JPS599665B2 - Spinning oil for polyester fibers - Google Patents

Description

Detailed Description of the Invention [Field of the Invention and Object of the Invention] The present invention relates to a spinning oil for polyester suitable for high-speed spinning processes. (b) Reduces fiber wrapping around rollers; (c) Excellent antistatic properties; (d) Part of the spinning machine where polymers or oligomers rotate or move due to fiber damage. It is an object of the present invention to provide a spinning oil that can reduce as much as possible process troubles caused by falling off and accumulating as scum, and (e) imparting good spinnability even when blended with other fibers.

[Prior art]

In recent years, in the spinning industry for polyester fibers, there has been an urgent need to take measures to save labor in order to reduce processing costs.In this sense, high-speed spinning is not only satisfactory when polyester fiber is used alone, but also when it is blended with other fibers. There is a strong desire for a spinning oil that can

However, since polyester cotton has a smoother surface than cotton or wool, conventional oils cannot ensure a smooth spinning process, and it is particularly prone to cylinder wrapping during the carding process. Depending on the type of oil agent used, during blending, the oil agent for polyester fibers may be trapped by other fibers being blended, such as rayon, cotton, wool, etc., and the elasticity of the polyester fibers themselves may be impaired, resulting in poor spinnability. There are many cases where this happens.

Furthermore, since spinning properties are greatly influenced by the type of oil, research into oils for polyester spinning has been carried out enthusiastically.

In particular, the goal was to create a versatile spinning lubricant that would improve the efficiency of the spinning process by improving fiber cohesiveness, while at the same time reducing the amount of scum that would fall off or accumulate in the spinning machine from the viewpoint of workability. There is.

In general, spinning oils consist of a smoothing agent component and an antistatic agent component, and the smoothing agent components have traditionally been animal and vegetable oils, mineral oils, fatty acid esters, fatty acid esters of aliphatic higher alcohols or polyhydric alcohols, ethylene oxide, propylene oxide, etc. Alternatively, nonionic surfactants such as adducts of both or anionic surfactants such as alkyl sulfates or even alkyl phosphates are used.

On the other hand, as antistatic agents, cationic activators such as alkyl phosphates, alkyl sulfates, terkylamine ethylene monoxide adducts, quaternary ammonium salts, or amphoteric activators such as alkyl betaines are used; These ingredients are combined and used as a spinning oil.

However, it is generally well known that nonionic activators, animal and vegetable oils, mineral oils, or fatty acid esters used alone or in combination mainly increase friction between fibers and improve cohesiveness. During the opening process and drawing process, sticky substances may adhere to rubber rolls, metal rolls, etc., and the stickiness of the oil may cause the rollers to wrap around, and the antistatic properties may be insufficient. There are various troubles in the spinning process.

On the other hand, anionic activators are generally used in the form of alkali metal salts, and because of their low stickiness, they often work well when wrapped around a roller, but they are known to have problems with cohesiveness due to the small stiffness between the fibers. There is.

Further, cationic activators generally have excellent antistatic properties, and are known to have excellent antistatic properties even at low humidity.

However, these materials are highly hygroscopic and are easily affected by changes in humidity, and it is also known that they have the disadvantage of causing roller wrapping and rusting of the metal parts of spinning machines when the humidity is high. ing.

Amphoteric activators also have excellent antistatic properties and have excellent antistatic properties even at low humidity, but they also have the disadvantages of high hygroscopicity, which can cause roller wrapping and yellowing of the fibers when heated. Are known.

In addition, recently, oils containing alkyl phosphate as the main component have become well known as oils with relatively good performance.These oils have the advantage of being less likely to wrap around the rollers, but they are difficult to control at low humidity. It has drawbacks such as insufficient electrical conductivity and poor fiber cohesiveness.

To improve this, proposals have been made such as adjusting the degree of phosphorylation, selecting the type of alkyl group, selecting the degree of neutralization, and introducing ethylene oxide chains into the molecule, but the fundamental goal is to improve the focusing property. It is difficult to do so.

Therefore, for these improvements, alkyl phosphate esters are further used, and in order to compensate for the shortcomings of alkyl phosphate esters, spinning oils containing alkyl phosphates and other surfactants have been provided for a long time. It is well known that it is in practical use as one of the important spinning oils.

For example, according to Japanese Patent Publication No. 48-33193, an oil agent containing 40 to 60% by weight of alkyl phosphate potassium salt, 20 to 40% by weight of polyoxyalkylene ether or polyoxyalkylene ester, and 10 to 30% by weight of fatty acid ester, etc. , Japanese Patent Publication No. 52-63497 proposes a blended oil agent with an alkyl phosphate containing a block copolymer of propylene oxide and ethylene oxide with a molecular weight of 5000 or more at 30% or more by weight in the total oil component as a spinning oil agent. .

However, in actual practice, it is not the case that any combination of alkyl phosphates and other surfactants will have good spinnability, and the structure and type of alkyl phosphates There is very strict selectivity in selecting the type of surfactant to be blended, and there is no general regularity between phosphates and the combination oil agent.

Therefore, we conducted spinning tests on each of the blended oils.
The current situation is that we have to decide whether it is good or bad.

In other words, there is no additivity in terms of properties between the type of alkyl phosphate and the surfactant to be blended, and the properties will not be exhibited even if two components are combined that have excellent properties individually. In addition, the properties of the blended lubricant are greatly affected by the blending ratio, and when it comes to not only the spinnability of polyester fiber alone but also blending with other fibers, it is difficult to express all the properties of the individual components. be.

[Structure and operation of the invention] Against this background, the present inventors have worked diligently to develop a spinning oil that has high convergence and low scum while achieving the high speed and high efficiency that are the objectives of the present invention. The present invention was achieved as a result of repeated research.

That is, the present invention provides a method for reacting P205 with a linear or side chain alcohol having an average carbon number of 8 to 16, and the degree of phosphorylation obtained from the reaction is 0.6 to 1.0, and the acid value of the alkyl phosphate ester reaction product is 0.6 to 1.0. General formula (1) and/or general formula (
2) [However, R is a straight chain or a side chain having 8 to 18 carbon atoms
a saturated or unsaturated alkyl group, and further (where R' is R
), n is a positive integer of 2 to 3, and p is O or a positive integer of 1 to 3.

] [However, R is a straight chain or a side chain having 8 to 1 carbon atoms
8 represents a saturated or unsaturated alkyl group (wherein R' is the same group as R), and X represents a C1 to C4 lower alkyl group or a cyanethyl group.

5 ethylene oxide to the alkyl amines shown in
11 to 6 phosphoric acid ester salts of compounds added with ~20 moles
This is a spinning oil agent for polyester fibers, characterized in that it contains 7 parts by weight.

To explain the present invention more specifically, first, the phosphoric ester compound used in the present invention has the general formula (1) and/or ( In order to exhibit the effect of the present invention when used in combination with the POE adduct of alkylamines in 2), an alcohol having a straight chain or a side chain having an average carbon number of 8 to 16 and P205 are heated at 100°C or less. The degree of phosphorylation obtained by reacting at temperature is 0.6 to 1.0
and by neutralizing Kariupe hydroxide with an inorganic alkali hydroxide such as sodium hydroxide, lithium hydroxide, etc. so that the acid value of the reaction product is in the range of 0 to 50. can get.

For example, the alkyl groups of higher alcohols include n-octyl, 2-ethylhexyl, n-nonyl, ny" syl, n-
-undecyl, 2-methyldecyl, n-dodecyl, n
Synthetic alcohols such as -triy'-cynodi, 2-methyldodecyl, n-tetradecyl, cetyl groups, and n-oxocol (manufactured by Nissan Chemical Co., Ltd.) and dopanol (manufactured by Shell Chemical Co., Ltd.) are used, The average alkyl chain length of these higher alcohols is in the range of 8 to 16 carbon atoms, and those with longer or shorter chains than this can be used in combination with the compounds of general formulas (1) and (2). However, the purpose of the present invention cannot be achieved.

That is, if the chain length of the alkyl is too short, the hygroscopicity increases and the physical change in the properties of the phosphoric ester itself increases, resulting in increased winding during spinning.

Furthermore, if the chain length is long, it becomes impossible to maintain convergence, which is inappropriate.

Further, the degree of phosphorylation needs to be in the range of 0.6 to 1.0.

Here, if the degree of phosphorylation is less than 0.6, white powder scum during spinning will increase and the cohesiveness will deteriorate.

Furthermore, if the degree of phosphorylation exceeds 1.0, the original properties as an alkyl phosphate ester will be lost and the heat resistance will be rather poor.

In addition, the degree of neutralization by inorganic alkali hydroxide has a large effect on spinning properties, and if the acid value exceeds 50, antistatic properties will be insufficient, increasing the amount of wrapping around the roller during spinning, and greatly reducing heat resistance. However, the disadvantage is that white powder scum also increases.

Therefore, in the present invention, the average carbon number is 8 to 16, preferably 1.
0 to 14 linear or branched alkyl groups, and the degree of phosphorylation is 0.6 to 1.0, preferably 0.7 to 0.9, and the acid value is preferably 0 to 50, preferably 0 to 40. Inorganic salts of alkyl phosphates selected from a range are used.

In addition, examples of inorganic salts include lithium, sodium, potassium, etc., 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 is determined by calculating whether the

Regarding the acid value, the obtained inorganic salt of the alkyl phosphate ester is 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 is determined from the titration value.

In other words, an acid value of O means complete neutralization.
An acid value of 50 indicates that the salt is a half-neutralized alkyl phosphate salt.

゛Next, general formula (1) and/or (2) used in combination with the alkyl phosphate ester to exhibit the effects of the present invention
The following describes the phosphate salts of ethylene oxide adducts of alkylamines and alkenylamines.

Specifically, K in the general formula (1) is P-00, which is a phosphate of a compound obtained by adding 5 to 20 moles of ethylene oxide to this, and examples of specific alkyl groups in this case include octyl, Representative examples include lauryl, stearyl, and oleyl.

Further, examples of alkyl having a side chain include alkylamines such as 2-ethylhexyl, tridecyl, incetyl, and α-methylalkyl, but the present invention is not limited thereto.

In addition, hydroxyalkylamines, alkoxyprobylamines, alkyl monoglyceride amines and ethylene oxide 5-
A 20 molar adduct of phosphate can be used as well.

When p=1, it is an alkyldiamine represented by; when n is 2, it is an ethylene group; when n=3, it is a propylene group.

These are phosphoric acid ester salts of adducts of 5 to 20 moles of ethylene oxide.

Specifically, phosphoric acid salts of polyethylene oxyethylene adducts such as N-alkyl (C8-C18) ethylene diamines, N-alkyl (08-C18) propylene diamines, and β-oxyalkyl diamines are used.

When p=2, it becomes an ethylene group, and when n=3, it becomes a propylene group, and ethylene oxide 5 to 20
It is a phosphate ester salt of a molar adduct.

Specifically, they are phosphates of ethylene oxide adducts such as N-alkyl (C8-C18) ethylene diamines, N-alkyl (C8-C18) propylene diamines, and β-oxyalkyl ethylene diamines.

Ethylene oxide adducts of alkylamines in which X in the general formula is represented by a lower alkyl group having 1 to 4 carbon atoms such as cyanide or ethylmethyl are also preferably used.

For example, N-octyl-N-cyanoethylamine, N-
Phosphates of 5 to 20 moles of ethylene oxide adducts such as lauryl N-ethylamine and N-stearin-N-butylamine are used.

The same also applies to adducts of hydroxyalkylamines, alkoxyhydroxypropylamines, and alkyl monoglyceride amines with 5 to 20 moles of ethylene oxide, where R is represented by .

The phosphates of the polyoxyethylene adducts of alkylamines and alkenylamines of general formula (1) and/or general formula (2) described above are used in combination with the alkyl phosphate inorganic salts described above. Demonstrate effective results.

The phosphoric acid salt of the ethylene oxide adduct of the compound of the general formula (K) and (Shin 2) does not compensate for the antistatic properties of the alkyl phosphate ester, but when used in combination, provides even better antistatic properties.

Furthermore, although amines generally have poor heat resistance, by converting them into phosphates, the heat resistance of the blended oil itself is also improved.

What is particularly interesting is that the main point of the compounded oil agent of the present invention is not only 100% polyester fibers, but also polyester fibers such as polyester-cotton blends, polyester-rayon blends, polyester-wool blends, and polyester-linen blends. It is a unique spinning oil in the sense that it can improve the spinnability of blended products, and it is versatile and has advantages that cannot be achieved with ordinary blended oils.

However, the effect of the present invention does not mean that good results can be obtained in all cases with the inorganic salt of alkyl phosphate and the phosphate of the amine-POE adduct of general formula (1) or (2), but rather There is also a large fWIJ limit.

That is, the phosphate of the amine-POE adduct of the general formula (1) or (2) can only be achieved by blending 11 to 67 parts by weight with respect to 100 parts by weight of the alkyl phosphate ester salt.

That is, the phosphate of the ethylene oxide adduct of the compound of general formula (1) or (2) is less than 11% (by weight) of the alkyl phosphate salt, which is insufficient to exhibit the effects of the present invention. On the other hand, if it exceeds 67%, the convergence etc. will be good, but there will be a drawback that scum will increase during spinning.

The amount of the oil agent of the present invention attached to polyester fibers is 0,
06-0.3% (by weight) preferably 0.10-0.2%
(weight).

If the amount of adhesion is less than the lower limit, static electricity is likely to be generated due to uneven adhesion, while if the amount of adhesion is greater than the upper limit, tackiness increases, resulting in more spinning scum and increased carding. There is a tendency to

The spinning oil of the present invention can be diluted with water to form an aqueous emulsion or the like, and can be applied to tow or 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, other auxiliary agents such as other surfactants such as nonionic active agents, anionic active agents, amphoteric active agents, etc. may be added to the oil agent of the present invention as long as the effects of the present invention are not lost. It is also possible to add other smoothing agents, brighteners, dyes, etc.

EXAMPLES Hereinafter, the present invention will be explained with reference to Examples, but the present invention is not limited in any way by the following Examples.

Example 1 Polyethylene terephthalate fibers (1.5 denier) with an intrinsic viscosity of 0465 determined by IIJ in a phenol solution were cut into lengths of 38 mm, and immersed in the 16 types of solutions shown in the following table. The fibers were deposited so that the amount of adhesion was 0.15% (weight) based on the weight of the fibers, and then heat-treated at 120°C, at 25°C and relative humidity 65%R.
The material was aged for a day and night under the conditions of H and spun at an equilibrium moisture content, and the cohesiveness (wrap bulk) and scum during spinning were measured.

Regarding the convergence, the bulk specific gravity of the lap was measured, and the scum from spinning was actually measured by collecting the scum that adhered to the rubber roller and metal roller during the drawing process.

Regarding the convergence and spinning scum, those with good results were marked as ○, and then it was qualitatively shown that the results were poor in the order of ○, △, △, and ×.

As can be seen from the results in Table 2, it can be seen that the oil agent of the present invention exhibits excellent spinnability.

Example 2 In the same manner as in Example 1, the oil agent composition shown in Table 3 was obtained by changing the blending ratio using the oil agent shown in Table 10B.
These were attached to the fibers, and after a period of time, they were spun in the same manner as in Example 1 and evaluated.

The results are shown in Table 3.

As can be seen from Table 3, the present invention shows very stable spinnability.

Example 3 In the same manner as in Example 1, the spinnability of cotton having a polyester-cotton mixing ratio of 65:35 was tested using the oil shown in Table 4.

The results are summarized in Table-5.

As can be seen from Table 5, the examples of the present invention exhibited very stable spinnability.

Claims (1)

[Claims] 1. Phosphorylation degree 0 obtained by reacting P205 with a linear or side chain alcohol having an average carbon number of 8 to 16
．． 6 to 1.0 and the acid value of the alkyl phosphate reaction product is in the range of 0 to 50, based on 100 parts by weight of the alkyl phosphate inorganic salt obtained by neutralizing with an inorganic alkali hydroxide. General formula (1) and/or general formula (2)
) [However, R is a straight chain or a side chain having 8 to 18 carbon atoms
saturated or unsaturated alkyl groups, and further groups), n is 2 to
A positive integer of 3, P represents O or a positive integer of 1 to 3. ] [However, R is a straight chain or a side chain having 8 to 1 carbon atoms
8 represents a saturated or unsaturated alkyl group (wherein R' is the same group as R), and X represents a 01 to C4 lower alkyl group or a cyanethyl group. 5 ethylene oxide to the alkyl amines shown in
11 to 6 phosphoric acid ester salts of compounds added with ~20 moles
A spinning oil agent for polyester fibers, characterized in that it contains 7 parts by weight.