DE2659463C2 - - Google Patents

Description

The subject of the present invention is the Use of (A) polyamides consisting of a reaction product out:

• a) dimerized fatty acid containing 70% by weight to 100 wt .-% of dimeric fatty acid in the mixture with monocarboxylic acids containing 12 to 22 carbon atoms wherein the total mixture is up to 50% by weight of monocarboxylic acids,
• b) an aliphatic unbranched co-dicarboxylic acid with 6 to 13 carbon atoms,

wherein the ratio of the carboxylic acids according to a) to Carboxylic acid according to b) 0.05: 1 to 5: 1, based on Carboxyl groups, is

• c) one of the acids mentioned under a) and b) in the Substantially equivalent amount of an aliphatic unbranched diprimary diamine having 6 to 12 carbon atoms
• d) caprolactam and / or ε-aminocaproic acid and
• e) caprolactone and / or ε-hydroxycaproic acid in one Amount of 0.05 to 1 mole per mole d)

and (B) polyamides consisting of a reaction product the components a) to e), wherein the starting component a) Monocarboxylic acids containing less than 12 C atoms have, contains for bonding textiles according to patent 26 59 464, which thereby characterized in that the polyamides (A) and (B) have a Melt viscosity (measured at 220 ° C) of 25 to 600 Pa · s and in the preparation of these polyamides per mole of the acids mentioned under a) and b) <1.5 to 2.5 mol Caprolactam and / or ε-aminocaproic acid d) used become.  

Preference is given to using polyesteramides in which as co-dicarboxylic acid according to b) sebacic acid and as diamine component according to c) hexamethylenediamine is used and in which the ratio of Carboxylic acids according to a) to the carboxylic acids according to b) 0.1: 1 to 3: 1 and in which per mole of carboxyl groups mentioned under a) and b) Acids <1.5 to 2 moles of caprolactam can be used and at those per mole of caprolactam and / or ε-aminocaproic acid 0.1 to 0.5 Caprolactone and / or ε-hydroxycaproic be concomitantly used.

For the preparation of the polyester amides used in the invention is as dimerized fatty acid according to a) preferably one with contents of more than 90% by weight of dimer fatty acid.

The hot melt adhesive used in the invention, based on the sufficient available dimer fatty acid, caprolactam or ε-aminocaproic acid, caprolactone or ε-hydroxycaproic acid, diamines and codicarboxylic acids show good resistance against halogenated hydrocarbons and at the same time against Washing liquors at 60 ° C and sometimes also at 95 ° C. This resistance expresses itself by

• 1. the very good initial tear strengths, d. h., values before Load through the washing or cleaning process, and through
• 2. the very high wet tensile strengths, d. h., values after cleaning in still wet condition, and through  
• 3. the excellent tensile strength values after drying, which almost after many washing or cleaning cycles be reached again.

When using distilled dimer fatty acid are melt adhesive obtained with improved color number. On the other hand, that is Use of commercial technical polymerized fatty acid for the production of hot melt adhesives for special purposes possible. When using technical dimer fatty acid is only pointed out that the content of trimeric fatty acid a maximum Limit should not exceed. This limit depends from the respective content of dimeric and monomeric fatty acid of polymerized fatty acid and can by an orienting Attempt, as he to the manual routine routine of the average expert be heard.

The term dimerized fatty acid refers to more general Form on polymerized acids obtained from "fatty acids". The term "fatty acid" includes unsaturated natural and synthetic monobasic aliphatic acids having 12 to 22 carbon atoms, preferably 18 carbon atoms. Leave these fatty acids polymerize by known processes (cf DE-OS 14 43 938, US Pat. DE-OS 14 43 968; DE-PS 21 18 702 and DE-PS 12 80 852).

Typical commercially available polymeric fatty acids have about the following Composition:

monomeric acids (Mo) 5 to 15 weight percent, dimer acids (Di) 60 to 80 percent by weight, trimeric acids (tri) 10 to 35 weight percent.

The content of dimer acid can be determined by well-known distillation methods be increased up to 100 percent by weight.

For the polyesteramides used in the invention are preferred dimerized fatty acids with a content greater than 90% by weight of dimeric fatty acid and small amounts of trimeric fatty acid (Wt .-% 2 to 6) and monomeric fatty acid (wt .-% 0 to 1.5), as commercially available. It is also possible to use the dimerized fatty acid in its hydrogenated form.

The polyesteramides used in the invention are in a specific Melt viscosity range, some molecular weight operation reflects.

The adjustment of the melt viscosity can in a known manner Termination of the reaction at the desired degree of polymerization or by working with non-equivalent amounts of carboxylic acids or Amines done. Because of certain disadvantages of these methods, the Use of monofunctional or monofunctional acting Compounds (amines or carboxylic acids) are preferred as chain terminators. Monocarboxylic acids have proven to be particularly favorable.  

The possible proportion of monocarboxylic acids in the invention used polymerized fatty acid can by adding monocarboxylic acids up to 50 equivalent%, based on total carboxyl groups of the mixture of polymeric fatty acid and monocarboxylic acid become. Is the proportion of chain breaker required (Viscosity regulator), here the monocarboxylic acid, high, are preferred higher molecular weight monocarboxylic acids, such as oleic, stearic, linoleic, Linolenic acid or mixtures thereof, such as tall oil fatty or soybean oil fatty acid or other hydrophobic monocarboxylic acids used.

As examples of the present invention used aliphatic unbranched co-dicarboxylic acids having 6 to 13 carbon atoms Adipic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid and brassylic acid. These dicarboxylic acids can be alone or used in a mixture.

Instead of the carboxylic acids may optionally also their esters be used with low alcohols. Here it is recommended especially when the proportion of ester is high, the caprolactam polymerization to start by adding water.

For the aliphatic unbranched used in the invention diprimary diamines of 6 to 12 carbon atoms are, for example 1,6-diamino-hexane, 1,9-diaminononane, 1,12-diaminododecane.  

Related to moles of carboxyl groups of the acids used Caprolactammenge and the lactam / lactone ratio depends according to the height of the desired melting point. So is the lactam amount when using the hot melt adhesive as a textile adhesive per mole Carboxyl groups of the polymerized fatty acid and the co-dicarboxylic acid or co-dicarboxylic acids <1.5 to 2.5 mol and the amount of lactone 0.05 to 1 mole per mole of lactam. For the materials to be bonded are textiles, possibly also siliconized fabrics, which can be glued together.

The polyesteramides to be used according to the invention can be obtained by Melt condensation in substantially equivalent amounts of the above specified reactants at temperatures between 200 and 290 ° C, especially at 250 ° C, under inert gas.

In this case, in the first stage, the dimerized fatty acid (Component a) or their amide-forming derivatives with the caprolactam and / or the β-aminocaproic acid condensed. It is initially preferably a low Temperature used (i.e., about 150 ° C), so that the reaction easy to control. To end the reaction, the temperature then increased to the required height. The proportions the reactants of this first stage will vary depending on the desired Addition rate of aminocaproic acid or caprolactam.

In the second stage, this reaction product required added to other components and the reaction in the for the Amide production completed the usual way.

To facilitate the reaction, solvents or diluents be used.  

Example 1

In a descending cooler, stirrer and thermometer provided 55.77 g of dimerized tall oil fatty acid, 9.83 g of stearic acid, 92.99 g of sebacic acid (ratio of the carboxyl groups of the fatty acid mixture according to a) 1 and 2 to co-dicarboxylic acid according to b) = 0.25: 1.0), 66.86 g of 1,6-diaminohexane, 207.92 g of caprolactam (1.6 mol Caprolactam per mole of carboxyl groups according to a) and b)) and 26.22 g Caprolactone (molar ratio of caprolactam: caprolactone = 1.0: 0.125) weighed and under nitrogen within 2 hours at 250 ° C. heated and kept at this temperature for a further 7 hours. While For the last 4 hours, a vacuum of 266.6 Pa (2 mm Hg column) was applied.

The polyesteramide had the following values:

Softening point: | 120 ° C Melt viscosity at 220 ° C: 58.0 Pa · s Separation strength in N / 5 cm: 35 (60 ° C wash, wet torn) Separation strength in N / 5 cm: 45 (perchlorethylene cleaning, wet-torn) Initial value in N / 5 cm: 61

The polyesteramides listed in the table below were made in the same way:  

Table 1

Table 2

Claims (3)

Use of (A) polyamides consisting of a reaction product of:

• a) dimerized fatty acid containing from 70% to 100% by weight of dimer fatty acid in admixture with monocarboxylic acids having from 12 to 22 carbon atoms, the total mixture being up to 50% by weight of monocarboxylic acids,
• b) an aliphatic unbranched co-dicarboxylic acid having 6 to 13 carbon atoms,

wherein the ratio of the carboxylic acids according to a) to the carboxylic acid according to b) from 0.05: 1 to 5: 1, based on carboxyl groups

• c) one of the acids mentioned under a) and b) substantially equivalent amount of an aliphatic unbranched diprimary diamine having 6 to 12 carbon atoms
• d) caprolactam and / or ε-aminocaproic acid and
• e) caprolactone and / or ε-hydroxycaproic acid in an amount of 0.05 to 1 mol per mol d)

and (B) polyamides consisting of a reaction product of components a) to e), wherein the starting component a) monocarboxylic acids having less than 12 carbon atoms, for bonding textiles according to patent 26 59 464, characterized in that the Polyamides (A) and (B) have a melt viscosity (measured at 220 ° C) of 25 to 600 Pa · s and in the preparation of these polyamides per mole of the acids mentioned under a) and b) <1.5 to 2.5 Mol caprolactam and / or ε-aminocaproic acid d) can be used.