JPS6160192B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a spinning oil for polyester that is suitable for high-speed spinning processes, and its purpose is to improve fiber cohesiveness and improve spinnability, reduce roller wrapping, and have excellent antistatic properties. In addition, we provide a spinning oil agent that reduces as much as possible process troubles caused by polymers or oligomers falling off and accumulating as white powder scum in rotating or moving parts of the spinning machine due to fiber damage, and imparting good spinning properties. This is what we aim to provide. In recent years, in the spinning industry of synthetic fibers such as polyester fibers, there has been an urgent need to take measures to save labor in order to reduce processing costs, and in this sense, there is a strong desire for a spinning oil that is fully satisfactory even in high-speed spinning. However, because polyester cotton has a smoother surface than real cotton or wool, the spinning process cannot be carried out smoothly using conventional oils, and problems such as cylinder wrapping during the guarding process can be caused by treatments on the surface of the fibers. Because spinning oils for polyester fibers are greatly influenced by the type of oil used, research has been carried out enthusiastically. In particular, the goal is to create a spinning oil that improves fiber cohesiveness and improves the efficiency of the spinning process, while also reducing the amount of white powder scum that falls off and accumulates in the spinning machine from the viewpoint of workability. Generally, spinning oils consist of a smoothing agent component and an antistatic agent component, and the smoothing agent components include animal and vegetable oils,
Mineral oil, fatty acid esters, or nonionic surfactants such as aliphatic higher alcohols or polyhydric alcohols, fatty acid esters, ethylene oxide, propylene oxide, or adducts of both, or alkyl sulfates; Anionic activators are used. On the other hand, as the antistatic agent, a cationic activator such as an alkyl phosphate, an alkyl sulfate, an alkylamine ethylene monoxide adduct, a quaternary ammonium salt, or a rain activator such as an alkyl betamen is used. Usually, these components are combined and used as a spinning oil. but,
In general, non-ionic active agents, animal and vegetable oils, mineral oils, and
It is well known that the use of fatty acid esters alone or in combination improves cohesiveness mainly by increasing the mass between fibers. In many cases, sticky substances adhere to rubber rolls and metal rolls, and the sticky nature of the oil agent causes the rollers to wrap around, and various problems occur during the spinning process due to insufficient antistatic properties. . On the other hand, anionic activators are generally used in the form of alkali metal salts, and because of their low tackiness, they tend to roll well with rollers, but they are known to have problems with cohesiveness due to the small stiffness between fibers. Further, cationic activators generally have excellent antistatic properties, and are known to have excellent antistatic properties even at low humidity. However, because it is extremely hygroscopic, it is easily affected by changes in humidity, and is known to have the disadvantage of causing roller wrapping and rusting of the metal parts of spinning machines at high temperatures. Rain-based activators also have excellent antistatic properties, even at low humidity, but they also have drawbacks such as high hygroscopicity, which can cause wrapping around rollers and yellowing of fibers when heated. It is being Recently, oils containing alkyl phosphate esters as the main component have become well known as oils with relatively good performance.These oils have the advantage of being less likely to get wrapped around the rollers, but they do not have the ability to prevent static electricity at low humidity. It has the drawbacks of insufficient elasticity and poor fiber collection performance. In order to improve these, proposals have been made such as adjusting the degree of phosphorylation, selecting the type of alkyl group, selecting the degree of neutralization, and introducing an ethylene oxide chain into the molecule, but the fundamental goal is to improve the focusing property. It is difficult to do so.
Therefore, in order to improve these properties, alkyl phosphate esters are used, and in order to overcome the drawbacks of alkyl phosphate esters, spinning oils in which alkyl phosphate esters are blended with other surfactants have been proposed for a long time. It is put into practical use as an oil agent. For example, in Japanese Patent Publication No. 48-33193, 40-60% by weight of alkyl phosphate potassium salt, polyoxyalkylene ether, or 20-40% by weight of polyoxyalkylene ester and fatty acid ester.
Oil containing 10 to 30% by weight, special publication 52-
Publication No. 63497 proposes a blended oil agent with alkyl phosphates as a spinning oil agent, which contains a block copolymer of propylene oxide and ethylene oxide with a molecular weight of 5000 or more at 30% or more by weight of the total oil component. However, in practice, not all blends of alkyl phosphates and other surfactants will have good spinnability; There is very strict selectivity in selecting the type of oil, and there is no general regularity in blended oils based on alkyl phosphates. Therefore, each blended oil must be subjected to a spinning test to determine its quality. In other words, there is no additivity in terms of properties between the type of alkyl phosphate and the surfactant blended, and the properties will not be exhibited even if two components are combined that have excellent properties individually. Furthermore, the properties of a blended oil are greatly affected by the blending ratio, and it is difficult to express all the properties of the individual components. Against this background, the present inventors have carried out extensive research aimed at developing a spinning oil that has high convergence and low scum properties even when increasing speed and efficiency, and have arrived at the present invention. Thus, according to the invention, the average carbon number is 8 to 16
A linear or side chain alcohol consisting of P ₂ O ₅
an alkyl phosphate ester obtained by neutralizing it with an inorganic alkali hydroxide so that the degree of phosphorylation obtained by reacting is 0.6 to 1.0 and the acid value of the alkyl phosphate reaction product is in the range of 0 to 50. A random copolymer of an inorganic salt, propylene oxide, and ethylene oxide with a polymerization ratio of 75:25 to 30:70 and a polyether having a molecular weight of 1000 to 4000, in which case the polyether is the entire oil component. 10-45% during
(Weight) A spinning oil agent for polyester fibers is provided. Furthermore, to specifically discuss the phosphoric ester compounds used in the present invention, among the known phosphoric esters obtained from higher alcohols that have been widely used in the past, they are used in combination with polyethers to exhibit the effects of the present invention. As the phosphoric acid ester compound for the reaction, alcohols having linear or side chains having an average carbon number of 8 to 16, preferably alcohols P ₂ O having 8 to 12 carbon atoms, are reacted at 100°C or less. The degree of phosphorylation of the product obtained is 0.6 to 1.0.
potassium hydroxide and sodium hydroxide so that the acid value of the reaction product is in the range of 0 to 50.
It is obtained by neutralizing with an inorganic alkali hydroxide such as aluminum, lithium hydroxide, etc., and is generally similar to known compounds as an inorganic salt of an alkyl phosphate ester itself. More specifically, higher alcohols include n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl,
Synthetic alcohols such as n-undecyl, 2-methyldecyl, n-dodecyl, tridecyl, tetradecyl, and cetyl, as well as oxocol (manufactured by Nissan Chemical Co., Ltd.) and dopanol (manufactured by Ciel Chemical Co., Ltd.) are used, but these higher alcohols The average alkyl chain length is in the range of 8 to 16 carbon atoms, and if the chain is longer or shorter than this, the object of the present invention cannot be achieved even if it is used in combination with a polyether compound. That is, if the chain length of the alkyl group is too short, hygroscopicity increases, physical changes in the properties of the phosphoric ester itself increase, and winding during spinning increases. Furthermore, if the chain length is long, it becomes impossible to reduce the focusing property, which is inappropriate. In addition, regarding the degree of phosphorylation, the degree of phosphorylation is
If it is less than 0.6, white powder scum during spinning will increase and convergence will also deteriorate. Also, the degree of phosphorylation is 1.0.
If it exceeds this value, the original properties as an alkyl phosphate ester will be lost, and the heat resistance will even become poor. In addition, the degree of neutralization with inorganic alkali hydroxides has a large effect on spinning properties, and when the acid value exceeds 50, antistatic properties are insufficient, winding around the roller during spinning increases, and heat resistance also decreases significantly. The drawback is that white powder scum also increases. Therefore, in the present invention, the average carbon number is 8 to 16, preferably 10 to
An inorganic salt of an alkyl phosphate ester having 14 linear or branched alkyl groups, a degree of phosphorylation of 0.6 to 1.0, preferably 0.7 to 0.9, and an acid value of 0 to 50, preferably 0 to 40 is used. be done. Examples of inorganic salts include lithium salts, sodium salts, and potassium salts, with potassium salts being preferred. In the present invention, the degree of phosphorylation refers to the number of moles of phosphorus bound to 1 mole of alcohol used, based on the phosphorus content (weight) obtained by the phosphomolybdic acid colorimetric method based on the known quantitative analysis method for phosphorus. The degree of phosphorylation was determined by calculating the degree of phosphorylation. As for the acid value, the obtained inorganic salt of the alkyl phosphate ester was dissolved in glacial acetic acid and titrated with a perchloric acid and glacial acetic acid solution using crystal violet as an indicator, and the acid value was determined from the titration value. That is, an acid value of 0 indicates complete neutralization, and an acid value of 50 indicates a half-neutralized alkyl phosphate salt. On the other hand, in the present invention, the oil agent used in combination with the inorganic salt of the alkyl phosphate ester phosphate is a random copolymer of propylene oxide and ethylene oxide with a polymerization ratio of 75:25 to 30:70.
It is a polyether with a molecular weight of 1,000 to 4,000, and must be blended in an amount of 10 to 45% (by weight) in the total oil component. These random polyethers have extremely poor heat resistance and cannot be used alone, but when blended with an alkyl phosphoric acid ester salt as in the present invention, the heat resistance is surprisingly improved and has a heat resistance that is practical for the purpose of the present invention. show. More specifically, some or all of the terminal groups of these random copolymers are substituted with aliphatic alcohols, alicyclic alcohols, aromatic hydroxyl group-containing compounds, aromatic-aliphatic alcohols, fatty acids, aromatic family acids, aromatic-aliphatic acids,
Alicyclic acids, aliphatic amines, alicyclic amines,
Compounds blocked with aromatic amines, aromatic-aliphatic amines, mercaptans, etc., in other words, functional groups that can react with propylene oxide or ethylene oxide, such as -OH, -COOH, -NH ₂ , -
As long as the compound has an NH, -SH group, etc., there is no particular restriction on the terminal end. These random polyethers are copolymers of propylene oxide and ethylene oxide, and the copolymerization ratio is 75:25.
~30:70 and a molecular weight of 1000 to 4000. More specifically, aliphatic alcohols with a carbon number of 1 such as butyl alcohol, lauryl alcohol, and stearyl alcohol
-22 monohydric alcohol as well as glycerin,
Polyhydric alcohols such as pentaerythritol, trimethylolpropane, and sorbitol are also included, and examples of aliphatic amines include polyvalent amines such as monoamines, diamines, and triamines, and the terminal group is not particularly limited. For the purpose of the present invention, among copolymers, random copolymers are preferentially used, but block copolymers have a higher rolling viscosity than random copolymers and are less likely to be rolled around by rollers during the drawing process. In addition, the effects of the present invention cannot be obtained in terms of convergence. There is also a lot of spinning scum, and the exact reason is unknown〓〓〓〓〓
is inappropriate. In the random polyether of the present invention, the copolymerization ratio of propylene oxide and ethylene oxide is in the range of 75:25 to 30:70, preferably 65:35 to 40:60. If the ratio exceeds 75:25, that is, if the amount of propylene oxide increases, the water dispersibility of the copolymer itself will be poor, and the antistatic properties in the card and drawing during the spinning process will decrease significantly, so it is unsuitable. .
On the other hand, if the copolymerization ratio of ethylene oxide is less than 30:70, the antistatic property will be somewhat better, but when used in combination with an alkyl phosphate ester salt, the tackiness will increase, resulting in an increase in spinning scum. . Furthermore, in terms of molecular weight, those in the range of 1000 to 4000, preferably 1500 to 3000, are selected;
When it is less than 1000, it has the disadvantage of poor heat resistance and volatilization during the manufacturing process of polyester cotton. Moreover, when the value exceeds 4000, the antistatic property decreases significantly, although the reason is unknown. On the other hand, the desired effect of the present invention cannot be achieved with any combination ratio, as there are large restrictions on the blending ratio of the alkyl phosphate ester salt and random polyethers. Preferably 10-45% (weight) in the oil component
Good results are obtained with 20-35% (by weight). In other words, if the random copolymerized polyether is less than 10% (by weight) of the total oil component, the effect will be insufficient in terms of cohesion, and if it exceeds 45% (by weight), the cohesiveness will be good, but the antistatic properties and spinning will be poor. There are disadvantages in terms of scum, etc. The amount of the oil agent of the present invention attached to polyester fibers is 0.1 to 0.3% (by weight), preferably 0.1 to 0.2%.
(weight) is desirable. If the amount of adhesion is too small, the adhesion becomes uneven and static electricity is likely to be generated. However, the oil of the present invention does not have the drawback of deterioration in terms of cohesiveness or spinning scum even if the amount of the oil adhered is large, and is a particularly excellent spinning oil.
It is best to keep it within range. The spinning oil of the present invention can be diluted with water to form an aqueous emulsion, etc., and can be applied to tow/cut cotton by dipping or spraying in the spinning and drawing steps. The polyester fiber thus obtained has good high-speed card passing properties, passes through the drawing process very smoothly, and has minimal shedding of scum and the like. In addition, the oil agent of the present invention may contain other auxiliary agents, such as nonionic active agents or anionic, cationic or amphoteric active agents, as other surfactants if necessary, as long as the effects of the present invention are not lost. In addition, a leveling agent, emulsifier, brightener, dye, or pigment may also be added. The present invention will be explained below with reference to examples, but the invention is not limited in any way by the examples. Example 1 A polyethylene terephthalate fiber (1.5 denier) with an intrinsic viscosity of 0.65 measured with an orthochlorophenol solution was cut into a length of 38 mm and immersed in an oil solution (1% emulsion) shown in Table 1. However, the amount of oil adhering to the fiber weight is 0.15
Table 2 shows the results of spinning the fibers, which were squeezed to % (weight) and then heat-treated at 120°C, at 25°C and 65% RH. The magnitude of static electricity in the carded web and the drawing strip, the bulk specific gravity of the lap in the carding process, and the weight of the scum adhering to the drawing roll, that is, the rubber roller and the metal roller after spinning, were measured and compared. The results are summarized in Table 2. In addition, those with good results are shown as ◎, good results as ○, intermediate results as △, and poor results as ×. Note that the results of spinning with currently widely used spinning oils are shown as △ for comparison.

[Table] 〓〓〓〓〓

【table】

[Table] 〓〓〓〓〓

[Table] As can be seen from the results in Table 2, it can be seen that the present invention exhibits excellent spinnability. Example 2 The results shown in Table 3 were obtained in the same manner as in Example 1 using the oil agent A in Table 1 and varying the blending ratio.

[Table] As can be seen from Table 3, it can be seen that stable spinnability is exhibited within the scope of the present invention. Example 3 When the oil agent A of the present invention was compared with a typical spinning oil agent currently widely used in the market using a method similar to Example 1, the results shown in Table 4 were obtained, indicating that the oil agent of the present invention It can be seen that stable spinnability is exhibited.

[Table] 〓〓〓〓〓

[Table] 〓〓〓〓〓

Claims (1)

[Claims] 1 The degree of phosphorylation obtained by reacting a linear or side chain alcohol with an average carbon number of 8 to 16 with P ₂ O ₅ is 0.6 to 1.0, and the acid value of the alkyl phosphate ester reaction product is 0 to 1. Random copolymer of alkyl phosphate inorganic salt, propylene oxide, and ethylene oxide obtained by neutralizing with an inorganic alkali hydroxide so that the polymerization ratio is in the range of 75:25 to 30:70. and a polyether having a molecular weight of 1,000 to 4,000, wherein the polyether is blended in an amount of 10 to 45% (by weight) in the total oil component.