JPS6031942B2 - Oil agent for thermoplastic synthetic fibers - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oil agent for rubber reinforcing thermoplastic synthetic fibers that is formulated by combining specific compounds, and its purpose is to prevent the aging deterioration of the adhesion of thermoplastic synthetic fibers to rubber that have been treated with an adhesive treatment liquid. An object of the present invention is to provide an oil agent for thermoplastic synthetic fibers for rubber reinforcement. Thermoplastic synthetic fibers such as nylon and polyester are widely used as rubber reinforcing fibers in belts, tire cords, etc. due to their excellent properties such as dimensional stability, high strength, heat resistance, and fatigue resistance. Automobile tires are often used under harsh conditions due to high-speed driving on expressways, etc., and it is important to improve the performance of tire cord, which is a tire reinforcing material, particularly in terms of adhesion to rubber and adhesive retention rate over time. The current situation is what is desired. In other words, if fibers are left in the air, high temperature, or ozone after being treated with an adhesive treatment solution, moisture in the air,
Heat, oxidizing gases, light (especially ultraviolet rays), etc. can cause the adhesive strength with rubber to decrease over time, and when driving at high speeds, tire cords are exposed to high temperatures due to the heat generated by the tires, so the bond between rubber and fibers can deteriorate. There is a strong desire to prevent the adhesive from deteriorating over time, as this can lead to a decrease in the adhesive strength and lead to tire failure. For this reason, as an oil agent for thermoplastic synthetic fibers for rubber reinforcement, a fiber treatment in which an equal type of antioxidant is added to a mixture of mineral oil or fatty acid alkyl ester oil and a nonionic and/or anionic surfactant. There have been proposals for oil agents for use in thermoplastic synthetic fibers (such as Samurai Sekishokyu-13-ban No. 97), but the present inventors have proposed combining specific antioxidants with oil agents to reduce other properties of thermoplastic synthetic fibers. The present inventors have discovered that excellent prevention of adhesive deterioration over time of fibers treated with an adhesive treatment liquid can be achieved without causing any damage to the fibers. That is, the present invention provides one or more smoothing agents selected from the group consisting of esters of monohydric alcohols and monobasic fatty acids or dibasic fatty acids, and esters of polyhydric alcohols and monobasic fatty acids, and nonionic smoothing agents. and/
Alternatively, it is an oil agent for thermoplastic synthetic fibers prepared by blending a phosphonate represented by formula [1] with an anionic surfactant and a compound represented by formula [b] or formula [m]. The alcohol esters of fatty acids contained in the oil agent of the present invention act as a smoothing agent, and are particularly effective in preventing the generation of smoke, tar, etc., taking into account the heat treatment conditions in the manufacturing process of thermoplastic synthetic fibers for rubber reinforcement. Although it is necessary to select one with good heat resistance, higher fatty acid esters are preferred. Examples of monohydric alcohol esters of fatty acids include butyl stearate, octyl stearate, lauryl oleate, and oleyl oleate. Examples of esters of monobasic fatty acids include dioctyl cel/cate,
These include dilauryl azelate and dioleyl adibate. Examples of polyhydric alcohol esters include glycerin trioleate, glycerin trilaurate, trimethylolpropane tridodecanoate, neobentyl glycol dilaurate, and bisphenol A dilaurate. Natural mixed fatty acid triglycerides such as rapeseed oil and coconut oil can also be used.
'', nonionic and anionic surfactants are mainly used as emulsifiers to emulsify these smoothing agents, and nonionic surfactants include, for example, polyoxyalkylene type polyoxyethylene lauryl ether, Polyoxyethylene oleyl ether, polyoxyethylene laurate ester, polyoxyethylene nonylphenyl ether, polyoxyethylene castor oil, polyoxyethylene notopolyoxypropylene stearyl ether, etc. Polyhydric alcohol type includes sorbitan mono Examples include oleate, sorbitan trioleate, glycerin monolaurate, trimethylolpropane dilaurate, and their ethylene oxide adducts. Examples of anionic surfactants include lauryl phosphate potassium salt, oleyl phosphate jetanolamine salt, lauryl sulfate sodium salt, and lauryl sulfonate sodium salt. Also, the formula used in the present invention [
1],

Compounds represented by [0] and [m] have good compatibility with oil agents, and have extremely high heat resistance, making them suitable for hot stretching and
In heat treatment, smoke generation on a hot plate or hot roller, tar formation resistance is very good, and especially [1] and [
A more excellent effect can be obtained by mixing it with [n] or [1] and [blood] in an oil agent. The preferred ratio of each component of the oil agent of the present invention is 40% of the above-mentioned smoothing agent.
-8% by weight of the nonionic and/or anionic surfactant, 0.2 to 5 parts by weight of the compound represented by the above formula [1], 20 to 6% by weight of the nonionic and/or anionic surfactant, the formula

It contains 0.1 to 3 parts by weight of a compound represented by [0] or [m]. The lubricant of the present invention can be applied to fibers in the form of a straight or emulsion by a conventionally known lubricating method such as a roller lubricating method, a spraying method, or a dipping method. The amount of the oil agent of the present invention attached to the fibers is 0.2 to 3. Broad weight percentages are appropriate. Thermoplastic synthetic fibers to which the oil agent of the present invention can be applied include nylon 6, nylon 6,
6. Although it is mainly used for rubber reinforcing fibers such as polyester, it is particularly useful for polyamide fibers. Next, examples of the present invention will be shown, but the present invention is not limited to these examples. Note that parts in the examples indicate parts by weight. Example 1 Nylon 6 chips with a relative viscosity of 3.35 (based on a 2 mm concentrated sulfuric acid solution) were made using a melting paper thread machine with a hole diameter of 0.3 ribs and a number of holes of 20.
The material was ejected from four nozzles and wound onto a bobbin at a speed of 500 mm/min. Before rolling up, the oil shown in Table 1 was applied at an emulsion concentration of 20% by a conventional roller oiling method. Then, using a drawing machine equipped with a 190qo heater plate, the film was hot-stretched to 52 times at a stretching rate of 250/min.
When a drawn yarn of 60 denier was obtained, the amount of oil attached was approximately 0.8% based on the drawn yarn. In the hot drawing process, both the invention products (■) had good convergence and no yarn breakage, and exhibited extremely good operability with almost no smoke, tar-like substance accumulation, or staining on the heater plate. Next, this drawn yarn was first twisted 40 times/10 times, and then twisted into two threads while being twisted 4M/10 times to form a tire cord. This tire cord was soaked in a fiber treatment adhesive (hereinafter referred to as RFL liquid) consisting of a resorcinol formaldehyde initial condensate and rubber latex, dried at 120 qo for 2 minutes, and then dried at 200°C for 2 minutes under a 7% stretch. It was heat set and made into a treated cord. RF to processing code
The amount of L liquid solid content deposited was approximately 5.7%. This treated cord was embedded in unvulcanized rubber, and after vulcanization, the pulling strength of the treated cord from the rubber was measured using an Instron to evaluate the adhesive strength. Also, the processing code is 150
It was heat-treated for 01 hours, embedded in unvulcanized rubber in the same manner as above, and after vulcanization, the pull-out strength from the rubber was measured and the adhesion retention rate was calculated. The results are shown in Table 1 along with the oil composition. As a result, the adhesive retention rate of oil agent (■), which is a product of the present invention, was extremely good. Table 1 *Borioxyethylene ■: False open side 53-139897 Examples Example 2 Nyio with relative viscosity 2.95 (based on 5 pm concentrated sulfuric acid solution)
Using a melt-spinning machine, spin out 6.6 chips using a conventional method through a nozzle with a hole diameter of 0.3 and a number of holes of 204.
It was wound onto a bobbin at a speed of min. Before rolling up, apply the oil shown in Table 2 at an emulsion concentration of 18% using the usual roller lubrication method, and then
Using a drawing machine equipped with a qo heater plate, the yarn was hot-stretched to 5.1 times at a drawing speed of 250 m/min to obtain a drawn yarn of 1260 denier. %Met. Next, this drawn yarn was first coated with 40
After first twisting the threads in a similar manner, the two yarns were twisted together 40 times/10 arcs to form a tire cord. I used this tire code. This tire cord was soaked in RFL liquid, then dried at 120qo for 2 minutes, and then 5%
A heat set was applied for 2 minutes at 22 and 0 under the stretch, and the treatment code was applied. The amount of RFL liquid/solid content adhered to the treated cord was approximately 5.5%. This treated cord was embedded in unvulcanized rubber, and after vulcanization, the pulling strength of the treated cord from the rubber was measured using an Instron to evaluate the adhesive strength. In addition, the treated cord was heat treated at 150°C for 1 incubation period, and then embedded in unvulcanized rubber in the same manner as above.
After vulcanization, the pull-out strength from the rubber was measured and the adhesion retention rate was calculated. The results are shown in Table 2 along with the oil composition.
As a result, the adhesive retention rate of oil agent (■), which is a product of the present invention, was extremely good. Table 2 * River Example 3 of Sifurohirene 3 A polyethylene terephthalate chip with an intrinsic viscosity of 0.97 (based on a 30 oo parachlorophenol and tetrachloroethane mixture) was melted using a thread spinning machine, with a hole diameter of 0.4 and a hole number of 19. Melt paper is ejected from a solid nozzle using the usual method, 500
It was wound onto a bobbin at a speed of m'min. Before rolling, dilute the oil shown in Table 3 to 50% concentration with rat sand mineral oil using the usual roller lubrication method, and after straight lubrication, use a stretching machine equipped with a 230°C heater plate to stretch at a speed of 250. /min of 5. When a drawn yarn of 1,500 denier was obtained by hot drawing at the sound of a needle, the amount of oil adhering to the drawn yarn was approximately 0.7%. Next, this drawn yarn is first twisted 49 times/10 times, and then twisted 45 times/10 times to make a tire cord. After drying at 150° C. for 2 minutes, the cord was heat set at 0% stretch for 23 and 02 minutes to obtain a treated cord. Adhesive solids adhesion to the treated cord was approximately 5.0%. This treated cord was embedded in unvulcanized rubber, and after vulcanization, the pulling strength of the treated cord from the rubber was measured using an Instron to evaluate the adhesive strength. In addition, as a test for aging deterioration of adhesive strength, treatment code 15
The sample was subjected to a heat treatment of P01, embedded in unvulcanized rubber in the same manner as above, and after vulcanization, the pull-out strength from the rubber was measured and the adhesion retention rate was calculated. The results are shown in Table 3 along with the oil composition. As a result, the adhesive retention rate of oil agent (■), which is a product of the present invention, was extremely good. Table 3

Claims (1)

[Scope of Claims] 1. One or more smooth monomers selected from the group consisting of esters of monohydric alcohols and monobasic resin acids or dibasic fatty acids, and esters of polyhydric alcohols and monobasic fatty acids. and nonionic and/or anionic surfactants are phosphonates represented by formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or formula [ III〕 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ An oil agent for thermoplastic synthetic fibers that contains the compound represented by the following. 2 40 to 80% by weight of a smoothing agent, 20 to 60% by weight of a nonionic and/or anionic surfactant, 0.2 to 5 parts by weight of a phosphonate represented by formula [I], and formula [II]
The oil agent for thermoplastic synthetic fibers according to claim 1, which contains 0.1 to 3 parts by weight of the compound represented by formula [III].