JPH0470423B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to an oil agent for treating synthetic fibers such as polyester, nylon, and acrylic fibers, and more specifically,
The spinning process such as spinning and drawing is applied to the synthetic fiber in the subsequent processing process, and the synthetic fiber is heat-treated at high temperature, giving it excellent smoothness and cohesiveness, with little alteration such as smoking or tarring, and This invention relates to a treatment oil agent with excellent heat resistance that does not become oil droplets and scatter and contaminate the process. Synthetic fibers such as polyester, nylon, and acrylic are often heat-treated using hot rollers, hot plates, high-temperature steam, etc. during the drawing process, and heat-set using heater plates during the crimping and bulking process. Ru. Furthermore, the synthetic fiber tire cord yarn is coated with an adhesive such as resorcin, formalin, latex, etc., and then baked at a high temperature. In this heat treatment process, an oil agent is applied to the synthetic fibers, but the oil agent may cause environmental pollution due to fumes, fuzz due to dirt around the heating device, increase in thread breakage, and other process problems, and furthermore, the amount of applied oil agent may be reduced. Various problems occur, such as similar process failures due to heating reduction, and the reality is that these are obstacles to the stable production of high-quality synthetic fibers. Particularly in recent years, efficiency has been improved by speeding up the spinning and processing processes for synthetic fibers, and as a result, heat treatment conditions have become even more severe. There is a strong demand for the emergence of an oil agent that can <Prior art and its problems> Various types of oil agents for treating synthetic fibers have been known. However, the mineral oils that have been known for a long time are insufficient in either smoking (low viscosity products) or tarring (high viscosity products), and lack smoothness after the heat treatment process. There is a problem. Those whose main component is common esters (for example, oleyl oleate, octyl stearate, etc.) have difficulty in producing both smoke and tar, and have the same problems as mineral oils. Examples of compounds whose main components are compounds with good heat resistance include quaternary carbon-containing esters (for example, esters of trimethylolpropane, pentaerythritol, etc. and long-chain fatty acids), sulfide bond-containing esters (for example, thiodipropionic acid, alkylthio Products that use esters of propionic acid, etc. and long-chain aliphatic alcohols) and aromatic-containing esters (e.g., POE bisphenol A/fatty acid esters, trimellitic acid alkyl esters) generally emit less smoke;
Although it has the advantage that it is relatively difficult to turn into tar, the oil that falls onto the heat treatment equipment becomes oil drops and contaminates the surrounding area, or it ends up turning into tar on the heat treatment equipment, making it necessary to clean it, which reduces productivity. There is a problem of lowering the Similarly, products that use polyethers (for example, polymerized alcohols with ethylene oxide or propylene oxide), which are mainly composed of compounds with good heat resistance, have problems in terms of smoke generation, tar formation, and oil drop. However, there is a problem that it is easily subjected to radical oxidation due to heat treatment, and the smoothness and cohesiveness after heat treatment deteriorate. In short, the conventional oils for treating synthetic fibers exemplified above do not solve the problems of smoke generation, tar formation, and oil drops that are required for the oil agents for treating synthetic fibers that are currently subjected to severe heat treatment at high speeds and high temperatures. However, there is no material that satisfies the smoothness and cohesiveness inherent to oil agents after heat treatment. On the other hand, polybutene containing 70% by weight or more of isobutene units in its molecule can satisfy the above requirements as a whole if its molecular weight is appropriately selected. However, polybutene with a molecular weight of 500 or more, which can be used as a smoothing agent with excellent heat resistance, has a serious problem in that it is difficult to obtain an aqueous emulsion thereof. Conventionally, a method has been proposed in which an oil agent prepared by diluting this type of polybutene with, for example, low-viscosity mineral oil is directly applied to synthetic fibers (Japanese Unexamined Patent Application Publication No. 1989-1999).
73999, U.S. Patent No. 3977979, U.S. Patent No. 4098702, U.S. Pat.
4098703, 4105569), the straight lubrication method is inferior in uniformity of adhesion to synthetic fibers compared to the lubrication method using aqueous emulsions of oil agents, is unsuitable for high-speed processing, and is not suitable for high-speed processing. The cost is also high;
Furthermore, there are many problems such as environmental pollution caused by the diluent. Conventionally, a method has also been proposed in which the above-mentioned polybutene is dispersed in an aqueous system with a nonionic emulsifier using mechanical force such as a homogenizer or a colloid mill (JP-A-50-100317, JP-A-51
-32897), the dispersed particles of the aqueous dispersion are large (for example, the permeability of the aqueous dispersion is low), the uniform adhesion is poor as in the case of straight oil supply, and creaming etc. occur, making it impossible to use stably for a long period of time. , which also has many problems. <Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a new oil agent for treating synthetic fibers that solves the conventional problems as described above, especially the problems when using polybutene. . However, in view of the above-mentioned circumstances, the present inventors turned polybutene with a molecular weight of 500 or more into an aqueous emulsion with small dispersed particles and stable over a long period of time, similar to other general oils for treating synthetic fibers. We investigated its use as an oil for treating synthetic fibers that require heat resistance under high-temperature, high-speed conditions. As a result, the conventional means of using POE alkyl ethers, POE alkyl phenyl ethers, POE polyhydric alcohol esters, alkyl phosphates, etc. as emulsifiers for this type of polybutene do not allow stable emulsification for practical purposes. I couldn't do it. At this time, by using mechanical force such as a homogenizer or colloid mill, it was possible to obtain a homogeneous aqueous dispersion, but since the dispersed particle size was large, the aqueous dispersion was used to make synthetic fibers. Even after treatment, it is difficult to uniformly adhere the oil, and furthermore, the aqueous dispersion is prone to phenomena such as agglomeration of dispersed particles and oil layer separation due to external physical influences (e.g. temperature changes, aging, etc.). Since so-called creaming occurs, it cannot be used stably for a long period of time, and as a result, it cannot provide the smoothness and cohesiveness inherent to oil agents to synthetic fibers after heat treatment. Therefore, the present inventors created a stable aqueous emulsion of polybutene with a molecular weight of 500 or more, which itself has excellent properties, and used this as a treatment oil for synthetic fibers that are spun and processed under the current harsh heat treatment conditions. In order to do so, as a result of further intensive research, we found that by blending a specific polybutene with a certain average molecular weight range with a specific salt of maleic acid of the polybutene in a predetermined ratio to prepare a composition containing a predetermined amount or more of these salts,
From this composition, an aqueous emulsion with extremely small dispersed particles and excellent emulsion stability can be obtained, and when this aqueous emulsion is used, problems such as smoking, tarring, oil drops, and even smoothness and cohesiveness after heat treatment can be obtained. It has been found that the requirements regarding the above can be satisfied as a whole. That is, the present invention comprises 30 to 70% by weight of polybutene having an average molecular weight of 500 to 300 and having 70% by weight or more of isobutene units in the molecule, and an alkali metal salt and/or ammonium salt and/or maleate of the polybutene. or 15 to 40% by weight of a salt of an amine selected from the following amine group, and a composition containing 60% by weight or more of the polybutene and a maleated salt of the polybutene in total. This invention relates to an oil agent for treating synthetic fibers consisting of an aqueous emulsion. Amine group: Alkylamine, alkanolamine, or aromatic amine, all of which have a molecular weight of 200 or less In the present invention, the composition that is the active ingredient of the aqueous emulsion has an average molecular weight of 70% by weight or more of isobutene units in its molecules. It contains 30 to 70% by weight of polybutene having a molecular weight of 500 to 3,000. In this case, the isobutene units are less than 70% by weight,
If the average molecular weight is less than 500 or the content is less than 30% by weight, the heat resistance of the aqueous emulsion or oil agent prepared from such a composition will be insufficient, and, for example, smoke will be increased. On the other hand, if the average molecular weight exceeds 3000 or the content exceeds 70% by weight, the emulsion stability of the aqueous emulsion, ie, oil agent prepared from such a composition will be insufficient. Specific examples of polybutenes that can be advantageously used in the present invention include homopolymers obtained from isobutene and copolymers obtained from isobutene and a small amount of normal butene. In the present invention, the composition also contains 15 to 40% by weight of an alkali metal salt and/or an ammonium salt and/or an amine salt of a polybutene maleate. In this case, the alkali metals used to obtain the alkali metal salts are sodium,
Potassium, lithium, etc. are selected as appropriate, and the amine used to obtain the amine salt is an alkylamine, alkanolamine, or aromatic amine, all of which have a molecular weight of 200 or less. Such a polybutene maleate salt is an essential component for stably emulsifying the polybutene into fine particles as an aqueous emulsion. If the average molecular weight range of the polybutene to be maleated is outside of 500 to 3000, or if its content in the crude product is less than 15% by weight, the above-mentioned emulsifying power for the polybutene will be insufficient. Conversely, if the content exceeds 40% by weight, or if the molecular weight of the amine used to obtain the amine salt is
If it exceeds 200, the heat resistance of the water-based emulsion, ie, the oil agent prepared from the composition in such a case will be insufficient. Such polybutene maleide salts are
It is obtained by reacting an average of 0.3 to 2 moles of maleic anhydride with 1 mole of the polybutene to obtain maleated polybutene, hydrolyzing the maleated polybutene, and then neutralizing this with alkali hydroxide, amine, etc. . Specific examples of polybutene maleate salts that can be advantageously used in the present invention include sodium salts and triethanolamine salts of polybutene maleates having a molecular weight of 1000. Furthermore, in the present invention, the composition comprises a total amount of polybutene and a maleated salt of the polybutene.
It contains 60% by weight or more. This is to ensure that the aqueous emulsion prepared from the composition, ie, the oil agent, fully exhibits the performance required. The present invention relates to an oil agent for treating synthetic fibers comprising an aqueous emulsion of a composition containing the above-described polybutene and a maleated salt of the polybutene in a predetermined ratio and in a predetermined amount or more. Other conventional oils, emulsifiers, antistatic agents, etc. can be used in combination to the extent that they are not included in the composition, and their emulsification may be carried out, for example, by gradually adding them to a mixture of polybutene and a salt of its maleate while stirring. , a mixture of polybutene, a salt of its maleate, and water may be emulsified using a homogenizer, a colloid mill, etc. while stirring, and the emulsification method is not limited. The thus obtained oil agent according to the present invention is applied to synthetic fibers as an emulsion by a dipping method, an oiling roller method, a guide oiling method, etc. at a stage before the heat treatment step, and the oil agent is applied to the synthetic fibers as an emulsion by a dipping method, an oiling roller method, a guide oiling method, etc. Usually, 0.3 to 2.0% by weight of synthetic fibers is added as an oil composition. EXAMPLES Hereinafter, the structure and effects of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples listed here. <Example> Using the oil components listed in Table 1, the compositions listed in Table 2 (corresponding to Examples 1 to 11) and the compositions listed in Table 3 (corresponding to Comparative Examples 1 to 21) were prepared. An oil agent for treating synthetic fibers was prepared in the following manner. Comparative Example 7: A composition was mixed in a mortar while gradually adding water to the composition, the concentration was 10% by weight, and the mixture was subjected to a homogenizer (in the method of the Examples described later, a separated emulsion was obtained). Comparative Example 16: Adding 30 seconds of mineral oil to the composition,
The concentration is 10% by weight (straight oil supply). All Examples and Other Comparative Examples: Emulsion by gradually adding water to each composition while stirring to give a concentration of 10% by weight. The emulsion stability of each oil agent prepared as described above was measured and evaluated using the following methods and standards. Polyester partially oriented yarn (115 denier/24 filament ) as a sample thread and measure its friction coefficient.
Furthermore, the polyester partially oriented yarn was stretched at a stretching ratio of 1.52,
Stretching and false-twisting was performed at a heat treatment temperature of 220°C and a stretching and false-twisting speed of 600 m/min, and the smoke generation, tar formation, and oil drops from the heater plate were evaluated with the naked eye, and the number of yarn breakages was also measured. did. The results are shown in Table 4 (Examples) and Table 5 (Comparative Examples). ●●Emulsion stability) Transmittance: Each prepared oil agent was placed in a quartz cell (cell length 10 mm), and the transmittance (%) at 760 mm was measured. In addition, the transmittance is 1%
If it is above, it is good. ) Stability over time: 100ml of each prepared oil agent,
Place in a graduated cylinder with a stopper and heat to 25°C.
After being allowed to stand for 24 hours, the condition of the oil agent was evaluated based on the following criteria. 〇: No creaming △: Creaming ×: Separation
207 grams, yarn speed of 100 m/min or 300 m/min, run in contact with titanium oxide ceramic friction body,
The tension ratio was measured using a μ meter (manufactured by Eiko Sokki Co., Ltd.). At this time, when heat setting was performed, the sample yarn was run into a 1 m tube heater (220°C) before entering the friction body. Note that if the measurement results are within the range of Table 4, the smoothness and convergence are good. ●●Fume generation, tar formation, oil drop Evaluation was made using the following criteria.

[Table] ... Yarn breakage Yarn breakage during stretch false twisting was measured in turns/Kg.

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[Table] As is clear from the results in Table 4 relative to Table 5, the oil agent according to the present invention is a water-based emulsion with stable fine particles, and therefore the oil agent can be heated under high temperature and high speed. Because it can be uniformly attached to synthetic fibers subjected to severe heat treatment,
By making full use of the original excellent properties of polybutene mentioned above, it satisfies all requirements regarding heat resistance such as smoke generation, tar formation, and oil drop, as well as requirements such as smoothness and cohesiveness after heat treatment, and is therefore efficient. It is clear that high-quality synthetic fibers can be stably manufactured and processed. <Effects of the Invention> As is already clear, the present invention described above completely satisfies the requirements regarding heat resistance such as smoke generation, tar formation, and oil drop, as well as the requirements regarding smoothness and cohesiveness of synthetic fibers after heat treatment. The polybutene, which has excellent properties, can be uniformly applied as a stable fine aqueous emulsion to synthetic fibers subjected to severe heat treatment, so that the spinning and processing of the synthetic fibers can be carried out extremely efficiently and without resistance. Therefore, there is an effect that high quality synthetic fibers can be stably obtained.

Claims (1)

[Scope of Claims] 1. 30 to 70% by weight of polybutene having an average molecular weight of 500 to 3,000 and having 70% by weight or more of isobutene units in its molecule, and an alkali metal salt and/or ammonium salt of a maleate of the polybutene. and/or salts of amines selected from the following amine groups 15
An oil agent for treating synthetic fibers comprising an aqueous emulsion of a composition containing 60% by weight or more of the polybutene and a maleated salt of the polybutene in a total amount of 60% by weight or more. Amine group: Alkylamines, alkanolamines, or aromatic amines, all with a molecular weight of 200 or less