DE2104097C3 - Process for the production of preparations of reaction products from epoxides, fatty amines and basic polyamides and their use - Google Patents

Description

The invention is a method for Making stable preparations in water

soluble or dispersible reaction products from epoxides, fatty amines and basic polyamides, which is characterized by the fact that one

f) a) a reaction product of at least

a ') an epoxy, which per molecule at least

contains two epoxy groups and at least a ") a fatty amine of the formula

HjC- (CH ₂ ), - NH ₂

where x is an integer ranging from 11 to 23

means,

where the equivalent ratio of epoxy groups to amino groups is 1: 0.1 to I: 0.85 v>, with

b) a basic polyamide, which by condensation of

b ') aliphatic, ethylenically unsaturated di- bis

trimeric fatty acids and ^wl b ") polyalkylenepolyamines of the formula

IbN- (CH ₂ -CH ₂ -NH) _n -CH ₂ -CH ₂ -NH ₂

where π is 1, 2 or 3, has been obtained, possibly with the use of

c) 0.20 to 0.25 mol of a mono- or bifunctional compound which is different from a) and b),

per amino group equivalent of component b) reacts, components a) and b) and optionally c)

in the presence of an organic solvent at temperatures up to 95 "C, the Equivalent ratio of epoxy groups of component a) to amino groups of component b) 1: 1 up to 1: 6, preferably 1: 1 to 1: 5, and one by adding acid at the latest after the end of the reaction ensures that a sample of the reaction mixture has a pH of 2 to 8 has

An equivalent is to be understood as the amount of basic polyamide in grams that corresponds to one mole

Monoamine is equivalent

The epoxides a ') from which component a) is obtained are preferably derived from polyhydric phenols or polyphenols, such as resorcinol, Phenol-formaldehyde condensation products of the resol or novolak type. In particular Bisphenols such as bis (4-hydroxyphenyl) methane and especially 2,2-bis (4'-hydroxyphenyl) propane are used as Starting compounds for the preparation of the epoxyde preferred

Epoxides of 2 ^ -Bis- (4'-hydroxyphenyl) propane, which have an epoxy content, are particularly mentioned here from 1.8 to 5.8 epoxy group equivalents / kg, but preferably at least 5 epoxy group equivalents / kg own and which of the formula

CH,

0-CH ₁ -CHOH-CH,

CH,

correspond, where: ζ means an average number in the range from 0 to 0.65. Epo ^v yde of this type are obtained by reacting epichlorohydrin with 2,2-bis- (4'-hydroxyphenyl) propane.

Particularly suitable components a ^J ) have proven to be monofatty amines with 12 to 24 carbon atoms. As a rule, these are amines of the formula

HjC- (CH ₂ ^ -NH ₂

wherein χ is an integer from 11 to 23, preferably 17 to 21, The amines are thus z. B. to lauryl, palmityl, stearyl, arachidyl or behenylamine. Mixtures of such amines, such as are available as technical products, can also be used.

The reaction of component a ') with component a ") is expediently carried out at 80 to 120 ^° C., preferably 100 ^° C.

According to the invention, the ratio of epoxides a 'to amines a ″) in component a) is chosen so that an excess of epoxy is used so that there is more than one epoxy group for each amino group. The reaction products a) contain epoxy end groups. The amount of the components is in accordance with the invention a ') and a ") to be defined in such a way that an equivalent ratio of 1 epoxy group to 0.1 to 0.15 amino groups is present, d. H. the amount of epoxy, which corresponds to an epoxy group equivalent, becomes with the amount Amine, which corresponds to an amino group equivalent of 0.1 to 0.85, implemented. Preferably that questions Equivalent ratio of epoxy groups to amino groups 1: 0, 1 to I: 0.5 or in particular 1: 0.25 to 1: 0.5.

The polymeric unsaturated polymers used as component b ') for the production of the basic polyamides b) Fatty acids are aliphatic, ethylenically unsaturated dibis trimeric fatty acids. Preferably the Reaction products b) here from the polyalkylene pol- Iyamines b ") and aliphatic unsaturated di- bis trimeric fatty acids b '), which are derived from monocarboxylic acids with 16 to 22 carbon atoms, manufactured. These monocarboxylic acids are fatty acids with at least one, preferably 2 to 5, ethylenic unsaturated bonds. Representative of the ChC3 class of Acids are e.g. B. oleic acid, hiragonic acid, elaostearic acid, licanic acid, arachidonic acid, clupanodonic acid and especially the linoleic and linolenic acids. These fatty acids can be obtained from natural oils in which they are found occur mainly as glycerides.

The di- to trimeric fatty acids b ') used according to the invention are processed in a known manner Obtained dimerization of monocarboxylic acids of the specified type. The so-called dimeric fatty acids always have a trimeric and a small monomeric acid content.

The dibis: rimerized linoleic or linolenic acid are particularly suitable as component b '). The technical products of these acids usually contain 75 to 9! 5 percent by weight of dimeric acid, 4 to 25

Weight percent trimeric acid and a trace of up to 3%

monomeric acid. The molar ratio of dimer to trimeric acid is accordingly 5: 1 to 36: 1.

Diethyl triamine are suitable as component b "),

Triäthylenetetramine or Tetraäthylenpentamin, so Amines of the formula

H ₂ N- (CH ₂ CH ₂ -NH) _n -CH ₂ CH ₂ --- NH ₂ | 3 |

where η is 1, 2 or 3.

In the case of amine mixtures, one can also assume a non-integer average value, / .. B.

between 1 and 2.

A basic polyamide made from di- to trimerized linoleic or linoleum is a component of particular interest Linolenic acid and a polyamine of formula (3) used

As organic solvents, in the presence of which the reaction of component a) with b) takes place, primarily .Linie water-soluble organic solvents come into consideration, and expediently those that can be mixed with water as required. Examples include dioxane, isopropanol and ethanol and methanol, ethylene glycol n-butyl ether (= n-butyl glycol), Diethylene glycol monobutyl ether.

In addition, however, it is also possible to carry out the reaction in the presence of water-insoluble organic solvents perform, e.g. B. in gasoline hydrocarbons such as gasoline or petroleum ether, benzene, halogenated benzenes or benzenes substituted by lower alkyl groups, such as toluene, xylene, chlorobenzene; acyclic compounds such as tetralin or cyclohexane: halogenated hydrocarbons such as methylene chloride, methylene bromide, chlorofor-n, carbon tetrachloride, Ethylene chloride, ethylene bromide, s-tetrachloroethane and especially trichlorethylene or perchlorethylene.

The reaction products obtained in this way are soluble or at least dispersible in water.

The reaction products of a) epoxy-fatty amine and b) polyamide can optionally also under Use of a third component c), namely a further mono- or bifunctional compound, which is different from a) and b). we get the. These mono- or bifunctional compounds have mobile groups or atoms as functional groups Halogen atoms, vinyl, acid, ester, acid anhydride, isocyanate or epoxy groups.

These components c) are preferably aralkyl or alkyl halides, nitriles or amides of acids the acrylic acid series, aliphatic or aromatic carboxylic acids, their esters or anhydrides as well aliphatic or aromatic isocyanates, epoxies or epihalohydrins.

Advantageous monofunctional components c) are alkyl halides such as ethyl bromide or butyl chloride, aralkyl halides such as benzyl chloride; Nitrile or amide "; acrylic or methacrylic acid such as acrylonitrile or acrylic acid amide; Alkanecarboxylic acids with up to 18 carbon atoms such as coconut fatty acid or stearic acid, or their esters with alkanols, which have a maximum of 5 carbon atoms? included, e.g. B. methanol, ethanol or n-butanol, or their anhydrides such as acetic anhydride; aromatic isocyanates such as phenyl isocyanate; or aliphatic or aromatic epoxides such as propylene oxide, butylene oxide, dodecene oxide or styrene oxide. The preferred bifunctional component c) is epichlorohydrin.

Particularly suitable components c) are alkylene oxides with a maximum of 12 carbon atoms, alkanecarboxylic acids with a maximum of 18 carbon atoms, monocyclic aralkyl halides or acrylonitrile.

The order in which the implementation of the polyamides with the monofunctional compounds and epoxy-fatty amine reaction products are of minor importance. You can React polyamides first with a monofunctional compound and then with the epoxy-fatty amine reaction product or vice versa. In some In cases where there are no major differences in responsiveness, so can implementation can be done at the same time.

The conversion to the reaction product from components a) and b) is now in the manner carried out that soluble or dispersible polyadducts are formed in water by the pH value, at the latest after the end of the reaction, to 2 to 8, preferably to 2 to 7, but in particular to 5 to 6, adjusts To adjust this pH value

ίο one uses z. B. inorganic or organic acids, advantageously volatile organic acids such as formic acid or acetic acid. It is advisable to add a certain amount of acid to the reaction mixture immediately or shortly after the beginning of the combination of the basic polyamide with the epoxide and to add further acid continuously or in portions during the further reaction. Further, eg, the thus obtained set to 80 ° C, of 25 to 80 ⁰ C, especially 45 to 7O ⁰ C, worked with acid to the mentioned pH-value of preferably at temperatures up to, and advantageously with an organic solvent or preferably with Solutions or dispersions adjusted to a content of 10 to 30% reaction product - mostly weakly opalescent to cloudy solutions - are characterized by high resistance.

Products with advantageous properties are also obtained if, after the addition of the acid and des Water the preparation is still stored at room temperature or at an elevated temperature, e.g. B. during 4 Hours at 70 ° C or for longer periods at a lower temperature.

The preparations of the type indicated at the beginning are suitable for finishing textiles, in particular for making wool feltproof, whereby either the wool is added with an aqueous liquor to which the preparation and, if desired, further additives such as wetting agents, dispersants and / or acids have been added, impregnated, then dried and subjected to an elevated temperature treatment. Particularly advantageous but the method for dyeing and Filzfestmachen proved to be of wool, in which the one hand dyed sequentially in any order by the exhaust the full and with the other hand, at temperatures of 35 to 100 ⁰ C and a pH of 7-3 The preparations made from epoxies and basic polyamides can be used for dyeing and felting in a simple manner

-, o combined and carried out in the same apparatus without removing the wool from the apparatus between the two operations. The Filzfestmacheti can also expire after a foulard be performed.

One can dye here in the usual, known manner with any suitable for Woile Dyes, e.g. B. acidic wool dyes, 1: 1 or 1: 2 metal complex dyes, reactive dyes. You can also use the additives commonly used in the dyeing of wool, such as sulfuric acid, Acetic acid, sodium sulfate, ammonium sulfate and leveling agents, polyglycol compounds in particular as leveling agents higher aliphatic amines come into consideration, which may also be quaternized

bi and / or din hydroxyl groups can be esterified with polybasic acids.

In addition to the preparation of the polyaddition products *, the liquor used for making felts

nor the base required for setting the alkaline medium, e.g. B. ammonia, di- or trisodium phosphate. The amount of polyaddition product (not including solvent and water), based on the weight of the wool, is expediently 0.5 to 5%. As mentioned, one works at temperatures of 35 to 100 ^° C. and usually requires between 20 and 80 minutes for an extensive to practically complete fixation of the polyamide product.

The order of the two processes is arbitrary, im in general it is more advantageous to dye it first and then to make it felt-proof.

The combined process of dyeing and felting wool is particularly suitable in the actual apparatus dyeing, where the material to be dyed stands still and the liquor is moved.

Advantageous felt effects are also achieved through the addition of oxidizing agents such as hydrogen peroxide achieved to the treatment baths. If necessary, the permanence of the permanent felt finishes can be improved if the wool is treated with a preparation that contains a reaction product, pretreated with a dilute aqueous solution of dichloroisocyanuric acid or its alkali metal salt will.

When using treatment baths with a high content of organic, especially water-insoluble Solvents, or even anhydrous baths containing only organic solvents, works one expedient in closed apparatus, z. B. those used in dry chemical cleaning be used.

The preparations can also be used as sizing agents for paper.

When using the preparations in combination with an aminoplast precondensate on textiles, especially cotton, a wash-resistant “soil release” effect is achieved. It is also with the Preparations possible to finish textiles so-called non-iron.

Furthermore, with the help of preparations which contain the present reaction products , reu uaiinic,

i c rvcaniiviai Ubiuiie aui

Textiles, especially wool, are well fixed, which is reflected in improved perspiration fastness.

Furthermore, equipments with the present reaction products also improve the mechanical ones Properties, e.g. B. tear resistance, elongation at break, abrasion resistance, tendency to pilling, of the treated Textile material.

Furthermore, it is sometimes also possible to use the reaction products in an organic solvent to apply, d. H. either as a solution or as a dispersion in an organic solvent. as Solvents are the same as those described for the preparation

If the reaction products are insoluble in water-insoluble organic solvents, they can be used disperse in the presence of an organosoluble surfactant in the water-insoluble solvent. For this purpose, the reaction product, the solvent and the surface-active agent can be used Combine stirring or, preferably, the reaction product with the surface-active agent Pour into a paste and then add to the solvent while stirring. A stable dispersion is obtained.

These dispersions are applied in the same way as described for the aqueous preparations.

Percentages in the following manufacturing documents and examples are percentages by weight.

Manufacturing regulations

A) 1% g (I epoxy group equivalent) of one of 2,2-bis (4'-hydroxyphenyl) propane and epichlorohydrin F.poxydes formed are combined with 31g (0.1 Amino group equivalent) of a mixture of I-Ami-

No-cikosan and 1-amino-dokosan were stirred for one hour at 100 ° C. A clear, viscous liquid was obtained Product with an epoxy group equivalent weight of 255.

B) 196 g (1 epoxy group equivalent) of the epoxy described under A] are added together with 62 g (0.2 amino group equivalent) of the fatty amine described under A) stirred for one hour at 100 ° C. Man receives a clear, viscous product with an epoxy group equivalent weight of 313.

C) 196 g (1 epoxy group equivalent) of the epoxy described under A) are added together with 77.5 g (0.25 amino group equivalent) of the fatty amine described under A) was stirred at 100 ° C. for one hour. Man receives a highly viscous product with an epoxy group equivalent weight of 379.

D) 196 g (1 epoxy group equivalent) of the epoxy described under A) are added together with 93 g (0.3 amino group equivalent) of the fatty amine described under A) was stirred at 100 ° C. for one hour. Man receives a highly viscous product with an epoxy group equivalent weight of 436.

E) 196 g (1 Epoxydgruppenäquivalent) described under A) the epoxide is stirred with 108.5 g (0.35 amino group equivalent) described under A) Fatty Amines one hour at 100 ⁰ C. A highly viscous product with an epoxy group equivalent weight of 498 is obtained.

F) 196 g (1 epoxy group equivalent) of the epoxy described under A) are added together with 124 g

ι (0.4 amino group equivalent) of that described under A) Fettamines stirred at 100 ° C for one hour. A highly viscous product with an epoxy group equivalent is obtained from 507.

G) 196 g (1 epoxy group equivalent) of the epoxy described under A) are added together with 155 g (0.5 amino group equivalent) of the fatty amine described under A) was stirred at 100 ° C. for one hour. Man receives a highly viscous product with an epoxy group equivalent weight of 685.

ι H) 91.2 g Butandiolglycidyläther (0.8 Epoxydgruppenäquivalent), together with 62 g (0.2 Amir group equivalent.) of a mixture of 1-amino-1-eicosane and Aminodokosan stirred for one hour at 100 ⁰ C to give a clear , viscous product with an epoxy group equivalent weight of 257.

I) 99 g of hexahydrophthalic acid diglycidyl ester (0.6 Epoxydgruppenäquivalent), together with 46.5 g (0.15 amino group equivalent) of a mixture of 1 - amino-eicosane stirred and 1-amino-docosane one hour at 100 ⁰ C. A clear, viscous product with an epoxy equivalent weight of 395 is obtained.

J) 98 g of of 2,2-bis (4'-hydroxyphenyl) propane and epichlorohydrin formed the epoxide (0.5 Epoxydgruppenäquivalent) are stirred together with 33.7 g Stearylaiüin (0.125 Arninogrdppenäquivaieni) ί hour at 100 ⁰ C Man receives a clear, viscous product with an epoxy group equivalent of 400.

K) 96 g of an epoxy of the formula

OCIl, CH CII ₂

CH, CH CII, OCII,
O

· CII, O CII ₂ CII (H ₂

j O

CW ₁ O CH ₂ CII CH ₂

(4)

(0.6 Epoxydgruppe.iäquivalent) are stirred together with 46.5 g (0.15 amino group equivalent) of a mixture of 1-amino-eikosan and 1-amino-dokosan at 100 ⁰ C for 1 hour. A clear, viscous product with an epoxy group equivalent weight of 278 is obtained.

L) 99.6 g of triglyeidyl isocyanurate (0.6 epoxy group equivalent) are together with 46.5 g (0.15 amino group equivalent) of a mixture of l-amino-eikosan and l-amino-dokosan was stirred at 100 ° C. for 1 hour. A clear product with an epoxide group equivalent weight of 208 is obtained.

M) a 156,8g of 2,2-bis (4'-hydroxyphenyl) propane and epichlorohydrin formed the epoxide (0.8 Epoxydgruppenäquivalent), together with 37.1 g of laurylamine (0.2 amino group equivalent) for 1 hour at 100 ⁰ C. touched. A clear product with an epoxide group equivalent weight of 403 is obtained.

N) 98 g of of 2,2-bis (4'-hydroxyphenyl) propane and epichlorohydrin, the epoxide formed (0.5 Epoxydgruppenäquivalent) are heated to 85 to 90 ⁰ C internal temperature. 124 g (0.4 amino group equivalent) of a mixture of 1-amino-eikosan and 1-amino-dokosan are then added over the course of 15 minutes. The mixture is then stirred at an internal temperature of 00 ° C. for a further 6 hours. A highly viscous product with an epoxy group equivalent weight of 2220 is obtained.

example 1

49.4 g of a polyamide made from polymerized linoleic acid and diethylenetriamine (0.2 amino group equivalent) are dissolved in 50 g of butyl glycol and heated to 53.degree Internal temperature warmed. A solution of 18.95 g of epoxy C) (0.05 epoxy group equivalent) is then left. in 20 g of n-butyl glycol within 30 Drop in minutes. One hour thereafter, a solution of 8 g of glacial acetic acid and 195 g of deionized water is added and let stir until cold. A thin liquid solution is obtained whose dry content is 20% and their pH is 7.0

Example 2

49.4 g (0.2 amino group equivalent) of the polymer from Example 1 are dissolved in 50 g of n-butyl glycol and heated to an internal temperature of 58 ° C. Then left a solution of 34.25 g of epoxy G) (0.05 epoxy group equivalent) and 35 g of n-butyl glycol within add dropwise from 40 minutes. One hour thereafter, a solution of 7 g of glacial acetic acid and 226 g is added deionized water and stir until it cools. A thin liquid solution is obtained with a dry content of 20% and a pH of 7.0

Example 3

61.8 g of a polyamide made from polymerized linoleic acid and diethylenetriamine (0.25 amino group equivalent) are dissolved in 61.8 g of isopropanol and heated to 53.degree Internal temperature warmed. Then leave one

in solution of 12.85 g epoxy H (0.05 epoxy group equivalent) add dropwise in 12.85 g of isopropanol within 30 minutes. A solution is dispensed one hour later Add 15 g of glacial acetic acid in 200 g of deionized water and stir until it cools down. You get one

r, thin liquid solution with a dry content of 20% and a pH value of 6.0.

Example 4

49.4 g (0.2 amino group equivalent) of the polyamide ίο according to Example 3 are dissolved in 49.4 g of ethanol and heated to 53 ° C internal temperature. Then a solution of 19.8 g of epoxy I (0.05 epoxy group equivalent) add dropwise in 19.8 g of ethanol within 30 minutes. One hour later, 24 g of glacial acetic acid are added Add 180 g of deionized water and stir until it cools. A clear, thin liquid is obtained Solution with a dry content of 20% and a pH of 5.9.

_4n example 5

49.4 g (0.2 amino group equivalent) of the polyamide: » according to Example 3 are dissolved in 49.4 g of butyl glycol

UIlU aul 54 v ^ iiinciitciiipciuiui ctwaiini. ouuaiin laui

a solution of 20 g of Epoxy J (0.05 epoxy group equivalent) in 20 g of butyl glycol within 30 Drop in minutes. One hour thereafter, 12 g of glacial acetic acid in 190 g of deionized water are added and the mixture is stirred until to cool down further. A clear, thin liquid solution is obtained, its dry content 20% and its pH value

-, o is 5.4.

Example 6

49.4 g (0.2 amino group equivalent) of the polyamide according to Example 3 are dissolved and dissolved in 49.4 g of dioxane 55 ° C internal temperature is then left a solution of 133 g of Epoxy K (0.05 epoxy group equivalent) add dropwise in 133 g of dioxane within 30 minutes.

One hour later, 12 g of glacial acetic acid are added to 172 g

bo deionized water and stir until cool Further. A thin liquid solution is obtained with a dry content of 20% and a pH of 5.4

Example 7

79 g (0.32 amino group equivalent) of the polyamide according to Example 3 are in 79 g of butylglyco! solved and heated to an internal temperature of 55 "C. Then a solution of 16.6 g of epoxy L (0.08 epoxy groups

Il

equivalent) and 16.6 g of butyl glycol are added dropwise over the course of 30 minutes. 40 minutes thereafter, 19.2 g are added Glacial acetic acid and 260 g of deionized water are added and the mixture is stirred until it cools. A thin fluid is obtained Solution with a dry content of 20% and a pH of 5.6.

Example 8

a) In a reaction vessel, which is equipped with a stirrer, Thermometer, inlet tube for nitrogen and a distillation head will be 187 g polymerized fatty acid and 68.5 g diethylenetriamine added. The polymerized fatty acid obtained by Polymerization of oleic acid, has the following properties: 95% dimerized oleic acid; Equivalent weight: 289.

The reaction mixture is under a nitrogen atmosphere and with stirring within 1½ hours 200 ° C heated, at 160 ° C internal temperature begins to split off water. After another 2 Hours at 200 ° C a total of 13 parts of water are collected. Then for 3 hours in Concentrated vacuum (14 mm Hg) at 200-210 ° C. 210 g of a viscous, yellowish, clear product are obtained with an amine equivalent weight of 372.

b) 74.4 g of the condensation product described under a) (0.2 amino groups equivalent) are in 74.4 g of butyl glycol and heated to 55 ° C internal temperature. Then leave within 30 minutes a solution of 20.2 g of Epoxy M (0.05 epoxy group equivalent) and 20.2 g of butyl glycol are added dropwise. 30th Minutes thereafter, 12 g of glacial acetic acid and 265 g of deionized water are added and the mixture is stirred until it cools Further. A clear, thin liquid solution is obtained with a dry content of 20% and a pH of 6.0 amounts to.

Example 9

44.6 g of the condensation product described under 8a) (0.12 amino group equivalent) are in Dissolved 44.6 g of butyl glycol and heated to an internal temperature of 60 ° C. Then leave within 30 minutes from 2 separate dropping funnels 7.2 g of glacial acetic acid and a solution of 44.4 g of epoxy N (0.02 epoxy content equivalent) and 44.4 g of butyl glycol are added dropwise. The mixture is then stirred at an internal temperature of 60 ° C. for 6 1/2 hours and then add another 10 g of glacial acetic acid. After a further 30 minutes, the mixture is diluted with 180 g of butyl glycol. Man receives a clear, thin liquid solution with a dry content of 20%.

A sample diluted 1:20 with water has a pH of 5.8.

Example 10

66.6 g of epoxy N (0.03 epoxy group equivalent) are dissolved in 66.6 g of butyl glycol and heated to 60.degree Internal temperature heated. Then, within 30 minutes, 5.6 g are left from 2 separate dropping funnels Glacial acetic acid and a solution of 33.4 g of the condensation product described under 8a) (0.09 amino group equivalent) and 33.4 g of butyl glycol are added dropwise.

Then stirred for 6 '/ 2 hours at 6O ⁰ C inner temperature, and then another 10 g of glacial acetic acid. After a further 30 minutes, the mixture is diluted with 283 g of butyl glycol. A clear, thin liquid solution is obtained, the dry content of which is 20%. A sample diluted 1:20 with water has a pK value of 5.8.

Example 11

68.5 g of epoxy G (0.1 epoxy group equivalent) are dissolved in 37 g of isopropanol and heated to 88.degree > Internal temperature warmed up. Then you leave within from 30 minutes a solution of 24.7 g (0.1 amino group equivalent) of the polyamide according to Example 3 and Add 15 g of isopropanol dropwise.

The mixture is then stirred at about 88 ^° C. for a further 5 hours

κι internal temperature (reflux) and then gives 1.85 g Epichlorohydrin (0.02 mol). After a further 10 minutes, a solution of 16 g of glacial acetic acid and 312 g is added deionized water and stir until it cools. A thin liquid product is obtained, its

ι ; Dry content 20% and its pH value is 4.6.

Example 12

79 g (0.32 amino group equivalent) of the polyamide according to Example 3 are heated to an internal temperature of 180.degree. Within 2 hours, allowed to 16.7 g Dodecenoxyd (0.08 mol) added dropwise, keeping a further 2 hours at 180 ° C, then cooled to 5O ⁰ C internal temperature, and the product is dissolved in 32 g butyl glycol. Then is allowed (0.08 Epoxydgruppenäquivalent) and 20.4 g of butyl glycol were added dropwise within 30 minutes at 50 ⁰ C inner temperature, a solution of 20.4 g of epoxy A. The internal temperature is then increased to 60 ° C. and stirring is continued for VU hours at this temperature. Then 20 g of glacial acetic acid and 391 g of deionized water are added and the mixture is stirred until it cools down. A thin liquid solution is obtained whose dry content is 20% and whose pH value is 4.9.

j. Example 13

79 g (0.32 amino group equivalent) of the polyamide according to Example 3 are added together with 10.1 g Benzyl chloride (0.08 mol) was stirred at an internal temperature of 100 ° C. for 2 hours. Then you cool the product to an internal temperature of 60 ° C. and 32 g of butyl glycol are added. A solution is then left out at this temperature 20.4 g of epoxy A (0.08 epoxy group equivalent) and 2ö, 4 Bui.yigiykoi zuiropien within 30 minutes. 25th Minutes thereafter, 20 g of glacial acetic acid and 364 g of deionized water are added and the mixture is stirred until it cools Further. A thin liquid solution is obtained whose dry content is 20% and whose pH value is 4.6.

Example 14

79 g (0.32 amino group equivalent) of the polyamide according to Example 3 are dissolved in 32 g of butyl glycol and heated to 50 ° C internal temperature. 4.3 g of acrylonitrile (0.08 mol) are then added and the mixture is stirred for 2 hours 50 ° C internal temperature. A solution of 20.4 g of epoxy A (0.08 Epoxy group equivalent) and 20.4 g of butyl glycol are added dropwise. 11/2 hours thereafter, add 20 g of glacial acetic acid and 339 g of deionized water are added and the mixture is stirred until it cools. A thin liquid solution is obtained, their dry content is 20% and their pH value is 5.0

Application examples
Application example 1

100 kg of woolen yarn are added to 1000 liters of water in a cross-thread dyeing machine as usual After the dyer, is dyed reactive dyes

rinsed thoroughly.

A fresh bath of 40 ^° C., consisting of 1000 liters of water and 1.4 kg of ammonia (25%), is prepared. This is followed by the addition of 8 kg of the product according to Example 1. A stable emulsion is formed which is absorbed evenly onto the wool in about 30 minutes. Trisodium phosphate is then added, the mixture is allowed to run for 10 minutes and a further 2 kg of a 12.5% strength solution of a condensation product of 1 mole of octadecyl alcohol and 25 moles of ethylene oxide are added. After a further 20 minutes, it is rinsed thoroughly with cold water, drained and dried. The yarn treated in this way is felt-resistant in accordance with IWS specifications 7B, 7C and 71.

Instead of a product according to Example 1, a product from Examples 2 to 16 can be used.

Application example 2

On a horizontal two-roll foulard a woven is made of pure wool with the following preparation impregnated and squeezed to a liquor pick-up of 100%:

120 g / l
2 g / l

30 ml / 1
848 ml / l

Product according to example 1

of a condensation product of

I mole of p-tert-octylphenol and

8 moles of ethylene oxide

Hydrogen peroxide 33%

water

1000 g foulard liquor

After padding, the goods are dried on a stenter. Then, still pressed for 5 minutes at 120 ⁰ C with moderate pressing pressure (on a "Hoffmann press").

The goods treated in this way show the following shrinkage values when tested according to IWS specification 71:

Untreated goods
Treated goods

53% shrinkage
2.1% shrinkage

If the tissue is subjected to the known reductive treatment before the treatment just described subjected to monoethanolamine sulfite, the product is also stable in terms of surface area, i. H. she stays too smooth and wrinkle-free even after one wash.

Application example 3

3.0 The preparation according to Example 1 is made into a paste with 10.0 g of a surfactant of the composition given below and this mixture is diluted to 1000 ml with perchlorethylene. Brief stirring gives a stable dispersion. At 20 ^° C., 20 g of a knitted piece made of wool are treated with this liquor for 50 minutes. After removing excess -, liquor by centrifugation, it is dried and fixed at 100 ° C. for 10 minutes. The knitted piece treated in this way is felt-proof.

The following products serve as surfactants:

I: condensation product of 1 mole of coconut fatty acid and 2 moles of diethanolamine, each containing about 2% Water and acetic acid.

Ii: Acid phosphoric acid ester of a condensation product of 1 mol of 2-ethylhexanol and 5 mol of ethylene oxide, neutralized with sodium hydroxide, as an 80% aqueous solution.
Ill: Aqueous solution containing:

38.5% of an Öisäurepoiygiykoiesters,
- "38.5% of a condensation product of 1 mol

p-tert-octylphenol and 8 moles of ethylene oxide. 15.5% oleic acid.

Application example 4

100 kg of bleached sulphite pulp are ground in the Hollander in the usual way and then in a Mixing vessel drained. In the mixing vessel, 20 kg of calcium carbonate are added as filler. jo After the filler is well in the pulp suspension has distributed, the addition of 0.3 to 0.7% of the product according to Example 11, based on pulp and Solids content. The mixture of substances reaches the paper, machine.

To increase filler retention, a retention aid can be added shortly before the headbox will.

Papers made with this or a similar composition of matter are mainly used as writing and Printing papers are used and have excellent ink strengths, which is a consequence of the good Sizing is.

Aluminum sulphate, available in smaller or larger Amounts introduced into this system through the use of scrap paper interferes with the sizing in no way.

In this system, the calcium carbonate can also be replaced by commercially available kaolin. the The sizing effect is the same as when using calcium carbonate.

Claims (1)

Claims; 1. Process for the production of stable preparations of soluble or dispersible in water Reaction products of epoxides, fatty amines and basic polyamides, characterized in that one a) a reaction product of at least a ') an epoxy, which per molecule at least contains two epoxy groups and at least a ") a fatty amine of the formula H ₃ C- (CH ₂ ) ^ - NH ₂ where χ is an integer of 11 to 23 means the equivalent ratio of epoxy groups to amino groups I: 0.1 to 1: 0.85 amounts to b) a basic polyamide, soft through Condensation of b ') aliphatic, ethylenic unsaturated di- to trimeric fatty acids and b ") Polyalkylenepolyamines of the formula H ₂ N- (CH ₂ -CH ₂ -NH) _n -CH ₂ -CH ₂ NH ₂ where π is 1, 2 or 3, has been obtained, and possibly with the use of c) 0.20 to 0.25 mol of a mono- or bifunctional compound, which is different from a) and b), per amino group equivalent of Component b) reacts, components a) and b) and optionally c) in the presence of an organic solvent at temperatures of up to 95 ° C, the Equivalent ratio of epoxy groups of component a) to amino groups of the component b) is 1: 1 to I: 6 and you can do so by adding acid at the latest after the end of the reaction ensures that a sample of the reaction mixture has a pH of 2 to 8 after the addition of water owns. 2. The method according to claim 1, characterized in that the equivalent ratio of epoxy groups of component a ') to amino groups of component a ") is 1: 0.1 to 1: 0.5, the equivalent ratio of epoxy groups of component a) to amino groups the component b) is 1: 1 to 1: 5 and the reaction of the components a) and b) at temperatures up to 80 ⁰ C. 3. The method according to claim 2, characterized in that there is an epoxy as component a ') used, which is derived from a bisphenol. 4. The method according to claim 3, characterized in that as component a ') one Polyglycidyl ether of ^ -Bis-H'-hydroxyphenyl) propane is used. 5. The method according to claim 4, characterized in that component a ') has an epoxy content of at least 5 epoxy group equivalents per kg. 6. The method according to claim 4, characterized in that one as component a ') Reaction product of epichlorohydrin with 2 ^ -Bis- (4'-hydroxyphenyl) -propane used 7. The method according to claim 1, characterized in that in the formula of component a ") χ is an integer from 17 to 21 8. The method according to claim 1, characterized in that there is used as component b ') fatty acids uses those derived from aliphatic unsaturated monocarboxylic acids containing 16 to 22 carbon atoms derive. 9. The method according to claim 8, characterized in that as component b ') di- bis trimerized linoleic or linolenic acid is used 10. The method according to any one of claims 1 and 9, characterized in that the component b) a basic polyamide from di- to trimerized linoleic or linolenic acid and a polyamine of formula H ₂ N- (CH ₂ -CH ₂ -NH) _n -CH ₂ -CH ₂ -NH ₂ where π is 1, 2 or 3 is used i I. The method according to any one of claims 1 to 10, characterized in that the organic solvent used is a solvent which is freely miscible with water IZ method according to one of claims 2 to 11, characterized in that the reaction is carried out at 25 to 80 ° C 13. Use of the according to any one of claims 1 up to 12 available preparations for finishing textiles.