WO2015008591A1 - Synthetic fiber treatment agent and use of same - Google Patents
Synthetic fiber treatment agent and use of same Download PDFInfo
- Publication number
- WO2015008591A1 WO2015008591A1 PCT/JP2014/066756 JP2014066756W WO2015008591A1 WO 2015008591 A1 WO2015008591 A1 WO 2015008591A1 JP 2014066756 W JP2014066756 W JP 2014066756W WO 2015008591 A1 WO2015008591 A1 WO 2015008591A1
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- Prior art keywords
- alkyl ether
- weight
- group
- polyoxyalkylene alkyl
- treatment agent
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
- D02G1/02—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
- D02G1/0206—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
- D02G1/026—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting in the presence of a crimp finish
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
- D06M13/17—Polyoxyalkyleneglycol ethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Definitions
- the present invention relates to a synthetic fiber treating agent 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.
- the treating agent for synthetic fiber is mainly composed of a smoothing agent such as polyoxyalkylene alkyl ether, polyether compound, ester compound and the like.
- 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.
- the components may be separated depending on the storage conditions (for example, at low temperatures in winter).
- a treatment agent that is, a treatment agent in a state where the components are separated
- 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 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.
- An object of the present invention is to provide a synthetic fiber treating agent that is excellent in product stability during low-temperature storage and has excellent emulsion stability of the treating agent. Moreover, it is providing the manufacturing method of a synthetic fiber filament yarn and synthetic fiber using the same.
- PO is an oxypropylene group
- EO represents an oxyethylene group
- [(PO) b / (EO) c ] is a polyoxyalkylene group formed by randomly adding b moles of PO and c moles of EO.)
- R 1 represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure.
- R 2 has 1 carbon atom.
- PO represents an oxypropylene group
- EO represents an oxyethylene group
- [(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.
- the weight ratio of the polyoxyalkylene alkyl ether in the non-volatile content of the treating 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.
- the weight ratio of the polyoxyalkylene alkyl ether ester in the non-volatile content of the treating agent is preferably 1 to 50% by weight.
- the treatment agent of the present invention preferably contains the polyoxyalkylene alkyl ether and the polyoxyalkylene alkyl ether ester.
- an alkyl sulfonate salt an alkyl phosphate salt, an alkyl succinate salt, an alkyl sulfate salt, a fatty acid soap and an alkyl imidazolinium salt.
- the synthetic fiber is a polyester fiber, a polyamide fiber or a polypropylene fiber.
- the treating agent for synthetic fibers 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, drawing 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.
- 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.
- the average added mole number a in the general formula (1) is not particularly limited, but is usually 1 to 10 moles, preferably 2 to 6 moles, and more preferably 3 to 4 moles.
- the average added mole number a in the general formula (1) is 1 to 10 mol, the hydrophilicity increases, so that the stability of the synthetic fiber treating 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 usually 1 to 10 mol, preferably 2 to 8 mol, more preferably 3 to 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 moles, preferably 2 to 30 moles, more preferably 3 to 20 moles, most preferably 4 to 10 moles. 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.
- 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.
- 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 device HLC-8220GPC manufactured by Tosoh Corporation.
- the method for producing the polyoxyalkylene alkyl ether of the present invention has the following general formula (A): ROH (A)
- the process of supplying only ethylene oxide hereinafter referred to as the third stage
- 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 monohydric alcohols 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.
- 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 number of carbon atoms 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.
- Straight chain alcohols such as diol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, and triacosanol; 2-ethylhexanol, 2 -Propyl heptanol, 2-butyl octanol, 1-methyl heptadecanol, 2-hexyl octanol, 1-hex Branched alkanols such as luheptanol, isodecanol, isotridecanol, 3,5,5-trimethylhexanol; hexenol, heptenol, octen
- alcohols may be used alone or in combination of two or more.
- Specific examples of alcohol products are not particularly limited.
- 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.
- 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
- 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, sodium orthosilicate, and zeolite; Al-Mg complex oxides such as calcined aluminum hydroxide / magnesium, magnesium 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.
- the amount of the catalyst used is not particularly limited, but is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 8 parts by weight, and still more preferably 0.01 to 6 parts by weight with respect to 100 parts by weight of the alcohol. 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.
- 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.
- the dehydration process is performed by, for example, a heat dehydration method, a vacuum dehydration method, a vacuum dehydration method, or the like.
- the production form is not particularly limited, and may be a continuous type or a batch type.
- reaction container For example, the tank-type reaction container provided with the stirring blade, the micro reactor, etc. can be mentioned.
- a stirring blade A max blend blade, a tornado blade, a full zone blade, etc. can be mentioned.
- 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.
- 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.
- 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 0 to 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 the gauge pressure is preferably 0 to 5.0 MPa, more preferably 0 to 4.0 MPa, still more preferably 0 to 3.0 MPa, particularly preferably 0 to 2.0 MPa, most preferably 0.1 to 1.0 MPa.
- the pressure in the reaction vessel during the addition reaction is less than 0 MPa, the reaction rate may be slow.
- 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 to 180 ° C. 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.
- 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, 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.
- 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.
- an inert solvent can be used as necessary.
- a solid alcohol such as triaconsenol
- an inert solvent is used, a heat removal effect can be expected.
- inert solvent 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.
- 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
- methyl ethyl ketone examples include 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. 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 the 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 the 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.
- 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.
- an acid such as hydrochloric acid, phosphoric acid, acetic acid, lactic acid, citric acid, succinic acid, acrylic acid, methacrylic acid, etc.
- the neutralization of the catalyst is preferably carried out in an inert gas atmosphere.
- 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.
- 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.
- 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.
- the method for solid-liquid separation of the neutralized salt produced by neutralization include filtration and centrifugation.
- 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.
- Centrifugation may be performed, for example, using a centrifuge such as a decanter or a centrifugal clarifier. If necessary, about 1 to 30 parts by weight of water can be added to 100 parts by weight of the liquid before solid-liquid separation.
- the filter aid is not particularly limited.
- 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.)
- 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.
- 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.
- 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 conditions for removing the catalyst are not particularly limited.
- the adsorbent is stirred and mixed at a temperature of 20 to 140 ° C. for 5 to 120 minutes under any of reduced pressure, normal pressure, or pressurized pressure, and then the catalyst is removed.
- eliminate are mentioned.
- a water-soluble solvent such as water or a lower alcohol represented by ethanol
- 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.
- 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.
- 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) 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.
- 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.
- 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).
- R 1 O- (EO) e - [(PO) f / (EO) g] - (EO) h -CO-R 2 (2)
- R 1 represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure.
- R 2 has 1 carbon atom.
- PO represents an oxypropylene group
- EO represents an oxyethylene group
- [(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.
- the kinematic viscosity of the polyoxyalkylene alkyl ether ester represented by the general formula (2) preferably 10 ⁇ 100 mm 2 / s, more preferably 10 ⁇ 80 mm 2 / s, more preferably 10 ⁇ 50mm 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
- 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.
- the weight ratio of the polyoxyalkylene alkyl ether in the non-volatile content of the treatment agent is preferably 3 to 70% by weight, more preferably 5 to 65% by weight. 60% by weight is more preferred, and 15 to 55% by weight is most preferred.
- 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.
- the weight percentage 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, It is more preferably 3 to 30% by weight, and most preferably 5 to 20% by weight. 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.
- 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).
- the viscosity of a processing agent falls and it can adhere a processing agent to a fiber uniformly.
- the weight ratio of polyoxyalkylene alkyl ether to 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.
- 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.
- 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.
- a false-textured yarn Draw Texting Yarn; hereinafter abbreviated as DTY
- a friction false twist treatment agent to produce a partially oriented yarn (Partially Oriented Yarn; hereinafter abbreviated as POY)
- a heating device It is obtained by heating the yarn with a heater
- drawing it it is obtained by heating the yarn with a heater
- 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.
- 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.
- 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
- the treatment agent for synthetic fibers of the present invention may contain a lubricant, an emulsifier, a penetrating agent, an antistatic agent, and the like as necessary within a range not impairing the effects of the present 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.
- lubricant there are no particular limitations on the lubricant, and known lubricants can be employed.
- 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.
- an emulsifier and a penetrant A well-known thing is employable.
- 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.
- 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 the 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.
- the antistatic agent is not particularly limited, and known ones can be used.
- 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;
- cationic surfactants such as amine salts, alkyl imidazolinium salts, and quaternary ammonium salts; amphoteric surfactants such as lauryl dimethyl betaine and stearyl dimethyl betaine.
- 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.
- lubricants such as lubricants, emulsifiers, penetrants, antistatic agents, components such as antioxidants, preservatives, rust inhibitors, and antifoaming agents 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.
- the treatment agent for synthetic fibers of the present invention preferably further contains an appearance modifier.
- 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.
- the appearance modifier is not particularly limited, and known ones can be used.
- 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.
- 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.
- the treatment agent is usually produced by mixing the constituent components described above in an arbitrary order.
- 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 adhesion amount of the non-volatile content of the treating agent for synthetic fibers is preferably 0.1 to 1.0% by weight, more preferably 0.2 to 0.8% by weight with respect to the (raw material) synthetic fiber filament. More preferred is 3 to 0.6% by weight.
- 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.
- (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 twist processing of synthetic fibers such as polyester fibers, polyamide fibers, and polypropylene fibers.
- 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.
- polyester (PLA) as a structural unit
- examples of polyamide fibers include nylon 6 and nylon 66
- polypropylene fibers include polypropylene.
- 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.
- the method of false twisting A well-known method is employable. For example, the method etc. which were described in WO2009 / 034692 are mentioned.
- the false twisting conditions 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.
- a hot plate contact heating type false twisting machine is one in which the heater temperature is 160 ° C. to 230 ° C., the heater length is 150 cm to 250 cm, and the synthetic fiber filament yarn 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.
- 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 ⁇ 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.
- 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
- 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.
- polyoxyalkylene alkyl ether esters POAEE-13 to 18 and POAEE-D 13 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.
- a reaction vessel equipped with a stirring blade, a heating device, and a dehydrating tube was charged with 775 g of polyoxyalkylene alkyl ether and 248 g of lauric acid, and an esterification reaction was carried out at 180 to 210 ° C. for 8 hours.
- polyoxyalkylene alkyl ether ester POAEE-13
- ⁇ Production Examples 14 to 20 and Production Comparative Examples 13 to 20> POAEE-14 to 20 and POAEE-D 13 to 20 were the same as in Production Example 13 except that the alcohols in each example described in Tables 5 to 6, the number of moles of ethylene oxide and propylene oxide added, and the fatty acid were changed.
- the kinematic viscosity of the polyoxyalkylene alkyl ether ester was measured as follows.
- 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.
- aqueous emulsion in which the weight ratio of nonvolatile content was 10% by weight.
- 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.
- 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
- ⁇ 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 a treating agent for synthetic fibers 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% Uniform transparent transmittance even after standing at 40 ° C. for 1 week Over 95 to less than 100%: Slightly blue-white transparent transmittance after standing at 40 ° C. for 1 week 95% or less: White turbid state after standing at 40 ° C. for 1 week
- ⁇ 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 ⁇ : Some staining spots are observed ⁇ : Many staining spots are observed
- Examples 2 to 12 Comparative Examples 1 to 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.
- 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
- Example 13 to 18, Comparative Examples 13 to 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.
- Example 19 to 30, Comparative Examples 19 to 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.
- 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. .
- the treatment agent can be uniformly attached to the fiber, so that there are few false twisting yarns and less fluff.
- Comparative Examples 19 to 30 are selected from the group consisting of 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. 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.
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Abstract
Description
RO-(EO)a-[(PO)b/(EO)c]-(EO)d-H (1)
(但し、式(1)中、Rは炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。POはオキシプロピレン基、EOはオキシエチレン基を示す。a、b、cおよびdは、各々の平均付加モル数を示し、a=1~10、b=1~10、c=1~10、d=1~40である。[(PO)b/(EO)c]はbモルのPOとcモルのEOとがランダム付加してなるポリオキシアルキレン基である。)
R1O-(EO)e-[(PO)f/(EO)g]-(EO)h-CO-R2 (2)
(但し、式(2)中、R1は炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。R2は炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。POはオキシプロピレン基、EOはオキシエチレン基を示す。e、f、gおよびhは、各々の平均付加モル数を示し、e=1~10、f=1~10、g=1~10、h=1~40である。[(PO)f/(EO)g]はfモルのPOとgモルのEOとがランダム付加してなるポリオキシアルキレン基である。) 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 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)
(In the formula (2), R 1 represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of 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, and 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.)
まず、下記一般式(1)で表されるポリオキシアルキレンアルキルエーテルについて説明する。
RO-(EO)a-[(PO)b/(EO)c]-(EO)d-H (1)
(但し、Rは炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。POはオキシプロピレン基、EOはオキシエチレン基を示す。a、b、cおよびdは、各々の平均付加モル数を示し、a=1~10、b=1~10、c=1~10、d=1~40である。[(PO)b/(EO)c]はbモルのPOとcモルのEOとがランダム付加してなるポリオキシアルキレン基である。) [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.
なお、重量平均分子量は、東ソー(株)製高速ゲルパーミエーションクロマトグラフィー装置HLC-8220GPCを用い、試料濃度3mg/ccで、昭和電工(株)製分離カラムKF-402HQ、KF-403HQに注入し、RI検出器で測定した最大ピーク値のことをいう。 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 device HLC-8220GPC manufactured by Tosoh Corporation. The maximum peak value measured by the RI detector.
一般式(1)で表されるポリオキシアルキレンアルキルエーテルの製造方法としては、特に限定はなく、公知の方法を採用できる。例えば、本発明のポリオキシアルキレンアルキルエーテルの製造方法は、下記一般式(A):
ROH (A)
で表されるアルコールに対して、エチレンオキサイドのみを供給して付加反応させる工程(以後、1段目という)と、1段目の後にエチレンオキサイドおよびプロピレンオキサイドを供給してランダム付加反応させる工程(以後、2段目という)と、最後にエチレンオキサイドのみを供給する工程(以後、3段目という)を、1段目から3段目まで連続して行ってもよいし、一度各工程で得られた付加物を回収して、引き続き反応を行っても良い。 [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.
これらの中でも、ブタノール、オクタノール、ノナオール、デカノール、ドデカノール、トリデカノール、テトラデカノール、ヘキサデカノール、オクタデカノール、ノナデカノール、オクタデセノールが好ましく、ブタノール、オクタノール、デカノール、ドデカノール、トリデカノール、テトラデカノール、ヘキサデカノール、オクタデカノール、オクタデセノールが好ましい。 Examples of the monohydric alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, and heptadecanol. Straight chain alcohols such as diol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, and triacosanol; 2-ethylhexanol, 2 -Propyl heptanol, 2-butyl octanol, 1-methyl heptadecanol, 2-hexyl octanol, 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, heptacenol, 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.
一般式(1)で表されるポリオキシアルキレンアルキルエーテルの製造方法では、アルコール、触媒等の原料を反応容器に仕込み、そしてその反応容器に対して脱ガス処理や脱水処理が行われると好ましい。脱ガス処理は、たとえば、減圧脱気方式、真空脱気方式等で行われる。また、脱水処理は、たとえば、加熱脱水方式、減圧脱水方式、真空脱水方式等で行われる。 The amount of the catalyst used is not particularly limited, but is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 8 parts by weight, and still more preferably 0.01 to 6 parts by weight with respect to 100 parts by weight of the alcohol. 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.
一般式(1)で表されるポリオキシアルキレンアルキルエーテルの製造方法では、付加反応を減圧状態から開始してもよいし、大気圧の状態から開始してもよいし、さらには加圧状態から開始してもよい。大気圧状態や加圧状態から開始する場合には不活性ガスの雰囲気下で行われることが好ましい。付加反応が不活性ガスの雰囲気下で行われるとエチレンオキサイドやプロピレンオキサイド等のアルキレンオキサイドと酸素との副反応等に起因して生成する不純物を十分に除去することが可能となり、また、安全性の観点からも有用であるので好ましい。不活性ガスとしては特に限定はないが、たとえば、窒素ガス、アルゴンガス、二酸化炭素ガス等が挙げられる。これらの不活性ガスは1種または2種以上を併用してもよい。不活性ガスの雰囲気下における反応容器内の酸素濃度については、特に限定はないが、好ましくは10体積%以下、より好ましくは5体積%以下、さらに好ましくは3体積%以下、特に好ましくは1体積%以下、最も好ましくは0.5体積%以下である。反応容器内の酸素濃度が10体積%超であると不純物を十分に除去できないことがあり、また安全性の観点からも好ましくないことがある。 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.
エチレンオキサイド、プロピレンオキサイドの付加反応の反応温度としては特に限定はないが、好ましくは70~240℃、より好ましくは80~220℃、さらに好ましくは90~200℃、特に好ましくは100~190℃、最も好ましくは110~180℃である。反応温度が70℃未満であると、付加反応が十分に進行しないことがある。一方、反応温度が240℃超であると、得られるポリオキシアルキレンアルキルエーテルの着色およびポリオキシアルキレンアルキルエーテル中のポリオキシアルキレン基の分解が促進されることがある。 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 the gauge pressure is preferably 0 to 5.0 MPa, more preferably 0 to 4.0 MPa, still more preferably 0 to 3.0 MPa, particularly preferably 0 to 2.0 MPa, most preferably 0.1 to 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 to 180 ° C. 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.
エチレンオキサイド、プロピレンオキサイドの供給が完了すると反応容器内の内圧はエチレンオキサイド、プロピレンオキサイドが消費されることにより徐々に低下していく。エチレンオキサイド、プロピレンオキサイドの付加反応は内圧の変化が認められなくなるまで継続することが好ましい。エチレンオキサイド、プロピレンオキサイドの付加反応は一定時間における内圧の変化が認められなくなった時点で反応を終了する。必要に応じて加熱減圧操作等を実施し、未反応のエチレンオキサイド、プロピレンオキサイドを回収してもよい。 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, 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.
不活性溶媒としては特に限定はないが、たとえば、ジエチルエーテル、エチレングリコールジメチルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類;ジエチレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート等のエステル類;アセトン、メチルイソブチルケトン、メチルエチルケトン等のケトン類;スルホラン、ジメチルスルホンホキシド等のスルホン類;ジクロロメタン、クロロホルム等のハロゲン化炭化水素類;ベンゼン、トルエン、キシレン等の芳香族炭化水素類;ペンタン、ヘキサン、シクロペンタン、シクロヘキサン等の脂肪族炭化水素類等が挙げられ、1種または2種以上を併用してもよい。なかでも、芳香族炭化水素類が好ましく、より好ましくはトルエンである。 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.
エチレンオキサイド、プロピレンオキサイドの付加反応の終了後は、必要に応じて、触媒を中和および/または除去したり、不活性溶媒を除去したりすると好ましい。 The amount of the inert solvent used is not particularly limited, but when used to dissolve the 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 the 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.
触媒の中和は不活性ガスの雰囲気下で行われると好ましい。不活性ガスとしては、特に限定はないが、たとえば、窒素ガス、アルゴンガス、二酸化炭素ガス等が挙げられ、1種または2種以上を併用してもよい。 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.
触媒の中和により、上記付加反応により得られる反応生成物のpHが好ましくは4~10に調整され、さらに好ましくは5~8、特に好ましくは6~8である。また、触媒中和の際に、必要に応じて、キノン類やフェノール類等の酸化防止剤を併用することもできる。 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.
濾過助剤としては、特に限定はないが、たとえば、セライト、ハイフロースーパーセル、セルピュアの各シリーズ(Advanced Minerals Corporation製)、シリカ#645、シリカ#600H、シリカ#600S、シリカ#300S、シリカ#100F(中央シリカ社製)、ダイカライト(グレフコ社製)等の珪藻土;ロカヘルプ(三井金属鉱業社製)、トプコ(昭和化学社製)等のパーライト;KCフロック(日本製紙社製)、ファイブラセル(Advanced Minerals Corporation製)等のセルロース系濾過助剤;サイロピュート(富士シリシア化学社製)等のシリカゲル等が挙げられる。これらの濾過助剤は、1種または2種以上を併用してもよい。 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 elevated pressure at a temperature 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. If necessary, about 1 to 30 parts by weight of water can be added to 100 parts by weight of the liquid before solid-liquid separation. 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.
触媒の除去については、特に限定はないが、たとえば、触媒を吸着剤に吸着させた後、固液分離する方法が好ましい。 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.
吸着剤の使用量は、たとえば、触媒100重量部に対して、好ましくは100~5000重量部、より好ましくは300~3000重量部である。 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.
触媒の除去後の残存量については、特に限定はないが、好ましくは300ppm以下、より好ましくは200ppm以下、さらに好ましくは100ppm以下、特に好ましくは50ppm以下、最も好ましくは20ppm以下である。 The conditions for removing the catalyst 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 of reduced pressure, normal pressure, or pressurized pressure, and then the catalyst is removed. 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 the adsorbent and passing the reaction mixture at a temperature of 20 to 140 ° C. to adsorb the catalyst. The method etc. which remove | eliminate are mentioned. At this time, if necessary, 1 to 20 parts by weight of a water-soluble solvent such as water or a 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.
なお、触媒の中和および/または除去と不活性溶媒の除去とを行う場合、各工程の順序は特に限定はなく、たとえば、触媒の中和および/または除去を行った後に、不活性溶媒の除去を行うと、得られるポリオキシアルキレンアルキルエーテルの精製効率に優れるために好ましい。 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.
一般式(1)で表されるポリオキシアルキレンアルキルエーテルの1重量%水溶液の曇点は、60℃以上が好ましく、70℃以上がより好ましく、75℃以上がさらに好ましく、この順に処理剤のエマルション安定性が向上する。好ましい上限値は100℃未満である。60℃未満では、処理剤のエマルション安定性が悪くなる可能性がある。 [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.
一般式(1)で表されるポリオキシアルキレンアルキルエーテルの融点が15℃以下であることが好ましく、10℃以下がより好ましく、8℃以下がさらに好ましく、5℃以下が最も好ましく、この順に繊維用処理剤の低温安定性が向上する。好ましい下限値は-30℃であり、より好ましい下限値は-20℃であり、更に好ましい下限値は-10℃である。15℃超では、貯蔵条件によっては(例えば低温となる冬場)処理剤の成分が分離する可能性がある。 [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).
次に、下記一般式(2)で表されるポリオキシアルキレンアルキルエーテルエステルについて説明する。
R1O-(EO)e-[(PO)f/(EO)g]-(EO)h-CO-R2 (2)
(但し、式(2)中、R1は炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。R2は炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。POはオキシプロピレン基、EOはオキシエチレン基を示す。e、f、gおよびhは、各々の平均付加モル数を示し、e=1~10、f=1~10、g=1~10、h=1~40である。[(PO)f/(EO)g]はfモルのPOとgモルのEOとがランダム付加してなるポリオキシアルキレン基である。) [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)
(In the formula (2), R 1 represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of 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, and 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.)
一般式(2)で表されるポリオキシアルキレンアルキルエーテルエステルの動粘度は、10~100mm2/sが好ましく、10~80mm2/sがより好ましく、10~50mm2/sが更に好ましく、20~40mm2/sが最も好ましい。
10mm2/s未満では、処理剤の粘度が過剰に低くなり、給油工程で処理剤の飛散が発生する可能性がある。また、100mm2/s以上では、処理剤の粘度が高くなり、合成繊維フィラメント糸条への拡展性が悪化するため、繊維への付着性が劣る可能性がある。 [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 10 ~ 100 mm 2 / s, more preferably 10 ~ 80 mm 2 / s, more preferably 10 ~ 50mm 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.
本発明の合成繊維用処理剤には、一般式(1)で表されるポリオキシアルキレンアルキルエーテルおよび下記一般式(2)で表されるポリオキシアルキレンアルキルエーテルエステルからなる群より選ばれる少なくとも1種が必須に含有される。このような成分が必須に含有されることにより、本発明の効果が発揮される。
前記ポリオキシアルキレンアルキルエーテルを必須に含有する場合、処理剤の不揮発分に占める、ポリオキシアルキレンアルキルエーテルの重量割合は、3~70重量%が好ましく、5~65重量%がより好ましく、10~60重量%が更に好ましく、15~55重量%が最も好ましい。3重量%未満では、処理剤のエマルションの曇点が低く分離する可能性があり、70重量%超では、平滑性や集束性が劣る可能性がある。
なお、本発明における不揮発分とは、処理剤を105℃で熱処理して溶媒等の揮発分を除去し、恒量に達した時の絶乾成分をいう。 [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 ratio of the polyoxyalkylene alkyl ether in the non-volatile content of the treatment agent is preferably 3 to 70% by weight, more preferably 5 to 65% by weight. 60% by weight is more preferred, and 15 to 55% by weight is most preferred. 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.
これら両成分を併用する場合の、ポリオキシアルキレンアルキルエーテルとポリオキシアルキレンアルキルエーテルエステルとの重量比(ポリオキシアルキレンアルキルエーテル:ポリオキシアルキレンアルキルエーテルエステル)は、20:80~99:1が好ましく、40:60~95:5がより好ましく、55:45~90:10がさらに好ましい。 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.
一般に仮撚り加工糸(Draw Texturing Yarn;以下DTYと略す)は、摩擦仮撚り用処理剤を付与して部分配向糸(Partially Oriented Yarn;以下POYと略す)を生産した後、次に加熱装置(ヒーター)により糸条を加熱し、仮撚り装置にて糸条に撚りを与えながら延伸することで得られる。
この時、摩擦仮撚り用処理剤の付与量が多いほど、仮撚り加工の工程で発生する毛羽・断糸・白粉・染色斑の問題を抑えられるが、加熱装置(ヒーター)上への摩擦仮撚り用処理剤の脱落量が増大する。そのため、摩擦仮撚り用処理剤によってヒーターが汚れてしまい、ヒーター清掃のために多大な時間と労力を要し、生産性の低下につながってしまう。
よって、合成繊維用処理剤の付与量が通常、(原料)合成繊維に対して、1.0重量%であるのに対して、摩擦仮撚り用処理剤の付与量は、0.25~0.80重量%と低く設計されている。以上の事から、摩擦仮撚り用処理剤は、その合成繊維への付与量が低いため、なお更繊維への均一付着性が重要であることが分かる。 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.
これらの潤滑剤は必要に応じて2種類以上のものを適宣併用することができる。処理剤の不揮発分に占める潤滑剤の重量割合は特に限定はないが、0~30重量%が好ましく、0~10重量%がさらに好ましい。 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.
本発明の合成繊維用処理剤の製造方法については、特に限定なく、公知の方法を採用することができる。処理剤は、通常、構成する前記の各成分を任意の順番で混合することによって製造される。 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.
本発明の合成繊維フィラメント糸条は、本発明の合成繊維用処理剤を(原料)合成繊維フィラメント糸状に付着させたものであり、合成繊維の仮撚り加工糸の生産において、仮撚り加工の工程で発生する毛羽・断糸・白粉・染色斑の加工欠点を低減させることができ、ヒーターの清掃周期も延長させることができる。合成繊維用処理剤の不揮発分の付着量は、(原料)合成繊維フィラメントに対して、0.1~1.0重量%が好ましく、0.2~0.8重量%がより好ましく、0.3~0.6重量%がさらに好ましい。
(原料)合成繊維フィラメントに本発明の合成繊維用処理剤を付与する方法としては、特に限定はなく、公知の方法を採用することできる。通常、合成繊維フィラメントの紡糸工程または延伸工程で付与され、(原料)合成繊維フィラメントに対して、不揮発分のみからなる処理剤、不揮発分を低粘度鉱物油で希釈した処理剤、または水中に不揮発分を乳化した水系エマルション処理剤をローラーオイリング、ガイドオイリング等で給油する方法等が挙げられる。 [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 adhesion amount of the non-volatile content of the treating agent for synthetic fibers is preferably 0.1 to 1.0% by weight, more preferably 0.2 to 0.8% by weight with respect to the (raw material) synthetic fiber filament. More preferred is 3 to 0.6% by weight.
(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.
本発明の仮撚り加工糸の製造方法は、前述の本発明の合成繊維用処理剤を付着させた合成繊維フィラメント糸条を加熱して、延伸し、仮撚り加工する工程を含むものであり、仮撚り加工の工程で発生する毛羽・断糸・白粉・染色斑の加工欠点を低減させることができ、ヒーターの清掃周期も延長させることができる。仮撚り加工の方法としては、特に限定はなく、公知の方法を採用できる。例えば、WO2009/034692号公報に記載された方法等が挙げられる。
仮撚り加工条件としては、特に制限しないが、より効果を発揮できる点から、熱源の熱板に直接合成繊維フィラメント糸条を接触させて加熱する接触タイプ(熱板接触加熱方式)の仮撚り加工機を用いて仮撚り加工を行うことが好ましい。かかる熱板接触加熱方式の仮撚り加工機とは、ヒーター温度が160℃~230℃、ヒーター長は150cm~250cmであり、合成繊維フィラメント糸状が、ヒータープレートの表面と接触して走行するもののことである。加工速度は、通常500~1000m/min、好ましくは600~800m/minである。 [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 is one in which the heater temperature is 160 ° C. to 230 ° C., the heater length is 150 cm to 250 cm, and the synthetic fiber filament yarn 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.
<製造例1>
撹拌、温度調節が可能で、アルキレンオキサイドチャージタンク、窒素供給管、圧力調整バルブの付いた2Lのオートクレーブ内に、アルコールとしてC12~13アルコール193gと、アルカリ触媒である苛性カリ0.9gを仕込んだ。オートクレーブ内を窒素置換した後、撹拌しながら100~110℃にて1時間脱水操作を行った。次に、所望のモル比率となるよう、1段目としてエチレンオキサイドを132g、2段目として、プロピレンオキサイド116gとエチレンオキサイド132gの混合物を、3段目としてエチレンオキサイドを264g、ゲージ圧力0.0~0.4MPa、反応温度140~150℃で投入して、約8時間付加重合反応を行った。その後得られたポリオキシアルキレンアルキルエーテルを乳酸1.4gで中和処理し回収した。このようにして、ポリオキシアルキレンアルキルエーテル(POA-1)を得た。
<製造例2~12および製造比較例1~12>
表1~4に記載の各例のアルコールと、エチレンオキサイドおよびプロピレンオキサイドの付加モル数を変更した以外は、製造例1と同様にして、POA-2~12およびPOA-D1~12を得た。ポリオキシアルキレンアルキルエーテルの1重量%水溶液の曇点およびポリオキシアルキレンアルキルエーテルの融点を次のように測定した。 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 ~ 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 to 12 and Production Comparative Examples 1 to 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 addition of the alcohols of each example described in Tables 1 to 4 and ethylene oxide and propylene oxide was 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.
ポリオキシアルキレンアルキルエーテルの1重量%水溶液を調製した。次いで、加温して一旦曇点試験液を濁らせ、濁りが無くなる温度を曇点とした。
<ポリオキシアルキレンアルキルエーテルの融点>
ポリオキシアルキレンアルキルエーテルを規定寸法の両端開管の毛細管にとり、これを温度計の水銀球に密着させ、空気浴中で徐々に昇温し、試料が溶融して透明となった時の温度を融点とした。 <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.
<製造例13>
表5に記載のアルコールと、エチレンオキサイドおよびプロピレンオキサイドの付加モル数を変更した以外は、製造例1と同様にして、ポリオキシアルキレンアルキルエーテルを得た。得られたポリオキシアルキレンアルキルエーテルを、次のようにして脂肪酸とエステル化反応を行った。
撹拌翼、加熱装置、脱水管を付した反応容器中に、ポリオキシアルキレンアルキルエーテルを775g、ラウリン酸248gを仕込み、180~210℃にて8時間エステル化反応を行った。このようにして、ポリオキシアルキレンアルキルエーテルエステル(POAEE-13)を得た。
<製造例14~20および製造比較例13~20>
表5~6に記載の各例のアルコールと、エチレンオキサイドおよびプロピレンオキサイドの付加モル数と、脂肪酸を変更した以外は、製造例13と同様にして、POAEE-14~20およびPOAEE-D13~20を得た。ポリオキシアルキレンアルキルエーテルエステルの動粘度を次のように測定した。 Next, polyoxyalkylene alkyl ether esters POAEE-13 to 18 and POAEE-D 13 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.
A reaction vessel equipped with a stirring blade, a heating device, and a dehydrating tube was charged with 775 g of polyoxyalkylene alkyl ether and 248 g of lauric acid, and an esterification reaction was carried out 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-D 13 to 20 were the same as in Production Example 13 except that the alcohols in each example described in Tables 5 to 6, the number of moles of ethylene oxide and propylene oxide added, and the fatty acid were changed. Got. The kinematic viscosity of the polyoxyalkylene alkyl ether ester was measured as follows.
キャノンフェンスケ粘度計に試料を約10g入れ、25℃に温度調節した恒温槽中に15分間保持する。その後、試料が粘度計の標線間を通過する流出時間(秒)を測定し、粘度計係数を乗じた値を動粘度とした。 <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.
次に、表7に記載の配合成分を混合撹拌して、実施例1の合成繊維用処理剤を調製した。その結果を表7に示す。 <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.
熱板接触加熱方式である仮撚り加工機の延伸仮撚り条件
仮撚り加工機:帝人製機(株)製 HTS-15V
加工速度:600m/min
延伸比(DR):1.60
撚り掛け装置:3軸ディスク摩擦方式 1-5-1
(ガイドディスク1枚-ワーキング(ポリウレタン)ディスク5枚-ガイドディスク1枚)
ディスク速度/糸速度(D/Y):1.8
オーバーフィード率:3%
第一ヒーター(加撚側)温度:200℃
第二ヒーター(解撚側)温度:室温
加工日数:10日間 <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
ポリオキシアルキレンアルキルエーテルを配合した、実施例および比較例に記載の合成繊維用処理剤を、10℃、5℃、-5℃の雰囲気下で1週間放置し、処理剤の外観を目視で判定した。
◎ : -5℃、1週間放置後でも均一透明
○ : 5℃、1週間放置後でも均一透明
△ : 5℃、1週間放置後に分離
× : 10℃、1週間放置後に分離 <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, uniform transparent even after standing for 1 week △: 5 ° C, separated after standing for 1 week ×: 10 ° C, separated after standing for 1 week
実施例および比較例で調製された合成繊維用処理剤のエマルション安定性は、エマルションの透過率で評価した。透過率は合成繊維用処理剤の10%濃度エマルションを、40℃の雰囲気下で1週間放置し、(株)日立製作所製分光光度計
U-1900Spectrophotometerにて測定した。測定条件は、波長750nm、測定温度25℃に規定した。
透過率が95%超を合格とした。
透過率 100% : 40℃、1週間放置後でも均一透明
透過率 95超~100%未満 : 40℃、1週間放置後にやや青白色透明
透過率 95%以下 : 40℃、1週間放置後に白濁状態 <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 a treating agent for synthetic fibers 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%: Uniform transparent transmittance even after standing at 40 ° C. for 1 week Over 95 to less than 100%: Slightly blue-white transparent transmittance after standing at 40 ° C. for 1 week 95% or less: White turbid state after standing at 40 ° C. for 1 week
延伸仮撚り加工を行った後、断糸回数を以下のように評価した。断糸回数が多いほど、毛羽も発生しやすくなる。
◎:0回
○:1~2回
△:3~4回
×:5回以上 <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 to 2 times △: 3 to 4 times ×: 5 times or more
延伸仮撚り加工を行った後、ヒーターの汚染状況を目視により、以下のように評価した。
◎:ヒーターが汚れていない。
○:ヒーターが一部分のみ汚れている。
△:ヒーターが半分ほど汚れている。
×:ヒーターが全部汚れている。 <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.
延伸仮撚り加工を行った後、仮撚りディスクと、その周辺の白粉発生量を目視により、以下のように評価した。
◎:10日間加工後に白粉なし。
○:10日間加工後に一部白粉あり。
△:5日間加工後白粉が発生、堆積。
×:加工開始から白粉が発生、堆積。 <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.
延伸仮撚り加工を行った後、得られた加工糸を(株)小池機械製作所製の丸編み機で筒編みを作製し、ポリエステル編地の染色処理を行った。得られた編地の染色性を、以下のように評価した。
◎:染色斑無し
△:染色斑が少し認められる
×:染色斑が多く認められる <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
表7および表8に記載の各例の配合成分に変更して合成繊維用処理剤を調製する以外は実施例1と同様にして、評価した。その結果を表7および表8に示す。なお、表7~12中のポリエーテル1およびポリエーテル2は以下のポリエーテルである。
ポリエーテル1 : PO/EO=50/50、重量平均分子量5000
ポリエーテル2 : PO/EO=50/50、重量平均分子量2000 (Examples 2 to 12, Comparative Examples 1 to 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
一方、比較例1~12では、一般式(1)で表されるポリオキシアルキレンアルキルエーテルを含有していないために、実施例で得られたような効果は得られない。 As can be seen from Tables 7 and 8, in Examples 1 to 12, if the treating agent for synthetic fibers containing the polyoxyalkylene alkyl ether represented by the general formula (1) of the present invention is used, the 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, Comparative Examples 1 to 12 do not contain the polyoxyalkylene alkyl ether represented by the general formula (1), and thus the effects as obtained in the examples cannot be obtained.
表9に記載の各例の配合成分に変更して合成繊維用処理剤を調製する以外は実施例1と同様にして、評価した。その結果を表9に示す。 (Examples 13 to 18, Comparative Examples 13 to 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.
一方、比較例13~18では、一般式(2)で表されるポリオキシアルキレンアルキルエーテルエステルを含有していないために、実施例で得られたような効果は得られない。 As can be seen from Table 9, in Examples 13 to 18, if the treating agent for synthetic fibers containing the polyoxyalkylene alkyl ether ester represented by the general formula (2) of the present invention is used, 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), and thus the effects obtained in the examples cannot be obtained.
表10および表11に記載の各例の配合成分に変更して合成繊維用処理剤を調製する以外は実施例1と同様にして、評価した。その結果を表10および表11に示す。 (Examples 19 to 30, Comparative Examples 19 to 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.
一方、比較例19~30では、本願発明の一般式(1)で表されるポリオキシアルキレンアルキルエーテル及び本願発明の一般式(2)で表されるポリオキシアルキレンアルキルエーテルエステルからなる群より選ばれる少なくとも1種を含有していないために、実施例で得られたような効果は得られない。 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, Comparative Examples 19 to 30 are selected from the group consisting of 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. Therefore, the effects obtained in the examples cannot be obtained.
Claims (12)
- 下記一般式(1)で表されるポリオキシアルキレンアルキルエーテルおよび下記一般式(2)で表されるポリオキシアルキレンアルキルエーテルエステルからなる群より選ばれる少なくとも1種を含有する、合成繊維用処理剤。
RO-(EO)a-[(PO)b/(EO)c]-(EO)d-H (1)
(但し、式(1)中、Rは炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。POはオキシプロピレン基、EOはオキシエチレン基を示す。a、b、cおよびdは、各々の平均付加モル数を示し、a=1~10、b=1~10、c=1~10、d=1~40である。[(PO)b/(EO)c]はbモルのPOとcモルのEOとがランダム付加してなるポリオキシアルキレン基である。)
R1O-(EO)e-[(PO)f/(EO)g]-(EO)h-CO-R2 (2)
(但し、式(2)中、R1は炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。R2は炭素数1~30のアルキル基またはアルケニル基を示し、直鎖または分枝鎖のいずれの構造から構成されていてもよい。POはオキシプロピレン基、EOはオキシエチレン基を示す。e、f、gおよびhは、各々の平均付加モル数を示し、e=1~10、f=1~10、g=1~10、h=1~40である。[(PO)f/(EO)g]はfモルのPOとgモルのEOとがランダム付加してなるポリオキシアルキレン基である。) 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 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)
(In the formula (2), R 1 represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of 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, and 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.) - 前記ポリオキシアルキレンアルキルエーテルの融点が15℃以下である、請求項1に記載の合成繊維用処理剤。 The processing agent for synthetic fibers according to claim 1, wherein the polyoxyalkylene alkyl ether has a melting point of 15 ° C or lower.
- 前記ポリオキシアルキレンアルキルエーテルの1重量%水溶液の曇点が60℃以上100℃未満である、請求項1または2に記載の合成繊維用処理剤。 The processing agent for synthetic fibers according to claim 1 or 2, wherein a cloud point of a 1% by weight aqueous solution of the polyoxyalkylene alkyl ether is 60 ° C or higher and lower than 100 ° C.
- 処理剤の不揮発分に占める、前記ポリオキシアルキレンアルキルエーテルの重量割合が3~70重量%である、請求項1~3のいずれかに記載の合成繊維用処理剤。 The treatment agent for synthetic fibers according to any one of claims 1 to 3, wherein a weight ratio of the polyoxyalkylene alkyl ether to a non-volatile content of the treatment agent is 3 to 70% by weight.
- 前記ポリオキシアルキレンアルキルエーテルエステルの25℃における動粘度が10mm2/s以上100mm2/s未満である、請求項1~4のいずれかに記載の合成繊維用処理剤。 The treating agent for synthetic fibers according to any one of claims 1 to 4, wherein the polyoxyalkylene alkyl ether ester has a kinematic viscosity at 25 ° C of 10 mm 2 / s or more and less than 100 mm 2 / s.
- 処理剤の不揮発分に占める、前記ポリオキシアルキレンアルキルエーテルエステルの重量割合が1~50重量%である、請求項1~5のいずれかに記載の合成繊維用処理剤。 The treatment agent for synthetic fibers according to any one of claims 1 to 5, wherein a weight ratio of the polyoxyalkylene alkyl ether ester in a non-volatile content of the treatment agent is 1 to 50% by weight.
- 前記ポリオキシアルキレンアルキルエーテルおよび前記ポリオキシアルキレンアルキルエーテルエステルを含有する、請求項1~6のいずれかに記載の合成繊維用処理剤。 The treating agent for synthetic fibers according to any one of claims 1 to 6, comprising the polyoxyalkylene alkyl ether and the polyoxyalkylene alkyl ether ester.
- 更にアルキルスルホネート塩、アルキルホスフェート塩、アルキルサクシネート塩、アルキルサルフェート塩、脂肪酸石鹸およびアルキルイミダゾリニウム塩からなる群より選ばれる少なくとも1種を含む、請求項1~7のいずれかに記載の合成繊維用処理剤。 The synthesis according to any one of claims 1 to 7, further comprising 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. Treatment agent for textiles.
- 前記合成繊維が、ポリエステル繊維、ポリアミド繊維またはポリプロピレン繊維である、請求項1~8のいずれかに記載の合成繊維用処理剤。 The treating 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.
- 摩擦仮撚り用である、請求項1~9のいずれかに記載の合成繊維用処理剤。 The treating agent for synthetic fibers according to any one of claims 1 to 9, which is used for friction false twisting.
- 請求項1~10のいずれかに記載の合成繊維用処理剤を(原料)合成繊維フィラメント糸条に付着させた、合成繊維フィラメント糸条。 A synthetic fiber filament yarn in which the synthetic fiber treating agent according to any one of claims 1 to 10 is adhered to a (raw material) synthetic fiber filament yarn.
- 請求項11に記載の合成繊維フィラメント糸条を加熱して、延伸し、仮撚り加工する工程を含む、仮撚り加工糸の製造方法。 A method for producing a false twisted yarn, comprising a step of heating, drawing and false twisting the synthetic fiber filament yarn according to claim 11.
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WO2017150229A1 (en) * | 2016-03-04 | 2017-09-08 | 松本油脂製薬株式会社 | Synthetic fiber treatment agent and use thereof |
RU2746324C1 (en) * | 2020-03-26 | 2021-04-12 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ивановский государственный химико-технологический университет" | Composition for processing yarn from polyester fibers |
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JP5881267B1 (en) * | 2015-06-25 | 2016-03-09 | 竹本油脂株式会社 | Synthetic fiber treatment liquid and synthetic fiber treatment method |
JP5878261B1 (en) * | 2015-06-30 | 2016-03-08 | 松本油脂製薬株式会社 | Treatment agent for synthetic fiber and its use |
JP6625449B2 (en) * | 2016-03-07 | 2019-12-25 | 松本油脂製薬株式会社 | Synthetic fiber treatment agent and its use |
CN106319970B (en) * | 2015-06-30 | 2020-06-19 | 松本油脂制药株式会社 | Treating agent for synthetic fiber and use thereof |
KR102355502B1 (en) * | 2018-04-16 | 2022-02-08 | 다케모토 유시 가부시키 가이샤 | Treatment agent for synthetic fibers and synthetic fibers |
JP6386206B1 (en) * | 2018-06-15 | 2018-09-05 | 竹本油脂株式会社 | Polyolefin-based nonwoven fabric treating agent, polyolefin-based synthetic fiber, and method for treating polyolefin-based synthetic fiber |
JP7400394B2 (en) * | 2019-11-25 | 2023-12-19 | セイコーエプソン株式会社 | Defibration method and fibrous body forming method |
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