JP4624844B2 - Synthetic fiber treatment agent and synthetic fiber treatment method - Google Patents

Description

  The present invention relates to a synthetic fiber treating agent (hereinafter simply referred to as a treating agent) and a synthetic fiber treating method (hereinafter simply referred to as a treating method). It is important that synthetic fibers such as polyamide fibers and polyester fibers do not generate fuzz or yarn breakage in the synthetic fibers during the yarn production process. Among them, synthetic fibers for industrial materials used for tire cords, belts, hoses, seat belts, airbags, etc., are produced under severe conditions of high temperature and high contact pressure in the synthetic fiber, Since fluff and thread breakage are likely to occur in synthetic fibers, it is particularly important to prevent such fluff and thread breakage from occurring. For this reason, the treatment agent attached to the synthetic fiber has a high lubricity that can sufficiently suppress the occurrence of fluff and yarn breakage in the synthetic fiber even when the yarn is produced at high temperature and high contact pressure. Is required. The present invention relates to a treatment agent and a treatment method that meet such a demand.

  Conventionally, as a treating agent for imparting lubricity to a synthetic fiber even under high temperature and high contact pressure, 1) an alcohol component having an alkylene oxide adduct of an ester compound of polyhydric alcohol and hydroxymonocarboxylic acid as an essential component, and maleic acid A treating agent containing an ester compound with a carboxylic acid component having an essential component (see, for example, Patent Document 1), 2) a carboxylic acid component comprising a dicarboxylic acid and a monocarboxylic acid having no hydroxyl group, and castor oil and / or hydrogenated castor oil (3) A diol component consisting of a random polymer of tetrahydrofuran and alkylene oxide, a dicarboxylic acid component and a monocarboxylic acid Treatment containing ester compounds with ingredients (For example, see Patent Document 3), 4) treating agent containing a compound having a polytetramethylene glycol residues in the molecule (for example, see Patent Document 4) it has been proposed.

However, these conventional treatment agents have a problem that they cannot satisfy the high lubricity required in recent years.
JP 59-223368 A JP 63-50572 A JP-A 63-235576 JP 59-59978 A

  The problem to be solved by the present invention is that, even in the case where yarn is produced under severe conditions of high temperature and high contact pressure in the yarn production process, such as synthetic fibers for industrial materials, the synthetic fibers are fuzzed or broken. Therefore, the present invention provides a treatment agent and a treatment method that can provide a high degree of lubricity that can sufficiently suppress the occurrence of water.

  Accordingly, as a result of researches to solve the above problems, the present inventors have found that a treatment agent containing a specific hardened castor oil derivative in a predetermined ratio as at least a part of the lubricant is suitable.

  That is, the present invention is a treatment for synthetic fibers containing a lubricant and an emulsifier, comprising 1 to 50% by mass of a hardened castor oil derivative represented by the following chemical formula 1 as at least a part of the lubricant. It relates to the agent.

In chemical formula 1,
X: Residue obtained by removing all hydrogen atoms from two hydroxyl groups of a dicarboxylic acid having 3 to 22 carbon atoms A: From a reaction product having a number average molecular weight of 990 to 10,000 obtained by reacting hardened castor oil with ethylene oxide and / or propylene oxide Residue from which one hydroxyl group is removed or a residue from which one hydroxyl group is removed from a partial ester compound of the reaction product and an organic monocarboxylic acid having 2 to 30 carbon atoms B: Oxyethylene unit as an oxyalkylene unit in the molecule And / or a residue obtained by removing one hydroxyl group from a polyoxytetramethylene polyoxyalkylene random copolymer having a number average molecular weight of 500 to 10,000 having an oxypropylene unit, or the polyoxytetramethylene polyoxyalkylene random copolymer; From partial ester compounds with organic monocarboxylic acids having 2 to 30 carbon atoms Residue obtained by removing One of hydroxyl

  Moreover, this invention relates to the processing method characterized by making the synthetic fiber processing agent which concerns on said this invention adhere so that it may become 0.2-1.5 mass% with respect to synthetic fiber.

  First, the treatment agent of the present invention will be described. The treatment agent of the present invention contains a lubricant and an emulsifier, and contains a hardened castor oil derivative represented by Chemical Formula 1 at a predetermined ratio as at least a part of the lubricant.

  The raw material which will form X of Chemical formula 1 is dicarboxylic acid. Examples of such dicarboxylic acids include 1) aliphatic dicarboxylic acids having 3 to 22 carbon atoms such as malonic acid, maleic acid, itaconic acid, adipic acid, sebacic acid, and pentadecenyl succinic acid, and 2) phthalic acid, isophthalic acid, Examples include aromatic dicarboxylic acids having 8 to 22 carbon atoms such as terephthalic acid, and 3) sulfur-containing aliphatic dicarboxylic acids having 3 to 22 carbon atoms such as thiodipropionic acid, thiodioctanoic acid, thiodilauric acid, and thiodistearic acid. Of these, aliphatic dicarboxylic acids having 3 to 10 carbon atoms are preferable, and aliphatic dicarboxylic acids having 4 to 6 carbon atoms are more preferable.

  The raw materials that will form A in Chemical Formula 1 are: 1) a reaction product obtained by reacting hardened castor oil with ethylene oxide and / or propylene oxide, 2) the reaction product, and an organic monocarboxylic acid having 2 to 30 carbon atoms; Of the partial ester compound. Here, a reaction product obtained by reacting a hydrogenated castor oil with ethylene oxide and / or propylene oxide includes a) a reaction product obtained by addition reaction of ethylene oxide and / or propylene oxide with a hydroxyl group of the cured castor oil, and b) an ester bond of the cured castor oil. In addition, a reaction product in which ethylene oxide and / or propylene oxide are subjected to insertion reaction, and c) a reaction product in which such addition reaction and insertion reaction have occurred are included.

  In the raw material that will form A in Chemical Formula 1, the reaction product obtained by reacting ethylene oxide and / or propylene oxide with hardened castor oil is assumed to have a number average molecular weight of 990 to 10,000, but has a number average molecular weight of 1,000 to 5,000. Preferably. Such preferred reactants include hardened castor oil polyoxyethylene (m = 5, m is the number of oxyethylene units, the same shall apply hereinafter), hardened castor oil polyoxyethylene (m = 10), hardened castor oil polyoxyethylene (m = 25) , A reaction product obtained by reacting ethylene oxide with hardened castor oil, such as hardened castor oil polyoxyethylene (m = 35), 2) hardened castor oil polyoxypropylene (n = 5, n is the number of oxypropylene units, the same shall apply hereinafter), Hardened castor oil polyoxypropylene (n = 10), hardened castor oil polyoxypropylene (n = 25), etc., a reaction product obtained by reacting hardened castor oil with propylene oxide, 3) hardened castor oil polyoxyethylene (m = 5) polyoxy Propylene (n = 5), hardened castor oil polyoxyethylene (m = 10) polyoxyp Pyrene (n = 10), hydrogenated castor oil polyoxyethylene (m = 15) polyoxypropylene (n = 15), such as, the reaction product obtained by reacting ethylene oxide and propylene oxide to hydrogenated castor oil. A reaction product obtained by reacting hardened castor oil with ethylene oxide and / or propylene oxide can be obtained by a known synthesis method. This includes, for example, the synthesis method described in Journal of the American Oil Chemical Society Vol.

  In the raw material that will form A in Chemical Formula 1, a partial ester compound of a reaction product obtained by reacting a hardened castor oil with ethylene oxide and / or propylene oxide and an organic monocarboxylic acid having 2 to 30 carbon atoms is 1) Partial ester compound of 1 mol of reaction product obtained by reacting hardened castor oil with ethylene oxide and / or propylene oxide and 1 mol of organic monocarboxylic acid having 2 to 30 carbon atoms, 2) ethylene oxide and / or propylene oxide with hardened castor oil A partial ester compound of 1 mol of a reaction product obtained by reacting with 2 mol of an organic monocarboxylic acid having 2 to 30 carbon atoms is included. Here, the reaction product obtained by reacting the hardened castor oil with ethylene oxide and / or propylene oxide is as described above. Examples of the organic monocarboxylic acid having 2 to 30 carbon atoms include 1) acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, lauric acid, 2-ethylhexanoic acid, stearic acid, isostearic acid, oleic acid, erucic acid, etc. 2) Aromatic monocarboxylic acids having 2 to 30 carbon atoms, 2) Aromatic monocarboxylic acids such as benzoic acid, methylbenzene carboxylic acid, naphthalene carboxylic acid, etc. 3) Lactic acid, glyceric acid, ricinoleic acid, 12-hydroxystearic acid, etc. 3) C3-C30 aliphatic hydroxy monocarboxylic acid, 4) Sulfur-containing monocarboxylic acid having 3 to 30 carbon atoms such as propylthioacetic acid, laurylthioacetic acid, laurylthiopropionic acid, and phenylmercaptoacetic acid. However, an aliphatic monocarboxylic acid having 2 to 22 carbon atoms is preferred, and an aliphatic monocarboxylic acid having 8 to 18 carbon atoms. Acid is more preferable. In the raw material that forms A in Chemical Formula 1, the partial ester compound described above can be obtained by a known synthesis method. For example, 1 mol of a reaction product obtained by reacting hardened castor oil with ethylene oxide and / or propylene oxide and 1 mol of an organic monocarboxylic acid are heated at 120 to 140 ° C. in the presence of an acid catalyst, The method of esterifying is mentioned.

  The raw materials for forming B in Chemical Formula 1 are: 1) a polyoxytetramethylene polyoxyalkylene random copolymer having oxyethylene units and / or oxypropylene units as oxyalkylene units in the molecule; 2) the poly Examples thereof include partial ester compounds of an oxytetramethylene polyoxyalkylene random copolymer and an organic monocarboxylic acid having 2 to 30 carbon atoms.

  In the raw material that will form the chemical formula B, the polyoxytetramethylene polyoxyalkylene random copolymer has a number average molecular weight of 500 to 10,000, but a number average molecular weight of 1,000 to 5,000. preferable. As such a preferred polyoxytetramethylene polyoxyalkylene random copolymer, 1) polyoxytetramethylene (s = 5, s is the number of oxytetramethylene groups, the same shall apply hereinafter) polyoxyethylene (m = 5) random copolymer Polyoxytetramethylene (s = 15) polyoxyethylene (m = 15) random copolymer, polyoxytetramethylene (s = 25) polyoxyethylene (m = 25) random copolymer, etc. Methylene polyoxyethylene random copolymer, 2) polyoxytetramethylene (s = 5) polyoxypropylene (n = 5) random copolymer, polyoxytetramethylene (s = 15) polyoxypropylene (n = 15) Random copolymer, polyoxytetramethylene (s = 25) polyoxypropylene (N = 15) Polyoxytetramethylene polyoxypropylene random copolymer such as random copolymer, 3) Polyoxytetramethylene (s = 5) Polyoxyethylene (m = 5) Polyoxypropylene (n = 5) Random copolymer, polyoxytetramethylene (s = 15) polyoxyethylene (m = 15) polyoxypropylene (n = 15) random copolymer, polyoxytetramethylene (s = 25) polyoxyethylene (m = 25) Polyoxytetramethylene polyoxyethylene polyoxypropylene random copolymers such as polyoxypropylene (n = 25) random copolymers are exemplified, among which polyoxytetramethylene polyoxyethylene random copolymers are preferable. . The polyoxytetramethylene polyoxyalkylene random copolymer described above can be obtained by a known synthesis method. This includes, for example, a method in which tetrahydrofuran and ethylene oxide and / or propylene oxide are subjected to a random copolymerization reaction in the presence of an alkali catalyst.

  In the partial ester compound of the polyoxytetramethylene polyoxyalkylene random copolymer and the organic monocarboxylic acid, the polyoxytetramethylene polyoxyalkylene random copolymer is as described above, and has 2 to 30 carbon atoms. The organic monocarboxylic acid is as described above for the raw material that will form A in Chemical Formula 1. A partial ester compound of a polyoxytetramethylene polyoxyalkylene random copolymer and an organic monocarboxylic acid can be obtained by a known synthesis method. This includes, for example, a method in which 1 mol of a polyoxytetramethylene polyoxyalkylene random copolymer and 1 mol of an organic monocarboxylic acid are heated at 120 to 140 ° C. to cause an esterification reaction.

  Each of the hardened castor oil derivatives represented by Chemical Formula 1 forms Chemical Formula 1 A per mole of dicarboxylic acid, which is a raw material that will form Chemical Formula X, using the raw materials described above. In a ratio of 1 mol of the reaction material or a partial ester compound thereof, or 1 mol of the polyoxytetramethylene polyoxyalkylene random copolymer or the partial ester compound thereof that is a raw material that will form B of Chemical Formula 1, It can be obtained by heating and reacting while distilling off the water produced under a nitrogen gas stream in the presence of a catalyst.

  The treating agent of the present invention contains a lubricant and an emulsifier, and contains 1 to 50% by mass of the hardened castor oil derivative represented by Chemical Formula 1 described above as at least a part of the lubricant in the treating agent. It is.

  Known emulsifiers can be applied as the emulsifier used in the treatment agent of the present invention. This includes, for example, 1) polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene hardened castor oil ether, polyoxyalkylene alkylamino ether, etc. A nonionic surfactant having 2) a polyhydric alcohol partial ester type nonionic surfactant such as sorbitan monolaurate, sorbitan trioleate, glycerin monolaurate, diglycerin dilaurate, 3) 3-6 valent Of a partial ester of an alcohol and a fatty acid with addition of an alkylene oxide, a partial or complete ester of a 3 to 6 valent alcohol and a fatty acid with an alkylene oxide added, a 3 to 6 valent alcohol and a hydroxy fat Esters such as those obtained by adding an alkylene oxide with, polyoxyalkylene polyhydric alcohol fatty acid ester type nonionic surface active agents. Although the content rate in the processing agent of the emulsifier demonstrated above is not restrict | limited in particular, Usually, it shall be 50-99 mass%.

  The treatment agent of the present invention preferably contains a specific complete ester compound as a part of the lubricant. As such a complete ester compound, 1) a complete ester compound of a C2-C30 divalent to tetravalent aliphatic polycarboxylic acid and a C2-C30 aliphatic monoalcohol, 2) a C2-C30 Examples thereof include a complete ester compound of an aliphatic monocarboxylic acid and a C2-C30 divalent aliphatic alcohol, and 3) a mixture of the above 1) and 2). Here, in the case of 1), the complete ester compound is a compound in which all carboxyl groups of the divalent to tetravalent aliphatic polycarboxylic acid are blocked by ester bonds by an esterification reaction with an aliphatic monoalcohol. In the case of 2), it means that all hydroxy groups of the divalent to tetravalent aliphatic alcohol are blocked by ester bonds by an esterification reaction with an aliphatic monocarboxylic acid.

  In the complete ester compound of a C2-C30 divalent aliphatic polycarboxylic acid having 2 to 30 carbon atoms and an aliphatic monoalcohol having 2 to 30 carbon atoms used in the treatment agent of the present invention, 2 to 4 having 2 to 30 carbon atoms Divalent aliphatic polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, α, ω-dodecanedicarboxylic acid, dodecenylsuccinic acid, octadecenyl dicarboxylic acid, cyclohexanedicarboxylic acid, 2,3,5- Hexatricarboxylic acid, 1,2,3-butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 2- (3-carboxypropyl) -1,1,5,6-heptanetetracarboxylic acid, etc. Can be mentioned. Examples of the aliphatic monoalcohol having 2 to 30 carbon atoms include ethyl alcohol, butyl alcohol, octyl alcohol, lauryl alcohol, stearyl alcohol, seryl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol, isododecyl alcohol, isohexadecyl alcohol, Stearyl alcohol, isotetracosanyl alcohol, 2-propyl alcohol, 12-eicosyl alcohol, vinyl alcohol, butenyl alcohol, hexadecenyl alcohol, oleyl alcohol, eicosenyl alcohol, 2-methyl-2-propylene-1 -Ol, 6-ethyl-2-undecen-1-ol, 2-octen-5-ol, 15-hexadecene-2-ol and the like. The complete ester compound of a C2-C30 divalent aliphatic polycarboxylic acid having 2 to 30 carbon atoms and an aliphatic monoalcohol having 2 to 30 carbon atoms used in the treating agent of the present invention has 2 to 2 carbon atoms as exemplified above. It is obtained by an esterification reaction using an arbitrary combination of 30 2 to 4 valent aliphatic polycarboxylic acid and an aliphatic monoalcohol having 2 to 30 carbon atoms, among which aliphatic having 6 to 10 carbon atoms A complete ester compound of a dicarboxylic acid and an aliphatic monoalcohol having 16 to 20 carbon atoms is preferred. This includes, for example, dihexadecenyl adipate, dihexadecenyl azelate, dihexadecenyl sebacate, dioleyl adipate, diisostearyl adipate, dioleyl azelate, dioleyl sebacate, bis (1-cyclohexylhexyl) adipate, dieicosenyl adipate, dieicocenyl sebacate, bis (1-cyclohexylhexyl) sebacate and the like.

  In the complete ester compound of an aliphatic monocarboxylic acid having 2 to 30 carbon atoms and a divalent to tetravalent aliphatic alcohol having 2 to 30 carbon atoms used in the treatment agent of the present invention, an aliphatic monocarboxylic acid having 2 to 30 carbon atoms Acids include acetic acid, butyric acid, propionic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, triacontanoic acid, 2- Examples include ethylhexanoic acid, isostearic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, and erucic acid. Examples of the divalent to tetravalent aliphatic alcohol having 2 to 30 carbon atoms include ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol. The complete ester compound of an aliphatic monocarboxylic acid having 2 to 30 carbon atoms and a divalent to tetravalent aliphatic alcohol having 2 to 30 carbon atoms to be used in the treatment agent of the present invention has 2 to 30 carbon atoms as exemplified above. Is obtained by an esterification reaction in an arbitrary combination of an aliphatic monocarboxylic acid and an aliphatic alcohol having 2 to 30 carbon atoms, especially an aliphatic monocarboxylic acid having 8 to 20 carbon atoms. A complete ester compound of an acid and a C 4-6 divalent aliphatic alcohol is preferred. For example, neopentyl glycol dilaurate, 1,4-butanediol dioleate, 1,6-hexanediol dioleate, glycerin = triisostearate, glycerin = tripalmitreato, trimethylolpropane trinona NART, pentaerythritol tetraoleate and the like.

  In the treatment agent of the present invention, the complete ester compound described above is contained in an amount of 10 to 80% by mass in the treatment agent. The treatment agent of the present invention preferably further contains an organic carboxylic acid metal salt having 2 to 30 carbon atoms.

  A well-known thing can be applied as a C2-C30 organic carboxylic acid metal salt used for the processing agent of this invention. Examples thereof include 1) alkali metal salts of aliphatic monocarboxylic acids having 2 to 18 carbon atoms such as acetic acid, propionic acid, caproic acid, lauric acid, 2-ethylhexanoic acid, isostearic acid, oleic acid and erucic acid, Alkaline earth metal salts 2) Alkali metals of aliphatic dicarboxylic acids having 3 to 22 carbon atoms such as malonic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, dodecenyl succinic acid, pentadecenyl succinic acid, etc. 3) Alkali metal salts and alkaline earths of aromatic (poly) carboxylic acids having 7 to 30 carbon atoms such as benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene monocarboxylic acid, etc. 4) Aliphatic hydroxycarboxylic acids having 3 to 30 carbon atoms such as lactic acid, tartaric acid, ricinoleic acid, 12-hydroxystearic acid Potassium metal salts and alkaline earth metal salts, 5) Sulfur-containing aliphatics having 3 to 30 carbon atoms in total such as laurylthioacetic acid, laurylthiopropionic acid, phenylmercaptoacetic acid, thiodisuccinic acid, thiodipropionic acid, methylenebisthiopropionic acid Examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. Among them, alkali metal salts of aliphatic monocarboxylic acids having 8 to 18 carbon atoms and alkali metals of aliphatic dicarboxylic acids having 8 to 22 carbon atoms. Salts are preferred. The organic carboxylic acid metal salts described above can be used alone or in combination.

  In the treatment agent of the present invention, the organic carboxylic acid metal salt described above is contained in the treatment agent in an amount of 0.2 to 20% by mass. The treatment agent of the present invention preferably further contains an antioxidant.

  As the antioxidant used for the treatment agent of the present invention, known antioxidants can be applied. This includes, for example, 1) triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethyl Benzyl) hindered phenolic antioxidants such as isocyanuric acid 2) bis [2-methyl-4- (3-n-laurylthiopropionyloxy) -5-t-butylphenol Sulfuric antioxidants such as sulfide, dilaurylthiodipropionate, diisostearylthiodipropionate, mercaptobenzthiazole, 3) phenyl-β-naphthylamine, N, N′-diphenyl-p-phenylenediamine, Amine antioxidants such as phenothiazine, 4) Phosphorous antioxidants such as di (nonylphenyl) dinonylphenyl phosphite, triphenyl phosphite, trioctadecyl phosphite, etc. Among them, hindered phenol oxidation Inhibitors are preferred.

  In the treatment agent of the present invention, the antioxidant described above is contained in the treatment agent in an amount of 0.2 to 10% by mass. The treatment agent of the present invention preferably further contains an organic sulfonic acid type surfactant.

  As the organic sulfonic acid type surfactant used in the treatment agent of the present invention, known ones can be applied. Examples thereof include 1) Alkyl sulfonic acid alkali metal salts having 10 to 18 carbon atoms of alkyl groups such as sodium decane sulfonate, sodium dodecane sulfonate, lithium tetradecane sulfonate, potassium hexadecane sulfonate, potassium octadecane sulfonate, etc. 2) Alkyl group having 4 to 18 carbon atoms of alkyl group such as sodium butylbenzenesulfonate, sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, potassium tetradecylbenzenesulfonate, potassium octadecylbenzenesulfonate, sodium dibutylnaphthalenesulfonate Substituted aromatic sulfonic acid alkali metal salt, 3) 1,2-bis (butyloxycarbonyl) -1-ethanesulfonic acid lithium, 1,2-bis (octyloxycarbonyl)- Sodium ethanesulfonate, 1,2-bis (decyloxycarbonyl) -1-ethanesulfonic acid sodium, 1,2-bis (dodecyloxycarbonyl) -1-ethanesulfonic acid sodium, 1,2-bis (tetradecyl) Sodium oxycarbonyl) -1-ethanesulfonate, sodium 1,2-bis (hexadecyloxycarbonyl) -1-ethanesulfonate, sodium 1,2-bis (octadecyloxycarbonyl) -1-ethanesulfonate, 2- Sulfonate dodecyl acetate = alkali sulfonic acid alkali metal salt having an ester bond in the molecule having 10 to 30 carbon atoms, such as potassium, among them, alkyl sulfonic acid alkali metal salt having 8 to 16 carbon atoms, alkyl group Of alkyl-substituted aromatic sulfonic acid having 8 to 16 carbon atoms Li metal salt is preferred.

  In the treatment agent of the present invention, the organic sulfonic acid type surfactant described above is contained in the treatment agent in an amount of 0.2 to 10% by mass.

  The treating agent of the present invention comprises the above-described cured castor oil derivative, complete ester compound, organic carboxylic acid metal salt, antioxidant, organic sulfonic acid type surfactant and emulsifier, and the cured castor oil derivative is contained in an amount of 5 to 30% by mass. 25-60 mass% of complete ester compound, 0.5-10 mass% of organic carboxylic acid metal salt, 0.5-10 mass% of antioxidant, 0.5-10 mass of organic sulfonic acid type surfactant. What contains 10 to 65 mass% (total 100 mass%) of an emulsifier and an emulsifier is especially preferable.

  Next, the processing method of the present invention will be described. The treatment method of the present invention is a method in which the treatment agent of the present invention as described above is adhered to the synthetic fiber so as to be 0.2 to 1.5% by mass. Examples of the step of attaching the treatment agent of the present invention to the synthetic fiber include a spinning step, a step of simultaneously performing spinning and stretching, and the like. Examples of the method for attaching the treatment agent of the present invention to synthetic fibers include a roller oiling method, a guide oiling method using a metering pump, an immersion oiling method, and a spray oiling method. Further, examples of the form when the treatment agent of the present invention is attached to the synthetic fiber include neat, organic solvent solution, aqueous liquid, and the like, and an aqueous liquid is preferable. When the aqueous liquid of the treatment agent of the present invention is attached, the treatment agent of the present invention is attached to the synthetic fiber so as to be 0.2 to 1.5% by mass, preferably 0.3 to 1.2% by mass. Let

  Synthetic fibers to which the treatment method of the present invention is applied include 1) Polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polylactic acid ester 2) Polyamide fibers such as nylon 6 and nylon 66 3) Poly Polyacrylic fibers such as acrylic and modacrylic, 4) Polyolefin fibers such as polyethylene and polypropylene, 5) Polyurethane fibers, etc. are mentioned, and the type and use are not particularly limited, but high temperature and high contact pressure in the yarn making process The effect is high when applied to synthetic fibers for industrial materials exposed to harsh conditions, and the effect is particularly high when applied to polyester fibers or polyamide fibers.

  In the present invention described above, even if the yarn is produced under severe conditions of high temperature and high contact pressure in the yarn production process, such as a synthetic fiber for industrial materials, fluff and yarn breakage occur in the synthetic fiber. There is an effect that it is possible to provide a high degree of lubricity that can be sufficiently suppressed.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test category 1 (synthesis of hardened castor oil derivative)
-Synthesis of hydrogenated castor oil derivative (C-1)-Synthesis of partial ester compound (A-1) that will form A in Chemical Formula 1 Charge 938 g (1 mol) of hydrogenated castor oil and 4 g of sodium hydroxide in an autoclave, After purging with nitrogen gas, 1100 g (25 mol) of ethylene oxide was injected over 3 hours while maintaining the temperature at 120 to 140 ° C., then aging was performed for 1 hour at the same temperature, and the catalyst was removed to obtain a reaction product. It was. When the reaction product obtained here was analyzed, it had a hydroxyl value of 82 and a number average molecular weight of 2040 (GPC method, converted to polystyrene, the same applies hereinafter), and a reaction product (NMR) in which 25 moles of ethylene oxide reacted with 1 mole of hardened castor oil. Analysis method, the same applies hereinafter). 204 g (0.1 mol) of this reaction product, 28 g (0.1 mol) of stearic acid and 0.6 g of sulfuric acid were charged into a flask and heated to 120 to 130 ° C. while stirring under a nitrogen gas stream. While removing water produced at the same temperature under reduced pressure, the reaction was continued for 2 hours to obtain a product. The product obtained here was a partial ester compound (A-1) having a number average molecular weight of 1200 in which one stearic acid was introduced into one hydroxyl group of the reaction product.

Synthesis of partial ester compound (B-1) that will form B in Chemical Formula 1 After the reactor is filled with dry bleaching earth in the form of small rods having a diameter of 2 to 3 mm and an average length of 4 mm as a catalyst bed, 47 While maintaining the catalyst bed at ˜49 ° C., a mixture of 1080 g (15 mol) of tetrahydrofuran, 4.4 g (0.1 mol) of ethylene oxide and 54 g (3 mol) of water was continuously circulated and supplied. Further, ethylene oxide was blown at a rate of 60 g per hour, and 660 g (15 mol) of ethylene oxide was subjected to the reaction over 10 hours. The reaction was further continued for 3 hours to obtain a reaction product. When this reaction product was analyzed by NMR, GC-MASS, GPC (using pullulan for conversion of the number average molecular weight, the same shall apply hereinafter) and the like, polyoxytetramethylene (s = 15) polyoxyethylene having a number average molecular weight of 1740 (s = 15) m = 15) It was a random polymer. 174 g (0.1 mol) of this polyoxytetramethylene (s = 15) polyoxyethylene (m = 15) random copolymer, 28 g (0.1 mol) of stearic acid and 0.5 g of sulfuric acid were charged into a flask, and nitrogen was added. The mixture was heated to 120 to 130 ° C. while stirring under a gas stream. While removing water produced at the same temperature under reduced pressure, the reaction was continued for 2 hours to obtain a product. The product obtained here was a polyoxytetramethylene (s = 15) polyoxyethylene (m = 15) random copolymer having a number average molecular weight of 2,000 in which one stearic acid was introduced into one hydroxyl group. It was an ester compound (B-1).

.. Synthesis of hardened castor oil derivative (C-1) represented by Chemical Formula 1 120 g (0.1 mol) of the partial ester compound (A-1), 200 g (0.1 of the partial ester compound (B-1) Mol), 11.6 g (0.1 mol) of maleic acid and 1 g of sulfuric acid were charged into a flask and heated to 120 to 130 ° C. while stirring under a nitrogen gas stream. While removing water generated at the same temperature under reduced pressure, the reaction was continued for 2 hours to obtain a hardened castor oil derivative. In the cured castor oil derivative (C-1) obtained here, X in Chemical Formula 1 is a residue obtained by removing all hydrogen atoms from two hydroxyl groups of maleic acid, and A is one from the partial ester compound (A-1). Residues excluding one hydroxyl group, B was a residue obtained by removing one hydroxyl group from the partial ester compound (B-1).

-Synthesis | combination of hardened castor oil derivative (C-2)-(C-13) Hardened castor oil derivative (C-2)-(C-13) was synthesize | combined similarly to the case of the hardened castor oil derivative (C-1). Table 1 summarizes the contents of the hardened castor oil derivatives synthesized above.

In Table 1,
X-1: residue obtained by removing all hydrogen atoms from two hydroxyl groups of maleic acid X-2: residue obtained by removing all hydrogen atoms from two hydroxyl groups of adipic acid X-3: two hydroxyl groups of malonic acid Residues obtained by removing all hydrogen atoms from X-4: Residues obtained by removing all hydrogen atoms from two hydroxyl groups of sebacic acid X-5: Residues obtained by removing all hydrogen atoms from two hydroxyl groups of isophthalic acid X-6: a residue obtained by removing all hydrogen atoms from two hydroxyl groups of thiodipropionic acid

A-1: Residue obtained by removing one hydroxyl group from a partial ester compound of 1 mole of hardened castor oil polyoxyethylene (m = 25) (number average molecular weight 2040) and 1 mole of stearic acid A-2: Hardened castor oil polyoxyethylene (M = 12) (Number average molecular weight 1470) Residue obtained by removing one hydroxyl group from a partial ester compound of 1 mol and 2 mol of stearic acid A-3: Hardened castor oil polyoxyethylene (m = 10) polyoxypropylene ( n = 10) Residue obtained by removing one hydroxyl group from a partial ester compound of 1 mol (number average molecular weight 1960) and 1 mol of lauric acid A-4: 1 mol of hardened castor oil oxyethylene (number average molecular weight 990) and stearic acid Residue obtained by removing one hydroxyl group from 1 mol of partial ester compound A-5: Hardened castor oil polyoxyethylene (m = 38) ( Residue obtained by removing one hydroxyl group from a partial ester compound of 1 mol of number average molecular weight 2610) and 1 mol of stearic acid A-6: hydrogenated castor oil polyoxyethylene (m = 70) (1 mol of number average molecular weight 4020) and capron Residue obtained by removing one hydroxyl group from a partial ester compound with 1 mol of acid A-7: From a partial ester compound of 1 mol of hydrogenated castor oil polyoxyethylene (m = 100) (number average molecular weight 5340) and 1 mol of benzoic acid Residue excluding one hydroxyl group A-8: Residue obtained by removing one hydroxyl group from hardened castor oil polyoxyethylene (m = 12) (number average molecular weight 1470) A-9: Hardened castor oil polyoxyethylene (m = 25) ) (Number average molecular weight 2040) Residue obtained by removing one hydroxyl group from a partial ester compound of 1 mol and 1 mol of 12-hydroxystearic acid A 10: residue obtained by removing one hydroxyl group from hardened castor oil polyoxypropylene (n = 10) (number average molecular weight 1520)

B-1: Residue obtained by removing one hydroxyl group from a partial ester compound of polyoxytetramethylene (s = 15) polyoxyethylene (m = 15) random copolymer (number average molecular weight 1740) and stearic acid B- 2: Residue obtained by removing one hydroxyl group from a partial ester compound of polyoxytetramethylene (s = 15) polyoxyethylene (m = 5) random copolymer (number average molecular weight 1300) and stearic acid B-3: Residue obtained by removing one hydroxyl group from a partial ester compound of polyoxytetramethylene (s = 30) polyoxyethylene (m = 50) random copolymer (number average molecular weight 4360) and lauric acid B-4: Polyoxy A partial copolymer of tetramethylene (s = 5) polyoxypropylene (n = 5) random copolymer (number average molecular weight 650) and propionic acid. Residue obtained by removing one hydroxyl group from a tellurium compound B-5: Partial ester compound of polyoxytetramethylene (s = 40) polyoxypropylene (n = 40) random copolymer (number average molecular weight 5200) and behenic acid Residue obtained by removing one hydroxyl group from B-6: Partial ester of polyoxytetramethylene (s = 5) polyoxypropylene (n = 5) random copolymer (number average molecular weight 650) and 12-hydroxystearic acid Residue obtained by removing one hydroxyl group from a compound B-7: From a partial ester compound of polyoxytetramethylene (s = 40) polyoxypropylene (n = 40) random copolymer (number average molecular weight 5200) and propiothioacetic acid Residue excluding one hydroxyl group B-8: polyoxytetramethylene (s = 15) polyoxyethylene (m = 15 Residue obtained by removing one hydroxyl group from a random copolymer (number average molecular weight 1740) B-9: polyoxytetramethylene (s = 15) polyoxyethylene (m = 5) random copolymer (number average molecular weight 1300) Residues from which one hydroxyl group is removed

Test Category 2 (Preparation of treatment agent)
Example 1 {Preparation of treating agent (P-1)}
6 parts of hardened castor oil derivative (C-1) synthesized in Test Category 1, 30 parts of the following complete ester compound (D-1), 0.8 part of the following organic carboxylic acid metal salt (E-1), and the following oxidation Example 1 was prepared by mixing 0.8 part of the inhibitor (F-1), 1.4 parts of the following organic sulfonic acid type surfactant (G-1) and 61 parts of the following emulsifier (H-1). A treating agent (P-1) was prepared.
Complete ester compound (D-1): Dioleyl adipate Organic carboxylic acid metal salt (E-1): Sodium oleate Antioxidant (F-1): Triethylene glycol-bis [3- (3-t-butyl -5-methyl-4-hydroxyphenyl) propionate]
Organic sulfonic acid type surfactant (G-1): Sodium dodecylbenzene sulfonate Emulsifier (H-1): Hardened castor oil polyoxyethylene (m = 25)

Examples 2 to 29 and Comparative Examples 1 to 6 {Preparation of treating agents (P-2) to (P-29) and (R-1) to (R-6)}
In the same manner as the treating agent (P-1) of Example 1, the treating agents (P-2) to (P-29) and (R-1) to (R) of Examples 2 to 29 and Comparative Examples 1 to 6 were used. -6) was prepared. Table 2 summarizes the contents of the treatment agents prepared in each example, including Example 1.

Test category 3 (Adhesion and evaluation of treatment agents on synthetic fibers)
-Adhesion of processing agent to synthetic fiber Polyethylene terephthalate chip with intrinsic viscosity of 1.10 and carboxyl end concentration of 15 equivalents / 10 ⁶ g was melt-spun with an extruder-type spinning machine equipped with a die with 192 holes. did. Continuously by a guide oiling method using a metering pump so that a 10% aqueous liquid of the treatment agent described in Table 2 is 1.0% as a treatment agent with respect to the spun yarn. And attached. The spun yarn to which the aqueous liquid is adhered is converged with a guide, taken up by a take-up roll having a surface speed of 3000 m / min, and then the total draw ratio is 1.7 times through a draw roll and a relaxation roll at 240 ° C. Was stretched. The fineness of the drawn yarn that passed through the relaxation roll was 1670 dtex (1500 denier), and this was wound up as 10 kg of rolled cheese to obtain a treated polyester fiber.

-Evaluation About the said processed polyester fiber, the frequency | count of a yarn breakage and extending | stretched fluff were evaluated as follows. The results are summarized in Table 2.
.. Number of yarn breaks The number of yarn breaks per ton of the treated polyester fiber was measured 10 times, and the average value of the measured values was evaluated according to the following criteria.
◎: Number of yarn breaks less than 0.5 ○ to ◎: Number of yarn breaks from 0.5 to less than 1.0 times ○: Number of yarn breaks from 1.0 to less than 1.5 times Δ: Break Number of times of yarn is 1.5 times or more and less than 2.0 times ×: Number of times of yarn breakage is 2.0 times or more

.. Stretched fluff The number of fluffs per 100,000 m of the treated polyester fiber was measured using a fly counter (manufactured by Toray Engineering Co., Ltd.) and evaluated according to the following criteria.
◎: Less than 1 ○: 1 or more to less than 3 △: 3 or more to less than 5 ×: 5 or more

In Table 2,
amount to use:%
Adhering amount: Adhering amount of treatment agent to spun yarn (%)
C-1 to C-13: Hardened castor oil derivatives shown in Table 1 synthesized in test category 1

D-1: Dioleyl adipate D-2: Diisostearyl adipate D-3: Bis (1-cyclohexylhexyl) sebacate D-4: Trimethylolpropane trinonanato D-5: Pentaerythritol tetraoleate

E-1: Sodium oleate E-2: Potassium isostearate E-3: Dipotassium dodecenyl succinate E-4: Potassium ricinoleate E-5: Sodium lauryl thiopropionate E-6: Potassium benzoate

F-1: Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate]
F-2: 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid F-3: bis [2-methyl-4- (3-n-laurylthio) Propionyloxy) -5-t-butylphenyl] sulfide F-4: phenyl-β-naphthylamine F-5: di (nonylphenyl) dinonylphenyl phosphite

G-1: Sodium dodecylbenzenesulfonate G-2: Sodium dodecanesulfonate G-3: Sodium decanesulfonate G-4: Sodium tetradecylbenzenesulfonate G-5: 1,2-bis (octyloxycarbonyl)- 1-sodium ethanesulfonate

H-1: Hardened castor oil polyoxyethylene (m = 25)
H-2: α-dodecyl-ω-hydroxy-polyoxyethylene (m = 10)
H-3: α- (p-dodecylphenyl) -ω-hydroxy-polyoxyethylene (m = 6)

r-1 to r-4: The following compounds not corresponding to the hardened castor oil derivative represented by Chemical formula r-1: 1 mol of tridecanedicarboxylic acid, 1.5 mol of stearic acid, and hardened castor oil polyoxyethylene (m = 25) Partial ester compound with 1 mol r-2: Complete ester compound with 1 mol of maleic acid and 2 mol of hardened castor oil polyoxyethylene (m = 30) r-3: Polyoxytetramethylene (s = 30) polyoxyethylene ( m = 70) Partial ester compound of 2 mol of random copolymer, 1 mol of adipic acid and 1.8 mol of oleic acid r-4: copolymer obtained by random copolymerization of ethylene oxide and propylene oxide with polytetramethylene glycol (Number average molecular weight 1000) Partial ester compound of 1 mol and 1 mol of lauric acid

Claims (14)

A synthetic fiber treatment agent comprising a lubricant and an emulsifier, wherein the hardened castor oil derivative represented by the following chemical formula 1 is contained in an amount of 1 to 50% by mass as at least a part of the lubricant.

(In chemical formula 1,
X: Residue obtained by removing all hydrogen atoms from two hydroxyl groups of a dicarboxylic acid having 3 to 22 carbon atoms A: From a reaction product having a number average molecular weight of 990 to 10,000 obtained by reacting hardened castor oil with ethylene oxide and / or propylene oxide Residue from which one hydroxyl group is removed or a residue from which one hydroxyl group is removed from a partial ester compound of the reaction product and an organic monocarboxylic acid having 2 to 30 carbon atoms B: Oxyethylene unit as an oxyalkylene unit in the molecule And / or a residue obtained by removing one hydroxyl group from a polyoxytetramethylene polyoxyalkylene random copolymer having a number average molecular weight of 500 to 10,000 having an oxypropylene unit, or the polyoxytetramethylene polyoxyalkylene random copolymer; From partial ester compounds with organic monocarboxylic acids having 2 to 30 carbon atoms Residue obtained by removing One of hydroxyl   In the castor oil derivative, X in Chemical Formula 1 is a residue obtained by removing all hydrogen atoms from two hydroxyl groups of an aliphatic dicarboxylic acid having 3 to 10 carbon atoms, and A is a residue of ethylene oxide and / or propylene in the cured castor oil. A residue obtained by removing one hydroxyl group from a partial ester compound of a reaction product having a number average molecular weight of 1000 to 5000 and an aliphatic monocarboxylic acid having 2 to 22 carbon atoms, wherein B is a number average molecular weight 2. The residue obtained by removing a hydroxyl group from a partial ester compound of a polyoxytetramethylene polyoxyalkylene random copolymer of 1000 to 5000 and an aliphatic monocarboxylic acid having 2 to 22 carbon atoms. Treatment agent for synthetic fibers.   Further, as a part of the lubricant, a complete ester compound of a C2-C30 divalent aliphatic polycarboxylic acid and a C2-C30 aliphatic monoalcohol and / or C2-C30 aliphatic The processing agent for synthetic fibers according to claim 1 or 2, comprising 10 to 80% by mass of a complete ester compound of a monocarboxylic acid and a C2-C30 divalent aliphatic alcohol.   The complete ester compound is a complete ester compound of an aliphatic dicarboxylic acid having 6 to 10 carbon atoms and an aliphatic monoalcohol having 16 to 20 carbon atoms and / or an aliphatic monocarboxylic acid having 8 to 20 carbon atoms and 4 to 4 carbon atoms. The processing agent for synthetic fibers according to claim 3, which is a complete ester compound of 6 with a divalent to tetravalent aliphatic alcohol.   Furthermore, the processing agent for synthetic fibers of Claim 3 or 4 which contains 0.2-20 mass% of C2-C30 organic carboxylic acid metal salt.   The processing agent for synthetic fibers according to claim 5, wherein the organic carboxylic acid metal salt is an alkali metal salt of an aliphatic monocarboxylic acid having 8 to 18 carbon atoms and / or an alkali metal salt of an aliphatic dicarboxylic acid having 8 to 22 carbon atoms.   Furthermore, the processing agent for synthetic fibers of Claim 5 or 6 containing 0.2-10 mass% of antioxidant.   The processing agent for synthetic fibers according to claim 7, wherein the antioxidant is a hindered phenol-based antioxidant.   The processing agent for synthetic fibers according to claim 7 or 8, further comprising 0.2 to 10% by mass of an organic sulfonic acid type surfactant.   The organic sulfonic acid type surfactant is an alkylsulfonic acid alkali metal salt having an alkyl group having 8 to 16 carbon atoms and / or an alkyl-substituted aromatic sulfonic acid alkali metal salt having an alkyl group having 8 to 16 carbon atoms. The processing agent for synthetic fibers of description.   5-30% by weight of hardened castor oil derivative, 25-60% by weight of complete ester compound, 0.5-10% by weight of organic carboxylic acid metal salt, 0.5-10% by weight of antioxidant, organic sulfonic acid type The processing agent for synthetic fibers according to claim 9 or 10, comprising 0.5 to 10% by mass of a surfactant and 10 to 65% by mass (100% by mass in total) of an emulsifier.   A synthetic fiber treatment method, comprising attaching the synthetic fiber treatment agent according to any one of claims 1 to 11 to 0.2 to 1.5 mass% with respect to the synthetic fiber.   The synthetic fiber processing method according to claim 12, wherein the synthetic fiber is a synthetic fiber for industrial materials. The synthetic fiber processing method according to claim 13, wherein the synthetic fiber for industrial material is a polyester fiber or a polyamide fiber.