KR870001576B1 - Composition of adhesive agent - Google Patents

Abstract

An adhesive agent is produced by addn. of org. oxdn.inhibiting- agent(of formula (I), 2-mercaptobenzoimidazole), urea resin(of formula(II), to luenediisocyanate) and alk. metal iodide(KI, NaI) to the latex. In the formula, R is hydrocarbon (carbon no. of aromatic or aliphatic = 1-7), n=0.1 or 2. Amts. of adding (I), (II) and alk. metal iodide are 0.1-6 wt.%, 0.5-15 wt.% and 0.02-7 wt.%, respectively, by rubber 100 phr.

Description

[Name of invention]

Adhesive composition with improved heat resistance

Detailed description of the invention

The present invention relates to an adhesive used for bonding a polyamide-based synthetic fiber material with rubber, in particular an adhesive composition having improved heat resistance.

Polyamide-based synthetic fiber materials such as nylon-6 are generally suitable as reinforcing materials for rubber products such as automobile tires, conveyor belts and hoses because of their excellent properties such as tensile strength, impact resistance and adhesion. However, in spite of its excellent adhesion with rubber, the adhesive layer is destroyed by deterioration factors such as heat, ozone, ultraviolet rays, etc. depending on the storage period and the packing condition during processing or product production process. It has been pointed out that there is a large drawback in that the adhesion of.

The decrease in the heat resistance is a very important problem in rubber reinforcement products using polyamide-based synthetic fibers. Especially in the present tires, which are required to improve tire running performance by expanding the highway network. The problem of deterioration of heating is very important.

Conventionally, REL, which is a ternary adhesive of resorcinol-formalin-latex (hereinafter referred to as REL), has been widely used as an adhesive for polyamide synthetic fibers. In other words, it is an adhesive used to bond polyamide-based fibers with rubber, and is produced by the addition condensation reaction of resorcinol and formalin with RF (resorcinol-formalin) resin and natural rubber latex or synthetic rubber latex such as styrene. -RFL adhesive manufactured by mixing butadiene rubber latex and vinylpyridine rubber latex is a rubber vulcanization seat of rubber due to thermal energy, ultraviolet rays and ozone. The adhesion with and is significantly reduced, which is outlined as follows.

First of all, the adhesion state between RFL adhesive and rubber to be reinforced is based on the first-order bond, ie the hydrogen bond, by the potential difference between the amine of the amine group in nylon-6 and the hydrogen in the phenolic hydroxyl group of the RF resin. (Hydrogen bonds between molecules) occur and a curing agent such as sulfur, selenium (Se), and tellurium (Te) in the rubber to be reinforced between the double bond of the rubber to be reinforced and the double bond of the latex as a rubber component in the RFL adhesive. Vulcanization occurs to form a CS _x -C bond, resulting in a stronger adhesion. At this time, in the above-mentioned adhesive treatment process, the deterioration factor of the RFL adhesive layer is lost due to deterioration factors such as heat deterioration during the vulcanization process, deterioration during the storage period, deterioration during the transportation period, in particular heat, ultraviolet ray, and ozone. It can be seen that the adhesion is severely reduced as a result of the loss of opportunity.

In other words, heat alone decomposes the oxygen in the atmosphere, producing highly reactive radicals in the radical and monopolymeric states, breaking the π-bonds during C = C double bonds, which are vulcanizations with rubber. This eliminates the opportunity for adhesion with the rubber (reaction opportunity).

Ultraviolet rays, which have very short wavelengths in the daylight, radiate powerful energy to excite stable oxygen molecules, and O ₃ forms ozonide due to its unique dissolvability. Due to the relationship of attacking the vulcanization seat and dropping the reactor circuit, the performance of rubber reinforcing fiber materials such as tire cord is reduced.

In this way, the rubber-reinforced fiber material of which the adhesive performance is deteriorated is put into a tire, and the tire is manufactured to test the finished tire by running the ply-ply (co-deed layer) and the carcass part. Separation between the cord layers is a major cause of tire accidents.

This phenomenon occurs because the adhesion performance between the tire cord and the rubber deteriorates, which is a significant obstacle in the use of tires in the high speed era.

Accordingly, the present invention solves the problems of the polyamide-based rubber reinforced synthetic fiber material such as nylon-6 treated with the conventional RFL adhesive as described above, and maintains the adhesive strength in a stable state between the rubber and the fiber material, and as an excellent adhesive composition In order to provide a novel adhesive composition obtained by dispersing a compound such as a heat-resistant additive in a conventional RFL, the present invention provides an adhesive composition according to the method of the present invention to a fibrous material, thereby over time. It has been shown to greatly improve the heat resistance.

Hereinafter, the present invention will be described in detail.

The present invention is 0.1 to 6% by weight of the organic antioxidant represented by the following general formula (I) and the fluoride of urea resin and alkaline earth metal represented by the general formula (II) with respect to rubber 100Phr (amount relative to 100 rubber), respectively. , 0.5 to 15% by weight and 0.02 to 7% by weight of the RFL adhesive composition, characterized in that it is mixed with the latex as an added amount.

(Where X is an electron donor type element)

(Where R is an aromatic or aliphatic hydrocarbon group having 1 to 7 carbon atoms and n is 0, 1 or 2)

The present invention is described in more detail as follows.

The basis of the expression of the performance of the additive compounds used in the present invention is generally the same as the theory of antioxidant effect of rubber products or plastics.

In other words, organic antioxidants are easily decomposed by heat, ultraviolet light, ozone, etc., and exist in a radical state, and oxygen is decomposed by heat, ultraviolet light, etc., so that the generated oxygen radicals are formed from high molecular weight materials such as rubber in latex. Due to the weak binding force or rich reactivity, it is reacted by organic antioxidants before approaching the aging or oxidizing part easily, so it shows the effect of antioxidant. It is assumed to represent.

Thus, by protecting the rubber component in the latex to protect the co-occupation with the rubber substrate it is possible to prevent the time-lapse adhesion degradation phenomenon.

When explaining the composition of the adhesive prepared according to the present invention based on the theoretical basis for the adhesion degradation phenomenon and the oxidation prevention in comparison with the conventional adhesive as follows.

First, the preparation of RF resin is about 1 to 3% by weight of 10% caustic soda solution based on 100% by weight of pure water from which both anions and cations are removed, and resorcinol 5 to 7% by weight and formalin 8 to 10% by stirring. After adding%, the mixture is stirred well at a stirring speed of 50 to 70 rpm under an alkaline catalyst of caustic soda solution and aged at 20 to 25 ° C. for 5 to 10 hours.

In this case, the total solid content is preferably 6 to 8%.

Then, RFL solution is prepared, RFL solution is a vinyl pyridine latex, which is generally used among natural rubber latex or synthetic rubber latex, the additive used in the present invention, for example, heat-resistant organic oxidation represented by general formula (I). Inhibitors; Oxides of 2-mercaptobenzoimidazole and alkaline earth metals, for example, potassium iodide or sodium iodide, and urea resins represented by the above general formula (II); 0.1 to 6% by weight, 0.02 to 7% by weight and 0.5 to 15% by weight, and then added at 70 to 150 rpm in a liquid layer of latex until the mixture is stirred for 3 to 5 hours until the suspended solids disappear. Disperse well and prepare.

Next, natural rubber latex, SBR latex, vinylpyridine latex prepared by dispersing additives in advance, and ammonia water 30 to 50% by weight, 90 to 130% by weight, 140 to 160% by weight, and 8 to 15, respectively, based on 100% by weight of pure water. After the mixture was added in weight% and stirred for about 0.5 to 1.5 hours, the pre-prepared RF resin was added and stirred and aged at a stirring speed of 50 to 70 rpm for 12 to 20 hours at a temperature of 20 to 25 ° C.

The polyamide-based synthetic fiber material used in the present invention is a nylon-6 yarn prepared by melt spinning stretching by extracting, drying and solid phase polymerizing a high molecular weight nylon-6 chip made by solution polymerization of caprolactam. It is made by twisting with soft water 370TPM and sea water 370TPM, and is a slope for 1260D / 204F × 2 ply tire cord fabric.

The present invention as described above will be described in detail with reference to Examples.

로 표시한 것이다.In the present embodiment, the H-adhesive force refers to the adhesive force between the fiber material and the rubber, and the adhesive-coated cord is embedded in the rubber block and vulcanized for 30 minutes at a temperature of 150 ° C. under a pressure of 50 kg / cm 2. When the load is drawn from the rubber block at a speed of 200 mm / min, the load detected in kg /

It is indicated by.

The nylon-6 co-de 1260D / 2P was immersed in the RFL adhesive composition thus prepared and dried at a temperature of 100 to 150 ° C. for 120 seconds, followed by heat treatment at 180 to 210 ° C. for 50 seconds to produce an adhesive treatment code. Next, an H-adhesion test was conducted to prove the superiority of the present invention.

[Examples and Comparative Examples]

The adhesive used in this example was prepared and processed as follows.

TABLE 1

Preparation of RF Solution

TABLE 2

How to Add Additives to Latex

TABLE 3

RFL ternary glue manufacturing method

In the RFL adhesive thus prepared, the nylon-6-coded 1260D / 2P untreated coded was subjected to heat treatment by passing through an immersion bucket. At this time, the adhesive solution must be continuously stirred to prevent floating substances from being generated. Thus, after the coded immersed in the adhesive liquid, and dried for 120 seconds at 120 ℃ and then continuous heat treatment at 200 ℃ for 50 seconds to give the physical properties of the code after winding to prepare a treated co-dr. In order to measure the heat resistance of this heat-treated code, a comparative code that was processed with a conventional RFL adhesive was also subjected to a thermal deterioration test.

의 단위로 측정하였다.The thermal deterioration test is performed by adding a treatment cod to a test tube and heating it at 120 ° C. for a specified time, i.e., 12, 18, 24, .48, 72 hours. Planted in the uncured rubber of the tire carbus formulation, and vulcanized under pressure of 50 kg / cm for 30 minutes at a temperature of 150 ° C.

It was measured in units of.

In the standard test of the present invention, the cord and other RFL-treated cords according to the present invention are also applied to the unvulcanized rubber of the tire carcass composition, which is composed mainly of natural rubber, without any adhesive-treated cords being exposed to heat. -Ed was planted at the same time, and H-adhesive force was measured as the initial attachment force by the same method as the deterioration co-de for comparison test.

Therefore, the results of calculating the adhesion performance measurement results of the Examples and Comparative Examples by calculating the heat-resistant adhesion performance of the adhesion treatment code as a percentage of the initial adhesion of the corresponding code is shown in Table 4 below.

TABLE 4

Adhesion performance measurement result comparison table

EXAMPLES Codes Treated with RFL of the Invention

Comparative example: coded with conventional RFL

As can be seen from Table 4 above, it can be seen that the cords obtained by treatment according to the present invention are significantly superior in heat-resistant adhesion performance than the RFL treatment cords of the conventional method as the comparative example.

Claims (2)

(Correction) In the RFL adhesive composition nothing, heat resistance characterized in that the organic antioxidant represented by the following general formula (I) and the urea resin and alkaline earth metal oxide represented by the following general formula (II) are added and mixed with the latex. Adhesive composition with improved adhesion.

(Where X is an electron donor type element)

Wherein R is a hydrocarbon group having 1 to 7 carbon atoms in the aromatic or aliphatic group, and n is 0, 1 or 2; (Correction) The method according to claim 1, wherein the addition amount of the oxides of the general formula (I), the general formula (II) and the alkaline earth metal is 0.1 to 6% by weight, 0.5 to 15% by weight, and 0.02 to 7, respectively, based on the rubber component 100PHR. The improved heat-resistant adhesive composition, characterized in that the addition by weight percent.