IE46225B1 - Fusible adhesives especially for the adhesion of textiles - Google Patents

Description

The invention relates to polyester-amide fusible adhesives suitable for the adhesion of textiles to one another or to other materials.

The fusible adhesives based on dimeric fatty acid or 5 caprolactam known hitherto do not fulfil satisfactorily practical requirements regarding properties and range of use.

This invention is an improvement in, or modification of, the invention of Patent No. 43040 which describes and claims a process for adhesively uniting two surfaces, one of textile, siliconised fabric or rubber and the other of textile, siliconised fabric, rubber or leather, v/hich comprises applying a polyamide comprising units derivable from (a) a carboxylic acid component comprising (1) a dimerised fatty acid having a content of 70 to 100% by weight of dimeric fatty acid, (b) a dicarboxylic acid component comprising an aliphatic unbranched dicarboxylic acid having from 6 to 13 carbon atoms, wherein the ratio of the carboxylic acid component (a) to dicarboxylic acid component (b) is from 0.05:1 to 5:1, calculated on carboxyl groups, (c) a diamine component comprising an aliphatic unbranched diprimary diamine having from 6 to 12 carbon atoms, and (d) caprolactam and/or ε-aminocaproic acid, to one or both of the surfaces and bringing the surfaces together, the polyamide being fused by the application of heat and pressure so that an adhesive bond is formed.

The carboxylic acid component (a) may, if desired, i nclude (2)a rnonocarboxylic (monomeric) acid as viscosity regulator (chain breaker), wherein the total of monomeric acid in (al) and (a2) is 15 no more than 50% of the total acid component, calculated on carboxyl groups.

Patent 43040 also claims a composition for the preparation of a polyamide suitable as fusible adhesive, which comprises ZO (a) a carboxylic acid component comprising (1) a dimerised fatty acid having a content of from 70 to 100% by weight of dimeric fatty acid or a polyamide-forming derivative thereof, (2) a monocarboxylic acid (monomeric) or a polyamide-forming derivative thereof, as chain breaker, wherein the total proportion of monomeric acid in components 5 (al) and (a2), calculated as carboxyl equivalents, is more than 15% and up 'to 50%; (b) a dicarboxylic acid component comprising an aliphatic unbranched dicarboxylic acid having from 6 to 13 carbon atoms, or a polyamide-forming derivative thereof, wherein the ratio of carboxylic acid component (a) to dicarboxylic acid component (b), calculated as carboxyl equivalents, is from 0.05:1 to 5:1; (c) a diamine component comprising an aliphatic unbranched diprimary diamine having from 6 to 12 carbon atoms, or a polyamide-forming derivative thereof, and (d) caprolactam and/or ε-aminocaproic acid, and the polyamide prepared therefrom, and a process for adhesively uniting two surfaces each of textile, siliconised fabric, leather or rubber, which comprises applying this polyamide to one or both of the surfaces and bringing the surfaces together, the polyamide being fused by the application of heat and pressure so that an adhesive bond is formed.

We have now found that a fusible polyester-amide adhesive may be obtained by inclusion of caprolactone and/or e-hydroxy-caproic acid in an amount of from 0.05 to 1.0 mol per mol of caprolactam and/or aminocaproic acid used in preparing the polyamide used in the adhesive process of Patent 43040 and that, if desired, the amount of caprolactam and/or aminocaproic acid may be increased to 2.5 mols per mol of carboxyl groups of the components (a) and (b).

Patent Specification No. 46224 describes and claims a process of adhesively uniting a textile, siliconised fabric, leather or rubber substrate to the same, or a different, substrate in this list, which comprises applying a polyamide comprising units derived from (a) a carboxylic acid component comprising (1) a dimerised fatty acid having a content of 70 to 100% by weight of dimeric fatty acid, or a polyamide-forming derivative thereof, (b) a dicarboxylic acid component comprising an aliphatic unbranched dicarboxylic acid having from 6 to 13 carbon atoms, or a polyamide-forming derivative thereof, wherein the ratio of the carboxylic acid component (a) to carboxylic acid component (b) is from 0.05:1 to 5:1, - 5 4 6 2 2 5 calculated as carboxyl equivalents, (c) a diamihe component comprising an aliphatic unbranched diprimary diamine having from 6 to carbon atoms, or a polyamide-forming derivative thereof, and (d) caprolactam and/or ε-aminocaproic acid, and which has been prepared by reacting, in a first stage, some or all of the acid constituent (a) and (b) with some or all of component (d) and, in a second of the first stage stage, reacting the product/with the remaining components, to a surface of one or both substrates and bringing the surfaces together, the polyamide being fused by the application of heat and pressure so that an adhesive bond is formed, and a polyamide comprising units derived from (a) a carboxylic acid component comprising (1) a dimerised fatty acid having a content of from 70 to 100% by weight of dimeric fatty acid or a polyamide-forming derivative thereof, and (2) a rnonocarboxylic acid (monomeric) or a polyamide-forming derivative thereof, as chain breaker, wherein the total proportion of monomeric acid in components (al) and (a2), calculated as carboxyl equivalents, is up to 50%; 4-6225 (b) a dicarboxylic acid component comprising an aliphatic unbranched dicarboxylic acid having from 6 to 13 carbon atoms, or a polyamide-forming derivative thereof, wherein the ratio of carboxylic acid component (a) to dicarboxylic 5 acid component (b), calculated as carboxyl equivalents, is from 0.05:1 to 5:1; and (c) a diamine component comprising an aliphatic unbranched diprimary diamine having frora ό to 12 carbon atoms, or a polyamide-forming derivative thereof, (d) caprolactam and/or ε-aminocaproic acid, and which has been prepared by reacting, in a first stage, some or all of the acid constituent (a) and (b) with some or all of component (d) of the first stage and, in a second stage, reacting the product/with the remaining 15 components, We have Further found that in a preferred method of preparation of the polyester-amide used in the adhesive process of the invention, in a first stage the dimerised fatty acid (component (al)) is reacted with the total quantity or part of the caprolactam and/or of the ε-aminocaproic acid (component (d)), and in a second stage reaction is effected with the remainder of the composition. The block condensates thereby produced have improved water resistance. - 7 4 6 2 2 5 We have also found that other satisfactory block condensates may be obtained if the caprolactam/c-aminocaproic acid component or part thereof is precondensed with one of the other acid components, e.g. the co-dicarboxylic acid (b) or acid (a2).

When the dimerised fatty acid component (al) is used for the precondensation, the components (al) and (a2) are usually precondensed together with the caprolactam/e-aminocaproic acid. Alternatively, the chain breaker (a2) may be introduced later with the remaining components.

The present invention provides a process of adhesively uniting a textile, siliconised fabric, leather or rubber substrate to the same, or a different, substrate in this group, which comprises applying a polyester-amide comprising units derivable from (a) a carboxylic acid component comprising lb (1) a dimerised fatty acid having a content of 70 to 100% by weight of dimeric fatty acid, (b) a dicarboxylic acid component comprising an aliphatic unbranched dicarboxylic acid having from 6 to 13 carbon atoms, wherein the ratio of the carboxylic acid component (a) to carboxylic acid component (b) is from 0.05:1 to 3:1, calculated as carboxyl groups, (c) a diamine component comprising an aliphatic unbranched diprimary diamine having from 5 to 12 carbon atoms, - 8 4622S (d) caprolactam and/or ε-aminocaproic acid, and (e) caprolactone and/or hydroxycaproic acid, to the surface of one or both substrates, and bringing the surfaces together, the polyester-amide being fused so that an adhesive bond is formed.

The carboxylic acid component (a) may include (2) a monocarboxylic (monomeric) acid wherein the total proportion of monomeric acid in components (al) and (a2), calculated as carboxyl equivalents, is up to 50%.

The use of polyester-amides in which the carboxylic acid component (a) includes (2) a monocarboxylic (monomeric) acid having from 12 to 22 carbon atoms, and preferably the weight of monomeric acid is up to 50% of the weight 20 of the total mixture, should be mentioned.

Thus some or all of (al), some or all of (a2) and/or some or all of (b) is used for the precondensation, especially some or all of components (al) and/or (b) and optionally (a2). For example the acid or acids of component (a) is/are first precondensed with some or all of component (i) and then reacted with the remaining components[1(b), (c) and (e) and, if any remain, (a) and (d)J . The present invention also provides a - 9 46228 polyester-amide which has been prepared by one of such processes.

It should be understood that, where appropriate, one or more of the components may be present in the form of a poTyamide-/polyesterforming derivative. Each component (al), (a2), (b), (c), (d) and (e) may contain one or more of the substances specified thereunder.

According to the present invention the polyester-amides used as fusible adhesives, especially for textiles, advantageously for this latter purpose have a fusion viscosity (measured at 220°C) of from 25 to 500 Pa.s (Pascal seconds).

The fusible adhesives used according to the invention, which are built up on the basis of dimeric fatty acid, available in sufficient quantity, caprolactam or ε-aminocaproic acid, caprolactone or e-hydroxycaproic acid, diamines and co-dicarboxylic acids, have a good resistance to halogenated hydrocarbons and to washing liquors at 60°C and, in the case of some of them, also at 95°C. This resistance is evidenced by 1. the very good initial tenacities, that is before being subjected to stress by the washing or cleaning process, 2. the very high wet tenacities, that is after cleaning and when still in the damp state, and 3. the excellent tear resistance values after drying which are almost completely retained even after many washing or cleaning cycles. - 10 .46 22S When a distilled dimeric fatty acid is used, a fusible adhesive with an improved colour number may be obtained. On the other hand, industrial polymerised fatty acid may also be used for producing fusible adhesives for special purposes. However, when using industrial dimeric fatty acid it is necessary to ensure that the content of trimeric fatty acid does not exceed a maximum limit. This limiting value depends on the content of dimeric and monomeric fatty acid in the polymerised fatty acid and can be determined by an orientating test such as is part of the daily routine of the average man skilled in the art.

The term dimerised fatty acid is used herein in a general sense to denote polymerised acids obtained from fatty acids. Thus, the dimerised fatty acid component may consist only of dimeric acid or may comprise the dimeric acid and optionally the monomeric and/or higher polymeric, primarily trimeric, acid. The term fatty acid includes unsaturated natural and synthetic monobasic aliphatic acids having from 12 to 22 carbon atoms, preferably 18 carbon atoms. These fatty acids can be polymerised by known processes (cf. German Offenlegungsschriften 1,443,936 and 1,443,96b and German Patent Specifications 2,118//02 and 1,280,852).

Typical polymeric fatty acids available commercially have approximately the following composition: monomeric acids (Mo) 5-15 percent by weight dimeric acids (Di) 60-80 percent by weight 25 trimeric acids (Tri) 10-35 percent by weight - 11 The content of dimeric acid may be increased to up to 100% by weight by known methods of distillation.

Preferably the fatty acid component (al) has a content of dimeric fatty acid at least 90% by weight. More especially, there are used dimerised fatty acids containing more than 90% of dimeric fatty acid and small amounts of trimeric fatty acid (2 to 6% by weight) and monomeric fatty acid (0 to 1.5% by weight); dimerised fatty acids generally obtainable commercially are suitable.

It is also possible to use a saturated dimerised fatty acid or one of 10 the above dimerised fatty acids in hydrogenated form.

The polyester-amides used according to the invention come within a specific range of fusion viscosities, usually 25-500 Pa.s (measured at 220°C), especially 25-150 Pa.s, which reflects a specific molecular weight range.

The fusion viscosity may be adjusted in known manner by breaking off the reaction at the desired degree of polymerisation or by working with non-equivalent quantities of carboxylic acids or amines. Because of certain disadvantages in these methods it is preferable to use monofunctional or mono-functionally-acting amines and/or carboxylic acids as chain breakers. Monocarboxylic acids have proved to be especially favourable.

The proportion'of monocarboxylic (monomeric) acid in the polymerised fatty acid used according to the invention may be increased by the addition of monocarboxylic acids up to the 50 equivalents %, calculated - 12 46225 on total carboxyl groups of the mixture of polymeric fatty acid and monomeric monocarboxylic acid. If the proportion of the necessary chain-breaker (viscosity regulator), in this case the monocarboxylic acid, is high, monocarboxylic acids of higher molecular weight (hydrophobic chain breakers) are preferably used. Examples are oleic, stearic, linoleic or linolenic acid or mixtures thereof, e.g. tall oil fatty acid or soya oil fatty acid, and other hydrophobic monocarboxylic acids.

For example, the acid of both components (al) and (a2) may have from 10 12 to 22 carbon atoms. Especially there may be used a commercially available dimerised fatty acid and additional fatty acid in its monomeric form, or a dimerised fatty acid having more than 15 equivalents % of monomeric monocarboxylic acid, and, if desired, additional chain breaker component (2).

The present invention also provides a polyester-amide comprising units derivable from (a) a carboxylic acid component comprising (1) a dimerised fatty acid having a content of from 70 to 100% by weight of dimeric fatty acid, or a polyamide-forming derivative thereof, and (2) a monocarboxylic acid (monomeric) or a polyamideforming derivative thereof, as chain breaker, - 13 4622S v/herein the total proportion of monomeric acid in components (al) and (a2), calculated as carboxyl equivalents, is up to 50% and preferably more than 15%, (b) a dicarboxylic acid component comprising an aliphatic 5 unbranched dicarboxylic acid having from 6 to 13 carbon atoms, or a polyamide-forming derivative thereof wherein the ratio of carboxylic acid component (a) to dicarboxylic acid component (b), calculated as carboxyl equivalents, is from 0.05:1 to 5:1, (c) a diamine component comprising an aliphatic unbranched diprimary diamine having from 6 to 12 carbon atoms, or a polyamide-forming derivative thereof, (d) caprolactam and/or ε-aminocaproic acid, and (e) caprolactone and/or hydroxycaproic acid.

The present invention also provides a process for preparing a polyester· amide of the invention which comprises condensing components (a), (b), (c), (d) and (e) specified above, or which comprises reacting, in a first stage, some or all of the acid constituent (a) and (b), with some or all of component (d) and, in a second stage, reacting the reaction product from the first stage with the remaining components. - 14 46225 The present invention further provides a composition for the preparation of a polyester-amide of the present invention which comprises components (a) (i.e.(al) and (a2)), (fa), (c), (d) and (e) specified above.

Suitable aliphatic unbranched co-dicarboxylic acids having from ό to 13 5 carbon atoms (component (b)) are, for example, adipic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid and brassylic acid. Sebacic acid is preferred. The dicarboxylic acids may be used singly or in admixture.

Optionally, instead of the carboxylic acids, esters thereof with lower aliphatic alcohols may be used. In this case, especially when the proportion of ester is high, it is recommended to initiate the caprolactam polymerisation by the addition of water.

Preferably, the ratio of component (a) to component (b) is from 0.1:1 to 3:1.

Suitable aliphatic unbranched diprimary diamines having from 6 to 12 carbon atoms (component (c)) are, for example, 1,5-diaminohexane, 1,9-diaminononane and 1,12-diaminododecane, 1,5-diaminohexane is preferred.

As is known in the art, in the preparation of the polyester-amide the amount of component (c) should generally be substantially equivalent to the amount of acid constituent (i.e. components (a) and (b)), The quantity of caprolactam/c-aminocaproic acid used, calculated on mols of carboxyl groups of the acids used, and the lactam/lactone - 15 >46325 ratio chosen depends on the melting point desired. Usually this should be no more than 140°C. The amount of lactam/ε-aminocaproic acid may, for example, be 0.5 to 1.5 mol per mol of carboxyl groups, or amounts over 1.5, e.g. up to 2.5, mol per mol of carboxyl groups may be used. Thus preferably 0.5 to 2.5 mol, especially 0.8 to 2 mol, of lactam-aminocaproic acid per -mol of carboxyl groups is used. Up to 1.0 mol, especially 0.05 to 1.0 mol, very especially 0.1 to 0.5 mol, of lactone/ε-hydroxycaproic acid per mol of lactam/aminocaproic acid is preferred.

Suitable materials for adhesively uniting are textiles, and also siliconised fabrics which may be adhesively joined to one another, or to leather, rubber or other materials. According to the present invention the polyester-amides may be used together with one or more other additives commonly used in the textile field, e.g. lubricants for improving the trickling ability of textile adhesive powders, plasticisers optical brighteners and/or antioxidants.

A polyester-amide used in the adhesive process of the present invention may be prepared by fusion condensation of the above-mentioned reactants in substantially equivalent quantities at temperatures of from 200 to 290°C, and especially at 250°C under inert gas. In the final phase of the reaction it is appropriate to apply a vacuum in order to obtain satisfactory products.

Alternatively, the polyester-amide may, if desired, be prepared in a two-stage process: for example in the first stage the dimerised fatty acid (component (al)) or an amide-forming derivative thereof is condensed - 16 46325 optionally together with component (a2) with some or all of the caprolactam and/or the ε-aminocaproic acid. In doing this, a low temperature is preferably used initially (i.e. approximately 150°C) so that the reaction is easy to control. At the end of the reaction the temperature is increased to the necessary level. The ratios of the reactants in this first stage vary according to the desired degree or addition of aminocaproic acid or caprolactam. In the second stage reaction with the other constituents is effected.

Solvents or diluents may be used to facilitate the reaction.

According to the invention the fusion viscosity of the polyester-amide should preferably be from 25 to 600 Pa.s, measured at 220°C.

The following Examples illustrate the invention, the polymerised fatty acids being used in the following respective Examples being as follows: Examples 1, 2, 4, 5, 7, 9 and 11. dimerised tall oil fatty acid having the following composition: monomeric fatty acid dimeric fatty acid 3.6% by weight 94.2% by weight 2.2% by weight trimeric fatty acid Examples 3, 6, 8 and 10. dimerised oleic acid of the following composition: - 17 46225 monomeric fatty acid dimeric fatty acid trimeric fatty acid .3% by weight 93.3% by weight 1.4% by weight Determination of the softening point.

The determination was carried out on a Kofler hot block in the following manner: The finely ground polyester-amide powder having a particle size from 0.3 to 0.5 mm was strewn on to the Kofler hot block. Then a small sheet of paper was pressed on to the softening region and after 90 seconds was remove^ slowly from colder side of the block. At a certain temperature polyester-amide filaments form between the block and the paper being withdrawn. This temperature limit is considered to be the softening point.

Produation of the adhesive joins.

Strips of fabric of polyester/wool (55%/45%) 5 cm wide were adhesively joined. The polyester-amide powder had a particle size of 300 to 500 u. The quantity applied was 20 grams per square metre of fabric.

The coated strips of fabric were adhesively united at temperatures of about 20 to 30 degree C above the softening point of the polyester20 amide adhesive to a second uncoated strip of fabric. The time taken to cause adhesion was about 15 to 20 seconds and the adhesion pressure was 400 grams per cm2. - 18 Separation-resistance tests.

The test portions of fabric were subjected, wet, at room temperature to a separation-resistance test according to DIN 53274. The width of the test portion was, however, 5 cm.

Washing and cleaning process.

Washing was carried out with a 3% strengtn washing liquor of a commercial machine detergent at temperatures of 60° C and 95°C. The washing process at 60°C lasted for 45 minutes, and at 95°C for 90 minutes.

The washing programme included a rinsing and centrifuging operation.

The resulting test portions of fabric were subjected, wet, at room temperature to a separation-resistance test according to DIN 53274.

The width of the test portion was, however, 5 cm.

Chemical cleaning was carried out with perchloroethylene for 30 minutes at room temperature. The cleaned test portions of fabric were again tested wet.

Example 1. 27.02g of dimerised tall oil fatty acid, 18.00g of tall oil fatty acid, 57.70g of adipic acid, 79.35g of sebacic acid, - 19 4 6 2 2 5 (ratio of the carboxyl groups according to (a) 1 & 2: codicarboxylic acid according to (b) = 0.1:1) 101. 05g of 1,6-diaminohexane, 178.54g of caprolactam, (0.9 mol of caprolactam per mol of carboxyl groups according to (a) & (b)) and 18.01g of caprolactone (molar ratio of caprolactam: caprolactone = 1:0.1) were weighed into a 10 reactor provided with a descending condenser, stirrer and thermoneter.

The whole was heated under nitrogen in the course of 2 hours to 250°C and maintained at this temperature for 7 hours.

For the last 4 hours a vacuum of 2 mm mercury was applied.

The polyester-amide obtained has the following values: Softening point: Fusion viscosity at 220°C: Separation resistance (i) initial value: (ii) after 60°C wash: (iii) after perchloroethylene 123°C 57,1 Pa.s .8 kp/5 cm 2.9 kp/5 cm (torn wet) cleaning: .1 kp/5 cm (torn wet) - 20 4622S The polyester-amides given in the following Table were prepared in the same manner. - 21 4 6 2 2 5 -σ' χ ο ο ιη ο ο ο «tf LQ _J CQ < ί •Ρ i? «Ρ re +£ •P re +Ο CL ε σ ο Ο C <ϋ r— X ι—· re «Ό Ό ω 4J ·«- ·ι- Ο EC υ ο c re ο -σ re re ·ρ- +j +j ω Ε ο ο ιη ο u re re re •ι— ·Γ” *r-T“r—^s- j- υ -σ ο ο re re re ι i. xE ΦΧΙΙΟ CLO •r· -ρ re re ro •σ tn tn«— u a cn cn ct cn cn σ re i— x «— re re Ό Ό -c re +J.r-.p- Ο Ξ C ο υ c re o •σ re re +j +» Φ Ε υ O tn u u re re re •r~ ·γ· ·γ··γ·γ—γ— i_ s- u ·σ ο ο re re re ι ί- ίε QJ XI ιο ο. ο. r- -ρ re « re re -a tn tn«— υ a σι cn cn cn cn a «tf oj cn m r— o r-- I— LO ID Γ— OJ I— re x UJ co Γ-. ο ο «Ρ ♦r· φ O C re »— x r— re re το Ό -sc a; •Ρ ·ι- ·γ> o e c υ o c re c σ re re t- -p +- re ε υ υ in a a re re re L i. fOXJ O C re re r- ι s- χε re re io cl c τ- +j n « re re *o in rer- u u cn cn cn cn cn σ «tf •r- re o c re r— X r— re re -σ -re re +j ·ι- ο ε c o re re o •σ re ·»- ·ρ -ρ re ε a a tn o re re re Γ u ’ΐ ο o re re ι s- sE X» IO CL CL •r· re « re re -σ tn υ u cn σ» cn cn ct in to 04 oj o o cn io oj oj OJ f“ * in limerised tall oil fatty acid precondensed with e-caprolactam -σ * 46226 CM TABLE ethylene torn wet CO CO CM cn ε o KD X. CL Φ O c fO- •P w •r- W Φ Ι- Ε: o •P ro S- <0 Cl Φ Perchloro cleaning CM CM CO co 60°C wash torn wet 3.0 3.5 ] . . 1 Γχ CM 2.9 c Initial Values 5.0 KD CO LD LO Fusion viscosity at 220°C (Pa.s) 52.4 © t— «4* 9‘96 94.5 Softening point ί- ο co O © «0· o cp o KD o o o Example CM co *0* LD - KD Q.

E «3 Ό Ό +J ·,- ΤΟ O Ό tO fO ω woo T £’o Φ ro (0 £ φ Xl «ι- -Ρ Φ -σ w w KD o o CM o?3 ·© ίο Φ i3 P X •a ίο o o fO E w CL Ό 3 p o o <0 · cn 1— >5 ·· P KD >> P CM X «0 · o 4- O Q i- Φ H (0 x: o •P X3 q- O O O W -P O CL Φ E 3 cn c o c rd S- J- *r- X Φ en-a Φ CL s- x: i— O ο E E >> o C ro rO X o •P O ro Ε u O J3 (0 <0 rtJ i- T) T- r— <0 Τ- -a O o Ο o t £- i- Mo x o 5f P CO (0 O S_ *rkd r* KD O CM Ό C rd co CM I provided with a descending condenser, stirrer and thermometer. The whole was heated in OJ ε rO t/i Φ _C +J -σ OJ sro CL Φ ίΟ. Φ c. Φ ? Φ s to l·cn c •r5 o 4Φ 4-3 C SΦ 4-» manner •5f Cd I Example Composition Ratio of Mol of (d) per mol Molar ratio o u cn o p“ 1:0.07 1:0.059 1:0.125 LD to ld CM to r-» •ζ o 1“· CM CM o O O o v-' r_ r— P“ ID O σ o ό r- co CO XS X5 XS X) •r— •r· o u u U (d fd rd rd i? 5- P i? p 40 •P P fd to <0 q- 4- 4- 4~lr_ r- r—tf- φ *Γ“ Φ •r- Ql ‘f OJ o c o c o c O C <0 ro P~ X r— X r— X r— X Ρ- Φ r— Φ r—· φ r— φ fO Ό Ό -C Φ fd Ό XJ JZ Φ -τ: φ rd XI -C φ p Ο E C 4-> -r- -r- O E C 4J.r-.r- ο E C P ·»“ © ε c O U C fd O U U C rd O u o e rd © U C fO O *O (0 fd ·Γ- Ρ P X) rd rd ·<- Ρ P X3 fd id t- P P X rtJ ·ρ- p P φ Ε υ u φ E U U Φ E u U Φ sou m u o (0 ni l/i O U Π3 nJ rd σι O U w U <0 ro fd ‘r- Ρ ·Ρ“ Ρ~· P“ i- u ·© © o J. J. (JO Ο O i. i. Λ *σ O O $- U X3 Ο Ο Oi fO fO 1 S- Ι- φ nJ f0 1 U S- dj rd «— 1 5- S- QjrdlS-i- Ε Φ -D CO CL Cl. ε φ a to o. a. g φ Φ LO CL CL E -Q LO CX O. •ρ- P (U » Ιβ Λ •r- Ρ φ « tti fd .,- ρ N « id rd r* φ « rd fd O Ul ΙΛ r— u u X» ΙΛ (Λ r— Ο o xs tn fd r- υ o XJ W i— U U Cn cn cn cn cn cr. cn cn σι cn cn cn ©> cn cn cn oi ct cn cn cn cn cn σι oscn on Γ^. CM «fi· LD LD LD LO CO Γ-» r— LD σ co ld CO co ro CM r*-. r- LO CO LD f— r*. CM co r* cm r— co «cr i— CM r— CO O «d· co cm cm co o cn cm o co r* «fi «fi· ro CM 1— t— CM CO CM r— co LD cn moon CM r- LD ID 07 r— co cm in p- »— CO CM lo cn CM CM r— CM * P*. co cn o r-“ p u «5 i— o ΙΟ.

CD ΙΟ.

$ P fd 4Ο) 5 >> c .e i•p o QJ 4-» O s_ cn o c ·ιx: c υ «ο s- QJ ω ρω. ο LO LO o -C -Ρ ω Φ S* ο£ Ο C Ο ·Ρ LO CM CO co CM r— (Λ O QE 3 O £- S(D cn CL r— Ό X ' o (Ο -Ρ CM LO LO CM i •p <0 (0 cc *—* > ο ε: ο ο CM CM CM Γ-* •P -c •P -P (O cn H~ E QJ I— S•r- «Ρ ο ω CL ε (0 X UI ο ο CM ω ο σ» CM Ο ο co co O o co CM Lf) O CL ε o o qj I— CM φ Ε -P »0· i—· re σ» x: U 133.69 g 1,6 di aminohexane 17.1 g of caprolactone cm) Perchloroethylene 1 cleaning torn wet _ r“ lo ion resistance (kp/5 60°C wash L . 3.6 J Separat Initial value 1“ 10 Fusion viscosity at 220°C (Pa.s) r“ Softening point i O O Cd r—

Claims (78)

1. WHAT WE CLAIM IS:1. A process of adhesively uniting a textile, siliconised fabric, leather or rubber substrate to the same, or a different substrate in this list, which comprises applying a polyester-amide comprising 5 units derivable from (a) a carboxylic acid component comprising (1) a dimerised fatty acid having a content of 70 to 100% by weight of dimeric fatty acid, (b) a dicarboxylic acid component comprising an aliphatic 10 unbranched dicarboxylic acid having from 6-13 carbon atoms, wherein the ratio of the carboxylic acid component (a) to carboxylic acid component (b) is from 0.05:1 to 5:1, calculated as carboxyl equivalents, (c) a diamine component comprising an aliphatic unbranched 15 diprimary diamine having from 6 to 12 carbon atoms, (d) caprolactam and/or ε-aminocaproic acid, and (e) caprolactone and/or e-hydroxycaproic acid, to a surface of one or both substrates and bringing the surfaces together, the

2. O polyester-amide being fused by the application of heat and pressure so that an adhesive bond is formed. - 2846226 2, A process as claimed in claim 1, wherein the amount of component (e) is from 0.05 to 1.0 mol per mol of component (d).

3. A process as claimed in claim 2, wherein the amount of component (e) is from 0.1 to 0.5 mol per mol of component (d). 5

4. A process as claimed in any one of claims 1 to 3, wherein the amount of component (d) is from 0.5 to 2.5 mols per mol of carboxyl groups of components (a) and (b),

5. A process as claimed in claim 4, wherein the amount of component (d) is from 0.8 to 2 mols per mol of carboxyl groups of components 10 (a) and (b).

6. A process as claimed in any one of claims 1 to 3, wherein the amount of component (d) is from 0,5 to 1.5 mols per mol of carboxyl groups of components (a) and (b).

7. A process as claimed in any one of claims 1 to 3, wherein the 15 amount of component (d) is more than 1.5, and up to 2.5, mols per mol of carboxyl groups of components (a) and (b).

8. A process as claimed in claim 7, wherein the amount of component (d) is from 1.5 to 2 mols per mol of carboxyl groups of components (a) and (b). 20

9. A process as claimed in any one of claims 1 to 8, wherein the carboxylic acid component (a) includes (2) a monocarboxylic - 29 ,., 46325 (monomeric) acid as chain breaker, wherein the total proportion of monocarboxylic acid in (al) and (a2) of component (a), calculated as carboxyl equivalents, is up to 50%,

10. A process as claimed in claim 9, wherein the monocarbo„ylic 5 acid (component-(a2))has from 12 to 22 carbon atoms.

11. A process as claimed in claim 10, wherein component (a2) comprises oleic, stearic, linoleic or linolenic acid, tall oil fatty acid or soya oil fatty acid.

12. A process as claimed in any one of claims 9 to 11, wherein the 10 total proportion of monomeric acid in components (al) and (a2), calculated as carboxyl equivalents, is more than 15%.

13. A process as claimed in any one of claims 1 to 12, wherein component (al) contains at least 90% by weight of dimeric fatty acid. 15

14. A process as claimed in claim 13, wherein component (al) contains from 2 to 6% by weight of trimeric fatty acid and from 0 to 1.5% by weight of monomeric fatty acid.

15. A process as claimed in any one of claims 1 to 14, wherein the fatty acid of component (al) is an unsaturated natural or synthetic 20 monobasic acid having 18 carbon atoms.

16. A process as claimed in claim 15, wherein component (al) is dimerised tall oil fatty acid, oleic acid, soya oil fatty acid, stearic, linoleic or linolenic acid. - 30 46225

17. A process as claimed in any one of claims 1 to 16, wherein the ratio of carboxylic acid component (a) to dicarboxylic acid component (b), calculated as carboxyl equivalents, is from 0.1:1 to 3:1. 5

18. A process as claimed in any one of claims 1 to 17, wherein component (b) comprises sebacic acid, adipic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid or brassylic acid or a mixture of two or more such compounds.

19. A process as claimed in claim 18, wherein component (b) 10 is sebacic acid.

20. A process as claimed in any one of claims 1 to 19, wherein component (c) comprises hexamethylenediamine, 1,9-diaminononane or 1,12-diaminododecane or a mixture of two or more such compounds

21. A process as claimed in claim 20, wherein component (c) is 15 hexamethylenediamine.

22. A process as claimed in claim 1, where the polyester-amdde is substantially as described in any one of the Example 1 to 4 herein.

23. A process as claimed in claim 1, wherein the poylester-amide 20 is substantially as described in any one of the Examples 6 to 9 herein.

24. A process as claimed in claim 1, wherein ι the polyester-amide - 31 46225 is substantially as described in Example 5 or Example 10 or Example 11 herein.

25. A process as claimed in any one of claims 1 to 24, wherein the polyester-amide has been prepared by condensing together components 5 (a), (b), (c), (d) and (e).

26. A process as claimed in any one of claim 1 to 24, wherein the polyester-amide has been prepared by reacting, in a first stage, some or all of the acid constituent (a) and (b) with some or all of component (d) and, in a second stage, reacting the product with 10 the remaining components.

27. A process as claimed in claim 26, wherein in preparing the polyester-amide some or all of component (al) is added in the first stage and components(b), (c)and (e) and, if any remain, (d) and (al) in the second stage, component (a2) if used being added at 15 either stage.

28. A process as claimed in claim 26, wherein all of components (al) is used in the first stage.

29. A process as claimed in claim 27, wherein component (a2) is added in the first stage. 20

30. A process as claimed in claim 26, wherein some or all of component (b) is used in the first stage and (al), (a2) if used, (c) and (e) and, if any remain, (d) and (b) in the second stage. - 32 46225

31. A process as claimed in claim 26, wherein some or all of component (a2) is used in the first stage and (al), (b), (c) and (e) and, if any remain, (d) and (a2) in the second stage.

32. A process as claimed in claim 25, wherein the polyester-amide 5 is, and has been prepared, substantially as described in any one of the Examples 1 to 4 herein,

33. A process as claimed in claim 25, wherein the polyesteramide is, and has been prepared, substantially as described in any one of the Examples 6 to 9 herein. 10

34. A process as claimed in claim 26, wherein the polyester-amide is, and has been prepared, substantially as described in Example 5 or Example 10 or Example 11 herein.

35. A process as claimed in any one of claims 1 to 34, wherein the polyester-amide has a fusion viscosity of from 25 to 600 Pa.s, 15 measured at 220°C.

36. A process as claimed in any one of claims 1 to 35, wherein the polyester-amide is applied in the form of a fusible adhesive composition containing an additive comprising a lubricant, plasticiser, optical brightener or antoxidant or a mixture of two 20 or more such additives. - 33 46225

37. A polyester-amide comprising units derivable from (a) a carboxylic acid component comprising (1) a dimerised fatty acid having a content of 70 to 100% by weight of dimeric fatty acid, and 5 (Z) a rnonocarboxylic (monomeric) acid as chain breaker, wherein the total proportion of rnonocarboxylic acid in (al) and (a2) of component (a), calculated as carboxyl equivalents, is up to 50%, (b) a dicarboxylic acid component comprising an aliphatic unbrancheddicarboxylic acid having from 6 to 13 carbon 10 atoms, wherein the ratio of the carboxylic acid component (a) to carboxylic acid component (b) is from 0.05:1 to 5:1, calculated as carboxyl equivalents, (c) a diamine component comprising an aliphatic unbranched 15 diprimary diamine having from 6 to 12 carbon atoms, (d) caprolactam and/or e-aminocaproic acid, and (e) caprolactone and/or ε-hydroxcaproic acid. - 34 46225

38. A polyester-amide as claimed in claim 37, wherein the amount of component (e) is from 0.05 to 1.0 mol per mol of component (d).

39. A polyester-amide as claimed in claim 38, wherein the amount of component (e) is from 0.1 to 0.5 mol per mol of component (d) 5

40. A polyester-amide as claimed in any one of claims 37 to 39, wherein the amount of component (d) is from 0.5 to 2.5 mols per mol of carboxyl groups of components (a) and (b).

41. A polyester-amide as claimed in claim 40, wherein the amount of component (d) is from 0.8 to 2 mols per mol of carboxyl groups 10 of components (a) and (b),

42. A polyester-amide as claimed in any one of claims 37 to 39, wherein the amount of component (d) is from 0.5 to 1.5 mols per mol of carboxyl groups of components (a) and (b).

43. Λ polyester-amide as claimed in any one of claims 37 to 39, 15 wherein the amount of component (d) is more than 1.5, and up to 2.5, mols per mol of carboxyl groups of components (a) and (b),

44. A polyester-amide as claimed in claim 43, wherein the amount of component (d) is from 1.5 to 2 mols per mol of carboxyl groups of components (a) and (b). 20 45. A polyester-amide as claimed in any one of claims 37 to 44, wherein the monocarboxylic acid (component (a2)) has from 12 - 35 to 22 carbon atoms.

4. Ο Λ Λ ϊ»

46. A polyester-amide as claimed in claim 45, wherein component (a2) comprises oleic, stearic, linoleic or linolenic acid, tall oil fatty acid or soya oil fatty acid.

47. A polyester-amide as claimed in any one of claims 37 to 46,

5. Wherein the total proportion of monomeric acid in components (al) and (a2), calculated as carboxyl equivalents, is more than 15%.

48. A polyester-amide as claimed in any one of claims 37 to 47, wherein component (al) contains at least 90% by weight of dimeric fatty acid.

6. 10 49. A polyester-amide as claimed in claim 48, wherein component (al) contains from 2 to 6% by weight of trimeric fatty acid and from 0 to 1.5% by weight of monomeric fatty acid.

50. A polyester-amide as claimed in any one of claims 37 to 49, wherein the fatty acid of component (al) is an unsaturated

7. 15 natural or synthetic monbasic acid having 18 carbon atoms.

51. ' A polyester-amide as claimed in claim 50, where component (al) is dimerised tall oil fatty acid, oleic acid, soya oil fatty acid, stearic, linoleic or linolenic acid,

52. A polyester-amide as claimed in any one of claims 37 to 51,

8. 20 wherein the ratio of carboxylic acid component (a) to dicarboxylic acid component (b), calculated as carboxyl equivalents, is from 0.1:1 to 3:1. - 36

53. A polyester-amide as claimed in any one of claims 37 to 52, wherein component (b) comprises sebacic acid, adipic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid or brassylic acid or a mixture of two or more such compounds. 5

54. A polyester-amide as claimed in claim 53, where component (b) is sebacic acid.

55. A polyester-amide as claimed in any one of claims 37 to 54, wherein component (c) comprises hexamethylenediamine, 1,9-diaminOononane or 1,12-diaminododecane or a mixture of two or more 10 such compounds.

56. A polyester-amide as claimed in claim 55, wherein component (c) is hexamethylenediamine.

57. A polyester-amide as claimed in claim 37 which is substantially as described in any one of the Examples 1 to 4 herein, 15

58, A polyester-amide as claimed in claim 37, which is substantially as described in any one of the Examples 6 to 9 herein.

59. A polyester-amide as claimed in any one of claims 37 to 58, which has been prepared by condensing together components (a), (b), (c), (d) and (e). 20

60. A polyester-amide as claimed in any one of claims 37 to 58, which has been prepared by reacting, in a first stage, some or all of the acid constituent (a) and (b) with some or all of component (d) of the first stage and, in a second stage, reacting the product/with the remaining components. - 37 46226

61. A polyester-amide as claimed in claim 60, wherein some or all of component (al) is added in the first stage and components (b), (c) and (e) and, if any remain, (d) and (al) in the second stage, component (a2) being added at either stage. 5

62. A polyester-amide as claimed in claim 60, wherein all of component (al) is used in the first stage.

63. A polyester.-amide as claimed in claim 61, wherein component (a2) is added in the first stage.

64. A polyester-amide as claimed in claim 60, wherein some or all 10 of component (b) is used in the first stage and (al), (a2), .(c) ' and (e) and, if any remain, (d) and (b) in the second stage.

65. A polyester-amide as claimed in claim 60, wherein some or all of component (a2) is used in the first stage and (al), (b), (c) and (e) and, if any remain, (d) and (a2) in the second stage. 15

66. A polyester-amide as claimed in claim 59, which is and which has been prepared substantially as described in any one of the Examples 1 to 4 herein.

67. A polyester-aniide as claimed in claim 59, which is and which has been prepared substantially as described in any one of the 20 Examples 6 to 9 herein.

68. A composition for the preparation of a polyester-amide, which -38 46225 comprises components (a), (b), (c), (d) and (e) as specified in any one of claims 37 to 56.

69. A process for the preparation of a polyester-amide as claimed in claim 37, which comprises condensing a composition as claimed 5 in claim 68.

70. A process as claimed in claim 69, which is carried out at a temperature in the range of from 200 to 290°C,

71. A process as claimed in claim 69, which is carried out substantially as described in any one of the Examples 1 to 4 herein. 10

72. A process as claimed in claim 69, which is carried out substantially as described in any one of the Examples 6 to 9 herein.

73. A process for the preparation of a polyester-amide as claimed in claim 37, which comprises reacting some or all of the acid constituent (a) and (b) with some or all of component (d) and the product so obtained 15 subsequently reacting/with the remaining components.

74. A process as claimed in claim 73, wherein all of component (al) is added in the first stage and components (b), (c) and (e) and (d) (if any) in the second stage, component (a2) being added at either stage. 20

75. A polyester-amide as claimed in claim 37, whenever prepared by a process as claimed in any one of claims 69 to 74. - 39

76. A polyester-amide as claimed in any one claims 37 to 67 and 75, which has a fusion viscosity of from 25 to 600 Pa.s, measured at 220°C.

77. A fusible adhesive composition suitable for textiles, 5 containing an additive comprising a lubricant, plasticiser, optical brightener or antioxidant or a mixture of two or more such additives.

78. Substrates which have been united by a process as claimed in any one of claims 1 to 36.