JPS6245351B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a lubricating agent for synthetic fibers, and particularly to a lubricating agent for synthetic fibers that undergoes a heating process. Conventionally, when producing synthetic fibers, yarns spun by a melt spinning method are heated to draw them or heat-set to improve their properties. In addition, thermoplastic synthetic fibers that go through a false twisting process are generally heat treated to fix their shape, and synthetic fibers used for industrial materials such as tire cord yarns have high strength. It is customary to draw the yarn under severe heating conditions to obtain the yarn. In various manufacturing processes, fiber threads are often processed at fairly high speeds, and the lubricating composition used on the fiber threads is highly Heat resistance, smoothness, and antistatic properties are required. In order to satisfy these demands, lubricant components that are conventionally blended with emulsifiers, antistatic agents, etc. have been esters of mineral oils and higher alcohols with fatty acids, and dibasic acids such as adipic acid and sebacic acid. Esters, fatty acid esters of polyhydric alcohols such as trimethylolpropane and glycerin have been used. However, although these conventionally used lubricating agents exhibit good smoothness,
Synthetic fiber yarns that undergo particularly harsh heating processes such as hot drawing and false twisting do not have sufficient heat resistance, causing smoke to worsen the working environment or forming tar-like substances on the heater. The dirt on the thread path is noticeable〓〓〓〓〓
Otherwise, single thread wrapping or thread breakage will occur. As a result, smooth stretching and false twisting cannot be performed, and the machine must be shut down and cleaned to remove the tar-like substances, causing problems in the process and reducing efficiency. On the other hand, it does not form tar-like substances on the heater,
Fatty acid ester of aromatic polybasic acid as an oil agent for textiles that reduces smoke generation (Special Publication No. 16133, 1977)
and esters of oxyalkylene adducts of higher alcohols and aromatic polybasic acids (Special Publication No. 41-17039,
and JP-A-50-59516), polyoxyalkylene monobenzyl phenol, polyoxyalkylene monostyryl phenol (JP-A-50-59516), polyoxyalkylene monobenzyl phenol, polyoxyalkylene monostyryl phenol
154525, 51-4322), polyether urethane compounds (Japanese Patent Publication No. 48-17516), aromatic diurethane compounds (Japanese Patent Publication No. 112298-1982), and the like. The present inventors conducted additional tests on the compounds described in these documents, and found that the heat resistance was considerably improved compared to ordinary fatty acid esters that do not have an aromatic ring. It was discovered that the requirements for heat resistance have not yet been fully met. In order to suppress the generation of smoke and tar-like substances during the heating process, the inventors of the present invention have conducted further intensive research, and as a result, they have discovered a compound that substantially emits almost no smoke and does not form tar-like substances. completed. That is, the present invention provides a lubricating agent for synthetic fibers, which contains as an active ingredient a product obtained by reacting a compound represented by the following general formula () with an isocyanate. . (In the formula (), X: a hydrogen atom or a halogen atom R ₁ : an alkylene group having 1 to 5 carbon atoms R ₂ : an alkylene group having 2 to 4 carbon atoms R ₃ : a hydrogen atom or a phenyl group m: an integer of 1 to 3 n: represents a real number from 0 to 100 on average.) Examples of the compound represented by the general formula () of the present invention include polyoxyethylene (10 mol) (hereinafter
(abbreviated as POE(10)) benzylphenol, POE(7) dibenzylphenol, POE(10) tribenzylphenol, polyoxypropylene (5 mol) (hereinafter referred to as
Polyoxyalkylenebenzylphenols such as dibenzylphenol (abbreviated as POP(5)), polyoxyethylene (5 mol), polyoxypropylene (3 mol) (hereinafter abbreviated as POE(5)POP(3)), tribenzylphenol, POE(8) styrylphenol,
Polyoxyalkylene styryl phenols such as polyoxybutylene (5 mol) (hereinafter abbreviated as POB(5)) distyryl phenol, POE(5) POB(3) distyryl phenol, POP(10) tristyryl phenol, or benzyl Examples include polyoxyalkylene halogenated benzyl phenols and polyoxyalkylene halogenated styryl phenols having a halogen group in the benzene nucleus of the group or styryl group. Also included are benzylphenol and styrylphenol to which oxyalkylene is not added. As the isocyanate of the present invention, any of monoisocyanate, diisocyanate, and triisocyanate can be used, but diisocyanate is preferable. Examples of the monoisocyanate include isobutyl isocyanate, phenyl isocyanate, tolyl isocyanate, naphthyl isocyanate, and the like. As the diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1.
3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isopropylbenzole-2,4-diisocyanate, ω・ω'-diisocyanate-1,2-dimethylbenzole,
4,4'-diphenylmethane diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, biphenyl-2,4'-diisocyanate,
Mention may be made of aromatic diisocyanates such as biphenyl-4,4'-diisocyanate.
As triisocyanate, benzene-1, 2,
4-triisocyanate, 2,4,6-triisocyanate/toluene, 4,4′,4″-tripheni〓〓〓〓〓
Examples include methane triisocyanate and the like. The ratio (molar ratio) of the compound represented by the general formula () to the isocyanate used in the reaction is:
1.0 in the case of monoisocyanates, 1.0 to 2.0, preferably 2.0 in the case of diisocyanates and 1.0 in the case of triisocyanates.
from 2.0 to 3.0, preferably from 2.0 to 3.0. When the compound represented by the general formula () is reacted with isocyanate in a stoichiometrically equimolar amount or less, unreacted isocyanate groups remain. It may also be reacted with alcohol. However, it is desirable that the compound represented by the general formula () and the isocyanate react in equimolar terms stoichiometrically, and that all the isocyanate groups have reacted. Although the reaction conditions are not particularly limited, the reaction is usually carried out by heating the compound represented by the general formula () and an isocyanate in the presence or absence of an inert solvent. Examples of inert solvents include hydrocarbon solvents such as benzene, toluene, xylene, and petroleum ether; You can also use The mechanism of how the reaction product of the present invention exhibits excellent heat resistance and smoothness is not necessarily clear, but a few presumed structural formulas of the reaction product of the present invention are shown below, but it is likely that This is thought to be due to its unique structure. The reaction product of the present invention as described above has a unique structure, particularly a unique structure derived from the compound of the general formula ().
This structure provides excellent heat resistance and allows the fiber manufacturing process to proceed smoothly. The lubricating agent for synthetic fibers of the present invention can of course be used alone, but it can also be used in combination with other conventional synthetic or natural fiber lubricants. EXAMPLES The present invention will be specifically described below with reference to Examples, but it goes without saying that the present invention is not limited to these Examples. Note that all percentages in the examples are percentages by weight unless otherwise specified. Synthesis Example 1 1370 g (3.03 mol) of POE(2) tribenzylphenol was placed in a 4-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, and heated to 50°C while stirring for 2.4 hours. −Tolylene diisocyanate 261
g (1.5 mol) was gradually added dropwise, and after the addition was completed, the temperature was increased to 90°C.
The temperature was raised to 100, and stirring was continued for 3 hours to complete the reaction, and urethane compound A was obtained. It was confirmed by infrared absorption spectrum that the isocyanate group of the reaction product had disappeared. Estimated structural formula Synthesis example 2 POE(10) tribenzylphenol 1608g (2.00mol) and hexamethylene diisocyanate 168g
(1.0 mol) was used to carry out the same reaction as in Synthesis Example 1 to obtain urethane compound B. Estimated structural formula Synthesis Example 3 POE(10) distyrylphenol 1499g (2.02mol) and 2,4-tolylene diisocyanate 174g
The same reaction as in Synthesis Example 1 was carried out using 1.0 mol of urethane compound C. Estimated structural formula〓〓〓〓〓
Synthesis example 4 POE(6)POP(2) distyrylphenol 1432g
(2.10 mol) and 174 g (1.0 mol) of 2,4-tolylene diisocyanate, the same reaction as in Synthesis Example 1 was carried out to obtain urethane compound D. Estimated structural formula Synthesis example 5 POE (23) tribenzylphenol 1445g
(1.05 mol) and 87 g (0.5 mol) of 2,4-tolylene diisocyanate, the same reaction as in Synthesis Example 1 was carried out to obtain urethane compound E. Estimated structural formula Synthesis Example 6 (Comparative product) POP(6)POE(3) octyl ether 1232g (2.02mol) and 2,4-tolylene diisocyanate 174
The same reaction as in Synthesis Example 1 was carried out using 1.0 mol of urethane compound F. Estimated structural formula〓〓〓〓〓
Synthesis Example 7 (Comparative product) POE(6) nonylphenol 978g (2.02mol) and diphenylmethylene diisocyanate 250g
(1.0 mol), the same reaction as in Synthesis Example 1 was carried out to obtain urethane compound G. Estimated structural formula Synthesis example 8 (comparative product) Cetyl alcohol 532g (2.20mol), toluene
500ml and diphenyl methylene diisocyanate
The same reaction as in Synthesis Example 1 was attempted using 250 g (1.0 mol). However, as the reaction progressed, a white gel-like substance was generated, and the shape became unsuitable for use as an oil component for textiles, so the process was discontinued. Example 1 The results of a comparative study of the heat resistance of the compound of the present invention and conventionally used known lubricating agent components are shown in Table 1 (heat resistance at 200°C) and Table 2 (heat resistance at 250°C).
Heat resistance at °C). Incidentally, the smoke generation amount, tar conversion rate, etc. were measured as follows, and the smaller the number, the better. [Measurement method of smoke amount] Place 0.01g of sample on No. 2 paper and heat at 200℃ or
The smoke generated by the sample when heated to 250°C was introduced into a spectrometer, and the value obtained by integrating the light attenuation rate over 2 minutes or 5 minutes was defined as the amount of smoke generated. Note that the light attenuation rate is 0 when no smoke is generated. [Measurement method for heating loss] 0.5g of sample was collected in a commercially available aluminum dish,
This is placed in a hot air dryer, heated at 200°C or 250°C for 4 hours, and then taken out. After cooling at room temperature, measure the weight and calculate the loss on heating. [Method for measuring tar rate] Take approximately 0.5g of sample into a commercially available aluminum dish, place it in a hot air dryer, and heat at 200°C or 250°C.
After heating at ℃ for 4 hours, take out. After cooling to room temperature, wash the aluminum dish with acetone. Generally, the remaining sample that does not dissolve in acetone is a black resinous substance, and the larger the amount, the higher the rate of taring. The tar conversion rate was calculated using the following formula. Tarring rate (%) = Weight of acetone-insoluble remaining sample (g) / Weight of collected sample (g) x 100

[Table] 〓〓〓〓〓

【table】

[Table] As is clear from Tables 1 and 2, the urethane compound of the present invention produces less smoke than the comparative product.
Almost no tar is generated. Example 2 Fiber-metal (F-
Table 3 shows the results of measuring the frictional resistance value of M). The frictional resistance was measured under the following conditions. A commercially available semi-double polyester filament yarn (250d) was coated with 0.5% of the oil agent of the following composition, and 25
The initial tension of the sample yarn is 15 in an atmosphere of 50% relative humidity and ℃.
g was applied, the thread was run in contact with a chrome pin, and the subsequent tension was measured using a μ meter (manufactured by Eiko Sokki). Formulation example A Urethane compound (A) 38% Butyl carbitol 14% EO/PO random copolymer MW≒500 48% Formulation example B Urethane compound (B) 60% Butyl cellosolve 20% PEG200 dilaurate 20% Formulation example C Urethane compound (C) 55% Butyl cellosolve 18% PEG200 dilaurate 18% POE (35) hydrogenated castor oil 7% EO/PO modified silicone 2% Comparative formulation example A EO/PO block copolymer MW≒2500 60% EO/PO random copolymer MW≒500 30% POE Potassium alkyl phosphate 5% Potassium oleate soap 4% Sodium paraphin sulfonate 1% Comparative formulation B Refined rapeseed oil 20% POE(2) Bisphenol A dilaurate 40% POE(10) Tribenzylated phenol ether 20% POE ( 25) Hydrogenated castor oil 20% Comparative formulation example C Trimethylolpropane trioleate 60% POE(10) hydrogenated castor oil 35% Alkyl sesquiphosphate potassium salt 5%

[Table] As shown in Table 3, the products of the present invention are manufactured by combining conventionally known lubricants (e.g. fatty acid esters, silicones), etc.
〓〓〓〓〓
Showing properties equivalent to Comparative Formulation Example C, Tables 1 and 2
As shown in the figure, it shows superior properties in terms of heat resistance compared to conventional oils, especially when compared to POE(2) bisphenol A dilaurate, which has been evaluated as having better heat resistance among conventional oils. It is clear that the compounds of the present invention have superior properties since they exhibit better performance. 〓〓〓〓〓

Claims (1)

[Scope of Claims] 1. A lubricating agent for synthetic fibers, which contains as an active ingredient a product obtained by reacting a compound represented by the general formula () with an isocyanate. (In the formula (), X: a hydrogen atom or a halogen atom R ₁ : an alkylene group having 1 to 5 carbon atoms R ₂ : an alkylene group having 2 to 4 carbon atoms R ₃ : a hydrogen atom or a phenyl group m: an integer of 1 to 3 n: represents a real number from 0 to 100 on average.) 2. The synthetic fiber according to claim 1, wherein the reaction ratio of the compound represented by the general formula () and the isocyanate is stoichiometrically equimolar. lubricating agent for use. 3. The lubricating agent for synthetic fibers according to claim 1 or 2, wherein the isocyanate is a diisocyanate. 4. The lubricating agent for synthetic fibers according to claim 3, wherein in the general formula (), n is 0 to 50.