KR800000049B1 - Process for improving the adhesion of high-temperature-resistant aromatic poly-1,3,4-oxadiajole filaments to rubber - Google Patents

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Description

Method for improving the adhesion of high temperature resistant aromatic poly-1,3,4-oxadiazole fibers to rubber

The present invention provides a method for improving the adhesion of high-temperature aromatic poly-1,3,4-oxadiazole filaments to rubber and a community in which rubber-coated fibers, spun yarns, filaments and knits, woven and nonwoven fabrics prepared therefrom ), A method for use in materials and objects such as hoses, electric belts, conveyor belts and tires.

In the present invention, the term high temperature aromatic poly-1,3,4-oxadiazole filament refers to a polymer solution having high melting point and decomposition point of 325 ° C. or higher along the filament axis, without spinning from the polymer melt. In principle, it refers to linear high molecular weight aromatic poly-1,3,4-oxadiazole filaments obtained by spinning.

The linear high molecular weight aromatic poly-1,3,4-oxadiazole is obtained by reacting hydrazine or a suitable inorganic hydrazine salt with an aromatic dicarboxylic acid or a derivative of this carboxylic acid. Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, 5-methylisophthalic acid, 5-chloro-isophthalic acid, 4-chloroisophthalic acid, tetrachloroterephthalic acid, naphthalene-1,4-1,5-or-2,6-di Carboxylic acids, benzophenone-4.4'-dicarboxylic acids, terephthalophenone-4,4'-dicarboxylic acids, azobenzene-4,4'-dicarboxylic acids, whether or not naturally colored but colorless starting materials are preferred Functional derivatives such as alkali salts, acid chlorides, amides and nitriles. All these compounds can be used singly or as mixtures /. Particularly preferred high molecular weight linear aromatic poly-1,3,4-oxadiazoles are those which use terephthalic acid, isophthalic acid or a mixture of terephthalic acid and isophthalic acid as aromatic dicarboxylic acids, ie polyphenylene-1,3,4-oxa Diazole. Fibers, filaments, yarns and fabrics made from high molecular weight linear aromatic poly-1,3,4-oxadiazoles have excellent mechanical and thermomechanical strength and chemical properties, so they are not subject to stress such as belt hoses, conveyor belts and ties. Used for exposed rubber products. It has high heat resistance, high strength and high mechanical coefficient, so it can be used for tires. However, this approach is problematic because the adhesion of aromatic poly-1,3,4-oxadiazoles to rubber is worse than for other synthetic polymeric materials. When using nylon or aliphatic polyamide, another treatment process has already been necessary, but before the cord or cord fabric made of nylon is combined with rubber, it is immersed in a soaking bath called "Dip". Indeed, this problem has been solved.

This deposition is an aqueous dispersion called a soaking bath that contains a mixture of resorcinol formaldehyde architecture and latex (RFL bath). This type of deposition bath deposits the filaments or cord fabrics before they are introduced into the rubber composition, and the treated mixture is dried and heat treated to fix it. Manipulation in the case of such nylons is described in the literature (Mechanics of Pneumatic Tires, NBS Monograph Nr 122, p. 274, 1971).

A typical immersion bath of this kind consists of a dispersed phase of 428 parts (weight) of 41% Gentac Latex, 107 parts (weight) of water and 465 parts (weight) of 6.5% resorcinol / formaldehyde solution. This is obtained by dissolving 0.3 part (weight) of caustic soda, 11 parts (weight) of resorcinol, and 16.2 parts (weight) of formarin solution (37% aqueous solution of formalin) in 238.4 parts (weight) of water at room temperature.

However, even after such treatment process, it is possible to obtain complete and satisfactory results with sufficient adhesive strength for rubber in case of nylon filament, but in case of filament made of aromatic poly-1,3,4-oxadiazole, Adhesion strength is not sufficient. In other words, aromatic poly-1,3,4-oxadiazole filaments can be extracted from rubber with very little force. Of course, if the adhesive strength is not sufficient, it is very disadvantageous to use aromatic poly-1,3,4-oxadiazole filaments, fiber spun yarns, and fabrics in impact rubber products. The action of reinforcing with such filaments is effective because it lacks sufficient adhesive force.

However, the present inventors have found that when at least one N-glycidyl compound or N-glycidyl compound is applied to an aromatic poly-1,3,4-oxadiazole filament material, the adhesive strength is sufficiently and completely basic. It has been found that the adhesion to the increased to obtain a good product.

Thus, the present invention applies an N-glycidyl compound or a mixture of N-glycidyl compounds as an adhesive to aromatic poly-1,3,4-oxadiazole filaments and, if necessary, then resorcinol / formaldehyde. The present invention relates to a method for improving the adhesion of high temperature resistant aromatic poly-1,3,4-oxazole filaments by treating with a latex bath. One or more N-glycidyl compounds may be applied to the aromatic poly 1,3,4-oxadiazole filaments and then treated with a normal dipping bath.

기를 함유하는 모든 질소화합물이며, 이러한 화합물은 예를들면 1급 및 2급 지방족, 환상지방족, 아르알라파틱, 방향족 및 사이클로모노 및 폴리아민과 아마이드 즉 카보-및 설포아마이드와 락탐이미드 및 우레아, 티오우레아, 구아니딘, 비유제트, 멘라민, 우레탄등에서 유도할 수 있다.Essentially suitable as an N-glycidyl compound is at least one nitrogen atom

And all nitrogenous compounds containing groups, such as primary and secondary aliphatic, cycloaliphatic, aralapatic, aromatic and cyclomono and polyamines and amides, such as carbo- and sulfoamides and lactamides and ureas, thio It can be derived from urea, guanidine, biuzet, menramine, urethane, and the like.

Particularly suitable N-glycidyl compounds are as follows.

N, N-bis-glycidyl-butylamine-cyclohexylamine,

N, N, N ', N'-tetraglycidyl-tetramethylenediamine

N, N, N ', N'-tetraglycidyl hexamethylenediamine,

N, N, N ', N'-tetraglycidyl-3-ethylamino-3,5,5-trimethylcyclohexylamine,

N, N, N ', N'-tetraglycidyl- (1,3- and 1,4-bis-aminomethyl) -benzene and N, N-bis-glycidyl-aniline, -toluidine, -P A mixture of chloroaniline,

N, N, O-triglycidyl-m-and-P-aminophenol,

N, N, N ', N'-tetraglycidyl-m- and -P-phenylenediamine,

N, N, N'N'-tetraglycidyl-2,2-bis- (P-aminophenyl) -propane,

N, N, N'N'-tetraglycidyl-4,4'-diaminodiphenylmethane,

N, N, N'N'-tetraglycidylbenzidine,

N, N-bis-glycidylbenzoic acid amide,

N, N-bis-glycidylbenzenesulfonate amide,

N, N, N'N'-tetraglycidyl sulfanilinic acid amide,

N, N, S-triglycidylaminothiophenol,

N, N-bis-glycidyl acrylic acid amide,

N-glycidyl caprolactam,

N, N, N'N'-tetraglycidyl-urea, -thiourea, -guanidine

N, N, N ', N', N ", N" -hexaglycidylmelamine,

N, N, O-triglycidyl-aminoethanol, -aminopropanol,

N, O, O-triglycidyl diethanolamine,

N, N-bis-glycidylaminoacetic acid glycid ester,

N, N-bis-glycidyl-P-aminobenzoic acid glycid ester

N, N, N ', N'-tetraglycidyl arylenediamine and especially N, N, N', N'-tetraglycidyl-P-phenylenediamine are known to be the most effective N-glycidyl compounds .

ttingen, Heidelberg, 페지 367(1958).The preparation of N-glycidyl compounds is well known and they can be easily prepared by reacting epihalogen hydrin with a suitable compound having at least one> -H or -NH ₂ group, followed by alkali treatment. Epoxydverbindungen und Epoxydharze (epoxy compound and epoxy resin) by AM Pauguin, Springer Verlag, Berlin, G

ttingen, Heidelberg, p. 367 (1958).

Significantly improving the adhesion strength to rubber by introducing N-glycidyl compounds onto aromatic poly-1,3,4-oxadiazole filaments, these filaments are essentially polymerized, filament-produced and chemically structured. In addition to being different, it is surprising that the thermal, mechanical, physical and physicochemical properties of these compounds are very different from polyesters.

Polyethylene terephthalate, for example, rapidly decomposes in concentrated sulfuric acid and has a melting point below 270 ° C, whereas aromatic poly-1,3,4-oxadiazole is dissolved in concentrated sulfuric acid and does not decompose when dissolved. . And melting point and decomposition point is more than 325 ℃ and does not dissolve without decomposition phenomenon.

The application of the N-glycidyl compound to the aromatic poly-1,3,4-oxadiazole filaments is very simple and does not cost any more. The liquid N-glycidyl compound can be applied simply by depositing and removing the filament from the application roll or the deposition tank. Of course, the N-glycidyl compound can be sprayed or applied in other suitable ways. N-glycidyl compounds can be simply applied as a solution (eg water soluble emozone).

Moreover, the concentration of N-glycidyl compound is not a decisive factor in the quality of the product and the amount can be applied in a wide range. The concentration can be applied once in a range of 0.001% or more and less than 10% by weight of the N- glycidyl compound.

In order to make the reaction process more convenient, it is necessary to adjust the filament, for example, to make a good fiber bond or to improve the friction state in order to reduce proper charging.

Another advantageous method for applying the N-glycidyl compound is to apply it with the adhesive at the same time as it is prepared and of course can also be applied continuously. If necessary, simultaneous application of solution or emulsifier can be applied without adversely affecting the improvement of adhesion to rubber. The amount of N-glycidyl compound to be applied is not a decisive factor in product quality and can be applied in a wide range without adversely affecting the improved adhesive properties. When only 0.001% (weight) of N-glycidyl compound or N-glycidyl compound mixture (corresponding to 0.001 part (weight) of N-glycidyl compound relative to 100 parts (weight) of filaments), the effect is relatively Very few This lower limit can be applied from the value up to several percent, but this upper limit should be taken into account economically. In particular, the amount of the N-glycidyl compound or a mixture of these compounds to be applied is about 0.05 to 5% based on the amount of filament.

The applied adhesive or its adjuvant is dried and heat bonded to the filament material. In special cases, their application is carried out in a pre-heated state after stretching the aromatic polyphenylene-1,3,4-oxadiazole. The treatment step is basically to improve the mechanical properties of this fiber material. In this way, a secondary treatment reaction for drying or fixing the adhesive is unnecessary, and the process is therefore simpler and cheaper by using N-glycidyl compounds.

N-glycidyl compounds applied to improve adhesion strength to rubber do not affect other properties of aromatic polyphenylene-1,3,4-oxadiazole filaments. They are not rough or hard and can be done in a conventional manner to twist or bind.

The adhesive force between filament and rubber is determined by known U-test method Rubber Chemistry and Technology, Vol. 42, p. 245 (1967). The test puts the filament into the rubber test object, then secures the rubber body and pulls out the loaded filament, and measures the value. The force required to extract the filament from the rubber body is measured repeatedly and averaged 10 times. The force measured in this way is divided by the area of the contact surface between rubber and filament to determine the adhesive strength between rubber and filament.

Next, examples of the present invention are exemplified, which does not impose any limitation on the present invention.

Example 1 (Comparative Example without N-glycidyl compound)

10 parts (weight) of poly-P-phenylene-1,3,4-oxadiazole (weight) and 90 parts of concentrated sulfuric acid through a spinneret having 400 nozzles having a diameter of 0.120 mm at a pressure of 2.7 atm at 30 ° C. Weight) is spun into dimethylformamide solution. After passing the condensation passage of 165cm length, the spun yarn is introduced into a hot water bath of 80 ℃ and 125cm length and stretched according to the usual method. The spun yarn is wound in a paddle and washed overnight in running water and dried at 70 ° C. In order to improve the mechanical properties, the filament is filled with nitrogen, passed through a heating tube having a length of 115 cm and an internal temperature of 430 ° C., followed by post-heating treatment. The filaments are twisted in a conventional manner and then passed through a bath consisting of an emulsion of resorcinol / formaldehyde and latex, then the mixture is dried at 160 ° C. and fused at 220 ° C. Such operation is carried out as it is with nylon. The twisted yarn treated in this way is vulcanized and commercialized into a conventional rubber composition composed of the following components.

50 parts of natural rubber (weight)

50 parts of polybutadiene rubber (PBR) (weight)

4 parts of zinc oxide (weight)

20 parts of carbon black (weight)

1.5 parts by weight of phenyl-β-naphthylamine

Sulfur 2.5 parts (weight)

0.7 parts (weight) of VULCAFOR-HBS (Imperial Chemical) company

The force required to remove the yarn from the rubber at room temperature is measured by the known U test method. The force per unit of contact surface between rubber and aromatic yarn was a measure of the bond strength between yarn and rubber, which was only 9.2 kg / cm 2.

Example 2

The same method as in Example 1, except that the filament was passed through a dipping tank containing 0.10% (by weight) of N, N, N ', N'-tetra glycidyl-P-phenylenediamine before heating after heating. Do it. The weld strength value for rubber is 49.4 kg / cm 2.

Example 3-10

The N-glycidyl compound in the following table is used as a water emulsion zone containing 2.5%, and 1,200 denier thickness poly-P-phenylene-1,3,4-oxadiazole 850 filaments are applied to the constructed filaments. The applied N-glycidyl compound is controlled by the rotational speed of Lola. The filament is heat-treated at 250 ° C. to dry the N-glycidyl compound and then twisted in a conventional manner. As in Example 1, the twisted yarn was treated in an RFL deposition bath, the RFL mixture was applied to the twisted yarn, dried at 155 ° C, and then fused at 225 ° C. The rest is carried out as in Example 1. As in Example 1, the adhesive strength value obtained by the U test is as shown in the table.

Example 11

Reaction as in Example 3 except that the total thickness of the poly-P- and -m-phenylene-1,3,4-oxadiazole (proportion of P and m = 5: 1) filament was applied to 1,150 denier Let's do it. However, the processing in the RFL deposition bath is omitted. The amount of N, N, N ', N'-tetraglycidyl-P-phenylenediamine applied was 0.14% (weight), and the adhesive strength value of the U test was 39.9 kg / cm 2.

Claims (1)

Adhesion aids in improving the rubber adhesion of high temperature stable filaments from aromatic poly-1,3,4-oxadiazoles by the use of adhesion aids and optionally in continuous resorcinol / formaldehyde / latex baths. High temperature resistant aromatic poly-1, characterized by treating one N-glycidyl compound or a mixture of N-glycidine compounds with 0.001 to 10% on aromatic poly-1,3,4-oxadiazole filaments. A method for improving rubber adhesion of, 3,4-oxadiazole filaments.