JPS6153473B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a smoothing agent for thermoplastic synthetic fibers that has excellent heat resistance. The object of the present invention is to obtain a smoothing agent that has both high heat resistance and high smoothness by using a compound having a particularly special thioether group. Thermoplastic synthetic fibers are coated with a smoothing agent to impart smoothness, cohesiveness, antistatic properties, etc. to the fibers in order to ensure smooth operation during the manufacturing process. Thermoplastic synthetic fibers may be subjected to heat treatment during the manufacturing process depending on their use.
In addition to the above-mentioned properties, smoothing treatment requires heat resistance such as prevention of smoke and tar. Conventionally, treatment agents based on mineral oil, monovalent esters of higher fatty acids and lower alcohols, and divalent esters of higher alcohols and aliphatic dicarboxylic acids have been used as smoothing agents, but they generate a lot of smoke during heat treatment. Problems have occurred, such as significantly worsening the working environment and the accumulation of thermally decomposed or repolymerized processing agents as tar on the plates, rollers, etc. where heat treatment is performed, deteriorating operability. In recent years, fibers for tire cords, etc., have been subjected to heat treatment at high temperatures in order to achieve their characteristic performance, and the smoothing agent that adheres to the fibers is now required to have an increasingly high degree of heat resistance. Summer. Many studies have been carried out to improve the heat resistance of smoothing agents for thermoplastic synthetic fibers. A treatment agent whose main component is an oxidized ester-added alkyl ether (Japanese Patent Publication No. 29474/1983) has been proposed. These processing agents have certainly reached a nearly satisfactory level in terms of heat resistance with respect to smoke generation, tar, etc., but all of them are unsatisfactory in terms of smoothness, causing thread breakage and yarn breakage during fiber manufacturing and processing operations. It has the disadvantage of causing problems such as a decrease in strength.
In other words, it has conventionally been recognized that a processing agent with good heat resistance has poor smoothness, and a processing agent with excellent smoothness has poor heat resistance. It hasn't been done yet. On the other hand, in order to streamline the manufacturing process for fibers,
As processing speeds have increased, there has been a strong demand for the development of smoothing agents that have both high heat resistance and high smoothness. The present invention has been made in response to the above requirements. That is, the present invention provides that at least some of the hydroxyl groups of the polyhydric alcohol have the general formula: RSQ(COOH)n [] [wherein R is an aliphatic group having 1 to 22 carbon atoms, an aromatic group, or an aliphatic-aromatic group] group, Q is an alkenyl group that may have a side chain, n is a number of 1 or 2]
The present invention relates to a smoothing agent for thermoplastic synthetic fibers containing a compound esterified with a carboxylic acid having a thioether group represented by the formula and a higher fatty acid having 12 or more carbon atoms. In the compound having a group represented by the formula [] used in the present invention, R represents an aliphatic group, an aromatic group, or an aliphatic-aromatic group having 1 to 22 carbon atoms, preferably an aliphatic group having 8 to 18 carbon atoms. A saturated or unsaturated alkyl group or alkylphenyl group that may have a side chain. In particular, a saturated or unsaturated alkyl group is preferable to improve smoothness, but in order to obtain higher heat resistance. is preferably an alkyl phenyl group. Examples of alkyl groups include octyl, 2-ethylhexyl, lauryl, tridecyl, cetyl, stearyl, oleyl and alkyl groups having side chains derived from synthetic alcohols. Typically it is a lauryl or oleyl group. Q is an alkenyl group which may have a side chain, and preferably has 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, which is advantageous for production. The side chain is methyl or ethyl. The number of carboxyl groups, ie, n, is 1 or 2, with 1 being particularly preferred. The carboxyl group may be bonded to any carbon atom of the alkenyl group represented by Q. The esterified compound used in the present invention is mainly a carboxylic acid represented by the formula: RSQ(COOH)n [] [wherein R, Q and n have the same meanings as above] or its precursor (carboxylic acid anhydride). , carboxylic acid lower alkyl ester, acid chloride) and a higher fatty acid or its precursor. The carboxylic acid represented by the formula [] or its precursor can be obtained, for example, by reacting an unsaturated carboxylic acid with a mercaptan, or by reacting a halogenated carboxylic acid such as monochloroacetic acid with a mercaptan. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, itaconic acid or its ester, acid anhydrides such as maleic anhydride, and nitriles such as acrylonitrile. Preferred are lower alkyl esters such as methyl acrylate and ethyl acrylate. The carboxylic acid represented by the above formula [] or its precursor is reacted with a suitable polyhydric alcohol together with a higher fatty acid having 12 or more carbon atoms or its precursor to obtain a compound useful in the smoothing agent of the present invention. When the carboxylic acid represented by the formula [] or its precursor has two carboxyl groups, it is sufficient that one of them is subjected to esterification. Of course, it may be further esterified. Compounds suitable as polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitan, sorbitol, polyglycerin, etc., or alkylene oxides thereof. adducts (approximately 1 to 20 moles of addition), etc. It is sufficient that at least one carboxylic acid represented by the formula [] is bonded to the polyhydric alcohol, and all or a portion of the remaining carboxylic acid is blocked with another higher fatty acid or the like. In some cases, the hydroxyl groups may not be completely blocked, but a portion may remain as a hydrophilic group to be used as a surfactant, particularly as an emulsifier. A reaction product of a polyhydric alcohol and a carboxylic acid represented by the formula [] or its precursor and a higher fatty acid is an esterification reaction between a polyhydric alcohol and an acid anhydride or free acid of the above carboxylic acid and higher fatty acid, an oil or fat. It may be produced by transesterification reaction with etc. The higher fatty acid used in the esterified compound of the present invention has 8 or more carbon atoms, more preferably 12 to 18 carbon atoms.
is a saturated or unsaturated alkyl group that may have side chains of Typically, they are lauric acid, oleic acid, stearic acid, etc. The carboxylic acid and higher fatty acid represented by the formula [] are both used so that at least one equivalent thereof is bound to the polyhydric alcohol. For example, if the polyhydric alcohol is glycerin, it may be blended so that 1 equivalent of the carboxylic acid of formula [] and 1 equivalent of higher fatty acid: 2 equivalents of the former and 1 equivalent of the latter: 1 equivalent of the former and 2 equivalents of the latter. (Of course, it may be of an intermediate blending ratio). Although more of the compound represented by the formula [] may be used, it is not only extremely expensive, but also the effect of using a large amount is not significant. On the contrary, smoke-emitting properties tend to decrease. Therefore, even in the case of polyhydric alcohols such as pentaerythritol, it is sufficient to use 1 to 2 equivalents of the compound represented by the formula []. The smoothing agent for thermoplastic synthetic fibers of the present invention usually contains about 10 to 90% by weight, preferably about 50 to 80% by weight of the ester compound of the present invention. Furthermore, other components such as emulsifiers and antistatic agents, and if desired, conventionally known components that impart smoothness may be added within a range that does not impair heat resistance and smoothness. Examples of emulsifiers include polyoxyethylene castor oil ether, Polyoxyethylene hydrogenated castor oil ether, polyoxyethylene nonyl phenyl ether and its laurate, polyoxyethylene thiolauryl ether and its laurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate, oleyl phosph as an antistatic agent. ates and their salts (Na, K, etc.), polyoxyethylene oleyl phosphate and its salts (Na, K, etc.), examples of smoothing agents include alkyl silicones, copolymers of ethylene oxide and propylene oxide, and their stearyl ethers. can. The smoothing agent of the present invention may be applied to the fibers by a conventional method, such as a roller oiling method, a spraying method, or a pump extrusion method, and can be applied in either an emulsion or straight state. The amount of the smoothing agent of the present invention attached to fibers is
0.2 to 3.0% by weight (0.1 to 2.4% by weight in terms of amount of compound []) is preferred. The smoothing agent of the present invention is used in the manufacturing and processing processes of thermoplastic synthetic fibers, and has good heat resistance and smoothness even in heat processes of 180 to 250°C. Suitable for smoothing in the manufacturing process of filaments for industrial materials such as. The present invention will be explained below with reference to Examples. In addition, POE in the examples indicates a polyoxyethylene residue. Example 1 1 mol of thioether group-containing carboxylic acid obtained by reacting lauryl mercaptan and acrylic acid,
Two moles of oleic acid and one mole of glycerin are reacted at 230° C. for about 7 hours under a nitrogen atmosphere. This reaction product D was blended with the following formulation to obtain a smoothing agent D. Smoothing agent D Prescription weight part Reaction product D 65 POE (40 mol) Castor oil ether 20 POE (20 mol) Sorbitan trioleate 15 Example 2 Thioether group-containing carboxylic acid obtained by reacting lauryl mercaptan and acrylic acid 1 mole of oleic acid, 1 mole of polyethylene glycol (MW: 200) are reacted at 180 to 190° C. for 8 hours in a nitrogen atmosphere using p-toluenesulfonic acid as a catalyst. Reaction product B was blended with the following formulation to obtain smoothing agent B. Smoothing agent B Prescription weight part Reaction product B 70 POE (40 mol) Castor oil ether 20 POE (20 mol) Sorbitan trioleate 9 Example 3 Thioether group-containing carboxylic acid 1 obtained by reacting lauryl mercaptan and acrylic acid Mol,
Two moles of oleic acid and one mole of trimethylolpropane are reacted at 230° C. for about 8 hours under a nitrogen atmosphere.
This reaction product E was blended with the following formulation to obtain a smoothing agent E. Smoothing agent E Formula parts by weight Reaction product E 65 POE (40 mol) Castor oil ether 20 POE (20 mol) Sorbitan trioleate 15 Example 4 Treatment agents B, D and E and conventional smoothing agents (Comparative example 1, The fuming properties and tar formation of 2 and 3) were evaluated by the following test methods. Table of results-1
Shown below.

[ Table ] Smoothing agent ) Castor oil ether 25 POE (20 mol) Sorbitan trioleate 10 Smoothing agent Z Formula weight part C ₁₂ H ₂₅ OCH ₂ CH ₂ COOC ₁₈ H ₃₅ 65 POE (40 mol) Castor oil ether 27 POE (20 mol) Sorbitan trioleate 8 Test method: (1) Smoke generation test method: Place 1g of smoothing agent in a stainless steel plate with a diameter of 100 mm, place it in a hot air dryer with the bottom of the plate horizontal, and measure the amount of smoke generated for 5 minutes at 220℃ using digital dust. Measured with a meter (P-3 type; manufactured by Shibata Kagaku Kiki Kogyo Co., Ltd.). (2) Tarring test method: Treat the smoothing agent at 220°C for 4 hours in the same manner as the smoke test, and judge the tarring state with the naked eye. The evaluation criteria are as follows: ○: No tarring △: Slight tarring ×: Significant tarring Example 5 A commercially available 70 denier nylon filament was washed and dried with hot water, and the smoothing agents B, D, and E were applied to it. ,X,
Roller oiling was performed using 15% each of Y and Z emulsions to obtain a filament with 1% by weight of the smoothing agent attached. The fibers when this treated filament was applied to a fiber-metal running friction measuring machine.
The coefficient of friction between metals was measured. The results are shown in Table-2.

[Table] As is clear from Examples 1 to 5, the conventional smoothing agent It has excellent performance regarding smoke generation and tar formation, but has a large friction coefficient and poor smoothness. On the other hand, the smoothing agent obtained in the present invention is
It shows good performance in both smoothness (fiber-metal friction coefficient) and heat resistance (smoke resistance and tarring resistance).

Claims (1)

[Claims] 1 At least a part of the hydroxyl groups of the polyhydric alcohol has the general formula: RSQ(COOH) _o [] [In the formula, R is an aliphatic group having 1 to 22 carbon atoms, an aromatic group, an aliphatic group] aromatic group, Q is an alkenyl group that may have a side chain, n represents the number 1 or 2]
A smoothing agent for thermoplastic synthetic fibers containing a compound esterified with a carboxylic acid having a thioether group represented by the formula and a higher fatty acid having 12 or more carbon atoms. 2. The smoothing agent according to item 1, wherein R is an aliphatic group having 8 to 22 carbon atoms. 3. The smoothing agent according to item 1, wherein Q is any one of a methylene group, an ethylene group, a trimethylene group, and a propylene group. 4. The first polyhydric alcohol is selected from alkylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitan, polyglycerin, and alkylene oxide adducts thereof.
Smoothing agent as described in section. 5. The smoothing agent according to item 1, wherein the esterified compound is a compound obtained by esterifying 1 equivalent of a carboxylic acid having a thioether group and 2 equivalents of a higher fatty acid with 1 mole of glycerin. 6. The smoothing agent according to item 1, which contains 10 to 90% by weight of an esterified compound.