JPS6324119B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oil agent for treating synthetic fiber filaments for false twisting (hereinafter abbreviated as oil agent). The present invention also relates to an oil agent that exhibits a high degree of heat treatment heater contamination prevention ability (hereinafter abbreviated as heater contamination resistance) in addition to antistatic properties. In recent years, the production and processing of thermoplastic synthetic fibers has focused on the production of partially oriented yarn (hereinafter abbreviated as POY) and the production of partially oriented yarn (hereinafter abbreviated as POY), in part to improve productivity through labor saving and process shortening.
It has been proposed to produce bulky textured yarn by simultaneously or simultaneously performing drawing and false twisting using POY, and efforts are being made to further increase the speed of the process. It is progressing rapidly. As speeds increase in this way, the lubricants used will also need to (i) increase the speed and contact pressure of the yarn as it runs in contact with various contacting bodies (e.g. rollers, guides, heat treatment heaters, disks, etc.); As a result, there is a need for an oil agent that provides a high degree of lubricity, cohesiveness, and antistatic properties to the false-twisting yarn, especially to the drawn false-twisting yarn. (ii) Due to an increase in the amount of yarn passing through the heat treatment heater per unit time and an increase in centrifugal force due to increased torsion deformation of the yarn, various types of shedding onto the heat treatment heater is promoted, and crimping of the filament. In order to supply the amount of heat necessary for fixation to the filament, it is necessary to increase the length of the heat treatment heater and to raise the surface temperature, so that the falling components are more likely to be thermally degraded. When heat-deteriorating components (for example, tar) accumulate on the surface of the heat treatment heater, adverse effects such as fuzz, thread breakage, and crimp spots occur. Therefore, there is a need for an oil agent that suppresses such shedding and has excellent resistance to heater contamination. Oil agents containing various compounds have already been proposed to be applied during the spinning process in order to smoothly carry out the subsequent false twisting process. However, such previously proposed lubricants are no longer able to adequately meet the increasingly severe false twisting conditions as described above. For example, the actual state of the process regarding heater contamination resistance of oil agents is that the machine has to be stopped every time and the heater surface is cleaned, which results in a loss of thermal efficiency and a reversal of labor savings due to the use of cleaning personnel. , resulting in a reduction in production efficiency, etc., and these have become important problems that need to be solved. Nowadays, the speed of false twisting processing is increasing rapidly, and in order to fully meet the requirements (i) and (ii) mentioned above, the oil used for this process has to have heater contamination resistance, lubricity, It is essential that the material has a high degree of overall convergence, anti-static properties, etc. Conventionally, as a means to improve the heat resistance in the heat treatment process of supplied yarn, it has been considered important to improve the heat resistance of the oil agent itself applied to the fibers, so that it does not deteriorate due to heat and contaminate the heater. Various oils have been studied, examples of which are listed below, but each has its own drawbacks. First, regarding lubricants, which are the main components of oil agents, mineral oils and fatty acid esters lack smoke resistance and anti-tarring properties. Ester compounds with a quaternary carbon introduced into the molecule (Japanese Patent Publication No. 53695/1989) and esters of polyoxyalkylenated bisphenols with a phenyl group introduced into the molecule and fatty acids (Japanese Patent Publication No. 53/1986)
No. 43239, etc.) lack anti-taring properties. Polydimethylsiloxane and its terminally modified products (Special Publication 1983-
No. 12391, JP-A-55-67075) generates significant static electricity and lacks scouring properties and compatibility with other oil components. Methylphenylpolysiloxane and polyepoxysiloxane (JP-A-49-30621, JP-A-51-
When modified silicones such as No. 67415) are used in large amounts (more than 10% by weight as a guide) as a component in the oil formulation, they themselves produce thermally degraded insoluble sludge on the surface of the heater. Polyether compounds (Japanese Unexamined Patent Publication No. 1983
-31077), as mentioned above, due to severe changes in various processing conditions due to the increase in speed in the false twisting process, heater contamination is a problem even in this type of processing oil, and emulsifiers and antistatic agents added to it are also a problem. It has also been pointed out that the degree of contamination can become even more significant depending on the type and amount added. Next, regarding components other than such lubricants, an example of adding a small amount of antioxidant (Japanese Patent Publication No. 17517/1983)
JP-A No. 53-19500) is somewhat effective, but cannot withstand high-speed machining conditions. Add a small amount of polydimethylsiloxane, methylphenylpolysiloxane or polyepoxysiloxane (as a guide)
Example of adding (10% by weight or less) (Special Publication No. 54-5040,
JP-A No. 55-137273) has insufficient anti-tar properties and is generally not water-soluble (this also applies when large amounts are used), and the emulsifier added to disperse these compounds in water as an oil component is On the contrary, it becomes a source of heater contamination. Similarly, regarding a component other than a lubricant that uses polyalkylene oxide modified polysiloxane, an example of using polyethylene oxide modified polysiloxane (Japanese Patent Publication No. 44-27518)
has not yet achieved sufficient resistance to heater contamination as a raw yarn oil for false twisting. An example of using a linear organopolysiloxane with a kinematic viscosity of 15 cst or more together with a polyether compound (Japanese Patent Application Laid-open No. 48-5309) is an example of this.For example, methyl (polyethylene oxide) polysiloxane has less durability against heater contamination. . An example of using a large amount (35% by weight or more) of polyalkylene oxide-modified silicone in combination with a polyalkylene oxide with affinity (Japanese Patent Application Laid-open No. 59551/1983) shows that the threads of the modified silicone are transferred onto the heater. This is an attempt to reduce shedding and thereby improve the drawback of generating white sludge on the heater, but as mentioned above, increasing the false twisting or drawing false twisting speed causes a large centrifugal force to be applied to the yarn. Therefore, it is extremely difficult to prevent the oil component from being squeezed and shaken off from the fiber surface by physical means. An example of using a polyalkylene oxide-modified polysiloxane and a reactive silicone compound together in a ratio of 5 to 400/100 parts by weight of the former/latter (Japanese Patent Application Laid-open No. 1983-96297) shows that the modified polysiloxane is used as an oil component in an amount of 10 parts by weight. % or more produces an insoluble sludge on the heater surface that is itself heat degraded. The present invention provides an improved lubricant that eliminates the above-mentioned conventional drawbacks and meets the requirements for high-speed processing, and is used to false-twist or process thermoplastic synthetic fibers such as polyester fibers and polyamide fibers. Comprehensively exhibits a high degree of resistance to heater contamination, lubricity, cohesiveness, and antistatic properties when producing bulky textured yarn at high speed by sequentially or simultaneously drawing and false twisting. The purpose is to provide an oil solution that can As mentioned above, even today, most of the methods for improving resistance to heater contamination in heat treatment processes focus only on improving the anti-tarring properties of the oil agent itself applied to fibers. ing. However, as a result of investigating the cause of heater contamination still being a problem even in polyether compounds whose tar formation has been improved compared to other base components mentioned above, we found that It was discovered that the accumulated sludge contained, in addition to the deterioration of the oil agent, a large amount of oligomers and some polymers generated from the running yarn itself, as well as their thermally degraded products. Only oils that can simultaneously and highly reduce tar compounds, oligomers, polymers, etc. that fall off from yarn, and their degraded products (tar compounds) can sufficiently achieve high-speed false twisting and stretch false twisting on an industrial scale. I came up with the idea that it can be done. As a result of further intensive research, we found that a predetermined small amount of polyalkylene oxide-modified polysiloxane with a limited molecular structure and molecular weight that had undergone specific modification was added to an oil containing a predetermined amount of an antistatic agent and a lubricant. We found that the heater sludge as mentioned above can be significantly reduced.
The present invention has now been completed. That is, the present invention relates to the following oil agent that can extremely smoothly industrially perform high-speed processing of synthetic fiber yarns for false twisting, which is progressing more and more rapidly these days. A lubricant whose main component is a polyether compound derived from an alkylene oxide having 2 to 4 carbon atoms is used as a base oil, and a polyalkylene oxide-modified polysiloxane having an average molecular weight of 2500 or more expressed by the following general formula (2) is used as a base oil. 10% by weight,
and an oil agent for treating synthetic fiber filaments for false twisting, comprising 0.5 to 8% by weight of an anionic surfactant having a lipophilic group having 8 to 18 carbon atoms in the molecule. General formula (): [However, X is

[Formula] l is an integer from 20 to 100. Also, Y is

[Formula] m is an integer from 1 to 9. And here, R ₁ is an alkylene group having 3 to 4 carbon atoms, and R ₂ is an alkylene group having 2 to 4 carbon atoms.
The alkyl group of 8, a and b, are integers satisfying 15≦a+b≦80 and 2/8≦b/a≦8/2. In addition, polydimethylsiloxane represented by X and Y
The repeating part with polyalkylene oxide-modified siloxane and the repeating part with polyethylene oxide bound by a and polypropylene oxide bound by b may be repeated in either a block or random manner. . ] In the present invention, the polyalkylene oxide-modified polysiloxane represented by the general formula () is added in small amounts as an essential component of the oil agent;
Molecular weight is 2500 or more, number of repeats of Y is 1 to 9
, the alkylene oxide chain in Y is a repeating (block or random) of ethylene oxide (hereinafter abbreviated as EO) and propylene oxide (hereinafter abbreviated as PO), the repeating number a of the EO and the repeating number b of the PO. is 15≦a+b≦80 and 2/8≦b/a≦8/2, the number of repetitions of Y is m
and the number of repetitions l of X is m/l=1/100~45/
100, which satisfies the requirements of ~100 or more,
The compound of the general formula () subjected to such specific modification exhibits the desired effects, particularly remarkable resistance to heater staining. Even if any of the requirements added to the general formula () is missing, the object of the present invention cannot be fully achieved. For example, if the molecular weight is less than 2,500, the material itself cannot withstand the severe heat treatment conditions in the false-twisting process, smokes or evaporates, and is less effective, probably because it is unable to form a stable oil film. m
is 10 or more, or l is 19 or less, the properties are similar to those of polyether, and oligomers often fall off from the running yarn, resulting in only the same effect as when this compound is not added. l is 100
If it exceeds this value, perhaps because the properties become similar to those of polydimethylsiloxane, not only the resistance to heater staining decreases, but also the composition itself begins to form a varnish-like substance. If a or b deviates from the above requirements, sufficient effects will not be obtained, probably because a uniform and stable oil film will not be formed on the fiber surface due to their own properties and reduced compatibility with other oil components. Such a compound represented by the general formula () can be easily synthesized, for example, by a method such as the following hydrosilylation reaction between the compound (i) and the compound (ii). (i) A compound in which the terminal (ω-position) hydroxy group of the EO and PO adducts of allyl alcohol is octyl etherified. (ii) Methylhydrodiene polysiloxane with hydrogen atoms located randomly or in blocks...
… A mixture of CH ₃ and H arranged randomly or in blocks. In addition, in the present invention, the anionic surfactant having a lipophilic group with 8 to 18 carbon atoms in its molecule suppresses the amount of triboelectric charge generated on the running yarn and quickly leaks the generated charge, and is used as a sulfonate surfactant. salt,
One or more types of sulfate salts, phosphate salts, or carboxylic acid salts are used, but all of them have a hydrophilic group and a lipophilic group with 8 to 18 carbon atoms in the molecule and are used as antistatic agents. can be targeted. Specific examples include alkali metal salts or organic amine salts such as alkanesulfonates and alkylbenzene sulfonates as sulfonate salts, alkali metal salts or organic amine salts such as higher alcohol sulfates or polyoxyalkylene alkyl ether sulfates, and phosphates as sulfate salts. Salts include various natural alcohols, primary or secondary synthetic alcohols, alkali metal salts or organic amine salts of phosphates such as alkylene oxide adducts of these, and aliphatic monocarboxylic acid salts, dicarboxylic acid salts, etc. as carboxylic acid salts. There is. Among these, sodium, potassium or alkanolamine salts having an alkyl group or alkenyl group having 8 to 18 carbon atoms as a lipophilic group in the molecule are preferred. Furthermore, in the present invention, the polyether compound, which is the main component of the lubricant that serves as the base oil, provides good cohesiveness to the yarn during the fiber manufacturing process, exhibits an excellent lubricating effect under severe false twisting conditions, and It has features such as less generation of heater tars due to thermal deterioration, and its chemical structure is not particularly limited, but the average molecular weight
700 or above is good. If the average molecular weight is less than 700, smoke resistance, cohesiveness, and lubricity during the false-twisting or stretch-false-twisting process tend to decrease. Specific examples include alcohols (monohydric alcohols such as saturated alcohols having 1 to 18 carbon atoms, oleyl alcohol, synthetic alcohols having 10 to 15 carbon atoms, reduced alcohols, and hexadecanol; diols having 2 to 12 carbon atoms;
Polyhydric alcohols such as glycerin and trimethylolpropane. alkylphenols, etc.), carboxylic acids (capric acid, adipic acid, trimellitic acid, etc.), amine compounds (laurylamine, ethylenediamine, triethanolamine, etc.), thioether compounds or mercaptan compounds (thioglycol, triethylene glycol dimercaptan, etc.) etc.), cyclic ether monomers such as EO, PO, butylene oxide, or tetrahydrofuran are subjected to block or random ring-opening addition polymerization in the presence of a catalyst, and these terminal hydroxy groups are etherified or silylated. There are also those in which the terminal hydroxy groups of these two molecules are condensed by formalization or silylation. It is also effective to use such a polyether compound in combination with an ester compound and/or mineral oil as a lubricant component. These ester compounds and/or mineral oils are not particularly limited as long as they have a substantial effect as a lubricant/frictional resistance reducing agent.
In terms of effectiveness and resistance to heater staining, mono- or diesters of aliphatic alcohols and monovalent fatty acids, mono- or diesters of polyoxy(ethylene/propylene) aliphatic alcohols and monovalent or divalent fatty acids, 30 The red viscosity at °C is
Refined mineral oils of 40 to 200 seconds are preferred, respectively. The oil agent of the present invention is made by blending the above-described polyalkylene oxide-modified polysiloxane and anionic surfactant in a specific ratio into a lubricant whose main component is a polyether compound. By blending them in a specific ratio, the desired synergistic effect can be achieved. Therefore, is 0.05-10% by weight, is 0.5
~8% by weight, with the remainder being 82~99.45% by weight.
If it is less than 0.05% by weight, the effect will not be sufficiently exhibited, and the tar of the oil agent on the heater, the oligomers generated from the yarn, the falling off of polymers, and their deteriorated products will increase, while 10% by weight If the temperature exceeds 100%, insoluble sludge which itself has deteriorated due to heat will be generated, which will cause contamination of the heater. Moreover, if it is less than 0.5% by weight, various electrical problems will occur, while if it exceeds 8% by weight, heater tar will increase. Incidentally, the oil agent according to the present invention may appropriately contain an emulsification regulator, a wetting agent, a fungicide, a rust preventive agent, etc. in addition to the above-mentioned compounds. Next, a method for treating fibers using the oil agent described above will be explained. The oil agent of the present invention is applied to synthetic fibers as a spinning oil agent and exhibits its effect, but when used, it can be used as an aqueous emulsion, as an organic solvent solution, or as an oil agent as it is (straight oiling). It can be applied to fibers. At this time, the amount of the oil attached to the synthetic fibers is usually determined as the effective component of the oil compared to the filament.
It is about 0.2 to 1.0% by weight. The objects to which the oil agent of the present invention is applied are synthetic fibers containing polypropylene, polyacrylonitrile, etc., but in particular polyester and polyamide fibers are to be applied, and are wound at a winding speed of 2000 to 4500 m/min. Add the oil of the present invention to POY from 0.25 to
When about 0.7% by weight is added and then subjected to false twisting or stretching false twisting, the effect aimed at by the present invention is extremely remarkable. As explained above, the oil agent of the present invention is composed of the three specific components mentioned above in a specific ratio, and due to the synergistic effect, the oil agent of the present invention has excellent overall stability for high-speed manufacturing and processing, which is not found in conventional oil agents. properties, especially resistance to heater contamination. The main reason for this remarkable effect is that conventional oil agents have been improved only by reducing the tar formation of the oil agent itself, but in the present invention, the heater tar constituents other than the oil agent, such as oligomers in the threads and This also reduces the amount of polymer falling off, and prevents thermal deterioration of the falling material on the heater. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following description, the composition ratio of the oil agent is expressed in percent by weight unless otherwise specified. Examples 1 to 5, Comparative Examples 1 to 10 The oils of Examples 1 to 5 and the oils of Comparative Examples 1 to 10 listed in Table 1 were blended and adjusted. Using each of these oils, POY is produced by the following method, and the POY is stretched and false-twisted to produce POY.
Four items were evaluated: twilling, electrostatic voltage of the running yarn, fuzz of the drawn false-twisted yarn, and heater contamination. The results are shown in Table 1. The results in Table 1 also show that, according to the oil agent of the present invention, no occurrence of POY traverse, heater contamination, or static electricity damage during POY drawing false twisting was observed, and good false twisted yarn without fuzz was obtained. It can be seen that the excellent performance is fully demonstrated. ●Manufacture of POY Immediately after melt spinning polyethylene terephthalate, oil is applied using a 10% emulsion of oil agent using the roller touch method, and the yarn is wound at a speed of 3300 m/min.
A 12Kg rolled cake of POY of 115 denier x 36 filaments was obtained. Oil adhesion amount is 0.4 to 0.5 for POY
It was expressed as weight%. ●Stretched false twisting Twisting method = 3-axis friction method (solid ceramic disk), Yarn running speed = 400 m/min, Stretching ratio = 1.518, Twisting side heater = 2 m length, surface temperature
210℃, untwisting side heater = None, target number of twists =
3200T/m, ●Evaluation of POY traverse (travel in each table) Visual observation was made to see if the filament protruded in a straight line from the end surface of the POY cake. This phenomenon causes yarn breakage when the POY is unwound during stretching and false twisting. ●Evaluation of the electrostatic voltage of the running yarn (electrostatic voltage in each table) In the above-mentioned false twisting process, the electrostatic voltage of the running yarn immediately after passing through the twisting device and the delivery roller was measured using a current collector potential measuring device ( (manufactured by Kasuga Denki Co., Ltd.) and evaluated based on the following criteria. 〇: Charge voltage 0 to 300 volts △: 〃 301 to 1000 volts The presence or absence of fuzz on the end face of the specimen was visually observed and evaluated according to the following criteria. 〇: No fluff occurred △: 1 to 2 fluffs ×: 3 or more fluffs ●Evaluation of heater contamination (heaters in each table) After continuous operation for 20 days under the stretching and false twisting conditions described above, twisting was performed. The occurrence of tar, scum, etc. in the yarn path of the side heater was observed using a magnifying glass, and evaluated based on the following criteria. 〇: Almost no heater contamination is observed ×: Heater contamination is observed

【table】

[Table] Examples 6-11, Comparative Examples 11-14 Oils of Examples 6-11 listed in Table 2 and Comparative Examples
The formulations of 11 to 14 oils were adjusted. Using each of these oils, POY is produced by the following method, and the POY is subjected to drawing false twisting, and POY draping, running yarn charging voltage, fluffing of drawn false twisting yarn, heater contamination, and heater 5 of the amount of polyester oligomer in the contaminated material (oligomer in Table 2, weight %)
The items were evaluated. The results are shown in Table 2. From the results in Table 2, it can be seen that according to the oil of the present invention,
It can be seen that no twilling of the POY, no heater contamination, and no electrostatic damage occurred during POY stretching and false twisting, and that a good false twisted yarn without fuzz was obtained. Regarding the heater contaminant composition, Comparative Example 14 is cited as a representative example. This example consists of 96% by weight of polyether lubricant and 4% by weight of anionic surfactant, but as is clear from the table. In addition, heater contamination was observed, and the drawn false-twisted yarn also had a lot of fuzz, probably because the yarn ran on this contaminant. Then, this heater contaminant was collected, and the components were separated, identified from specific absorption by infrared absorption spectrum, and the melting point was measured (the same method was used for the oligomers in Table 2). Analysis of the contaminants revealed that 60% by weight of polyester cyclic oligomers, 5% by weight of polymers, 5% by weight of oil components, and 30% by weight of thermally degraded products (tarred products) of oils, oligomers, and polymers. and
It contained a large amount of oligomers. ●Manufacture of POY Immediately after melt spinning polyethylene terephthalate, oil is applied using a roller touch method using a 10% oil emulsion, and the POY is wound at a speed of 3500 m/min to produce 12 kg of POY of 76 denier x 36 filaments.
I got a rolled cake. The amount of oil adhered is relative to POY.
The content was 0.30 to 0.35% by weight. ●Stretched false twisting Twisting method = 3-axis friction method (hard urethane rubber disc), Yarn running speed = 800 m/min, Stretching ratio =
1.518, twisting side heater = length 2m, surface temperature 220
°C, untwisting side heater = none, target number of twists = 3450T/
m, ...Evaluations of POY tread, electrostatic voltage of running yarn, fuzz of drawn false twist, and heater contamination are shown in Examples 1 to 5.
Same as in the case of

【table】

[Table] Examples 12 to 16, Comparative Examples 15 to 29 The same procedures as in Examples 1 to 5 were carried out using the oils listed in Table 3 and in the following manner. The results are shown in Table 3, which also shows the excellent performance of the oil agent of the present invention. ●Manufacture of POY Immediately after melt-spinning polyamide (6,6 nylon), oil was applied using a guide oiling method using a 13% oil emulsion, and the POY was wound at a speed of 4000 m/min to form a POY of 36 denier x 7 filaments. 8Kg
I got a rolled cake. The amount of oil adhered is relative to POY.
The content was 0.45 to 0.55% by weight. ●Stretched false twisting Twisting method = 3-axis friction method (hard urethane rubber disc), Yarn running speed = 1100 m/min, Stretching ratio = 1.200, Twisting side heater = 2.5 m in length and surface temperature
230℃, untwisting side heater = None, target number of twists =
3000T/m, ...Evaluations of POY tread, electrostatic voltage of running yarn, fuzz of drawn false-twisted yarn, and heater contamination were carried out in Example 1.
Same as for ~5. However, the evaluation of the latter two was conducted after 10 days of continuous operation.

【table】

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. A polyalkylene having an average molecular weight of 2500 or more represented by the following general formula (), using a lubricant whose main component is a polyether compound derived from an alkylene oxide having 2 to 4 carbon atoms as a base oil. A lubricant for treating synthetic fiber filaments for false twisting, comprising 0.05 to 10% by weight of oxide-modified polysiloxane and 0.5 to 8% by weight of an anionic surfactant having a lipophilic group having 8 to 18 carbon atoms in the molecule. General formula (): [However, X is [Formula] l is an integer from 20 to 100. Further, Y is [Formula] m is an integer from 1 to 9. And here, R ₁ is an alkylene group having 3 to 4 carbon atoms, and R ₂ is an alkylene group having 2 to 4 carbon atoms.
The alkyl group of 8, a and b, are integers satisfying 15≦a+b≦80 and 2/8≦b/a≦8/2. In addition, polydimethylsiloxane represented by X and Y
The repeating part with polyalkylene oxide-modified siloxane and the repeating part with polyethylene oxide bound by a and polypropylene oxide bound by b may be repeated in either a block or random manner. . 2. The lubricant for treating synthetic fiber filaments for false twisting according to claim 1, wherein the lubricant contains an ester compound and/or mineral oil.