JPS5947478A - Spinning oil for synthetic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention relates to a spinning oil for synthetic fibers. For more details,
This invention relates to a spinning lubricant for synthetic fibers that suppresses rusting in fiber manufacturing equipment used in synthetic fiber manufacturing processes and processing processes that involve thermal processes, and has excellent heat resistance and antistatic properties. In general, spinning oils are mineral oils, neutral oils such as J1h fatty acid esters, or ethylene oxide adducts of fatty acids, higher alcohols or polyhydric alcohol fatty acid esters.
Nonionic active agents, or anionic active agents such as alkyl acetate salts or alkyl phosphate esters (or salts), cationic active agents such as quaternary ammonium salts, or amphoteric active agents such as alkyl betaines. An activator is used. As a specific example, for polyester fiber, Japanese Patent Laid-Open No. 48-5
A combination oil agent of a salt of an alkyl phosphate ester and an ether and/or ester type nonionic activator is described in JP-A No. 5193, and 1 is described in JP-A-54-1.58694.
VT salt of alkyl phosphoric acid ester and a block copolymer of ethylene oxide and propylene oxide, a blended oil agent, a salt of alkyl phosphoric acid ester and alkyl amines or substituted alkyl amines described in JP-A-56-140178. BACKGROUND OF THE INVENTION A blended oil agent is known that contains a phosphate of a compound to which ethylene oxide has been added, and a single adduct of ethylene oxide or propylene oxide to an alkylphenyl ether, or an adduct of a copolymer of ethylene oxide and propylene oxide. For polyacrylonitrile fiber, Katako 45-212
No. 77 discloses an oil agent containing a salt of an alkyl phosphate alone or a combination of a salt of an alkyl phosphate and an ether and/or a Nisder type nonionic surfactant. In addition, for synthetic fibers including not only polyester fibers and polyacrylonitrile fibers but also polyamide fibers, Japanese Patent Publication No. 52-31999 r16 JP-A No. 54
- An oil agent containing an alkyl phosphate metal salt as a main component, described in 7Q in Publication No. 125797, Japanese Patent Publication No. 56-20391
Oil agents are known that contain the sialgyl phosphate ester salt described in the above publication alone or containing it. Although such conventional oil agents have excellent antistatic properties under normal temperature and humidity conditions and western humidity conditions, their effectiveness is significantly reduced under paper humidity conditions and has 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 to maintain a certain appropriate temperature and humidity, but this requires a huge amount of operating costs. For these reasons, there is an increasing demand for an M-resource, energy-saving uf@ oil solution that meets the needs of the times and does not require temperature or humidity control. From this point of view, quaternary ammonium salts have particularly excellent antistatic properties, and are useful because they maintain their antistatic properties even under low humidity. It was difficult to use for tt because it caused rusting, and because it had poor heat resistance, it changed the whole fabric. Specifically, Japanese Patent Publication No. 51-22558, Japanese Patent Publication No. 54-44798, USF4.25
Although the quaternary ammonium salts described in Specification No. 9,078 have excellent antistatic properties, they are still insufficient in terms of heat resistance and rust resistance (Table 1). 1. “A5~1
(see 0). The reason why heat resistance is an inseparable characteristic of oil agents is as follows. In other words, it is well known that synthetic fibers do not inherently have crimps, so in order to make fibers for spinning, they are mechanically crimped, and then the heat-setting properties of synthetic fibers are improved. It is widely practiced to apply heat to the woven fabric or knitted fabric using heat. Place J
'J Concealment needs to be heated to a high temperature. However, while the conventional quaternary ammonium salt is an oil agent that gives fibers excellent antistatic properties, it has poor thermal properties.
It emits smoke during heat treatment, and if the temperature exceeds 160°C, 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 shortcomings of conventional small quaternary ammonium salts. As a result, the 41st & ammonium salts with a specific structure have good antistatic properties under low humidity, and are heat resistant. The present invention was completed after discovering that it has excellent properties and no rusting properties. 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). R2 3 [In the formula, R1 is an alkyl group having 8 to 22 carbon atoms or an alkyl or alkenyl group having 21 carbon atoms, s, m is 1
-5 integer) or a β-hydroxyalkyl or alkenyl group having 10 to 24 carbon atoms, R2, R, each independently an alkyl or alkenyl group having 1 to 22 carbon atoms,
benzyl group or +AO% H (A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 20), or R
2 is +0H(R6) 0H2-KOH (R6 is H or an alkyl group having 1 to 18 carbon atoms, ! is an integer of 1 to 5), and xo is the general formula (R7-0+-A'0iP(l- O
H), q (wherein R7 is a monoalkyl 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, q is 1 or 2), or an anion of a hydroxyalkanecarboxylic acid with carbon ICy, 2.about.6. ] The quaternary ammonium salt represented by general formula (1) according to the present invention can be easily produced by the method shown in F. That is, a 6th class amine (a) represented by general formula (2) (wherein R,, R2 and R are the same as in (1)) and general formula (3) % formula % (3) An epoxy compound (C) represented by the general formula (4) (wherein R6 is as defined above) is reacted. The above reaction is preferably (a) : (b) : (
The molar ratio of C) is 0.9 to 1.2: 1.0 to 2.5
Let's do it. Specific examples of the tertiary amine represented by -B formula (2) are listed. The phosphoric acid ester represented by the general formula (3) is an algylene oquinide additive of a higher alcohol or a lower alcohol, which is added to phosphorus pentateta, orthophosphoric acid, polyphosphoric acid, or oxyphosphoric acid. It is a compound that can be phosphoric acid esterified with a phosphorylating agent such as specific phosphorus (a compound that leaks L, specifically e, off-boul phosphorus c < CS dioctyl phosphorus),
Dodecyl phosphoric acid, didodecyl phosphoric acid, octadecyl phosphoric acid, dimecucdecyl phosphoric acid, octadecenyl phosphoric acid,
Dioctagcenyl phosphate, polyoxyethylene (8 mol) (hereinafter abbreviated as PoE(8)) dodecyl phosphorus r.1
(s) Dodecyl phosphoric acid, polyoxypropylene (3 mol) (hereinafter abbreviated as poP(3)) octadecyl phosphoric acid, bis POI) (3) octadecyl

[・Phosphate book. can be mentioned. Specific examples of the hydroxyalkane carboxylic acid having a carbon number of 2.-6 include glycolic acid and hydroxypropionic acid. Examples of the epoxy compound's proboscis represented by the general formula (4) include ethylene oxide, propylene oxide, butylene oxide, 1,2-epoxyoctane, 1
, 2-epoxydodecane, 1,2-epoxyoctadecane, and the like. 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 oleic acid methyl ester and stearic acid butyl ester, or fatty acids, face number alcohols, polyalcohols, and ethylene oxide adducts of fatty acid esters. A nonionic activator or the like is used. Conventional quaternary ammonium salts, for example (32H), have rust-prone properties when used in an amount exceeding 30% by weight based on the agent, so it was necessary to limit the amount used, but the quaternary ammonium salt of the present invention Since it has no rusting properties, it can be added in any proportion.However, in order to achieve a satisfactory band and prevention effect, the amount of quaternary ammonium salt used in the present invention should be adjusted to the total amount of oil. It is preferable to add 3% or more.The spinning oil of the present invention can be applied to all synthetic fibers such as polynisder fibers, polyacrylonitrile fibers, and polyamide yarn fibers.The spinning oil of the present invention can be applied to aqueous R11, which is usually used as an emulsion, is stirred (if processed by VC)
[Melon Mo] is suitable for use as an emulsion with a concentration of about 5 to 5 mm, but it can also be treated by a roller contact method or a spray method, with particular limitations depending on the treatment method. It's not something you can do. The layered contribution to fibers is generally 0.01 to 1% Owf.
, preferably 0.1 to 0.5 coefficient Owf. The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. Synthesis of organic phosphate ester> (1) ROH (R:O,, sos, a1617%,
Place 2 moles of 13 ml of mixed alkyl groups in a four-eye flask, raise the temperature to about 80°C, stir well, and add P2O.
, 1 mol is added at regular intervals. The entire amount of P2O was added, and the mixture was aged 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(OH
20H20), I((R:O11!804.01617
%, 01,5% of mixed alkyl groups) and P2O, respectively (
It was synthesized in the same manner as in 1) by adding the same number of moles. (The organic phosphoric acid ester synthesized here is referred to as (B).) Synthesis of quaternary ammonium salt> Synthesis example 1 *Pour 0.44 mol of phosphoric acid ester (A) into a 1i four-eye flask. , melt at 60-70℃, then C1,3
mixed alkyl group) 0.44 moltiMF, 60
Stir at ~70°C for 1 hour. 11th item out of these! In an autoclave, add Improvil alcohol 115f,
45 grams 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 raised to approximately 90°C, and the reaction was carried out for 7 hours with thorough stirring. The reaction product is a slightly colored liquid. This is referred to as the product (I) of the present invention. Analysis + i: Acid value: 0.2 Amine content @: o, 5 water Moisture: 10% Instead of ester (A), use h&! J y rq
The product of the present invention (It) was prepared by adding Nisdel (B) in the same number of moles as in Synthesis Example 1 and using the same method. Synthesis Example 3 174, c, l+ mixed alkyl group of 5'A, n1+n
All products of the present invention (m) were synthesized by adding the same number of moles and using the same method as in Synthesis Example 1, except that 2=8) was used. Synthesis Example 4 0.66 mol of mixed alkyl group of CIll'' and 1BOf of isopropyl alcohol are placed in a 17 autoclave, and then 0.70 mol of glycol m and 1151 mol of water are added at room temperature to neutralize. Then, 1.52 mol of ethylene oxide was blown in, and about 60 mol of ethylene oxide was added.
The temperature was raised to .degree. C., and the reaction was allowed to proceed for 2 hours while stirring well. The obtained reaction product is referred to as the product of the present invention (g). Comparative synthesis 141 Monoalkyltrimethylammonium chloride (alkyl group carbon number 110 6 O% l C168 17%, o, 5c4) and potassium salt of cultivated phosphate ester (A) were mixed in equimolar proportions, and the mixture was heated at room temperature. By stirring for 2 hours, monoalkyltrimethylammonium.
Alkylphosphate'f: Irita. This is referred to as comparative product (1). Example 1 For polyester stable (1.5d, 38mm),
For comparison, the oil agent of the present invention and an oil agent that has been used in the United States and the United States were treated with 0.615 ml of oil at 80°C.
Heat treatment and drying were performed for a period of time. 25% RH and 35fQRH + 50% at 25°C.
Under the conditions of RH, the results of measuring the insulation resistance value as ρE of the anti-corrosion effect, rusting property, and +n+1 heat property were measured on Kuyu that had been aged to reach an equilibrium moisture content. The results are shown in Table 1. Rust resistance ii: Washed i% 7t (GROZ-Bl
r, 0KKRT (i”;) 25 (Ill095,6
4 GOl) was immersed in a 1% solution of each oil agent, and the rusting state of the knitted hooks was observed. In addition, the heat resistance is 150% for each oil treated with O and TS%
The fibers were heat-treated at ℃ for 2 hours, and the color property of the fibers was determined by visual observation. In addition, the card passability was determined by heat-treating the fibers treated with 0.15 of each r)1 agent at 80°C for 2 hours, drying them, aging them at 25°C and 50°RH under constant temperature and humidity for a day and night, and then placing them in a small petri dish. Card passability was measured using a spinning tester. Note that the card passageability was calculated using the following formula. As is clear from the results in Table 1, A5. It can be seen that the quaternary ammonium salts of Groups 6 and A9 have inferior heat resistance 9 and are also inferior in rust R prevention properties compared to the quaternary ammonium salts of the present invention. 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 (A% -I A 7 ) described in U, S, P, 4259078, tra Ko H (, I54
The quaternary salts described in Publication No. 44798 (Table 17 shows 8>t) have good heat resistance but lack rust prevention properties. =P-
When expressed as 0, since the iiB portion of R is small (Off),
. It is thought that the rust was not sufficiently effective in suppressing rust. Compared to these quaternary salts, the quaternary ammonium salt of the present invention has an antistatic property of l + J'l 4, has vague heat resistance, and has the advantage of not causing rust. I know that there is. A quaternary ammonium salt (
The present invention product N) is the present invention product (1), CI+) 1(
Compared to the quaternary ammonium salt of Ill), curd]... is slightly inferior in prematureness, so it is preferable to use it in combination with other ingredients. Example 2 Other than using polyacrylonitrile fiber 11 (2d, 51mm), center 7/I! Processing was performed in the same manner as i-shio 1. Table 2 shows the measurement results of the insulation resistance values under the conditions of 25° C./50% RH. In addition, in order to examine the heat resistance, the results of measuring the insulation resistance 1' directly after heat-treating the same sample at 7150° C. for 2 hours, and the results of the degree of coloration of the sample are also shown. From Table 2, the quaternary ammonium salt of the present invention is 150
Even after heat treatment at .degree. C. for 2 hours, satisfactory performance was maintained with less decrease in antistatic properties compared to conventional quaternary salts, and it was observed that no coloring of the sample occurred at all.

Claims (1)

[Claims] 1 General formula (1) [In the formula, R1 is alkyl having 8 to 22 carbon atoms or 7 to 21 carbon atoms]
is an alkyl or alkenyl group having 1 to 3 carbon atoms) or a β-hydroxyalkyl or alkenyl group having 10 to 24 carbon atoms, R2, R, each independently is an alkyl group having 1 to 22 carbon atoms or alkenyl group, benzyl group, or its AO-), -H (A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 1 to 2o), H or mineral coal number 1 to 1
8 alkyl groups! is 11 LR7-0+A'oQyaPmoOH), -9 (in the formula, 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 an organic phosphate ester having 2 to 6 carbon atoms
A spinning lubricant for synthetic fibers containing a quaternary ammonium compound represented by the following hydroxyalkane carboxylic acid anion.