WO2016021211A1 - 合成繊維用処理剤及びその利用 - Google Patents
合成繊維用処理剤及びその利用 Download PDFInfo
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- WO2016021211A1 WO2016021211A1 PCT/JP2015/051291 JP2015051291W WO2016021211A1 WO 2016021211 A1 WO2016021211 A1 WO 2016021211A1 JP 2015051291 W JP2015051291 W JP 2015051291W WO 2016021211 A1 WO2016021211 A1 WO 2016021211A1
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N CC1CCCC1 Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
-
- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
- D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
Definitions
- the present invention relates to a treatment agent for synthetic fibers and use thereof. More specifically, the present invention relates to a synthetic fiber treating agent used in the production of synthetic fibers, a method for producing a synthetic fiber filament yarn using the treating agent, and a fiber structure including the synthetic fiber filament yarn.
- a fiber treated with a fiber oil agent is once wound up and subjected to a drawing process. Recently, a method of shortening this process and directly applying oiling yarn to a drawing process has been adopted. In this method, once trouble such as yarn breakage occurs in the drawing process, a large amount of fiber is lost. Therefore, it is necessary to avoid occurrence of trouble in the drawing process as much as possible.
- the main cause of trouble is fiber damage such as thread breakage, and in order to prevent this, a treatment agent for synthetic fibers having excellent lubricity and heat resistance is required.
- Patent Document 1 proposes a treatment agent for synthetic fibers using a phosphate anionic surfactant and a sulfonate anionic surfactant in combination.
- the heat resistance and lubricity are not sufficient to use this treatment agent in the spindle system, and heat-degraded oil component etc. accumulates in the drawing roll and friction increases with time.
- Patent Document 1 proposes a treatment agent in which a specific ester and an antioxidant are used in combination with the anionic surfactant.
- satisfactory heat resistance cannot be obtained under severe spinning conditions.
- Patent Document 2 uses an ester of a polyhydric alcohol, an ester of a carboxylic acid having a thioether group and an alcohol, a secondary sulfonate, an alkyl phosphate, and a hindered phenol antioxidant.
- Treatment agents have been proposed.
- this treatment agent is used for fluff and thread breakage caused by roll dirt, which has not been a problem until now due to improvements in productivity such as high strength, low shrinkage, and high speed. Even if it was, it was not improved.
- the antioxidant described in Patent Document 2 is used, there is a defect that the fiber is often discolored during storage of the fiber.
- An object of the present invention is a synthetic fiber treating agent that is used when producing synthetic fibers and can reduce roll stains and has excellent heat resistance, a method for producing a synthetic fiber filament yarn using the treating agent, and the producing method It is providing the fiber structure containing the synthetic fiber filament yarn obtained by.
- the raw material containing the organic sulfonic acid compound represented by the general formula (1) contains a large amount of sodium sulfate and sodium chloride, and 2) the treatment agent.
- the synthetic fiber treatment agent of the present invention contains the smooth component (A) and the organic sulfonic acid compound (B) represented by the following general formula (1), and occupies the non-volatile content of the treatment agent.
- the weight ratio of the acid compound (B) is 1.25 to 12% by weight
- the weight ratio of sulfate ion (SO 4 2 ⁇ ) detected from the non-volatile content of the treatment agent by ion chromatography is 200 ppm or less
- chlorine This is a synthetic fiber treating agent having an ion (Cl ⁇ ) weight ratio of 200 ppm or less.
- M is a hydrogen atom, an alkali metal, an ammonium group or an organic amine group.
- the weight ratio of the smooth component (A) in the treating agent is preferably 20 to 70% by weight.
- the weight ratio of the organic sulfonic acid compound (B) in the nonvolatile content of the treating agent is preferably 1.25 to 7% by weight.
- the treatment agent of the present invention further contains an organophosphate compound (C), and the weight ratio of phosphate ions (PO 4 3 ⁇ ) detected from the non-volatile content of the treatment agent by ion chromatography is 500 ppm or less. It is preferable.
- the weight ratio of the organophosphate compound (C) in the non-volatile content of the treating agent is preferably 0.05 to 5% by weight.
- the organophosphate compound (C) is preferably at least one selected from a compound represented by the following general formula (2) and a compound represented by the following general formula (3).
- R 1 is a hydrocarbon group having 6 to 24 carbon atoms
- a 1 O is an oxyalkylene group having 2 to 4 carbon atoms
- m is an integer of 0 to 15.
- M 1 is a hydrogen atom, an alkali metal, an ammonium group or an organic amine group.
- R 1 is a hydrocarbon group having 6 to 24 carbon atoms
- a 1 O is an oxyalkylene group having 2 to 4 carbon atoms
- m is an integer of 0 to 15.
- 1 is a hydrogen atom, an alkali metal, an ammonium group or an organic amine group
- Q 1 is M 1 or R 1 O (A 1 O) m
- Y is 1 or 2.
- the treatment agent of the present invention preferably further contains a nonionic surfactant (D).
- the weight ratio of the nonionic surfactant (D) in the non-volatile content of the treating agent is preferably 20 to 70% by weight.
- the synthetic fiber filament yarn of the present invention is obtained by adding the above-mentioned treatment agent to a raw material synthetic fiber filament yarn.
- the method for producing a synthetic fiber filament yarn of the present invention includes a step of applying the treatment agent to a raw material synthetic fiber filament yarn.
- the fiber structure of the present invention includes the above synthetic fiber filament yarn and / or the synthetic fiber filament yarn obtained by the above production method.
- the treatment agent for synthetic fibers of the present invention When the treatment agent for synthetic fibers of the present invention is used, roll stains when producing synthetic fibers can be reduced and heat resistance is excellent. As a result, the cleaning interval between rolls can be increased, the number of cleanings can be reduced, and the productivity of synthetic fibers can be improved. According to the production method of the present invention, the occurrence of scum and yarn breakage can be reduced, and a synthetic fiber filament yarn excellent in yarn quality can be obtained.
- the fiber structure of the present invention is excellent in quality.
- the treatment agent for synthetic fibers of the present invention contains a smoothing component (A) and an organic sulfonic acid compound (B) represented by the above general formula (1), and is detected from the non-volatile content of the treatment agent by ion chromatography. Sulfate ions and chloride ions are set to a predetermined concentration or less. Details will be described below.
- the smooth component (A) is an essential component of the treatment agent of the present invention.
- the smooth component (A) 1) an ester compound having a structure in which an aliphatic monohydric alcohol and a fatty acid are ester-bonded (A1), and 2) an ester compound having a structure in which an aliphatic polyhydric alcohol and a fatty acid are ester-bonded (A2), 3) an ester compound (A3) having a structure in which an aliphatic monohydric alcohol and an aliphatic polycarboxylic acid are ester-bonded, 4) an aromatic ester compound (A4) having an aromatic ring in the molecule, 5 Examples thereof include known smoothing components generally employed as synthetic fiber treating agents such as sulfur-containing ester compounds (A5) and 6) mineral oil (A6).
- the smoothing component (A) can use 1 type (s) or 2 or more types.
- ester compound (A1) is a compound having a structure in which an aliphatic monohydric alcohol and a fatty acid (aliphatic monovalent carboxylic acid) are ester-bonded, and is a compound having no polyoxyalkylene group in the molecule. 1 type (s) or 2 or more types can be used for an ester compound (A1).
- the ester compound (A1) is preferably a compound represented by the following general formula (4).
- R 2 represents an alkyl group or alkenyl group having 4 to 24 carbon atoms
- R 3 represents an alkyl group or alkenyl group having 6 to 24 carbon atoms.
- R 2 preferably has 6 to 22 carbon atoms, more preferably 8 to 20 carbon atoms, and still more preferably 10 to 18 carbon atoms.
- R 2 may be either an alkyl group or an alkenyl group, but is preferably an alkyl group from the viewpoint of excellent heat resistance.
- R 3 preferably has 6 to 22 carbon atoms, more preferably 8 to 20 carbon atoms, and still more preferably 10 to 18 carbon atoms.
- fluff may increase due to weak oil film.
- R 3 may be either an alkyl group or an alkenyl group, but is preferably an alkenyl group from the viewpoint that oil film strength is high and fluff is less likely to occur.
- the ester compound (A1) is not particularly limited.
- 2-decyltetradecanoyl oleate 2-octyldodecyl stearate, isooctyl palmitate, isooctyl stearate, lauryl oleate, isotridecyl stearate, hexadecyl stearate, isostearyl oleate, Oleyl oleate is preferred.
- the ester compound (A1) can be synthesized and obtained by a known method using a commercially available fatty acid and an aliphatic monohydric alcohol.
- ester compound (A2) is a compound having a structure in which an aliphatic polyhydric alcohol and a fatty acid (aliphatic monovalent carboxylic acid) are ester-bonded, and is a compound having no polyoxyalkylene group in the molecule. 1 type (s) or 2 or more types can be used for an ester compound (A2).
- the aliphatic polyhydric alcohol constituting the ester compound (A2) is not particularly limited as long as it is divalent or higher, and one or two or more types can be used. From the viewpoint of oil film strength, the polyhydric alcohol is preferably trivalent or more, more preferably 3 to 4, more preferably 3. Examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol.
- glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose are preferable, and glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan Are more preferable, and glycerin and trimethylolpropane are more preferable.
- the fatty acid constituting the ester compound (A2) may be saturated or unsaturated.
- the number of unsaturated bonds is not particularly limited, but when there are three or more, one or two is preferable because deterioration proceeds due to oxidation and the treatment agent is thickened to impair lubricity.
- the number of carbon atoms of the fatty acid is preferably from 8 to 24, more preferably from 10 to 20, and even more preferably from 12 to 18 in terms of both oil film strength and lubricity. 1 type, or 2 or more types may be used for a fatty acid, and a saturated fatty acid and an unsaturated fatty acid may be used together.
- fatty acids examples include butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetyl acid, margarine Acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, isoeicosaic acid, gadoleic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosane Examples include acids, isotetracosanoic acid, nervonic acid, serotic acid, montanic acid, and melicic acid.
- the ester compound (A2) is a compound having two or more ester bonds in the molecule, but is preferably a compound having three or more ester bonds in the molecule, from the viewpoint of yarn production. More preferably, it is a compound having three ester bonds. There is no limitation in particular about the iodine value of ester compound (A2).
- the weight average molecular weight of the ester compound (A2) is preferably from 300 to 1200, more preferably from 300 to 1000, and even more preferably from 500 to 1000. If the weight average molecular weight is less than 300, the oil film strength may be insufficient, and fluff may increase or smoke generation during heat treatment may increase. On the other hand, when the weight average molecular weight exceeds 1200, smoothness is insufficient and fluff frequently occurs, and not only high-quality fibers cannot be obtained, but also the quality in the weaving or knitting process may be inferior.
- the weight average molecular weight in the present invention is a separation column KF-402HQ, KF-403HQ manufactured by Showa Denko KK using a high-speed gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation at a sample concentration of 3 mg / cc. And calculated from the peak measured by the differential refractive index detector.
- ester compound (A2) examples include trimethylolpropane tricaprylate, trimethylolpropane tricaprinate, trimethylolpropane trilaurate, trimethylolpropane trioleate, trimethylolpropane (laurate, myristylate, palmitate), trimethylol.
- ester compound (A2) a compound synthesized by a known method using a commercially available fatty acid and aliphatic polyhydric alcohol may be used. Further, natural esters obtained from nature such as natural fruits, seeds or flowers, and natural esters satisfying the constitution of the ester compound (A2) can be used as they are, or natural esters can be obtained by known methods as necessary. You may refine
- the ester compound (A3) is a compound having a structure in which an aliphatic monohydric alcohol and an aliphatic polyvalent carboxylic acid are ester-bonded, and is a compound having no polyoxyalkylene group in the molecule. 1 type (s) or 2 or more types can be used for an ester compound (A3).
- the aliphatic monohydric alcohol constituting the ester compound (A3) is not particularly limited, and one or more kinds can be used.
- the aliphatic monohydric alcohol may be saturated or unsaturated. There is no particular limitation on the number of unsaturated bonds, but when there are two or more, one is preferable because deterioration proceeds due to oxidation and the treatment agent is thickened and lubricity is impaired.
- the number of carbon atoms of the aliphatic monohydric alcohol is preferably 8 to 24, more preferably 14 to 24, and still more preferably 18 to 22 from the viewpoint of smoothness and oil film strength.
- One or more aliphatic monohydric alcohols may be used, and a saturated aliphatic monohydric alcohol and an unsaturated aliphatic monohydric alcohol may be used in combination.
- Examples of the aliphatic monohydric alcohol include octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Bacenyl alcohol, gadryl alcohol, arachidyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetracosanyl alcohol, nerbonyl alcohol, Examples include serotonyl alcohol, montanyl alcohol, and melinyl alcohol.
- octyl alcohol isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, vaccenyl alcohol Gadolyl alcohol, arachidyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignoserinyl alcohol, isotetradocosanyl alcohol, nerbonyl alcohol are preferred, myristolyl Alcohol, palmitoleyl alcohol, oleyl alcohol, elaidyl alcohol, baxenyl alcohol Call, gadoleyl alcohol, eicosyl cell noil alcohol, erucic alkenyl alcohol, more preferably flannel isobornyl alcohol, oleyl
- the aliphatic polyvalent carboxylic acid constituting the ester (A3) is not particularly limited as long as it is divalent or higher, and one or two or more types can be used.
- the aliphatic polyvalent carboxylic acid used in the present invention does not contain a sulfur-containing polyvalent carboxylic acid such as thiodipropionic acid.
- the valence of the aliphatic polycarboxylic acid is preferably divalent. Similarly, it is preferable that no hydroxyl group is contained in the molecule.
- Aliphatic polycarboxylic acids include citric acid, isocitric acid, malic acid, aconitic acid, oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelain An acid, sebacic acid, etc. are mentioned.
- aconitic acid, oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are preferred, and fumaric acid, maleic acid, adipine Acid, pimelic acid, suberic acid, azelaic acid and sebacic acid are more preferred.
- ester compound (A3) examples include dioctyl adipate, dilauryl adipate, dioleyl adipate, secondary isocetyl adipate, dioctyl sebacate, dilauryl sebacate, dioleyl sebacate, diisocetyl sebacate and the like.
- the ester compound (A3) is a compound having two or more ester bonds in the molecule. There is no limitation in particular about the iodine value of an ester compound (A3).
- the weight average molecular weight of the ester compound (A3) is preferably 500 to 1000, more preferably 500 to 800, and even more preferably 500 to 700.
- the weight average molecular weight is less than 500, the oil film strength may be insufficient, and fluff may increase or smoke generation during heat treatment may increase.
- the weight average molecular weight exceeds 1000, the melting point becomes high, which may cause scum in the weaving or knitting process, and the quality may be inferior.
- the ester compound (A3) can be synthesized and obtained by a known method using a commercially available aliphatic monohydric alcohol and aliphatic polyvalent carboxylic acid.
- Aromatic ester compound (A4) is an ester compound having at least one aromatic ring in the molecule. Specifically, an ester compound (A4-1) having a structure in which an aromatic carboxylic acid and an alcohol are ester-bonded and an ester compound (A4-2) having a structure in which an aromatic alcohol and a carboxylic acid are ester-bonded are mentioned. Can do.
- the aromatic ester compound (A4) is a compound that does not have a polyoxyalkylene group in the molecule.
- An aromatic ester compound (A4) can use 1 type (s) or 2 or more types.
- the aromatic carboxylic acid constituting the ester compound (A4-1) may be a monocarboxylic acid or a polyvalent carboxylic acid. You may use 1 type, or 2 or more types.
- Examples of the aromatic carboxylic acid include benzoic acid, toluic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, melittic acid, cinnamic acid, trimellitic acid, and pyromellitic acid. Among these, trimellitic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and trimellitic acid is more preferable.
- the alcohol constituting the ester compound (A4-1) may be a monohydric alcohol or a polyhydric alcohol. Moreover, any of aliphatic alcohol, alicyclic alcohol, and aromatic alcohol may be sufficient.
- the monohydric alcohol can use 1 type (s) or 2 or more types. Among these, monohydric alcohols are preferable, and aliphatic monohydric alcohols are more preferable.
- Monohydric alcohols include alkylbenzene alcohol, dialkylbenzene alcohol, octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristol alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol , Elidyl alcohol, bacenyl alcohol, gadrel alcohol, arachidyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetracosanyl alcohol , Nerbonyl alcohol, serotinyl alcohol, montanyl alcohol, melicini Alcohol and the like.
- Examples of the polyhydric alcohol include aliphatic polyhydric alcohols described for the ester compound (A2) and aromatic polyhydric alcohols described for the ester compound (A4-
- the aromatic alcohol which comprises ester compound (A4-2) can use 1 type (s) or 2 or more types.
- an aromatic polyhydric alcohol is preferable, and an aromatic trihydric alcohol is more preferable.
- the aromatic alcohol include aromatic monohydric alcohols such as alkylbenzene alcohol, aromatic polyhydric alcohols such as dialkylbenzene alcohol, bisphenol A, bisphenol Z, and 1,3,5-trihydroxymethylbenzene. Among these, bisphenol A, bisphenol Z, and 1,3,5-trihydroxymethylbenzene are preferable, and 1,3,5-trihydroxymethylbenzene is more preferable.
- the carboxylic acid constituting the ester compound (A4-2) may be either an aliphatic carboxylic acid or an aromatic carboxylic acid. Either a monovalent carboxylic acid or a polyvalent carboxylic acid may be used. You may use 1 type, or 2 or more types. Among these, monovalent carboxylic acids are preferable, and fatty acids are more preferable.
- the fatty acid is preferably saturated from the viewpoint of persistence.
- the fatty acid may be linear or branched.
- Monovalent carboxylic acids include alkylbenzene carboxylic acid, dialkylbenzene carboxylic acid, butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristic acid, Pentadecylic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, isoicosanoic acid, gadoleic acid, Examples include eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoceric acid, isotetracosanoic acid, nervonic acid
- Sulfur-containing ester compound is at least one selected from a diester compound of thiodipropionic acid and an aliphatic alcohol and a monoester compound of thiodipropionic acid and an aliphatic alcohol.
- the sulfur-containing ester compound is a component having antioxidant ability. By using the sulfur-containing ester compound, the heat resistance of the treatment agent can be increased. 1 type (s) or 2 or more types can be used for a sulfur-containing ester compound.
- the molecular weight of the thiodipropionic acid constituting the sulfur-containing ester compound is preferably 400 to 1000, more preferably 500 to 900, and still more preferably 600 to 800.
- the aliphatic alcohol constituting the sulfur-containing ester compound may be saturated or unsaturated.
- the aliphatic alcohol may be linear or have a branched structure, but preferably has a branched structure.
- the aliphatic alcohol has preferably 8 to 24 carbon atoms, more preferably 12 to 24 carbon atoms, and still more preferably 16 to 24 carbon atoms.
- Examples of the aliphatic alcohol include octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, isocetyl alcohol, oleyl alcohol and isostearyl alcohol. Among these, oleyl alcohol and isostearyl alcohol are exemplified. preferable.
- the sulfur-containing ester compound is a diester compound of thiodipropionic acid and an aliphatic alcohol (in this paragraph, simply referred to as a diester), a monoester compound of thiodipropionic acid and an aliphatic alcohol (in this paragraph, simply referred to as a monoester).
- the molar ratio of the diester to the monoester is preferably 100/0 to 70/30, more preferably 100/0 to 75/25, and still more preferably 100/0 to 80/20.
- the processing agent for synthetic fibers of this invention may contain mineral oil as a smoothing component other than the above.
- the mineral oil here is not a low-viscosity diluent used for diluting the treatment agent, but is contained in the nonvolatile matter.
- the mineral oil is not particularly limited, and examples thereof include machine oil, spindle oil, and liquid paraffin.
- One or more mineral oils may be used.
- the viscosity of the mineral oil at 30 ° C. is preferably 100 to 500 seconds.
- the smoothing component (A) from the viewpoint of improving heat resistance, it is preferable to use a purified product after removing the catalyst and the like.
- Organic sulfonic acid compound (B) represented by the general formula (1) is an essential component of the treatment agent of the present invention. Contains a smoothing component (A) and an organic sulfonic acid compound (B), and the weight ratio of sulfate ions (SO 4 2 ⁇ ) detected from the non-volatile content of the treatment agent by ion chromatography is 200 ppm or less, chloride ions (Cl - When the weight ratio of) and 200ppm or less, can be dramatically reduced fuzz, yarn breakage, a roll staining.
- sulfate ion SO 4 2 ⁇
- chlorine ion Cl ⁇
- a + b is less than 5
- the effect of reducing roll contamination is reduced.
- a + b is more than 17, the melting point is high, the compatibility with the treatment agent is deteriorated, and it cannot be used.
- a + b is preferably from 7 to 17, and more preferably from 10 to 15.
- M is a hydrogen atom, an alkali metal, an ammonium group, or an organic amine group.
- the alkali metal include lithium, sodium, and potassium.
- the ammonium group and the organic amine group include a group represented by NR a R b R c R d .
- R a , R b , R c and R d each independently represent a hydrogen atom, an alkyl group, an alkenyl group or a polyoxyalkylene group.
- the alkyl group and alkenyl group preferably have 1 to 24 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 18 carbon atoms.
- the polyoxyalkylene group is represented by “— (A 1 O) m H”, and (A 1 O) m is the same as that represented by the general formula (2).
- Examples of the group represented by NR a R b R c R d include an ammonium group, a methyl ammonium group, an ethyl ammonium group, a propyl ammonium group, a butyl ammonium group, a hexyl ammonium group, an octyl ammonium group, a dimethyl ammonium group, and a diethyl ammonium group.
- the raw material containing the organic sulfonic acid compound (B) (hereinafter referred to as raw material X) contains sodium sulfate and / or sodium chloride due to its production method.
- the ratio of sodium sulfate and sodium chloride contained in the raw material X can be calculated from the weight ratio of sulfate ions and chlorine ions detected from the raw material X by ion chromatography.
- the weight ratio of the sulfate ion detected from the raw material X is 20000 ppm or more with respect to the organic sulfonic acid compound (B).
- the weight ratio of the chlorine ion detected from the raw material X is 20000 ppm or more with respect to the organic sulfonic acid compound (B).
- the organic sulfonic acid compound (B) when such a raw material X is used as a treating agent, as described above, sodium sulfate and sodium chloride fall off and accumulate on the drawing roll during spinning, causing an increase in yarn breakage.
- sodium sulfate and sodium chloride accelerate tar accumulation and cause roll soiling on the rolls subjected to hot stretching.
- Examples of such a raw material X include HOSTAPUR SAS (manufactured by Hoechst) and mersolate H (manufactured by Bayer).
- the treatment agent of the present invention uses a raw material (hereinafter referred to as raw material Y) containing an organic sulfonic acid compound (B) in which sodium sulfate and sodium chloride are reduced from the raw material X.
- raw material Y a raw material
- B organic sulfonic acid compound
- the weight ratio of sulfate ions detected from the raw material Y by ion chromatography is 5000 ppm or less with respect to the organic sulfonic acid compound (B), and the weight ratio of chloride ions is the organic sulfonic acid compound ( It is preferable that it is 5000 ppm or less with respect to B).
- the weight ratio of the sulfate ion detected from the raw material Y is more preferably 4000 ppm or less, further preferably 3000 ppm or less, and particularly preferably 2000 ppm or less with respect to the organic sulfonic acid compound (B). .
- the weight ratio of chlorine ions detected from the raw material Y is more preferably 4000 ppm or less, still more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less with respect to the organic sulfonic acid compound (B).
- the method for analyzing sulfate ions and chloride ions by ion chromatography in the present invention is as described in the examples.
- the method for reducing sodium sulfate and sodium chloride from the raw material X containing the organic sulfonic acid compound (B) is not particularly limited, and a known method can be employed.
- a method such as adding a solvent such as methanol or water to the raw material X and precipitating and separating an inorganic substance such as sodium sulfate may be used.
- the raw material X contains sodium chloride
- the method of removing the sodium chloride contained in the raw material X with an ion exchange membrane, the method of adsorbing with an ion exchange resin, etc. are mentioned.
- the above organic sulfonic acid compound (B) is a monosulfonic acid compound having one sulfonic acid group.
- the treating agent of the present invention may contain a disulfonic acid compound represented by the following general formula (5) in addition to the monosulfonic acid compound.
- c + d + e 4 to 16.
- c + d + e is less than 4
- c + d + e is more than 17
- compatibility with the treatment agent is deteriorated, and it may be impossible to use.
- c + d + e is preferably 6 to 16, and more preferably 9 to 14.
- M is a hydrogen atom, an alkali metal, an ammonium group or an organic amine group. Details of M are the same as M described in the general formula (1).
- the weight ratio of the monosulfonic acid compound which is the organic sulfonic acid compound (B) and the disulfonic acid compound represented by the general formula (5) is 50 / 50 to 99/1 is preferred, 70/30 to 99/1 is more preferred, and 80/20 to 98/2 is even more preferred.
- the treatment agent of the present invention preferably further contains an organic phosphate compound (C) in addition to the smoothing component (A) and the organic sulfonic acid compound (B) from the viewpoint of reducing fluff.
- the organophosphate compound (C) is preferably at least one selected from the compound represented by the general formula (2) and the compound represented by the general formula (3).
- R 1 is a hydrocarbon group having 6 to 24 carbon atoms.
- a 1 O is an oxyalkylene group having 2 to 4 carbon atoms, and m is an integer of 0 to 15.
- n is an integer of 1 to 2.
- M 1 is a hydrogen atom, an alkali metal, an ammonium group or an organic amine group.
- Q 1 is M 1 or R 1 O (A 1 O) m .
- Y is 1 or 2.
- Examples of the hydrocarbon group for R 1 include an alkyl group and an alkenyl group.
- R 1 preferably has 8 to 24 carbon atoms, more preferably 12 to 24 carbon atoms.
- the carbon number of R 1 may be distributed, R 1 may be linear or branched, and may be saturated or unsaturated.
- a 1 O is an oxyalkylene group having 2 to 4 carbon atoms.
- M which is the number of repeating oxyalkylene units, is an integer from 0 to 15, preferably from 0 to 10, more preferably from 0 to 3, particularly preferably when m is 0 and no polyoxyalkylene group is contained.
- (A 1 O) m is preferably a polyoxyalkylene group having 50 mol% or more of oxyethylene units as oxyalkylene units.
- n is an integer of 1 to 2.
- the two organic groups [R 1 O (A 1 O) m ] — constituting the compound represented by the general formula (2) may be the same or different.
- Q R 1 O (A 1 O) m
- the two organic groups [R 1 O (A 1 O) m ] — constituting the compound represented by the general formula (3) may be the same or different. It may be.
- M 1 is a hydrogen atom, an alkali metal, an ammonium group or an organic amine group.
- alkali metal include lithium, sodium, and potassium.
- ammonium group and the organic amine group include a group represented by NR a R b R c R d .
- the group represented by NR a R b R c R d is the same as M described for the organic sulfonic acid compound (B).
- the organic phosphoric ester compounds (C1), (C2), (C3) and (C4) and the P nuclear integral ratio (%) of inorganic phosphoric acid are calculated from the integrated values of the peaks derived from each phosphorus atom in 31P-NMR. be able to.
- P nucleus integral ratio (%) says what was calculated by making the sum total of the integral value of organophosphate ester compound (C1), (C2), (C3), (C4) and inorganic phosphoric acid 100%.
- the inorganic phosphoric acid will be described later.
- the P nuclear integral ratio (%) of the organic phosphate compound (C1) is preferably 25 to 85%, more preferably 35 to 80%, and even more preferably 40 to 70%.
- the P nuclear integral ratio (%) of the organic phosphate compound (C2) is preferably 15 to 65%, more preferably 20 to 60%, and even more preferably 25 to 55%.
- the P nuclear integral ratio (%) of the organic phosphate compound (C3) is preferably 0 to 50%, more preferably 0 to 45%, and further preferably 0 to 40%.
- the P nuclear integral ratio (%) of the organic phosphate compound (C4) is preferably 0 to 7%, more preferably 0 to 6%, and further preferably 0 to 5%.
- the P nuclear integral ratio (%) of the inorganic phosphoric acid is preferably 0 to 10%, more preferably 0 to 9%, and further preferably 0 to 8%.
- an organic phosphate compound (C) there is no limitation in particular as a manufacturing method of an organic phosphate compound (C).
- a well-known method is employable.
- a reaction product is obtained by reacting an organic hydroxyl compound represented by R 1 O (A 1 O) m H with anhydrous phosphoric acid P 2 O 5 (I ).
- the reaction may be carried out by adding inorganic phosphoric acid or water.
- the method for producing the organic phosphate compound (C) may include, after the step (I), a step (II) in which water is added to the reaction product for hydrolysis.
- the ratio of the organic phosphate ester compounds (C3) and (C4) contained in the organic phosphate ester compound (C) can be adjusted.
- the amount of water added to the reaction product is preferably 0.01 to 5% by weight, more preferably 0.05 to 4% by weight, and more preferably 0.1 to 3% by weight with respect to the organophosphate compound (C). More preferred is weight percent. When the amount of water added is less than 0.01% by weight and more than 5% by weight, it may be difficult to adjust the amount of the organic phosphate compound (C3) or (C4).
- the method for producing the organic phosphate compound (C) may include a step (III) of neutralizing with an alkali compound having M 1 after the step (I) or the step (II).
- the organic phosphate ester compound (C) contains a heavy metal compound such as arsenic as a source of impurities in anhydrous phosphoric acid or inorganic phosphorus.
- the treatment agent of the present invention may contain a heavy metal compound such as arsenic.
- the weight ratio of the heavy metal compound to the non-volatile content of the treatment agent is preferably 0.01% by weight or less, more preferably 0.005% by weight or less, from the viewpoint of influence on the human body and environmental safety, and 0.001% by weight or less. More preferably, it is not more than% by weight.
- the raw material containing the organic phosphate compound (C) (hereinafter referred to as raw material Z) contains inorganic phosphoric acid and / or a salt thereof.
- the ratio of inorganic phosphoric acid and / or salt thereof can be adjusted by the ratio of organic hydroxyl compound and anhydrous phosphoric acid P 2 O 5 , reaction conditions, and the like.
- Nonionic surfactant (D) The treatment agent of the present invention provides a nonionic surfactant (D) in addition to the above smoothing component (A) and organic sulfonic acid compound (B) from the viewpoint of imparting oil film strength and sizing properties to the raw yarn and improving the yarn-making property. ) Is further preferably contained.
- nonionic surfactant (D) says what remove
- Nonionic surfactant (D) includes polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester (hereinafter sometimes referred to as polyhydroxy ester), an ester in which at least one hydroxyl group of polyhydroxy ester is blocked with fatty acid, polyoxy Examples include alkylene polyhydric alcohol ether, polyoxyalkylene polyhydric alcohol fatty acid ester, polyoxyalkylene aliphatic alcohol ether, polyalkylene glycol fatty acid ester, polyhydric alcohol fatty acid ester, and the like.
- the polyhydroxyester is structurally an ester of a polyoxyalkylene group-containing hydroxy fatty acid and a polyhydric alcohol, and it is preferable that two or more hydroxyl groups of the polyhydric alcohol are esterified. Therefore, the polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester is an ester having a plurality of hydroxyl groups.
- the polyoxyalkylene group-containing hydroxy fatty acid has a structure in which a polyoxyalkylene group is bonded to a fatty acid hydrocarbon group via an oxygen atom, and one end that is not bonded to the fatty acid hydrocarbon group of the polyoxyalkylene group is It is a hydroxyl group.
- the polyhydroxyester include an alkylene oxide adduct of an esterified product of a hydroxy fatty acid having 6 to 22 carbon atoms (preferably 16 to 20 carbon atoms) and a polyhydric alcohol.
- Examples of the hydroxy fatty acid having 6 to 22 carbon atoms include hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxystearic acid, and ricinoleic acid, and hydroxyoctadecanoic acid and ricinoleic acid are preferable.
- Examples of the polyhydric alcohol include ethylene glycol, glycerin, sorbitol, sorbitan, trimethylolpropane, pentaerythritol and the like, and glycerin is preferable.
- Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide.
- the number of moles of alkylene oxide added is preferably 3 to 60, and more preferably 8 to 50.
- the proportion of ethylene oxide in the alkylene oxide is preferably 50 mol% or more, more preferably 80 mol% or more.
- the order of addition is not particularly limited, and the addition form may be either a block form or a random form.
- the addition of the alkylene oxide can be performed by a known method, but it is generally performed in the presence of a basic catalyst.
- the polyhydroxyester can be produced, for example, by esterifying a polyhydric alcohol and a hydroxy fatty acid (hydroxymonocarboxylic acid) under normal conditions to obtain an esterified product, and then subjecting the esterified product to an alkylene oxide addition reaction.
- the polyhydroxyester can be suitably produced also by using an oil and fat obtained from nature such as castor oil or a hardened castor oil obtained by adding hydrogen to this, and further subjecting it to an addition reaction with an alkylene oxide.
- Nonionic surfactant (D) includes an ester obtained by blocking at least one hydroxyl group of the above-mentioned polyhydroxyester with a fatty acid.
- the number of carbon atoms of the fatty acid to be blocked is preferably 6-24, more preferably 12-18.
- the carbon number of the hydrocarbon group in the fatty acid may be distributed, the hydrocarbon group may be linear or branched, may be saturated or unsaturated, It may have a polycyclic structure.
- Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, eicosanoic acid, behenic acid, lignoceric acid and the like.
- Examples of the polyhydroxy ester and an ester obtained by blocking at least one hydroxyl group of the polyhydroxy ester with a fatty acid include, for example, hardened castor oil ethylene oxide adduct, castor oil ethylene oxide adduct, hardened castor oil ethylene oxide adduct monooleate, and hardened castor oil ethylene oxide adduct.
- the polyoxyalkylene polyhydric alcohol ether is a compound having a structure in which an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide is added to the polyhydric alcohol.
- alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide
- examples of the polyhydric alcohol include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose. Of these, glycerin, trimethylolpropane, and sucrose are preferable.
- the number of moles of alkylene oxide added is preferably 3 to 100, more preferably 4 to 70, and still more preferably 5 to 50.
- the proportion of ethylene oxide in the alkylene oxide is preferably 50 mol% or more, and more preferably 80 mol% or more.
- the weight average molecular weight of the polyoxyalkylene polyhydric alcohol ether is preferably from 300 to 10,000, more preferably from 400 to 8000, and even more preferably from 500 to 5,000. When the molecular weight is less than 300, the occurrence of fuzz and yarn breakage may not be reduced. On the other hand, when the molecular weight exceeds 10,000, the friction of the treatment agent becomes high, and not only the generation of fluff and yarn breakage cannot be reduced, but also it may deteriorate.
- Polyoxyalkylene polyhydric alcohol ethers include polyethylene glycol, glycerin ethylene oxide adduct, trimethylolpropane ethylene oxide adduct, pentaerythritol ethylene oxide adduct, diglycerin ethylene oxide adduct, sorbitan ethylene oxide adduct, sorbitan ethylene oxide propylene oxide adduct, sorbitol Examples thereof include, but are not limited to, an ethylene oxide adduct, a sorbitol ethylene oxide propylene oxide adduct, a ditrimethylolpropane ethylene oxide adduct, a dipentaerythritol ethylene oxide adduct, and a sucrose ethylene oxide adduct.
- a polyoxyalkylene polyhydric alcohol fatty acid ester is a compound having a structure in which a compound obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to a polyhydric alcohol and a fatty acid are ester-bonded.
- the polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose. Among these, glycerin, diglycerin, sorbitan, and sorbitol are preferable.
- fatty acids examples include lauric acid, myristic acid, myristic acid, palmitic acid, palmitoleic acid, isocetyl acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidic acid, eicosenoic acid, behenic acid, Examples include isodocosanoic acid, erucic acid, lignoceric acid, and isotetracosanoic acid.
- the number of added moles of alkylene oxide is preferably 3 to 100, more preferably 5 to 70, and still more preferably 10 to 50.
- the proportion of ethylene oxide in the alkylene oxide is preferably 50 mol% or more, and more preferably 80 mol% or more.
- the weight average molecular weight of the polyoxyalkylene polyhydric alcohol fatty acid ester is preferably 300 to 7000, more preferably 500 to 5000, and still more preferably 700 to 3000.
- smoke may be generated in the heat treatment process, which may deteriorate the environment.
- occurrence of yarn breakage may not be reduced.
- the molecular weight exceeds 7000 the friction of the treatment agent becomes high, and not only the generation of fluff and yarn breakage cannot be reduced, but also it may deteriorate.
- polyoxyalkylene polyhydric alcohol fatty acid esters examples include glycerin ethylene oxide adduct monolaurate, glycerin ethylene oxide adduct dilaurate, glycerin ethylene oxide adduct trilaurate, trimethylolpropane ethylene oxide adduct trilaurate, sorbitan ethylene oxide adduct monooleate, sorbitan ethylene oxide adduct dioleate Sorbitan ethylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide adduct monooleate, sorbitan ethylene oxide propylene oxide adduct dioleate, sorbitan ethylene oxide propylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide adduct trilaurate, ® sugar ethylene oxide adducts Toriraureto like although not limited thereto.
- the polyoxyalkylene aliphatic alcohol ether is a compound having a structure in which an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide is added to an aliphatic monohydric alcohol.
- alkylene oxides such as octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol. Addenda may be mentioned.
- the number of moles of alkylene oxide added is preferably 1 to 100 moles, more preferably 2 to 70 moles, and still more preferably 3 to 50 moles. Further, the ratio of ethylene oxide to the whole alkylene oxide is preferably 20 mol% or more, more preferably 30 mol% or more, and further preferably 40 mol% or more.
- the fatty acid ester of polyalkylene glycol is a compound having a structure in which polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and a fatty acid are ester-bonded.
- the weight average molecular weight of the polyalkylene glycol is preferably from 100 to 1,000, more preferably from 150 to 800, and even more preferably from 200 to 700.
- Polyalkylene glycol fatty acid esters include polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene polypropylene glycol monolaurate, polyethylene Examples thereof include, but are not limited to, polypropylene glycol dilaurate, polyethylene polypropylene glycol monooleate, and polyethylene polypropylene glycol dioleate.
- the polyhydric alcohol fatty acid ester is a compound having a structure in which a polyhydric alcohol and a fatty acid are ester-bonded, and is a compound excluding the smooth component (A).
- the polyhydric alcohol include ethylene glycol, trimethylolpropane, pentaerythritol, erythritol, diethylene glycol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, and sucrose.
- ethylene glycol, glycerin, diglycerin, sorbitan, and sorbitol are preferable.
- fatty acids examples include lauric acid, myristic acid, myristic acid, palmitic acid, palmitoleic acid, isocetyl stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, tuberculostearic acid, isoicosanoic acid, gadoleic acid Eicosenoic acid, behenic acid, isodocosanoic acid, erucic acid, lignoceric acid and the like.
- the polyhydric alcohol fatty acid ester has at least one or two or more hydroxyl groups.
- the weight average molecular weight of the polyhydric alcohol fatty acid ester is preferably from 100 to 1,000, more preferably from 200 to 800, and even more preferably from 300 to 600.
- fatty acid esters examples include glycerol monolaurate, glycerol dilaurate, glycerol monooleate, glycerol dioleate, sorbitan monooleate, sorbitan dioleate, sucrose monolaurate, and sucrose dilaurate. It is not limited to.
- nonionic surfactant (D) from the viewpoint of improving heat resistance, it is preferable to use a purified product obtained by removing a catalyst or the like.
- the processing agent of this invention contains a smoothing component (A) and the organic sulfonic acid compound (B) shown by the said General formula (1). Furthermore, the weight ratio of sulfate ions (SO 4 2 ⁇ ) detected from the non-volatile content of the treatment agent by ion chromatography is 200 ppm or less, and the weight ratio of chloride ions (Cl ⁇ ) is 200 ppm or less. As described above, when the sulfate ion and the chlorine ion detected from the non-volatile content of the treatment agent are set to a predetermined weight ratio or less, fluff, yarn breakage, and roll dirt can be dramatically reduced.
- the weight ratio of the sulfate ion exceeds 200 ppm or the weight ratio of the chloride ion exceeds 200 pm, sodium sulfate or sodium chloride drops and accumulates on the drawing roll during spinning, and increases the yarn breakage yarn. On the roll that causes heat stretching, the accumulation of tar is accelerated and roll fouling is caused.
- the method for analyzing sulfate ions and chloride ions by ion chromatography in the present invention is as described in the examples. Further, 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 the solvent and the like and reach a constant weight.
- the weight ratio of the sulfate ion is preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less.
- the weight ratio of the chlorine ions is preferably 200 ppm or less, more preferably 150 ppm or less, and further preferably 100 ppm or less.
- the weight ratio of sulfate ions and chloride ions can be adjusted by reducing sodium sulfate and sodium chloride contained in the raw material X containing the organic sulfonic acid compound (B).
- the weight ratio of the smoothing component (A) to the non-volatile content of the treating agent is preferably 20 to 70% by weight, more preferably 30 to 65% by weight, further preferably 40 to 65% by weight, particularly 40 to 60% by weight. preferable.
- the weight ratio is less than 20% by weight, fluff may increase due to lack of smoothness.
- the weight ratio is more than 70% by weight, the convergence may be insufficient, or when emulsified, the emulsion stability may be poor and cannot be used.
- the weight ratio of the organic sulfonic acid compound (B) in the nonvolatile content of the treating agent is 1.25 to 12% by weight, preferably 1.25 to 10% by weight, more preferably 1.25 to 8% by weight, More preferred is 1.25 to 7% by weight, and particularly preferred is 1.5 to 6% by weight.
- the weight ratio is less than 1.25% by weight, roll dirt may not be reduced.
- the weight ratio is more than 12% by weight, the friction increases and fluff may increase.
- the weight ratio of phosphate ions (PO 4 3 ⁇ ) detected from the non-volatile content of the treating agent by ion chromatography is 500 ppm or less. It is preferable. When the weight ratio of the phosphate ion is more than 500 ppm, it may fall off on the drawing roll and cause an increase in yarn breakage.
- the weight ratio of the phosphate ion is more preferably 400 ppm or less, further preferably 300 ppm or less, and particularly preferably 200 ppm or less.
- the phosphate ion (PO 4 3 ⁇ ) is sometimes simply referred to as phosphate ion.
- the inorganic phosphoric acid and / or salt thereof contained in the raw material Z containing the organic phosphate compound (C) is reduced, or the amount of the raw material Z is blended.
- a filter aid such as diatomaceous earth as a treatment agent.
- the weight ratio of the organic phosphate compound (C) in the nonvolatile content of the treatment agent is preferably 0.05 to 10% by weight, The content is more preferably 08 to 8% by weight, and further preferably 0.1 to 7% by weight.
- the weight ratio of the nonionic surfactant (D) in the nonvolatile content of the treatment agent is preferably 20 to 70% by weight, and preferably 25 to 65% by weight. More preferably, it is 30 to 65% by weight, further preferably 30 to 60% by weight.
- the treatment agent for synthetic fibers of the present invention is for emulsification of the treatment agent, assisting adhesion to the fiber, washing the treatment agent from the fiber with water, antistatic property to the fiber, lubricity, imparting convergence, etc.
- You may contain surfactant other than said organic sulfonic-acid compound (B), organophosphate ester compound (C), and nonionic surfactant (D).
- surfactants include anionic surfactants such as fatty acid soaps; cationic surfactants such as alkylamine salts, alkylimidazolinium salts, and quaternary ammonium salts; amphoteric compounds such as lauryl dimethyl betaine and stearyl dimethyl betaine.
- Surfactant dimethyl lauryl amine oxide etc. are mentioned. These surfactants can be used alone or in combination of two or more.
- the weight ratio of the surfactant to the non-volatile content of the treatment agent in the case of containing these surfactants is not particularly limited, but is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight. preferable.
- a surfactant here means a thing with a weight average molecular weight of less than 1000.
- the synthetic fiber treating agent of the present invention may further contain an antioxidant in order to impart heat resistance.
- the antioxidant include known ones such as phenol, thio, and phosphite.
- One or more antioxidants can be used.
- the weight ratio of the antioxidant to the non-volatile content of the treatment agent in the case of containing the antioxidant is not particularly limited, but is preferably 0.1 to 5% by weight, and more preferably 0.1 to 3% by weight.
- the treating agent for synthetic fibers of the present invention may further contain a stock solution stabilizer (for example, water, ethylene glycol, propylene glycol).
- a stock solution stabilizer for example, water, ethylene glycol, propylene glycol.
- the weight ratio of the stock solution stabilizer in the treating agent is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight.
- 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, may be composed of a non-volatile content and a stock solution stabilizer, and the non-volatile content is diluted with a low-viscosity mineral oil. It may be a water-based emulsion obtained by emulsifying nonvolatile components in water.
- the concentration of nonvolatile components is preferably 5 to 35% by weight, more preferably 6 to 30% by weight.
- the viscosity of the treatment agent and the non-volatile content was diluted with a low viscosity mineral oil (30 ° C.), from the viewpoint of uniformly applied to the fiber material, preferably 3 ⁇ 120mm 2 / s, more preferably 5 ⁇ 100mm 2 / s.
- the method for producing the treatment agent for synthetic fibers of the present invention is not particularly limited, and a known method can be employed.
- the treating agent for synthetic fiber is produced by adding and mixing the above-mentioned respective components constituting in any or specific order. Each component may be purified by removing the catalyst and the like from the viewpoint of improving heat resistance.
- the smoothing component (A) and the nonionic surfactant (D) used in the present invention may contain inorganic substances, and when the effects of the present invention are significantly reduced, the inorganic substances may be removed and purified. desirable.
- a known method can be used as a method of removing and purifying the inorganic substance.
- the smooth component (A) can be removed by filtration using diatomaceous earth, and the nonionic surfactant (D). If so, it can be purified by adsorption removal using an inorganic synthetic adsorbent.
- the method for producing a synthetic fiber filament yarn of the present invention includes a step of applying the synthetic fiber treating agent of the present invention to a raw material synthetic fiber filament yarn. According to the manufacturing method of the invention, the occurrence of scum and yarn breakage can be reduced, and a synthetic fiber filament yarn excellent in yarn quality can be obtained.
- the raw material synthetic fiber filament yarn in this invention means the synthetic fiber filament yarn to which the processing agent is not provided.
- the step of applying the synthetic fiber treating agent there is no particular limitation on the step of applying the synthetic fiber treating agent, and a known method can be employed.
- a synthetic fiber treating agent is applied in the spinning process of the raw synthetic fiber filament yarn. After the treatment agent is applied, stretching and heat setting are performed by a heat roller, and the film is wound up.
- the processing agent for synthetic fibers of this invention can be used conveniently.
- polyester and nylon are assumed to be 210 to 260 ° C. for industrial materials and 110 to 220 ° C. for clothing.
- the synthetic fiber treatment agent applied to the raw material synthetic fiber filament yarn is a treatment agent consisting of only the non-volatile content, a treatment agent obtained by diluting the non-volatile content with low-viscosity mineral oil, or emulsifying the non-volatile content in water. And water-based emulsion treatment agents.
- a treatment agent consisting of only the non-volatile content, a treatment agent obtained by diluting the non-volatile content with low-viscosity mineral oil, or emulsifying the non-volatile content in water.
- water-based emulsion treatment agents are not specifically limit as an application method.
- Guide oil supply, roller oil supply, dip oil supply, spray oil supply, etc. are mentioned. Among these, guide oil supply and roller oil supply are preferable because of easy management of the applied amount.
- the non-volatile content of the synthetic fiber treatment agent is preferably 0.05 to 5% by weight, more preferably 0.1 to 3% by weight, and more preferably 0.1 to 2% by weight based on the raw synthetic fiber filament yarn. % Is more preferable. If it is less than 0.05% by weight, the effects of the present invention may not be exhibited. On the other hand, if it exceeds 5% by weight, the non-volatile content of the treatment agent tends to fall off the yarn path, the tar on the heat roller increases significantly, and may lead to fluff and yarn breakage.
- Synthetic fiber filament yarns include synthetic fiber filament yarns such as polyester fiber, polyamide fiber, and polyolefin fiber.
- the treatment agent for synthetic fibers of the present invention is suitable for synthetic fibers such as polyester fibers, polyamide fibers, and polyolefin 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
- polyamide fibers include nylon 6 and nylon 66
- polyolefin fibers include polypropylene and polyethylene.
- a well-known method is employable.
- the fiber structure of the present invention includes the synthetic fiber filament yarn obtained by the production method of the present invention. Specifically, a fabric woven by a water jet loom, an air jet loom, or a rapier loom using a synthetic fiber filament yarn provided with the synthetic fiber treatment agent of the present invention, and a circular knitting machine, a warp knitting machine, Or it is the knitted fabric knitted with the weft knitting machine.
- Examples of the use of the fiber structure include industrial materials such as tire cords, seat belts, airbags, fish nets, ropes, and clothing. There is no limitation in particular as a method of manufacturing a textile fabric and a knitted fabric, A well-known method is employable.
- the raw materials Y-1 and Y-2 containing the organic sulfonic acid compound (B) are obtained by purifying the raw materials X-1 and X-2 containing the organic sulfonic acid compound (B) and removing the inorganic substances. Can do.
- a method for removing the inorganic substance a known method can be used, and it is not limited to the purification method shown in the examples.
- the P nuclear integral ratio of the organic phosphate ester compounds (C1), (C2), (C3), (C4) and inorganic phosphoric acid was calculated by the following method using 31 P-NMR.
- About 30 mg of the non-volatile content of the measurement sample was weighed into an NMR sample tube having a diameter of 5 mm, dissolved by adding about 0.5 ml of heavy water (D 2 O) as a deuterated solvent, and 31 P-NMR measurement apparatus (BRUKER) (AVANCE400, 162 MHz)
- Examples 1 to 11, Comparative Examples 1 to 9 The components described in Tables 2 and 3 were mixed and stirred until uniform to prepare a treatment agent. Using each of the prepared treatment agents, pin dirt accumulation, pin dirt wiping property, and tension fluctuation were evaluated by the following methods. The results are shown in Tables 2 and 3. In addition, the number of the non volatile matter composition of the processing agent of Table 2, 3 shows the weight ratio of each component (raw materials X, Y, and Z are those non volatile matters) which occupy for the non volatile matter of a processing agent. Details of the treating agent components in Tables 2 and 3 are shown in Table 1.
- ODS a silica gel having an octadecyl group chemically bonded
- Detection was carried out under the following ion chromatographic conditions. The detection amount was measured by the peak area ratio with respect to a standard solution with a known concentration, and the amounts of sulfate ion (SO 4 2 ⁇ ), phosphate ion (PO 4 3 ⁇ ), and chlorine ion (Cl ⁇ ) were converted.
- the limit of quantification was 0.6 ppm or less for sulfate ion (SO 4 2 ⁇ ), 1.0 ppm or less for chlorine ion (Cl ⁇ ), and 0.3 ppm or less for phosphate ion (PO 4 3 ⁇ ). * In Tables 2 and 3 indicates below the limit of quantification.
- the degree of pin accumulation was evaluated according to the following criteria. ⁇ : Dirt is hardly recognized ⁇ : Dirt is slightly recognized x: Dirt is clearly accumulated
- the tension fluctuation value was calculated by the following formula.
- Tension fluctuation value (g) tension after running the yarn for 4 hours (g)-initial tension (g) Further, tension fluctuation was evaluated from the tension fluctuation value according to the following criteria. A: 0 g to less than 30 g ⁇ : 30 g or more and less than 50 g x: 50 g or more
- the pin wipeability was evaluated by the following method.
- the dirt generated on the chrome pin at the time of pear was wiped off by immersing a solution of sodium hydroxide in water and glycerin into gauze.
- the wiping property was evaluated by the number of times required for wiping. ⁇ : Can be wiped off by wiping less than 5 times ⁇ : Can be wiped by wiping 5 times or more and less than 20 times ⁇ : Cannot be wiped by wiping 20 times or more
- the treatment agent with sulfate ions and chloride ions detected from the non-volatile content of the treatment agent is used at a predetermined ratio or less is used. It is extremely superior. That is, the roll dirt at the time of manufacturing a synthetic fiber can be reduced, the cleaning interval of a roll can be lengthened, and the frequency
- the ratio of sulfate ions or chlorine ions detected from the non-volatile content of the treatment agent is high, so that there is a lot of accumulation of dirt on the pins and the wiping property is inferior. Moreover, it can be seen that the tension fluctuation value is extremely large, and fluff and yarn breakage frequently occur.
- the synthetic fiber treatment agent of the present invention is suitable for synthetic fiber filament yarns used for industrial materials such as tarpaulins, tire cords, seat belts, airbags, fish nets, ropes, slings, and clothing such as woven fabrics and knitted fabrics. .
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Abstract
Description
この方法では延伸工程で一旦糸切れなどのトラブルが発生すると、大量の繊維の損失をまねくため、延伸工程でのトラブル発生は極力避ける必要がある。トラブル発生の主たる原因は糸切れなどの繊維損傷にあり、これを防ぐため、潤滑性と耐熱性に優れた合成繊維用処理剤が必要となる。
さらには、繊維の高強力化、低収縮率化といった物性向上や、生産時の他エンド化、高速化といった生産性向上が図られており、これまで問題とならなかったロール汚れが原因で、毛羽、糸切れが増加する問題が発生している。この為、ロールを清浄な状態に保つため、ロールの清掃間隔が短く、その清掃回数が多くなり、生産性の低下が指摘されている。
また、特許文献1には、上記アニオン界面活性剤に、特定のエステルと酸化防止剤とを併用した処理剤が提案されている。しかし、このような処理剤であっても、きびしい製糸条件では満足する耐熱性を得ることができない。
本発明の製造方法によれば、スカムや糸切れの発生を低減することができ、糸品位に優れた合成繊維フィラメント糸条を得ることができる。本発明の繊維構造物は、品質に優れる。
平滑成分(A)は、本発明の処理剤の必須成分である。平滑成分(A)としては、1)脂肪族一価アルコールと脂肪酸とがエステル結合した構造を有するエステル化合物(A1)、2)脂肪族多価アルコールと脂肪酸とがエステル結合した構造を有するエステル化合物(A2)、3)脂肪族一価アルコールと脂肪族多価カルボン酸とがエステル結合した構造を有するエステル化合物(A3)、4)分子内に芳香環を有する芳香族エステル化合物(A4)、5)含硫黄エステル化合物(A5)、6)鉱物油(A6)等、合成繊維処理剤として一般的に採用されている公知の平滑成分を挙げることができる。平滑成分(A)は1種又は2種以上を使用できる。
エステル化合物(A1)は、脂肪族一価アルコールと脂肪酸(脂肪族一価カルボン酸)とがエステル結合した構造を有する化合物であり、また分子内にポリオキシアルキレン基を有しない化合物である。エステル化合物(A1)は1種又は2種以上を使用できる。
エステル化合物(A1)としては、下記一般式(4)で示される化合物であることが好ましい。
エステル化合物(A2)は、脂肪族多価アルコールと脂肪酸(脂肪族一価カルボン酸)とがエステル結合した構造を有する化合物であり、また分子内にポリオキシアルキレン基を有しない化合物である。エステル化合物(A2)は1種又は2種以上を使用できる。
脂肪族多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2-メチル-1,3-プロパンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、シクロヘキサンジオール、シクロヘキサンジメタノール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジグリセリン、ソルビタン、ソルビトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリグリセリン、テトラグリセリン、ショ糖等が挙げられる。これらの中でも、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジグリセリン、ソルビタン、ソルビトール、ジトリメチロールプロパン、ジペンタエリスリトール、ショ糖が好ましく、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジグリセリン、ソルビタンがより好ましく、グリセリン、トリメチロールプロパンがさらに好ましい。
これらの中でも、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、ミリストレイン酸、ペンタデカン酸、パルミチン酸、パルミトレイン酸、イソセチル酸、マルガリン酸、ステアリン酸、イソステアリン酸、オレイン酸、エライジン酸、バクセン酸、リノール酸、リノレン酸、ツベルクロステアリン酸、アラキジン酸、イソエイコサ酸、ガドレイン酸、エイコセン酸、ドコサン酸、イソドコサン酸、エルカ酸、テトラコサン酸、イソテトラコサン酸、ネルボン酸が好ましく、カプリン酸、ラウリン酸、ミリスチン酸、ミリストレイン酸、ペンタデカン酸、パルミチン酸、パルミトレイン酸、イソセチル酸、マルガリン酸、ステアリン酸、イソステアリン酸、オレイン酸、エライジン酸、バクセン酸、リノール酸、リノレン酸、ツベルクロステアリン酸、アラキジン酸、イソエイコサ酸、ガドレイン酸、エイコセン酸がより好ましく、ラウリン酸、ミリスチン酸、ミリストレイン酸、ペンタデカン酸、パルミチン酸、パルミトレイン酸、イソセチル酸、マルガリン酸、ステアリン酸、イソステアリン酸、オレイン酸、エライジン酸、バクセン酸、リノール酸、リノレン酸がさらに好ましい。
エステル化合物(A2)のヨウ素価については、特に限定はない。
エステル化合物(A3)は、脂肪族一価アルコールと脂肪族多価カルボン酸とがエステル結合した構造を有する化合物であり、また分子内にポリオキシアルキレン基を有しない化合物である。エステル化合物(A3)は1種又は2種以上を使用できる。
脂肪族多価カルボン酸としては、クエン酸、イソクエン酸、リンゴ酸、アコニット酸、オキサロ酢酸、オキサロコハク酸、コハク酸、フマル酸、マレイン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等が挙げられる。これらの中でも、アコニット酸、オキサロ酢酸、オキサロコハク酸、コハク酸、フマル酸、マレイン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸が好ましく、フマル酸、マレイン酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸がより好ましい。
芳香族エステル化合物(A4)は、分子内に少なくとも1つの芳香環を有するエステル化合物である。詳細には、芳香族カルボン酸とアルコールとがエステル結合した構造を有するエステル化合物(A4-1)、芳香族アルコールとカルボン酸とがエステル結合した構造を有するエステル化合物(A4-2)を挙げることができる。また、芳香族エステル化合物(A4)は、分子内にポリオキシアルキレン基を有しない化合物である。芳香族エステル化合物(A4)は、1種又は2種以上を使用できる。
芳香族カルボン酸としては、安息香酸、トルイル酸、ナフトエ酸、フタル酸、イソフタル酸、テレフタル酸、サリチル酸、没食子酸、メリト酸、ケイ皮酸、トリメリット、ピロメリット酸等が挙げられる。これらの中でも、トリメリット酸、フタル酸、イソフタル酸、テレフタル酸が好ましく、トリメリット酸がさらに好ましい。
多価アルコールとしては、エステル化合物(A2)で説明した脂肪族多価アルコールやエステル化合物(A4-2)で説明する芳香族多価アルコール等を挙げることができる。
芳香族アルコールとしては、アルキルベンゼンアルコール等の芳香族1価アルコール、ジアルキルベンゼンアルコール、ビスフェノールA、ビスフェノールZ、1,3,5-トリヒドロキシメチルベンゼン等の芳香族多価アルコール等を挙げることができる。これらの中でもビスフェノールA、ビスフェノールZ、1,3,5-トリヒドロキシメチルベンゼンが好ましく、1,3,5-トリヒドロキシメチルベンゼンがより好ましい。
多価のカルボン酸としては、エステル化合物(A3)で説明した脂肪族多価カルボン酸や、エステル化合物(A4-1)で説明した芳香族多価カルボン酸等を挙げることができる。
含硫黄エステル化合物は、チオジプロピオン酸と脂肪族アルコールとのジエステル化合物及びチオジプロピオン酸と脂肪族アルコールとのモノエステル化合物から選ばれる少なくとも1種である。
含硫黄エステル化合物は、抗酸化能を有する成分である。該含硫黄エステル化合物を使用することで、処理剤の耐熱性を高めることができる。含硫黄エステル化合物は、1種又は2種以上を使用できる。該含硫黄エステル化合物を構成するチオジプロピオン酸の分子量は、400~1000が好ましく、500~900がより好ましく、600~800がさらに好ましい。該含硫黄エステル化合物を構成する脂肪族アルコールは、飽和であっても不飽和であってもよい。また、脂肪族アルコールは、直鎖状であっても分岐構造を有していてもよいが、分岐構造を有するものが好ましい。脂肪族アルコールの炭素数は8~24が好ましく、12~24がより好ましく、16~24がさらに好ましい。脂肪族アルコールとしては、例えば、オクチルアルコール、2-エチルヘキシルアルコール、デシルアルコール、ラウリルアルコール、ミリスチルアルコール、イソセチルアルコール、オレイルアルコールおよびイソステアリルアルコールなどが挙げられ、これらの中でもオレイルアルコール、イソステアリルアルコールが好ましい。
含硫黄エステル化合物は、チオジプロピオン酸と脂肪族アルコールとのジエステル化合物(本段落において、単にジエステルという)とチオジプロピオン酸と脂肪族アルコールとのモノエステル化合物(本段落において、単にモノエステルという)の混合物であってもよい。その際のジエステルとモノエステルのモル比は、100/0~70/30が好ましく、100/0~75/25がより好ましく、100/0~80/20がさらに好ましい。
また、本発明の合成繊維用処理剤は、上記以外の平滑成分として、鉱物油を含有してもよい。ここでいう鉱物油は処理剤を希釈するために用いる低粘度希釈剤ではなく、不揮発分に含まれる。鉱物油としては、特に限定はないが、マシン油、スピンドル油、流動パラフィン等を挙げることができる。鉱物油は、1種又は2種以上を使用してもよい。鉱物油の30℃における粘度は、100~500秒が好ましい。
上記一般式(1)で示される有機スルホン酸化合物(B)は、本発明の処理剤の必須成分である。平滑成分(A)と有機スルホン酸化合物(B)を含有し、かつイオンクロマトグラフ法によって処理剤の不揮発分から検出される硫酸イオン(SO4 2-)の重量割合を200ppm以下、塩素イオン(Cl-)の重量割合を200ppm以下とすることにより、毛羽、糸切れ、ロール汚れを劇的に低減できる。なお、硫酸イオン(SO4 2-)を単に硫酸イオン、塩素イオン(Cl-)を塩素イオンということがある。
一般式(1)中、a及びbは、0以上の整数であって、a+b=5~17を満たす整数である。a+bが5未満の場合、ロール汚れを低減する効果が小さくなる。一方、a+bが17超の場合、融点が高く、処理剤での相溶性が悪くなり、使用できなくなる。a+bは7~17が好ましく、10~15がさらに好ましい。
原料Xが硫酸ナトリウムを含む場合、原料Xから検出される硫酸イオンの重量割合は、有機スルホン酸化合物(B)に対して20000ppm以上である。また、原料Xが塩化ナトリウムを含む場合、原料Xから検出される塩素イオンの重量割合は、有機スルホン酸化合物(B)に対して20000ppm以上である。
このような原料Xを処理剤に用いると、前述したように、硫酸ナトリウムや塩化ナトリウムが紡糸時に延伸ロール上に脱落、蓄積し、糸切れ断糸の増加を引き起こす。また熱延伸を行うロール上では、硫酸ナトリウムや塩化ナトリウムがタールの蓄積を早め、ロール汚れを引き起こす。このような原料Xとしては、HOSTAPUR SAS(ヘキスト社製)、メルソラートH(バイエル社製)等を挙げることができる。
本願効果をより発揮させる点から、原料Yから検出される当該硫酸イオンの重量割合は、有機スルホン酸化合物(B)に対して4000ppm以下がより好ましく、3000ppm以下がさらに好ましく、2000ppm以下が特に好ましい。同様に、原料Yから検出される塩素イオンの重量割合は、有機スルホン酸化合物(B)に対して4000ppm以下がより好ましく、3000ppm以下がさらに好ましく、2000ppm以下が特に好ましい。
なお、本発明におけるイオンクロマトグラフ法による硫酸イオン、塩素イオンの分析方法は、実施例に記載されたものによる。
Mは水素原子、アルカリ金属、アンモニウム基又は有機アミン基である。Mについての詳細は、一般式(1)のところで説明したMと同様である。
本発明の処理剤は、毛羽を減少させるという点から、上記の平滑成分(A)、有機スルホン酸化合物(B)に加え、有機リン酸エステル化合物(C)をさらに含有することが好ましい。有機リン酸エステル化合物(C)としては、上記一般式(2)で示される化合物及び上記一般式(3)で示される化合物から選ばれる少なくとも1種であることが好ましい。
A1Oは炭素数2~4のオキシアルキレン基である。オキシアルキレン単位の繰り返し数であるmは0~15の整数であり、0~10が好ましく、0~3がさらに好ましく、mが0でポリオキシアルキレン基を含有しない場合が特に好ましい。(A1O)mは、オキシアルキレン単位としてオキシエチレン単位を50モル%以上有するポリオキシアルキレン基が好ましい。
また、Q=R1O(A1O)mの場合、一般式(3)示される化合物を構成する2つの有機基[R1O(A1O)m]-は、同一でもよく、異なっていてもよい。
有機リン酸エステル化合物(C1)のP核積分比率(%)は、25~85%が好ましく、35~80%がより好ましく、40~70%がさらに好ましい。有機リン酸エステル化合物(C2)のP核積分比率(%)は、15~65%が好ましく、20~60%がより好ましく、25~55%がさらに好ましい。有機リン酸エステル化合物(C3)のP核積分比率(%)は、0~50%が好ましく、0~45%がより好ましく、0~40%がさらに好ましい。有機リン酸エステル化合物(C4)のP核積分比率(%)は、0~7%が好ましく、0~6%がより好ましく、0~5%がさらに好ましい。無機リン酸のP核積分比率(%)は、0~10%が好ましく、0~9%がより好ましく、0~8%がさらに好ましい。
本発明の処理剤は、原糸に油膜強度、集束性を与え、製糸性を向上させる点から、上記の平滑成分(A)、有機スルホン酸化合物(B)に加え、ノニオン界面活性剤(D)をさらに含有することが好ましい。なお、ノニオン界面活性剤(D)は、前記の平滑成分(A)を除くものいう。ノニオン界面活性剤(D)は、1種又は2種以上を使用してもよい。
ポリヒドロキシエステルは、構造上、ポリオキシアルキレン基含有ヒドロキシ脂肪酸と多価アルコールとのエステルであり、多価アルコールの水酸基のうち、2個以上の水酸基がエステル化されていることが好ましい。したがって、ポリオキシアルキレン基含有ヒドロキシ脂肪酸多価アルコールエステルは、複数の水酸基を有するエステルである。
ポリヒドロキシエステルとしては、例えば、炭素数6~22(好ましくは16~20)のヒドロキシ脂肪酸と多価アルコールとのエステル化物のアルキレンオキシド付加物を挙げることができる。
2種類以上のアルキレンオキシドを付加する場合、それらの付加順序は特に限定されるものでなく、付加形態はブロック状、ランダム状のいずれでもよい。アルキレンオキシドの付加は公知の方法により行うことができるが、塩基性触媒の存在下にて行うことが一般的である。
ポリオキシアルキレン多価アルコールエーテルとは、多価アルコールに対して、エチレンオキシド、プロピレンオキシド、ブチレンオキシドなどのアルキレンオキシドが付加した構造を持つ化合物である。
多価アルコールとしては、エチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジグリセリン、ソルビタン、ソルビトール、ジトリメチロールプロパン、ジペンタエリスリトール、ショ糖等が挙げられる。これらのなかでもグリセリン、トリメチロールプロパン、ショ糖、が好ましい。
ポリオキシアルキレン多価アルコールエーテルの重量平均分子量は、300~10000が好ましく、400~8000がより好ましく、500~5000がさらに好ましい。該分子量が300未満の場合、毛羽、断糸の発生を低減できないことがある。一方、該分子量が10000を超えると、処理剤の摩擦が高くなり、毛羽、断糸の発生を低減できないばかりか、かえって悪化することがある。
ポリオキシアルキレン多価アルコール脂肪酸エステルは、多価アルコールに対して、エチレンオキシド、プロピレンオキシド、ブチレンオキシドなどのアルキレンオキシドが付加した化合物と、脂肪酸とがエステル結合した構造を持つ化合物である。
多価アルコールとしては、グリセリン、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジグリセリン、ソルビタン、ソルビトール、ジトリメチロールプロパン、ジペンタエリスリトール、ショ糖等が挙げられる。これらのなかでも、グリセリン、ジグリセリン、ソルビタン、ソルビトールが好ましい。
ポリオキシアルキレン多価アルコール脂肪酸エステルの重量平均分子量は、300~7000が好ましく、500~5000がより好ましく、700~3000がさらに好ましい。該分子量が300未満の場合、熱処理工程で発煙が発生し、環境を悪化する場合がある。また、断糸の発生を低減できないことがある。一方、該分子量が7000を超えると、処理剤の摩擦が高くなり、毛羽、断糸の発生を低減できないばかりか、かえって悪化することがある。
ポリオキシアルキレン脂肪族アルコールエーテルとは、脂肪族一価アルコールに対し、エチレンオキシド、プロピレンオキシド、ブチレンオキシドなどのアルキレンオキシドを付加した構造を持つ化合物である。
ポリオキシアルキレン脂肪族アルコールエーテルとしては、例えば、オクチルアルコール、2-エチルヘキシルアルコール、デシルアルコール、ラウリルアルコール、トリデシルアルコール、ミリスチルアルコール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコールなどの脂肪族アルコールのアルキレンオキシド付加物が挙げられる。
アルキレンオキシドの付加モル数としては、1~100モルが好ましく、2~70モルがより好ましく、3~50モルがさらに好ましい。また、アルキレンオキシド全体に対するエチレンンオキシドの割合は、20モル%以上が好ましく、30モル%以上がより好ましく、40モル%以上がさらに好ましい。
ポリアルキレングリコールの脂肪酸エステルとはポリオキシエチレングリコール、ポリオキシエチレンポリオキシプロピレングリコールと、脂肪酸とがエステル結合した構造を持つ化合物である。ポリアルキレングリコールの重量平均分子量は、100~1000が好ましく、150~800がより好ましく、200~700がさらに好ましい。
多価アルコール脂肪酸エステルは、多価アルコールと脂肪酸がエステル結合した構造を持つ化合物であり、上記の平滑成分(A)を除く化合物である。
多価アルコールとしては、エチレングリコール、トリメチロールプロパン、ペンタエリスリトール、エリスリトール、ジエチレングリコール、ジグリセリン、ソルビタン、ソルビトール、ジトリメチロールプロパン、ショ糖等が挙げられる。これらのなかでも、エチレングリコール、グリセリン、ジグリセリン、ソルビタン、ソルビトールが好ましい。
多価アルコール脂肪酸エステルの重量平均分子量は、100~1000が好ましく、200~800がより好ましく、300~600がさらに好ましい。
本発明の処理剤は、平滑成分(A)と、上記一般式(1)で示される有機スルホン酸化合物(B)とを含有するものである。さらに、イオンクロマトグラフ法によって処理剤の不揮発分から検出される硫酸イオン(SO4 2-)の重量割合が200ppm以下であり、かつ塩素イオン(Cl-)の重量割合が200ppm以下である。このように、処理剤の不揮発分から検出される硫酸イオン及び塩素イオンを所定の重量割合以下とすることにより、毛羽、糸切れ、ロール汚れを劇的に低減できる。
当該硫酸イオンの重量割合が200ppm超となる場合又は当該塩素イオンの重量割合が200pm超となる場合、硫酸ナトリウムや塩化ナトリウムが紡糸時に延伸ロール上に脱落、蓄積し、糸切れ断糸の増加を引き起こしたり、熱延伸を行うロール上では、タールの蓄積を早めロール汚れを引き起こしたりする。
なお、本発明におけるイオンクロマトグラフ法による硫酸イオン、塩素イオンの分析方法は、実施例に記載されたものによる。また、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を除去し、恒量に達した時の絶乾成分をいう。
本発明の合成繊維用処理剤は、処理剤のエマルション化、繊維への付着性補助、繊維からの処理剤の水洗、繊維への制電性、潤滑性、集束性の付与等のために、上記の有機スルホン酸化合物(B)、有機リン酸エステル化合物(C)及びノニオン界面活性剤(D)以外の界面活性剤を含有してもよい。このような界面活性剤としては、脂肪酸石鹸等のアニオン界面活性剤;アルキルアミン塩、アルキルイミダゾリニウム塩、第4級アンモニウム塩等のカチオン界面活性剤;ラウリルジメチルベタイン、ステアリルジメチルベタイン等の両性界面活性剤;ジメチルラウリルアミンオキサイド等が挙げられる。これら界面活性剤は、1種又は2種以上を使用できる。これら界面活性剤を含有する場合の処理剤の不揮発分に占める当該界面活性剤の重量割合は、特に限定はないが、0.01~15重量%が好ましく、0.1~10重量%がより好ましい。なお、ここでいう界面活性剤は、重量平均分子量が1000未満のものをいう。
本発明の合成繊維フィラメント糸条の製造方法は、原料合成繊維フィラメント糸条に、本発明の合成繊維用処理剤を付与する工程を含むものである。発明の製造方法によれば、スカムや糸切れの発生を低減することができ、糸品位に優れた合成繊維フィラメント糸条を得ることができる。なお、本発明における原料合成繊維フィラメント糸条とは、処理剤が付与されていない合成繊維フィラメント糸条をいう。
本発明の繊維構造物は、上記の本発明の製造方法で得られた合成繊維フィラメント糸条を含むものである。具体的には、本発明の合成繊維用処理剤が付与された合成繊維フィラメント糸条を用いてウォータージェット織機、エアジェット織機、または、レピア織機で織られた織物、および丸編み機、経編み機、または、緯編み機で編まれた編物である。また繊維構造物の用途としては、タイヤコード、シートベルト、エアバッグ、魚網、ロープ等の産業資材、衣料用等が挙げられる。織物、編物を製造する方法としては、特に限定はなく、公知の手法を採用できる。
(原料X-1)
有機スルホン酸化合物(B)を含む原料X-1として、HOSTAPUR SAS93(ヘキスト社製、有機スルホン酸化合物(B)93重量%)を用いた。原料X-1には、多量のボウ硝が含まれている。原料X-1に含まれる硫酸イオン(SO4 2-)及び塩素イオン(Cl-)の含有量(重量割合)をイオンクロマトグラフにて測定したところ、有機スルホン酸化合物(B)に対して、硫酸イオンは25950ppmであり、塩素イオンは62ppmであった。
有機スルホン酸化合物(B)を含む原料X-2として、メルソラートH95(バイエル社製、有機スルホン酸化合物(B)95重量%)を用いた。原料X-2には、多量の塩化ナトリウムが含まれている。原料X-2に含まれる硫酸イオン(SO4 2-)及び塩素イオン(Cl-)の含有量(重量割合)をイオンクロマトグラフにて測定したところ、有機スルホン酸化合物(B)に対して、硫酸イオンは820ppmであり、塩素イオンは30170ppmであった。
有機スルホン酸化合物(B)を含む原料Y-1、Y-2は、上記の有機スルホン酸化合物(B)を含む原料X-1、X-2を精製し、無機物を除去することにより得ることができる。無機物の除去方法は公知の方法を用いることができ、実施例に示す精製方法に限定されない。
メタノール550部とイオン交換水400部を混合し、45±5℃で調温し、攪拌しながら上記の原料X-1 700部を徐々に投入し、完全に溶解させた。次にこの溶解液を室温で20時間静置し、ボウ硝を沈降させた。ボウ硝の含まれない上澄み液を取り出し、60~80℃で減圧蒸留を行い、メタノールと水の一部を除去し、有機スルホン酸化合物(B)を70重量%含む原料Y-1を得た。
原料Y-1に含まれる硫酸イオン(SO4 2-)及び塩素イオン(Cl-)の含有量(重量割合)をイオンクロマトグラフにて測定したところ、有機スルホン酸化合物(B)に対して、硫酸イオンは1085ppmであり、塩素イオンは60ppmであった。
イオン交換水600部を80±5℃に加温し、撹拌しながら上記の原料X-2 400部を徐々に投入し、完全に溶解させた。次にこの溶解液を40℃に冷却後、イオン交換樹脂を用いて塩化ナトリウムを除去し、有機スルホン酸化合物(B)を40重量%含む原料Y-2を得た。
原料Y-2に含まれる硫酸イオン(SO4 2-)及び塩素イオン(Cl-)の含有量(重量割合)をイオンクロマトグラフにて測定したところ、有機スルホン酸化合物(B)に対して、硫酸イオンは105ppmであり、塩素イオンは2115ppmであった。
(原料Z-1の調製)
反応容器にイソセチルアルコール820部を仕込み、攪拌しながら60±5℃で五酸化二燐180部を反応温度に注意しながら少量ずつ投入した。その後、75±5℃で3時間熟成し、不揮発分が100量%の有機リン酸エステル化合物(C)を含む原料Z-1を調製した。
有機リン酸エステル化合物(C1)、(C2)、(C3)、(C4)及び無機燐酸のP核積分比率は、それぞれ33.05%、29.81%、33.82%、2.76%、0.56%であった。
反応容器に炭素数C11~15のアルコール800部を仕込み、攪拌しながら60±5℃で五酸化二燐200部を反応温度に注意しながら少量ずつ投入した。その後、75±5℃で3時間熟成し、有機リン酸エステル化合物(C)を含む原料Z-2を調製した。
有機リン酸エステル化合物(C1)、(C2)、(C3)、(C4)及び無機燐酸のP核積分比率は、それぞれ44.23%、40.31%、13.79%、1.09%、0.58%であった。
上記で調製した原料Z-2 997部に、イオン交換水3部を投入し、90℃で3時間の加水処理を行った。その後、115℃で3時間の脱水処理を行い、有機リン酸エステル化合物(C)を含む原料Z-3を調製した。
有機リン酸エステル化合物(C1)、(C2)、(C3)、(C4)及び無機燐酸のP核積分比率は、それぞれ56.72%、40.49%、0.00%、0.00%、2.78%であった。
反応容器にオレイルアルコール600部を仕込み、攪拌しながら70±5℃で五酸化二燐110部を反応温度に注意しながら少量ずつ投入した。その後、75±5℃で3時間熟成し、有機リン酸エステル化合物(C)を含む原料Z-4を調製した。
有機リン酸エステル化合物(C1)、(C2)、(C3)、(C4)及び無機燐酸のP核積分比率は、それぞれ57.65%、35.26%、4.57%、0.44%、2.07%であった。
反応容器にオレイルアルコール600部を仕込み、攪拌しながら70±5℃で五酸化二燐110部を反応温度に注意しながら少量ずつ投入した。その後、70±5℃で3時間熟成した。次にイオン交換水15部を投入し、90℃で3時間の加水処理を行い、次いでジブチルエタノールアミン200部を徐々に投入して中和を行い、有機リン酸エステル化合物(C)を含む原料Z-5を調製した。
有機リン酸エステル化合物(C1)、(C2)、(C3)、(C4)及び無機燐酸のP核積分比率は、それぞれ55.18%、35.38%、2.43%、0.00%、7.01%であった。
上記で調製した原料Z-1 970部に、イオン交換水30部を投入し、90℃で3時間の加水処理を行った。その後、115℃で3時間の脱水処理を行い、有機リン酸エステル化合物(C)を含む原料Z-3を調製した。
有機リン酸エステル化合物(C1)、(C2)、(C3)、(C4)及び無機燐酸のP核積分比率は、それぞれ65.43%、31.74%、0.00%、0.00%、2.83%であった。
測定試料の不揮発分約30mgを直径5mmのNMR用試料管に秤量し、重水素化溶媒として約0.5mlの重水(D2O)を加えて溶解させて、31P-NMR測定装置(BRUKER社製AVANCE400、162MHz)で測定した。
表2、3に記載の成分を混合して、均一になるまで攪拌し、処理剤を調製した。調製した各処理剤を用いて、下記の方法でピンの汚れ蓄積、ピンの汚れ拭き取り性、張力変動を評価した。その結果を表2、3に示す。
なお、表2、3の処理剤の不揮発分組成の数字は、処理剤の不揮発分に占める各成分(原料X、Y、Zは、それらの不揮発分)の重量割合を示す。また、表2、3の処理剤成分の詳細は表1に示す。
試料(処理剤の不揮発分又は原料X、Y、Zの不揮発分)5gを正確に量りとり、撹拌しながら超純水95gを少しずつ加え、水溶液を作製し、100mlメスフラスコで定容とする。作製した水溶液2mlを、ODS(シリカゲルにオクタデシル基を化学結合させた)前処理カートリッジに通し、親油性の物質を除去した液を、イオンクロマトグラフ分析に供する。以下のイオンクロマトグラフ条件により検出を行った。濃度既知の標準液に対するピーク面積比にて検出量を測定し、硫酸イオン(SO4 2-)、リン酸イオン(PO4 3-)、塩素イオン(Cl-)の量を換算した。なお、定量限界は、硫酸イオン(SO4 2-)では0.6ppm以下、塩素イオン(Cl-)では1.0ppm以下、リン酸イオン(PO4 3-)では0.3ppm以下であった。表2、3における*は、定量限界以下を示す。
<イオンクロマトグラフ条件>
装置:Dionex製 ICS-1500 サプレッサ使用
分析カラム:Dionex IonPac AS14 内径4.0mm×長さ50mm
ガードカラム:Dionex IonPac AG14 内径4.0mm×長さ250mm
溶離液:3.5mmolNa2CO3、1.0mmolNaHCO3
流量:1.5ml/min
上記で調製した処理剤を1000デニール、96フィラメントの無給油ポリエステルフィラメントに定量的に20重量%付与させ、走糸法摩擦測定機にて150℃に加熱したローラーを通過させ揮発分を除去した後、250℃に加温した梨地クロムピンと接触させ、初期張力500g、走糸速度2m/分で4時間走行させ、ピンの汚れ蓄積の程度、ピンの汚れ拭き取り性、張力変動を評価した。なお、より厳しい評価を行うため、処理剤を20重量%付与した。
◎:汚れがほとんど認められない
○:汚れが僅かに認められる
×:明らかに汚れが蓄積している
張力変動値(g)= 糸を4時間走行させた後の張力(g)- 初期の張力(g)
また、張力変動値から、下記基準で張力変動を評価した。
◎:0gから30g未満
○:30g以上50g未満
×:50g以上
梨時クロムピン上に発生した汚れを、水酸化ナトリウムを水とグリセリンに溶解した溶液をガーゼにしみこませて拭き取った。拭き取るまでに要した回数により、拭き取り性を評価した。
◎:5回未満の拭取りで汚れをふき取ることができる
○:5回以上20回未満の拭取りで拭き取ることができる
×:20回以上の拭取りで拭き取れない
一方、比較例では、処理剤の不揮発分から検出される硫酸イオン又は塩素イオンの割合が高く、そのためピンの汚れ蓄積が多くあり、また拭き取り性に劣っている。また、張力変動値が極めて大きく、毛羽、糸切れが多発することがわかる。
Claims (11)
- 処理剤に占める前記平滑成分(A)の重量割合が、20~70重量%である、請求項1に記載の処理剤。
- 処理剤の不揮発分に占める前記有機スルホン酸化合物(B)の重量割合が1.25~7重量%である、請求項1又は2に記載の処理剤。
- 有機リン酸エステル化合物(C)をさらに含有し、
イオンクロマトグラフ法によって処理剤の不揮発分から検出されるリン酸イオン(PO4 3-)の重量割合が500ppm以下である、請求項1~3のいずれかに記載の処理剤。 - 処理剤の不揮発分に占める前記有機リン酸エステル化合物(C)の重量割合が0.05~5重量%である、請求項4に記載の処理剤。
- 前記有機リン酸エステル化合物(C)が、下記一般式(2)で示される化合物及び下記一般式(3)で示される化合物から選ばれる少なくとも1種である、請求項4又は5に記載の処理剤。
- さらにノニオン界面活性剤(D)を含む、請求項1~6のいずれかに記載の処理剤。
- 処理剤の不揮発分に占める前記ノニオン界面活性剤(D)の重量割合が20~70重量%である、請求項7に記載の処理剤。
- 原料合成繊維フィラメント糸条に、請求項1~8のいずれかに記載の処理剤が付与された合成繊維フィラメント糸条。
- 原料合成繊維フィラメント糸条に、請求項1~8のいずれかに記載の処理剤を付与する工程を含む、合成繊維フィラメント糸条の製造方法。
- 請求項9に記載の合成繊維フィラメント糸条及び/又は請求項10の製造方法で得られた合成繊維フィラメント糸条を含む、繊維構造物。
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KR101896536B1 (ko) | 2018-09-07 |
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