JPWO2015008591A1 - Treatment agent for synthetic fiber and its use - Google Patents

Abstract

The objective of this invention is providing the processing agent for synthetic fibers which was excellent in the product stability at the time of the low temperature storage of the processing agent for synthetic fibers, and excellent in the emulsion stability of the processing agent. The present invention is a treating agent for synthetic fibers containing a polyoxyalkylene alkyl ether represented by the following general formula (1). RO- (EO) a-[(PO) b / (EO) c]-(EO) d-H (1) (wherein R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, It may be composed of any branched chain structure, PO represents an oxypropylene group, EO represents an oxyethylene group, a, b, c and d represent the average number of moles added, and a = 1 -10, b = 1 to 10, c = 1 to 10, and d = 1 to 40. [(PO) b / (EO) c] is obtained by randomly adding b mol PO and c mol EO. A polyoxyalkylene group.)

Description

  The present invention relates to a treating agent for synthetic fibers and its use. More specifically, the present invention relates to a synthetic fiber treatment agent having excellent product stability during low-temperature storage and excellent emulsion stability of the treatment agent, and a method for producing synthetic fiber filament yarn and false twisted yarn using the same. is there.

  In recent years, the production base of synthetic fibers has been expanded, and synthetic fibers are produced in various countries and regions. Along with this, the use conditions of the synthetic fiber treating agent have also been diversified, and, for example, those that can be used in a wide temperature range are desired.

  In general, the treating agent for synthetic fibers is mainly composed of a smoothing agent such as polyoxyalkylene alkyl ether, polyether compound, ester compound and the like.

  At this time, a polyoxyalkylene alkyl ether conventionally used, for example, a random type PO / EO copolymer, or a block type PO / EO copolymer, for example, the treatment agent described in Patent Document 1 is used. The stability of the treatment agent and the stability of the emulsion of the treatment agent were insufficient.

  If the stability of the treatment agent is poor, the components may be separated depending on the storage conditions (for example, in winter when the temperature is low). When such a treatment agent, that is, a treatment agent in a state where the components are separated, is attached to the synthetic fiber, the treatment agent does not uniformly adhere to the synthetic fiber, which causes frequent problems in the yarn making process and the processing process. Similarly, even if the emulsion stability of the treatment agent is poor, the treatment agent does not uniformly adhere to the synthetic fiber, which causes frequent problems in the yarn making process and the processing process. The problems in the yarn production process and the processing process referred to here are fluff, yarn breakage, white powder, dyed spots, and the like of the synthetic fiber, which is an important issue that affects the quality of the synthetic fiber.

Japanese Unexamined Patent Publication No. 7-252774

  The objective of this invention is providing the processing agent for synthetic fibers which was excellent in the product stability at the time of the low temperature storage about the processing agent for synthetic fibers, and excellent in the emulsion stability of the processing agent. Moreover, it is providing the manufacturing method of a synthetic fiber filament yarn and synthetic fiber using the same.

As a result of extensive research, the present inventors have selected from the group consisting of a polyoxyalkylene alkyl ether represented by the following general formula (1) and a polyoxyalkylene alkyl ether ester represented by the following general formula (2). Thus, the present inventors have found that the above-mentioned problems can be solved by using a synthetic fiber treating agent containing at least one selected from the above, and have reached the present invention.
RO- (EO) _a -[(PO) _b / (EO) _c ]-(EO) _d -H (1)
(In the formula (1), R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure. PO is an oxypropylene group, EO Represents an oxyethylene group, a, b, c and d represent the average number of moles added, a = 1 to 10, b = 1 to 10, c = 1 to 10, and d = 1 to 40. [(PO) _b / (EO) _c ] is a polyoxyalkylene group formed by randomly adding b moles of PO and c moles of EO.)
_{^{R 1 O- (EO) e -}} [(PO) f / (EO) g] - (EO) h -CO-R 2 (2)
(However, in Formula (2), R ¹ represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure. R ² has 1 carbon atom. Represents an alkyl group or an alkenyl group of ˜30, and may be composed of a linear or branched structure, PO represents an oxypropylene group, EO represents an oxyethylene group, e, f, g and h Represents the average number of moles added, e = 1 to 10, f = 1 to 10, g = 1 to 10, and h = 1 to 40. [(PO) _f / (EO) _g ] is f (This is a polyoxyalkylene group formed by randomly adding mol PO and g mol EO.)

  The melting point of the polyoxyalkylene alkyl ether is preferably 15 ° C. or lower.

  The cloud point of a 1% by weight aqueous solution of the polyoxyalkylene alkyl ether is preferably 60 ° C. or higher and lower than 100 ° C.

  It is preferable that the weight ratio of the polyoxyalkylene alkyl ether in the nonvolatile content of the treatment agent is 3 to 70% by weight.

The polyoxyalkylene alkyl ether ester preferably has a kinematic viscosity at 25 ° C. of 10 mm ² / s or more and less than 100 mm ² / s.

  It is preferable that the weight ratio of the polyoxyalkylene alkyl ether ester in the nonvolatile content of the treating agent is 1 to 50% by weight.

  The treating agent of the present invention preferably contains the polyoxyalkylene alkyl ether and the polyoxyalkylene alkyl ether ester.

  Further, it preferably contains at least one selected from the group consisting of alkyl sulfonate salts, alkyl phosphate salts, alkyl succinate salts, alkyl sulfate salts, fatty acid soaps and alkyl imidazolinium salts.

  The synthetic fiber is preferably a polyester fiber, a polyamide fiber or a polypropylene fiber.

  More preferably, the synthetic fiber treating agent is for friction false twisting.

  The synthetic fiber filament yarn of the present invention is obtained by attaching the synthetic fiber treating agent of the present invention to a (raw material) synthetic fiber filament yarn.

  The manufacturing method of the false twisted yarn of the present invention includes the steps of heating, stretching and false twisting the synthetic fiber filament yarn to which the synthetic fiber treating agent of the present invention is attached.

  The synthetic fiber treatment of the present invention containing at least one selected from the group consisting of a polyoxyalkylene alkyl ether represented by the general formula (1) and a polyoxyalkylene alkyl ether ester represented by the following general formula (2) The agent is excellent in product stability during low-temperature storage, and in the emulsion stability of the treatment agent. In the case of the synthetic fiber filament yarn to which the treatment agent for synthetic fibers of the present invention is applied, the treatment agent is uniformly attached, so that there are few fuzz and yarn breakage. If it is the manufacturing method of the false twisted yarn of this invention, since the processing agent has adhered uniformly, there are few fuzz and yarn breakage.

[Polyoxyalkylene alkyl ether represented by the general formula (1)]
First, the polyoxyalkylene alkyl ether represented by the following general formula (1) will be described.
RO- (EO) _a -[(PO) _b / (EO) _c ]-(EO) _d -H (1)
(However, R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure. PO represents an oxypropylene group, and EO represents an oxyethylene group. A, b, c and d represent the average number of moles added, where a = 1 to 10, b = 1 to 10, c = 1 to 10, and d = 1 to 40. [(PO) _b / (EO) _c ] is a polyoxyalkylene group formed by random addition of b mol of PO and c mol of EO.

  Although there is no limitation in particular as the average addition mole number a in General formula (1), Usually, 1-10 mol, Preferably it is 2-6 mol, More preferably, it is 3-4 mol. When the average added mole number a in the general formula (1) is 1 to 10 mol, hydrophilicity increases, and thus the stability of the emulsion of the synthetic fiber treatment agent is excellent.

  The average added mole numbers b and c in the general formula (1) are not particularly limited, but b is usually 1 to 10 mol, preferably 2 to 8 mol, more preferably 3 to 4 mol, c is 1-10 mol normally, Preferably it is 2-8 mol, More preferably, it is 3-6 mol. Since PO and EO are present at random in the center of the molecular chain of the polyoxyalkylene alkyl ether, the low-temperature stability of the treating agent for synthetic fibers is improved because the crystallinity is lowered and the melting point is lowered. Estimated.

  The average added mole number d in the general formula (1) is not particularly limited, but is usually 1 to 40 mol, preferably 2 to 30 mol, more preferably 3 to 20 mol, and most preferably 4 to 10 mol. It is. The presence of EO at the end of the molecular chain increases the hydrophilicity and improves the emulsifying power, thereby improving the stability of the synthetic fiber treating agent emulsion.

The weight average molecular weight of the polyoxyalkylene alkyl ether represented by the general formula (1) is 500 to 4000, preferably 550 to 2500, and particularly preferably 600 to 1000. When the weight average molecular weight is less than 500, smoke generation may occur due to the low molecular weight when the heat treatment is performed in the false twisting process, which may cause heater contamination. When the weight average molecular weight is more than 4000, when the treatment agent is attached to the synthetic fiber due to an increase in viscosity due to the high molecular weight, the dynamic friction coefficient increases, which may cause fluff and yarn breakage.
The weight average molecular weight was injected into separation columns KF-402HQ and KF-403HQ manufactured by Showa Denko KK at a sample concentration of 3 mg / cc using a high-speed gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation. The maximum peak value measured by the RI detector.

[Method for Producing Polyoxyalkylene Alkyl Ether Represented by General Formula (1)]
There is no limitation in particular as a manufacturing method of polyoxyalkylene alkyl ether represented by General formula (1), A well-known method is employable. For example, the method for producing the polyoxyalkylene alkyl ether of the present invention has the following general formula (A):
ROH (A)
A process of supplying only ethylene oxide to the alcohol represented by the following reaction (hereinafter referred to as the first stage), and a process of supplying ethylene oxide and propylene oxide after the first stage to cause a random addition reaction ( Hereinafter, the process of supplying only ethylene oxide (hereinafter referred to as the third stage) may be performed continuously from the first stage to the third stage, or obtained once in each process. The resulting adduct may be recovered and the reaction continued.

  Examples of the monohydric alcohol include aliphatic monohydric alcohols. Aliphatic monohydric alcohols are preferred from the viewpoints of cost, reactivity, and smoothness as a treating agent for synthetic fibers. The monohydric alcohol is preferably a primary alcohol or a secondary alcohol, more preferably a primary alcohol. Moreover, the hydrocarbon group which is a residue obtained by removing a hydroxyl group from a monohydric alcohol may be linear or branched, and may be saturated or unsaturated. The carbon number of the monohydric alcohol is preferably 4 to 24, more preferably 8 to 22, and still more preferably 8 to 18 from the viewpoint of product stability during low-temperature storage of the fiber treatment agent.

Examples of the monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, and heptadecanol. 2-ethylhexanol, 2-ethyl hexanol, 2; linear alcohols such as diol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, and triacosanol; -Propylheptanol, 2-butyloctanol, 1-methylheptadecanol, 2-hexyloctanol, 1-hex Branched alkanols such as luheptanol, isodecanol, isotridecanol, 3,5,5-trimethylhexanol; hexenol, heptenol, octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, pentadecenol, hexadecenol, heptadenol Linear alkenols such as octadecenol, nonadecenol, eisenol, docosenol, tetracosenol, pentacosenol, hexacosenol, heptacosenol, octacosenol, nonacosenol and triaconsenol; isohexenol, 2-ethylhexenol, isotridecenol, 1-methylheptadel Senol, 1-hexyl heptenol, isotri Senoru, and branched alkenols such as iso octadecenyl Knoll and the like. These alcohols may be used alone or in combination of two or more. Specific examples of alcohol products are not particularly limited. For example, higher alcohols derived from natural fats and oils such as coconut alcohol and palm alcohol, the calcoal series (made by Kao), the conol series (made by Shin Nippon Rika), oxo Examples include the Cole series (manufactured by Kyowa Hakko Chemical), the Neodoll series (manufactured by Shell Chemical), the ALFOL series (manufactured by Sasol), the EXXAL series (manufactured by Exxon Mobil), and the like. These higher alcohol products may be used alone or in combination of two or more.
Among these, butanol, octanol, nonaol, decanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol, nonadecanol, octadecanol are preferred, butanol, octanol, decanol, dodecanol, tridecanol, tetradecanol, hexadecane Nord, octadecanol and octadecenol are preferred.

  The method for producing the polyoxyalkylene alkyl ether represented by the general formula (1) may be performed in the presence of a catalyst. The catalyst is not particularly limited. For example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide; potassium oxide Alkali (earth) metal oxides such as sodium oxide, calcium oxide, barium oxide, magnesium oxide, strontium oxide; alkali metals such as metal potassium and metal sodium; metal hydrides such as sodium hydride and potassium hydride ; Carbonates of alkali (earth) metals such as sodium carbonate, sodium bicarbonate and potassium carbonate; sulfates of alkali (earth) metals such as sodium sulfate and magnesium sulfate; organics such as methanesulfonic acid and trifluoromethanesulfonic acid Sulfonic acid; sodium paratoluenesulfonate, patorue Aromatic sulfonates such as pyridinium sulfonate; amine compounds such as monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, and triethylamine; iron powder, aluminum powder, antimony powder, aluminum (III) chloride, Aluminum bromide (III), iron (III) chloride, iron (III) bromide, cobalt (III) chloride, antimony (III) chloride, antimony (V) chloride, antimony (III) bromide, tin tetrachloride, four Lewis acids such as titanium chloride, boron trifluoride and boron trifluoride diethyl ether; proton acids such as sulfuric acid and perchloric acid; potassium perchlorate, sodium perchlorate, calcium perchlorate, magnesium perchlorate, etc. Alkali (earth) metal perchlorate; calcium metho Alkali (earth) metal alkoxides such as sid, sodium ethoxide and lithium ethoxide; Alkali (earth) metal phenoxides such as potassium phenoxide and calcium phenoxide; Sodium silicate, potassium silicate, sodium aluminosilicate, potassium aluminosilicate, Silicates such as sodium metasilicate, orthosilicate sodium, zeolite; Al-Mg complex oxides such as calcined aluminum hydroxide and magnesium, metal ion-added magnesium oxide, calcined hydrotalcite, or surface modified products thereof, lanthanoids A complex etc. are mentioned. These catalysts may be used alone or in combination of two or more.

Although there is no limitation in particular about the usage-amount of a catalyst, Preferably it is 0.001-10 weight part with respect to 100 weight part of alcohol, More preferably, it is 0.001-8 weight part, More preferably, it is 0.01-6. Part by weight, particularly preferably 0.05 to 5 parts by weight, most preferably 0.05 to 3 parts by weight. If the amount of the catalyst used is less than 0.001 part by weight, the addition reaction may not proceed sufficiently. On the other hand, if the amount of the catalyst used exceeds 10 parts by weight, the polyoxyalkylene alkyl ether may be easily colored.
In the method for producing the polyoxyalkylene alkyl ether represented by the general formula (1), it is preferable that raw materials such as alcohol and catalyst are charged into a reaction vessel, and the reaction vessel is subjected to degassing treatment or dehydration treatment. The degassing process is performed by, for example, a vacuum degassing system, a vacuum degassing system, or the like. Further, the dehydration process is performed by, for example, a heat dehydration method, a vacuum dehydration method, a vacuum dehydration method, or the like.

In the production method of the polyoxyalkylene alkyl ether represented by the general formula (1), the production form is not particularly limited, and may be a continuous type or a batch type. Although there is no limitation in particular about reaction container, For example, the tank-type reaction container provided with the stirring blade, the micro reactor, etc. can be mentioned. Although there is no limitation in particular as a stirring blade, A max blend blade, a tornado blade, a full zone blade, etc. can be mentioned.
In the method for producing the polyoxyalkylene alkyl ether represented by the general formula (1), the addition reaction may be started from a reduced pressure state, may be started from an atmospheric pressure state, and further from a pressurized state. You may start. When starting from an atmospheric pressure state or a pressurized state, it is preferably carried out in an inert gas atmosphere. When the addition reaction is carried out in an inert gas atmosphere, it is possible to sufficiently remove impurities generated due to side reactions between alkylene oxides such as ethylene oxide and propylene oxide and oxygen, and safety. From the viewpoint of this, it is preferable because it is useful. The inert gas is not particularly limited, and examples thereof include nitrogen gas, argon gas, and carbon dioxide gas. These inert gases may be used alone or in combination of two or more. The oxygen concentration in the reaction vessel under an inert gas atmosphere is not particularly limited, but is preferably 10% by volume or less, more preferably 5% by volume or less, still more preferably 3% by volume or less, and particularly preferably 1% by volume. % Or less, and most preferably 0.5% by volume or less. If the oxygen concentration in the reaction vessel exceeds 10% by volume, impurities may not be sufficiently removed, and it may not be preferable from the viewpoint of safety.

  The initial pressure in the reaction vessel is not particularly limited. For example, the gauge pressure is preferably 0 to 0.50 MPa, more preferably 0 to 0.45 MPa, still more preferably 0 to 0.40 MPa, and particularly preferably 0. It is -0.35 MPa, Most preferably, it is 0-0.30 MPa. If the initial pressure in the reaction vessel is less than 0 MPa, the amount of impurities generated may increase. On the other hand, when the initial pressure in the reaction vessel is more than 0.50 MPa, the reaction rate may be slow.

The pressure in the reaction vessel during the addition reaction is affected by the supply rate of ethylene oxide and propylene oxide, the reaction temperature, the amount of catalyst, and the like. The pressure in the reaction vessel during the addition reaction is not particularly limited, but is preferably 0 to 5.0 MPa, more preferably 0 to 4.0 MPa, further preferably 0 to 3.0 MPa, and particularly preferably 0 to 0 in terms of gauge pressure. 2.0 MPa, most preferably 0.1-1.0 MPa. When the pressure in the reaction vessel during the addition reaction is less than 0 MPa, the reaction rate may be slow. On the other hand, if the pressure in the reaction vessel during the addition reaction is more than 5.0 MPa, the production may be difficult.
The reaction temperature for the addition reaction of ethylene oxide and propylene oxide is not particularly limited, but is preferably 70 to 240 ° C, more preferably 80 to 220 ° C, still more preferably 90 to 200 ° C, and particularly preferably 100 to 190 ° C. Most preferably, it is 110-180 degreeC. If the reaction temperature is less than 70 ° C., the addition reaction may not proceed sufficiently. On the other hand, when the reaction temperature exceeds 240 ° C., coloring of the resulting polyoxyalkylene alkyl ether and decomposition of the polyoxyalkylene group in the polyoxyalkylene alkyl ether may be promoted.

The time required for the addition reaction (reaction time) is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.1 to 80 hours, still more preferably 0.1 to 60 hours, and particularly preferably. 0.1 to 40 hours, most preferably 0.5 to 30 hours. If the reaction time is less than 0.1 hour, the addition reaction may not proceed sufficiently. On the other hand, when the reaction time exceeds 100 hours, the production efficiency may deteriorate.
When the supply of ethylene oxide and propylene oxide is completed, the internal pressure in the reaction vessel gradually decreases as the ethylene oxide and propylene oxide are consumed. The addition reaction of ethylene oxide and propylene oxide is preferably continued until no change in internal pressure is observed. The addition reaction of ethylene oxide and propylene oxide ends when no change in internal pressure is observed over a certain period of time. If necessary, heating / depressurization operation or the like may be performed to recover unreacted ethylene oxide or propylene oxide.

In the addition reaction of ethylene oxide and propylene oxide, an inert solvent can be used as necessary. For example, when a solid alcohol such as triaconsenol is used as the alcohol, it is preferable to use it by dissolving it in an inert solvent in advance before the reaction, thereby improving the reactivity more sufficiently, and handling properties. high. In addition, if an inert solvent is used, a heat removal effect can be expected.
There are no particular limitations on the inert solvent, but examples include ethers such as diethyl ether, ethylene glycol dimethyl ether, dioxane, and tetrahydrofuran; esters such as diethylene glycol methyl ether acetate and propylene glycol methyl ether acetate; acetone, methyl isobutyl ketone, and methyl ethyl ketone. Ketones such as sulfolane, sulfones such as sulfolane and dimethylsulfonoxide, halogenated hydrocarbons such as dichloromethane and chloroform, aromatic hydrocarbons such as benzene, toluene and xylene, and the like such as pentane, hexane, cyclopentane and cyclohexane. Aliphatic hydrocarbons etc. are mentioned, You may use together 1 type (s) or 2 or more types. Of these, aromatic hydrocarbons are preferable, and toluene is more preferable.

The amount of the inert solvent used is not particularly limited, but when used to dissolve alcohol, it is preferably 10 to 1000 parts by weight, more preferably 10 to 500 parts by weight with respect to 100 parts by weight of alcohol. Parts, more preferably 10 to 400 parts by weight, particularly preferably 10 to 300 parts by weight, and most preferably 10 to 200 parts by weight. If the amount of the inert solvent is more than 1000 parts by weight with respect to 100 parts by weight of the alcohol, the addition reaction may not proceed sufficiently. On the other hand, if the amount of the inert solvent is less than 10 parts by weight, the alcohol may not be sufficiently dissolved. When an inert solvent is used, it is preferably removed after the addition reaction. By removing the inert solvent, it is possible to sufficiently prevent the generation of impurities due to the remaining inert solvent, and it is possible to obtain a polyoxyalkylene alkyl ether having better physical properties. The solvent removal step is as described later.
After completion of the addition reaction of ethylene oxide and propylene oxide, it is preferable to neutralize and / or remove the catalyst or remove the inert solvent as necessary.

The neutralization of the catalyst may be performed by an ordinary method. For example, when the catalyst is an alkaline catalyst, an acid such as hydrochloric acid, phosphoric acid, acetic acid, lactic acid, citric acid, succinic acid, acrylic acid, methacrylic acid, etc. may be used. It is preferable to perform the addition.
The neutralization of the catalyst is preferably carried out in an inert gas atmosphere. Although there is no limitation in particular as an inert gas, For example, nitrogen gas, argon gas, a carbon dioxide gas etc. are mentioned, You may use 1 type (s) or 2 or more types together.

The temperature during neutralization of the catalyst is not particularly limited, but is preferably 50 to 200 ° C, more preferably 50 to 190 ° C, still more preferably 60 to 180 ° C, particularly preferably 60 to 170 ° C, and most preferably. 60-160 ° C. If the temperature during neutralization of the catalyst is less than 50 ° C., the time required for neutralization may become long. On the other hand, if the temperature at the time of neutralization of the catalyst is higher than 200 ° C., coloring of the resulting polyoxyalkylene alkyl ether and decomposition of the polyoxyalkylene group in the polyoxyalkylene alkyl ether may be promoted.
By the neutralization of the catalyst, the pH of the reaction product obtained by the above addition reaction is preferably adjusted to 4 to 10, more preferably 5 to 8, particularly preferably 6 to 8. Moreover, antioxidants, such as quinones and phenols, can also be used together as necessary during catalyst neutralization.

The neutralized salt produced by neutralization may be further subjected to solid-liquid separation. Examples of the method for solid-liquid separation of the neutralized salt produced by neutralization include filtration and centrifugation. For filtration, for example, a filter paper, a filter cloth, a cartridge filter, a two-layer filter of cellulose and polyester, a metal mesh filter, a sintered metal filter, etc., under reduced pressure or pressurized conditions of 20 to 140 ° C. It is good to do. Centrifugation may be performed, for example, using a centrifuge such as a decanter or a centrifugal clarifier. Moreover, about 1-30 weight part of water can also be added with respect to 100 weight part of liquids before solid-liquid separation as needed. As the solid-liquid separation, particularly when filtration is performed, it is preferable to use a filter aid because the filtration rate is improved.
The filter aid is not particularly limited. For example, each series of Celite, High Flow Supercell, and Cell Pure (manufactured by Advanced Minerals Corporation), silica # 645, silica # 600H, silica # 600S, silica # 300S, silica # 100F Diatomaceous earth such as Daikalite (manufactured by Chuo Silica Co.), diatomite such as Daikalite (manufactured by Grefco); Perlite such as RocaHelp (manufactured by Mitsui Mining & Smelting), Topco (manufactured by Showa Chemical Co., Ltd.); KC Flock (manufactured by Nippon Paper Industries), Fibracell ( Cellulose-based filter aids such as Advanced Minerals Corporation); silica gels such as silopute (Fuji Silysia Chemical Co., Ltd.) and the like. These filter aids may be used alone or in combination of two or more.

For the filter aid, a precoat method for forming a filter aid layer on the filter surface such as filter paper in advance may be used, or a body feed method for directly adding to the filtrate may be used, or both of these may be used in combination. Good. The amount of the filter aid used is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the liquid before solid-liquid separation. The filtration rate depends on the size of the filter surface, the degree of vacuum or pressurization, the treatment humidity, etc., but is preferably 100 kg / m ² · hr or more, more preferably 300 kg / m ² · hr or more. More preferably 500 kg / m ² · hr or more.
The removal of the catalyst is not particularly limited, but for example, a method of solid-liquid separation after adsorbing the catalyst to the adsorbent is preferable.

Examples of the adsorbent include silicates such as aluminum silicate and magnesium silicate, activated clay, acid clay, silica gel, ion exchange resin and the like. Examples of commercially available adsorbents include KYOWARD 600, 700 (manufactured by Kyowa Chemical Co., Ltd.), Mizuka Life P-1, P-1S, P-1G, F-1G (manufactured by Mizusawa Chemical Co., Ltd.), Tomita-AD600, 700. Silicates (Tomita Pharmaceutical Co., Ltd.), etc .; Amberlist (Rohm and Haas), Amberlite (Rohm and Haas), Diaion (Mitsubishi Chemical), Dowex (Dow Chemical) And the like, and the like. These adsorbents may be used alone or in combination of two or more.
The amount of the adsorbent used is, for example, preferably 100 to 5000 parts by weight, more preferably 300 to 3000 parts by weight with respect to 100 parts by weight of the catalyst.

The catalyst removal conditions are not particularly limited. For example, the adsorbent is stirred and mixed at a temperature of 20 to 140 ° C. for 5 to 120 minutes under any one of reduced pressure, normal pressure, and pressurized conditions. A method of separating the adsorbent adsorbed by the above-mentioned solid-liquid separation method, or by preliminarily filling a column or the like with an adsorbent and passing the reaction mixture at a temperature of 20 to 140 ° C. to adsorb the catalyst. The method etc. which remove | eliminate. At this time, if necessary, 1 to 20 parts by weight of a water-soluble solvent such as water or lower alcohol represented by ethanol may be added to 100 parts by weight of the reaction mixture.
The remaining amount after removal of the catalyst is not particularly limited, but is preferably 300 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less, particularly preferably 50 ppm or less, and most preferably 20 ppm or less.

The removal of the inert solvent is preferably performed by distillation, for example.
In addition, when performing neutralization and / or removal of a catalyst and removal of an inert solvent, the order of each step is not particularly limited. For example, after neutralization and / or removal of a catalyst, Removal is preferable because the resulting polyoxyalkylene alkyl ether is excellent in purification efficiency.

  In the method for producing the polyoxyalkylene alkyl ether represented by the general formula (1), the content of the unreacted remaining alcohol is not particularly limited, but relative to 100 parts by weight of the obtained polyoxyalkylene alkyl ether. The amount is preferably 1 part by weight or less, more preferably 0.01 part by weight or less, further preferably 0.001 part by weight or less, particularly preferably 0.0001 part by weight or less, and most preferably 0.00001 part by weight or less. If the content of the unreacted remaining alcohol is more than 1 part by weight based on 100 parts by weight of the polyoxyalkylene alkyl ether, odor may be generated.

[Cloud point of 1% by weight aqueous solution of polyoxyalkylene alkyl ether represented by general formula (1)]
The cloud point of a 1% by weight aqueous solution of the polyoxyalkylene alkyl ether represented by the general formula (1) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 75 ° C. or higher. Stability is improved. A preferred upper limit is less than 100 ° C. If it is less than 60 degreeC, the emulsion stability of a processing agent may worsen.

[Melting point of polyoxyalkylene alkyl ether represented by general formula (1)]
The melting point of the polyoxyalkylene alkyl ether represented by the general formula (1) is preferably 15 ° C. or less, more preferably 10 ° C. or less, still more preferably 8 ° C. or less, most preferably 5 ° C. or less, and fibers in this order. The low temperature stability of the treatment agent is improved. A preferred lower limit is −30 ° C., a more preferred lower limit is −20 ° C., and a still more preferred lower limit is −10 ° C. If it exceeds 15 ° C., components of the treatment agent may be separated depending on the storage conditions (for example, in winter when the temperature is low).

[Polyoxyalkylene alkyl ether ester represented by the general formula (2)]
Next, the polyoxyalkylene alkyl ether ester represented by the following general formula (2) will be described.
_{^{R 1 O- (EO) e -}} [(PO) f / (EO) g] - (EO) h -CO-R 2 (2)
(However, in Formula (2), R ¹ represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure. R ² has 1 carbon atom. Represents an alkyl group or an alkenyl group of ˜30, and may be composed of a linear or branched structure, PO represents an oxypropylene group, EO represents an oxyethylene group, e, f, g and h Represents the average number of moles added, e = 1 to 10, f = 1 to 10, g = 1 to 10, and h = 1 to 40. [(PO) _f / (EO) _g ] is f (This is a polyoxyalkylene group formed by randomly adding mol PO and g mol EO.)

The polyoxyalkylene alkyl ether ester represented by the general formula (2) is a compound having a structure obtained by esterifying the polyoxyalkylene alkyl ether represented by the general formula (1) described above with a fatty acid. Accordingly, R ¹ , e, f, g, and h in the general formula (2) correspond to R, a, b, c, and d in the general formula (1), respectively. That is, R ¹ corresponds to R, e corresponds to a, f corresponds to b, g corresponds to c, and h corresponds to d. The preferable ranges of R ¹ , e, f, g, and h in the general formula (2) are also the same as R, a, b, c, and d in the general formula (1).

R ² is a residue obtained by removing a carboxy group from a fatty acid (R ² COOH). R ² preferably has 3 to 23 carbon atoms, more preferably 5 to 19 carbon atoms, and still more preferably 7 to 17 carbon atoms. It is preferably a primary alkyl or alkenyl group R ^2.

Examples of the fatty acid (R ² COOH) for esterifying the polyoxyalkylene alkyl ether represented by the general formula (1) include acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, Examples include myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, erucic acid, and lignoceric acid. These fatty acids may be used alone or in combination of two or more. Specific examples of the fatty acid product are not particularly limited, and examples thereof include the LUNAC series (manufactured by Kao). Among these, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and oleic acid are more preferable from the viewpoint of lubricity.

There is no limitation in particular as a manufacturing method of the polyoxyalkylene alkyl ether ester represented by General formula (2), A well-known method is employable. For example, as described above, after the polyoxyalkylene alkyl ether represented by the general formula (1) is produced, esterification with a fatty acid (R ² COOH) is performed according to a known method to obtain the general formula (2 ) Can be produced.

[Kinematic viscosity of polyoxyalkylene alkyl ether ester represented by the general formula (2)]
The kinematic viscosity of the polyoxyalkylene alkyl ether esters of the general formula (2), preferably from 10 to 100 mm ² / s, more preferably from 10 to 80 mm ² / s, still more preferably 10 to 50 mm ² / s, 20 Most preferred is ˜40 mm ² / s.
If it is less than 10 mm < ² > / s, the viscosity of a processing agent will become low too much and scattering of a processing agent may generate | occur | produce in an oil supply process. At 100 mm ² / s or more, the viscosity of the treatment agent becomes high and the spreadability to the synthetic fiber filament yarn deteriorates, so that the adhesion to the fiber may be inferior.

[Treatment agent for synthetic fibers]
The treating agent for synthetic fibers of the present invention includes at least one selected from the group consisting of a polyoxyalkylene alkyl ether represented by the general formula (1) and a polyoxyalkylene alkyl ether ester represented by the following general formula (2). Species are contained essential. The effects of the present invention are exhibited when such components are contained essentially.
When the polyoxyalkylene alkyl ether is essential, the weight percentage of the polyoxyalkylene alkyl ether in the nonvolatile content of the treatment agent is preferably 3 to 70% by weight, more preferably 5 to 65% by weight, 60% by weight is more preferable, and 15 to 55% by weight is most preferable. If it is less than 3% by weight, the cloud point of the emulsion of the treatment agent may be low, and if it exceeds 70% by weight, smoothness and convergence may be inferior.
The non-volatile content in the present invention refers to an absolutely dry component when the treatment agent is heat treated at 105 ° C. to remove volatile components such as a solvent and reach a constant weight.

  When the polyoxyalkylene alkyl ether ester is contained essentially, the weight proportion of the polyoxyalkylene alkyl ether ester in the nonvolatile content of the treatment agent is preferably 1 to 50% by weight, more preferably 1 to 40% by weight, 3 to 30% by weight is more preferable, and 5 to 20% by weight is most preferable. If it is less than 3% by weight, the adhesion and lubricity of the treatment agent may be inferior, and if it exceeds 50% by weight, the cloud point of the emulsion of the treatment agent will be low, and the treatment agent may be separated.

Moreover, it is preferable that the processing agent of this invention contains the polyoxyalkylene alkyl ether represented by General formula (1) and the polyoxyalkylene alkyl ether ester represented by General formula (2). By containing both these components essential, the viscosity of a processing agent falls and it can adhere a processing agent to a fiber uniformly. As a result, it is possible to further reduce the fluff and yarn breakage generated in the yarn making process and the processing process.
When these two components are used in combination, the weight ratio of polyoxyalkylene alkyl ether to polyoxyalkylene alkyl ether ester (polyoxyalkylene alkyl ether: polyoxyalkylene alkyl ether ester) is preferably 20:80 to 99: 1. 40:60 to 95: 5 is more preferable, and 55:45 to 90:10 is more preferable.

  When the treatment agent for synthetic fibers of the present invention contains polyoxyalkylene alkyl ether and polyether, the effect of improving the product stability during storage at low temperature of the treatment agent and the effect of improving the emulsion stability of the treatment agent are exhibited. easy. In the treatment agent for synthetic fibers of the present invention, the weight ratio of the polyoxyalkylene alkyl ether and the polyether in the nonvolatile content of the treatment agent is preferably 30% by weight or more, more preferably 35% by weight or more, and 40% by weight or more. Is more preferable, and 50% by weight or more is most preferable. In this order, the effect of improving the product stability when the treating agent is stored at a low temperature and the effect of improving the emulsion stability of the treating agent are easily obtained. The upper limit of the weight ratio of the polyoxyalkylene alkyl ether and the polyether in the nonvolatile content of the treating agent for synthetic fibers of the present invention is preferably 100% by weight or less, more preferably 95% by weight or less, and 90% by weight or less. Further preferred.

The treatment agent for synthetic fibers of the present invention is particularly suitable when it is a treatment agent for friction false twisting of synthetic fibers from the viewpoint described below.
In general, a false-textured yarn (Draw Texting Yarn; hereinafter abbreviated as DTY) is provided with a friction false twist treatment agent to produce a partially oriented yarn (Partially Oriented Yarn; hereinafter abbreviated as POY), and then a heating device ( It is obtained by heating the yarn with a heater) and drawing it while twisting the yarn with a false twisting device.
At this time, the larger the amount of the friction false twist treatment applied, the less fuzz, yarn breakage, white powder and dyeing spots that occur during the false twisting process. The amount of the treatment agent for twisting increases. For this reason, the heater is contaminated by the friction false twisting treatment agent, and it takes a lot of time and labor to clean the heater, leading to a decrease in productivity.
Therefore, the applied amount of the treating agent for synthetic fiber is usually 1.0% by weight with respect to the (raw material) synthetic fiber, whereas the applied amount of the treating agent for friction false twist is 0.25 to 0. Designed as low as 80% by weight. From the above, it can be seen that the friction false twist treatment agent has a low application amount to the synthetic fiber, so that uniform adhesion to the additional fiber is still important.

  In recent years, the production of special yarns such as fine denier yarns, full-dal yarns, bright modified cross-sectional yarns with high added value has been increasing as types of processed yarns using this method. In general, these special yarns are prone to problems such as fiber misalignment, tension fluctuation, and antistatic failure due to friction between fibers and rollers, fibers and guides, fibers and false twisting units, and fibers. It is known. Such special yarn brands also tend to generate fiber scraps, so high quality false twisted yarns could not be obtained with high productivity.

  In other words, for the brands that are likely to produce fluff, yarn breakage, white powder, and dyed spots that have been increasing in recent years, it is sufficient to suppress fuzz, yarn breakage, white powder, and dyed spots, and to prevent dirt accumulated in the heater. The results were not satisfactory.

  When the treating agent for synthetic fibers of the present invention is for friction false twisting, the stability of the treating agent and the stability of the emulsion of the treating agent are improved, so that the uniform adhesion to the fiber is greatly improved, and the synthetic fiber In the production of false twisted yarn, it is possible to reduce the processing defects of fuzz, broken yarn, white powder, and dyed spots that occur in the false twisting process, and it is also possible to extend the cleaning cycle of the heater.

  Moreover, the processing agent for synthetic fibers of this invention may contain a lubricant, an emulsifier, a penetrant, an antistatic agent etc. as needed in the range which does not impair the effect of this invention. The total weight ratio of these lubricants, emulsifiers, penetrants, antistatic agents, etc. in the non-volatile content of the treatment agent is preferably 50% by weight or less from the standpoint of more manifesting properties such as fiber convergence and oil film reinforcement. 40% by weight or less, more preferably 30% by weight or less, and most preferably 20% by weight or less.

There are no particular limitations on the lubricant, and known lubricants can be employed. For example, methyl oleate, butyl palmitate, butyl stearate, butyl oleate, isooctyl laurate, isooctyl palmitate, isooctyl stearate, isooctyl oleate, lauryl oleate, isotridecyl stearate, hexadecyl stearate, iso Fatty acid ester compounds (esters of monohydric alcohol and monohydric carboxylic acid) such as stearyl oleate, oleyl octanoate, oleyl laurate, oleyl palmitate, oleyl stearate, oleyl oleate; diethylene glycol dilaurate, diethylene glycol dioleate, hexamethylene Glycol dilaurate, hexamethylene glycol dioleate, neopentyl glycol dilaurate, trimethylolpropane tricaprylate, Esters of polyhydric alcohols such as limethylolpropane trilaurate, trimethylolpropane tripalmitate, trimethylolpropane trioleate, glycerol trioleate, pentaerythritol tetralaurate, pentaerythritol tetraoleate and monovalent carboxylic acids; Many such as malate, diisotridecyl adipate, dicetyl adipate, dioleyl adipate, dioctyl sebacate, dilauryl sebacate, distearyl sebacate, dioctyl azelate, distearyl azelate, dioctyl phthalate, trioctyl trimellitate Ester of monovalent carboxylic acid and monohydric alcohol; neodol 23 (synthetic alcohol manufactured by Shell) added with 2 moles of ethylene oxide and ester of lauric acid Diester of 2 moles of ethylene oxide added to neodol 23 and adipic acid, ester of 2 moles of propylene oxide added to isotridecyl alcohol and lauric acid, block or random copolymer of ethylene oxide and propylene oxide Examples include an ester of an alcohol and a carboxylic acid to which an alkylene oxide is added such as a polymer in which both ends or one end of the polymer is blocked with a carboxylic acid.
Two or more kinds of these lubricants can be used in combination as needed. The weight ratio of the lubricant to the nonvolatile content of the treatment agent is not particularly limited, but is preferably 0 to 30% by weight, and more preferably 0 to 10% by weight.

  An emulsifier and a penetrating agent may be used to emulsify the treatment agent, to assist adhesion to the fiber, or to allow the treatment agent to be washed from the fiber to which the treatment agent is adhered. Good. There is no limitation in particular as an emulsifier and a penetrant, A well-known thing is employable. For example, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonylphenyl ether and the like having a weight average molecular weight of 300 or more and less than 1000 can be mentioned. In addition, polyoxyethylene lauryl amino ether, polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol diolate, glycerin monooleate, sorbitan monooleate, polyoxyethylene glycerin monolaurate, polyoxyethylene sorbitan trio Non-ionic surfactants such as rate, polyoxyethylene castor oil ether, polyoxyethylene hydrogenated castor oil ether, etc., and nitrogen-containing nonionic surfactants such as oleic acid diethanolamide, polyoxyethylene lauric acid monoethanolamide, etc. An agent etc. can be mentioned. These emulsifiers and penetrants can be used alone or in combination of two or more as required. The weight ratio of the emulsifier and penetrant in the nonvolatile content of the treatment agent is not particularly limited, but is preferably 0.1 to 40% by weight, and more preferably 0.1 to 30% by weight. These emulsifiers and penetrants may be used to impart antistatic properties to the fiber yarns, or to impart lubricity and convergence.

  There is no limitation in particular as an antistatic agent, A well-known thing is employable. For example, anionic surfactants such as metal salts / or amine salts of alkyl phosphate esters (hereinafter abbreviated as phosphates), metal salts / or amine salts of polyoxyethylene alkyl phosphates, alkane sulfonates, fatty acid soaps; And cationic surfactants such as amine salts, alkyl imidazolinium salts, and quaternary ammonium salts; amphoteric surfactants such as lauryl dimethyl betaine and stearyl dimethyl betaine. These antistatic agents can be used alone or in combination of two or more as required. The weight ratio of the antistatic agent in the nonvolatile content of the treatment agent is not particularly limited, but is preferably 0.1 to 10% by weight, and more preferably 0.1 to 5% by weight.

  In addition to the components such as the lubricant, the emulsifier, the penetrating agent, and the antistatic agent described above, components such as an antioxidant, an antiseptic, a rust preventive, and an antifoaming agent may be used as necessary.

  The treatment agent for synthetic fibers of the present invention is generally applied to a synthetic fiber filament as a treatment agent having a non-volatile content in the treatment agent of 80% by weight or more from the viewpoint of transportation cost and stability of the treatment agent. Transferred to the factory. The treatment agent of the present invention has very good stability of the treatment agent, and can prevent poor appearance and separation of components. As a result, the treatment agent uniformly adheres to the synthetic fiber, and the problems occurring in the yarn making process and the processing process can be greatly improved.

  It is preferable that the processing agent for synthetic fibers of this invention contains an external appearance regulator further. The appearance modifier can improve the stability of the treatment agent. The appearance adjusting agent is a component that is volatilized and removed by heat treatment in the synthetic fiber manufacturing process. The weight ratio of the appearance modifier to the entire treatment agent is preferably 0.1 to 20% by weight, and more preferably 0.1 to 10% by weight. When the weight ratio of the appearance modifier exceeds 20% by weight, the performance as a fiber treating agent deteriorates, and in the production of false twisted yarn of synthetic fiber, fluff, broken yarn, white powder, The processing defects of the dyeing spots cannot be reduced, but there is a possibility that the processing defects are increased.

  There are no particular limitations on the appearance modifier, and known ones can be employed. Appearance preparation agents include water and lower alcohols. Examples thereof include water, ethylene glycol, propylene glycol, isopropyl alcohol, glycerin, butyl diglycol and the like. Among these, water, ethylene glycol, and glycerin are preferable. Appearance preparation agents can be used alone or in combination of two or more as required.

The treatment agent for synthetic fibers of the present invention may be composed of the above-mentioned components consisting only of a non-volatile content, or may be composed of a non-volatile content and an appearance modifier, and the non-volatile content is diluted with a low-viscosity mineral oil. The thing may be sufficient and the water-system emulsion which emulsified the non volatile matter in water may be sufficient. In the case of an aqueous emulsion obtained by emulsifying nonvolatile components in water, the concentration of nonvolatile components is preferably 5 to 20% by weight, more preferably 6 to 15% by weight, and even more preferably 8 to 12% by weight.
About the manufacturing method of the processing agent for synthetic fibers of this invention, there is no limitation in particular and a well-known method is employable. The treatment agent is usually produced by mixing the constituent components described above in an arbitrary order.

[Synthetic filament yarn]
The synthetic fiber filament yarn of the present invention is obtained by adhering the synthetic fiber treating agent of the present invention to a (raw material) synthetic fiber filament yarn, and in the production of synthetic fiber false twisted yarn, the process of false twisting The processing defects of fluff, yarn breakage, white powder, and dyed spots generated in the process can be reduced, and the cleaning cycle of the heater can be extended. The amount of non-volatile matter deposited on the synthetic fiber treating agent is preferably 0.1 to 1.0% by weight, more preferably 0.2 to 0.8% by weight relative to the (raw material) synthetic fiber filament. 3 to 0.6% by weight is more preferable.
(Raw material) The method for applying the synthetic fiber treating agent of the present invention to the synthetic fiber filament is not particularly limited, and a known method can be employed. Usually given in the spinning process or drawing process of synthetic fiber filaments, (raw material) treatment agent consisting only of non-volatile content, treatment agent in which non-volatile content is diluted with low-viscosity mineral oil, or non-volatile in water Examples thereof include a method in which a water-based emulsion treatment agent emulsified with oil is supplied by roller oiling, guide oiling, or the like.

  The treatment agent for synthetic fibers of the present invention is particularly suitable for false twisting of synthetic fibers such as polyester fibers, polyamide fibers, and polypropylene fibers. As the polyester fiber, polyester (PET) having ethylene terephthalate as a main constituent unit, polyester (PTT) having trimethylene ethylene terephthalate as a main constituent unit, polyester (PBT) having main constituent unit of butylene ethylene terephthalate, and lactic acid are mainly used. Examples thereof include polyester (PLA) as a structural unit, examples of polyamide fibers include nylon 6 and nylon 66, and examples of polypropylene fibers include polypropylene.

[Method for producing false twisted yarn]
The manufacturing method of the false twisted yarn of the present invention includes a step of heating, stretching, and false twisting the synthetic fiber filament yarn to which the above-described synthetic fiber treating agent of the present invention is attached, It is possible to reduce processing defects such as fuzz, yarn breakage, white powder, and dyed spots that occur in the false twisting process, and it is possible to extend the cleaning cycle of the heater. There is no limitation in particular as the method of false twisting, A well-known method is employable. For example, the method etc. which were described in WO2009 / 034692 are mentioned.
There are no particular restrictions on the false twisting conditions, but from the point that it can be more effective, it is a contact type (hot plate contact heating method) false twisting that directly heats the synthetic fiber filament yarn to the hot plate of the heat source. It is preferable to perform false twisting using a machine. Such a hot plate contact heating type false twisting machine has a heater temperature of 160 ° C. to 230 ° C., a heater length of 150 cm to 250 cm, and a synthetic fiber filament thread that travels in contact with the surface of the heater plate. It is. The processing speed is usually 500 to 1000 m / min, preferably 600 to 800 m / min.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to the Example described here. The percentage (%) shown in the text and the table indicates “% by weight” unless otherwise specified. In Examples and Comparative Examples, each evaluation was performed based on the following method.

First, polyoxyalkylene alkyl ethers POA-1 to 12 and POA-D1 to 12 of Production Examples 1 to 12 and Production Comparative Examples 1 to 12 were obtained as follows.
<Production Example 1>
Stirring, the temperature can be adjusted, alkylene oxide charge tank, nitrogen supply tube, into a 2L autoclave equipped with a pressure regulating valve, was charged with _{C 12 to 13} alcohol 193g as the alcohol, the potassium hydroxide 0.9g alkali catalyst . After the atmosphere in the autoclave was replaced with nitrogen, dehydration was performed at 100 to 110 ° C. for 1 hour with stirring. Next, to obtain the desired molar ratio, 132 g of ethylene oxide is used as the first stage, a mixture of 116 g of propylene oxide and 132 g of propylene oxide is used as the second stage, 264 g of ethylene oxide is used as the third stage, and the gauge pressure is 0.0. The addition polymerization reaction was carried out for about 8 hours by adding at 0.4 MPa and a reaction temperature of 140-150 ° C. Thereafter, the polyoxyalkylene alkyl ether obtained was neutralized with 1.4 g of lactic acid and recovered. In this way, polyoxyalkylene alkyl ether (POA-1) was obtained.
<Production Examples 2-12 and Production Comparative Examples 1-12>
POA-2 to 12 and POA-D1 to 12 were obtained in the same manner as in Production Example 1 except that the number of moles of each of the alcohols listed in Tables 1 to 4 and ethylene oxide and propylene oxide were changed. . The cloud point of a 1% by weight aqueous solution of polyoxyalkylene alkyl ether and the melting point of polyoxyalkylene alkyl ether were measured as follows.

<Cloud point of 1% by weight aqueous solution of polyoxyalkylene alkyl ether>
A 1% by weight aqueous solution of polyoxyalkylene alkyl ether was prepared. Next, the mixture was heated to make the cloud point test solution turbid, and the temperature at which the turbidity disappeared was taken as the cloud point.
<Melting point of polyoxyalkylene alkyl ether>
Take the polyoxyalkylene alkyl ether in a capillary tube with both ends open to the specified dimensions, attach it to the mercury bulb of a thermometer, gradually raise the temperature in an air bath, and adjust the temperature at which the sample melts and becomes transparent. The melting point.

Next, polyoxyalkylene alkyl ether esters POAEE-13 to 18 and POAEE-D13 to 18 of Production Examples 13 to 18 and Production Comparative Examples 13 to 18 were obtained as follows.
<Production Example 13>
A polyoxyalkylene alkyl ether was obtained in the same manner as in Production Example 1, except that the number of moles of the alcohol listed in Table 5 and ethylene oxide and propylene oxide were changed. The obtained polyoxyalkylene alkyl ether was esterified with a fatty acid as follows.
In a reaction vessel equipped with a stirring blade, a heating device, and a dehydrating tube, 775 g of polyoxyalkylene alkyl ether and 248 g of lauric acid were charged, and an esterification reaction was performed at 180 to 210 ° C. for 8 hours. In this way, polyoxyalkylene alkyl ether ester (POAEE-13) was obtained.
<Production Examples 14 to 20 and Production Comparative Examples 13 to 20>
POAEE-14 to 20 and POAEE-D13 to 20 in the same manner as in Production Example 13 except that the alcohols in each example described in Tables 5 to 6, the number of added moles of ethylene oxide and propylene oxide, and the fatty acid were changed. Got. The kinematic viscosity of the polyoxyalkylene alkyl ether ester was measured as follows.

<Kinematic viscosity of polyoxyalkylene alkyl ether ester>
About 10 g of the sample is put into a Cannon-Fenceke viscometer and kept in a thermostatic bath adjusted to 25 ° C. for 15 minutes. Thereafter, the outflow time (seconds) for the sample to pass between the marked lines of the viscometer was measured, and the value multiplied by the viscometer coefficient was taken as the kinematic viscosity.

<Example 1>
Next, the compounding ingredients shown in Table 7 were mixed and stirred to prepare the synthetic fiber treating agent of Example 1. The results are shown in Table 7.

  Next, water was added to the prepared treating agent for synthetic fibers to prepare an aqueous emulsion in which the weight ratio of the nonvolatile content was 10% by weight. Next, the non-volatile content of the treatment agent was discharged by a guide oiling method using a metering pump device on polyethylene terephthalate fuller yarn having a titanium oxide content of 2.5%, which was discharged from the die with an extruder and cooled and solidified. A water-based emulsion was applied so that the amount of the adhering powder became 0.6 wt%, and 89 decitex / 72 filament POY was spun and wound at a speed of 2800 m / min to obtain 10 kg of cheese. Next, using the obtained POY, with a false twisting machine that is a hot plate contact heating method, the drawing false twisting is performed continuously for 10 days under the following false twisting conditions, and false twisted yarn (DTY) was obtained. The following methods were used for evaluation of false twisting yarn breakage, contact heater contamination, white powder generation amount, and knitted fabric dyeing section. The results are shown in Table 7.

<False twist processing conditions>
Stretch false twist condition false twisting machine of false twisting machine that is hot plate contact heating method: HTS-15V manufactured by Teijin Seiki Co., Ltd.
Processing speed: 600m / min
Stretch ratio (DR): 1.60
Twisting device: 3-axis disk friction system 1-5-1
(1 guide disk-5 working (polyurethane) disks-1 guide disk)
Disk speed / thread speed (D / Y): 1.8
Overfeed rate: 3%
First heater (twisted side) temperature: 200 ° C
Second heater (untwisting side) Temperature: Room temperature Processing days: 10 days

<Product stability>
The synthetic fiber treating agent described in Examples and Comparative Examples, which is blended with polyoxyalkylene alkyl ether, is allowed to stand for 1 week in an atmosphere of 10 ° C, 5 ° C, and -5 ° C, and the appearance of the treating agent is visually determined. did.
◎: -5 ° C, uniformly transparent even after standing for 1 week ○: 5 ° C, uniformly transparent even after standing for 1 week △: 5 ° C, separated after standing for 1 week ×: 10 ° C, separated after standing for 1 week

<40 ° C emulsion stability>
The emulsion stability of the treatment agents for synthetic fibers prepared in Examples and Comparative Examples was evaluated by the transmittance of the emulsion. The transmittance was measured with a spectrophotometer U-1900 Spectrophotometer manufactured by Hitachi, Ltd. after leaving a 10% concentration emulsion of the treating agent for synthetic fiber in an atmosphere at 40 ° C. for 1 week. The measurement conditions were defined as a wavelength of 750 nm and a measurement temperature of 25 ° C.
The transmittance exceeded 95%.
Transmittance 100%: 40 ° C, uniform transparent transmittance even after standing for 1 week, more than 95 to less than 100%: Slightly bluish white transparent transmittance, 95% or less after standing at 40 ° C, 1 week: 40 ° C, cloudy after standing for 1 week

<False twisted yarn>
After drawing and false twisting, the number of yarn breaks was evaluated as follows. As the number of yarn breaks increases, fluff is more likely to occur.
◎: 0 times ○: 1-2 times △: 3-4 times ×: 5 times or more

<Contact heater contamination>
After performing the drawing false twisting, the contamination state of the heater was visually evaluated as follows.
A: The heater is not dirty.
○: Only a part of the heater is dirty.
Δ: About half of the heater is dirty.
X: The heater is completely dirty.

<White powder generation amount>
After performing the drawing false twisting process, the false twisting disk and the amount of white powder generated around it were visually evaluated as follows.
A: No white powder after processing for 10 days.
○: Some white powder after processing for 10 days.
Δ: White powder generated and accumulated after processing for 5 days.
X: White powder is generated and accumulated from the start of processing.

<Knit fabric dyeing group>
After performing the drawing false twisting process, the obtained processed yarn was knitted with a circular knitting machine manufactured by Koike Machinery Co., Ltd., and the polyester knitted fabric was dyed. The dyeability of the obtained knitted fabric was evaluated as follows.
A: No staining spots Δ: Some staining spots are observed ×: Many staining spots are observed

(Examples 2-12, Comparative Examples 1-12)
Evaluation was performed in the same manner as in Example 1 except that the synthetic fiber treating agent was prepared by changing to the blending components in each example described in Table 7 and Table 8. The results are shown in Table 7 and Table 8. In Tables 7 to 12, polyether 1 and polyether 2 are the following polyethers.
Polyether 1: PO / EO = 50/50, weight average molecular weight 5000
Polyether 2: PO / EO = 50/50, weight average molecular weight 2000

As can be seen from Tables 7 and 8, in Examples 1 to 12, if the treatment agent for synthetic fibers contains the polyoxyalkylene alkyl ether represented by the general formula (1) of the present invention, product stability and Excellent emulsion permeability, false twisting yarn breakage, contact heater contamination, white powder generation amount and knitted fabric dyeing are small, and excellent in yarn production.
On the other hand, in Comparative Examples 1-12, since the polyoxyalkylene alkyl ether represented by General formula (1) is not contained, the effect obtained in the Example cannot be obtained.

(Examples 13-18, Comparative Examples 13-18)
Evaluation was conducted in the same manner as in Example 1 except that the synthetic fiber treating agent was prepared by changing to the blending components in each example shown in Table 9. The results are shown in Table 9.

As can be seen from Table 9, in Examples 13 to 18, if the treatment agent for synthetic fibers contains the polyoxyalkylene alkyl ether ester represented by the general formula (2) of the present invention, product stability and emulsion permeation can be obtained. Excellent in yield, false twisting, contact heater contamination, white powder generation amount and knitted fabric dyeing are small, and is excellent in yarn production.
On the other hand, Comparative Examples 13 to 18 do not contain the polyoxyalkylene alkyl ether ester represented by the general formula (2), so that the effects obtained in the examples cannot be obtained.

(Examples 19-30, Comparative Examples 19-30)
Evaluation was performed in the same manner as in Example 1 except that the synthetic fiber treating agent was prepared by changing to the blending components in each example described in Table 10 and Table 11. The results are shown in Table 10 and Table 11.

As can be seen from Table 10 and Table 11, in Examples 19 to 30, the polyoxyalkylene alkyl ether represented by the general formula (1) of the present invention and the polyoxyalkylene represented by the general formula (2) of the present invention Synthetic fiber treatment agents containing alkyl ether esters have excellent product stability and emulsion permeability, low false twisting yarn, contact heater contamination, white powder generation and knitted fabric dyeing, and excellent yarn production. . In particular, in these examples, the treatment agent can be uniformly attached to the fiber, so that there are few false twisting yarns and less fluff.
On the other hand, in Comparative Examples 19 to 30, the polyoxyalkylene alkyl ether represented by the general formula (1) of the present invention and the polyoxyalkylene alkyl ether ester represented by the general formula (2) of the present invention are selected. Therefore, the effects obtained in the examples cannot be obtained.

  The synthetic fiber treatment agent of the present invention is excellent in product stability during low-temperature storage, and in the emulsion stability of the treatment agent, so there is little fuzz and yarn breakage during the production of synthetic fiber filaments, increasing production efficiency. be able to.

Claims (12)

A treating agent for synthetic fibers, containing at least one selected from the group consisting of a polyoxyalkylene alkyl ether represented by the following general formula (1) and a polyoxyalkylene alkyl ether ester represented by the following general formula (2) .
RO- (EO) _a -[(PO) _b / (EO) _c ]-(EO) _d -H (1)
(In the formula (1), R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure. PO is an oxypropylene group, EO Represents an oxyethylene group, a, b, c and d represent the average number of moles added, a = 1 to 10, b = 1 to 10, c = 1 to 10, and d = 1 to 40. [(PO) _b / (EO) _c ] is a polyoxyalkylene group formed by randomly adding b moles of PO and c moles of EO.)
_{^{R 1 O- (EO) e -}} [(PO) f / (EO) g] - (EO) h -CO-R 2 (2)
(However, in Formula (2), R ¹ represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure. R ² has 1 carbon atom. Represents an alkyl group or an alkenyl group of ˜30, and may be composed of a linear or branched structure, PO represents an oxypropylene group, EO represents an oxyethylene group, e, f, g and h Represents the average number of moles added, e = 1 to 10, f = 1 to 10, g = 1 to 10, and h = 1 to 40. [(PO) _f / (EO) _g ] is f (This is a polyoxyalkylene group formed by randomly adding mol PO and g mol EO.)   The processing agent for synthetic fibers according to claim 1, wherein the polyoxyalkylene alkyl ether has a melting point of 15 ° C or lower.   The processing agent for synthetic fibers according to claim 1 or 2, wherein a cloud point of a 1 wt% aqueous solution of the polyoxyalkylene alkyl ether is 60 ° C or higher and lower than 100 ° C.   The processing agent for synthetic fibers according to any one of claims 1 to 3, wherein a weight ratio of the polyoxyalkylene alkyl ether in a non-volatile content of the processing agent is 3 to 70% by weight. The kinematic viscosity at 25 ° C. of polyoxyalkylene alkyl ether esters is less than 10 mm ² / s or more 100 mm ² / s, the synthetic fiber-processing agent according to claim 1.   The processing agent for synthetic fibers in any one of Claims 1-5 whose weight ratio of the said polyoxyalkylene alkyl ether ester which occupies for the non volatile matter of a processing agent is 1 to 50 weight%.   The processing agent for synthetic fibers according to any one of claims 1 to 6, comprising the polyoxyalkylene alkyl ether and the polyoxyalkylene alkyl ether ester.   Furthermore, the synthesis | combination in any one of Claims 1-7 containing at least 1 sort (s) chosen from the group which consists of alkyl sulfonate salt, alkyl phosphate salt, alkyl succinate salt, alkyl sulfate salt, fatty acid soap, and alkyl imidazolinium salt. Treatment agent for textiles.   The processing agent for synthetic fibers according to any one of claims 1 to 8, wherein the synthetic fibers are polyester fibers, polyamide fibers, or polypropylene fibers.   The processing agent for synthetic fibers according to any one of claims 1 to 9, which is used for friction false twisting.   A synthetic fiber filament yarn, wherein the synthetic fiber treating agent according to any one of claims 1 to 10 is attached to a (raw material) synthetic fiber filament yarn.   A method for producing a false twisted yarn, comprising the steps of heating, stretching and false twisting the synthetic fiber filament yarn according to claim 11.