JPS636674B2 - - Google Patents

Description

2 (A) 40 to 80 parts by weight of a compound represented by the general formula R ₁ CO(OXOOCYCO)nOXOZ, and (B) (a) a higher fatty acid, a polyhydric alcohol, and a polyethylene glycol and/or polypropylene glycol component. the reaction product and/or (b) a compound consisting of ethylene oxide and/or propylene oxide adducts of castor oil or hydrogenated castor oil in a proportion of 60 to 20 parts by weight, and the total amount of the two is 100 parts by weight. A fiber treatment agent containing the above formula R ₁ CO- is a monovalent fatty acid residue having 6 to 30 carbon atoms, Z is -OCR ₂ , and -OCR ₂ is a monovalent fatty acid residue having 1 to 30 carbon atoms. Monovalent fatty acid residue, -OXO- is a polyhydric alcohol residue, a residue of a polyhydric alcohol alkylene oxide adduct, a residue of a polyhydric phenol alkylene oxide adduct, a residue of an alkylene oxide adduct of bisphenols. A divalent group selected from the group consisting of -OCYCO- is -OCA ₁ SA ₂ CO
-, -OCA ₃ OA ₄ CO-, -OCA ₅ CO-, and n means an integer of 1 to 6. In addition, in the above, A ₁ , A ₂ , A ₃ and A ₄ are each independently C ₁ to
C ₆ alkylene group, A ₅ is C ₁ to C ₃ alkylene group,
And S means a sulfur atom. 3 (A) 40 to 80 parts by weight of a compound represented by the general formula R ₁ CO(OXOOCYCO)nOXOZ, (B) a tripartite reaction product of a higher fatty acid, a polyhydric alcohol, and polyethylene glycol and/or polypropylene glycol, castor 5 to 59 parts by weight of a compound selected from the group of ethylene oxide and/or propylene oxide adducts of oil or hydrogenated castor oil; and (C) 1 to 15 parts of an ethylene oxide and/or propylene oxide adduct of an alkylamine.
The fiber treatment agent is contained in the proportion of parts by weight and the total amount of the three is 100 parts by weight; however, the formula R ₁ CO- is a monovalent fatty acid residue having 6 to 30 carbon atoms. , Z is -OCR ₂ , -OCR ₂ is a monovalent fatty acid residue with 1 to 30 carbon atoms, -OXO- is a polyhydric alcohol residue, a residue of a polyhydric alcohol alkylene oxide adduct, a polyhydric phenol -OCYCO- is a divalent group selected from the group consisting of residues of alkylene oxide adducts and residues of alkylene oxide adducts of bisphenols.
OCA ₁ SA ₂ CO―, ―OCA ₃ OA ₄ CO―, ―
It is a dicarboxylic acid residue selected from the group consisting of OCA ₅ CO-, and n means an integer of 1 to 6. Furthermore, in the above, A ₁ , A ₂ , A ₃ and A ₄
are each independently a C ₁ to C ₆ alkylene group, A ₅
represents a _C1 - _C3 alkylene group, and S represents a sulfur atom.

[Detailed description of the invention]

The present invention relates to a treatment agent for fibers. Among the series of processes in which thermoplastic synthetic polymers such as polyethylene terephthalate, polyproamide, and polyhexamethylene adipamide are melt-spun into fibers, there is a step of applying an oil agent to the fiber surface. Conventionally, there are various oils used in this process, but when a known oil composition is applied to the fiber surface, thread breakage occurs during the hot drawing and heat treatment processes that follow the oil application process. Additionally, the oil composition evaporates or decomposes, producing so-called smoke. Particularly, smoke is produced significantly in the process of manufacturing fibers such as polyethylene terephthalate, polycapramide, and polyhexamethylene adipamide fibers, which are hot-drawn at high temperatures and in a dry manner. When yarn breakage occurs, operability decreases, and more waste is generated, leading to increased costs. In recent years, there has been a strong demand for high-strength yarns for industrial synthetic fibers, and in order to stably produce high-strength yarns, it is strongly desired to reduce yarn breakage. In addition, when smoke is generated, it not only pollutes the air in the process and worsens the working environment, causing abnormalities to the throats and eyes of workers, but also causes the contaminated air to escape outside the factory and cause a nuisance to surrounding residents. As environmental issues become more widespread,
There is a strong demand for technology to prevent this smoke generation more than ever before. Therefore, in recent years, certain types of oil compositions have been proposed that reduce the occurrence of thread breakage and do not emit smoke, and although they have been shown to be reasonably effective, it is not possible to stably produce high-strength threads without deteriorating the working environment. Furthermore, when the fibers are used as rubber reinforcement, the adhesion between the fibers and the rubber is reduced. Therefore, the present inventors investigated this problem and found that by applying an oil composition containing the specific compounds described below to the fibers, the problems of thread breakage and smoking were greatly improved. This has led to the present invention. Therefore, an object of the present invention is to reduce fiber breakage and smoke generation when thermoplastic synthetic fibers are heated by heating stretching, heat treatment, etc., and to reduce both the smoothness of the fibers and the adhesion to rubber. The purpose of the present invention is to provide a treatment agent for fibers, a so-called oil composition, which can be used to produce thermoplastic synthetic fibers that prevent the occurrence of oxidation and have good quality and quality. The above object is achieved by employing the following fiber treatment agent. A fiber treatment agent containing a compound represented by the general formula (A) R ₁ CO(OXOOCYCO)nOXOZ; however, the formula R ₁ CO- is a monovalent fatty acid residue with 6 to 30 carbon atoms, and Z is -OCR ₂ and -OCR ₂
is a monovalent fatty acid residue with 1 to 30 carbon atoms, -OXO
- is a divalent selected from the group consisting of polyhydric alcohol residues, residues of polyhydric alcohol alkylene oxide adducts, residues of polyhydric phenol alkylene oxide adducts, and residues of alkylene oxide adducts of bisphenols. Group, -OCYCO- is -OCA ₁ SA ₂ CO-, -OCA ₃ OA ₄ CO-, -
It is a dicarboxylic acid residue selected from the group consisting of OCA ₅ CO-, and n means an integer of 1 to 6. Furthermore, in the above, A ₁ , A ₂ , A ₃ and A ₄ each independently represent a C ₁ to C ₆ alkylene group, A ₅ represents a C ₁ to _{C 8} alkylene group, and S represents a sulfur atom. More preferably, 40 to 80 parts by weight of the compound (A) is combined with (B) (a) a reaction product of a higher fatty acid, a polyhydric alcohol, and a polyethylene glycol and/or polypropylene glycol component, and/or (b) A treatment for fibers containing castor oil or a compound consisting of an ethylene oxide and/or propylene oxide adduct of hydrogenated castor oil in a proportion of 60 to 20 parts by weight, and the total amount of the two is 100 parts by weight. as a drug. Even more preferably, 40 to 80 parts by weight of the compound (A), 5 to 59 parts by weight of the compound (B), and (C) ethylene oxide of the alkylamine and/or
Alternatively, the treatment agent for fibers may contain a propylene oxide adduct in a proportion of 1 to 15 parts by weight, and the total amount of the three components may be 100 parts by weight. This will be explained in detail below. The compound represented by R ₁ CO [OXOOCYCO] nOXOZ, which is the main component of the fiber treatment agent according to the present invention, is (a) a monovalent fatty acid having 6 to 30 carbon atoms;
R ₁ COOH, (b)HOOCA ₁ SA ₂ COOH
HOOCA ₃ OA ₄ Obtained from dicarboxylic acids represented by COOH etc. and glycols selected from polyhydric alcohols, alkylene oxide adducts of polyhydric alcohols, alkylene oxide adducts of polyhydric phenols, and alkylene oxide adducts of bisphenol A. and (iii) a monovalent fatty acid R ₂ COOH having 1 to 30 carbon atoms. The monovalent fatty acid R ₁ COOH is caproic acid,
Enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, araonic acid, behenic acid, lignoceric acid, cerotic acid , montanic acid, melisic acid, oleic acid, erucic acid, linoleic acid, and linolenic acid. Particularly preferred fatty acids include oleic acid, linoleic acid and linolenic acid. A ₁ , A ₂ , A ₃ and A ₄ of the dicarboxylic acid are each independently a C ₁ to C ₆ alkylene group, such as a direct alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, or a hexamethylene group. Chain alkylene group, propylene group, butylene group,
Examples include alkylene groups having side chains such as amylene groups and hexylene groups. Further, _A5 is a _C1 to _C8 alkylene group, and includes _C7 and _C8 alkylene groups in addition to the above-mentioned straight chain and side chain alkylene groups. The dicarboxylic acids forming the above-mentioned residues include thiodicarboxylic acids such as thiodiacetic acid and thiodipropionic acid, oxydicarboxylic acids such as oxydiacetic acid and oxydipropionic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid. Examples include fatty acid dicarboxylic acids. Among these, thiodicarboxylic acid is preferred. The glycols include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, generally bisphenol A, bisphenol F, bisphenol B, Dioxydiethyl ether and dioxydipropyl ether of bisphenols such as bisphenol S, diols such as 1,4-butenediol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaeryscutol, sorbitol , polyols such as trimethylolethane or their partial esters (but
having at least 2 hydroxyl groups)
Examples of alkylene oxide adducts of polyhydric alcohols include compounds in which alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) are added to the above polyhydric alcohols (including block additions and random additions of two or more types). or its partial esters (those having at least two hydroxyl groups); examples of alkylene oxide adducts of polyvalent phenols include catechol, resorcinol, hydroquinone, pyrogallol, phloroglycine, etc. Compounds with alkylene oxide added thereto or partial esters thereof (however, examples include those having at least two hydroxyl groups. Regarding alkylene oxide adducts of bisphenols, the same applies to bisphenol A and bisphenol S). Examples include compounds in which alkylene oxide is added.The number of moles of these alkylene oxides added is not particularly limited, but is usually 1 to 30 moles.Among the above compounds, preferred are glycols, and particularly preferred are glycols. Neopentyl glycol. Monovalent fatty acid R ₂ COOH having 1 to 3 carbon atoms includes the fatty acid represented by R ₁ COOH and formic acid,
Examples include acetic acid, propionic acid, butyric acid, valeric acid, and isovaleric acid. Preferred fatty acids include oleic acid, ricinoleic acid, and ricinoleic acid. The most preferred compound (A) represented by R ₁ CO(OXOOCYCO)nOXOZ, which is the main component of the fiber treatment agent of the present invention, is the following compound. The fiber treatment agent of the present invention preferably contains the above-mentioned compound.
(A) contains (a) a reaction product of a higher fatty acid, a polyhydric alcohol, and a polyethylene glycol and/or a polypropylene glycol component, and/or
(b) Castor oil or ethylene oxide and/or propylene oxide adducts of hydrogenated castor oil
A composition in which (B) is mixed is used. Examples of higher fatty acids include saturated fatty acids with 12 to 26 carbon atoms such as lauric acid, palmitic acid, stearic acid, and cerotic acid, and 18 carbon atoms such as oleic acid, elaidic acid, linoleic acid, and linolenic acid.
~22 unsaturated fatty acids, saturated aliphatic dicarboxylic acids such as dodecanoic acid, octadecanoic acid, etc. are used. The polyhydric alcohol is preferably trivalent or higher glycerin, monoalkylglycerin, 1,
2,3-butanetriol, 1,2,3-pentanetriol, dialkyl-substituted glycerin, trialkyl-substituted glycerin, erythrift, pentaerythrift, adonite, xylitol, solpit, mannitol, etc. are used. As the polyalkylene glycol, polyethylene glycol is preferably used, but polypropylene glycol may also be used, or it may be used in combination. Polyalkylene glycol has 5 repeating units
-60, preferably 10-45 are used. To produce the above-mentioned ester, first a condensate of a polyhydric alcohol and a polyalkylene glycol is produced. For example, alkylene oxide is allowed to act on polyhydric alcohol. Next, the condensate is reacted with a higher fatty acid to form an ester. In this case, it may be a partial ester. Other esters are also produced according to the above method.
That is, a condensate of a partial ester of a higher fatty acid and a polyhydric alcohol and an alkylene oxide, and/
Or ester. To make the latter esters, for example, aliphatic dicarboxylic acids are used. Therefore, all of the compounds are compounds in which higher fatty acids, polyhydric alcohols, and polyalkylene glycols are bonded. Any compound may be used as long as it is an oxide adduct. The reason why the number of moles of the alkylene oxide adduct added and the number of moles of alkylene oxide in the compounds (a) and (b) are limited as described above is as follows. That is, if a compound with an alkylene oxide addition mole number of less than 5 moles is used, it is not only difficult to improve the smoke generation property, but also the heating element is often contaminated, the drawn yarn frequently breaks, and moreover, the synthetic In applications where the fibers are treated with an adhesive, such as in tire cords, this is even more undesirable since the strength decreases significantly after the adhesive treatment. On the other hand, if a compound with more than 60 moles of alkylene oxide added is used, the heating element is often contaminated, yarn breakage occurs frequently during stretching, friction during spinning becomes too high, and the fiber processing agent itself emulsifies. This is not preferred because stability deteriorates. As the castor oil or hydrogenated castor oil, conventionally known ones are used, and the number of moles of ethylene oxide and/or propylene oxide added thereto is 5 to 60 moles, preferably 10 to 45 moles. In the present invention, particularly preferred compounds (B) include the following. Ethylene oxide adduct of hydrogenated castor oil, ethylene oxide adduct of sorbitan triolate. The fiber treatment agent of the present invention is a mixture of 40 to 80 parts by weight of the compound (A) and 60 to 20 parts by weight of the compound (B). Even more preferably, the fiber treatment agent is a composition obtained by mixing the compounds (A) and (B) with a compound (C) to which ethylene oxide and/or propylene oxide of an alkylamine is added. The alkylamine has 2 to 30 carbon atoms.
primary and secondary amines are used. Preferred are lauryl, cetyl and stearylamine. The number of moles of ethylene oxide and propylene oxide added is preferably 5 to 30, more preferably 10 to 20. If the number of moles is less than 5 moles, no smoke generation prevention effect is observed. Furthermore, if it is more than 30 moles, the heating element will be contaminated a lot, yarn breakage will occur frequently during drawing, friction during spinning will become too high, and the emulsion stability of the fiber treatment agent will deteriorate, which is not preferable. In the present invention, the compounds (A), (B), and (C) are
(A)/(B)/(C)=40-80/5-59/1-15, preferably 40-70/30-80/2-10. In addition to the above (A), (B), and (C), antistatic agents, etc.
Components may be mixed. The fibers targeted by the present invention are thermoplastic synthetic fibers such as polyethylene terephthalate, polyhexamethylene adipamide, and polycaproamide.
In particular, the above-mentioned fibers obtained through a spinning process using a heating element of 170° C. or higher or a heating atmosphere are targeted. In the present invention, treatment with a treatment agent refers to the treatment of the fibers,
The above compound (A), or (A), (B), or (A), (B), (C)
means an operation in which the composition comes into contact with the composition. Therefore, the fiber treatment agent of the present invention may be added to the synthetic fibers at any stage after spinning by conventional means. For example, it can be added to the yarn during or after drawing in the form of a water-containing oil such as a water emulsion or a non-water-containing oil using a roller or the like. In particular, it is preferable to add it to the undrawn yarn before drawing in order to improve drawability and prevent smoking during drawing. When synthetic fibers are produced by applying a fiber treatment agent using the method of the present invention, yarn breakage during heating and drawing is reduced, making it possible to stably manufacture high-strength yarns, and vaporization of the fiber treatment agent due to heat treatment. This has an excellent effect in that it can sufficiently improve the problem associated with smoke generation. Moreover, if smoke generation is prevented by the method of the present invention,
There is no contamination of the heating element during the manufacturing process, and the emulsion stability of the fiber treatment agent is good, and the process can be carried out without any disadvantages in other respects. The present invention will be explained below using examples. Examples 1 to 6, Comparative Example 1 Polyethylene terephthalate filament yarn of 1500 denier and 288 filaments was spun in a conventional manner, and a 15% water emulsion type fiber treatment agent having the composition shown in the table was applied by a roller, and then the yarn was heated at 230°C. It was stretched at a stretching rate of 5.7 times using a hot roller and a hot plate. The amount of fiber treatment agent attached to the fiber is
It was 1.0%. The smoke generation properties of the hot roller and hot plate during stretching, the dirtiness of the hot roller and hot plate, the stretchability (number of thread breakages during stretching), and the emulsion stability of the fiber treatment agent were measured according to the following criteria, and Table 1
It was shown to. Smoke generation property: The state of smoke generation on the hot roller and hot plate during stretching was observed with the naked eye. ◎: No smoke generation ○: Almost no smoke generation △: More than most. Contamination of the hot roller and hot plate: This is indicated by the time until the stain increases and yarn breakage occurs 4 times/ton based on the same standard as the drawability shown below, and yarn breakage occurs frequently. Stretchability: Indicated by the number of thread breaks during stretching that occurred during stretching of polyethylene terephthalate filament equivalent to 1 ton of polymer weight. Emulsion stability of fiber treatment agent: The emulsion stability after being adjusted to a water emulsion type fiber treatment agent at 50℃ and left at room temperature for 3 days is as follows: ◎: Very good 〇: Good ×: Separation occurred. Ta. Adhesiveness: 1500D/2, number of first twists 40T/10cm, number of first twists 40T/
PEXUL (ICI product name) / 10cm untreated cord
The specimens were treated with a latex adhesive and heat set to evaluate the pull-out adhesion to rubber.

[Table] Example 7 During the production of a 1260 denier, 204 filament polycapramide yarn by a normal direct spinning/drawing method, a normal water-containing fiber treatment agent, which is an antistatic composition, was applied after spinning and before drawing. Furthermore, apply a 1.0% stretch using a pre-stretch roll. Next, a non-water-containing fiber treatment agent having the composition shown in Example 6 was applied using a roller, and then stretched at 230°C using a hot roller to obtain a drawn yarn with a maximum stretching ratio of 9.7 g/d. At this time, in the case of the fiber treatment agent of the present invention, 1.1 times per ton of polycapramide is stretched.
The number of yarn breakages was 1.5 tons and good operability was demonstrated. On the other hand, when the fiber treatment agent used in the above-mentioned comparative example was used instead of the fiber treatment agent of the present invention, the number of yarn breakages was
The number of defects was 8.2 times/ton. Examples 1 to 2 4 to 5 An amine compound was added to the fiber treatment agents of Examples 1 to 6, and the results were experimentally evaluated in the same manner as in Examples 1 to 6, and the results are shown in Table 2.

【table】

Claims (1)

[Claims] 1. A fiber treatment agent containing a compound represented by the general formula R ₁ CO(OXOOCYCO)nOXOZ; however, the formula R ₁ CO- is a monovalent fatty acid residue having 6 to 30 carbon atoms, Z is -OCR ₂ , -OCR ₂ - is a monovalent fatty acid residue with 1 to 30 carbon atoms, -OXO- is a polyhydric alcohol residue, a residue of a polyhydric alcohol alkylene oxide adduct, a polyhydric phenol alkylene A divalent group selected from the group consisting of residues of oxide adducts and alkylene oxide adducts of bisphenols, -OCYCO- is -OCA ₁ SA ₂ OC
-, -OCA ₃ OA ₄ CO-, -OCA ₅ CO-, and n means an integer of 1 to 6. In addition, in the above, A ₁ , A ₂ , A ₃ and A ₄ are each independently C ₁ to
C ₄ alkylene group, A ₅ is C ₁ to C ₃ alkylene group,
And S means a sulfur atom.