JP2023054453A - Treatment agent for elastic fiber and use thereof - Google Patents

Abstract

To provide: a treatment agent for elastic fiber excellent in both preventing fiber conglutination over time under high temperature storage of wound yarn body and preventing disordered winding in an outer layer; and elastic fiber to which the treatment agent has been added.SOLUTION: The treatment agent for elastic fiber contains a hydrocarbon oil (A), where the weight percentage of a naphthenic component in the hydrocarbon oil (A) is greater than 0 wt.% and less than or equal to 13 wt.%. The elastic fiber is obtained by adding the treatment agent for elastic fiber. Preferably, the hydrocarbon oil (A) contains a Fischer-Tropsch synthetic oil.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a treatment agent for elastic fibers and its use.

In the spinning process, the elastic fibers are applied with a treatment agent and then wound into a cheese-like shape to form a wound body (hereinafter sometimes referred to as cheese). Elastic fibers are fibers that tend to stick due to their viscoelasticity. Especially in the wound body after aging, agglutination progresses over time due to the pressure applied during winding. Therefore, when using the elastic fiber wound body, unwinding becomes defective after a lapse of time, causing yarn breakage. Various treatment agents for elastic fibers have been developed in order to improve this poor unwinding.
For example, Patent Document 1 describes a treatment agent for elastic fibers containing a silicone resin (MQ resin), and Patent Document 2 describes a treatment agent containing carboxamide-modified silicone to suppress aggregation and sedimentation of magnesium salts of higher fatty acids. A treatment for elastic fibers is described. Further, Patent Document 3 describes a treatment agent for elastic fibers containing a metal salt of a higher fatty acid having an average particle size of 0.01 to 5 μm and having a needle shape.

Japanese Patent Application Laid-Open No. 09-078460 JP-A-11-12950 JP 2005-179874 A

However, although the treatment agents for elastic fibers described in these prior arts are excellent in preventing sticking of the wound body after the passage of time, the effect of the treatment agent to reduce the friction between the fibers/fibers causes the wound yarn to deteriorate. In the outer layer of the body, unwinding defects such as collapse of winding may occur. In other words, there is a trade-off relationship between the anti-adhesion property of the wound body after aging and the anti-roll collapse property in the outer layer portion, where one is emphasized and the other deteriorates.
Furthermore, with regard to the agglutination prevention property of the wound yarn after aging, even if there is no problem under normal storage conditions, the agglutination of the wound yarn progresses when it is stored under high temperatures for a long period of time in the summer or during shipping. There was a case where unwinding was defective. In other words, in the prior art, it is the actual situation to apply while maintaining a balance between anti-sticking property and anti-roll collapse property after the lapse of time, and a treatment agent for elastic fibers satisfying both has not been obtained.

Accordingly, an object of the present invention is to provide a treatment agent for elastic fibers and a method for producing elastic fibers, which have a small change in unwinding property over time under high-temperature storage of elastic fibers, and at the same time, are excellent in preventing unwinding of the wound body. to do.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a treatment agent for elastic fibers containing a specific hydrocarbon oil (A), and have completed the present invention.
That is, the elastic fiber treatment agent of the present invention is a treatment agent for elastic fibers containing a hydrocarbon oil (A), wherein the weight ratio of the naphthene component in the hydrocarbon oil (A) is more than 0% by weight and 13% by weight. It is a treatment agent for elastic fibers, which is not more than % by weight.

The hydrocarbon oil (A) preferably contains a Fischer-Tropsch synthetic oil.
It is preferable that the treatment agent further contains a silicone oil (B).
It is preferable that the treatment agent further contains an organic phosphoric acid ester (D).
The elastic fiber of the present invention is obtained by applying the treatment agent to the main body of the elastic fiber.
The method for producing an elastic fiber of the present invention is a method for producing an elastic fiber including the step of applying the treatment agent to the main body of the elastic fiber.

The elastic fiber to which the treatment agent for elastic fiber of the present invention is applied has little change in unwinding property over time under high-temperature storage, and at the same time, it is excellent in preventing collapse of the wound body.
The elastic fiber produced by the method for producing an elastic fiber of the present invention exhibits little change in unwinding properties over time under high-temperature storage, and at the same time, is excellent in preventing the unwinding of the wound body.

The schematic diagram explaining the measuring method of the unraveling speed ratio evaluation method. The schematic diagram explaining the measuring method of the friction between fibers.

The elastic fiber treatment agent of the present invention will be described in detail below.

[Hydrocarbon oil (A)]
The treatment agent for elastic fibers of the present invention essentially contains a hydrocarbon oil (A). The hydrocarbon oil (A) represents the sum of all hydrocarbons contained in the elastic fiber treatment agent.
Since the hydrocarbon oil (A) contains a naphthene component in a specific weight ratio, it can exhibit excellent unwinding properties and prevention of collapse of the wound body under high-temperature storage.
On the other hand, treatment agents for elastic fibers other than the present invention are excellent under high temperature storage because the hydrocarbon oil obtained by summing up all the hydrocarbons contained in the treatment agent does not contain a naphthene component in a specific weight ratio. At least one of the unwinding property and the prevention of winding collapse of the wound body cannot be solved.

Although it is not clear why the use of the hydrocarbon oil (A) containing a naphthene component in a specific weight ratio can exhibit excellent unwinding property under high-temperature storage and prevention of winding collapse of the wound body, By applying the hydrocarbon oil (A) containing a naphthene component in a specific range to the elastic fiber, the entire processing agent moves between the outer layer and the inner layer of the wound body over time, and the processing agent during stretching during processing. does not penetrate into the fiber, forms a strong oil film on the outermost layer of the elastic fiber, and exerts an excellent effect on unwinding and prevention of collapse of the wound body. Further, the "oil" of the hydrocarbon oil (A) of the present application means a smoothing component, and its state is not particularly limited.

The weight ratio of the naphthenic component in the hydrocarbon oil (A) used in the present invention is more than 0% by weight and 13% by weight or less. The upper limit of the weight ratio is more preferably 10% by weight or less, still more preferably 9% by weight or less, particularly preferably 8% by weight or less, and most preferably 7% by weight or less. On the other hand, the lower limit of the weight ratio is more preferably 1% by weight or more, still more preferably 3% by weight or more, particularly preferably 5% by weight or more, and most preferably 6% by weight or more. When the naphthene component is 13% by weight or more, the treating agent as a whole moves between the outer layer and the inner layer of the wound body over time, and the treating agent permeates inside the fiber during stretching during processing, resulting in excellent unwinding. unable to perform sexually. When the naphthene component is 0% by weight, the stability of the processing agent tends to deteriorate.

The hydrocarbon oil (A) used in the present invention may be a mixture of two or more hydrocarbon oils having a naphthenic component weight ratio of more than 0% and 13% by weight or less. It may contain hydrocarbon oils not in the range greater than 0% and less than or equal to 13% by weight. In short, even when a plurality of hydrocarbon oils are mixed and used, the weight ratio of the naphthenic component in the entire hydrocarbon oil (A) contained in the treating agent is more than 0% by weight and 13% by weight or less. It should be adjusted within the range.

The weight ratio of the paraffin component in the hydrocarbon oil (A) used in the present invention is not particularly limited, but is preferably 87% by weight to 99.9% by weight. When the weight ratio is within the above-mentioned range, the treatment agent is suppressed from penetrating into the fibers at high temperatures and efficiently remains on the fiber surface, thereby suppressing changes in unwinding properties over time during storage at high temperatures. have the effect of The upper limit of the weight ratio is more preferably 99% by weight, still more preferably 98% by weight, and particularly preferably 97% by weight. On the other hand, the lower limit of the weight ratio is more preferably 90% by weight, still more preferably 91% by weight, and particularly preferably 92% by weight.

The weight ratio of the aroma component in the hydrocarbon oil (A) used in the present invention is not particularly limited, but is preferably 1% by weight or less. When the weight ratio is within the above range, there is a tendency to suppress deterioration of the fiber. The upper limit of the weight ratio is more preferably 0.5% by weight, still more preferably 0.4% by weight, and particularly preferably 0.3% by weight.

In the present invention, the weight ratio of the naphthenic component, the paraffinic component and the aromatic component contained in the hydrocarbon oil (A) is _CN % measured by the ring analysis ndM method specified in ASTM D3238. , C _p % and C _A %.

The kinematic viscosity at 40° C. of the hydrocarbon oil (A) used in the present invention is not particularly limited, but is preferably 5 to 40 mm ² /s. The lower limit of the 40° C. kinematic viscosity of the hydrocarbon oil (A) is more preferably 6 mm ² /s, still more preferably 7 mm ² /s, particularly preferably 8 mm ² /s. On the other hand, the upper limit of the weight ratio is more preferably 30 mm ² /s, still more preferably 25 mm ² /s, particularly preferably 20 mm ² /s. If the kinematic viscosity of the hydrocarbon oil (A) is less than 5.0 mm ^{2 /} s, the oil film strength may be too low to suppress changes in unraveling properties over time. If it is too large, the compatibility with other components of the processing agent may deteriorate, and it may not be possible to suppress changes in unwinding properties over time. The dynamic viscosity of the hydrocarbon oil (A) was measured according to JIS K2283.

The hydrocarbon oil (A) used in the present invention is not particularly limited as long as the weight ratio of the naphthenic component is more than 0% and 13% by weight or less. and/or mineral oil, more preferably a Fischer-Tropsch synthetic oil.

FT synthetic oil is derived from natural gas, converted from natural gas, coal, or biomass into synthetic gas, converted into wax by the Fischer-Tropsch process, and further converted into lubricating oil by hydroisomerization and dewaxing processes. is called GTL (gas-to-liquid), coal-derived one is called CTL (coal-to-liquid), and biomass-derived one is called BTL (biomass-to-liquid). It has very low characteristics. The FT synthetic oil is not particularly limited, but examples thereof include XHVI 3 manufactured by Shell Lubricants, XHVI 4 manufactured by Shell Lubricants, XHVI 5.2 manufactured by Shell Lubricants, and XHVI 8 manufactured by Shell Lubricants. The FT synthetic oil may be used singly or in combination of two or more.

The mineral oil is not particularly limited. Cosmo Pure Spin E (trade name), Cosmo Pure Spin RC (trade name) manufactured by Cosmo Oil Lubricants Co., Ltd., Cosmo Pure Spin RB (trade name) manufactured by Cosmo Oil Lubricants Co., Ltd., Cosmo Neutral 100 (trade name) manufactured by Cosmo Oil Lubricants Co., Ltd., Cosmo Oil Lubricants Co., Ltd. trade name Cosmo Neutral 150, Cosmo Oil Lubricants Co., Ltd. trade name Cosmo Neutral 350, Cosmo Oil Lubricants Co., Ltd. trade name Cosmo White P200, Cosmo Oil Lubricants Co., Ltd. trade name Cosmo White P260, Cosmo Oil Lubricants Co., Ltd. trade name Cosmo White P350P, Cosmo Oil Lubricants Co., Ltd. trade name Cosmo Pure Safety 10, Cosmo Oil Lubricants Co., Ltd. trade name Cosmo Pure Safety 22, Cosmo Oil Lubricants Co., Ltd. trade name Product name Cosmo Pure Safety 32, product name Fukkol NT-60 manufactured by Fuji Kosan Co., Ltd., product name Fukkol NT-100 manufactured by Fuji Kosan Co., Ltd., product name Ultra-S 2, S-OIL manufactured by S-OIL Ultra-S 3, trade name manufactured by S-OIL, Ultra-S 4, trade name manufactured by S-OIL, Ultra-S 6, trade name manufactured by S-OIL, YUBASE 3, trade name manufactured by SK Lubricants, SK Lubricants trade name YUBASE 4, trade name YUBASE 4 Plus manufactured by SK Lubricants, trade name YUBASE 6 manufactured by SK Lubricants, trade name YUBASE 6 Plus manufactured by SK Lubricants, trade name YUBASE 6J manufactured by SK Lubricants, SK L YUBASE 8 manufactured by SK Lubricants, YUBASE 8J manufactured by SK Lubricants, Dianafrecia W8 manufactured by Idemitsu Kosan Co., Ltd., Dianafrecia W32 manufactured by Idemitsu Kosan Co., Ltd., and a trade name manufactured by Idemitsu Kosan Co., Ltd. Dianafresia G9, trade name Dianafrecia K8 manufactured by Idemitsu Kosan Co., Ltd., trade name Dianafresia S32 manufactured by Idemitsu Kosan Co., Ltd., trade name Crystal N72 manufactured by ExxonMobil, trade name SUN 60N manufactured by Nippon Sun Oil Co., Ltd., Machine oils and spindle oils such as liquid paraffin 40S manufactured by Sanko Chemical Industry Co., Ltd., liquid paraffin RCM manufactured by Sanko Chemical Industry Co., Ltd., liquid paraffin 80S manufactured by Sanko Chemical Industry Co., Ltd., and liquid paraffin 100S manufactured by Sanko Chemical Industry Co., Ltd. , liquid paraffin, and the like. Among these, liquid paraffin is preferable as the mineral oil because it generates less odor. Mineral oils may be used singly or in combination of two or more.

When the hydrocarbon oil (A) contains FT synthetic oil and / or mineral oil, the total weight ratio of the FT synthetic oil and mineral oil in the hydrocarbon oil (A) is not particularly limited, but is preferably 90% by weight. ~99% by weight. When the weight ratio is within the above range, there is a tendency that the change in unwinding property during high-temperature storage is further suppressed. The upper limit of the weight ratio is more preferably 98% by weight, still more preferably 97% by weight, and particularly preferably 96% by weight. On the other hand, the lower limit of the weight ratio is more preferably 91% by weight, still more preferably 92% by weight, and particularly preferably 93% by weight.

When FT synthetic oil and mineral oil are mixed and used, the mixing ratio is not particularly limited, but the weight ratio of FT synthetic oil/mineral oil is preferably 1/10 to 1000/1. When the weight ratio is within the above-mentioned range, it suppresses permeation into the fibers and efficiently remains on the surface of the fibers, so that there is a tendency to suppress changes in unwinding properties over time during high-temperature storage. The upper limit of the weight ratio is more preferably 500/1, still more preferably 100/1, particularly preferably 50/1. On the other hand, the lower limit of the weight ratio is more preferably 1/9, still more preferably 1/8, particularly preferably 1/7.

A poly-α-olefin can also be suitably selected as the hydrocarbon oil (A). Poly-α-olefin is literally a compound obtained by polymerizing α-olefin. The kinematic viscosity of the polyαolefin at 40° C. is 10 to 100 mm ² /s, preferably 15 to 70 mm ² /s, more preferably 15 to 50 mm ² /s. The kinematic viscosity of the polyαolefin compound is measured according to JIS K 2283. If the kinematic viscosity ^of the poly-α-olefin is less than 10 mm ² /s, the oil film strength will be too low to suppress changes in the unwinding property over time. Because the compatibility of the rubber becomes poor, the smoothness is lowered, and furthermore, weak adhesiveness appears, so that the change in the unwinding property over time cannot be suppressed.

The poly-α-olefin is an α-olefin polymer, preferably a tri- to octa-mer of an α-olefin having 6 to 18 carbon atoms that satisfies the above 40° C. kinematic viscosity. For example, poly-α-olefins are mainly composed of α-decene (10 carbon atoms) tri- to octa-mers or α-dodecene (12 carbon atoms) tri- to octa-mers, and dimers and pentamers thereof. It contains things.
A suitable example of the production of poly-α-olefin is synthesis of α-olefin having 6 to 18 carbon atoms by low polymerization of ethylene or thermal decomposition of wax, and synthesis by polymerizing and hydrogenating 3 to 8 units of this α-olefin. be done.
The average number of carbon atoms per molecule of the polyαolefin is not particularly limited as long as it is within the above 40° C. kinematic viscosity range, but is preferably 18 to 150, more preferably 24 to 140, and still more preferably 30. ~100.

When the hydrocarbon oil (A) contains a poly-α-olefin, the weight ratio of the poly-α-olefin in the hydrocarbon oil (A) is not particularly limited, but is preferably 1% by weight to 10% by weight. If the weight ratio is out of the above range, the compatibility with other components of the processing agent may deteriorate, and it may not be possible to suppress changes in unwinding properties over time. The upper limit of the weight ratio is more preferably 9% by weight, still more preferably 8% by weight, and particularly preferably 7% by weight. On the other hand, the lower limit of the weight ratio is more preferably 2% by weight, still more preferably 3% by weight, and particularly preferably 4% by weight.

Polyαolefin is not particularly limited, but for example, the product name PAO201 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., the product name PAO401 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., the product name PAO601 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and the product manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. name PAO801, product name Lipolube 40 manufactured by Lion Specialty Chemicals Co., Ltd., product name Lipolube 60 manufactured by Lion Specialty Chemicals Co., Ltd., and product name Lipolube 80 manufactured by Lion Specialty Chemicals Co., Ltd., and the like.

The hydrocarbon oil (A) may contain normal paraffin, alkylnaphthalene, etc. in addition to the above-mentioned FT synthetic oil, mineral oil and polyαolefin.

[Silicone oil (B)]
The elastic fiber treatment agent of the present invention may further contain a silicone oil (B). The silicone oil (B), when used in combination with the above-described hydrocarbon oil (A), has the effect of further suppressing changes in unraveling properties over time under high-temperature storage.
It is not clear why the inclusion of the silicone oil (B) enhances the effect of suppressing changes in unwinding properties over time under high-temperature storage. It is thought that the uniform adhesion to the surface is enhanced, and the effect of suppressing the change in unwinding property over time under high temperature storage is further enhanced.

The silicone oil (B) used in the present invention is not particularly limited, but examples include KF-96-10cs (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. , Shin-Etsu Chemical Co., Ltd. trade name KF-96-50cs, Shin-Etsu Chemical Co., Ltd. trade name KF-96-100cs, Shin-Etsu Chemical Co., Ltd. trade name KF-96-1000cs, Shin-Etsu Chemical Co., Ltd. Company product name KF-96-10,000cs, Shin-Etsu Chemical Co., Ltd. product name KF-50-100cs, Shin-Etsu Chemical Co., Ltd. product name KF-4003, Shin-Etsu Chemical Co., Ltd. product name KF-4917, trade name TSF451-5A manufactured by Momentive Performance Materials, trade name TSF451-10 manufactured by Momentive Performance Materials, trade name TSF451-20 manufactured by Momentive Performance Materials, Momentive・Trade name TSF451-30 manufactured by Performance Materials, trade name TSF451-50 manufactured by Momentive Performance Materials, trade name TSF451-100 manufactured by Momentive Performance Materials, Momentive Performance Materials trade name TSF451-1000 manufactured by Momentive Performance Materials, trade name TSF451-1M manufactured by Momentive Performance Materials, trade name SH200-10CS manufactured by Dow Corning Toray Co., Ltd., trade name SH200- manufactured by Dow Corning Toray Co., Ltd. 20CS, trade name SH200-50CS manufactured by Dow Corning Toray Co., Ltd., trade name SH510-100CS manufactured by Dow Corning Toray Co., Ltd., trade name WACKER SILICONE FLUID AK10 manufactured by Asahi Kasei Wacker Silicone Co., Ltd., manufactured by Asahi Kasei Wacker Silicone Co., Ltd. WACKER SILICONE FLUID AK20 (trade name) manufactured by Asahi Kasei Wacker Silicone Co., Ltd. and WACKER SILICONE FLUID AK50 (trade name) manufactured by Asahi Kasei Wacker Silicone Co., Ltd., polydimethylsiloxane, polyalkylsiloxane, polyalkylphenylsiloxane, and methyl hydrogen silicone oil. The silicone oil (B) may be used singly or in combination of two or more. It may also contain unreacted silanol groups derived from raw materials, unreacted halogen groups, polymerization catalysts, cyclic siloxanes, and the like.

The viscosity of the silicone oil (B) at 20° C. is preferably 5 to 30 mm ² /s, more preferably 5 to 25 mm ² /s, even more preferably 5 to 20 mm ² /s. If the viscosity is less than 5 mm ^{2 /} s, the silicone oil (B) may volatilize.
The average amount of siloxane bonds (SiOR ^a R ^b : R ^a and R ^b each independently represent an organic group) of the silicone oil (B) is preferably 3 to 900, more preferably 5 to 500, 7 to 200 are more preferred. The organic groups of R ^a and R ^b are hydrocarbon groups having 1 to 24 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, cyclo A propyl group, a cyclohexyl group, a phenyl group, a benzyl group and the like can be mentioned, and a methyl group and a phenyl group are particularly preferable.

[Ester oil (C)]
The treatment agent for elastic fibers of the present invention may use an ester oil (C) as a base component other than the hydrocarbon oil (A) and silicone oil (B) explained above.

The ester oil (C) is not particularly limited as long as it is an ester of a monohydric alcohol and a monocarboxylic acid, an ester of a monohydric alcohol and a polycarboxylic acid, or an ester of a polyhydric alcohol and a monocarboxylic acid. You may use 1 type, or 2 or more types without. As monohydric alcohols, monohydric aliphatic alcohols, aromatic alcohols, alicyclic alcohols, phenols, etc., which will be described later, can be used. Among these, monohydric aliphatic alcohols and aromatic alcohols are preferred.

The monohydric aliphatic alcohol is not particularly limited, but examples include octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, isotridecyl alcohol, and myristyl alcohol. , pentadecyl alcohol, 1-hexadecanol, palmitoleyl alcohol, 1-heptadecanol, stearyl alcohol, oleyl alcohol, isostearyl alcohol, nonadecyl alcohol, 1-eicosanol, behenyl alcohol, 1-tetracosanol, erucyl alcohol , lignoceryl alcohol, and the like. When the monohydric aliphatic alcohol has branches, the number of branches, branch chain length, and branch positions are not particularly limited.
Aromatic alcohols include phenol and benzyl alcohol.
Alicyclic alcohols include cyclooctanol, cyclododecanol, cyclohexanol, cycloheptanol, cyclopentanol, menthol and the like.

Polyhydric alcohols are not particularly limited, but examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, cyclohexanediol, glycerin, diglycerin , triglycerin, tetraglycerin, hexaglycerin, decaglycerin, polyglycerin, sorbitol, trimethylolpropane, pentaerythritol and the like.

As the monovalent carboxylic acid, a monovalent aliphatic carboxylic acid, an aromatic carboxylic acid, a hydroxycarboxylic acid, and the like, which are also described later, can be used. Among these, monovalent aliphatic carboxylic acids and aromatic carboxylic acids are preferred.

The monovalent carboxylic acid is not particularly limited, but examples include valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexylic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, and palmitoleic acid. , margaric acid, stearic acid, oleic acid, isostearic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, lignoceric acid, cetylonic acid, and benzoic acid.

Polyvalent carboxylic acids are not particularly limited, but examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, phthalic acid, trimellitic acid, pyromellitic acid, citric acid, and isocitric acid. is mentioned.

Specific examples of the ester oil (C) are not particularly limited, but include heptyl valerate, heptyl caproate, octyl caproate, cetyl caprylate, isooctyl laurate, isopropyl myristate, isopropyl palmitate, and iso palmitate. stearyl, butyl stearate, octyl stearate, oleyl laurate, isotridecyl stearate, octyl stearate, isooctyl stearate, tridecyl stearate, isobutyl stearate, methyl oleate, isobutyl oleate, heptyl oleate, oleyl oleate, Polyethylene glycol dilaurate, polyethylene glycol dimyristate, polyethylene glycol dioleate, polyethylene glycol distearate, polypropylene glycol dilaurate, polypropylene glycol dimyristate, polypropylene glycol dioleate, polypropylene glycol distearate, dicetyl oxalate, diisooctyl malonate, succinate Dilauryl acid, diisodecyl adipate, isononyl adipate, dioctyl adipate, diisooctyl fumarate, diisooctyl phthalate, dioctyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, triisooctyl trimellitate, tri-trimellitate Isobutyl, Triisodecyl Trimellitate, Triisostearyl Trimellitate, Triisooctyl Glycerine, Trilauryl Glycerine, Trimyristyl Glycerine, Trioleyl Glycerine, Tristearyl Glycerine, Sorbitan Monolaurate, Sorbitan Monopalmitate, Sorbitan Monostearate, Sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, sorbitan sesquioleate, sorbitan trilaurate, sorbitan tristearate, sorbitan tripalmitate and the like.

[Organic phosphate ester (D)]
The elastic fiber treatment agent of the present invention may further contain an organic phosphate (D). When the treating agent contains an organic phosphate (D), the weight ratio of the organic phosphate (D) in the treating agent is not particularly limited, but is preferably 0.1% by weight to 10% by weight. be. When the weight ratio of the organic phosphoric acid ester (D) is within the above range, there is a tendency that changes in unwinding properties during high-temperature storage are further suppressed. The upper limit of the weight ratio is more preferably 5% by weight, still more preferably 3% by weight, and particularly preferably 1% by weight. On the other hand, the lower limit of the weight ratio is more preferably 0.2% by weight, still more preferably 0.4% by weight, and particularly preferably 0.5% by weight.

The organic phosphate (D) is not particularly limited as long as it contains at least one hydrocarbon group or oxyalkylene group in the molecule. Examples include hexyl phosphate, octyl phosphate, decyl phosphate, Dodecyl Phosphate, Tetradecyl Phosphate, Hexadecyl Phosphate, Octadecyl Phosphate, Behenyl Phosphate, Trioctacosanyl Phosphate, Octadecenyl Phosphate, 2-Ethylhexyl Phosphate, Isoheptyl Phosphate acid ester, isooctyl phosphate, isononyl phosphate, isodecyl phosphate, isoundecyl phosphate, isododecyl phosphate, isotridecyl phosphate, isotetradecyl phosphate, isohexadecyl phosphate , iso-octadecyl phosphate, t-butyl phosphate, benzyl phosphate, octylphenyl phosphate, cyclohexyl phosphate, polyoxyethylene 5 mol addition hexadecyl ether phosphate, polyoxyethylene 15 mol addition hexadecyl Ether phosphate ester, polyoxyethylene 7 mol addition polyoxypropylene 3.5 mol addition secondary alkyl ether Phosphate ester, polyoxyethylene 2 mol polyoxypropylene 5 mol addition dodecyl phosphate ester, polyoxyethylene 3 mol addition secondary alkyl ether Phosphate ester, polyoxyethylene 2 mol-added dodecyl ether phosphate, polyoxyethylene 4 mol-added phenol phosphate, and the like can be mentioned. The organic phosphate may be an alkali metal salt and/or an alkaline earth metal salt.

[Other ingredients]
The treatment agent for elastic fibers of the present invention contains modified silicone, silicone resin, high-grade It may further contain at least one other component selected from alcohols, polyhydric alcohols, organic amines, metallic soaps, nonionic surfactants, cationic surfactants and anionic surfactants. Other components may be used alone or in combination of two or more.

The modified silicone generally refers to a reactive (functional) group or non-reactive It has a structure in which at least one (functional) group is bonded.

More specifically, the modified silicone includes an alkyl-modified silicone such as a modified silicone having a long-chain alkyl group (an alkyl group having 6 or more carbon atoms, a 2-phenylpropyl group, etc.); an ester which is a modified silicone having an ester bond; Modified silicone; polyether-modified silicone, etc., which is a modified silicone having a polyoxyalkylene group (for example, polyoxyethylene group, polyoxypropylene group, polyoxyethyleneoxypropylene group, etc.); aminopropyl group, N-(2-amino amino-modified silicone, which is a modified silicone having an ethyl)aminopropyl group; carbinol-modified silicone, which is a modified silicone having an alcoholic hydroxyl group; epoxy, which is a modified silicone having an epoxy group such as a glycidyl group or an alicyclic epoxy group modified silicone; carboxy-modified silicone which is modified silicone having a carboxyl group; mercapto-modified silicone which is modified silicone having a mercapto group;

The silicone resin is an organopolysiloxane resin, and means a silicone having a three-dimensional crosslinked structure. Silicone resins generally have at least one structural unit selected from monofunctional structural units (M), difunctional structural units (D), trifunctional structural units (T) and tetrafunctional structural units (Q). consists of units.

Examples of the silicone resin include, but are not limited to, silicone resins such as MQ silicone resin, MQT silicone resin, T silicone resin, and DT silicone resin. You may

Examples of the MQ silicone resin include a monofunctional structural unit R ^a R ^b R ^c SiO _1/2 (wherein R ^a , R ^b and R ^c are all hydrocarbon groups); Examples include silicone resins containing SiO _4/2 functional units.

Examples of ^the MQT silicone resin include a monofunctional ^structural unit ^RaRbRcSiO1 _/2 (wherein Ra, ^{Rb and Rc} are all hydrocarbon groups), and 4 A silicone resin containing a functional structural unit SiO _4/2 and a trifunctional structural unit RSiO _3/2 (where R is a hydrocarbon group) can be mentioned.

Examples of the T-silicone resin include a silicone resin containing a trifunctional structural unit, RSiO _3/2 (where R is a hydrocarbon group) (the terminal of which is a hydrocarbon group, a silanol group or an alkoxy group). It may be a base.) and the like.

Examples of the DT silicone resin include a bifunctional structural unit R ^a R ^b SiO _2/2 (wherein both R ^a and R ^b are hydrocarbon groups) and a trifunctional structural unit and RSiO _3/2 (where R is a hydrocarbon group).

The hydrocarbon groups of R, R ^a , R ^b and R ^c are hydrocarbon groups having 1 to 24 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, Isopentyl group, hexyl group, cyclopropyl group, cyclohexyl group, phenyl group, benzyl group and the like can be mentioned, and methyl group, ethyl group, propyl group, butyl group, pentyl group and phenyl group are particularly preferable.

When a silicone resin is contained, the blending ratio of the silicone resin to the entire treatment agent is preferably 0.1% to 9% by weight, more preferably 0.2% to 5% by weight, and 0.3% to 3% by weight. % by weight is more preferred. If the blending ratio is less than 0.1% by weight, the addition of the silicone resin may not sufficiently improve the anti-sticking property. If the blending ratio is more than 9% by weight, the anti-sticking property is excellent, but the outer layer portion may easily collapse when rolled up.

The higher alcohols are not particularly limited, but include straight-chain and/or branched-chain alcohols having 6 to 30 carbon atoms. Specific examples include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptakosanol, octacosanol, nonacosanol, and tria Linear alcohols such as cosanol; 2-ethylhexanol, 2-propylheptanol, 2-butyloctanol, 1-methylheptadecanol, 2-hexyloctanol, 1-hexylheptanol, isodecanol, isotridecanol, 3 , 5,5-trimethylhexanol; hexenol, heptenol, octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, eisenol, docosenol, tetracosene straight-chain alkenols such as Nol, pentacosenol, hexacosenol, heptacosenol, octacosenol, nonacosenol and triaconsenol; branched alkenols such as tridecenol and isooctadecenol;

Specific examples of the polyhydric alcohol include glycerin, diglycerin, sorbitan, erythritol, pentaerythritol, trimethylolpropane, sorbitol, and ditrimethylolpropane.

The organic amine is not particularly limited as long as it contains at least one hydrocarbon group or oxyalkylene group in the molecule. Examples include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, diethylamine, dioctylamine, Distearylamine, methylstearylamine, polyoxypropylene-added laurylamine, polyoxyethylene-added laurylamine, polyoxyethylene-added stearylamine, polyoxyethylene-added oleylamine, monoethanolamine, diethylethanolamine, dibutylethanolamine, triethanolamine , laurylethanolamine, trioctylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylstearylamine and the like.

Examples of the metal soap include monovalent, divalent or trivalent metal salts of fatty acids having 8 to 22 carbon atoms. Examples of metal soaps include calcium laurate, calcium palmitate, barium myristate, magnesium myristate, magnesium palmitate, magnesium laurate, magnesium stearate, magnesium 2-ethylhexylate, zinc behenate, aluminum tribehenate, and calcium stearate. , calcium 2-ethylhexylate, aluminum stearate, aluminum palmitate, barium stearate, zinc caprate, zinc stearate and the like. One or more of these metal soaps may be used.

The nonionic surfactant is not particularly limited, but for example, a polyoxyalkylene alkyl ether having an alkyl group having 8 to 22 carbon atoms (oxyalkylene is 1 to 20 mol, oxyalkylene is oxyethylene and / or oxypropylene , random and/or block), sorbitan fatty acid ester, oxyalkylene adduct of sorbitan fatty acid ester (oxyalkylene is 1 to 20 mol, oxyalkylene is oxyethylene and/or oxypropylene, random and/or Alkylene oxide adducts of polyhydric alcohols such as ), alkylphenols having alkyl groups of 6 to 22 carbon atoms, oxyalkylene adducts of alkylphenols having alkyl groups of 6 to 22 carbon atoms (oxyalkylene is 1 to 20 mol, oxyalkylene is oxyethylene and / or oxypropylene, random and / or block.), fatty acid polyoxyalkylene glycol ester (oxyalkylene is 1 to 20 mol, oxyalkylene is oxyethylene and / or oxy propylene, random and/or block.) and the like. One or more of these nonionic surfactants may be used.

Examples of the cationic surfactant include, but are not particularly limited to, the above organic amines or salts thereof, and quaternary ammonium salts. Specific examples of quaternary ammonium salts include didecyldimethylammonium salts, decyltrimethylammonium salts, dioctyldimethylammonium salts, octyltrimethylammonium salts and the like. One or more of these cationic surfactants may be used.

Examples of the anionic surfactant include, but are not limited to, alkanesulfonic acids and/or salts thereof, dialkylsulfosuccinic acids and/or salts thereof, alkylbenzenesulfonic acids and/or salts thereof, alkylnaphthalenesulfonic acids and/or salts thereof. salts, alkyl sulfuric acid and/or its salts, polyoxyethylene alkyl ether sulfuric acid and/or its salts, polyoxyethylene alkyl ether acetic acid and/or its salts, and the like. Specifically, alkanesulfonic acid having an alkyl group having 6 to 22 carbon atoms and/or a salt thereof, dialkylsulfosuccinic acid ester and/or a salt thereof described later, alkylbenzenesulfonic acid having an alkyl group having 6 to 22 carbon atoms and / or salts thereof, alkyl sulfuric acid having an alkyl group of 1 to 20 carbon atoms and / or salts thereof, polyoxyethylene alkyl ether sulfuric acid having an alkyl group of 6 to 22 carbon atoms and / or salts thereof, 6 to 22 carbon atoms and/or a polyoxyethylene alkyl ether acetic acid having an alkyl group of and/or a salt thereof. One or more of these anionic surfactants may be used.

[Treatment agent for elastic fibers]
The weight ratio of the hydrocarbon oil (A) in the treatment agent for elastic fibers of the present invention is preferably 1 to 99% by weight. If the content is less than 1% by weight, the effect of this component may be small and it may not be possible to suppress changes in unwinding properties over time under high-temperature storage. If the content of other components in the agent becomes too small, the effect such as antistatic properties may be reduced. The upper limit of the weight ratio is more preferably 90% by weight, still more preferably 80% by weight, and particularly preferably 70% by weight. On the other hand, the lower limit of the weight ratio is more preferably 10% by weight, still more preferably 15% by weight, and particularly preferably 20% by weight.

The weight ratio of the silicone oil (B) in the treatment agent for elastic fibers of the present invention to the total treatment agent is preferably 0.01 to 50% by weight. The upper limit of the weight ratio is more preferably 40% by weight, still more preferably 30% by weight, and particularly preferably 20% by weight. On the other hand, the lower limit of the weight ratio is more preferably 1% by weight, still more preferably 5% by weight, and particularly preferably 10% by weight. If the amount of the silicone oil (B) is less than 0.01% by weight, the effect of improving the uniform adhesion may not be sufficient, and if it is more than 50% by weight, the compatibility with other components of the treatment agent will be poor, resulting in poor storage conditions at high temperatures. In some cases, it becomes impossible to suppress changes in unwindability over time.

The viscosity of the treatment agent for elastic fibers of the present invention at 30° C. is not particularly limited, but is preferably 8 to 40 mm ² /s, more preferably 9 to 30 mm ² /s, still more preferably 9 to 20 mm ^{2 /} s. is s. If the viscosity is too low, the treatment agent may be sprayed in the form of a mist when running the elastic fibers in the spinning and post-processing steps, staining the surroundings or being inhaled by the operator. On the other hand, if the viscosity is too high, when the elastic fiber is run in the spinning and post-processing steps, the stickiness may cause the thread to wind around the running roller, resulting in thread breakage.

The method for producing the treatment agent for elastic fibers of the present invention is not particularly limited, and known methods can be employed. For example, some components may be blended in advance and then mixed with other components, or all components may be mixed at once. Further, when the treatment agent for elastic fibers of the present invention contains a higher fatty acid metal salt, it may be produced by mixing an already pulverized higher fatty acid metal salt with a base component or the like. and pulverized to a predetermined average particle size using a conventionally known wet pulverizer.

[Elastic fiber]
The elastic fiber of the present invention is obtained by applying the treatment agent for elastic fibers of the present invention to the main body of the elastic fiber. Although there is no particular limitation on the percentage of the elastic fiber treatment agent attached to the entire elastic fiber, it is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight. The method for applying the treatment agent for elastic fibers of the present invention to the main body of elastic fibers is not particularly limited, and known methods can be employed.

The elastic fiber (elastic fiber main body) of the present invention is an elastic fiber using polyether polyurethane, polyester polyurethane, polyether ester elastomer, polyester elastomer, polyethylene elastomer, polyamide elastomer, etc., and its elongation is usually 300% or more.

The elastic fiber of the present invention is composed of polyurethane or polyurethane urea obtained by reacting PTMG or polyester diol with organic diisocyanate and then chain-extending with 1,4-butanediol, ethylenediamine, propylenediamine, pentanediamine or the like. mentioned. For example, for polyurethane urea elastic fibers, polytetramethylene glycol (PTMG) with a molecular weight of 1000 to 3000 and diphenylmethane diisocyanate (MDI) are prepared, and dimethyl A 20 to 40% solution of a polyurethane urea polymer obtained by reaction in a solvent such as acetamide or dimethylformamide and chain extension with a diamine such as ethylenediamine or propanediamine is dry-spun at a spinning speed of 400 to 1200 m/min. It can be manufactured by The applicable fineness of the elastic fiber main body is not particularly limited.

The elastic fiber main body of the present invention may contain inorganic substances such as titanium oxide, magnesium oxide, hydrotalcite, zinc oxide and divalent metal soap. Divalent metal soaps include calcium 2-ethylhexylate, calcium stearate, calcium palmitate, magnesium stearate, magnesium palmitate, magnesium laurate, barium stearate, zinc caprate, zinc behenate, zinc stearate and the like. mentioned. One or two or more inorganic substances may be used.

When the elastic fiber main body contains an inorganic substance, the uniform unwinding property may become poor, but uniform unwinding property can be improved by applying the treatment agent of the present invention to the elastic fiber main body. Therefore, the treatment agent for elastic fibers of the present invention can be suitably used when the main body of elastic fibers contains an inorganic substance. The content of the inorganic substance in the elastic fiber body is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight.

The elastic fiber of the present invention can be used as a cloth by processed yarn such as covering yarn such as CSY, single covering, PLY, air covering, circular knitting, tricot, and the like. In addition, these processed yarns and fabrics are used to impart elasticity to products that require elasticity such as stockings, socks, underwear, and swimwear, as well as outerwear such as jeans and suits, for comfort. Also used for purposes. More recently, it has also been applied to disposable diapers.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples described herein. "Percent (%)" and "parts" shown in the following examples indicate "% by weight" and "parts by weight" unless otherwise specified. In Examples and Comparative Examples, each characteristic of the treatment agent for elastic fibers was evaluated according to the following methods.

(Unwinding speed ratio)
In FIG. 1, the fiber cheese (1) to which the treatment agent was applied was set on the unwinding side of the unwinding speed ratio measuring machine, and the winding-side paper tube (2) was set. After setting the winding speed to a constant speed, rollers (3) and (4) were started simultaneously. In this state, almost no tension was applied to the thread (5), so that the thread stuck on the cheese and did not come off, and the unraveling point (6) was in the state shown in FIG. By changing the unwinding speed, the unwinding point (6) of the yarn (5) from the cheese is changed, so the unwinding speed was set so that this point coincided with the point of contact (7) between the cheese and the roller. The unwinding speed ratio was determined by the following formula (1). A smaller value indicates better unwindability.
Unwinding speed ratio (%) = ((winding speed - unwinding speed) / unwinding speed) x 100 Equation (1)
The unwinding speed ratio after aging at room temperature indicates the unwinding speed ratio after aging the cheese for 6 months under the conditions of 20° C. and 65% RH.
The anti-sticking property over time at normal temperature was judged by the following index.
(index)
◎: The unwinding speed ratio after aging is less than 100, and the difference between before and after aging is less than 30 ○: The unwinding speed ratio after aging is less than 100, and the difference between before and after aging is 30 or more and less than 50 ×: The unwinding speed ratio after aging is 100 or more, or the difference between before and after aging is 50 or more. After that, the unraveling speed ratio of the cheese inner layer portion measured after being left in an atmosphere of 20° C. and 50% RH for 24 hours is shown.
The anti-sticking property over time at high temperature was judged by the following index.
(index)
◎: The unwinding speed ratio after aging is less than 100, and the difference between before and after aging is less than 30 ○: The unwinding speed ratio after aging is less than 100, and the difference between before and after aging is 30 or more and less than 50 ×: Unwinding speed ratio after aging is 100 or more, or difference between before and after aging is 50 or more

(Coefficient of friction between fibers (F/FμS))
In FIG. 2, 50 to 60 cm of a monofilament of polyurethane elastic fiber to which a treatment agent has been applied is taken, a load T1 (10) is hung on one end, and the other end is attached to a U gauge (8) via a roller (9). and pulled at a constant speed (for example, 3 cm/min), the secondary tension T2 at that time was measured with a U gauge (18), and the inter-fiber friction coefficient was determined by the following equation (2).
Friction coefficient (F/FμS) = 1/θ ln (T2/T1) Equation (2)
(In formula (2), θ = 2π, ln = natural logarithm, T1 is 1 g per 22 dtex)
The roll collapse prevention property was judged by the following indices.
(index)
○: The coefficient of friction between fibers is 0.22 or more ×: The coefficient of friction between fibers is less than 0.22

[Examples 1 to 10 and Comparative Examples 1 to 9]
(Adjustment of spinning dope)
Polytetramethylene ether glycol having a number average molecular weight of 2000 and 4,4'-diphenylmethane diisocyanate were reacted at a molar ratio of 1:2, followed by chain extension using a dimethylformamide solution of 1,2-diaminopropane to obtain a polymer concentration of 27%. of dimethylformamide solution was obtained. The viscosity at 30°C was 1500 mPaS.

The polyurethane spinning dope was discharged into a stream of _N2 at 190°C for dry spinning. After applying 6% by weight of a treatment agent (the amount in the table is parts by weight) to the running yarn during spinning using the components shown in Tables 2 to 5 with an oiling roller, it is spun at a rate of 500 m/min. It was wound on a bobbin at a high speed to obtain 44 dtex monofilament cheese (400 g winding amount). Tables 2 to 5 show the evaluation results of the performance of the oil agent with the obtained cheese. The components used in Tables 2 to 5 are as follows.

(hydrocarbon oil)
a-1: XHVI 4 (manufactured by Shell Lubricants)
a-2: XHVI 3 (manufactured by Shell Lubricants)
a-3: Dianafresia W-8 (manufactured by Idemitsu Kosan Co., Ltd.)
a-4: Liquid paraffin RCM (manufactured by Sanko Chemical Industry Co., Ltd.)
a-5: YUBASE 3 (manufactured by SK Lubricants)
a-6: PAO401 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)

(Silicone oil (B))
b-1: TSF451-10 (manufactured by Momentive Performance, dimethyl silicone 10mm ² /s (25°C))
b-2: WACKER SILICONE FLUID AK20 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., dimethyl silicone 20 mm ² /s (25 ° C.))

(Ester oil (C))
c-1: 2-ethylhexyl stearate

(Organic phosphate ester (D))
d-1: isotridecyl phosphate

(Other ingredients)
X-1: silicone resin (MQ resin) (500 mm ² /s (25° C.))
X-2: POE-modified silicone X-3: isostearyl alcohol X-4: sodium di-2-ethylhexyl sulfosuccinate X-5: magnesium stearate: average particle size 0.5 μm, acicular (1:5)

Table 1 shows the weight ratios of the naphthenic, paraffinic and aromatic components contained in the hydrocarbon oils used in Tables 2 to 5. The weight ratios of the naphthenic component, the paraffinic component and the aromatic component shown in Table 1 are C _N %, C _p % and C _A % measured by the ring analysis ndM method specified in ASTM D3238. is the value of

As can be seen from Tables 2 to 5, Examples 1 to 10 are elastic fiber treatment agents containing hydrocarbon oil (A), and the weight ratio of naphthene component in hydrocarbon oil (A) is 0 weight. % and 13% or less, the problem of the present application can be solved.
On the other hand, when the hydrocarbon oil (A) is not contained (Comparative Example 5), or when the weight ratio of the naphthenic component in the hydrocarbon oil is not in the range of more than 0% by weight and 13% by weight or less (Comparative Examples 1 to 4 , 6 to 9) have not solved at least one of the problem of the present invention, that is, the property to prevent agglutination over time and the property to prevent roll collapse under high-temperature storage.

1 cheese 2 winding side paper tube 3 roller 4 roller 5 thread unwound from cheese 6 unwinding point 7 point of contact with roller 8 U gauge 9 roller 10 load

Claims (6)

A treatment agent for elastic fibers containing a hydrocarbon oil (A), wherein the naphthene component accounts for more than 0% by weight and not more than 13% by weight of the hydrocarbon oil (A). . The treatment agent for elastic fibers according to claim 1, wherein the hydrocarbon oil (A) contains a Fischer-Tropsch synthetic oil. The treatment agent for elastic fibers according to claim 1 or 2, further comprising a silicone oil (B). The elastic fiber treatment agent according to any one of claims 1 to 3, further comprising an organic phosphate (D). An elastic fiber obtained by applying the elastic fiber treatment agent according to any one of claims 1 to 4 to an elastic fiber main body. A method for producing an elastic fiber, comprising the step of applying the elastic fiber treatment agent according to any one of claims 1 to 4 to an elastic fiber body.

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