JPS6249393B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a spinning oil for synthetic fibers. More specifically, the present invention relates to a spinning oil for synthetic fibers that suppresses rusting in fiber manufacturing equipment used in synthetic fiber manufacturing processes that involve thermal processes and processing processes, and has excellent heat resistance and antistatic properties. . Generally, spinning oils are neutral oils such as mineral oils and fatty acid esters, or nonionic activators such as ethylene oxide adducts of fatty acids, higher alcohols or polyhydric alcohol fatty acid esters, or alkyl sulfate salts or alkyl phosphate esters. Anionic active agents such as (or salts), cationic active agents such as quaternary ammonium salts, or amphoteric active agents such as alkyl betaines have been used. As a specific example, polyester fibers are
A combination oil containing a salt of alkyl phosphate and an ether and/or ester type nonionic activator as described in JP-A No. 48-33193, and a salt of an alkyl phosphate and oxidation as described in JP-A-54-138694. A compound oil containing a block copolymer of ethylene and propylene oxide, a phosphate of a compound obtained by adding ethylene oxide to a salt of an alkyl phosphate ester and an alkyl amine or a substituted alkyl amine described in JP-A-56-140178. Also known are blended lubricants of alkyl phenyl ether with a single adduct of ethylene oxide or propylene oxide, or an adduct of a copolymer of ethylene oxide and propylene oxide. For polyacrylonitrile fiber,
No. 21277 discloses a lubricant containing a salt of an alkyl phosphate alone or a combination of a salt of an alkyl phosphate and an ether and/or ester type nonionic surfactant. In addition, synthetic fibers including not only polyester fibers and polyacrylonitrile fibers but also polyamide fibers include alkyl phosphate metal salts as a main component as described in Japanese Patent Publication No. 52-31999 and Japanese Patent Application Laid-Open No. 54-125797. Oil agents containing dialkyl phosphate ester salts alone or containing dialkyl phosphate salts described in Japanese Patent Publication No. 56-20391 are known. Such conventional oil agents have excellent antistatic properties under normal temperature and humidity conditions as well as under high humidity conditions, but on the other hand, their effectiveness is significantly reduced under low humidity conditions, and they have the drawback of causing spinning troubles. Therefore, in order to prevent static electricity troubles, it is necessary to control the temperature and humidity in the spinning chamber so as to maintain it at a certain appropriate temperature and humidity, but this requires a huge amount of operating costs. For these reasons, there is currently no need for temperature and humidity control that meets the demands of the times, so to speak, resource saving,
There is an increasing demand for energy-saving spinning oils. From this point of view, quaternary ammonium salts have particularly excellent antistatic properties, and they also have excellent antistatic properties even under low humidity, so they are suitable for the purpose, but they do not cause rust on the metal parts of spinning machines. It was difficult to use because it caused yellowing of the fibers due to its poor heat resistance. Specifically, quaternary ammonium salts described in Japanese Patent Publication No. 51-22558, Japanese Patent Publication No. 54-44798, USP 4259078, etc. have excellent antistatic properties, but It is still insufficient in terms of heat resistance and rust resistance (see Table 1, Nos. 5 to 10). The reason why heat resistance is an inseparable characteristic of oil agent performance is as follows. In other words, synthetic fibers do not normally have crimps, so in order to make fibers for spinning, they are mechanically crimped, and then crimped in an appropriate manner using the heat-setting properties of synthetic fibers. Heat setting under suitable conditions is widely practiced. During this heat setting, the heat treatment temperature needs to be high in order to reduce the heat shrinkage rate in post-processing after the woven or knitted fabric. However, while conventional quaternary ammonium salts are oil agents that provide excellent antistatic properties to fibers, they lack heat resistance and emit smoke during heat treatment.
At high temperatures of 160°C or higher, thermal decomposition occurs and the oil changes in quality, not only coloring the fibers but also reducing their antistatic properties. Therefore, the present inventors conducted intensive research to improve the drawbacks of conventional quaternary ammonium salts, and as a result, found that quaternary ammonium salts with a specific structure have good antistatic properties under low humidity, and are heat resistant. They found that it has excellent properties and does not cause rust, and completed the present invention. That is, the present invention provides a spinning oil for synthetic fibers, which is characterized by containing a quaternary ammonium salt represented by the following general formula (1). [In the formula, R ₁ is an alkyl or alkenyl group having 8 to 22 carbon atoms,

[Formula] (R ₅ is an alkyl or alkenyl group having 7 to 21 carbon atoms, m
is an integer of 1 to 3) or a β-hydroxyalkyl or alkenyl group having 10 to 24 carbon atoms, and R ₂ , R ₃
are each independently an alkyl or alkenyl group having 1 to 22 carbon atoms, a benzyl group or -(AO)- _o H (A is an alkylene group having 2 to 4 carbon atoms, and n is 1 to 20
) or R ₂ and R ₃ are

A group forming [Formula], R ₄ is -(CH (R ₆ ) CH ₂ ) - _l OH (R ₆ is H or an alkyl group having 1 to 18 carbon atoms, and l is an integer of 1 to 5). Yes, X is a general formula

[Formula] (wherein, R ₇ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, A' is an alkylene group having 2 to 4 carbon atoms, p is an integer of 0 to 20, and q is 1 or 2) or an anion of a hydroxyalkane carboxylic acid having 2 to 6 carbon atoms. ] The quaternary ammonium salt represented by general formula (1) according to the present invention can be easily produced by the method shown below. That is, general formula (2) (In the formula, R ₁ , R ₂ and R ₃ are each the same as in (1).) A tertiary amine (a) represented by the general formula (3) (In the formula, R ₇ , A', p and q are each as described above) to a mixture with an organic phosphoric acid ester or a hydroxyalkane carboxylic acid (b) having 2 to 6 carbon atoms, and the general formula (4) (In the formula, R ₆ is as described above.) An epoxy compound (c) represented by the following is reacted. The above reaction is preferably carried out at a molar ratio of (a):(b):(c) of 1:0.9-1.2:1.0-2.5. Specific examples of tertiary amines represented by general formula (2) include:

【formula】

【formula】

【formula】

[Formula] (n ₁ + n ₂ = 10),

【formula】

【formula】

Examples include [Formula]. The organic phosphate ester represented by general formula (3) is
A compound obtained by phosphoric acid esterification of a higher alcohol or an alkylene oxide adduct of a higher alcohol with a phosphoric oxide such as phosphorus pentoxide, orthophosphoric acid, polyphosphoric acid, or phosphorus oxychloride, specifically octyl phosphoric acid. , dioctyl phosphoric acid, dodecyl phosphoric acid, didodecyl phosphoric acid, octadecyl phosphoric acid, dioctadecyl phosphoric acid, octadecenyl phosphoric acid, dioctadecenyl phosphoric acid, polyoxyethylene (8 mol) (hereinafter abbreviated as POE(8)) Dodecyl phosphoric acid, bisPOE(8) dodecyl phosphoric acid, polyoxypropylene (3 mol) (hereinafter,
POP(3)) octadecyl phosphate, bis
Examples include POP(3) octadecyl phosphate. Specific examples of the hydroxyalkane carboxylic acid having 2 to 6 carbon atoms include glycolic acid, hydroxypropionic acid, and the like. Specific examples of the epoxy compound represented by general formula (4) include ethylene oxide, propylene oxide, butylene oxide, 1,2-epoxyoctane, 1,2-epoxydodecane, 1,2-
Examples include epoxy octadecane. In carrying out the present invention, any spinning oil component may be blended in addition to the quaternary ammonium salt of the present invention within a range that does not impair the effects of the present invention. Such optional ingredients include animal and vegetable oils, mineral oils, fatty acid esters such as oleate methyl ester, stearate butyl ester, or non-fatty acids, higher alcohols, or polyhydric alcohols, such as ethylene oxide adducts of fatty acid esters. Ionic activators and the like are used. Conventional quaternary ammonium salts, e.g. However, since the quaternary ammonium salt of the present invention has no rusting property, it is necessary to limit the amount used because it causes rusting when used in an amount exceeding 30% by weight based on the total oil. It can be used in proportion. However, in order to exhibit a satisfactory antistatic effect, the amount of the quaternary ammonium salt of the present invention is preferably 3% by weight or more based on the total oil agent. The spinning oil of the present invention can be applied to all synthetic fibers such as polyester fibers, polyacrylonitrile fibers, and polyamide fibers. When the spinning oil of the present invention is processed by a dipping method, such as the one commonly used as an aqueous emulsion, it is appropriate to use it as an emulsion with a concentration of 0.5 to 5% by weight. It can also be treated by a spray method, and the treatment method is not particularly limited. The amount of adhesion to fibers is generally 0.01 to 1%.
Owf, preferably 0.1 to 0.5% Owf. The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples. <Synthesis of organic phosphate ester> (1) Place 2 mol of ROH (R: mixed alkyl group of 80% C ₁₈ , 17% C ₁₆ , 3% C ₁₄ ) in a four-necked flask, and raise the temperature to approximately 80°C. , P ₂ O ₅ 1 while stirring well.
Gradually add moles. After adding the entire amount of P ₂ O ₅ , aging was performed for about 5 hours to obtain the desired product. (The organic phosphate ester synthesized here is referred to as (A).) (2) In place of ROH in (1) above, RO
(CH ₂ CH ₂ O) ₈ H (R: C ₁₈ 80%, C ₁₆ 17%, C ₁₄ 3
% mixed alkyl group) and P ₂ O ₅ were added in the same number of moles as in (1) and synthesized in the same manner. (The organic phosphate ester synthesized here is referred to as (B).) <Synthesis of quaternary ammonium salt> Synthesis example 1 0.44 mol of organic phosphate ester (A) was placed in a 1 L four-necked flask and heated at 60 to 70°C. melted with and then

[Formula] (R: mixed alkyl group of 80% C ₁₈ , 17% C ₁₆ , 3% C ₁₄ ) 0.44 mol was added dropwise and stirred at 60-70°C for 1 hour. Transfer this neutralized product to 1 liter autoclave, add 113 g of isopropyl alcohol and 45 g of water.
was added, the temperature was raised to 45-50°C, 0.90 mol of ethylene oxide was blown into the mixture, the temperature was further raised to about 90°C, and the reaction was carried out for 7 hours with thorough stirring.
The reaction product is a slightly colored liquid. This is the product of the present invention (). Analytical values: Acid value: 0.2 Amine content: 0.3% Moisture: 10% Volatile content: 24% Synthesis example 2 In synthesis example 1

instead of [expression]

[Formula] (R: mixed alkyl group of C ₁₈ 80%, C ₁₆ 17%, C ₁₄ 3%), and organic phosphate ester (B) was used in place of organic phosphate ester (A) in the same manner as in Synthesis Example 1. The product synthesized in the same manner by adding the number of moles is referred to as the product of the present invention (). Synthesis Example 3 In Synthesis Example 1

instead of [expression]

[Formula] (R: mixed alkyl group of C ₁₈ 80%, C ₁₆ 17%, C ₁₄ 3%, n ₁ + n ₂ = 8) was used, but the same number of moles as in Synthesis Example 1 was added and the same method was used. The synthesized product is referred to as the product of the present invention (). Synthesis example 4

[Formula] (R: Mixed alkyl group of 80% C ₁₈ , 17% C ₁₆ , 3% C ₁₄ ) 0.66 mol and 180 g of isopropyl alcohol were placed in a 1 liter autoclave, and then
Neutralize by adding 0.70 mol of glycolic acid and 115 g of water at room temperature. After raising the temperature to 45-50℃, 1.32 mol of ethylene oxide was blown into it, and the temperature was further raised to about 60℃.
The reaction was allowed to proceed for 2 hours with good stirring. The obtained reaction product is referred to as the product of the present invention (). Comparative synthesis example 1 Monoalkyltrimethylammonium chloride (number of carbon atoms in alkyl group: C ₁₈ 80%, C ₁₆ 17%,
_{Monoalkyltrimethylammonium}
An alkyl phosphate was obtained. This is the comparative product (1). Example 1 A polyester staple (1.5 d, 38 mm) was treated with the oil of the present invention and a conventional oil for comparison at 0.15% per fiber weight, and heated at 80°C.
Heat treatment and drying were performed for 2 hours. After aging this at 25℃ and 25%RH, 35%RH, and 50%RH conditions for one day and night to reach equilibrium moisture content, we measured the insulation resistance value as a measure of the antistatic effect.
Table 1 shows the results of measuring the rust resistance and heat resistance. Rust resistance was determined using washed knitting needles (GROZ-BECKERT
250Lo95, 64G01) were immersed in a 1% solution of each oil agent, and the state of rust on the knitting needles was observed. In addition, the heat resistance of fibers treated with 0.15% of each oil agent
The fibers were heat-treated at 150°C for 2 hours, and the colorability of the fibers was determined by visual observation. In addition, card passability was determined by heat treatment of fibers treated with 0.15% of each oil agent at 80℃ for 2 hours, and after drying, 50% at 25℃.
After aging for a day and a night under constant temperature and humidity at RH, card passability was measured using a Schare compact spinning tester. Note that the card passability was calculated using the following formula. Card passing property (%) = Weight of web wound on drum / Weight of supplied stable x 100 As is clear from the results in Table 1, No. 5, No. 6 and
The quaternary ammonium salt No. 9 has inferior heat resistance compared to the quaternary ammonium salt of the present invention,
It can also be seen that it is inferior in terms of rust prevention properties. Comparative product (1) obtained in Comparative Synthesis Example has satisfactory antistatic properties, but is clearly inferior to the product of the present invention in terms of rust resistance and heat resistance. In addition, the quaternary salt described in USP 4259078 (Table 1 No. 7), the 4 described in Japanese Patent Publication No. 54-44798
Grade salt (No. 8 in Table 1) has good heat resistance, but is still insufficient in rust prevention. In these fourth grade salt, when the anion component is represented by a general formula 〓, the effect of suppressing the rust is sufficient because the R part is small. It can be seen that, compared to these quaternary salts, the quaternary ammonium salt of the present invention has remarkable antistatic properties, excellent heat resistance, and has the advantage of not rusting. In the present invention, the quaternary ammonium salts (products of the present invention) whose counter-anion moiety is OHCH ₂ COO are the products of the present invention (), (),
Since the card passing rate is slightly inferior to that of the quaternary ammonium salt (), it is preferable to use it in combination with other components.

【table】

[Table] Example 2 The same treatment as in Example 1 was carried out except that polyacrylonitrile fiber (2d, 51 mm) was used. twenty five
Table 2 shows the measurement results of insulation resistance values under the conditions of ℃/50%RH. In addition, in order to examine the heat resistance, the results of measuring the insulation resistance value after heat-treating the same sample at 150°C for 2 hours, and the results of the degree of coloration of the sample are also shown. Table 2 shows that the quaternary ammonium salt of the present invention exhibits satisfactory performance with less decrease in antistatic properties compared to conventional quaternary salts even after heat treatment at 150°C for 2 hours. It was observed that no coloration occurred at all.

【table】

【table】

Claims (1)

[Claims] 1 General formula (1) [In the formula, R ₁ is an alkyl or alkenyl group having 8 to 22 carbon atoms, [Formula] (R ₅ is an alkyl or alkenyl group having 7 to 21 carbon atoms, and m
is an integer of 1 to 3) or a β-hydroxyalkyl or alkenyl group having 10 to 24 carbon atoms, and R ₂ , R ₃
are each independently an alkyl or alkenyl group having 1 to 22 carbon atoms, a benzyl group or -(AO)- _o H (A is an alkylene group having 2 to 4 carbon atoms, and n is 1 to 20
) or R ₂ and R ₃ are a group forming [Formula], R ₄ is -(CH (R ₆ ) CH ₂ ) - _l OH (R ₆ is H or a group having 1 to 18 carbon atoms) (wherein R ₇ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and A' is an alkyl group having 2 to 22 carbon atoms, 4, p is an integer of 0 to 20, and q is 1 or 2). ] A spinning oil agent for synthetic fibers, characterized by containing a quaternary ammonium salt represented by: