DE2659463A1 - Polyamide and polyesteramide melt adhesives - for adhering textiles to give dry cleaning and wash-resistant bond - Google Patents

Abstract

Polyamide melt adhesives for bonding textiles, having melt viscosities (at 220 degrees C) of 25-600 pascal-sec., are prepd. from (a) a dimerised fatty acid contg. 70-100 wt; % fatty acid dimer, and opt. monocarboxylic acids as viscosity regulators (chain breakers); =50 equiv. % of the total COOH being from monocarboxylic acids. Prepn. is also from (b) >=1 6-13C unbranched aliphatic dicarboxylic coacids, the ratio of carboxylic acids in (a) to those in (b) being 0.05-5:1; and an amt., equiv. to the acids in (a) and (b) of (c) an unbranched 6-12C aliphatic diprimary diamine, and (d) caprolactam and/or epsilon-aminocaproic acid in an amt. 0.5-1.5 mole per mole COOH gps. of the acids in (a) and (b).

Description

Hot melt adhesive for bonding textiles

(Additional application to patent. ...........

(Patent application P 26 59 464.9) The invention relates to the use of polyester amides for bonding textiles.

GegenensJcand of the main patent ..... (patent application P 25 34 121.3) is the use of polyamides for bonding textiles with Schlemzvisities (measured at 2200C) from 25 to 150 Pa consisting of u) dimerized fatty acid with a content of 70% by weight to 100% by weight of dimeric fatty acid in a mixture with Monocarboxylic acids that have 12 to 22 carbon atoms, the total mixture can be up to 50 wt .-% of the monocarboxylic acids, and b) one or more aliphatic unbranched co-dicarboxylic acids with 6 to 13 carbon atoms, where the ratio of the carboxylic acids according to a) to carboxylic acids according to b) 0.05: 1 to 5 : 1, based on carboxyl groups, and consisting of one of the under a) and b) said acids substantially equivalent amount of a c) aliphatic unbranched diprimary diamine with 6 to 12 carbon atoms and of d) Caprolactam and / or e-aminocaproic acid, with per mole of carboxyl groups below acids mentioned a) and b) 0.5 to 1.5 mol of caprolactam and / or t-aminocaproic acid can be used.

Subject of the additional patent ...... (patent application P 26 15 765.3) is the use of polyamides for bonding textiles with melt viscosities (measured at 2200C) from 25 to 150 Pa, which is characterized in that the polyamides consist of a) 1. dimerized fatty acid with a content of 70 to 100 wt. - dimeric fatty acid and optionally from 2. monocarboxylic acids as viscosity regulators (Chain terminators), which can be used in such amounts that they are up to 50 equivalent% of the total carboxyl groups of the mixture a) 1. and 2. make up and from b) one or more aliphatic unbranched co-dicarbon traces with 6 to 13 carbon atoms, the ratio of the carboxylic acids according to a) to carboxylic acids according to b) 0.05: 1 to 5: 1, based on carboxyl groups, and consists from one of the acids mentioned under a) and b) essentially equivalent amounts a c) aliphatic unbranched diprimary diamine with 6 to 12 carbon atoms and from d) caprolactam and / or c-aminocaproic acid, with per mole Carboxyl groups of the acids mentioned under a) and b) 0.5 to 1.5 mol of caprolactam and / or e-aminocaproic acid can be used.

Subject of the additional patent ...... (patent application P 26 15 766.4) is the use of polyamides for bonding textiles according to the additional patent ...... (patent application P 26 15 765.3), which is characterized in that the polyamides have a melt viscosity of> 150 to 600 Pa s at 2200C.

Subject of the additional patent ............

(Patent application P 26 58 370.0) is the use of polyamides for the bonding of textiles according to the main patent ......... (patent application P 25 34 121.3) and according to the additional patent ....... (patent application P 26 15 765.3) and the further additional patent ....... (patent application P 26 15 766.4), which thereby is characterized in that polyamides are used in their manufacture in the first place Stage the implementation of the dimerized fatty acid (component a) with the total amount or partial amounts of caprolactam and / or z-aminocaproic acid (component d) and in the second stage the implementation with the other components takes place.

Subject of the additional patent .............

(Patent application P 26 59 464.9) - is the use of polyester amides for the bonding of textiles according to the main patent ........ (patent application P 25 34 121.3) with melt viscosities (measured at 2200C) of 25 to 150 Pa s and according to Additional patent (Patent application P26 15 766.4) with melt viscosities (measured at 220 °) from e> 150 to 600 Pa. s consisting of: a) dimerized Fatty acid with a content of 70% by weight to 100% by weight of dimeric fatty acid in the mixture with monocarboxylic acids having 12 to 22 carbon atoms, the total mixture according to the main patent can be up to 50 wt .-% of monocarboxylic acids and according to Additional patent ..... (patent application P 26 15 766.4) and the further additional patent . (Paterit application P 26 15 765.3) the monocarboxylic acids as viscosity regulators up make up 50 equivalent% of the total carboxyl groups, and b) one or more aliphatic unbranched co-dicarboxylic acids with 6 to 13 carbon atoms, where the ratio of the carboxylic acids according to a) to carboxylic acids according to b) 0.05: 1 to 5 : 1, based on carboxyl groups, and consisting of one of the under a) and b) said acids substantially equivalent amount of a c) aliphatic unbranched diprimary diamine with 6 to 12 carbon atoms and from d) caprolactam and / or e-aminocaproic acid, with those mentioned under a) and b) per mole of carboxyl groups Acids 0.5 to 1.5 moles of caprolactam and / or E-aminocaproic acid are used, and whereby according to the additional patent .......

(Patent application P-26 58 370.0) Polyamides can be used in their production, the first stage is the conversion of the dimerized fatty acid (Component a) with the total amount or partial amounts of Ge of the caprolactam and / or the e-aminocaproic acid (component d) and in the second stage the reaction with the further components takes place, which is characterized in that per mole of caprolactam and / or s-aminocaproic acid 0.05 to 1 mol of caprolactone and / or e-hydroxicaproic acid can also be used.

The subject of the present additional invention is further training the use of polyester amides for bonding textiles according to the patent ....... (patent application P 26 59 464.9.) With melt viscosities (measured at 220 ° C) from up to 600 Pa. s consisting of a) dimerized fatty acid with a content of 70 wt .-% to 100 wt .-% of dimeric fatty acid in a mixture with monocarboxylic acids, the Have 12 to 22 carbon atoms, the monocarboxylic acids as viscosity regulators make up to 50 equivalent percent of the total carboxyl groups, and b) one or more aliphatic unbranched co-dicarboxylic acids having 6 to 13 carbon atoms, where the ratio of the carboxylic acids according to a) to carboxylic acids according to b) 0.05: 1 to 5 : 1, based on carboxyl groups, and consisting of one of the under a) and b) a substantially equivalent amount of said acids c) aliphatic unbranched diprimary diamine having 6 to 12 carbon atoms and from d) caprolactam and / or e-aminocaproic acid, with the per mole of carboxyl groups acids mentioned under a) and b) 0.5 to 1.5 mol of caprolactam and / or ε-aminocuproic acid can be used.

polyamides can optionally be used in their In the first stage, the conversion of the dimerized fatty acid (component a) with the total amount or partial amounts of the caprolactam and / or the ε-aminocuproic acid (Component d) and in the second stage the reaction with the other components takes place, and according to the additional patent ...... (patent application P 26 59 464.9) per mole of caprolactam and / or s-aminocaproic acid 0.05 to 1 mol of caprolactone and / or e-hydroxicaproic acid are also used, which is characterized in that per mole of carboxyl groups of the acids mentioned under a) and b) 1.5 to 2.5 mol of caprolactam and / or ε-aminocaproic acid can be used.

Polyester amides are preferably used in which the co-dicarboxylic acid according to b) sebacic acid and used as the diamine component according to c) hexamethylenediamine and in which the ratio of the 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 the under a) and b) mentioned acids> 1.5 to 2 mol of caprolactam are used and at those per mole of caprolactam and / or e-aminocaproic acid 0.1 to 0.5 caprolactone and / or e-hydroxicaproic acid can also be used.

To produce the polyester amides used according to the invention, as the dimerized fatty acid according to a), preference is given to one with contents of more used as 90% by weight dimeric fatty acid.

The hotmelt adhesives used according to the invention, which are based on the sufficient available dimeric fatty acid, caprolactam or

c-aminocaproic acid, caprolactone or e-hydroxicuproic acid, diamines and codicarboxylic acids show good resistance to halogenated ones Hydrocarbons and at the same time also against detergents at 600C and partially even at 950C. This resistance is expressed by 1. the very good initial tear strength, d. That is, values before exposure to the washing or cleaning process, and through 2. the very high wet tensile strengths, i.e. values after cleaning in a still damp Condition, and by 3. the excellent tensile strength values after drying, which are almost reached again even after many washing or cleaning cycles.

When using distilled dimeric fatty acid, hot melt adhesives are used obtained with improved color number. On the other hand, the use of is more commercially available technical polymerized fatty acid for the production of fused liver for special Purposes possible. When using technical dimeric fatty acid, just pay attention pointed out that the content of trimeric fatty acid is a maximum border should not exceed. This limit depends on the respective content dimeric and monomeric fatty acids from the polymerized fatty acid and can through an orienting experiment, as it is part of the everyday craftsmanship of the average specialist heard, to be determined.

The term dimerized fatty acid refers in a general way to 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. These fatty acids can be polymerized by known processes (cf. DT-OS 1 443 938, DT-OS 1 443 968, - DT-PS 2 118 702 and DT-PS 1 280 852).

Typical commercially available polymeric fatty acids are as follows Composition: monomeric acids (Mo) 5 to 15 percent by weight dimeric acids (Di) 60 to 80 percent by weight trimeric acids (tri) 10 to 35 percent by weight.

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

The polyester amides used according to the invention are preferred dimerized fatty acids with a content of 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 they are generally available in the trade, is used. It is also possible to use the dimerized fatty acid in its hydrogenated form.

The polyester amides used according to the invention are in a certain range Melt viscosity range that reflects a certain range of molecular weights.

The melt viscosity can be adjusted 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. Because of certain disadvantages of these methods, the Use of monofunctional or monofunctional compounds (amines or carboxylic acids) are preferred as chain terminators. Have proven to be particularly cheap proven monocarboxylic acids.

The possible proportion of monocarboxylic acids in the used according to the invention polymerized fatty acid can be obtained by adding monocarboxylic acids up to 50 equivalent%, based on total carboxyl groups of the mixture of polymeric fatty acid and monocarboxylic acid, increase. If the proportion of the chain terminator (viscosity regulator) required is here the monocarboxylic acid, high, higher molecular weight monocarboxylic acids are preferred, such as oleic, stearic, linoleic, linolenic acid or mixtures thereof such as tall oil or Soya fatty acid or other hydrophobic monocarboxylic acids are used.

As examples of the aliphatic used according to the invention unbranched co-dicarboxylic acids with 6 to 13 carbon atoms are adipic acid, Nonamethylene dicarboxylic acid, deksmethylene dicarboxylic acid and brassylic acid. These dicarboxylic acids can be used alone or in a mixture.

Instead of the carboxylic acids, their esters can optionally also be used lower alcohols are used. Here it is particularly recommended if the ester content is high, caprolactam polymerization due to the addition of water to start.

For the aliphatic unbranched diprimary which can be used according to the invention Diamines with 6 to 12 carbon atoms are, for example, 1, G-diamino-hexane, 1,9-diominononane, Called 1,12-diaminododecane.

The amount of caprolactam based on the number of carboxyl groups of the acids used and the lactam / lactone ratio depends on the level of the desired melting point. The amount of lactum when using hot melt adhesives as textile adhesives is per mole Carboxyl groups of the polymerized fatty acid and the co-dicarboxylic acid or co-dicarboxylic acids 0.5 to 2.5 moles and the amount of lactone 0.05 to 1 mole per mole of lactam. With the ones to be glued Materials are textiles, possibly also siliconized fabrics, which can be glued together.

The polyester amides to be used according to the invention can be produced by melt condensation in essentially equivalent amounts of the reactants indicated above Temperatures between 200 and 290 ° C, especially at 250 ° C, produced under inert gas will.

According to the additional patent .... (Patent Application P 26 58 370.0), in the first Stage the dimerized fatty acid (component a) or its amide-forming derivatives with the caprolactam and / or the ß-aminocaproic acid condensed. A low temperature is preferably used initially (i.e. approx. 1500C), so that the reaction can be easily controlled. To terminate the reaction, the The temperature is then increased to the required level. The proportions of the Reactants in this first stage vary depending on the degree of attachment desired of aminocaproic acid or caprolactam.

In the second stage, this reaction product is required further components are added and the reaction is carried out in the manner customary for amide production Way to an end.

Solvents or diluents can be used to facilitate the conduct of the reaction be used.

Example 1 In one with descending condenser, stirrer and thermometer equipped reactor were 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 of caprolactam per mol of carboxyl groups according to a) and b)) as well as 26.22 g caprolactone (Molvexliältnis of Caprolaktam: Caprolakton- 1.0: 0.125) weighed and heated under nitrogen to 2500 C within 2 hours and more Maintained at this temperature for 7 hours. During the last 4 hours a Vacuum applied from 2 mm Hg column.

The polyester amide had the following values: Softening point: 120 ° C Melt viscosity at 2200C: 58.0 Pa. s Separation strength in kp / 5cm: 3.5 (600C wash, wet torn) Separation strength in kp / 5cm: 4.5 (perchlorethylene cleaning, wet torn) Initial value in kp / 5cm: 6.1 The polyester amides listed in the table below were made in the same way.

Table 1 Ratio of the moles of caprolactam Molar ratio of fatty acid mixture per mole of caprolactam: Example Composition a): Co-dicarboxylic acid carboxyl groups Caprolactone b) 2 94.39 g dim. Tall oil fatty acid 0.5. 1.0 1.66 1: 0.1 8.20 g stearic acid 72.77 g sebacic acid 62.79 g 1,6-diaminohexane 203.40 g caprolactam 20.52 g carolactone 3 129.67 g dim. Tall oil fatty acid 1.0: 1.0 1.75 1: 0.07 12.82 g stearic acid 50.54 g sebacic acid 58.15 g 1,6-diaminohexane 197.75 g capro oil lactam 14.25 carolactone 4 184.34 g dim. Tall oil fatty acid 3.0: 1.0 2.175 1: 0.059 3.76 g stewaric acid 22.23 g sebacic acid 51.17 g 1,6-diaminohexane 211.31 g caprolactam 12.45 g caprolactone Table 2 Separation strength (kg / 5 cm) Melting Vicos. 60 ° C wash Perchlorethylene cleaning Example softening point b. 220 ° C (Pa. S) Initial values wet tear wet tear 2 124 ° C 98.5 Pa. s 6.2 3.4 5.0 3 129 ° C 72.2 Pa. s 6.1 3.4 5.5 4 138 ° C 112.0 Pa. s 5.7 3.2 4.6

Claims (1)

Claim Further training in the use of polyester amides for the bonding of textiles according to patent ....... (Auntie registration P 26 59 464.9) w with melt viscosities (measured at 220 ° C) of 25 to 600 Pa s from: a) dimerized fatty acid with a content of 70 wt .-% to 100 wt .-% dimeric fatty acid mixed with monocarboxylic acids containing 12 to 22 carbon atoms have, the monocarboxylic acids as viscosity regulators up to 50 equivalent% of the total carboxyl groups, and b) one or more aliphatic unbranched Co-dicarboxylic acids with 6 to 13 carbon atoms, the ratio of the carboxylic acids according to a) to carboxylic acids according to b) 0.05: 1 to 5: 1, based on carboxyl groups, and essentially consisting of one of the acids mentioned under J) and b) equivalent amount of a c) aliphatic unbranched diprimary diamine with 6 up to 12 carbon atoms and from d) caprolactam and / or e-aminocaproic acid, where per mole of carboxyl groups of the acids mentioned under a) and b) 0.5 to 1.5 moles of caprolactam and / or e-aminocaproic acid are used, where appropriate Polyamides can be used in their production in the first stage the implementation of the dimerized fatty acid (component a) with the total amount or partial amounts of the Caprolactams and / or the e-aminocaproic acid (component d) and in the second stage the implementation with the other components takes place, and according to the additional patent ..... (patent application P 26 59 464.9) per mole of caprolactam and / or e-aminocaproic acid 0.05 to 1 mol of caprolactin and / or e-hydroxicaproic acid can be used, thereby characterized in that per mole of carboxyl groups of the acids mentioned under a) and b) > 1.5 to 2.5 mol of caprolactam and / or e-aminocaproic acid are used.