JPS6338389B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION The present invention relates to polyesteramide-based melt adhesives suitable for adhering fibers to each other or to other materials. PRIOR TECHNOLOGY AND PROBLEMS The previously known hot-melt adhesives based on dimeric fatty acids or hot-melt adhesives based on caprolactam do not fully meet the requirements of practice with regard to their properties and range of use. It's just an effect. Means for Solving the Problems The subject of the invention is (a) 1. Dimerized fatty acids containing 70-100% by weight of dimeric fatty acids and optionally 2. as viscosity modifiers (chain terminators). monocarboxylic acids (in which case up to 50 equivalent % of the total carboxyl groups in the mixture of (a) 1 and 2 may be derived from monocarboxylic acids); and (b) aliphatic non-carboxylic acids having 6 to 13 carbon atoms. one or more branched codicarboxylic acids (the ratio of the carboxylic acids according to (a) 1 and 2 to the carboxylic acids according to (b) with respect to the carboxyl groups being from 0.05:1 to 5:1) and ( (c) aliphatic unbranched di-1 of 6 to 12 carbon atoms in practical equivalents to the acids listed in a) and (b);
(d) caprolactam and/or ε-aminocaproic acid, in which case caprolactam and/or ε-aminocaproic acid per mole of carboxyl groups of the acids mentioned in (a) and (b)
- using 0.5-2.5 mol of aminocaproic acid),
and (e) caprolactone and/or hydroxycaproic acid (0.05 to 1.0 caprolactone and/or ε-hydroxycaproic acid per mole of caprolactam or aminocaproic acid mentioned in (d))
mol), where the dimerized fatty acid (component a) is optionally combined in the first step with the total amount or part of caprolactam and/or ε-aminocaproic acid (component d). Gluing fibers based on polyesteramides with a melt viscosity of 25 to 600 Pa·s (measured at 220 °C), in which polyesteramides produced by reaction and reaction with other components in a second step are used It is a melt adhesive for. Sebacic acid was used as the kodicarboxylic acid according to (b) and hexamethylene diamine was used as the diamine component according to (c), the ratio of the carboxylic acid according to (a) to the carboxylic acid according to (b) being 0.1:1 to 3:1. can be,
In the case of polyesteramides, 0.8 caprolactam per mole of carboxyl group of the acids listed in (a) and (b)
~2 mol of caprolactone and/or ε-hydroxycaproic acid are used per mole of caprolactam and/or ε-aminocaproic acid.
Preference is given to using polyesteramides, together with 0.1 to 0.5 mol. To prepare the polyesteramides used according to the invention, it is advantageous to use as dimerized fatty acids according to (a) those containing more than 90% by weight of dimeric fatty acids. Easily available dimeric fatty acids, caprolactam or ε-aminocaproic acid, caprolactone or ε
- The melt adhesive according to the invention, which is based on hydroxycaproic acid, diamines and kodicarboxylic acids, exhibits good stability against halogenated hydrocarbons and at the same time against cleaning fluids at 60°C and partly also at 95°C. have This stability is characterized by 1 very good initial tear strength, i.e. the value before loading by the washing or cleaning process, and 2 very high wet tear strength, i.e. the value while still wet after cleaning, and 3 a high number. This is reflected by the excellent tear strength after drying which is re-obtained after a washing- or washing cycle. When using distilled dimeric fatty acids, melt adhesives with improved color numbers are obtained. On the other hand, it is also possible to produce hot-melt adhesives for special purposes by using commercially available industrially polymerized fatty acids. It is only pointed out that when using technical dimeric fatty acids, the trimeric fatty acid content must not exceed a maximum limit. This limit value depends on the respective content of dimeric and monomeric fatty acids of the polymerized fatty acids and can be ascertained by preliminary tests, which are a routine and simple procedure for the average expert. The expression dimerized fatty acids generally refers to polymerized acids obtained from "fatty acids". The expression "fatty acids" includes unsaturated natural and synthetic basic aliphatic acids having from 12 to 22, preferably 18, C atoms. These fatty acids can be polymerized by known methods [West German Patent Application No. 1443938,
1443968, West German Patent No. 2118702 and the same
1280852 specification]. Typical commercially available polymeric fatty acids have approximately the following composition: Monomeric acid (Mo) 5-15% by weight Dimeric acid (Di) 60-80 Trimeric acid (Tri) 10-35 〃 The acid content of the dimer is generally determined by a known distillation method.
It can be increased up to 100% by weight. Regarding the polyesteramide according to the invention:
Commercially available products contain a large amount of dimeric fatty acids (more than 90% by weight) and a small amount of trimeric fatty acids (2 to 20% by weight).
6% by weight) and monomeric fatty acids (0-1.5% by weight)
It is advantageous to use dimerized fatty acids having . It is also possible to use dimerized fatty acids in their hydrogenated form. The polyesteramides according to the invention lie within a certain melt viscosity range, which represents a certain molecular weight range. Adjustment of the melt viscosity can be carried out in known manner by stopping the reaction at the desired degree of polymerization or by working with unequal amounts of carboxylic acid or amine. Since these methods have certain drawbacks, it is preferable to use monofunctional or monofunctionally acting compounds (amines or carboxylic acids) as chain terminators. Monocarboxylic acids have proven particularly advantageous in this case. The amount of monocarboxylic acids optionally present in the polymerized fatty acids used according to the invention is such that the monocarboxylic acids are added in an amount up to 50 equivalent %, based on the total carboxyl groups of the mixture of fatty acids and monocarboxylic acids of the polymer. It can be increased by
The necessary chain terminators (viscosity modifiers), here if the proportion of monocarboxylic acids is high, polymeric monocarboxylic acids such as oleic, stearic, linoleic, linolenic acids or mixtures thereof,
For example, it is advantageous to use tall oil fatty acids or soybean oil fatty acids or other hydrophobic monocarboxylic acids. Examples of aliphatic unbranched kodicarboxylic acids having 6 to 13 carbon atoms which can be used according to the invention include adipic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid and brazilic acid. These dicarboxylic acids can be used alone or in mixtures. Instead of carboxylic acids, their esters with lower alcohols may optionally be used. In this case, especially if the proportion of esters is high, it is recommended to start the caprolactam polymerization by adding water. Regarding the aliphatic unbranched diprimary diamines having 6 to 12 carbon atoms which can be used according to the invention, examples are 1,6-diamino-hexane, 1,9-diaminononane, 1,12-diaminododecane. Can be mentioned. The amount of caprolactam per mole of carboxyl groups of the acid used as well as the lactam/lactone ratio depend on the desired high melting point. When using polyesteramide melt adhesive as a fiber adhesive, the amount of lactam is 0.5 to 2.5 per mole of carboxyl group of polymerized fatty acid and cordicarboxylic acid.
Moles and lactone amounts are from 0.05 to 1 mole of lactam.
It is 1.0 mol. The materials to be bonded are fibers, possibly siliconized fabrics, which can be bonded to each other. The polyester amide used according to the invention is prepared with practically equivalent amounts of the above-mentioned reactants at a temperature of 200-290°C.
In particular, it can be produced by melt polymerization at 250°C under an inert gas. A vacuum is applied at the final stage of the reaction to obtain sufficient product. Polyesteramides, like polyamides, can optionally also be produced in a two-stage process. That is, in the first step, the dimerized fatty acid (component (a)) and its amide-forming derivative are mixed with caprolactam and/or
Alternatively, it is condensed with the whole or a partial amount of ε-aminocaproic acid. In this case initially low temperature (i.e. about 150℃)
By using , the reaction can be easily controlled. To terminate the reaction, the temperature is increased to the required height. The quantitative ratio of the reactants in this first step varies depending on the desired degree of addition of aminocaproic acid or caprolactam. In a second step, the necessary other components are added to the reaction product and the reaction is terminated in a manner customary for amide production. Vehicles or diluents can be used to facilitate the performance of the reaction. The melt viscosity of the polyesteramide according to the invention should generally be between 25 and 600 Pa·s, measured at 220°C. Determination of Softening Point This value is measured by Kofler-Bank.
A finely ground polyesteramide powder with a particle size of 0.3 to 0.5 mm was spread on a Koffler bank.
The paper strip was then pressed within the softening range and after 90 seconds was gradually pulled away from the cold side of the Koffler Bank. At certain temperature limits, polyesteramide threads are formed between the Koffler bank and the separating paper. This temperature limit is defined as the softening point. Manufacture of adhesive Width 5 made of polyester/wool (55/45%)
cm strips of material were glued. The polyesteramide powder had a particle size of 300-500μ. The application amount was 20 g/m ² of material. The coated material strip was bonded to a second uncoated material strip at a temperature of about 20-30° C. above the softening point of the polyesteramide adhesive. Gluing time is approximately 15
~20 seconds, and the adhesive pressure was 400g~ ^cm2 . Washing and cleaning treatment Using a 3% commercially available machine detergent wash solution at a temperature of 60°C
and washed at 95°C. Washing process at 60℃ for 45 minutes;
At 95°C, it took 90 minutes. The washing program included rinsing and centrifugation steps. The test materials were tested in a peel strength test according to DIN (West German Industrial Standard) 53274 when wet and at room temperature. However, the width of the test piece was 5 cm. Chemical cleaning was performed with perchlorethylene for 30 minutes at room temperature. The cleaned test material was measured again when wet. The following polymerized fatty acids were used in the polyesteramides listed in the following table: Examples 1, 2, 4, 5, 7, 9 Dimerized tall oil fatty acids with the following composition: Monomeric fatty acid (Mo) 3.6 wt. % Dimer 〃 (Di) 94.2 〃 Trimer 〃 (Tri) 2.2 〃 Examples 3, 6, 8, 10 Dimerized oleic acid with the following composition: Monomeric fatty acid (Mo) 5.3wt % Dimeric fatty acids (Di) 93.3 〃 Trimeric 〃 (Tri) 1.4 〃 Example 1 27.02 g of dimerized tall oil fatty acids in a reactor equipped with a downward condenser, a stirrer and a thermometer. Tall oil fatty acid 18.00g, adipic acid 57.70g, sebacic acid 79.85g (with carboxyl groups from (a) 1 and 2)
Ratio of codicarboxylic acid according to (b) = 0.1:1.0), 1,
6-diaminohexane 101.05g, caprolactam
178.54 g (0.9 mol of caprolactam per 1 mol of carboxyl groups according to (a) and (b)) and 18.01 g of caprolactone (mole ratio of caprolactam:caprolactone = 1:0.1) were charged and heated at 250° C. within 2 hours under nitrogen. and held at this temperature for 7 hours. A vacuum of 2 mm of mercury was applied during the last 4 hours.
The polyesteramide obtained had the following values: Softening point: 123°C Melt viscosity at 220°C: 57.1 Pa·s Peel strength (Kg/5cm): 2.9 (60°C - washed, wet tear) Peel strength (Kg/5cm): 5.1 (perchlorethylene cleaning, wet tear) Original value (Kg/5cm): 5.8 Brown polyesteramides shown in the table below were prepared in a similar manner.

[Table] * Precondensation of dimerized tall oil fatty acids with ε-caprolactam

[Table] Example 6 In a reactor equipped with a downward condenser, a stirrer and a thermometer, 55.77 g of dimerized tall oil fatty acids, 9.83 g of stearic acid, 92.99 g of sebacic acid (according to (a) 1 and 2) were added. Ratio of carboxyl group of fatty acid mixture to codicarboxylic acid according to (b) = 0.25:1.0), 1,6-diaminohexane 66.86g, caprolactam 207.92
g (1.6 mol of caprolactam per mol of carboxyl group according to (a) and (b)), and caprolactone
26.22 g (molar ratio of caprolactam:caprolactone = 1.0:0.125) was charged and heated to 250° C. within 2 hours under nitrogen and kept at this temperature for a further 7 hours. A vacuum of 2 mm of mercury was applied during the last 4 hours. The polyesteramide had the following values: Softening point: 120°C Melt viscosity at 220°C: 58.0 Pa·s Peel strength (Kg/5cm): 3.5 (60°C - wash, wet tear) Peel strength ( Kg/5cm): 4.5 (perchlorethylene cleaning, wet tearing) Initial value (Kg/5cm): 6.1 The polyester amides listed in the following table were produced in the same manner.

[Table] * Precondensation of dimerized tall fatty acids with ε-caprolactam

【table】

Claims (1)

[Scope of Claims] 1. A melt adhesive for bonding fibers based on polyesteramide having a melt viscosity of 25 to 600 Pa·s (measured at 220°C), comprising: (a) 1 dimeric fatty acid 70 -100% by weight of dimerized fatty acids and optionally 2 monocarboxylic acids as viscosity modifiers (chain terminators), in which case a) up to 50 equivalents % of the total carboxyl groups of the mixture of 1 and 2 are monocarboxylic (b) one or more aliphatic unbranched codicarboxylic acids having 6 to 13 carbon atoms, in which case the carboxylic acids according to 1 and 2 of (a) (b) with respect to the carboxyl groups with the carboxylic acid is from 0.05:1 to 5:1) and (c) with a practical equivalent of the acids mentioned in (a) and (b) containing from 6 to 12 carbon atoms. Di-1 of aliphatic unbranched chain
and (d) caprolactam and/or ε-aminocaproic acid, in which caprolactam and/or ε-aminocaproic acid per mole of carboxyl group of the acid mentioned in (a) and (b).
using 0.5-2.5 mol of aminocaproic acid),
and (e) caprolactone and/or hydroxycaproic acid (0.05 to 1.0 caprolactone and/or ε-hydroxycaproic acid per mole of caprolactam or aminocaproic acid mentioned in (d))
using moles), where the dimerized fatty acid (component a) is optionally combined with caprolactam and/or in the first step.
Alternatively, a polyesteramide produced by reacting with the whole amount or a part of ε-aminocaproic acid (component d) and reacting with other components in a second step may be used. agent.