DE1769833A1 - Improved gluing process - Google Patents

Description

THE IXJHLOP CQMPAHY LIMITED, London N-W. 1, UK

Improved gluing process

I) Ie present invention relates to a Kurists toffpolymer iaat-Zuiianirocnaetzt, which is for gluing with a textile » suitable material and a method for gluing a textile »materialea with a plastic polymer.

the present invention is in a method ittra gluing a Taxtllmateriaies with a plastic · polymer Ina t the textile material with the plastic polymer ÄUßamtöengesetät, in the presence of resin-forming Deotandtello, which are in Äer La ^ c, with the formation of an aldehyde condensate to react »and then OefU ^ e heated to the pre-adhesive

ÖÖ9S31 / 1I? S

ORIGINAL

Examples of gelatinous plastic polymers which can be used in the present invention are polyvinyl chloride, polyvinyl acetate, vinyl chloride / vinyl acetate copolymers, ethylene / vinyl acetate polyacrylates, ethyl acetate / ethyl acrylate mixed polymers, polyethylene and ionic oxide. UB Ethylen / Nafci'iutiirtvsthaorylatMieohpolyinerisate, Die EwKoltinung "Kunsts to ff polymerisate ¹¹ does not include the fully soluble natural and synthetic rubbers» never HuB. SBU, Bufcylknutnohiike, or an unsaturated xthylene / propylene chloro-alcohols, an unsaturated Xthylene / propylene-chloro-alcoholic powder of the general form) A- (BA), In the Λ ain «n alchtalastoiKeren BlooU with a temperature for the second order phase transition holier than

"Iiioitt duruh.'tithnlttlittlihen Moleltularßewicht b" 10 000 "dni.itoJ; t and U represents an elastoner polymer look with an oil temperature lower than 10 ° C and a molecular weight of 25,000 to 1,000,000, and η is an integer from 1 to 10.

The KurtQ "titof!" Polymerisat is contacted with the textile material in a range of constituents which are able to reagloron with the formation of a permeable aldehyde condom, in order to! suitable ingredients are a mixture of a formaldehyde generator and a

009831/1679

BATH ORIGINAL

Hydroxy compound. The Fortnaldehyde generator is a compound which, when heated, supplies formaldehyde and preferably a compound which is practically stable ^{up to a temperature of at least 100 4 C.} A particularly suitable formaldehyde generator is hexamethylenetetramine, although other formaldehyde generators, for example hexamethoxymethylrnelamine, lauryl oxymethylpyridinium chloride, cetyloxymethylpyrldlniuniohlorld, xthyloxyraethylpyridinium halide and polymers of the most stable formaldehyde groups can be used, as well as polymers of the most stable formaldehyde groups. Novolao hard resins can also be used in any case. The amount of fonaaldehyde generator used can suitably be 0.1 to 10 parts by weight and preferably 1.0 to 2 parts by weight per 100 parts by weight of plastic polymer.

The aromatic hydroxy compound which can be used can be a monohydroxy compound, but is preferably a compound formation «which contains two hydroxyl groups, and it is special it is preferred that the hydroxyl groups are meta ^ stallung to one another stand. Examples of suitable aromatic hydroxy compounds are resorcinol and!. ^ - dihydroxynaphthalene «If desired, melamine or urea or a compound which when heated, one of these two compounds is produced, instead of the aromatic hydroxy compound; be used.

009831/1679

BATH ORIGINAL

The amount of aromatic hydroxy compound or others Compound which is used to react with the formaldehyde generator may suitably represent 0.1 to 10 parts and preferably 1.0 to 4.0 parts per 100 parts of plastic polymer as a precaution sillolum dioxide is added to the resin-forming ingredients.

The aldehyde resin forming ingredients are preferred mixed together with the plastic polymer and the textile material is then applied to the resulting polymer composition. Alternatively or in addition to this, can the textile material can be provided with an upper layer of one or all of the aldehyde-resin-forming constituents and If required, the coating can be dried before the textile material is contacted with the plastic polymer.

If desired, the plastic polymer leat can be mixed with other additives, such as pigments, before heating and PUlI fabrics. In addition, the polymer was called While the textile material is hardening or in the process of being bonded, the plastic polyeneer can sdt Hardeners are mixed »e.g. ethylene thiourea and Magnetic oxide in the case of polyvinyl chloride and hardeners that deliver free radicals, such as diouayl peroxide 1 «case of

009831/1679

BATH ORIGINAL

«Μ * Λ <* ϊ

Xthylene / vinyl acetate mixed polymers. If the plastic polymer is a polyvinyl chloride, then e3 is preferably plasticized with the aid of a plasticizer, e.g. a Diallyl phthalate, and it can also be stabilized with the help of a stabilizer, e.g. lead carbonate or tribasic Lead sulfate.

The textile material can ζ, B * a polyester * a polyamide, rayon or cotton 3ind be "Suitable polyester polyethylene terephthalate, as is commercially available as terylene or Daoron, and poly-1 _t 4 ~ cyolohexylendimethylen" terephthalate _u Examples of suitable polyamides are Nylon 6, nylon 66 _y nylon 610 and aromatiaaha nylon types * v / ie those commercially available as Nomex HT-I. If a polyester * is used, its bonding with the plastic polymer can often be improved by removing it before joining exposing the ^ Kunststoffpolymerisat a OlUhentladung or an ultraviolet irradiation "a suitable tent for the Glühontladungsbehändlung would 1 second to 10 minutes and a suitable period for the ultraviolet treatment would be 15 minutes to 2 hours, respectively at a distance of l _k 27 om (l / 2 inch) from the ultraviolet well.

The textile material can, for example, in the form of a continuous woven fabric or one or more fibers,

009831/1679

BATH ORIGINAL

Threads or cords are present. The procedure of the present " the invention can be used with particular advantage for the manufacture of textile-reinforced flexible goods » e.g. straps * hoses, tarpaulins »car mats and cable sheaths.

The invention is illustrated by the following examples,

where the following abbreviations are used

NyI * nylon 66 cord with a denier of 2/840. ^Ray's viscose rayon "Cord with a denier of 2/1650.

A-NyI = aromatic nylon cord with a denier of 2/10/200, commercially available as Noroax HT-I.

ET c polyethylene terephthalate cord with a denier of 2/1000 (untreated).

V75-ET * Polyethylene terephthalate cord with a denier of

2/1000, which during production with a spinning equipment (primer adhesive) has been treated.

IUV-ET * Polyethylene terephthalate cord with a denier of 2 / IOOO, the one with two 45.7 om long (18 inch) Phillips (57415PAO TUV) 15 watt tubes, 1.9 cm 3/4 inch apart and 1/2 inch from the cord, UV-irradiated in air for 50 minutes.

2UV-ET «as for IUV-ET, but with one treatment 60 minutes instead of 30 minutes.

OD-ET * polyethylene terephthalate * = cord with a denier of 2/10000, the 5 second of an oil charge was exposed by passing it through an OlUhentla » dungaröhro hindu led, the air at a druok contained between 0.8 and 1.0 mm Hg.

PP ■ polypropylene.

009831/1679 bad original

In these examples, the adhesion between textile material and plastic polymerizates was tested in accordance with the "pull-through test" (J, 0. Wood, Trans. IRI, Vol. 32, Mo. 1, pages 1-18, 1956). In this test, the textile cords were glued at right angles to the length of a sheet of plastic-polymer composition, the embedded cord length was 1 cm, and the force required to pull cords from this sheet was determined (kg / cm). In general, the results are the average of 10 such tests. The test speed was 25.4 cm / minute (10 ineh / fclinute).

example 1

This example illustrates the improved adhesion of textile materials on an uninjured polyvinyl chloride = Composition.

The used plastic-Polyraerisatzusaramensetzimgon be » saden the recipes given in Table I below, all values are parts by weight:

ι 009831/1679

BATH ORIGINAL

- 8 Table I.

A. 0 B. C. D. E. 100, 0 100.0 100.0 100.0 100.0 50, 0 50.0 50.0 50.0 50.0 8th, 8.0 8.0 8.0 8.0 0 4.0 2.0 1.0 0 rain 0 2.6 1 * 5 0.75 1.5 0 0 0 0 3 * 0

Polyvinyl chloride

Plasticizers

stabilizer

Resorcinol

Hexamethylenetetramine

Phloroglucine

The polyvinyl chloride was a high molecular polymer " weight, commercially available as Geon 121, the plasticizer was a mixture of diheptyl * dioctyl «and dinonyl phthalates, commercially available as dialkyl "7S" phthalate and the stabilizer was a paste of lead carbonate in a plasticizer for polyvinyl chloride »

Each of the compositions was mixed on a three-roller dye mill, and then heated for 20 minutes at ITX) ⁰ C in contact with various textile cords. The strengths of the bonds (kg / cm) between the cords and the assemblies are given in Table II:

009831/1679

BATH ORIGINAL

T a b e 1 1 e "-il kg / cm (lb / cm)

Together- ""

Settlement NyI Ray A-NyI ET V75-ET IUV-ET OD-ET

4.0 7.6 12.9 4.67 3.9 3.94 3.72

(8.9) (16.8) (28.5) (10.3) (8.6) (8.7) (8.2)

9.75 11.9. 17.4 5.48 8.75 7 * 89

(21.6) (26.2) ⁺ (38.5) (12.1) (19.3) (17.4)

C 11.7 11.1 18.96 6.57 11.48 10.95 8.25

(25.9) (24.4) (41.8) (14.5) (25.4) (24.1) (l8.2)

D 11.6 11.04 15.45 5.12 9.98 7.2

(25.5) (24.3) (34.1) (11.3) (22.0) (15.5)

E 7.3 9.29 14.68 ~ 5.26 4.59 6.1

(16.1) (20.5) (32.4) (11.6) (10.1) (13.7)

⁺ 'The cords broke before the bond failed-

Example 2

U _r --- TW 11 mn ■ um *

This example illustrates the improved adhesion of Texti! Materials on a cross-linked polyvinyl chloride * Composition.

The plastic polymer compositions used had the formulations given in Table III, all fourths are weight points:

009831/1679

«AD ORIGINAL

- ίο -

Table III

100.0 100.0 6 * 0.0 60.0 15.0 15.0 3.0 3.0 0 2.0 0 1.5

Polyvinyl chloride Weichmaoher stabilizer Ethylene thioharoate Magnesia

Resorcinol

Hexamethylenetetramine

The polyvinyl chloride was a high molecular weight plastisol resin, commercially available as Korvinyl P2 _r the plasticizer was a mixture of diheptyl and dinonyl phthalates, commercially available as dialkyl ~ 79 »phthalate and the stabilizer was tribasic lead sulfate.

The compositions were made on a three-roll dye Rolling mill mixed and then in contact with different textile north heated to 180 ° C for 20 minutes. The strengths of the Adhesions (kg / cm) between the cords and the joint « Settlements are given in Table IV:

009831/1679

BAO ORlGJNAL

- li -

Table IV kg / cm (lb / cm)

Together
settlement NyI. Ray A = NyI P. 5.49
(12.1) 8.2
(18.1) 16.8
(37.0) G 9.98
(22.0) 9.58
(21.1) 18.4
(40.7) Example 3

This example illustrates the improved adhesion of textile materials to an ethylene / ylnyl acetate copolymer composition

The plastic polymer additives used had the formulations given in Table V, all values are parts by weight.

Table V

HI

Ethylene-vinyl acetate mixed polymer 100.0 100.0

Resorcinol 0 2.0

Hexamethylenetetramine 0 1.5

The ethylene / vinyl acetate copolymer contained 17 vinyl acetate units, possessed a sea flow index (ASTM D1238-57T) of 1.4 g / 10 minutes and had a density of 0.94J.

009831/1679

BAD ORiGINAi.

The compositions were mixed on a hot roll mill at 105 to Ia) ⁰ C and then heated to l60 ° C in the contact with various textile cords for 20 minutes. The strength of the bond (kg / cm) between the cords and the compositions are given in Table VI:

Table VI kg / cm (lb / cm)

Composition MyI Ray A-NyI ET V75-ET 2ÜV-ET OD-ET

H 3.96 4.76 6.66 6.66 6.52 7 * 3 7.8? (8.7) (10.5) (14.7) (14.7) (14 * 4) (16.1) (17.4)

I 12.16. 12.11 18.1 12.79 14.86 12.88 + 13.56 +

(26.8) ⁺ (26.7) (40.0) (28.2) (32.8) (28.4) (29.8)

⁺ 'The cords tore before the bond failed.

Example 4

This example illustrates the improved adhesion P of textile materials on an ethylene / ethyl acrylate mixed poly · ■ · merl phrase composition.

The plastic polymer compositions used are the recipes given in Table VII were used, all values are values:

009831/1679

BATH ORIGINAL Table VII

J K

Ethylene-ethyl acrylate copolymer 100.0 100.0 Resorcinol 0 2.0

Hexamethylenetetramine 0 1.5

The ethylene / ethyl acrylate "mixture" contained 15% ethyl aorylate units, had a melt flow index (ASTM D1238 "57T) of 6.0 g / 10 minutes and a density of 0.931 g / cctn. The compositions were applied to a hot rolling mill bai mixed and 105 to 110 ^e C then, after contact with different textile cords 20 minutes at l60 ^e C heated "The strength of the adhesive bond (kg / oin) between the cords and the compositions shown in Table VIII :

Table VIII kg / cm (lfo / cm)

Together » Build

Setting NyI Ray A-KyI ET V75-ET 2UV-ET CO) -ET wool

J 4.3 5.35 10.4 6.08 3 * 85 7 * 62 7 »26 4.6> +

(9.5) (11.8) (23.0) (13.4) (8.5) (16.8) (l6.0) (10.2)

K 11.26 10.71 16.8 10.45 13.3 9 * 29 11.3 6.12-i- «·

(24.8) (23.7) (37.0) (23.1) (29.2) (20.5) (24.9) (.13.5)

These results were obtained with 1/2 nrii samples, to avoid tearing the cord *

009831/1679

BATH ORIGINAL

Example 5

This example illustrates the improved adhesion of textile materials to an ionic core assembly. The plastic polymer compositions used were based on the formulations given in Table IX, all values are weighting points:

Table IX

L M

Ionomer 100.0 100.0

Resorcinol 0 2.0

Hexamethylenetetramine 0 1.5

The ionomer was a copolymer of ethylene and methacrylic acid with a content of 9 $ methacrylic acid units, of to which 6o # in the form of the sodium salt leave "Soin Schmelz flu3index (ASTM D1238-57T) was 2.0 and its density was 0.94 g / ocm.

The compositions were mixed on a roll mill at Heisson 115 to 120 ⁰ C and then, after contact with different Textiloorden heated for 20 minutes at l60 ° C. The strength of the bond (kg / cm) between the cords and the compositions are given in Table X;

009831/1679

BATH ORIGINAL

- 15 -

Table X kg / cm (lb / cni)

Collectively

setting NyI A-NyI ET V75-ET 2ÜV-ET GD-ET

L 7 ** 8 13.78 7.8 12.83 9.8 9.71

(16.5) (30.4) (17.2) (2§, 3) (21.6) (21.4)

M 11.48. 15.18 10.62 3.56. 11.85 11.17. (25.4) ⁺ (33.4) (23.5) (29.8) ⁺ (26.1) (24.6) +

⁺ 'The cords tore before the bond failed.

Example 6

This example illustrates the improved adhesion of text materials to a polyethylene composition. The plastic polymer compositions used had the recipes given in Table XI * all values are Parts by weight:

Table XI

H 0

Polyethylene 100.0 100.0

Resorcinol 0 2.0

Hexamethylenetetramine 0 1.5

The polyethylene had a melt flow index (ASTM D1238-57T) of 200 g / 10 minutes and a density of 0.915 g / cc. The compositions were mixed and on a hot roll mill at 95 to 100 ⁰ C then, after contact with different Textilcoröen in the case of composition M 20 minutes at l60 ° C

009831/1679

BATH ORIGINAL

and in the case of the composition N ^{heated to 140 °} C. for 50 minutes. ^ Ie strength of the bond (kg / cm) between the cords and the compositions are given in Table XII:

Table XII kg / cm (lb / cm)

Together ~

setting NyI Ray A-NyI ET V75-ET 2UV-ET OD-ET PP

N 3.68 5.04 10.34 3.58 2.54 3.58 3.36 4.48 (8.1) (11.1) (22.8) (7.9) (5.6) (7.9) (7.4) (9.9)

0 7.57 8.47 13.29 7.71 6.85 7 * 2 7.2 6.03 (16.7) (18.7) (29.2) (17, O) (15.1) (15.9) (15.9) (13.3)

Example 7

Example 1 was repeated using polyvinyl chloride, but the resorcinol is available from ilovo Iac resins, available at the trademark CELLOBOND. The compositions, some of which also contain hexamethylenetetramine are given in Table XIII:

Table XIII Connection PQR S T

Geon 121 100.0 100.0 100.0 100.0 100.0

DAP 50.0 50.0 50.0 50.0 50.0

White lead paste 8.0 8.0 8.0 8.0 8.0

Cellobond H831 0 3.5 0 0 0

Ceilobond H832 0 0 3.2 0 0

Cellobond H833 0 0 0 3.2 0

Cellobond H35 0 0 0 0 3.5 Hexamethyl 0 0 0.3 0.3 O

tetramin 009831/1679

BATH ORIGINAL

The strengths of the corresponding bonds are shown below Table XIV indicated:

Table XIV kg / cm (lb / cm)

P $ R S T

NyI 4.0 8.25 H * ° ⁸ 9.8 6.62

(8.9) (18.2) (24.2) (21.6) (i4.6)

A-NyI 12.92 17.11 15.0 l6.57 15.75

(28.5) (57.7) (55.0) (56.6) (30.5)

Ray 6.40 15.47 12.25 9.47 10.07

(14.1) (29.6) (27.1) (20.9) (22.2)

ET 4.67 5.8 5.94 5.75 5.57

(10.3) (12.8) (8.7) (12.7) (12.5)

UV-ET 5.94 6.75 6.85 7.11 6.08

(8.7) (14.9) (15.1) (15.7) (15.4)

OD-ET 3.72 7.16 6.66 7 * 80 i, 26

(8.2) (15.8) (14.7) (li.2) (11.6)

V75-ET 5.9 9.25 6.75 3.43 6.48

(8.6) (20.4) (14.9) (18.6) (14.3)

Example 8

Using an acid catalyzed system instead of the alkaline hexamesthylenetetramine system, Example .1 repeated.

009831/1679 sad original

Table XV

U V W. Geon 100.0 100.0 100.0 DAP 50.0 50.0 50.0 Lead white pa3te 8.0 8.0 8.0 Paraformaldehyde 0 2.0 1.5 Anhydrous ferric chloride 0 1.0 1.0 Resorcinol 0 2.0 0 Phloroglucine 0 0 3.0

The strength of the bonds is shown in Table XVI below specified:

Table XVI kg / cm (lb / cra)

AND MANY MORE

NyI 4.0 9.2 10.45

(8.9) (20.3) (23.1)

A NYI 12.92 18.37 17.97

(28.5) (40.6) (39.6)

Ray 6.4 12.6 19.34

(14.1) (27.9) (22.8)

ET 10.67 4.08 5.53

(10.3) (9.0) (12.2)

UV-ET 8.94 7.93 8.29

(8.7) (17.5) (18.3)

OD-ET 3.72 8.47 9.93

(8.2) (18.7) (21.9)

V75-ET 3.9 8.34 9.38

(8.6) (18.4) (20.7)

009831/1679 ^BAD original

Example 9

Example 1 was repeated using a phenolic resin which had not been thermoset, ie too little formaldehyde was present.

Table XVII

X Y Z AA ⁺ AWAY* Geon 121 100.0 100.0 100.0 100.0 100.0 DAP 50.0 50.0 50.0 50.0 50.0 White lead paste 8.0 8.0 8.0 8.0 8.0 Resorcinol 0 3 * 0 0 0 Hexamethylenetetramine 0 0.65 0.5 0 0 Cellobond H833 0 0 0 5 * 5 0 FRJ-631 0 0 0 0

The strength of the bonds is shown in the table below XVIII stated:

009831/1679

8AD ORIGINAL

Table XVIII kg / cra (lb / cm)

Z AA * AB ⁺

NyI 4.03 9.58 10.07 5, O8 5 * 8

4.03 9.58 10.07 5.08 5 * 8

(8.9) (21.1) (22.2) (11.2) (12.8)

A-NyI. 12.92 17.07 15.9 12.2 12.7

I'M ^{<57 6)}

(28.5) (37.6) (35.0) (27.0) (28.0)

Ray (14.1) 17 * 02 15.45 8.19 6.85

(37.5) (34.1) (17.9) (15.1)

ET 4.67 4.13 4.67 4.44 5.8

(10.3) (9.1) (10.3) (9.8) (12.8)

UV-ET 3.94 7.89 9.16 5.44 6.3

(8.7) U7.4) (20.2) (12.0) (13.9)

OD-ET 3.72 6.98 10.02 6.08 6.26

(8.2) (15.4) (22.1) (13.4) (13.8)

V75-ET 3.9 10.67 10.3 4.44 6.71

(8.6) (23.6) (22.7) (9.8) (l4.8)

* 'Compositions in which the resin before adding into which plastic has been preformed.

009831/1679

BAD ORJGJNAk

Claims (1)

Claims BSBESSSSSSBSeSSSSSBBSSaBSSSSBi 1. Method of gluing a textile material with a Plastic polymer, characterized in that the textile and the polymerizate is put together in the presence of resin-forming constituents which are capable of reacting to form an aldehyde condensation resin, and that OefUge is heated «in order to carry out the bonding. 2. The method according to claim 1, characterized in that the resin-forming ingredients are an aromatic hydroxy compound and a formaldehyde generator. 3. The method according to claim 2, characterized * that the aromatic hydroxy compound has at least two hydroxy groups in meta-3tposition to each other » 4. The method according to claim 3, characterized in that »that the aromatic hydroxy compound resorcinol or 1,3'-dihydroxynaphthalene 1st. 5. Process according to one of Claims 2-4, characterized in that 0.1 to 10 parts by weight of aromatic hydroxyl Compound per 100 parts of plastic polymer are available. 009831/1679 «AD ORIGINAL 6. The method naoh claim 5, characterized in that 1-4 parts by weight of aromatic hydroxy compound are present per 100 parts of plastic polymer 7. Process according to one of Claims 2-6, characterized in that the formaldehyde generator is hexamethylenetetramine. 8. The method according to any ^ r claims 2-6, characterized in that the formaldehyde generator is hexamethoxymethylmelamine, lauryloxymethylpyridiniuroohlorid, cetyloxymethylpyridiniumohlorid or Xthyloxymethylpyrldinluuohlorld 1st. 9. Process according to one of Claims 2-6, characterized in that the formaldehyde generator is polymeric formaldehyde 1st. 10. The method naoh one of claims 2-9 »characterized in that 0.1 to 10 Qewiohtsteile formaldehyde generator are present per 100 parts of plastic polymer. 11. The method according to Anspruoh 10, characterized in that 1 to 3 parts of formaldehyde generator per 100 parts of plastic polymer are present. 12. The method naoh one of the tests 1-11, thereby gekennaelohnet that silicon dioxide su dan harablldenden Beatandteile 009831/1679 • AD ORIGINAL will be added. Method according to one of claims 1 - 12 »characterized in that the textile material is a polyester» polyamide » Is rayon or cotton. 14. The method according to claim 15, characterized in »that The textile material is a polyester "that with a plasma" such as an oil charge, or by ultraviolet radiation has been pretreated. «Method according to one of claims 1 - 14, characterized in that the plastic polymer is a polymer from vinyl chloride »vinyl acetate» xthylene or from mixed polymer! sowed of it 1st « l6. Process according to one of Claims 1 to 14, characterized in that the plastic polymer is a copolymer of ethylene with ethyl acrylate or sodium methacrylate is. 009831/1679 SAD ORIGINAL