JPH0470421B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel oil for treating fibers (hereinafter simply referred to as oil) and a method for treating fiber threads using the oil. The present invention relates to a novel oil agent that imparts smoothness and antistatic properties to threads and exhibits significantly superior anti-tarring properties and oil film strength compared to conventional oil agents, and a method for treating fiber yarns using the oil agent. polyester, polyamide, polypropylene,
Various thermoplastic synthetic fibers such as polyacrylonitrile or cellulose fibers such as acetate are produced by integrating various processes such as spinning, drawing, false twisting, twisting, and sizing. It is made into cloth through appropriate weaving and knitting processes,
Various oils are used in these processes. Incidentally, it is well known that such oils are required to have smoothness, antistatic properties, anti-tarring properties, etc., and for this reason, in addition to mineral oils and fatty acid esters, polyoxyalkylene ethers (e.g. No. 3,338,830) has also been proposed. Of the oils using these compounds, polyoxyalkylene ethers have the best anti-tar properties, but they still require severe heat treatment (e.g., drawing and false twisting at yarn speeds exceeding 600 m/min). ) is not completely satisfactory. Therefore, it is hoped that an oil agent with anti-tarring properties superior to that of conventional polyoxyalkylene ethers will emerge. Nowadays, fiber yarns are becoming thinner due to higher quality and high-quality products, but in any case, there is a tendency for running yarn breakage, fuzz generation, static electricity damage, etc., especially when drawing at high speed. In the twisting process (yarn speed of 600 m/min or more) and the high-temperature (200°C or more) spin-draw process, there is a strong demand for improvements in tar adhesion to the heating machine and abrasion of the metal materials in contact with the running yarn. . Therefore, today, we have gone beyond the improvement of conventional oils to meet the requirements of a particularly high level of anti-tarring properties and the above-mentioned oil film strength in a broad sense that affects the wear of metal materials. There is a strong demand for a new oil agent with excellent smoothness and a high level of antistatic ability. There is a strong demand for the emergence of a new oil that highly satisfies the requirements while maintaining other properties such as smoothness and antistatic properties. As a result of intensive research to develop a new oil agent that meets these demands, the present inventors have determined that an oil agent whose main component is a phosphazene compound that belongs to a family that has never been proposed before is correct and suitable. They discovered that when the oil agent was applied to fiber threads, the desired effects were significantly superior, and the present invention was completed. That is, the present invention relates to the following novel oil agent and a method for treating fiber threads using the oil agent. A cyclic phosphazene compound represented by the following general formula () and an active hydrogen represented by the general formula () are combined into 1
1. An oil agent characterized in that it contains a phosphazene compound obtained by reacting a phosphazene compound with an organic compound in a ratio of 1 to 5 moles of the former to 2 moles of the latter. _{R ( -} You can leave it on. R is an alkoxy group having a straight chain or side chain having 1 to 30 carbon atoms (6 to 30 if m is 0).
Alkenoxy group, thioalkoxy group, thioalkenoxy group, acyloxy group, benzyloxy group, phenoxy group, or alkyl (1 to 18 carbon atoms) phenoxy group. X is an alkylene oxide unit having 2 to 4 carbon atoms, and (-X) _-n may be a single unit or a mixture of two or more types. m is an integer of 0 or 1 or more. ] In the fiber manufacturing process, the oil agent containing the phosphazene compound obtained as described above is applied to the fiber yarn at a ratio of 0.1 to 3.0% by weight to lubricate the fiber yarn. Characteristic method for processing fiber threads. The phosphazene compound used in the present invention is synthesized, for example, as follows. That is, a cyclic phosphazene compound represented by the general formula () and an organic compound having one active hydrogen represented by the general formula () are added at a ratio of 1 to 5 moles of the former to 2 moles of the latter, It is obtained by heating to around 200°C under reduced pressure to cause a reaction. In this case, if the number of moles of the cyclic phosphazene compound used exceeds 5 moles, it is not preferable in terms of taring of the resulting phosphazene compound. In addition, in the organic compound represented by the general formula (), there is no particular limitation on the number m of added moles of alkylene oxide X, but it is usually 1
~200 moles. Then, the number m of added moles is 0
In this case, from the viewpoint of volatility of the phosphazene compound obtained in this case, it is necessary that R has 6 or more carbon atoms. Examples of the organic compounds represented by the general formula () used in the above-mentioned synthetic methods include the following. Octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol,
Oleyl alcohol, behenyl alcohol, etc.
Alcohols derived from natural fatty acids. 2-
Ethylhexanol, isocetyl alcohol (e.g., ND-Ecol 160B, manufactured by Shin Nihon Rika Co., Ltd.),
Aldol condensation type synthetic alcohols such as isostearyl alcohol (for example, Diadol 18G, manufactured by Mitsubishi Kasei Corporation). Oxo-synthesized alcohols such as isotridecanol and mixed alcohols of linear and iso-forms (for example, Dovanol, manufactured by Mitsubishi Yuka Co., Ltd.). Lower alcohols such as methanol, ethanol, butanol. Monohydric alcohols having 1 to 30 carbon atoms, such as benzyl alcohol. n-hexyl mercaptan, n-octyl mercaptan,
Mercaptans such as n-dodecylmercaptan, t-dodecylmercaptan, and behenylmercaptan; fatty acids such as acetic acid, decanoic acid, lauric acid, and oleic acid; Phenols such as octylphenol and nonylphenol. For the above compounds,
Polyglycol ethers to which ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide are added singly or in combination, etc. Among these, monohydric alcohols having 1 to 30 carbon atoms, phenols, and polyglycol ethers obtained by adding alkylene oxides having 2 to 4 carbon atoms to these are preferred in view of the purpose of the present invention. The chemical structure of the phosphazene compound thus synthesized and used in the present invention is estimated to be represented by the following general formula (). [R′, R″ are the same as R ₁ to _{R 6} in general formula (). R,
X and m are the same as in the general formula (). n is 1 to 5
an integer of ] Due to the unique chemical structure described above, the phosphazene compound of the present invention has the following features compared to conventional polyoxyalkylene ethers when applied to fiber yarn as an oil component. have In other words, although the ability of the fiber threads to reduce the coefficient of friction is almost the same, the oil film strength under high loads (evaluated by four-ball load-bearing capacity, the same applies hereinafter) is stronger, and the wear of various metal materials that come into contact with the running fiber threads is stronger. Less is. In addition, the charging voltage of running threads of synthetic fibers is extremely low, and leakage of static electricity and tar adhesion to heaters during the heat treatment process of fiber threads are extremely low. The content of such a phosphazene compound in the oil agent according to the present invention is not particularly limited as long as the effect of the present invention can be obtained. and,
In addition to the phosphazene compound, the oil agent according to the present invention also contains other smoothing agents, antistatic agents, nonionic surfactants, emulsification regulators, wetting agents, antifungal agents, and/or antifungal agents.
Alternatively, it may contain a rust preventive agent or the like as appropriate. Such smoothing agents include refined mineral oil, fatty acid esters, aliphatic ether esters, or
There are polyethers derived from ethylene oxide and propylene oxide. In addition, the antistatic agents mentioned above include anionic surfactants such as sulfonate salts, phosphate salts, and carboxylates, cationic surfactants of quaternary ammonium salt type, and amphoteric surfactants of imidazoline type, betaine type, and sulfobetaine type. There are surfactants, etc. Furthermore, examples of the above-mentioned nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, and partial alkyl esters of polyhydric alcohols. The oil agent according to the present invention described above can be applied to thermoplastic synthetic fibers such as polyester, polyamide, polypropylene, and polyacrylonitrile, as well as polyaramid fibers, carbon fibers, cellulose fibers such as acetate, and various other natural fibers. ,
Demonstrates a high degree of desired effect. In other words, the aforementioned phosphazene compound, which is the core of the oil agent, has excellent anti-tarring properties, antistatic properties, and oil film strength (as a result) when compared with its components such as conventionally known smoothing agents. This can reduce wear on the metal materials that the running yarn comes into contact with. Moreover, this phosphazene compound has many advantages during synthesis, such as easy synthesis and easy removal of unreacted raw materials. The oil agent according to the present invention is applied to fibers as a spinning oil agent or a processing oil agent to exhibit its effects, but it can be used as an aqueous emulsion, as an organic solvent solution, or as an oil agent (straight). It is possible to apply it to fibers by oiling). The amount of the oil applied to the fiber threads is preferably 0.1 to 3.0% by weight based on the fiber threads, especially for synthetic fibers such as polyester, polyamide, polypropylene, and polyacrylonitrile. When applied in the manufacturing process, if the above-mentioned oil agent is applied to the synthetic fiber yarn in an amount of 0.1 to 3.0% by weight, preferably 0.2 to 2.0% by weight, all subsequent processes (heating (including the steps in which it is carried out), the above-mentioned effects are remarkable. Finally, in order to make the structure and effects of the present invention more specific, we will explain a synthesis example of a phosphazene compound in an oil agent according to the present invention, its estimated chemical structural formula, and
Examples for comparative examples will be listed, including their performance evaluations. In addition, all of PP-A to PP-H correspond to those added to the following synthesis examples. ●Synthesis example 1 (Synthesis of PP-A) Random addition polymerization of PO (1,2-propylene oxide, the same below)/EO (ethylene oxide, the same below) = 50/50 (weight ratio, the same below) to butanol MW (molecular weight, same below) = 2000
500 g (0.25 mol) of polyether and 61 g (0.125 mol) of the cyclic propoxyphosphazene represented by the general formula () were placed in a glass reaction vessel (equipped with a stirrer), and after uniform stirring, the mixture was stirred. While continuing to react under reduced pressure (1 mmHg) at a temperature of 200°C for 6 hours, the desired phosphazene compound was obtained in high yield.
Obtained over 95%. [R ₁ = C ₄ H ₉ , R ₂ = iso-C ₃ H ₇ ] ●Synthesis example 2 (synthesis of PP-B) Obtained by addition polymerization of EO to lauryl alcohol
375 g (0.25 mol) of polyether with MW = 1500,
The desired phosphazene compound was obtained in the same manner as in Synthesis Example 1 from 61 g (0.125 mol) of the cyclic propoxyphosphazene represented by the general formula (). [R ₁ = C ₁₂ H ₂₅ , R ₂ = iso-C ₃ H ₇ ] ●Synthesis Example 3 (Synthesis of PP-C) 186 g (1.0 mol) of lauryl alcohol and cyclic propoxy expressed by the above general formula () The desired phosphazene compound was obtained from 488 g (1.0 mol) of phosphazene in the same manner as in Synthesis Example 1. [R ₁ = C ₁₂ H ₂₅ , R ₂ = iso-C ₃ H ₇ ) Synthesis Example 4 (Synthesis of PP-D) 200 g (1 mol) of lauric acid and a cyclic propoxy group represented by the above general formula () The desired phosphazene compound was obtained from 244 g (0.5 mol) of phosphazene in the same manner as in Synthesis Example 1. [R ₁ = C ₁₁ H ₂₃ , R ₂ = iso-C ₃ H ₇ ] ● Synthesis example 5 (Synthesis of PP-E) MW obtained by random addition polymerization of PO/EO = 50/50 to butanol = 2000 polyether 500g
(0.25 mol) and 86.6 g (0.125 mol) of the cyclic phenoxyphosphazene represented by the above general formula () in the same manner as in Synthesis Example 1 to obtain the desired phosphazene compound. [R ₁ = C ₄ H ₉ ,

[Formula]] ● Synthesis Example 6 (Synthesis of PP-F) From 94 g (1 mol) of phenol and 244 g (0.5 mol) of the cyclic propoxyphosphazene represented by the general formula (), the same as in Synthesis Example 1 was used. The desired phosphazene compound was obtained. [R ₂ = iso-C ₃ H ₇ ] ●Synthesis example 7 (Synthesis of PP-G) 202 g (1 mol) of n-lauryl mercaptan,
Synthesis Example 1 from 244 g (0.5 mol) of cyclic propoxyphosphazene represented by the general formula ()
The desired phosphazene compound was obtained in the same manner as above. [R ₁ = C ₁₂ H ₂₅ , R ₂ = iso-C ₃ H ₇ ] ●Synthesis Example 8 (Synthesis of PP-H) 186 g (1 mol) of lauryl alcohol and cyclic propoxy expressed by the above general formula () The desired phosphazene compound was obtained from 976 g (2 moles) of phosphazene in the same manner as in Synthesis Example 1. [R ₁ = C ₁₂ H ₂₅ , R ₂ = iso-C ₃ H ₇ ] ●Examples 1 to 6, Comparative Examples 1 to 4 The oils of Examples 1 to 6 shown in Table 1 and Comparative Example 1
-4 oil agents were mixed and adjusted. A 10% by weight emulsion of each of these oils was applied to a commercially available nylon filament (semi-dull 70 denier, 24 filament), which had been degreased with cyclohexane and dried, using an oiling roller, and 0.8 to 1.0% by weight of the oil was applied.
Attached. The running thread friction coefficient of the nylon filament, the four-ball load carrying capacity and taring rate of the oil agent, and the friction generated electricity and electrical resistance were measured and evaluated using the following methods. The results are shown in Table 1. ●●Measurement of running yarn friction coefficient Using a nylon sample yarn treated with an oil agent, it was measured with a μ meter (manufactured by Eiko Sokki Co., Ltd.) under the following conditions. Friction body = diameter 25 with chromed surface treated with matte finish
mm cylinder, thread-friction body contact angle = 90 degrees, initial tension (T ₁ ) = 20 g, running speed = 300 m/min, atmosphere = 25
℃×65%RH. Measure the yarn tension (T ₂ ) immediately after passing through the friction body,
The friction coefficient was calculated using the following formula. Friction coefficient = 1.466log T ₂ /T ₁ The smaller the running thread friction coefficient, the better the smoothness. ●●Measurement of four-ball load-bearing capacity According to the four-ball load-bearing test method for petroleum products stipulated in JIS K2519, the value (Kg/cm ² ) on the oil pressure gauge at the time when seizure of the test steel ball occurred was measured. It was measured. ●●Measurement of tar rate Stainless steel shear (diameter 3cm, depth 8mm)
Precisely weigh 3g of oil and heat in a heated oven at 230℃
The mixture was treated for 48 hours, left to cool in a drying desiccator, and then accurately weighed again to determine the residual ratio relative to the active ingredients of the original oil solution, and the taring ratio (weight %) was measured. ●●Measurement of friction generated electricity Nylon filament (semi-dull 75 denier)
Similarly, 0.4±0.1% by weight of oil was applied to the multifilament yarn (36 filaments), and the temperature was 20℃ x 40%RH.
The sample yarn was prepared under an atmosphere of Using this sample yarn, the yarn was fed at an initial tension of 20 g and at a speed of 700 m/min, and was brought into contact with a heater at 200°C x 90 cm.
Immediately after contact friction was made with a chrome matte satin pin at a contact angle of 90 degrees, a current collecting potential measuring device was placed to measure the static electricity (volts) generated on the yarn. ●●Measurement of electrical resistance The sample yarn was adjusted in the same way as for the measurement of friction-generated electricity. Place 10g of this sample yarn in a box for electrical resistance measurement (40ml capacity), and
Electrical resistance (logΩ) was measured using an SM-5E insulation meter. ●●Evaluation Criteria Evaluation was made based on the criteria in Appendix Table 1 and Appendix 2 below.

【table】

【table】

【table】

[Table] ●Examples 7 to 11, Comparative Examples 5 and 6 The oils of Examples 7 to 11 shown in Table 2 and the oils of Comparative Examples 5 and 6 were mixed and adjusted, and the following is the same as in Table 1. It was evaluated as follows. In addition, in this Table 2, the knitting needle wear degree was measured and evaluated by the following method instead of the tar conversion rate in Table 1. ●●Measurement of knitting needle wear degree Prepare the sample yarn in the same way as in the case of measuring friction-generated electricity, run this sample yarn in contact with a knitting needle for tricot under the following conditions, and then observe the friction surface of the knitting needle with a microscope. The presence or absence of wear marks was examined. Sample yarn running speed = 400 m/min, tension = 40 g, contact angle between knitting needle and running yarn = 150 degrees, atmosphere = 25°C x 75
%RH. ●●Evaluation criteria Evaluation was made using the criteria in Appendix 3 below.

【table】

[Table] ●Example 12, Comparative Example 7 The oil agent of Example 12 and the oil agent of Comparative Example 7 shown in Table 3 were blended and adjusted. 10 of each of these oils
Stretching and false twisting of POY to which 0.4 to 0.5% by weight of an oil agent was applied by the roller touch method using a weight% emulsion was performed in the following manner. Both Example 12 and Comparative Example 7 had no problems in process passability, but the amount of tar adhering to the heater in Example 12 was better than in Comparative Example 7 after 10 days of operation. ●●Stretching false twisting Stretching false twisting was carried out under the following conditions. Twisting method = 3-axis friction method (hard urethane rubber disk), yarn running speed = 600 m/min, stretching ratio =
1.518, twisting side heater = length 2m, surface temperature 220
°C, untwisting side heater = none, target number of twists = 3200T/
m.

[Table] As is clear from the results of Examples 1 to 12 with respect to Comparative Examples 1 to 7, it can be seen that the oil agent according to the present invention satisfies all the items as a whole compared to the conventional oil agent. .

Claims (1)

[Scope of Claims] 1. A cyclic phosphazene compound represented by the following general formula () and an organic compound having one active hydrogen represented by the general formula () in a ratio of 1 to 5 moles of the former to 2 moles of the latter. An oil agent for textile treatment, characterized by containing a phosphazene compound obtained by reacting with. _{R ( -} You can leave it on. R is an alkoxy group having a straight chain or side chain having 1 to 30 carbon atoms (6 to 30 if m is 0).
Alkenoxy group, thioalkoxy group, thioalkenoxy group, acyloxy group, benzyloxy group, phenoxy group, or alkyl (1 to 18 carbon atoms) phenoxy group. X is an alkylene oxide unit having 2 to 4 carbon atoms, and (-X) _-n may be a single unit or a mixture of two or more types. m is an integer of 0 or 1 or more. ] 2 In the fiber manufacturing process, the following general formula ()
Contains a phosphazene compound obtained by reacting a cyclic phosphazene compound represented by the formula () with an organic compound having one active hydrogen represented by the general formula () in a ratio of 1 to 5 moles of the former to 2 moles of the latter. 1. A method for treating fiber yarns, which comprises applying a fiber treatment oil agent in a proportion of 0.1 to 3.0% by weight to the fiber yarns to lubricate the fiber yarns. _{R ( -} You can leave it on. R is an alkoxy group having a straight chain or side chain having 1 to 30 carbon atoms (6 to 30 if m is 0).
Alkenoxy group, thioalkoxy group, thioalkenoxy group, acyloxy group, benzyloxy group, phenoxy group, or alkyl (1 to 18 carbon atoms) phenoxy group. X is an alkylene oxide unit having 2 to 4 carbon atoms, and (-X) _-n may be a single unit or a mixture of two or more types. m is an integer of 0 or 1 or more. ]