JPS64507B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oil agent for treating synthetic fibers (hereinafter simply referred to as an oil agent), and more specifically, the present invention relates to an oil agent for treating synthetic fibers (hereinafter simply referred to as an oil agent), and more specifically, in manufacturing and processing processes that involve heat treatment of synthetic fibers, process failures such as smoke generation, tar formation, and oil scattering are generally significant. Regarding newer and fewer oils. In the manufacturing and processing processes of synthetic fibers, harsh heat treatments are often carried out, and therefore the oils applied to the fibers in these processes are used for example for processed yarns, sewing threads, technical fibers and tire cords. ,
Oils used for raw yarns such as carbon fibers are required to have appropriate heat resistance. In particular, the raw yarn used for processed yarn is subjected to false twisting at 170 to 230°C after being drawn, and at that time it undergoes heat setting at a high yarn speed of 200 to 1200 m/min. The oil applied to such threads has a high level of smoothness that can withstand high-speed processing, produces little smoke or tar, and also prevents any spills from being shaken off from the threads or becoming liquid. These are particularly required, such as the absence of dripping (hereinafter simply referred to as oil drops). Conventionally, many proposals have been made regarding smoothing agents as ingredients in oil agents used for the above-mentioned purposes. However, all of those smoothing agents
While each has its advantages, it also has its disadvantages. For example, mineral oil has excellent smoothness at room temperature, but when heated, its performance deteriorates and it emits a large amount of smoke, which significantly reduces its function as a smoothing agent. Esters synthesized from fatty acids and aliphatic alcohols, natural oils, and the like generally have excellent smoothness, but they have poor heat resistance and cause problems such as tar formation. Fatty acid esters of polyhydric alcohols, such as trimethylolpropane and pentaerythritol, which have a quaternary carbon in the molecule, are less tarred, but have poor smoothness and have many oil drops. In recent years, polyether, which is an alkylene oxide adduct, has been widely used as a material with excellent heat resistance.
The severe heat treatment conditions described above are still insufficient except for tar formation and oil drops. A diester of bisphenol A ethylene oxide adduct having an aromatic nucleus in the molecule has also been proposed, but this has poor smoothness, causes frequent thread breakage and fluff, and has many oil drops. Recently, compounds with sulfide bonds, such as thiocarboxylic acids, have been proposed as compounds that cause less tarring and smoke generation, but under severe heat treatment conditions of 200°C or higher, they have not been able to sufficiently resolve tarring, smoke generation, oil drops, etc. do not have. In short, it is difficult to obtain a lubricant for raw fibers such as processed yarns that satisfies the high degree of heat resistance that is actually required with the smoothing agents that have been proposed so far. In view of this situation, the present inventors conducted intensive research to obtain an oil agent with excellent performance that satisfies the above requirements by using it on fiber threads that are heat-treated at high temperatures, and as a result, the present invention has been developed. Reached. That is, the present invention relates to a molecular weight compound obtained by adding an alkylene oxide having 4 or less carbon atoms to a hydroxy compound having one or more sulfide bonds in the molecule and having 6 or less consecutive carbon-carbon bonds in the molecule.
500 or more alkylene oxide adducts and/or alkyl of the alkylene oxide adducts (however,
The present invention relates to an oil agent for treating synthetic fibers characterized by containing an etherified product (having 6 or less carbon atoms) (hereinafter, such an alkylene oxide adduct and/or an alkyl etherified product thereof are collectively referred to as the compound of the present invention). To obtain the compounds of the present invention, hydroxy compounds are used which have one or more sulfide bonds in the molecule and have not more than 6 consecutive carbon-carbon bonds in the molecule. Such hydroxy compounds include n
-Butyl mercaptoethanol (C ₄ H ₉ SC ₂ H ₄ OH), ethylene bis-2-hydroxyethyl sulfide (HOC ₂ H ₄ SC ₂ H ₄ SC ₂ H ₄ OH), thiodiglycol (HOC ₂ H ₄ SC ₂ H ₄ OH), 3-hydroxyethylmercapto-1,2-propanediol {HOC ₂ H ₄ SCH ₂ C(OH)HC(OH)H ₂ }, di(hydroxyethylthio)triglycol (HOC ₂ H ₄ SC ₂ H ₄ OC ₂ H ₄ OC ₂ H ₄ SC ₂ H ₄ OH). Sulfuride bonds have the property that they are more difficult to break than ether bonds and, conversely, easier to break than carbon-carbon bonds. This method takes advantage of such characteristics. At this time, if a hydroxy compound having more than 6 consecutive carbon-carbon bonds in the molecule is used, taring or oil drops will occur. Examples of alkylene oxides having 4 or less carbon atoms to be added to the above-mentioned hydroxy compounds include ethylene oxide, 1,2-propylene oxide, and 1,2-butylene oxide. In addition, as an etherification agent for an alkylene oxide adduct obtained by adding an alkylene oxide to a hydroxy compound as described above, an agent having a carbon number of 1 to 6 may be used.
There are alkyl chlorides, etc. The compounds of the present invention can be produced by adding an alkylene oxide to a hydroxy compound by a known method using a hydroxy compound, an alkylene oxide, an etherification agent, etc. as exemplified above, or by adding a hydroxyl group to the added product. Furthermore, it can be obtained by etherification using an etherification agent using a known method. At this time, the alkylene oxide may be used alone or in combination of two or more types. Further, the etherification may be partial etherification or complete etherification. The thus obtained compound of the present invention needs to have a molecular weight of 500 or more to prevent smoke generation and oil scattering, but preferably has a molecular weight of 10,000 or less in terms of smoothness. The content of the compound of the present invention in the oil agent according to the present invention is usually 5 to 99% by weight, preferably 50% by weight.
~95% by weight. As ingredients other than the compound of the present invention, other known smoothing agents, surfactants, etc. can be selected as appropriate, and antioxidants, preservatives, etc. can also be used in combination. Among these, polyethers, alkyl phosphate amine salts, amine soaps and the like are particularly preferred as ingredients. When applying the oil agent according to the present invention to fibers, it can be dissolved in an organic solvent or as an aqueous emulsion liquid, and applied during the spinning process, drawing process, or after drawing, by a known oiling method such as roller oiling or guide oiling. do. The oil agent according to the present invention containing the compound of the present invention exhibits excellent effects on both heat resistance and smoothness in terms of smoke generation, tar formation, oil drop, etc. It exhibits a remarkable effect that is not seen in oils, and can be used as an oil for applications involving heat-resistant processes for fibers, such as yarn for false twisting of polyester and nylon, yarn for sewing machines, engineering fibers, and tire cords. It is suitable as an oil agent for spinning and drawing raw yarn, etc., and an oil agent for manufacturing acrylic fibers for manufacturing carbon fibers. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. ●Preparation of compounds The following compounds were prepared. In addition, A to J are compounds of the present invention, and K to W are comparative or conventional compounds (smoothing agents). Also, EO is ethylene oxide, PO
is propylene oxide, POE is polyoxyethylene, POP is polyoxypropylene, MW is molecular weight, and EO/PO is weight ratio. A: C ₄ H ₉ SC ₂ H ₄ O− (EO/PO) _o −H MW=1000, EO/PO=1/1, random addition B: C ₆ H ₁₃ SC ₂ H ₄ O− (EO/PO ) _o −CH ₃ MW=1000, EO/PO=1/1, random addition C:H− (EO/PO) _n −OC ₂ H ₄ SC ₂ H ₄ SC ₂ H ₄ O−
(EO/PO) _o −H MW=1000, EO/PO=1/1, random addition D: [H−(EO/PO) _o −OC ₂ H ₄ ] ₂ S MW=1000, EO/PO=1 /1, random addition F: [H-(EO) _o +OC ₂ H ₄ ] ₂ S MW=1000 G: [H-(EO) _n -(PO) _o -OC ₂ H ₄ ] ₂ S MW=1000, EO/PO=1 /1, block addition H: [H-(EO/PO) _o -OC ₂ H ₄ ] ₂ S MW=600, EO/PO=1/1, random addition I: [H-(EO/PO) _o - OC ₂ H ₄ ] ₂ S MW=2000, EO/PO=1/1, random addition J: [H-(EO/PO) _o −OC ₂ H ₄ ] ₂ S MW=5000, EO/PO=1/ 1. Random addition K: [H-(EO/PO) _o -OC ₂ H ₄ ] ₂ S MW=450, EO/PO=1/1, Random addition L: C ₈ H ₁₇ SC ₂ H ₄ O-( EO/PO) _o -H MW=11000, EO/PO=1/1, random addition M: liquid paraffin (120 seconds) N: 2-ethylhexyl stearate O: oleyl oleate P: dioleyl thiodipropionate Q: Trimethylolpropane tridecanoate R: bisphenol A-(EO) ₂ -dilaurate S: rapeseed oil T: H-(EO/PO) _o -OH MW=1000, EO/PO=1/1, random addition U: bis [POE(3) lauryl ether] thiodipropionate V: POE(5) octyl ether myristylthiopropionate W: POE(10)/POP(10) thiodiglycol dilaurate ●Test category (prepared compounds A to W Heat resistance test) The heat resistance of the prepared compounds A to W was tested and evaluated by the following method. The results are shown in Table 1. (a) Loss on heating over time (item a in Table 1) Differential thermal balance standard model DTA-TG manufactured by Rigaku Denki Co., Ltd.
Accurately weigh 10 to 15 mg of the sample into an aluminum pan using
The temperature was raised at a rate of 10°C/min and held at 250°C for 1 hour. Immediately after raising the temperature to 200℃, 220℃, 250℃, or
The weight loss was determined after 1 hour at 250°C. Weight loss (%) = (sample amount - remaining amount / sample amount) x 100 (b) Heat loss and gelation rate (item b in Table 1) 1 g of sample was placed in a stainless steel plate with a diameter of 70 mm and a depth of 8 mm. Precisely weigh it and place it in a rotary hot air dryer.
It was kept at ±2°C for 24 hours and the remaining amount was measured. Then, tetrahydrofuran was added to the remaining amount, and the insoluble gelled portion was measured. Loss on heating (%) = (test amount - remaining amount / test amount) x 100 Gelation rate (%) = (tetrahydrofuran insoluble matter / test amount) x 100 (c) Smoke generation (c in Table 1) Section) Apply 3% of each compound to 5 g of sample cloth and apply 220
It was placed in an oven at 250°C and 250°C, and the smoke generated was determined by visual observation. Judgment criteria: ◎ = No smoke 〇 = Almost no smoke △ = Slight smoke × = Heavy smoke × × Extremely high smoke

[Table] conversion rate.
As is clear from Table 1, the compound of the present invention can be subjected to short-time heat treatment such as in the fiber manufacturing or processing process (200°C, 220°C,
It can be seen that in 1), there is little decomposition and therefore it exhibits stable performance as a smoothing agent. Also,
Since the heating loss (〓3 of b in Table 1) is large and the gelation rate (〓4 of b in Table 1) is small,
It can also be seen that there is little tar formation and oil drops.
Furthermore, it can be seen that the compounds of the present invention have good smoke generation properties (c in Table 1). Thus, compared to other compounds, the compound of the present invention maintains good smoothness even when fibers are subjected to severe heat treatment at temperatures exceeding 200°C, and exhibits excellent heat resistance against smoking, tar formation, oil drop, etc. It brings out the whole in its entirety. ●Test categories (Examples 1 to 5, Comparative Examples 1 to 10) Oils containing the compounds of the present invention (Examples 1 to 5) as shown in Table 2 and comparative or conventional compounds (smoothing agents) The oils contained (Comparative Examples 1 to 10) were adjusted, and partially oriented polyester yarns (115 denier/25 filament, 0.6% oil adhesion) to which each of these oils were attached were stretched at a stretching ratio of 1.52 and at a heat treatment temperature of 220°C. Stretching and false-twisting was carried out at a stretching and false-twisting speed of 600 m/min. Then, smoke generation, tar formation, and oil drops from the heater plate were visually observed and evaluated, and the friction coefficient was measured using the following criteria or methods. The results are shown in Table 3. ●●Evaluation criteria

[Table] ●●Measurement method of friction coefficient In an atmosphere of 20℃ x 65%RH, the sample yarn was
The yarn was run in contact with a friction body (titanium) at a yarn speed of 207 g and 100 m/min or 300 m/min, and the tension ratio was
Measured with a meter (manufactured by Eiko Sokki Co., Ltd.). When performing heat set, before entering the friction body,
A tube heater (220℃) was installed and the vehicle was run inside.

【table】

[Table] From the results in Table 3, it can be seen that the oil according to the present invention has excellent overall characteristics in terms of smoke generation, tarring, oil drop, and coefficient of friction (before and after heat setting). I understand.

Claims (1)

[Claims] 1. An alkylene oxide adduct with a molecular weight of 500 or more, which is obtained by adding an alkylene oxide having 4 or less carbon atoms to a hydroxy compound that has one or more sulfide bonds in the molecule and has 6 or less consecutive carbon-carbon bonds in the molecule. and/or an alkyl (but not more than 6 carbon atoms) etherified product of the alkylene oxide adduct.