JPS63295763A - Lubricating agent of thermoplastic 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] Ru.

Prior Art Thermoplastic synthetic fibers are coated with a lubricating agent in order to impart lubricity, cohesiveness, and antistatic properties to the fibers in order to ensure smooth operation during the manufacturing process.

In recent years, with the development of synthetic fiber manufacturing and processing technology to improve productivity and quality, and the expansion of direct spun drawn yarn (so-called DSD), fiber yarns have been processed at increasingly high speeds, and their thermal Processing conditions are also becoming extremely harsh.

Especially for fibers for industrial materials, etc., in order to obtain higher strength,
Although it is stretched at a higher temperature and a higher magnification, tar-like substances form and accumulate on the heat rollers and heaters, causing fuzz and thread breakage, which hinders smooth operation. There is a strong demand for properties that improve lubricity and do not cause tarring.

Conventionally used lubricating agents include mineral oils, animal and vegetable oils, esters of higher fatty acids and higher alcohols, and esters of higher fatty acids and polyhydric alcohols, but these lubricants have relatively poor lubrication performance. belongs to the good category, but due to the thermal influence in the stretching heat treatment process mentioned above,
It has the disadvantage that tar-like substances tend to form and accumulate on the heat roller and heater.

In addition, lubricants such as esters of aromatic polyhydric carboxylic acids and higher alcohols, esters of bisphenol A ethylene oxide adducts and higher fatty acids, etc. have been proposed as having excellent heat resistance; In recent high-strength tire cord yarn manufacturing operations at high temperatures of 250°C or higher, it is unavoidable that tar-like substances are generated and accumulated on heat rollers and heaters, and these substances have poor lubricity. It has the disadvantage of being prone to problems such as fuzz and thread breakage.

On the other hand, polyethers made by adding alkylene oxide to alcohol have been proposed as lubricating components with less accumulation of tar-like substances, but these generally have insufficient lubricity and damage to the yarn surface (polymer (scratches), white powder builds up on the guides, rollers, etc. that come into contact with them.
It has the disadvantage of easily inducing fluff and thread breakage.

Special Publication No. 50-373.19 and Special Publication No. 53-3
Publication No. 2438 describes a lubricating agent for thermoplastic synthetic fibers containing an ester of a secondary alcohol and an aromatic polycarboxylic acid. There are problems with the accumulation of tar-like substances in

In addition, US Pat. No. 3,578,594 describes the use of esters of ethoxylated aliphatic alcohols and fatty acids and terminal esters of ethoxylated phenols as lubricating agents, but this also tars. Not enough in terms of accumulation.

Problems to be Solved by the Invention The present invention provides a lubricating agent that generates and accumulates very little tar-like substances and has excellent lubricity in the process of producing thermoplastic synthetic fibers, particularly in the drawing and heat treatment processes at high temperatures. The purpose is to provide

Means for Solving the Problems The present invention basically consists of an alcohol component containing an aliphatic secondary alcohol having 8 to 18 carbon atoms, a branched aliphatic primary alcohol, and/or an alkylene oxide adduct thereof; The present invention relates to a lubricating agent for thermoplastic synthetic fibers containing a diester with a saturated aliphatic dicarboxylic acid having 5 or less carbon atoms.

The secondary alcohol and branched primary alcohol used in the ester of the present invention need to have 8 to 18 carbon atoms (preferably 10 to 16 carbon atoms). Carbon number 20
Above this, there is a tendency for tar accumulation to occur. Furthermore, if the number of carbon atoms is 7 or less, the lubrication performance decreases.

Such alcohols include, for example, those obtained by oxidation of paraffins or by the oxo method or other synthetic methods.

Alcohols obtained by oxidizing paraffin are mainly secondary alcohols, such as Softanol A.
(manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) and other synthetic alcohols. In addition, alkylene oxide adducts of secondary alcohols, which are commercially available under the prefix "softanol", can be used as they are, or can be further added with alkylene oxide to form the alkylene oxide-added secondary alcohol of the present invention. .

The alcohol obtained by the oxo method has a branched 1
Synthetic alcohols include, for example, dopanol (manufactured by Shell Chemical Co., Ltd.), oxocol (manufactured by Nissan Petrochemical Co., Ltd.), and Diadol (manufactured by Mitsubishi Chemical Industries, Ltd.).

In addition, isostearyl alcohol and 2-(1'
, 3°, 3°-trimethylbutyl)-5°7.7-trimethyloctanol and the like can be mentioned.

These secondary alcohols or branched alcohols are industrially sold as a mixture of normal primary alcohols, but if the amount is less than 50 mol%, they can be used as is without purification. can. Alternatively, a pure secondary or branched alcohol and a primary alcohol may be mixed and subjected to esterification. In that case, 2
It is preferable that the alcohol having a branched alcohol (or its alkylene oxide adduct) accounts for 50 mol % or more, more preferably 60 mol % or more, particularly 70 mol % or more in the alcohol component.

In the present invention, various alkylene oxides can be used to add to the alcohol, but ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof are preferred.

When adding two or more types of alkylene oxides, either random addition or block addition may be used.

The amount of alkylene oxide added can be varied within a wide range, but in particular it is 1-10% per mole of alcohol.
Molar addition is appropriate. When the amount exceeds 10 moles, the viscosity of the diester increases and the lubricating performance tends to decrease.

The dicarboxylic acid used in the diester of the present invention needs to be a saturated dicarboxylic acid having 5 or less carbon atoms.

Dicarboxylic acids having 6 or more carbon atoms or unsaturated dicarboxylic acids increase the formation and accumulation of tar.

Specific examples of saturated dicarboxylic acids having 5 or less carbon atoms (including derivatives such as anhydrides, lower alkyl esters, and acid chlorides) used in the ester of the present invention include glutaric acid,
Examples include succinic acid, methylsuccinic acid, malonic acid, methylmalonic acid, and oxalic acid.

The above-mentioned diester used in the treatment agent of the present invention is produced by a known method, for example, by reacting the above-mentioned alcohol and/or its alkylene oxide adduct with a dicarboxylic acid, or by transesterification with a lower alcohol ester of a dicarboxylic acid. It can be easily synthesized by

The alcohol component used in the present invention is most preferably used in an amount that substantially completely esterifies the dicarboxylic acid, but it may be used in an amount of 1.6 mol or more and up to 2 mol per 1 mol of dicarboxylic acid. In this case, the free carboxyl group may be used as an ester with polyalkylene glycol ether or other lower alcohol, various alkali salts, or as a free carboxyl group.

The lubricant treatment agent of the present invention further contains a copolymer of ethylene oxide with a molecular weight of 500 or more and another alkylene oxide, or a copolymer of the copolymer with an alcohol at its terminal end. A more favorable result is obtained.

The content of the diester compound of the present invention in the processing agent is:
It is usually 10 to 80% by weight, preferably 20 to 70% by weight. If it is less than 10%, the lubricity decreases and white powder deposition tends to increase.

On the other hand, if it is more than 80%, the emulsifying property in water may decrease or the viscosity of the emulsion may become high, which is not preferable.

In addition, the lower alkylene oxides constituting the polyether compound used as a compounding component include ethylene oxide, propylene oxide, butylene oxide, etc., and the end-blocking aliphatic alcohols include methanol, ethanol, octatool, butanol,
-Ethylhexanol, lauryl alcohol, isotridecyl alcohol and the like.

The above polyether compound may be a random copolymer or a block copolymer, but the molecular weight must be 500 or more, preferably 700 or more, in order to stably emulsify and disperse the diester compound according to the present invention. be.

If the molecular weight is less than 500, it becomes difficult to form a stable aqueous emulsion.

Further, in the polyether compound, ethylene oxide is preferably contained in an amount of 10% by weight to 90% by weight, and if the ethylene oxide is less than 0% by weight, a stable aqueous emulsion cannot be obtained. The amount of the polyether compound blended in the processing agent is 90 to 20% by weight, preferably 70 to 30% by weight, and if it is less than 20% by weight, it is difficult to obtain a stable aqueous emulsion.

Furthermore, even more favorable results can be obtained by incorporating a hindered phenolic antioxidant into the lubricating agent of the present invention. Various structural substances are commercially available as hindered phenolic antioxidants, such as 1,3.5-)lis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate. Acid (trade name Cyanox 1790. Manufactured by Nippon Cyanamid Co., Ltd.)
, 6-(4-hydroquine-3,5-di-t-butylaniline)-2,4-bis-octyl-thio-1,3,5-
) riazine (trade name Irganox 565, manufactured by Ciba Geigy), tetrakis [methylene-3 (3,5-di-t)
-butyl-4-hydroxyphenyl) propionate comethane (trade name Irganox 1010, manufactured by Ciba Geigy), and the like.

The above-mentioned hindered phenolic antioxidants may be used alone or in combination of two or more kinds, and it is also possible to use other kinds of antioxidants together.

The appropriate amount of antioxidant to be used is 0.1 to 5% by weight; less than 0.1% by weight is less effective, and more than 6% by weight may reduce the emulsion stability of the lubricating agent. Furthermore, the friction against metal becomes high, and an unfavorable tendency appears.

The lubricant treatment agent of the present invention may contain antistatic agents such as alkyl phosphates, polyoxyethylene amino ethers, fatty acid metal salts, etc., as necessary. Known emulsifiers, smoothing agents, antioxidants, etc. may be added as long as they do not cause loss of properties.

The lubricant treatment agent of the present invention is applied to the fiber yarn in the spinning process in the form of an emulsion emulsified with water or in the form of a straight oil agent. It is provided as a solid content of 0.5% to 2%.

The synthetic fiber treated with the lubricating agent of the present invention is 2506
Even in the drawing process at high temperatures reaching C or higher, it does not generate or accumulate tar-like substances, and has excellent tar resistance, lubricity,
Suitable for lubricating industrial materials such as nylon and polyester that require cohesiveness, and high-speed spun drawn yarn for false twisting.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. In the examples, (PO) represents propylene oxide, (EO) represents ethylene oxide, and (P O/E O) represents the weight ratio.

Example 1 Diester compounds in the present invention (No. 1 to No.

6) and lubricating components of conventional oils (No. 7 to No. 11)
), the tar resistance and lubrication performance were evaluated,
The results are shown in Table-1.

[note] ! , di-softanol 30 succinate means a diester obtained from 302 mol of softanol and 1 mol of succinic acid (hereinafter expressed similarly).

2. Softanol 30 and Softanol 70 are 3 mol and 7 mol ethylene oxide adducts of synthetic alcohols mainly composed of secondary alcohols having 12 to 14 carbon atoms, manufactured by Nippon Shokubai Kagaku Co., Ltd.

3. Dopanol 23 (P06 mol/Eo2 mol) is a synthetic alcohol mainly composed of a primary alcohol having branches with 12 to 14 carbon atoms, manufactured by Mitsubishi Yuka Co., Ltd., and contains 6 mol of propylene oxide and 2 mol of ethylene oxide. shows the random addition of .

4. Oxocol 1215 (2 moles of PO/6 moles of EO)
represents a random adduct of 2 moles of propylene oxide and 6 moles of ethylene oxide, a synthetic alcohol mainly composed of a primary alcohol having branches with 12 to 15 carbon atoms, manufactured by Nissan Petrochemical Co., Ltd.

5. Diadol 115 is a synthetic alcohol mainly composed of a branched primary alcohol having 12 to 14 carbon atoms and manufactured by Mitsubishi Chemical Industries, Ltd.

6. Fine Oxocol 180 is produced by Nissan Petrochemical (Aji)
It is a synthetic alcohol mainly composed of a primary alcohol with 18 carbon atoms and a tert-butyl terminal.

7. Oxocol 1215/Fine Oxocol 18
0 means the diester in the form obtained from 1215 t mol of oxocol and 1801 mol of fine oxocol and 1 mol of succinic acid.

[Test method] (1) Tar resistance: Sample 19 was placed in a stainless steel dish with a diameter of 60 mm, and the sample condition was evaluated when heated at 250°C for 12 hours in a hot air dryer. Then, carbon tetrachloride was added to it. In addition, the insoluble matter was measured and determined as the tar conversion rate.

◎ Almost no generation of tar-like substances O Very little generation of tar-like substances △ Considerable generation of tar-like substances After continuous degreasing with carbon, 0.7% of the sample was deposited to obtain a sample yarn, which was heated at 20°C and 65% relative humidity at a constant shear force (109) at 1001/min and 300 i/min. The friction coefficient was measured when the yarn ran in contact with satin chrome at a yarn speed of .

As shown in Table 1, the diester compounds No. 1 to N006 of the present invention have extremely excellent tar resistance compared to conventional lubricating components, and the lubricating performance is higher than that of lubricating components No. 1 to N006. 9, No. 10, No. 11, and almost the same as the others, it is clear that the ester compound of the present invention has excellent properties.

Example 2 To the blended composition Weight % example!
Lubricating component No. 1 60 (lubricating component of the present invention) Octatool PO-EO addition polyether 20 (
r'o/'EO = 70/30 molecular weight 1500) Butanol PO-EO addition polyether 18 (PO/
EO = 50150 molecular weight 1200) Isotridecyl phosphate 2 (alkanolamine salt) Blended composition B M amount% Blended composition A 96 Hindered phenolic antioxidant 4 (Cyanox 1
790/Irganox 565 = 1/1) Blended composition C Weight % Lubricating component No. of Example I, 4 60 (Lubricating component of the present invention) Isotridecyl alcohol PO-EO addition 25 Polyether (PO/EO = 60 /40, molecular weight 2000
) Isooctyl alcohol PO-EO addition 12
Methylene diether of polyether (PO/EO=
65/35, molecular weight 2500) Dioctylsulfosuccinate (Na salt) 3.
Composition C9B Hindered Phenol Antioxidant 2 (Cyanox 1790) Composition E Weight% Example 1
Lubricating component No. 6 55 (lubricating component of the present invention) Octatool PO-EO addition polyether 25 (
PO/EO = 50150, molecular weight 2000) Lauryl alcohol PO-EO addition poly 15 ether
(PO/EO = 60/40. Molecular weight 2000) Lauryl (EO 5 mol) phosphate (K salt) 4. Loquat skin loss 11 pods combination composition E
99 Hindered Phenol Antioxidant 1 Irganox 1010 = 1/
l) Blend composition G Weight % liquid paraffin (500 seconds) 20 Dioctyl sebacate 40 Castor oil ethylene oxide adduct (p=25) 20 Oleyl alcohol ethylene oxide I5 adduct (p
= 6) Dioctyl sulfosuccinate (Na salt) 5 Composition H weight % Dioleyl adipate 60 Hydrogenated castor oil ethylene oxide adduct 25 (p = 20
) Lauryl alcohol PO-EO addition polyether 15
(PO/EO = 60/4G, molecular weight 2000) Blended composition 1 By weight % bisphenol A (2 moles of EO) dilaurate 60 Hydrogenated castor oil ethylene oxide adduct 30 (p = 20) Octyl alcohol PO-EO adduct polyether lo
(PO/EO=60/40, molecular weight 2500) Blended composition J M amount% isooctyl stearate 40 Octatool PO-EO addition polyether 35
(PO/EO = 30/70, molecule fi 3500) Butanol PO-EO addition polyether 20 (P
O/EO = 50150, molecular weight 3000) Nonylphenol (EO4 mol) phosphate 5 (Na salt) Diester compound No. 1 according to the present invention, No. 1, No.
4.

Mixed compositions A-F containing N006 and conventionally used mixed compositions G-J, respectively, were made into a 20% emulsion, and 1.
After 0% (oil deposited amount) was deposited, the yarn was immediately drawn by a normal hot roller drawing method (temperature: 250°C) to obtain a drawn yarn of 1260D. At this time, tar formation on the roller was evaluated, and at the same time, single yarn breakage during drawing and the coefficient of friction of the drawn yarn against metal were measured using the running yarn method. The results are shown in Table-2.

Table 2 Note) l) The tar state on the hot roller was determined after continuous stretching for 10 hours. Note that the criteria for determination are the same as in Table 1.

2) The coefficient of friction of the drawn yarn against metal was measured using a fiber-metal (skinned chrome) running friction measuring device (temperature: 20° C., initial tension: 35 g).

As is clear from Table 2, the processing agent containing the diester compound of the present invention as a lubricating component has better tar resistance than conventional processing agents, has a lower coefficient of friction against metal, and is superior in drawing operability. it is obvious.

Effects of the Invention The lubricating agent for thermoplastic synthetic fibers of the present invention has extremely excellent performance that greatly exceeds conventional lubricating agents in preventing the formation and accumulation of tar-like substances during drawing at high temperatures and heat treatment. The purpose of the present invention is to provide an excellent lubricating agent that has excellent lubricity and is suitable for the processing conditions for synthetic fibers, which have become increasingly severe in recent years.

Claims (1)

[Claims] 1. An aliphatic secondary alcohol having basically 8 to 18 carbon atoms;
A lubricating agent for thermoplastic synthetic fibers containing a diester of an alcohol component containing a branched aliphatic primary alcohol and/or an alkylene oxide adduct thereof and a saturated aliphatic dicarboxylic acid having 5 or less carbon atoms. 2. The lubricating agent according to item 1, wherein the molar ratio of the saturated aliphatic dicarboxylic acid to the alcohol component is 1.6 to 2 mol to 1 mol of the former. 3. The first alcohol component contains 50 mol% or more of a secondary alcohol having 8 to 18 carbon atoms, a branched primary alcohol, and/or an alkylene oxide adduct thereof
Lubricating agent described in section. 4. The lubricating agent according to item 1, wherein the number of moles of alkylene oxide added to the alkylene oxide adduct of alcohol is 10 moles or less. 5. The lubricating agent according to item 1, wherein the lubricating agent contains 10 to 80% by weight of an ester of an alcohol component and a dicarboxylic acid. 6. (a) An alcohol component that basically contains an aliphatic secondary alcohol having 8 to 18 carbon atoms, a branched aliphatic primary alcohol, and/or an alkylene oxide adduct thereof, and a saturated alcohol having 5 or less carbon atoms. Diesters with aliphatic dicarboxylic acids and (b) Copolymers of ethylene oxide with a molecular weight of 500 or more and other alkylene oxides with an ethylene oxide content of 10% by weight or more, or products whose terminals are etherified with aliphatic alcohols. Lubricating agent for thermoplastic synthetic fibers. 7. The lubricating agent according to item 6, wherein the molar ratio of the saturated aliphatic dicarboxylic acid to the alcohol component is 1 mole of the former to 1.6 to 2 of the latter. 8. The lubrication treatment according to item 6, wherein the alcohol component contains a secondary alcohol having 8 to 18 carbon atoms, a branched primary alcohol, and/or an alkylene oxide adduct thereof based on the total alcohol component in an amount of 50 mol% or more. agent. 9. The lubricating agent according to item 6, wherein the number of moles of alkylene oxide added to the alkylene oxide adduct of alcohol is 10 moles or less. 10. The lubricating agent according to item 6, wherein the lubricating agent contains 10 to 80% by weight of an ester of an alcohol component and a dicarboxylic acid. 11. (a) An alcohol component basically containing an aliphatic secondary alcohol having 8 to 18 carbon atoms, a branched aliphatic primary alcohol, and/or an alkylene oxide adduct thereof, and a saturated alcohol having 5 or less carbon atoms. Diesters with aliphatic dicarboxylic acids; (b) copolymers of ethylene oxide with a molecular weight of 500 or more and other alkylene oxides, or copolymers of which the terminals are etherified with aliphatic alcohols; and (c) A lubricating agent for thermoplastic synthetic fibers containing a hindered phenolic antioxidant. 12. No. 11, wherein the molar ratio of the saturated aliphatic dicarboxylic acid to the alcohol component is 1 mole of the former to 1.6 to 2 of the latter
Lubricating agent described in section. 13. The lubrication treatment according to item 11, wherein the alcohol component contains a secondary alcohol having 8 to 18 carbon atoms, a branched primary alcohol, and/or an alkylene oxide adduct thereof, in an amount of 50 mol% or more based on the total alcohol component. agent. 14. The first alkylene oxide adduct of alcohol in which the number of moles of alkylene oxide added is 10 moles or less
The lubricating agent according to item 1. 15. The lubricating agent according to item 11, wherein the lubricating agent contains 10 to 80% by weight of an ester of an alcohol component and a dicarboxylic acid.