: 85. Example 49:

Proceed as described in Guide T, but using 210 parts of citric acid monohydrate (1 mol) (instead of 192 parts of trimetellitic anhydride), 270 parts of octadecanol (1 mol) and 521 parts of dioctadecylamine (1 mol) (instead of 540 parts of octadecanol). 909 parts of a yellowish waxy amide-ester mixture are obtained, containing CH-CO- (“OH) (186) Ho-r-ro- ((O- (CH) -CH) CH2-CO-) as the main ingredient. _ ~ / (ch2) 17-ch3

-OF

The amide ester of 17 (ch2) 17-ch3. Melting point: 54-67 ° C, acid number: 63. Example 50:

Proceed as described in Guide T, but using 174 parts of trans-aconitic acid (1 mole) (instead of 192 parts of trimellitic anhydride) and carry out the reaction in the presence of 1 part of hydroquinone acting as a polymerisation inhibitor at 160 ° C for 30 minutes (60 minutes). 650 parts of a colorless, waxy ester mixture are obtained, containing as main component the formula (187) -00C-C-CH2-C0- (^

Il 2 l_HJ

HC-C00- (((CH2> 17-CH3)) 2. Melting point: 42-43 ° C, acid number: 83. Example 51:

Proceed as in T, but using 105 parts of trans-aconitic acid (0.5 moles) (instead of 192 parts of trimetellitic anhydride) and 521 parts of dioctadecylamine (1 mole) (instead of 540 parts of octadecanol) and carry out the polymerization reaction. in the presence of 1 part of hydroquinone as an inhibitor. 560 parts (98% of theory) of a yellowish, waxy amide mixture are obtained, containing as main component the formula -oc-c-ch2-co- (_oh} (188) _ HC-CO- J Γ ^ / (CH2) 17-CH3

-OF

\ (ch2) a diamide according to 17-ch3. Melting point: 52-57 ° C, acid number: 47. Example 52:

Proceed as described in Guide GG, but using 170.4 parts (instead of 284 parts) of stearic acid (0.6 mol), 48.9 parts of Ν, Ν-bis (2-hydroxyethyl) -glycine (0.3 mol) ( 2,2-bis- (hydroxymethyl) -propionic acid instead of 67 parts), 1.2 parts (instead of 2.5 parts) of p-toluenesulfonic acid and 170 parts (instead of 200 parts) of p-xylene, giving 0.6 moles ( 1 mole) the water is removed azeotropically. 208 parts of a yellowish, waxy ester mixture are obtained, containing as main component the formula (189) O 0 ch3- (ch2) 16-c-o-ch2-ch2-n-ch2-ch2-o-c- (ch2) 16-ch3 CH2

ioOH

diester. Melting point: 64-68 ° C, acid number: 106. Example 53: 95.6 parts of nitrilotriacetic acid (0.5 mol) and 522 parts of dioctadecylamine (1 mol) are heated to 79579 106 160 ° C and kept at this temperature for 6 hours. After cooling the reaction mixture to 15-25 ° C, 565 parts of an ocher-colored, waxy amide mixture are obtained, containing as main component CH3- (CH2) jj (CH2), 7-CH3 NC-CH2-N-CH2 "CN / cH3 - (CH2) 'X (€ H2) 17-CH3 I 2

COOH

diamide according to Melting point: 44-51 ° C, acid number: 49.

Application Examples Examples 54 - 75:

A fibrous suspension of bleached birch sulphate cellulose and pine sulphate cellulose in a weight ratio of 1: 1 in 10 ° dH (German hardness) water with a Schopper-Riegler degree of grinding of 35 ° and a solids content of 0.5% in the table is optionally mixed in the following 20% filler and then 0.01% p PERCOL 292 (cationic, high molecular weight (molecular weight> 1 '10 /) polyacrylamide) used as an excipient to retain very fine cellulose fiber particles, thereby adjusting the pH of the fiber suspension shown in Table I. The percentages refer to the dry matter of the excipient and filler in relation to the solids content of the fiber suspension.

The sizing agent preparations also shown in Table I below are prepared by mixing the indicated sizing agents in powder form or as a reaction mixture as obtained in each case with the retention agents described below in the presence of deionized water and 2 mm diameter glass beads at room temperature (15-25 ° C). ). The resulting dispersions are castable, homogeneous and storage stable. The percentage of the preparation 107 79579 refers to the dry matter of the sizing and retention agent in relation to the total weight of the preparation. Retention agent No. 1 is POLYMIN E® (polyethylimine, molecular weight 10,000 to 100,000). Retention agent No. 2 is CATO 11C 2 (cationically modified starch modified with propylene oxide containing quaternary ammonium groups and having a pH of 4.2-4 in a slurry of 25% distilled water at 20 ° C, 6). Retainer No. 3 is a condensation product made from dicyanamide amide and triethylenetetramine, which is further reacted with epichlorohydrin and prepared according to Example 2 of DE Application No. 2,710,061.

An aqueous preparation of the sizing agent and retention agent is now added to the fiber suspension so as to form an application rate of 0.5% of the sizing agent dry matter relative to the solids content of the fiber suspension. The fiber suspension is then treated in a "Formette Dynamique" laboratory sheeting machine (Allimand, Grenoble, France) into sheets of paper having a basis weight of 80 g / m 2 after drying for 3 minutes at the first 130 ° C. The paper sheet thus obtained is subjected to an additional heat treatment at 140 ° C for 3 minutes.

Both surfaces of the resulting sheets of paper, i. the finished surface and the opposite or top side of the wire side of the sheet forming apparatus are tested for their gluing properties. For this purpose, the water absorption according to Cobb is measured over an exposure time of 30 seconds (WaCobb® g) in accordance with DIN 53 132. The results of Wa Cobb ^ g measurements in g / m2 of wire side (SS) and top side (OS) before and after heat treatment at 140 ° C and after day storage at 20 ° C are shown in the following Table I. The lower the water absorption is, the better is the gluing of the paper. WA Cobb ^ g values above 100 correspond to completely unsatisfactory sizing of the paper.

108 79579 ----, - £ ------- rt · Η ro uo oo rs G G O 1— 1- <-

G G -H <D

rt o <υ ______ ή> -μ x J) -H w H w tn ro tn ro ^ .- p: rOfO: (ÖO>, - t— * - · t- g · cn -p Cti G -ro e - h \ cn -------

Cn: r0 G

~ Λ! Φ CO cn T- o g- O

: ΟΦ · Ηθί— t— ro r ~ cn aii 6 Ή Φ ------ rt rt ffi o J-π cn co g · r- oo γ- οο cn i- i— t— g * X) - --------

J3 I G

O G icö «g cn r- ro σι o tn CJ Φ> lG G O r- t- r- ΙΟ). G Φ iti λ: gv * a) -------- £ H »ti O Ai: rö i>. — I cn r— g · to tn uo • ro -GW: ce5 10 r— cn gr— t— rt rt -ro

G Λ G I

0) -f -------- cn M CO r— tn en ro oo G O'- * - * - * - cn

-P -H

rt3 -P

> Φ ------- • H ffi G CO r- CO r- t- G · X CO (N CN U0 (N 00

I O

G> Q) G g: ro oo cn G * G i G G ^ ^ ^ en O I oo oo r- oo oo

G -H K

co en a i

<D G G G G G

-P Φ -P -P -P -P -P

G ’G Ή * H * H * H

CCO * H -H -G * G "G * G

E- «fO PJ Pl G! G) PJ

t— rN ro CN ro t— 1— Π3 CO <fl G (0 -P O-P OO -P OO-P O-P o cn ..en .... tn .. ..en ..en

• G G -G G G -G G G -G G -G G

dj rt rt rt rt X rt X G cd Ai (d (d Ai rt X (0

G -P G + J-PG -P -P G -P G -P B -PE -P -P g -P -P g -P g -P

O) (1) Old) ΦΦΦΦ

-P co Geo CCr-GGooccTiG

Cn '- CCJ -G t— Cd -G * G' - G -G -G '- Cd * G' - Cd * G

-G -P Cd -P Cd Cd -P <d <d -P <d -P id g G-Pen c-penen c-PcncnG-Pcn c-pen rG> 1 t) (U rllD ^ 1Ji'GIliiii ' rl (l)> l

G Ai G -P Ai G -P -P X G -P -P G -p Ai G -P

> p -G: <dp -G: n3: n3 p -G: cd: <C3 P -G: <d P -G: <d Φ (d φ (d T3 Ό Φ cd Ό Ό φ td Ό φ cd T3 g en * gg cn -G * gg cn -g * gg cn -gg cn * g • GG o. 'GG ftft -GG a ft -GG CU -GG Oi ento cn td en td en ns cn cd

H 11) g dP (DE ## Φ g <*> di ° Φ g <#> Φ g dP

G tn -g tn uo -G uo tn -g tn -G uo o dP -P, .. cf (0 -g - «· <#> -G - ·. <#> -G - de -G *

Ai r-iGror- ^ Hrorot ^ nHroror ^ rGror ^ iGro X ------

G

i — I I I

G -G P G O G- tn CO Γ— OO

ctj cn a) -g «. uo tn tn m uo E-I w g a: e, 09 79579

-j — g I

Md i> d co m eri 1— m r- Ή c H 5 ot— T- r- CM T— 6, I fl I ------- H -HMH cn r ~ r »mr * o» - ¢ 1 so | 0 ww I- T- t— t— mm _ -P & i V, -n ___ (N + j E Cfl WO) CN 'T T- tj <\: n) -H O'— r- » - T- cm r- tr> jg -P -------- e * ffi en σι oo vo σ, r ~ σι

; and CO »- τ- τ- τ- ΓΟ CN

o L S

mg'3 en »- τ- σ o m» »Λ 5 e O r-« - τ- <n »-

Λ G G -5 S

0 i Φ Q Dj -------- U »2 ti m en <n p- in oo t ~~ ^ a S! Φ w ™ - - mm ^ 5 Md O, m -ro ________ S -m G en m mm »a * cn vo * O« - i- r- »- (N Γνΐ

y * H

3 -p -------- δ <u g w .2 en vo co σ, oo σι 3 eneN »- τ— mm · ** _ * _______ I o e>

d) M

d, G (ö O O 'S' O 00 t- ~ MOI - - * * · - G -H 5C σ σν oo oo oo oo tn a a i <U 3 3 3 3 3 3

PO) -P -P -P -P -P -P

C Ή * H -H * H * H * H

Md Ή · Η · Η · Η · Η · Η · Η tH Id J dl μ}, 3 κΙ (3 tö (0 3 (0 (0 π) Ρ ·· Ρ ·· Ρ ·· Ρ ·· Ρ · - Ρ · ΜΟΜΟ MO MOMO MO • HC · Η 3 -HC -HC -HC -HC (On) n) n) n) 3 X Λ X ai X <Ö o! y oi y Λ

3 -P 3 -P 3-P 3 -P 3 -P 3-P

E-P6-P E -P E-PE-P e + J οι φ a) a) a) φ (D odr-d md md'td me -P mn) * h oi n) -hm ui -ri < nn) -hmn) -h <n 3 -hm -Pn) -P id -P3 -P Π) -Po) -P id • h d + Joi d -p ω d -pm d-pto d + JM d- ρω - E -H φ> 1 -rl <D> 1 -H <D> 1 -H <u> 1 -H 0)> 1 -H 0)> 1 3 ή y dp y dp xd-p Ai g - pxd -pa: d -p O n) p -hm) p -h ad p -h Md ρ -h: π) P -h: n) p -h: n) X> ai shy <Dn) O 0¾¾ il DO (1) 0) ¾ a) π) Ό -PE m -h E w -P 6w-h E m -h E w -Ρ βω-hn) -H 3 a -H 3 O, -H 3 Λ Ή 3 O, -H 3 Οι Ή 3 ft • m Ma) Ma) Ma) mo) Ma) Ma) - a> ε c * pa> 6 m E # mg # o) φ g # • h in -hr ~ -hm - H m -hmp in »- <#> -H * e # 0 · Η ^ dP · Η * dP · Η» dP Ή ** dP · Η ^ n- .H mr ~ Hm t "ή m n- ή m n- ih m r- —im O ------- λ; a: 3 H ii

3-HpdO σι O T- (N m • »T

n) m <D -P> · in vo vo vo vo vo E- · MEXG _ no 7 9 5 79 GG GGtn eo vo oo oo oo> i: td I -P CU O * - t- r- <- ft > cnCO) <D -P td PX ------- + J: id M-HrH en Γ "en <- θ 'cn -P (¾ td 0: id cn r ~ t— cn mn • H __> 4> l ~ _______ U) mOG en mn vo vo oo x <<U -p O <- «- <- * - * -

: 0 (U -P

ftx <D ------- -. & —I ® cn adad en m o ^ tr>

E X * r- en * - r- CN ro CN

\ - G ---------

Cn G · Η X

'-' (CNηο CN »- ro r ~ <D G -P: rd O <- i-» - <- * -, ¾ ad en -m H> to -------

O: cö -H p G

ro -n: id <d -P tn ro uo (N oo

Xl ft> G tn CN T- CN cn ro XI g --------- O eu u tn enro CNro vo XC O r- r- T- * - <-

<P

S -P -H --------

cd -P

> 0) -Hteeno eo o r ~ 3 en cn »- cn cn ro«

I O

G>

CU P

ft G td ld r ~ oo σν ro en O I - - - - 3 -P K oo oo oo oo oo en en a i <U 3 G G 3 3

4-> 0) -P -P -P -P + J

> 1 G -H -P -H -H -H

red ft * Ρ ft -H Ή ft EH front Xl Xl Xl XI Xl T— T— T— - T— cd cd <d td cd

p · · -P · -P · -P

enoenO eno enoeno

H G -H G -H G -H G -H G

td td td td td xi td x: td x: td x: td xi td

3 -P 3 -P 3-P G-PG-P

e-ρε-ρ e-p ε-pg-p

<U CU (U (U (U

vo G G oo G en G O G

(U CN td -H CN <d ft CN (d -H CN (d -H ΓΟ td -H

4J + jcd -p td -ptd -ptd -P td en G-Pen c-Pen G-Pen G-Pen G-Pen - -h -p <d> i -p eu> i -P <υ> n - p eu> i -p cu> i

<d E x; G -P Χί G -P X C-Μ X C X X C X

O ft p -P: td p ft: id p -P: td P -P: rd P ft: td X td iijidt) «idd eutdTd eu <d ό eu td tj + j> E tn -pg cn -p 6 tn -p E tn ft g tn -p td -p 3 ft ft 3 ft ft 3 ft ft 3 ft ft 3 ft • n tn td tn <d tntd en id tn id mg # oi g op eugdp mg <# m 6 # • pm · ρ m -P lo -pm -Pico T— dP -P «dP -P - dP -P - ° 8 ft - dP ft» r ^ rHeo n- pro r- ft ro t "ft to ft ro O ------------ x: x:

G

ft I I

G -P P G O

(deneu-P ·· ld no r- oo σ \

Eh W £ XC G vo vo vo vo en t, 79579 11 1 I 3 I «· 5 cm> G to» - in cn co c ill --------- i -HM 3 Μ Ό m "* <r- r-

<U: (0 fl: <0 to »- (N (N cg (N I

P. ft h 'Π ________ ->' Jn to n- m en m co

eg cm HO'- »-» - »-» - I

E £ + J --------

tn Ö4 K CO 00 in 00 CN

.5 co cn cn co cn eg I

Φ ‘3 co cn co CO * 3 ·» 3 * 00 °? g g O T- T- r- T- «- Λ 1 I co in m co m co co o a 3o S« w ^ M M w U »0. -fa ft -r -_______ <[5 G coco co co co co H1 2 3 $ O'- T- eg r- cn> - v> Ή --------

P -P

6 a) m ® co co in cn r- co co> com cm <o eg m cn 'Π, 5 _______ I 0 β> 0) p CP G m co ^ 3 «i— co eg Is» en o I - ^ ^ - »ρ -HK oo co en m oooo to tn Dj ω ρ pppp -P φ 4-» 4- * 4-) · - · 4-) 4-)> 1 G · Η -H * H 4c -Η Ή cm Ή · Η Ή * H · Η Ή

EH m ftl PI PI I PI PI

t— t— t— * - m · η m mm m 4-> * - -h -p · 4- »· 4-> · -p · CO Ή * -

cno cnotnocno-H

H G -H G -H G -H G 03 o m m mm m aj g -ρ o

Aim Ai m a: m a: ρ p wc Ρ -P p + Jp4-) p4-) g <0-H E -p g-PE-pg-P 4-) mm 2

φ Q) Ο) ft) O 4J A! P

ί-G <NGoo Geo G (N <1) p4-> mm-H nm-Chrom-H r-m-H me E <u _ ω -pm -pm -pm 4-> mc-p-H g

m 4-) G 4-) w c-p WG-PW G P W -H P (Cj ffi -H

ο ω · Η (ϋ> ι · Η (ΐ)> ι · Η <ΐ)> ι · Η (ΐ)> ιΑ; α) ΐη κ m m (O

S -ha: gpa; cpa; cpa: cppc> i ρ ω p Τι E p ή cm ph: m ρ -h cm ρ -h cm <u -h -pc -p -p -p ή Qjmtj cd m ό o ) m ts o) to ό E <o: mo> o>> io> .p, m E ω -new -hgw -π gw · η -hw ό 0) e: mc

> -H 3 a. -4 3 ft Ή p ft · Η P Qi W Ρ -Η TO -H 4-> -H

w m wm wm enm <u m λ .e «J m r- <V £ <*> dlgdP 0) 6 # 0) 6 # E O W dP 0)

• h m -h m -H m -nm # -4 # p m -P

O dP -H «dP-H» dP -H «· dp -H - Ν '-H« 3 · <#> <0 * ·> 1 ίί γήο r ~ rH co hn> hm rg h γ- ~ E < o) (0 M ---------

% -H

3 I I 0)

m -H p G O

w φ -η ·· o T-cg co m ^ W E A! C r- r- r- ~ r- ~ r ~ r * * 112 79579

Examples 76-79;

The procedure is as described in Examples 54 to 75, but using a preparation with 7% of the sizing agent according to Guide G and 3.5% of the retention agent no. 1. In addition to the non-ground fiber suspension, a fiber suspension containing bleached birch sulphate cellulose: bleached pine cellulose: bleached ground powder in a weight ratio of 1: 1.2 is used. The gluing results are shown in the following Table II: 1,3 79579 S ω § Λ S q jZ t / ι vo T- o o 3¾¾¾03 * - "N * -

>> -P -r-I

G tn i e /] cm ro n o 0) (d r — ί Οτ-Γ-τ-τ-

- <U P: «J

(M Ai <0 -ro-- e ή>

^ :( 0 C tji T- C -H

": rd G CC ld oo oo (N

G> C β Cn r- r- T- r- Q) -H -H d) o M: id O d) ro Ai O, -P Ai XI 3 ----

XJ -P

O <d en ro ro Γ'- ^ r U> O i- r- r-

•B

-B---

S «-P

0) K [C IA Is Is U3 M t- r- T- T- c 0

•B

en o C>

<1) P

a <d ld vo cd tn i - «· - PK vo ld vo en cu

•B

1 G

d) -H

-P d) P -H

> 1 G +> rH * * -P-P

: ed -H -HO ** 00

E- * fd · Η id Ή "H

J Ui en tn

G G

d) d) --O, Oi en en

P P

* en tn id d) +> λ; -p -p -p

O 111+ <d d) <D

-h G en G

X! 0 -H -H

P -P O <0 P -P +> d)

H CU d) -Π -P

H dJ O> i --λ; o: ed o a: a; -p a: o o

rUt G -H -H -H

P -H X X! d) Ή 1 Ai P -H p O I + <d end) ·· vo h oo oi *

En W G G f'- r- r-- t ~ - * * 114 79579

Examples 80-83;

The procedure is as described in Examples 54 to 75, but instead of only 0.3% to 0.5%, the dry matter of the sizing agent is used in relation to the solids content of the fiber suspension. 5 The gluing results are shown in Table III below.

115 79579 --— 1——1 ----- (Q · η ί> co ro οο m '•' Co f ~ * r — t f — 1 r— <

C -P

_: <B G_____ f> P> c

C -H -H

ST CU: <Ö O

M CU DcP to cm O O

^, y Ui co * o to ro cm (—i i— ib o: (0 u______

ro '1 i -O

X) £ co en m m O φ O »“ l »- * CM r- * u co t § 3 -H -----

P P

(B O)

h * j5j CO <t H O

00 in CM

d * e o

•B

C> CM CM CM O

(UM oo oo oo oo

Dc IB (0 I

d x.

W Dc

CU

C

•B

<o d d d d 91 -P P P p

-P · Ρ -P -P -P

P Ή -H -H

: cB id Dl id pj

Ep -------------

I I I I

• P -H * H CO

F * P -H -H d (• H pH i-H (¾ e- t- g c- fB (B (B »- Ή

P · -P · -P -H

CO O m O CD rH o

• H C -H e -HO G

<B (B cB G (B

a: cb m <b λ; + j cb d-p d p d <B co + j

g P g P g-p * P P

CU CU -P (BQ) to G O e c-QJ -X e

CU e— G -H (NCB-η cncBG d -H

-P -P (B 4J (B P-P g (B

CO G-P CO G-PCD G-PiB CO., LTD

H -PCU> i -P CU> i -P QJCO U> ig, * gp, * gpmg> i cbp H DP: cB P -P: <B Ρ -PP GP: ifl (B CU <B Ό CU cB < 0 CU (BaB a) Pd> g CO -P g CO -P g COTJ Q) Q) -p • pd Dc -pd Dc -p dp -n G Dc

, CO IB CO IB CO <B'Dc Λ -P

H CU g κ 0) g * -s Q) gM O Ok h in «n in to H K - K - K K» r- ~ io rs ro rs ro rs co O______ λ: i u d <u 1-1 g Q.

D -PGO § £ S S

CB CO -P. · Κ 00 °° gi ω λ: e 116 79579

Examples 84 and 85:

The procedure is as described in Examples 54 to 75, but the following sizing preparations are used, which are emulsified in the presence of water in each case in a molten state at 80 ° C.

Preparation used in Example 84: 7% sizing agent according to Example 16 3.5% retention agent no. 1 0.7% sorbitan monostearate (oil-in-water emulsifier) 0.7% addition product of ethylene oxide and sorbitan monostearate (water-in-oil emulsifier).

Preparation used in Example 85; 30% sizing agent according to Example 23 15% retention agent no. 1

Both preparations are homogeneous and unstable.

The gluing results are shown in Table IV below.

t, 117 79579 • and 8Λ φ Ρ: <Ö

V (Ο · η CO st CO

H> 0--1-1: <0 „ς__ I i & H -H S co ι / ο σ \ -—I: (o Q Φ co» —- cm (¾ -P Ä

•B

co co —I r- -; φ -h O —I t—-

cm X -P

E: 0 φ-- ob. g ® co ^ f-1 ': <a co ·—I co s'3Λ X> B: (0 co co Cti

Λ _ fp TO O rH mH

a § ^ __ <: y S - w o «a- * m -B -5 § w ^ 10 • ro: <d Q Φ cu -P iZ__

I co O

3 O rS r

Irt - Φ -p • ο φ co σ> oo g κ co · - * i / o 3 0

B

CO 0 3> 0) P I — I -t ·

MM

co I oo oo

3 SC

cn a φ 3

•B

. (0 Φ. -P. 3 3

> So -P -P

H. : ιΰ I · Η -H

Eh -ί Η ‘P

0 1-5 i-5 Λί, * 3 ------ i — I 0 3 3

Φ I I

Eh -P P 3 m CO φ -P 00 00 _WE, * __ 118 79579

Examples 86-93;

Proceed as described in Examples 54 to 75, but add the sizing agent and the retention agent separately to the fiber suspension, the sizing agent being mixed in powder form with 5% aqueous sodium or potassium hydroxide solution in the presence of water and glass beads to give self-emulsifying, homogeneous and adhesive preparations listed in Table V. The% Val shown is the amount of 10 equivalents of sodium or potassium hydroxide per 100 equivalents relative to the negative charge of the acidic groups of the acidic esters used in the adhesive in each case. 10 seconds before or after the addition of the sizing agent, 0.25% of the retention agent no. 1 / dry matter 15 in relation to the solids content of the fiber suspension. The lira results are also shown in Table V.

119 79579 ί

[—T-p -: - Τ '—---] --— I

tg-Xcrt '»» n 00 r— CM CM

| u Η Ο H ^ η Μ .-- «, - ι I

t --- 1_I __ ^ _ Section II ΗΙΛ w O 'Ό VO |> * <D λ w ^ 1-1 co rt .- (ί & S ___, ___ ol: to ro. -n Λ 43C woo “0 uo co vo r * θα) O'-1 ci (- * «- <.— (ri u tn ________

X

<C 3 -P

! S -P h-> {5 Ϊ to Ό t - ** - m r-i r- * o

'P CO c-1 (—1 CM CM r-t CO

3

X

c 0

•B

tn o G> fl) G

di g -i ^ ™ ^ ^ co

Wl CD CO CO CO 00 CO

3 K w a, "I I I —— · - · - 1 1 l_

I 3 3 3 3 G

o + j 4-1 -P -P -p g

.p Q) -Η -P · Ρ · Η · Η -P

> i G · Ρ Ή · Η · Η Ρ ^: <0 · Ρ γΗ ιΗ .Η ιΗ Γ-Η · η ε-ι m 1-1 - ^ --- nj —- (β — 1 ---- -

Η * Η I

I Ό I Ό to o I (0 I

Η -Η · Ρ -Ρ I · Ρ 3 G -H -H -H (0

-H (0 -H U) -Ρ Ό -H -H -H 'G · Ρ -H

γΗΛ; ΉΛ! · Η · Η · -Ιγ0'-Η -HrH Τί

o o> —t W -H ω -H

(0 P fÖ Ρ Λ * (0 CO <0 X «W

-ΡΌ-ΡΌίβο-ΡΛί-ρ o-p Λί

tn tn tn tn -Ρ P tn o tn P “P

• H Λ -H .G tn G -H P -H G -H p (OetOe-H ^ GtGG tn G G ^; G ^; G (ö ^^ i> i ^!> P

3 (0 -H 3 <d -Ρ At work E G Ä 3 work E

g -Ρ p g -Ρ P G-PG e Λβ E-P3 E -P E

+ j 4J jJ +) g -P-P -P G -P -H -P G

d) (D dl iC Ό (1) (Ö (Dpvo-P-HÖQJPUQJ-P

G r-CG '-GG mfi + J OJ ί-J ö + j - 5 ^ p .p -p T- -P G G -P G-PG G -P (0 to Q). t0 df · to Λ · t0 G · * P tO <U <0 G CU tö Ai tn -p Eco · E »· E tn EGG <u tn <u tn 0 (0 -P 3 (H -PG (H - p GdP -P tn -n G <#> -n 0 c #> to-p ia mm tn g G tn e · tn 3c #> .GG · .G to ·

g g d) E> 0) E> CU Εή <U -P · O E Ή OgrP

• P rH cd (H to G

'rj ^ tv; t; t * · * »-s £ κ ^ ^

m> o o · * m O

Cv * »- (n- r— * r ^ O r ^ O r» Or-ι (~~ O 'O' O '-f-- · -------- tn to G <0

I> i I -P I l-pl l-p I

• p: to tn -p + j -pi -p -p -pi -p -p -hi to tn tn -PO) to p -PO) mh -p cu g ή tn -ρ -phc entto he intto> pg entto tn-P tn * p G -n -p G -n P 3 'f-1 + J a) e (0 to GttJtO G ftJ <0>: t0 G t ~ i 0) tn gcccuinECGcutn EC e • d < 1) pg 0 -p Q) 0) GG -P CD CU CG -P <L) CL> O -P <1>: <d Gtö H 11 OI GtO -POJO) GtO -PtUO) X Oi)! »- n <Ug HGM CUE Ή CX CUE -PC * λ; 0 -----------

rH

Gil

Cd -PPG · Ό Γν ~ CO Ov o H

IA 1) -po 00 00 oo 00 a \ O 'ME * G _______ 120 79579 • n L 2 CO (N 00> ^ ° 1-4 I || CO VO ^ "*': $ S 1/5 ^ - 4 £ · §: (Ö & ^ 4-> 03

• n "(ti O

m G

G 4-1 -H

d) sf rH nj O ® CO r-t r4 G CXl o Λ O 03 ί ί 3 (0 O +> ___> 4->

O (ti -H -P

> -H O 03

<! Ή + J X X

& G Φ O

X X! 5 O (ti -H

co ^ 2 Λ

W + »G

03 3 ------ H 04 I (ti I K X (ti G 04 H 3

0) iti 4J

Di G O O O> 03

03 0> * - -H

G -H p Ό rs; nj nj CO 03 fö: rti x

-P rH

- - 1 — I (ti: π3> 1. ™ «X -H - P 03 .y * 03 03 • ίΓ S * I £ *. Ό: <0 -H P - · (ti 03

H (i.e. G <U X O

1 S ·· * o o

• r IRH

_______G

*, —J

(0 rH

f-s -P QJ

I id I -H O 03

• H -H · Η Ό -h -H

H> U -H -H 03 4-1

rH * H rH CO £ 4J

[5 -t ^ <D rö nj

43-3 $ B D. «G

03 P 03 03 44 4-> • Ho ’H> 1 G Ή 03

(5> i [S ·? 03 G G

121 79579

Examples 94-111:

The procedure is as in Examples 54-75, but the sizing agent and the retention agent are added separately to the fiber suspension, whereby, if a filler is used, the sizing agent 5 is added 10 seconds after the addition of the filler. The addition of the retention agent takes place 10 seconds after the addition of the adhesive and the addition of PERCOL 29 ^ ^ takes place 10 seconds after the addition of the retention agent. The fiber suspension used contains 0.3% of alum (calculated as dry Al 2 SO 4) relative to the solids content of the suspension and 1.5 g of sodium sulphate per liter of suspension. In addition to the non-ground suspension, a fiber suspension containing bleached birch sulphate cellulose: bleached pine sulphate-cellulose: bleached ground powder in a weight ratio of 1: 1: 2 is used.

To this part of the fiber suspension add the amounts of sulfuric acid or sodium hydroxide (as a pure substance in relation to the solids content of the suspension) given in Tables VI and VII below, using sulfuric acid and sodium hydroxide in the form of dilute aqueous solutions.

As a sizing agent, a 15.3% further dilutable, homogeneous and stable preparation of the ester mixture prepared according to Example 22 in powder form is used, which mixture is dispersed in 65% of ammonia in the presence of water and glass beads. In relation to the solids content of the fiber suspension, 0.5% of the indicated sizing agent (calculated as dry matter) and 0.25% of retention agent No. 1 (also calculated as dry matter) are used. The gluing results are shown in Tables VI and VII.

122 79579

Ai S

(Ο <D

Ö *>: fσ π 8cm r-- οο m tr »m n cm

^ -H M CM Ι-Ι r-ι m r-t IM r-t <r CM

* 1

CM -P

c .s Φ Q co ^ m m m r-ι r-ι cm cmo

G) O rH r - ^, r * H r · ^ * -H rH rH «H pH

w>

H «H (¾ C

e mj μ δ ----------

Sq> 3.

3 C: td ow ot -n tn to Ό r- r- n oo -a · oo r-> _cnn rl rl CM rl rt rt rt rl äs; ä.g 8 g Ä «____________ C c S λ co ιλ nn O -a · n mj- m cm

O '—1 r-t I — t CM r-l r-t i — t i— <i — I

•B

-P

Φ co on γμ oo rv n co mt r-tvo tn ni — I rl CM rl rl rl CM rl? S, r; S -3 O r- r- nu ~ »u-» η on in Π I * * · > rr * ·> r -

3 · ϋ w n VO ON O co Ό r-, ON ON

en tn tl 1-1 - ____, ____________ S _

5 I 3 z I

• H E W CM rs C -H 'S>, I -h <f | | | ° - ° - 6 ΰ £: 5S "^

ST (Ö> i -H

S z Ä M. .

3 - -h 6 - s · a * -P Λ tn -o ·

S, 3 .Jo1 ^ «I I I I I II

0 2 en o -P H -rl

4J Ä rH

- • H Φ s 3 -a -¾

3 fd · Η · Η * H * H

Qt | 11 11 3 3 2 3 | * β ^ ι · Η O »Ή 0 ^ * £ £: 33333 ------------- 1 I 3

3 -H M · »O 'O co cr o i-h <M

rd! /) d o ^ ^ o> on o o O o 6 "· W S £ 1— <I-H T- <\ 123 79579

co S

nj δ • η g ^ tom'JcMOO-j'O'J'iorn Η W Η —I Η Η Η Ν Η Η Η

3 S

* 3 __________ ij

Qc0i-II <O «MOON0 \ OO ·

til______j____I

; 0) C: (0 O 'H-1:! P' r_1 co in ro cm r- «cm m cn cn cm '

^ r1 J W r-H rH r-4 »-H r-H« Η rH rH r-H

11% -cs “! ----------- ZZ <CO ro CM eg rH CS rH CM r-i

^ O * “H r-H rH rH t-H rH rH rH rH

^ ___________ co eg m σ> σ \ co> d * ro o vo

co en cg γ-h cg r-π m cg cg rM

cq o

C i> CMO% vOf — I vO in MD 00 t — I

fll L *** · * «» «» »lLi ίο mmr ^ ooOvOvDr ^ oo E / Γ l» ~ (t

p K

m Cu_ ί I - en i -h v G s [n cm cm I -3 * g,. . r mt,, o ° f b § «ä ^ ^ I s ä a__________ i g - φ fr" "

-H 5>, ^ I I I I l l l I

2 S: 8 o • H H Ή fr .._ g. ^ __________

'S

Il 3 m t .h

Qj «3 d -H Äi -H M

-, I · «· '.¾ t 3 o s g f 3 J3 3 JS 5 o J —------------- 3 ^ n -H ^ · SoÄSl ^ 000'0'-'! $ g g 2 ^ 222223Ξ 124 79579

Examples. 112-116:

The procedure is as described in Examples 54-75, but the sizing agent and the retention agent are added separately to the fiber suspension and a fiber suspension containing pine sulphate-5 cellulose: bleached wood chips in a weight ratio of 1: 4 is used. 30% chalk is added as a filler to the fiber suspension. The addition of the adhesive takes place 10 seconds after the addition of the chalk, the addition of the retention agent takes place 10 seconds after the addition of the adhesive PERCOL 292® is added 10 seconds after the addition of the retention agent. As a sizing agent, a 35% further dilutable, homogeneous and stable preparation of the ester mixture obtained according to Example 22 is used in molten form, which is emulsified with 18% by weight of sodium hydroxide in the presence of water at 80 ° C. Instead of retention aids Nos. 1 to 3, retention aid No. 4 or No. 5 is used. according to Example 1. Retention agent No. 5 is RETAMINOL (polyethyleneimine with a molecular weight of 20 to 20,000-400). The amounts of sizing and retention agent shown in Table VIII below are used, with these amounts and the amount of filler (30% chalk) referring to the dry matter of the sizing, retention and filler and the solids content of the fiber suspension. The gluing results are also shown in Table Vili.

.25 79579 .5 LO e * σ% co ro

• 0 * "H

1 c M_______> 3 C: <«: (0 -r-i ^>

«M C -H C CO ΙΛ-00 r-l 00 i — I

β (D: rä -H co ui m r-ι n r- * 'V q & e £ 3_______: nj * 1 “o δ n o)

£ i M LO ΙΛ «-H O O O

ffi P O H r-l Cs | rH

° + J o Φ .e V) CO O * 3 · VO ro

in vo -a> - <sr rH

tn o

5 r »a · σ \ o cm <N

Ψ H M ft * A «t 6 y3 oo oo oo oo

3 K

W CU

Φ M

I -ä g · {§ cn m kL: n o esi io in

tl I | H »I A A M

jg ^ O O O O

-H tirt df> cu St ~

In ^ »a · in m m m $ S ό 6 6 d ό • h -H z z a a z

cu nJ

Jjl ^

i iS

.. § 1 s

H B Φ: d iT) <M

H * r | C E * H m »—I

g 3 -3 S

| H I ^ 3-HCl · im ro -a in.to

(jj CO Oi O H H rH r * H f-H

E ^ WkCh »" H r — I rH rH rH

126 79579

Examples 117-136:

Proceed as described in Examples 54 to 75 by adding 20% chalk as a filler, but using preparations with 7% of the adhesives shown in Table IX below and 3.5% of the retention aid No. 1, thus obtaining castable, homogeneous and storage-stable dispersions, which are added to the fiber suspension so as to form an application rate of 0.5 to 1.0% of the dry matter of the sizing agent relative to the solids content of the fiber suspensions. Glue-10 solutions are shown in Table IX.

li '127 79579 [Ο Λ! in <t r-4 m vo> j · m r · »in

fu r-H O VO I— <· —I r-H, -1 r- <I

Μ: · Ό ro -n> --------: ___> H w 00, OO n vo r— cm •• j'Sto r ~ r— y cm co cm cm, -η <f - CM_________ * 60 V _ «* - vOOvcMCMrHvDin-i

_ 6 CO VO cn r-H CM r-C r-H r-H CM

s I ° 5 Is ----------.

c m Φ to oo σ> cm m r- σν ov

Cn t— VO rH CM CM r-C ΙΛ Λί · η

So O CM I— r-H CM CM r-H CM

H S * * A * «« «k D

q1 Cj ON CO ON ON ON ON ON

w Ä

dP

I -: 0 + J: n3 in O mmommm

1) ^ I * «'« · »* A A

O <~ t OO ^ HOOO

3 1 II i 11 il lgf ^ ^ i ϋ -§ EQEQEQEQ BQ EQEQE 0 I «I ^ ^ (S Ö HC · Η Cj * H £ · Η CJ * HC ij C · Η C · Η X | j -r * Ί -n> I -I iS -I ί -® Ί0 -P »" S -n ij "-3 6S 6S 6 8 6S 6S 6S 5δ 62 I, £ gn] 03 ω -H ^ 2 2 fi ri CM CO -Hi- fi M grS HJ 2 '128 79579 w jl to cm äo <r <r es cm cm

(Ό r — i O T — i SO SO r-t i — 4 r-4 fH

«M

(0 -ΓΊ if *> Cc / jm o r-t ο o vo m ‘d'KWOJ Γ" 00 <N (VI r-l r-l

~ ftS

CM --------- m oo vo n -vr r- ~ vp ^ Stn1- · “0> Cr-l rl i <vo S tn ° 3 | g ---------- cg aj 3, 5 am N <n <rmo to 3 S co <J · r ^ cN <n erv r <

X -V-I

m n ^ CM CM CM CM ^ CM

J-H C »Λ M · M · *« r ct »σ> σ * σ * σ% ϊ 1 en a dP I -

+3: td ° o mo mm O

I \ t I *> »« · * »*» ς3 ^ rMOrMOOt-i g i -

• I J -jj J

- * j <o ^ (U m <υ in <u coo) oo 0) oo φ

S (0 2 -P 2 + 3 m 4J m + J Γ04- * CO -p CO + J

Μ g O g O OO O 0 0 SI a 5 oS -S3 -S3 a 3 -5 3 -5 5 5 3 g 3 g3 13 «3 15 * 83 13 a ^ &« j> S ^ § iS -S · § ϋ -¾ J ^ η, c Φ is d) jnowoj wtucoowo

OH OH & HWH WHWHWH

3 I Q

d i ^ ^ m \ o r- ~ oo ον O h

Ills 2 a a a a a a ί 129 79579! \ ^ γμ m, _ι

^ »“ * '- * 1—1 r — t r-4 G

(Ο -n * · "·>, ------ Λί C u. £ · £ <u · § S g

• H -rl 52 <- · ^ <r VO -H

: (rtQOT vo »- <« n cm r-ι (Λ ^ -n & -P <1) CM ----------

; P -H

eb «1

C? + J

C rn O 'Ό Γ "Γ0 Z

.om Q ^ · “<·“ · <- <r — t ^ jo H, _i o 3q -------- «« * § - * ”* · §Η JJ ιη.σν -a · 00 O ^ p: (0 1/5 vo it m cm cm λ; -n ·

_ M

G

0) 0)

§ A

• H π (Op o \ a \ cr \ σ \ co

Sir ***** * -,

QjS 00 00 00 00 00 .Jjj G S! Μ W a%

------- 4J

> 1: (0 dP </ i ~ * -H: S m m in m m 5 τ 'y * * * * * * - ».¾1: S o o o o o j. (O .g (0

JH PS »+ J

- c ω

(0 O

r- r * <- e c (0 <U

si SS § · 9 ”IIIII S5„ m σι oj OQ) rdllNdl Cllj W (0 05 G mg g ^ g ^ g ^ g * -p II ύ -§3 si% i || si II 11 13 13 P II s ! ^ jj ω "1" ω ω ω ω S ra Ί · Η Η ^ WM afiwfianwn «f" Ο .η η Μ -------- (0 3 * Η Ή 3 ι ί 9 .. G ( 0 ^ Jj lj 52 - »« n vo (0-Ρ S «SH 2 3 2 2 2 g ΕΪ ΗΕΜ ^ ^ rt> -3- _______] __] _ en m 130 79579

Examples 137-141;

Proceed as described in Examples 54 to 75 by adding 20% chalk as a filler, but using preparations containing 7% of the 5 sizing agents shown in Table X below and 3.5% of the retention aid No. 1 or No. 2, thus obtaining castable, homogeneous and storage-stable dispersions which are added to the fiber suspension so as to form a dry matter content of 0.4 or 0.5% of the sizing agent relative to the solids content of the fiber suspension.

10 The gluing results are shown in Table X.

Il 79579 131

I- IS a I

rH C: (0: (0 ra * n ς SS 8 w "2 2 ~

rH * ^ C

<U -Η -H

-P: (0 Q to m σι mm vo 4J Οι-P CO r- <r-1 rt * lH - .- .1. —I. .. il—— - - --- w: f0 (A cm cm m in Ώ id ° ^ r — 1 rH rH, -4

Qj £ φ ———_ fe 0> rC LO m 00 rH VO CÖ S »CÖ (1) C / 5 H H CS r4 i ^ ------—

V- / (0 rH

I U: r0 0 Ö) <o * i \ m -P. co cm -.

-0 "H r- 5 O rH rH rH rH _4 Λ * ri C · π om: j3 g ------ S c /} r- σ \ o <fr * <ft · &. £ w M - ST Γ-. '1—1 CO O f! P ». CN ^ 3-

c.hOCM i— (I— (CM

a} -p ------ 3¾ (Λ * - * σ> vo · * - co co cn -σ cn ^ § C <r <r ο σ \ ^ cL ro “* ·>« «en I oo oo r>

3 K

cn cu 1 I o *> g 2: s ro -.ro cn m m ~ 3 c C «* f0 * * · * ·» • H SJ β · O O O O £ w c ‘-P ____

C/O

- ^ 1 cn <- (f ~ <CN CN

3j g .....

• H -H 0 0 0 0 o (¾ (0 Z Z Z Z 25 —i _ j

-H -H -H

jj δ 0)

'3 E ^ Bn N'On'On’O

1 -I «I n iS ύ I § imi 1s la 1s

X ^ nS nSiiiS

q _ o n is a toilet toilet toilet.

1 1 g ft.51 ^ η.αοσο ^ Η * “2_ 2 2 2 132 7 9 5 7 9

Examples 142-167:

Proceed as described in Examples 54-75 by adding 20% chalk as a filler, but using preparations containing 7% of the adhesives shown in Table XI below and 3.5% of the retention aid no. 1 to obtain similarly castable, homogeneous and storage-stable dispersions which are added to the fiber suspension so as to form a dry matter content of 0.25, 0.35, 0.5 or 1.0% of the sizing agent relative to the solids content of the fiber suspension. The gluing results are shown in Table XI.

\ 133 79579 P Π

c: Asa a s a s s s s J-S

! / - “N ______ _____ _ ^ ________ _ _ _ __________ ^ __ ________

CM

'v I

w {8¾ ^ c ^ r-. O r-ι m vr jj'.tO Or — I i- <I— · i — t I — 1 (—I <J r-i O ^ c ---------

«N C-H

• O '> 5 o -H-H «° o σ>« Nm m m oo -a · ·

u: S> S

<^ 3 ----------- ä * 5 fS OltMtsI r — I rH, -1 <3 · M O '-I ι-l r-t, _ | , -1, -1 ^} -, -1 fs ------------

3¾ s S 3 S S 3 s £ S

ai u * * * * * * »·.

pt 00 00 00 00 00 CO CO CO

f ί _, ___

dP

4j: n3 jj t_ | Λ * Λ Ä * 1 A A d

Sira ooooooor _Si_________

1 tj8 L l8 ϊ. ^ ω ^ w ^ M

jg E-Ig D Φ> H ^ I X S jjj n jjj N8 η id 8 ΐ 1¾ 8 S 8 $ 8¾ 1¾ 8¾ S | O__6 8 »6 8 6 8 el 61 61 6 8 H I ύ * -H ^ cN fO id vD r-» oo 0 \ CO 10 fl) * H ^ <f> ^ <3 «λ- ^

eh w ε λ; γη ^, -, h S S

79579

ΐμΐ I I I I I

Ϊ2 ^ tN so es

Γ0 CO d * C \ | r — I »—I CM

if

> I

# -N CN -P

CM ---------

£, I

~ Sä s a 3 2 2 - m · γί 0> _______

«D | w £ 5 S 3 N

<ft-P

s --------

S 5? Γ- r-4 Csl CM CD

K O <N r— (r-C r-1, -1 is -------

Is- ~ i> -l ID CN

3: (0 oo <d cs, -ι cn M -n 8

•B

W P

C j> 00 ιΛ UO ID (T) cL ro oo oo oo co oo 3 & W ft

dP

1 - '

: S: r0 ΙΛ) O ID ID '<D

jr .b *> «·>« «

.o: [2 O ι-h o O O

i2 £ i § § § §

I f f f I

I 1 B 8 8 8 8 | a | ag

• Η φ * H S Η φ * Η S 'Μ φ M

h. hi (DröäjryajfyjajiDm X * ΓΊ · Η * ΓΊ · Η · ΓΊ · Η π -Ρ · η +)

0 δ I θ § 6 1 6 S SS

d I i § b -π ρ _ _

tOWCD-H O 1-1 CM CD

EnWEAi 21 ^ ^ u-1 id

1—1 · “* r-c i ~) f-C

\ 135 79579

w S

φ φ

J2 t "r».. Es i-t · “· m vO

_ Π ^ ro ι-n es en es p-J cm 11

~ J

es -------------

i, I

^ §3 Ϊ OS r-t CS rH CS rH

u: π3 ^ »" "* ·“ "<rH r- * ^ I — I i — 1 fo * ΓΊ O> ^ ________ s" §in MSH Ό rH oo <-t 00 σ> U: 3 0Wrr> ' "I CS ^ N r— <rl ^" r 3 --------- qj o es en m in es en

UJ ^ <N 1-1 p-1 r — f 1-1 h H

| s ---------- <0 Φ

O. CS 00 r-l rH rH

j3: nj <Λ <n es es es en es en

S

Ή

oj Q

ChP * o- m m id oo> »00

Q | H r m m, r rt »M

Ö4 <o 00 00 00 00 00 00 00 P s c / ί Ά d0: (W m mm +3 ‘2« s m en es m m m

O O O O O O O

S m ^ tn ^ tn m L ^ ^ tn "*

I I aj.Hj bj hJ 2 II II

h d -IS IS IS IS i I 1S 11 U r; tn r ω £ tn £ tn, g g tn tn tn g

* D tUOQ) Ö <U OO) OSWQJWS

0 _____

H I ri B

1 3 g -d S s E 'S S 3 s'

E "* W E r * Ή rH rH rH r-l r-li-H

79579 “jS c 1 13: ¾ ° *>: <Ö, rn CM 00 CM rH 15 ^ g'1" '1 C / 3 CNJ r — I CM CM »- <<7> i ^ ^

- tn f— <· O -P

H n) -n 01

5 d 01 G

pS1 en - + J

> -H ·· (0 13

Q O 03 -P

<M-P O 03 0)

cm ____: ______ O QJ O

E Ö 00 H Ό

\ | φ MO

«25 ΙΛ <-> <N CM CO CM CM iS-Sc pd ° MMM m - <- · mce 5-1-1 d 03 to O ^ c ------- m: d oi« G · π -H iH 03

S = 5 g · ^ S

O .0.3 co -. d O -Sow 00 M ΓΜ «O d G Ai • g.H M r-l CM CM <t CM 03 ··

<03 c *> G

Ο Γ '-H -P - Ό 0) O -H -P 03 G d G Ai ao 10 M O M ΙΛ' οωπ

V r-H γ-Ι CM CM 1-1 i — c G 03 -P

3 r · 03 Ai G

it S ------- o 13 (0 Φ 03 13 13

> 3 G 03 .P

3'dcn Ο Ο οί r »1» 3 · \ o - "G

3 ijp n cm <j co <r co 031) -1-1 -H C 13

- g -H

<H d C

d 03 o> G 03 e (0 o c e to • H 1) · Η -n

2 P 13 -H

o] L oo o \ oo σ \ co r- »c M d

cLro · * · »* a * * * H« P

GT i oo oooo coco oo dCw GK 03 d -H · co cu dd -P «- _ d -P d ·· g 13 d r- - · ρ -pp 0P -H 03 dd ..1 W rH 'rl D 01 £}: d - E -P 01

• P p m o to to m o G rj «1 (D

ICQ * · * λ * »λ * (lj flJ O ^

jdid O.-1 o O O i — t d> G -P

«S -p o x: _; __________ 13 in g d -P VO -H 03

§ S § § § § o J-S

• 5 -5 -5 -5 -S .5 3 «^ ω ^ 3 a £ p · vo" p d

E E E c E p * »- Ο -P

13 σν οι ο T- t— cm ro. m oi 8G -pm ld m tn m -dll • PP oi oi: d οι d 1) 3 1 -S 5 -S8 5 8% 5% 8 B 8 g ft I Ϊ8 i $ 15 8 -3 8 -Η · 3% iS ΐ «« g

w 'E 0) Ή 5] Η 3] * H S Ή Sh fl} * H

• h e S® So £ "d S3 .vipw + j

X iG 03 g 03 03 03g'03§0103 03g ge'c-H

Wd W 13 wd W fa W 03 w fa

8___________ W 03 d -H

3 ·. * * W W> Ό 3 I ο; i 3 p ΐ ^ cMn <jmvo r- Λ

SmS-h 2 - t

EhWS3 m M 1-1 M + * li '37 7 9 5 7 9

Examples 168-172;

The procedure is as in Examples 54-75, but the sizing agent and the retention agent are added separately to the fiber suspension, whereby 7% of the sizing agent in the liquid or molten state is mixed at 80 ° C with an aqueous 5% ammonia solution in the presence of water. -greatable, as well as castable, homogeneous and storage-stable emulsion, and the adhesive preparations shown in Table XII below are obtained. The Val% shown represent the amount of ammonia equivalents per 100 equivalents, in proportion to the number of -COOH groups present in the respective ester or amide mixture of the sizing agent. 10 seconds after the addition of 0.5% or 1% of the dry matter of the sizing agent, half of the application rate is added to the fiber suspension in each case, i.e. 0.25% or 0.5% of the dry matter of the retention agent No. 1, in which case the application rates of the adhesive and the retention agent are proportional to the solids content of the fiber suspension. The gluing results are also shown in Table XII.

138 7 9 5 7 9 r-τη — I — I-1-1-1-

«S

Id <d 8¾>: <d • r-i

S E

, v -3 co cm 'in is 0 il d in oo O cm ro m £ i ___ c9 co co co ro nr ^ ^ ^ «* 0 Ο' ί rH fH r-4 _j>; g | —--- -

t> G CO 00 ο Γ- ON

Ο · Η -H CO ΙΠ CM rH ON CM

jT as JO ---------- o o <i fi co co no co co Λ IS. Φ O CM rH, -ι η; 3 s --- ^ --- |! R co on is ao is o

-n co co CM i-l rH

§

U1 0 01 ^ ^ ™ 'CM

Jh K * * * ·. ^

Ml 00 00 00 co oo

UV I

flat______

Is! 3 ini ό o m m in co ε _ ** “*« „D: 8 ^ -. ° ^ o o o

Jj 3 '3 _-, .. 1 ____-_. . * I c c c I -π I -η φ 5J οι w -S H, "SH Φ ω φ ω Φο fi 5 ^ 3 i rh £ 83 £ 83 s s 3 8 8 I 01 3 ° .¾ 3 ° 3 3

Is II s "ä 11 * ag I -g £! Ji« til ® til ^ 3 g ^ 3 ^ 3 g ^ IS 8i ^ si ** g | "g -S ^ gg * 'S If' ig®> I b 11> IIs · IIs ·? sm> ·· <ppo ..03 0 0 o. · o. · o # Φ 4 ° dP φ ΦΟ, 'dP <1 o <#> <CO dP oo Ο · η B r- [ν-π Sir- <n— r '(¾ rsi i "¢ 5 * - 3 ^ * 8

3 '3. . “<* O rH CM

S Ä a rf Ό NO ΓΗ

^ WfcrX H rH rH rH rH

139 79579

Examples 173-180:

Proceed as described in Examples 54 to 75, but using the excipients shown in Table XIII below and add the sizing agent and retention agent separately to the fiber suspension, mixing 15% of the sizing agent in powder form with an aqueous 5% ammonia solution in the presence of water and glass beads. and self-emulsifying, as well as homogeneous and storage-stable, sizing agent preparations shown in Table XIII below are obtained. The Val or% shown denote the number of equivalents of ammonia per 100 equivalents, in proportion to the number of -COOH groups present in the respective ester or amide mixtures used as sizing agents. 10 seconds after the addition of the dry matter of the 0.4% sizing agent, 0.2% of the retention agent no. 1 dry matter. The amount of filler, glue and retention agent used is proportional to the solids content of the fiber pension. This also applies to the amount of alum. The gluing results are also shown in Table XIII.

\ 140 79579

w S

¢ 5 Φ on vo oo r-v §3 ° ^ ^ ^ ^>: © ^ • m! - H H Γ * · ** »- <rt- *

> 'g w <r <r <r S

κ-ν (N + J

CM -, ----- 'V w A, - ia · «o s s 2 s 0 ^ CJ ---- m C -H —---

• °: {0 S

£ ΰ 5 W CO «M o VO

3 «jjj w n ° - £ CN ro <r sr

C> T-t r-l rH rH

Se ----- Π3 1 I gal ^ a a a s g

B

C> ^ »n O O

Φ U · * *> · * · *

Qj (0 CO CO 00 00 d i __I__1____ ui I en i Q tn o en i d ac> ö: ro I: ©

* H rH Ή H: <b C

<3 —I i — I rä C (ÖU5 dc-r · g C o 3 ™ 3 nm

+ J T- 4. ia 3 v- ·· (0 -M -—-: <T3 -pr ^ rH

-H \ f> © P \ tT> U) -H TdM -H ^ Λ 1 -rl "3 U3 -H" 31 10 -HO © H O C (Il

© H Q UI ¢) H Q ΙΛ J) H Ä C 1/1 rH Ö5 ·· (B

4-) 0) (Λ ^ ι — i rH ^ 4. r — I '· (/ 2' - 'dp (0> 1 C dP JNr- r-H rv * - rH dP <N / P Q) dP Γ4 ©

· © * rl (0 Q dP (0 O rH LP i — I rH ID i — I

En © o 2 itj: nj o 2 ie: n! o <q », -h o <· 4 h

<N P G CN ^ P G (N ^ -r-0 Γ4 - 'r- O

P - $ ©. $ CO -H CO 4) -rl U)

* H ^ * | H -H jfl λ · Η * H

il i | 11 i | g gfl 1 e n I * 31 e «i e Sen © Pro e en © Pro • H © o <*> © en © ö <* ° © tn

(0 0) -Γ-ρφ · η O dP ΦΦ · η O dP

tÖP ptnr-j P © -ntOr-j ΡΦ

3 10 O -H © O ® H p -H © OÄrH

l'ä p> p <ö o p> -η λ ES dP © dP © 3> φ # t)>

HP P O -H dP P O -H

m -h (rt tn en o m S o m en o tn S o

H p> r- φ T- t S LO V— © r- V— S ID

s -J-

5 B S «ί m vO

w .5 C H · r- | r- © en -h ^ ^ 1-1 ^

Eh M P_ \ 141 79579 —it? 1: ---- S! ° * s 5 a I ί> 3 t 8 β -Η Λ <0 1 g -5 O 3 -η ί H S ΓΛ Ο θ \ os r * ~ i ^

H S o O ^ uS O C

> '3 1/5 - · r-ι 3 β 0! - CM B 5 -H o e I · nft to w U 3 O 00 rH CM Cd Cö d)

SÄ ° H CM - r- <Ai -P CU

*> ί — I -P CO

o β ------ 3 CU 3 f>. ζ -d> Ai ω -β: p B 0 3 • S .5 .¾ J2 σ \ IT * to r-. : 3 · Η -Ρ o: 8 0 n -1 --1: 3 Ä · Η Q.-P ______- Ρ 3 3. Μ 3 Αί ^: 3 Ο, · * ω β β ο 2 2 ο * 2 ω 3 ω m --1 cm cm -a- 3 β S ω cu

• 5 ---—---- 3 O

+ j S Ai o β (0 Φ O Ή Ιίΰ!> · § -n 3: 3 ^ in, w 5 2 S 2 3H «β -P cu n a) o m -no)

-H -H rH X

SCO -P rH

β -P <U: 3

H CU 3 β TN

ω o m to u-, 0.3 -h Ϊ> «·> r -v ω 4h 3 β

5 ^ ^ Ό Ό β rH UI CU

i3 n 3> 1 ω a 3 ω -P Ai W O. 4J> 1: 3> 1 ____- H -p Ό: 3

---- 3 β · H M

Ai: 3 3 CVH G -P rH

, -d - -d β -Ρ β Λ -5 0-5: 3 3 CU 3 β

I a -H a -H: 3 3 β Ai CU

φ J2h + J-P-HCU

-PCU «He CU M 3 * · β

λΟ ί-ϊ ί-ΐ I I 4-I-HCU3-H

• 3 · Η> ι 3 -Ρ: 0 3

g g: 3 Ai> i> i W

M N Ai rH: 3 e> 1

_______3 -P -P

o> β: 3 00 -rl 3 Ό i— ^ CU 3 -rl 3 3-3 3 T3 a 3 -P -P -P 3333 P ^ tn ω P 3 3 ^ §> * 8 il '"rP-cn ^

O »36 H? IeE: 3 rH CM Ai CU

8 m ^ P § β 3 E β p 3 fi3i «<U ·· O M

y e βω CU-P3 ω en φ ρ 3 ra w t- h ρ .3 9 o # Φ en ® ö # Φω -H -H ·· 30

£ 8 B -oSrH '£% * rSrH

w ρ tn £ -n 3 o ω η o · η 3 Ooh · ρ + ί

3-5 ΌΡ> Ρ> -H 3 Sh 3 3 3 CU

l_i g Ξ CU <#> £> <#> φ t #> T3> φ 3 ω -H β

H -H H <#> P O -H -PO -P £ HH CO lii -H

M -h 3 Λ no in EO in «o lo £ o hh 11 h« XP> i-CUr- f- Bin r-CUr- r- (3in UI 3 dj 3ω 8 ----- β 3 g He 5 ε

3 I Q * - O e -H

H I g β 00 on 00 3 -rl 3 -HM r * r-t OtOr-i e ala_ "Is | - 1__I * 142 79579

Examples 181-184:

The procedure is as described in Examples 54 to 75, but the sizing agent and the retaining agent are added separately to the fiber suspension and PERCOL 292: 3 is not used as an excipient. 20% chalk is added to the fiber suspension. The addition of the sizing agent takes place 10 seconds after the addition of the chalk and the addition of the retention agent takes place 10 seconds after the addition of the sizing agent. The emulsions or dispersions shown in Table XIV below are used as sizing agents. Detergent No. 6 or 7 is used in place of Detergent No. 1-3. Detergent No. 6 is an epichlorohydrin adduct of a reaction product made from dicyandiamide, diethylenetriamine and dimethyl adipate prepared according to Example 7,126 of GB 7,126. . Retention agent No. 7 is a copolymer having a molecular weight of 1,000 to 10,000 made from adipic acid and dimethylamino-hydroxypropyl-diethylenetriamine. The amounts of sizing and retaining agent shown in the following table are used, these amounts and the amount of filler (20% chalk) refer to the dry matter of the sizing, holding and filler solids and the solids content of the fiber suspension. The gluing results are also shown in the following Table XIV.

143 79579 I, SH 21 -I ssslii 3-¾ g ·· 6 ·· -H 3 P, d ω u cd u ^ .c _ S -In ---- o 0 pg> ίο ο ιβο «ma -, y 00 Λί co, y 01 \ .S -d ο Ο ο ω 00. * 55 a, cn oo Ο -T \ £> -n id -n i0 -n 0)

.p CO * tO ι-l <- · UOCOrH

ao - CQ - to »rH

-P id (U Id (0 (0 O

O ————— β H C H C: <t

to Q) H Q) iH 0) C

° t) O 11 O II Id • 5 _ -P: it -P: it 4-1: it u to to m cm in o rH I — I rH t — I -rl dl -rl ID Ή

<3 E: rd E: id E C

^ ___ I — I -—I I — I H H Q)

~ It It It -H

• h> q> q> e

• P 0) <U -H

S CO CO C OJ

CO · <* 03 r- ~ o <D <D <D 1) QJ Λ

CO to l-ι CM CU> 0)> 0) -H

C C CM

• rl ft Ή ft * H It

ft * H ft * H ft -—I

(0 TJ CO Ti Cfl - - 3 rl 3 Ή 3 it ft to ft tn ft · γί sememe .9 -HO - <HO -H cm O -HM rl Vl Ή 0) 2 5 Ό in m 00 H t H fl rl t aa _r *>,>. a »ftro oo oo oo oo it x; it £ ft>

S A C E C E C

β a Ή 3-H 3Ή It

pH * rH -—I Ή -—I -H

--— 1 1 * H P -H P -Η Χβ -H 4-> -H + J -rl Ai .k XJ ft Xl ft Λ ft I is id c ft c ft ή

rH p - -P -P -P C

Id> ι «B Id 10 It in O

CO: fX3 '- · m rH pH g

fr1 '* ·, * N ° O o, H id' I

atCP O r-l rH r-l It ·· ft ·· ft ft tQ 3 for G <*> C <#> £ iH φ a »a) a) <t

; CVi c E W rH in rH (/ 1 I-H

* —_ “--H ft Ή ft * H rH

c> c> c ·· a) 0) Φ <#>

I OJ 00 1) 03 0) H

m tj> m cr> oo dr> it «g m ° ^ ^ E Id E Id 'dc. i. . owomooocj -Η-p μ μ μ μ £ die me too (¾ <d z z zz OOm

__, .___ V -¾ * · Ό * ft CM

I it o it o rt tn

: 0 3 3 3 3 3 dl I

Ι-p (d E Id g Id o "ä sL ίο >>> T3m S .¾1 22. It ft it ft it o 1- 4-itn-PtnPC -

Q: it m in in m -Ptn-Ptn-PE

§Cp · «I. ; aj s o s <u <u ft o o o o G-PC-PC-Ctn 3 l) 3 1) 3 3 In M φ -P φ -P φ ft It

~~ "- 'β fd β β · Γ" ii — I

I I * H rH Ή Η * H * H

* -H * H <d 3 aJ 3 <d G -P

I * a eJS c JS d 01 ^ 3: S

m? nq PC-P3 -31¾ cccfta. 3 Φ Φ AJ E 5 E II 3 II 3 Φ t g> 9 -, - 3 3 q q H H m id u id o h: it □ .5 ^ S '3 ra § * If h tn tn oh

^ 3 .E .StS .a, S .3 in .gin rltHtrl tJlC

9 Ip Id £ 3 CD CM § W CM δ

uE OEWcmG W <NC Ί6 O t O t 1) Cl ^ - j-2 ------- <u tn Φ Cn qj Or C

HIAIC rH CM <o Vf. M

2 · Ρ Μ oooooo oo ** eS ä S 3 * ~ ~ * 5 i 144 79579

Example 185 and Comparative Experiment I;

The procedure is as described in Examples 54 to 75, but the sizing agent and the retaining agent are added separately to the fiber suspension and the excipient PERCOL 292 ^ 3 is not used. 20% chalk is added to the fiber suspension as filler 5. The addition of the sizing agent takes place 10 seconds after the addition of the chalk and the addition of the retaining agent takes place 10 seconds after the addition of the sizing agent. As the sizing agent, a 35%, further dilutable, homogeneous and stable preparation of the ester mixture prepared according to T is used in the molten state, which is emulsified with 58% by weight of sodium hydroxide in the presence of water at 80 ° C. Instead of the retention agent No. 1 to 3, the retention agent No. 8 is used. The retention agent No. 8 is a poly-N-methyldiallylamine epichlorohydrin adduct prepared according to Example 1 of U.S. Patent No. 4,279,794. The amounts of sizing and retaining agent shown in the following table are used, with these amounts and the amount of filler (20% chalk) referring to the dry matter of the sizing, retaining and filler and the solids content of the fiber suspension. The gluing results 20 are shown in the following Table XV.

In addition, to determine the degree of whiteness, the remission values are measured according to TAPPI (Technical Association of the Pulp and Paper Industry) standard test T 452. The higher the remission values, the better the whiteness of the paper.

145 79579 Β k w ω σι r-ι -h m .—.

O · Η -P r- »r ~.

^ Qj E Ο νο νο £ Si§ • S tn r-4 05

/ O O T-ι VO

9 C

~ n ---%> p

ob δ '· δ ‘ro tn VO

~ 5 · | ίΤ ^: (0 & fi____ • n o r * PO «- ° $

P S

o -¾ en cm i-i o R o <- · vo

3 g -H

· * -H + J ---- 3 ω λ: λ co CO r-t | g

•B

CQ o u 3 EC *, (Λ a ® · i g i3, tn: ixj> 1 C U νΛ £ δ il

'ϋ S B—' O O

H -1-4: D of ° P4 td -43 - '

I I

«£ | S | J e + J - o o -1 ----- ® JH as i Ti a | S | | J "

"3 E -P! /) E -PE

^ w ί§ δ ~ u) S en f

(ÖW> rHC W> 0) I

Eh - „146 7 9 5 7 9

Examples 186 to 188 and Comparative Experiment II:

The procedure is as described in Examples 54 to 75, but the sizing agent and the retention aid are added separately to the fiber suspension, and 0.075% of 4,4'-bis- {2- (di-6-hydroxyethylamino) -4- (p-sulfophenylamino) is also used as an optical brightener. no) -1,3,5-triazin (6) -ylamino) -stilbene-2,2'-disulfonic acid diethanolamine salt. 20% chalk is added as a filler. The addition of chalk occurs one minute after the addition of bleach, the addition of sizing agent 10 seconds after the addition of chalk 10, the addition of retention agent 10 seconds after the addition of sizing agent (h) and the addition of PERCOL 292 10 seconds after the addition of retention agent. The emulsions or dispersions shown in Table XVI below are used as sizing agents. Instead of the retention agent No. 1 to 3, the retention agent No. 8 is used. The amounts of adhesive and retention agent shown in the following table are used, in which case these amounts, the amount of bleach (0.075%) and the amount of filler (20% chalk) -, the amount of retention and filler and the solids content of the fiber suspension. The gluing methods are also shown in the following Table XVI.

In order to determine the degree of whiteness, the remission values are further measured according to TAPPI standard test T 452.

147 79 579 f,,

rn 52 1 — I Π3 i — III

g '3 Λ 3 to 3 to to o BS + J E to E to h 3 a ^ O - - - <D ·· QJ to OS Xl

9 (1) ¾ ro cm cm <0 0 <0 C-) <0 tO

3 $ 8 t "f" r-> r- X CD X O X to (dtn-H O oo O o O to p> <0 10 -I—) -I — I 00 -Γ-l (1)

<0 I — I

-------- to - <0 - H

r-.jj <0 10 tO 10 3 O

„Tn. co cm vo r- »r- G QJ G to G: t0

, ¾ Λ (Λ CM CM <—I -d · <U1H <DQJ <DC

> £ 3 QJ 1 — I QJ I — I QJ <0 {0 ^ 4-> o + j H 4-): <0

(CN _____tfl: t0 <0 O to H

I · H G H IfO * H

10 X EtogCEC

• Τ 'CH 00 H: <0 H <0 H Q)

^ SyttO0 ™ * 5 «3 H (0: rd <0 H

^ 8 2 H>> H> E

6b S C ----- G H

w H G H CQJCCGOJ

: tO-: rag QJ Ό (D <D <D XI

^ π .5 rn -I CO QJ QJ <U Ό QJ H

G: r O to cm cm h I 5 ^ 5 ^ SS

fl) cL + J. H H> H <0 c m ------ <0 to <0 to h H X tO H CO <0 tfl

3 Ό 3 -H 3 tO

O Irt <0 -H <0 Ό (0 Ή

o> co - <r Mt cm co EtoE-nE

* H O »h f — i 1— ♦ in * H ^ * H CO * H C

<3:. - <-Η Ο -H x -H (1) s, ¾ -H _____ H S- | H O h T3 to Ό P 0) X to> 1 <0 TO to>

G XI G> 1 G

CO CM VO H H E H, G H to

to CM CM CM I H 3 H E H H

_ H H H 3 Η Λ! • H J-l Η Η Η Λ <G Λ + J Λ J-l XI (0

0 <0 <0 to 4J to -H

-. -P C 4-1 (0 4-) c to to c to 0 W H O O O §

CU <0 »». »H * <0 * E

<0 I cj \ I <0 I — I <0 H <0 <0

3 $ C · C H C

M Pt __._____ QJ dP QJ .. QJ <0

1 C /} 1 — I CO c ^ P CO f ~ H

Jj Ή fO Ή 1 — I Ή i-H

> 1 a> c Π3 C ·: <0 Q) Q)> QJ <#>

, 'n ^ -m QJ 00 Q) 0) H

S, C’2 iC O 'ΙΟ (Τ' O '! O' <0 & S: ¾ ° Ί ™ O O 00 O>

LiSS: S o o o o EtoEE

Ό q, 6c O tfl O tO O OO · ä ’3 3 2- xi to x to xl cd -—.

1-4 u ^ o to _u

———- h ^ --— * “0 * ·> td * fd O

,. rd O Π3 rH 03 CO LO

, · EH G .L .1 G 3 G H G to OM

§ »- S trf td (OE ^ -PPOI

§ S.S CÄ «q ^ *>>> Ό <0

Etu aio $ ä * QJ 3 * <0 <0 <0 tO <0 O ^ -HG · π ^ Φ E «- 4-> 10 4-) tO 4-> 3 ^ d'3 Sl * § & ί 631, Ϊ SS § ti Ϊ «---------, - G 4-JG 4-) GX to G QJ G QJ G 3 to

Il QJ4-) QJ4-iQJ33 j r E <t3 E Ό E ti h

H Hi — I H 1 — I H H

go '| S <0 3 <0 3 <0 G 4-)

(JJ; <0 i — ItOHtOHtOtO

H I -I dp “Ί S G S G § -o E

3 g'H £ o o O O 0) tO QJ <0 QJ H: <0

t — 1 1 — I tO · —I fO '—I O 1 — I

T> - H Ό H Ό H CP G

. , QJ H QJ H QJ> 4 QJ

n.S3il.S ^ 'ύ ί 3X XJOOOXiQJQ)

5 XOJHX 3 ^ ^ 23 QJ Cri QJ Cn QJ CD G

1 s g o a a a a -s a g aj3? 88 a - a 2 S s n * ί 148 79579

Comparative experiments III - V

The procedure is as in Examples 112-116, but in Experiment III 0.5% of retention agent No. 5 without adhesive is used, in Experiment IV 0.5% of the indicated adhesive 5 without retention agent is used and in Experiment V no adhesive or retention agent is used. Only weak paper sizing is obtained, as seen from the WA Cobb values above 100 in Table XVII below.

Table XVII

_

Comparative test Suspension WA Cobb ^ Q (g / m) No. pH _after drying_, .. days of storage ____toxnn ft.

__SS Γ OS__SS OS

III 8.1 191 154 162 148 IV 8.0 173 146 150 124 V 8.1 240 196 197 176

Claims (42)

149 79579 1 X (R ") (H) or 2p" -rVp "/ * 3 NC-CH -CO-N2R4V '~ 1 ^ 2-q", wherein R "^, R ^ / R ,, 3 "R" 4, p "and q" have the meanings given in claim 36. A process for gluing paper or board by adding, in any order or simultaneously, a sizing agent (A) and a polymeric cationic retention agent (B) to an aqueous, cellulosic, optionally filler-containing fibrous suspension, characterized in that component (A) is used. one acidic group, optionally in the form of a salt, and at least two hydrophobic substituents each having at least 5 carbon atoms, the at least one hydrophobic substituent having at least 8 carbon atoms and at least two of the closest adjacent substituents being linked by a linker containing at least one carbon atom and at least two hetero atoms. 2 C = 0 0 = 0 »L * 3 * 2 A3-OX R -NQ \ 3-o-Ö-r2, • ARi / K HSQ-t - fco-R ..) ^ \ <3 t_1 • Vr2 S \ / \ or OR O II R.-iOA -N7 \ -A -OSR, oi Lo X-ox II 165 79579? HXR ^ NH-CHj-CH-CHj-N> K-CH2-CH-CH2-NH -R2, o «i C« o XS-CK2-r, 3 Γ »A. Q5-CH2-CH-CH2-y W-ch-ch ^ .0 = 0 '? H2- ^ h-ch2-q7? H OH X z H-CH2-A5-CH2-CH-CH2-N-R2 tei ? H? X q5-ch2-ch-ch2-a5-ch2-ch-ch2-q6 where q is an integer from 1 to 5, t is 1 or 2, Q5, Qg and Q7 each represent -C - C and X represents a residue of a polybasic, inorganic or organic acid having 2 to 18 carbon atoms, the substituent Χχ has the meaning of the substituent X, or if t is 1, it represents the group -CO-C6H4-COOH, -CO- (CH2) 2 "C00H, -CO -CH = CH-C00H, the substituent X2 has the meaning of the substituent X, or if q is 166 79579 1, it denotes the group -CO-CH = CH-COOH, "SO3H," and the substituents A3, A4, uH A5, / R2 and R3 has the meaning given in claim 28. Process according to Claim 1, characterized in that a sizing agent is used as component (A), in which at least two hydrophobic groups each have at least 8 carbon atoms. Process according to Claim 1, characterized in that component (A) is a monomeric-oligomeric sizing agent which contains at least one acidic group, optionally in the form of a salt, and at least two hydrophobic substituents, each containing at least 8 carbon atoms, the at least two hydrophobic substituents being combined to each other via a linker containing at least 2 heteroatoms. 150 79579 Process according to one of Claims 1 to 3, characterized in that a sizing agent is used as component (A), the hydrophobic groups of which in each case contain from 8 to 22 carbon atoms. Process according to one of Claims 1 to 4, characterized in that a sizing agent is used as component (A), which contains 1 to 6 anionic groups, in each case 1 or 2 negatively charged groups, and 2 to 10 hydrophobic substituents, at least two adjacent hydrophobic substituents are attached via 1-5 linking members, each containing 4-15 carbon atoms and at least two oxygen and / or nitrogen atoms. Process according to Claim 5, characterized in that a sizing agent is used as component (A), which can be prepared by reacting at least one (a) one aliphatic alcohol having 3 to 26 carbon atoms and 2 to 6 hydroxyl or hydroxy-C 1 -C 4 alkyl groups, optionally containing 1 to 5 nitrogen atoms and, in the presence of 2 hydroxyl groups, optionally one C6-C22 fatty amine residue, a heterocyclic alcohol or glycide having 3 nitrogen atoms in the heterocycle and 3 hydroxy-C1-C4-alkyl or glycide groups, an alkanediol diglycide having 2 to 6 carbon atoms in an alkane residue or a di- or triphenol or dihydroxynaphthalene to react with (b) a fatty acid, its halide or a primary or secondary fatty amine having 6 to 22 carbon atoms in the fatty residue and then (c) with a polybasic inorganic or organic acid having 2 to 18 carbon atoms or its anhydrides 151,79579. Process according to Claim 6, characterized in that a sizing agent is used as component (A), which can be prepared by reacting at least (a) 1,5-, 1,8-, 2,3- or 2,7-dihydroxynaphthalene, hydroxyhydroquinone, pyrogallol , phloroglucin, hydroquinone, pyrocatechol, resorcinol, tris (hydroxyethyl) isocyanurate, butane-1,4-diol diglycide, glycerin, butane-1,2,4-triol, pentaerythritol, sorbitol, sorbitan, triethanolamine, Cg- C22 fat “amine diethoxylate, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine or tris (hydroxymethyl) aminomethane to react (b) at least one fatty acid or alkyl having 16 to 20 carbon atoms. or with an alkenyl halide or a mono- or dialkylamine or a mono- or dialkenylamine each having 16 to 20 carbon atoms in the alkyl or alkenyl residue and then (c) sulfur trioxide, sulfuric acid, chlorosulfonic acid, phosphoric acid, phosphorus pentoxide, phthalic acid, phthalic acid, phthalic acid or with maleic anhydride. Process according to one of Claims 1 to 4, characterized in that a sizing agent is used as component (A), which contains 1 to 4 anionic or acidic groups each containing one or two charged substances and 2 to 5 hydrophobic substituents, at least two substantially adjacent substituents. they are connected via 1 to 5 linking members, each containing 1 to 15 carbon atoms and 2 to 6 nitrogen atoms. Process according to Claim 8, characterized in that a sizing agent is used as component (A), which can be prepared by reacting at least (a ') one optionally monosubstituted with N-C 8 -C 22 alkenyl or alkyl, 3 to 6 nitrogen atoms and 4 to 40 a carbon-containing polyalkylene polyamine to react with (b ') a fatty acid or an alkyl or alkenyl isocyanate having 6 to 22 carbon atoms, followed by (c') a polybasic, inorganic or organic acid having 2 to 18 carbon atoms, anhydride, a halocarboxylic acid or with snl.tor.in. Process according to Claim 9, characterized in that a sizing agent is used as component (A), which can be prepared by reacting at least (a ') N, N'-bis (3-aminopropyl) -1,4-diaminobutane, N- ( 3-aminopropyl) -1,4-diaminobutane, 1,2-bis (3-aminopropylamino) ethane, pentaethylenehexamine, tetraethylenepentamine, triethylenetetraamine, dipropylene triamine or diethylenetriamine to react with (b1) palmitin, stearin, oil - or with benzoic acid or octadecyl isocyanate, followed by (c1) 2-chlorobutyric acid, 3- or 2-chloropropionic acid, bromoacetic acid, chloroacetic acid or their alkali metal salts, propane sultone, benzophenone tetracarboxylic acid, 1,8-naphtho - or with pyromellitic acid, norbornene dicarboxylic acid, hexanoic or tetrahydrophthalic acid, phthalic, succinic, glutaric, maleic, dimethylmaleic, citraconic or itaconic anhydride. Process according to one of Claims 1 to 4, characterized in that a sizing agent is used as component (A) which contains 1 or 2 potentially anionic, acidic methylene or methine groups and 2 or 3 hydrophobic substituents, at least two of the substantially adjacent substituents being combined via 1 or 2 linkers each having 1 to 15 carbon atoms and 153 79579 to 2 nitrogen and / or oxygen atoms, and the potentially anionic, acidic methylene and methine groups exist as divalent or trivalent radicals -CO-CH2-CO- or -CO-CH-CO-. Process according to Claim 11, characterized in that a sizing agent is used as component (A), which can be prepared by reacting (α "i> malonic acid, malonic acid dihalide, acetonide carboxylic acid, or C 1 -C 4 alkyl of malonic acid, acetonedicarboxylic acid or methanetricarboxylic acid -ter to react with (b "i> a fatty alcohol or (a" 2) cyanoacetic acid or a C1-C4 alkyl ester thereof to react with (b "2) a fatty amine and then (c") C4-C12 alkylene-, With C8-C4 cycloalkylene or C8-C14 arylene diisocyanate. Process according to Claim 12, characterized in that component (A) is used as a sizing agent which can be prepared by reacting (a "1) malonic acid dichloride, malonic acid or acetonecarboxylic acid dimethyl or diethyl ester or methane tricarboxylic acid trimethyl or triethyl ester (b" i) with at least one optionally unsaturated aliphatic alcohol having from 8 to 22 carbon atoms. Process according to Claim 12, characterized in that a sizing agent is used as component (A), which can be prepared by reacting (an2) cyanoacetic acid methyl ester or ethyl ester with (b "2> mono- or dialkylamine or mono- or dialkenylamine, in each case has 8 to 22 carbon atoms in the alkyl or alkenyl residue, followed by (c ") butylene diisocyanate, dodecylene diisocyanate, decylene 1,10-diisocyanate, 154 79579 hexylene-1,6-diisocyanate, cyclohexyl or dicyclohexyl diisocyanate, naphthylene-1,5-diisocyanate, diphenylmethane-4,41-diisocyanate-phenylene-1,4-diisocyanate or toluene-2,4- or -2,6- with diisocyanate. Process according to one of Claims 1 to 4, characterized in that a sizing agent is used as component (A), which contains 1 to 6 groups of -cocP or -COOH as an anionic or acidic substituent and 2 to 10 hydrophobic substituents, at least two of the substantially adjacent the hydrophobic substituents are connected via 1-5 linking members each having 4 to 15 carbon atoms and 1 oxygen and 1 nitrogen atom or 2 oxygen or nitrogen atoms. Process according to Claim 15, characterized in that a sizing agent is used as component (A), which can be prepared by reacting at least (a "') one aliphatic or aromatic carboxylic acid having at least 3 carboxyl groups, polyalkylene polyamino polyacetic acid having 4 to 6 carboxyl groups or an aliphatic monocarboxylic acid or an aminomonocarboxylic acid containing 2 hydroxyl groups to react with (b "') fatty alcohols and / or fatty amines, or, if a monocarboxylic acid is used, with fatty acids. Process according to Claim 16, characterized in that a sizing agent is used as component (A), which can be prepared by subjecting at least (a "') hemimellite, trimellite, trimesin, prehnite, mellophane, pyromellite, nitric acid, benzenepentacarboxylic acid, benzophenonitrile-...-hexacarboxylic acid or their anhydrides, tricarballyl, aconite or citric acid, li 155 79579 bis (2-carboxyethyl) carboxymethylamine, propionic acid, nitrilon-trio-acid 1,2-dihydroxybutyric acid, 1,3- and 2,3-dihydroxy-valeric acid, 2,2-bis (hydroxymethyl) -propionic acid, Ν, Ν-bis (hydroxyethyl) -8-alanine or N, N-bis (hydroxyethyl) glycine to react with at least (b "') one optionally unsaturated aliphatic alcohol having 8 to 22 carbon atoms and / or a mono- or dialkylamine or a mono- or dialkenylamine each having 8 to 22 carbon atoms in the alkyl or an alk-phenyl residue, or, if present monocarboxylic acid as component (a "') with a fatty acid having 8 to 22 carbon atoms. Process according to one of Claims 1 to 17, characterized in that a sizing agent with a molecular weight of 400 to 3000 is used as component (A). Process according to one of Claims 1 to 18, characterized in that a sizing agent which is present at least in part as a salt and which can be prepared by further reacting with an alkali metal hydroxide, ammonia or an alkyl or alkanolamine having up to 6 carbon atoms is used as component (A). Process according to one of Claims 1 to 19, characterized in that a retention agent with a molecular weight of 1,000 to 2,000,000 is used as component (B). Process according to Claim 20, characterized in that the retention agent (B) used is a polyalkyleneimine, a reaction product prepared from polyalkylene polyamines and aliphatic dicarboxylic acids or polyalkylene polyamines, a diacidiamide addicyl and a diacarboxylate , reaction products of formaldehyde, ammonium salts of strong organic acids and alkylenediamines or polyalkylene polyamines, cationically modified starches or carbohydrates prepared from locust bean or guar flour, reacted with polyamylated amines, epihalohydrins and polymerized Process according to one of Claims 1 to 21, characterized in that 0.02 to 3% by weight of adhesive (A) and 0.02 to 3% by weight of retention agent (B) are used relative to the dry matter of substances (A) and (B), respectively. substance and the solids content of the fiber suspension. Process according to one of Claims 1 to 22, characterized in that condensation products of formaldehyde and urea, titanium dioxide, calcium sulphate, talc, kaolin, montmorillonite or chalk are used as optional fillers. Aqueous composition for carrying out the process according to any one of claims 1 to 23, wherein the sizing agent (A) and the retaining agent (B) are added to the fiber suspension in any order, characterized in that it contains at least partially the sizing agent (A) and optionally conventional additives. . An aqueous composition for carrying out the method according to any one of claims 1 to 23, wherein I: 15? 79579 the sizing agent (A) and the retaining agent (B) are added simultaneously to the fiber suspension, characterized in that it contains (A) 2 to 40% by weight of sizing agent, (B) 0.1 to 20% by weight of the retaining agent (B), in each case relative to the substances (A) and (B) to the dry matter and weight of the aqueous composition, and optionally conventional additives. Paper or paperboard glued according to the method of any one of claims 1 to 23. Use of a component (A) according to any one of claims 1 to 19 for gluing paper or board. 28. Intermediates from which the sizing agents (A) used according to the invention can be prepared, characterized in that they correspond to one of the formulas 158 79579 R 4-1 Γ_0_ϊΗ2 μ.] [M L-], 0 R -B-O-CH 1 2N R2 - $ - O-CH2- ^ C-CH2-OH 'R3 -? - O-CH2 r1 /> 2 ft n - E - ch2-oc-r2 CH2-OH ^ 4] -o-a5 (- | - a4-) 7T- | -a3-o- HL = 0 h 2 A-OH Rr <8 A -OCR '3 2 A ° -R1 i - ^ - R2 V0-R3 ι59 79579 / v \ 1 -f — TOR ° 1 R -C-Ο-Α, -ίΚ ^ lA - 0-CR. 0.1 Lo A3-OH q4-ch2-? H-ch2-n / Vch2-? H-ch2-qa ° v ° iH2 ^ -CH2-QA 9 «9H Qa-CH2-Ch-CH2-A5-CH2-CH- CH2-Qa where q is an integer from 1 to 5, t is 1 or 2, A3 and A4 in each case denote propylene, isopropylene or ethylene, A5 denotes straight-chain or branched alkylene having 1 to 6 carbon atoms Q4 denotes groups H CO-Rj r And R 1, R 2 and R 3 each represent alkyl or alkenyl of 6 to 22 carbon atoms, wherein R 1 and R 2 are different if q or t represents 1. 160 79579 29. Intermediates from which the sizing agents (A) used according to the invention can be prepared, characterized in that they can be prepared by reacting (a 1) 1 mole of optionally N-C 8 -C 22 alkyl or alkenyl monosubstituted with 3 to 6 nitrogen atoms and 4 to 40 carbon atoms. polyalkylene polyamine to react with an (b ') 1 - (h "-1) mole of an alkenyl or alkyl isocyanate having 6 to 22 carbon atoms, wherein (h') denotes the number of nitrogen atoms of component (a '^). An intermediate or its salts from which the sizing agents (A) used according to the invention can be prepared, characterized in that it corresponds to the formula NC-CH -CO-N 2 (RP p "-1 (H) 2-p" wherein p " represents the number 1 or 2 and R "^ and R" 2 each denote an alkenyl or alkyl having from 6 to 22 carbon atoms. Process for the preparation of intermediates according to Claim 28, characterized in that (a) 1 mole of butane-1,2,4-triol, pentaerythritol, tris (hydroxymethyl) aminomethane or an α3-° h HO of the formula -A3- [N3-Aa] -N-A3-OH, ν <or L i a3-oh IJ j J OH OH 161 79579 8 · ΗΟ-Α3- / \ -Α3 ~ 0Η JyL Α3 ~ οη in which the symbols q, A 3, A 2 and R 2 have the meanings given in claim 28, reacting with (m) (h1) a mole of an unsaturated or saturated fatty acid of the formula R 1 -COOH, R 2 -COOH and / or R 3 -COOH in which the substituents R R 1, R 2 and R 3 are as defined in claim 28 and (h) represents the number of hydroxyl groups of component (a), or (a) 1 mole of pyrogallol, hydroxyhydroquinone, floroglucin or 1 mole of dihydronaphthalene is reacted with (m1) a mole of formula Rrzi, An alkyl or alkenyl halide according to R2, Z2 and / or r3 to z3, in which the substituents R1, R2 and R3 are as defined in (28) denotes the number of hydroxyl groups of component (a) and Z 1, Z 2 and Z 3 in each case denote halogen, or (a) 1 mol of isocyanuric acid polyglyceride or 1 mol of formula 162 79579 A compound of the formula C1-C2H-CH2-O-A5-G-CH2-CH-CH2 in which the substituent has the meaning given in claim 28 is reacted with (b) a mole of (f ') a fatty acid of the formula R1-COOH , a primary fatty amine of the formula R 1 -Nh 2 and / or a secondary fatty amine of the formula R 1 and R 2, in which the substituents R 1 and R 2 have the meanings given in claim 28 and [h ') denotes the epoxy groups of component (a) the number. Process for the preparation of an intermediate according to claim 30, characterized in that 1 mole of cyanoacetic acid or its alkyl ester is reacted with 1 mole of a secondary or primary amine of the formula A (R? P »-1 (H) 2-p ··, wherein R '^, R "2 3a P" have the same meaning as in claim 30. Compounds or their salts which can be used as sizing agents and which can be prepared from the intermediates according to Claim 28 by reacting dialkyl ethers or dialkenyl ethers of hydroquinone, resorcinol or pyrocatechol having in each case 6 to 22 carbon atoms in the alkyl or alkenyl residue , with an inorganic or organic acid having 2 to 18 carbon atoms, characterized in that they correspond to one of the formulas -'a Γ i? · M 164 79579 O il R1-C-O-CH r2 - $ - o-ch2- ^ c -ch2-ox r3-So-ch2 R “fi / Xf2 β n - ^ - ch2-oC-r2 Ϊη — ΟΧ Compounds which can be used as sizing agents, characterized in that they can be prepared by reacting an intermediate formed from components (a'i) and (b'i) according to claim 29 with (c ') 1 to [hi "] moles of a polybasic , an anhydride of an inorganic or organic acid having 2 to 18 carbon atoms, a 2- or 3-halocarboxylic acid having 2 to 6 carbon atoms or a sultone wherein [hi "] means the free nitrogen of the intermediate formed from components (a'i> and (b'i>) the number of those who have not reacted with the component (b'i>. 35. Compounds which can be used as sizing agents, characterized in that they can be prepared by reacting (a'i> 1 mole of a polyalkylene polyamine having 3 to 6 nitrogen atoms and 4 to 20 carbon atoms (b'2 * l- [h "-1 ] with 1 mole of a fatty acid having 6 to 22 carbon atoms, wherein [h "] denotes the number of nitrogen atoms of component (a '), and then (ci) with 1 to [h" 2 moles of pyromellitic acid, norbornenedicarboxylic acid, dimethylmaleic or citriconic anhydride -chlorobutyric acid, 2- or 3-chloropropionic acid, bromoacetic acid or propane-sultone, where [h "2] denotes the number of free nitrogen atoms present in the intermediate formed from components (a'i) and (b'2 ^) which have not: reacted with the component ( b '2> with. 36. Compounds which can be used as sizing agents, 167 79579, characterized in that they correspond to the formula JS-OR "R ..- 0-SA, t5i o CN 0 0 CN 0 R" HIH ir 1 11 / * 3 -C-CH-C-NH-N 2 -NH-C-CH-CN 2 (H) 2 -p «« 'R 2, p "-1 4 q -1 lq where p" and q "in each case denote the number 1 or 2, R "1, R" 2, R "3 and R" 4 in each case denote alkyl or alkenyl having 6 to 22 carbon atoms and A "is cycloalkylene having 6 to 14 carbon atoms, alkylene having 4 to 12 carbon atoms or 6 to 14 carbon atoms containing arylene. Compounds which can be used as sizing agents, characterized in that they correspond to the formula «III O 0 1. ii II 2 C - A '·' - C - Q ^ 'or oo Il II R" J-C - 0 - A "2 - 0 - C - R" J where m "'and n"' denote the number 1 or 2, Q "'3 and Q"' 4 denote the group -O- or -NH in each case or, if m "' and / or n "'is 2, Q"' 3 and / or Q "'4 denote the group -N 2, R" "i» R "' 2 3a R" "2 in each case denote alkyl or alkenyl having at least 5 carbon atoms, wherein in at least one of the radicals R "'^ R" "i, 168 7 9 579 R"' 2 and R "" 2 are 8 to 22 carbon atoms, A "represents the formula X, M -CH2" CH-CH2-, X '" -CH2 - c - CH2-, CH3 -C-CH- or II CH X "· - (CH2) b", (CH2- (CH2) B ", xx- (CH2) t" 1_1 X '", or if Q "3 and Q" 4 are different, according to formula i L1 or K 2 p '"- 1 X"' -CH2-C-CH2-OH or if Q "'3 and Q"' 4 are similar and denote the groups -O- or Q "'3 and Q" \ are different from each other; 0 169 79579, of the formula _ y \ _h_y \ I II 0 II,>. ** · ^ <γ, 2 »ς ··· -ι« 'bV residue according to zV-1, and A "' 2 denotes the formula -CH -CH-1 I χ, Μ -CH-CCHj or | 2 n 1 I divalent residue according to ch3 x, m - (ch2) 2-n (ch2> 2- K χ ..., where X "'represents -COOH or -COC ^, Y"' 2 represents λ " '\ -CO-Q ”^ 1 iV'-ip"' is an integer from 1 to 4, q "'and q" n each denote the number 1, 2 or 3 and m "', n" ', s "' and t "'each represents a number 1 or 2 and the substituents Q" ^, R "' ^ and R" "^ have the meanings given. Process for the preparation of compounds according to Claim 33 or their salts, characterized in that 1 mole of the formula 170 7 9579 R 1 -yl-O-CH R 2 -? - O-CH 2 - C-CH 2 -OH r 3 -? - o-ch 2 Κι1ΑΓ2 ?. Nt-CH2-O-C-R2 Ch2-oh X-OH OH ϋ OH Q4-CH2-1H-CH2-ljr \ -CH2-CH-CH2-Q4 or o = ci = o VrvQ4 OH OH I »Q4-CH2 -CH-CH 2 -O-A 5 -O-CH 2 -CH-CH 2 -Q 4, wherein the substituents A 1, A 2, R 1, R 2, R 3 and Q 4 have the meanings given in claim 28, or 1 mole of the formula I: 171 7 ^ 579 fi-y - «- 'j-'TV'irTv [- J hl · K3 r2, wherein q is 2, 3, 4 or 5 and the substituents A3, R2 and R3 are as defined in claim 28 or 1 mole of butane-1,2,4-triol is reacted with 1-2 moles of a polybasic acid of formula H to X, wherein the substituent X is as defined in claim 33, or 1 mole of glycerin is reacted with 1-2 moles of the formula A polybasic acid according to H to XL, wherein X 1 represents a group -CO-C 6 H 4 -COOH, -CO- (CH 2) 2 -COOH, -CO-CH = CH-COOH or -SO 3 H, or 1 mole of the formula [1 -a3-n-a3-o- ~ ["] t an intermediate according to R2 -, wherein the substituents A3, R1 and R2 are as defined in claim a 28 are reacted with 1-2 moles of a polybasic acid of the formula H to X2, wherein X2 represents an amount of rvh- 172 79579 of -CO-CH = CH-COOH, -Ä or ~ SO3H 'or XOH 1 mole of the formula 0-R // 1 I -H — 0-R „Cai • · 2 \\ Vr3 / \ /% • · · i -ΐ — 1- ° - *! V 'A V * 2 intermediate or formula A compound according to O-R 1, wherein R 1, R 2 and R 3 have the meanings given in claim 28, is reacted with 1-2 moles of chlorosulfonic acid and the reaction products obtained are optionally converted into the corresponding salts. Process for the preparation of compounds according to Claim 36, characterized in that 1 mol of methanetricarboxylic acid C 1 -C 4 trialkyl ester is reacted with 3 mol of the formula R "^ - OH, R" 2 - OH or R "3 - OH a fatty alcohol in which the substituents R "x, R" 2 and R "3 have the meanings given in claim 36, or 1 mol of the formula 173 79579 A diisocyanate of the formula C = N-A "1-N = C = O, in which the substituent A" ^ has the meanings given in claim 36, is reacted with 2 moles of the formula NC-CH -CO-Ν ' Process for the preparation of compounds according to Claim 37, characterized in that 1 mole of a polycarboxylic acid of the formula oo II II HO - C - A "J - C - OH is reacted with 2 - (h" 1) moles of the formula R "- OH or R "'2 - OH fatty alcohol and / or with 2 - (h"' - 1) moles of formula 174 79579 Rt »IS * (H) ,,,-H or (R 1 n" '- l Τ} > I> (H) „, -H (R 2 n" '- 1 primary or secondary fatty amine or 1 mole of the formula HO-A "' 2" oh is reacted with 2 moles of the formula R "'-, -COOH or R "'2-COOH fatty acid, in which the symbols A"' ^, A "^, R" '· ^, R "^, r" "2 3a n" have the meanings given in claim 37 and h "' denotes the number of carboxyl groups of the polycarboxylic acid used as the starting component li 175 79579