CN105492688A - Treatment agent for synthetic fibers and use thereof - Google Patents

Treatment agent for synthetic fibers and use thereof Download PDF

Info

Publication number
CN105492688A
CN105492688A CN201580000248.0A CN201580000248A CN105492688A CN 105492688 A CN105492688 A CN 105492688A CN 201580000248 A CN201580000248 A CN 201580000248A CN 105492688 A CN105492688 A CN 105492688A
Authority
CN
China
Prior art keywords
acid
finishing agent
weight
alcohol
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201580000248.0A
Other languages
Chinese (zh)
Other versions
CN105492688B (en
Inventor
氏野郁也
奥泽政巨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Matsumoto Yushi Seiyaku Co Ltd
Original Assignee
Matsumoto Yushi Seiyaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Matsumoto Yushi Seiyaku Co Ltd filed Critical Matsumoto Yushi Seiyaku Co Ltd
Publication of CN105492688A publication Critical patent/CN105492688A/en
Application granted granted Critical
Publication of CN105492688B publication Critical patent/CN105492688B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • D06M13/248—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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

The purpose of the present invention is to provide a treatment agent for synthetic fibers, which is used for the production of synthetic fibers and is capable of reducing roll fouling, while having excellent heat resistance. The present invention is a treatment agent for synthetic fibers, which contains a smoothing component (A) and an organic sulfonic acid compound (B) represented by general formula (1). The weight ratio of the organic sulfonic acid compound (B) in the nonvolatile content of the treatment agent is 1.25-12% by weight. The weight ratio of sulfate ions (SO4 2-) detected from the nonvolatile content of the treatment agent by ion chromatography is 200 ppm or less, while the weight ratio of chlorine ions (Cl-) is 200 ppm or less. (In formula (1), each of a and b represents an integer of 0 or more; (a + b) is an integer from 5 to 17; and M represents a hydrogen atom, an alkali metal, an ammonium group or an organic amine group.)

Description

Synthetic fiber finishing agent and utilization thereof
Technical field
The present invention relates to synthetic fiber finishing agent and utilization thereof.In more detail, relate to the synthetic fiber finishing agent used when manufacturing synthetic fiber resin, the synthetic fiber filament yarn line employing this finishing agent manufacture method and comprise the fiber structure of this synthetic fiber filament yarn line.
Background technology
, with the fiber of fibre finishing process by temporarily curling, and be used in stretching process all the time, but shorten this operation recently, have employed method oil supply (oiling) yarn being directly used in stretching process.
In the method, in stretching process, once there is the problems such as broken yarn, a large amount of fiber losses can be caused, therefore, need to do one's utmost to avoid having problems in stretching process.The main cause of the generation of problem is the fibre damage of yarn breakage etc., in order to prevent this problem, needs the synthetic fiber finishing agent of lubricity and excellent heat resistance.
Moreover, achieve that the such physical property of the high-tenacity of fiber, low-shrinkageization improves, the multiterminal (his エ Application De) when producing, the so-called so productive raising of high speed, the roller that can not become problem so far pollutes the problem causing creating fine hair, broken yarn increases.Therefore be noted: in order to roller is remained clean conditions, the cleaning interval of roller is shortened, and cleaning number of times increases, and productivity reduces.
For this problem, in patent document 1, proposition has and uses the synthetic fiber finishing agent of phosphate series anion surfactant and sulphonic acid ester series anion surfactant.But, there is following shortcoming when using in spindle (spindle) mode in this finishing agent: heat resistance and lubricity insufficient, finish composition etc. after heat deterioration lodges in draw roll, rub through time rise, produce in stretching process broken yarn, fiber quality deterioration.
In addition, in patent document 1, also propose to have in above-mentioned anion surfactant and to have used the finishing agent of specific ester and antioxidant.But, even such finishing agent, the heat resistance of strict sliver part processed also cannot be met.
Moreover, for the problems referred to above, propose in patent document 2 and use the ester of polyalcohol, there is the ester of the carboxylic acid of thioether group and alcohol, secondary sulphonic acid ester, alkyl phosphate, hindered phenol system antioxidant and the finishing agent obtained.But, for realizing the so productive raising of high-tenacity, low-shrinkage, high speed thus the roller not becoming problem so far pollutes the fine hair, the broken yarn that cause, even if employ this finishing agent, can not improve.In addition, when employing the antioxidant recorded in patent document 2, also there is fiber in the keeping of fiber can the shortcoming of variable color gradually.
Therefore, expect to obtain to suppress because the cleaning interval of roller is shortened, cleaned number of times and increase and the finishing agent that causes productive reduction, excellent heat resistance.
At first technical literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 59-211680 publication
Patent document 2: Japanese Unexamined Patent Publication 8-120563 publication
Summary of the invention
The technical problem that invention will solve
The object of the present invention is to provide a kind of that use when manufacturing synthetic resin, can reduce that roller pollutes, the synthetic fiber finishing agent of its excellent heat resistance, employ the manufacture method of the synthetic fiber filament yarn line of this finishing agent, comprise the fiber structure of the synthetic fiber filament yarn line obtained by this manufacture method.
For the technological means of dealing with problems
Present inventor has performed the result of further investigation, first find: be 1) a large amount of containing sodium sulphate, sodium chloride in the raw material containing the organic sulfonic acid compound represented by general formula (1); 2) sodium sulphate contained in finishing agent or sodium chloride coming off when spinning, accumulating on draw roll, thus the increase causing broken yarn break and for the roller carrying out hot-stretch, accelerate accumulation tar, cause roller to pollute.Therefore, the sulfate ion (SO 3) by detecting from the nonvolatile component of finishing agent 4 2-) and chlorion (Cl -) be set in regulation ratio below, sharply can reduce roller and pollute, so far complete the present invention thus.
Namely, the organic sulfonic acid compound (B) that synthetic fiber of the present invention contain level and smooth composition (A) with finishing agent and represented by following general formula (1), and, the part by weight that described organic sulfonic acid compound (B) is shared in the nonvolatile component of finishing agent is 1.25 ~ 12 % by weight, the sulfate ion (SO detected from the nonvolatile component of finishing agent by the chromatography of ions 4 2-) part by weight be below 200ppm, chlorion (Cl -) part by weight be below 200ppm.
[changing 1]
(in formula (1), a and b is the integer of more than 0 and is the integer meeting a+b=5 ~ 17.M is hydrogen atom, alkali metal, ammonium or organic amino group).
The part by weight that preferred described level and smooth composition (A) is shared in finishing agent is 20 ~ 70 % by weight.
The part by weight that preferred described organic sulfonic acid compound (B) is shared in the nonvolatile component of finishing agent is 1.25 ~ 7 % by weight.
Preferred finishing agent of the present invention also containing organophosphorus compounds (C), and by phosphate anion (PO that the chromatography of ions detects from the nonvolatile component of finishing agent 4 3-) part by weight be below 500ppm.
The part by weight that preferred described organophosphorus compounds (C) is shared in the nonvolatile component of finishing agent is 0.05 ~ 5 % by weight.
Preferred described organophosphorus compounds (C) is at least one selected from the compound represented by following general formula (2) and the compound represented by following general formula (3).
[changing 2]
(in formula (2), R 1for the alkyl of carbon number 6 ~ 24.A 1o is the oxyalkylene of carbon number 2 ~ 4, and m is the integer of 0 ~ 15, and n is the integer of 1 ~ 2.M 1for hydrogen atom, alkali metal, ammonium or organic amino group).
[changing 3]
(in formula (3), R 1for the alkyl of carbon number 6 ~ 24.A 1o is the oxyalkylene of carbon number 2 ~ 4, and m is the integer of 0 ~ 15.M 1for hydrogen atom, alkali metal, ammonium or organic amino group.Q 1for M 1or R 1o (A 1o) m.Y is 1 or 2).
Preferred finishing agent of the present invention is also containing non-ionic surface active agent (D).
The part by weight that preferred described non-ionic surface active agent (D) is shared in the nonvolatile component of finishing agent is 20 ~ 70 % by weight.
Synthetic fiber filament yarn line of the present invention imparts the synthetic fiber filament yarn line after above-mentioned finishing agent to Material synthesis fiber filament yarn.
The manufacture method of synthetic fiber filament yarn line of the present invention comprises the manufacture method of Material synthesis fiber filament yarn being given to the operation of above-mentioned finishing agent.
Fiber structure of the present invention is the fiber structure of the synthetic fiber filament yarn line comprising above-mentioned synthetic fiber filament yarn line and/or obtain by above-mentioned manufacture method.
Invention effect
When using synthetic fiber finishing agent of the present invention, the roller that can reduce when manufacturing synthetic fiber pollutes, excellent heat resistance.Its result, the cleaning interval of roller is elongated, can reduce this cleaning number of times, and the productivity that can realize synthetic fiber improves.
Manufacturing method according to the invention, can reduce the generation of scum silica frost or broken yarn, can obtain the synthetic fiber filament yarn line of yarn excellent quality.Fiber structure excellent quality of the present invention.
Detailed description of the invention
The organic sulfonic acid compound (B) that synthetic fiber of the present invention contain level and smooth composition (A) with finishing agent and represented by above-mentioned general formula (1), and the sulfate ion making to utilize the chromatography of ions to detect from the nonvolatile component of finishing agent and chlorion are for below normal concentration.Below, be described in detail.
[level and smooth composition (A)]
The required composition that level and smooth composition (A) is finishing agent of the present invention.As level and smooth composition (A), can enumerate: the ester compounds (A1) 1) with the ester bond structure that aliphatic monobasic alcohol and aliphatic acid are formed, 2) there is the ester compounds (A2) of the ester bond structure that aliphatic polyol and aliphatic acid are formed, 3) there is the ester compounds (A3) of the ester bond structure that aliphatic monobasic alcohol and aliphatic polycarboxylic acid are formed, 4) there is in molecule the aromatic ester compound (A4) of aromatic rings, 5) ester compounds (A5) of sulfur-bearing, 6) mineral oil (A6) etc. are generally used as the known level and smooth composition of synthetic fibre treating agent.Level and smooth composition (A) can use one kind or two or more.
1) ester compounds (A1)
Ester compounds (A1) is the compound with the ester bond structure that aliphatic monobasic alcohol and aliphatic acid (aliphatic monocarboxylic acid) are formed, and is the compound in molecule without polyoxy alkylidene.Ester compounds (A1) can use a kind or 2 kinds.
As ester compounds (A1), the compound preferably represented by following general formula (4).
[changing 4]
R 2-COO-R 3(4)
(in formula, R 2represent alkyl or the thiazolinyl of carbon number 4 ~ 24, R 3represent alkyl or the thiazolinyl of carbon number 6 ~ 24.)
R 2carbon number be preferably 6 ~ 22, be more preferably 8 ~ 20, more preferably 10 ~ 18.If this carbon number is less than 4, then oil film dies down, and likely causes fine hair to increase.On the other hand, if this carbon number is more than 24, then the friction between fibre metal is increased, and also likely causes fine hair to increase.R 2can be arbitrary in alkyl or alkenyl, but consider from the point of excellent heat resistance, preferred alkyl.
R 3carbon number be preferably 6 ~ 22, be more preferably 8 ~ 20, more preferably 10 ~ 18.If this carbon number is less than 6, then oil film dies down, and therefore likely causes fine hair to increase.On the other hand, if this carbon number is more than 24, then the friction between fibre metal is increased, and likely causes fine hair to increase.R 3can be arbitrary in alkyl or alkenyl, but high from film strength, not easily to produce fine hair point be considered, preferred thiazolinyl.
As ester compounds (A1); be not particularly limited, such as, can enumerate: 2-decyl four capryl erucic acid ester, 2-decyl four capryl oleate, 2-octyldodecyl stearate, palmitic acid isooctyl acrylate, stearic acid isooctyl acrylate, palmitic acid butyl ester, stearic acid butyl ester, oleic acid butyl ester, oleic acid isooctyl acrylate, oleic acid Lauryl Ester, stearic acid isotridecyl ester, stearic acid different cetyl ester, oleic acid iso stearyl ester, sad oil base ester, laurate oil base ester, oleyl palmitate, stearic acid oil base ester, oleic acid oil base ester etc.In these, preferred 2-decyl four capryl oleate, 2-octyldodecyl stearate, palmitic acid isooctyl acrylate, stearic acid isooctyl acrylate, oleic acid Lauryl Ester, stearic acid isotridecyl ester, the different cetyl ester of stearic acid, oleic acid iso stearyl ester, oleic acid oil base ester.
Ester compounds (A1) can use usually commercially available aliphatic acid and aliphatic monobasic alcohol to be obtained by known method synthesis.
2) ester compounds (A2)
Ester compounds (A2) is the compound with the ester bond structure that aliphatic polyol and aliphatic acid (aliphatic monocarboxylic acid) are formed, and is the compound in molecule without polyoxy alkylidene.Ester compounds (A2) can use a kind or two or more.
Form ester compounds (A2) as long as aliphatic polyol binary more than be just not particularly limited, can use a kind or two or more.Consider from the point of film strength, polyalcohol is preferably more than ternary, more preferably ternary ~ quaternary, further preferred ternary.
As aliphatic polyol, such as can enumerate: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl isophthalic acid, ammediol, 1,5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, glycerine, trimethylolpropane, pentaerythrite, erythrite, two glycerine, sorbitan, D-sorbite, two trimethylolpropanes, dipentaerythritol, triglycerin, four glycerine, sucrose etc.Wherein, preferably glycerine, trimethylolpropane, pentaerythrite, erythrite, two glycerine, sorbitan, D-sorbite, two trimethylolpropanes, dipentaerythritol, sucrose, more preferably glycerine, trimethylolpropane, pentaerythrite, erythrite, two glycerine, sorbitan, further preferably glycerine, trimethylolpropane.
The aliphatic acid forming ester compounds (A2) can be saturated, also can be unsaturated.The quantity of unsaturated bond is not particularly limited, but when having more than 3, and oxidation causes more deteriorated, finishing agent thickening, destroys lubricity, therefore preferably 1 or 2.As the carbon number of aliphatic acid, consider from the point taking into account film strength and lubricity, preferably 8 ~ 24, more preferably 10 ~ 20, further preferably 12 ~ 18.Aliphatic acid can use a kind or two or more, also can be used together saturated fatty acid and unrighted acid.
As aliphatic acid, can enumerate: butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, laurate, myristic acid, nutmeg oleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, antiform oleic acid, vaccenic acid, linoleic acid, linolenic acid, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid (gadoleicacid), arachidonic acid (eicosenoicacid), behenic acid, isobehenic acid, erucic acid, tetracosa carbon acid, different tetracosa carbon acid, nervonic acid, cerinic acid, montanic acid, melissic acid etc.
In these, preferably octanoic acid, n-nonanoic acid, capric acid, laurate, myristic acid, nutmeg oleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, antiform oleic acid, vaccenic acid, linoleic acid, linolenic acid, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid, arachidonic acid, behenic acid, isobehenic acid, erucic acid, tetracosa carbon acid, different tetracosa carbon acid, nervonic acid, more preferably capric acid, laurate, myristic acid, nutmeg oleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, antiform oleic acid, vaccenic acid, linoleic acid, linolenic acid, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid, arachidonic acid, further preferred laurate, myristic acid, nutmeg oleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, antiform oleic acid, vaccenic acid, linoleic acid, linolenic acid.
Ester compounds (A2) is the compound of the ester bond in molecule with more than 2, but considers from the point of yarn processed, preferably has the compound of the ester bond of more than 3 in molecule, is preferably the compound in molecule with 3 ester bonds further.
The iodine value of ester compounds (A2) is not particularly limited.
The weight average molecular weight of ester compounds (A2) is preferably 300 ~ 1200, is more preferably 300 ~ 1000, and more preferably 500 ~ 1000.When this weight average molecular weight is less than 300, there is film strength deficiency, the situation that fine hair increases, and the situation about increasing of being fuming during heat treatment.On the other hand, when this weight average molecular weight is more than 1200, just flatness is not enough, fine hair is multiple, can't obtain the fiber of high-quality, and there is the situation of quality badness of weaving or knitting process.It should be noted that, weight average molecular weight of the present invention is the high speed gel permeation chromatography subtraction unit HLC-8220GPC utilizing Tosoh (strain) to manufacture, under sample solution concentration 3mg/cc, inject splitter KF-402HQ, KF-403HQ that Showa electrician (strain) manufactures, and calculated by the peak measured by differential refraction rate detector.
As ester compounds (A2), such as, can enumerate: trimethylolpropane tris caprylate, trimethylolpropane tris decylate, trimethylolpropane trilaurate, trimethylolpropane tris oleate, trimethylolpropane (laurate, myristinate, palmitate), trimethylolpropane (laurate, myristinate, oleate), trimethylolpropane (three palm kernel fatty acid esters), trimethylolpropane (three coconut oil fat acid esters), trimethylolpropane dicaprylate, trimethylolpropane dicaprate, trimethylolpropane dilaurate, trimethylolpropane dioleate, trimethylolpropane (laurate, myristinate), trimethylolpropane (laurate, oleate), trimethylolpropane (myristinate, oleate), trimethylolpropane (two palm kernel fatty acid esters), trimethylolpropane (two coconut oil fat acid esters), coconut oil, rapeseed oil, palm oil, trilaurin, glycerol trioleate, glycerol tristearate, diolein, glyceryl monolaurate, two dioleins, sorbitan trioleate, sorbitan (laurate, myristinate, oleate), sorbitan dilaurate, dehydrated sorbitol mono-fatty acid ester, pentaerythrite four caprylate, pentaerythrite four decylate, pentaerythrite four laurate, erythrite four laurate, pentaerythrite (four palm kernel fatty acid esters), pentaerythrite (four coconut oil fat acid esters), erythrite trioleate, erythrite dipalmitate, 1,6-hexylene glycol dioleate etc.
The aliphatic acid that ester compounds (A2) can use employing usually commercially available and aliphatic polyol, utilize known method to synthesize the material obtained.Or, also the natural natural esters that obtain such as natural fruit, seed or flower can directly be used and this natural esters meets the structure of ester compounds (A2), or as required, also can use and adopt known method to refine natural esters, then or can use and utilize fusing point difference to be separated by known method to the ester after refining, re-refine and the ester that obtains.In addition, also can use and ester exchange is carried out to natural esters of more than two kinds (grease) and the ester obtained.
3) ester compounds (A3)
Ester compounds (A3) is the compound with the ester bond structure that aliphatic monobasic alcohol and aliphatic polycarboxylic acid are formed, and is the compound in molecule without polyoxy alkylidene.Ester compounds (A3) can use a kind or two or more.
Form ester compounds (A3) aliphatic monobasic alcohol, be not particularly limited, can use a kind or two or more.Aliphatic monobasic alcohol can be saturated, also can be undersaturated.The quantity of unsaturated bond is not particularly limited, and when having more than 2, oxidation causes more deteriorated, finishing agent thickening, and lubricity is destroyed, and is therefore preferably one.As the carbon number of aliphatic monobasic alcohol, consider from the point of flatness and film strength, be preferably 8 ~ 24, be more preferably 14 ~ 24, more preferably 18 ~ 22.Aliphatic monobasic alcohol can use a kind or two or more, also can be used together saturated fatty acid monohydric alcohol and unsaturated aliphatic monohydric alcohol.
As aliphatic monobasic alcohol, can enumerate: octanol, isooctanol, laruyl alcohol, myristyl alcohol, nutmeg oleyl alcohol, cetanol, different cetanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, trans oleyl alcohol, different oleyl alcohol, gadoleyl alcohol, arachidic alcohol, Isoeicosane alcohol, tadenan, docosyl alcohol, different two lanolin alcohols, suitable sinapinic alcohol, tetracosanol, different tetracosanol, neural alcohol, ceryl alcohol, montanyl alcohol, melissyl alcohol etc.Wherein, preferred octanol, isooctanol, laruyl alcohol, myristyl alcohol, nutmeg oleyl alcohol, cetanol, different cetanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, trans oleyl alcohol, different oleyl alcohol, gadoleyl alcohol, arachidic alcohol, eicosanol, tadenan, docosyl alcohol, different two lanolin alcohols, along sinapinic alcohol, tetracosanol, different tetracosanol, neural alcohol, more preferably nutmeg oleyl alcohol, palmityl alcohol, oleyl alcohol, anti-oleyl alcohol, different oleyl alcohol, gadoleyl alcohol, two Lauryl Alcohols, along sinapinic alcohol, neural alcohol, more preferably oleyl alcohol, trans oleyl alcohol, different oleyl alcohol, gadoleyl alcohol, two Lauryl Alcohols, along sinapinic alcohol.
Form ester (A3) as long as aliphatic polycarboxylic acid's binary more than be just not particularly limited, can use a kind or two or more.The aliphatic polycarboxylic acid used in the present invention does not comprise the sulfur-bearing polybasic carboxylic acid of thio-2 acid etc.The valence mumber of aliphatic polycarboxylic acid is preferably binary.Equally, preferred not hydroxyl in molecule.
As aliphatic polycarboxylic acid, can enumerate: citric acid, isocitric acid, malic acid, aconitic acid, oxaloacetic acid, oxalosuccinic acid, butanedioic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid etc.Wherein, preferred aconitic acid, oxaloacetic acid, oxalosuccinic acid, butanedioic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, more preferably fumaric acid, maleic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid.
As ester compounds (A3), such as, can enumerate: adipic acid dibutyl ester, adipic acid two lauryl, adipic acid two grease, the different cetyl of adipic acid two, dioctyl sebacate, decanedioic acid two lauryl, decanedioic acid two grease, the different cetyl of decanedioic acid two etc.
Ester compounds (A3) is the compound of the ester bond in molecule with more than 2.The iodine value of ester compounds (A3) is not particularly limited.
The weight average molecular weight of ester compounds (A3) is preferably 500 ~ 1000, is more preferably 500 ~ 800, and more preferably 500 ~ 700.When this weight average molecular weight is less than 500, have film strength deficiency, fine hair increases, and the situation about increasing of being fuming during heat treatment.On the other hand, when this weight average molecular weight is more than 1000, fusing point increases, and becomes the scum silica frost Producing reason in weaving or knitting process, there is the situation of quality badness.
Ester compounds (A3) uses usually commercially available aliphatic monobasic alcohol and aliphatic polycarboxylic acid, adopts known method to be synthesized into.
4) aromatic ester compound (A4)
Aromatic ester compound (A4) is the ester compounds at least in molecule with 1 aromatic rings.Specifically, can enumerate: there is the ester compounds (A4-1) of the ester bond structure that aromatic carboxylic acid and alcohol are formed, there is the ester compounds (A4-2) of the ester bond structure that aromatic alcohols and carboxylic acid are formed.In addition, aromatic ester compound (A4) is the compound in molecule without polyoxy alkylidene.Aromatic ester compound (A4) can use a kind or two or more.
The aromatic carboxylic acid forming ester compounds (A4-1) can be monocarboxylic acid, also can be polybasic carboxylic acid.Can use a kind or two or more.
As aromatic carboxylic acid, can enumerate: benzoic acid, toluic acid, naphthoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), salicylic acid, gallic acid, mellitic acid, cinnamic acid, trimellitic acid, pyromellitic acid etc.Wherein, preferred trimellitic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), further preferred trimellitic acid.
The alcohol forming ester compounds (A4-1) can be monohydric alcohol, also can be polyalcohol.In addition, also can be any in aliphatic alcohol, alicyclic alcohol, aromatic alcohols.Monohydric alcohol can use a kind or two or more.Wherein, preferred monohydric alcohol, further preferred aliphat monohydric alcohol.
Can enumerate as monohydric alcohol: alkylbenzene alcohol, dialkyl benzene alcohol, octanol, isooctanol, laruyl alcohol, myristyl alcohol, nutmeg oleyl alcohol, cetanol, different cetanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, anti-oleyl alcohol, different oleyl alcohol, gadoleyl alcohol, arachidic alcohol, Isoeicosane alcohol, tadenan, docosyl alcohol, different two lanolin alcohols, suitable sinapinic alcohol, tetracosanol, different tetracosanol, neural alcohol, ceryl alcohol, montanyl alcohol, melissyl alcohol etc.
As polyalcohol, can enumerate: the aliphatic polyol illustrated in ester compounds (A2), the aromatic polyol etc. illustrated in ester compounds (A4-2).
Form ester compounds (A4-2) aromatic alcohols can use a kind or two or more.As fragrant family alcohol, optimization aromatic polyalcohol, further optimization aromatic trihydroxylic alcohol.
As aromatic alcohols, can enumerate: the aromatic monoalcohols such as alkylbenzene alcohol, the aromatic polyols etc. such as dialkyl benzene alcohol, bisphenol-A, bisphenol Z, 1,3,5-trihydroxy methyl benzene.Wherein, preferred bisphenol-A, bisphenol Z, 1,3,5-trihydroxy methyl benzene, more preferably 1,3,5-trihydroxy methyl benzene.
The carboxylic acid forming ester compounds (A4-2) can be any in aliphatic carboxylic acid, aromatic carboxylic acid.In addition, can be any in monocarboxylic acid, polybasic carboxylic acid.Can use a kind or two or more.Wherein, preferred monocarboxylic acid, further preferred fatty acid.Consider from the point of residual, aliphatic acid is preferably saturated.Aliphatic acid can be straight-chain, also can have side chain.
As monocarboxylic acid, can enumerate: alkylbenzene carboxylic acid, dialkyl benzene carboxylic acid, butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, laurate, myristic acid, nutmeg oleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, antiform oleic acid, vaccenic acid, linoleic acid, linolenic acid, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid (gadoleicacid), arachidonic acid (eicosenoicacid), behenic acid, isobehenic acid, erucic acid, tetracosa carbon acid, different tetracosa carbon acid, nervonic acid, cerinic acid, montanic acid, melissic acid etc.
As polybasic carboxylic acid, can enumerate: the aliphatic polycarboxylic acid illustrated in ester compounds (A3), the aromatic polycarboxylic acid etc. illustrated in ester compounds (A4-1).
5) ester compounds (A5) of sulfur-bearing
The ester compounds of sulfur-bearing is at least one selected from thio-2 acid and the diester compound of aliphatic alcohol and the monoester compound of thio-2 acid and aliphatic alcohol.
The ester compounds of sulfur-bearing is the composition with oxidation resistance.By using the ester compounds of this sulfur-bearing, the heat resistance of finishing agent can be improved.The ester compounds of sulfur-bearing can use a kind or two or more.The molecular weight forming the thio-2 acid of the ester compounds of this sulfur-bearing is preferably 400 ~ 1000, is more preferably 500 ~ 900, and more preferably 600 ~ 800.The aliphatic alcohol forming the ester compounds of this sulfur-bearing can be saturated, also can be undersaturated.In addition, aliphatic alcohol can be straight-chain, also can have branched structure, but preferably have branched structure.The carbon number of aliphatic alcohol is preferably 8 ~ 24, is more preferably 12 ~ 24, and more preferably 16 ~ 24.As aliphatic alcohol, such as, can enumerate: octanol, 2-ethylhexyl alcohol, decyl alcohol, laruyl alcohol, myristyl alcohol, different cetanol, oleyl alcohol and isooctadecanol etc., in these, preferred oleyl alcohol and isooctadecanol.
The ester compounds of sulfur-bearing can be the mixture of the diester compound (in this paragraph, referred to as diester) of thio-2 acid and aliphatic alcohol and the monoester compound (in this paragraph, referred to as monoesters) of thio-2 acid and aliphatic alcohol.Now, the mol ratio of diester and monoesters is preferably 100/0 ~ 70/30, is more preferably 100/0 ~ 75/25, and more preferably 100/0 ~ 80/20.
6) mineral oil (A6)
In addition, in synthetic fiber finishing agent of the present invention, as level and smooth composition other than the above, mineral oil can also be contained.Mineral oil alleged is not herein the low viscosity diluent used in order to dilution process agent, and is included in nonvolatile component.As mineral oil, be not particularly limited, can enumerate: machine oil, bobbin oil, atoleine etc.Mineral oil can use a kind or two or more.The viscosity of mineral oil at 30 DEG C is preferably 100 ~ 500 seconds.
As level and smooth composition (A), consider from the point improving heat resistance, preferably use removing catalyst etc. and refined material.
[organic sulfonic acid compound (B)]
The organic sulfonic acid compound (B) represented by above-mentioned general formula (1) is the neccessary composition of finishing agent of the present invention.By making containing level and smooth composition (A) and organic sulfonic acid compound (B) sulfate ion (SO that detected from the nonvolatile component of finishing agent by the chromatography of ions 4 2-) part by weight be below 200ppm, make chlorion (Cl -) part by weight be below 200ppm, thus can sharply reduce fine hair, broken yarn, roller pollute.It should be noted that, by sulfate ion (SO 4 2-) referred to as sulfate ion, chlorion (Cl -) referred to as chlorion.
In general formula (1), a and b is the integer of more than 0 and is the integer meeting a+b=5 ~ 17.When a+b is less than 5, the effect reducing roller pollution diminishes.On the other hand, when a+b is more than 17, fusing point is high, and the compatibility poor in finishing agent cannot use.A+b is preferably 7 ~ 17, and more preferably 10 ~ 15.
M is hydrogen atom, alkali metal, ammonium or organic amino group.As alkali metal, such as, can enumerate: lithium, sodium, potassium etc.As ammonium and organic amino group, can enumerate: by NR ar br cr dthe group represented.R a, R b, R c, R dindependently and be hydrogen atom, alkyl, thiazolinyl, polyoxy alkylidene.The carbon number of alkyl and thiazolinyl is preferably 1 ~ 24, is more preferably 1 ~ 20, and more preferably 1 ~ 18.Polyoxy alkylidene [-(A 1o) mh] represent, (A 1o) msame with the material represented by general formula (2).
As by NR ar br cr dthe group represented, such as, can enumerate: ammonium, methyl ammonium, ethyl ammonium, propyl group ammonium, butyl ammonium, hexyl ammonium, octyl group ammonium, dimethylammonio, diethyl ammonium, dipropyl ammonium, dibutyl ammonium, dihexyl ammonium, dioctyl ammonium, trimethyl ammonium, triethyl group ammonium, tripropyl ammonium, tributyl ammonium, three hexyl ammoniums, trioctylphosphine ammonium, tetramethyl ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrahexyl ammonium base, four octyl group ammoniums, ethyl-trimethyl ammonium, oxypropyl trimethyl ammonium, butyl trimethyl ammonium, hexyl trimethyl ammonium, octyl trimethyl ammonium, methyl alcohol ammonium, ethanol ammonium, propyl alcohol ammonium, butanols ammonium, hexanol ammonium, octanol ammonium, dimethanol ammonium, diethanolammonium group, two propyl alcohol ammoniums, two butanols ammoniums, two hexanol ammoniums, two octanol ammoniums, three methyl alcohol ammoniums, triethanol ammonium base, three propyl alcohol ammoniums, three butanols ammoniums, three hexanol ammoniums, three octanol ammoniums, (EO6) the amino ether of butyl, (EO6) hexylamino ether, (EO6) octyl amino ether, (EO6) Decylamino ether, (EO6) lauryl amino ether, (EO6) the amino ether of tetradecyl, (EO6) the amino ether of different cetyl, (EO6) the amino ether of oil base, (EO6) stearyl ether, (EO6) the amino ether of cod oil base, (EO6) the amino ether of tetracosyl, (EO10) the amino ether of oil base, (EO10) the amino ether/erucic acid salt of oil base, (EO3) lauryl amino ether, (EO3) lauryl amino ether, (EO7) lauryl amino ether, (EO15) the amino ether of oil base, (PO3, EO5) stearyl ether, (PO5, EO3) stearyl ether.
In the raw material (hereinafter referred to as raw material X) comprising organic sulfoacid compound (B), its manufacture method causes it to contain sodium sulphate and/or sodium chloride.The sodium sulphate that this raw material X comprises, the ratio of sodium chloride can utilize the chromatography of ions, and the part by weight according to the sulfate ion detected in raw material X, chlorion calculates.
When raw material X contains sodium sulphate, the part by weight of the sulfate ion detected from raw material X is, is more than 20000ppm relative to organic sulfonic acid compound (B).In addition, when raw material X contains sodium chloride, the part by weight of the chlorion detected from raw material X is, is more than 20000ppm relative to organic sulfonic acid compound (B).
When such raw material X is used as finishing agent, as previously mentioned, sodium sulphate, sodium chloride can come off when spinning and accumulate on draw roll, cause the increase that broken yarn breaks.In addition, for the roller carrying out hot-stretch, sodium sulphate, sodium chloride can be accelerated to accumulate tar, cause roller to pollute.As such raw material X, can enumerate: HOSTAPURSAS (manufacture of Hoechst company), MersolatH (Beyer Co., Ltd's manufacture) etc.
Considering from the point playing effect of the present invention, for finishing agent of the present invention, using the raw material (hereinafter referred to as raw material Y) containing reducing from the organic sulfonic acid compound (B) of the sodium sulphate in raw material X, sodium chloride to be important.Specifically, preferably, the part by weight of the sulfate ion detected from raw material Y by the chromatography of ions is below 5000ppm relative to organic sulfonic acid compound (B), and the part by weight of chlorion is below 5000ppm relative to organic sulfonic acid compound (B).
Consider from the point of the effect of the better the application of performance, relative to organic sulfonic acid compound, the part by weight of this sulfate ion detected from raw material Y is more preferably below 4000ppm, more preferably below 3000ppm, is particularly preferably below 2000ppm.Equally, relative to organic sulfonic acid compound (B), the part by weight of the chlorion detected from raw material Y is more preferably below 4000ppm, more preferably below 3000ppm, is more preferably below 2000ppm.
It should be noted that, the sulfate ion undertaken by the chromatography of ions in the present invention, the analytical method of chlorion are according to the method recorded in embodiment.
As the method reducing sodium sulphate or sodium chloride from the raw material X containing organic sulfonic acid compound (B), be not particularly limited, known method can be adopted.Such as, can enumerate: when raw material X comprises sodium sulphate, in raw material X, add methyl alcohol, water equal solvent, and make the method etc. of the inorganic matter Precipitations such as sodium sulphate, separation.In addition, when raw material X comprises sodium chloride, can enumerate: by the method for the sodium chloride that comprises in amberplex removing raw material X, carried out the method etc. of adsorbing by ion exchange resin.
Above-mentioned organic sulfonic acid compound (B) has a sulfonic single sulfoacid compound.Finishing agent of the present invention, can also containing the disulfonic acid compound represented by following general formula (5) except this single sulfoacid compound.
[changing 5]
In formula (5), c, d and e are the integer of more than 0, and are the integers meeting c+d+e=4 ~ 16.When c+d+e is less than 4, the effect sometimes reducing roller pollution diminishes.On the other hand, when c+d+e is more than 17, the compatibility poor in finishing agent, can not use sometimes.C+d+e is preferably 6 ~ 16, and more preferably 9 ~ 14.
M is hydrogen atom, alkali metal, ammonium or organic amino group.The details of M is identical with the M that general formula (1) place illustrates.
When containing above-mentioned disulfonic acid compound, 50/50 ~ 99/1 is preferably as single sulfoacid compound of organic sulfonic acid compound (B) and the part by weight (single sulfoacid compound/disulfonic acid compound) of the disulfonic acid compound represented by general formula (5), be more preferably 70/30 ~ 99/1, more preferably 80/20 ~ 98/2.
[organophosphorus compounds (C)]
In finishing agent of the present invention, consider from the point reducing fine hair, except above-mentioned level and smooth composition (A), organic sulfonic acid compound (B) are preferably also containing organophosphorus compounds (C).As organophosphorus compounds (C), at least one preferably selected from the compound represented by above-mentioned general formula (2) and the compound represented by above-mentioned general formula (3).
In general formula (2) and (3), R 1for the alkyl of carbon number 6 ~ 24.A 1o is the oxyalkylene of carbon number 2 ~ 4, and m is the integer of 0 ~ 15.N is the integer of 1 ~ 2.M 1for hydrogen atom, alkali metal, ammonium or organic amino group.Q 1for M 1or R 1o (A 1o) m.Y is 1 or 2.
As R 1alkyl, can enumerate: alkyl, thiazolinyl etc.R 1carbon number be preferably 8 ~ 24, more preferably 12 ~ 24.R 1carbon atom can have distribution, R 1can be straight-chain, also can have side chain, can be saturated or unsaturated.
A 1o is the oxyalkylene of carbon number 2 ~ 4.The repeat number m of oxygen alkylene unit is the integer of 0 ~ 15, is preferably 0 ~ 10, more preferably 0 ~ 3, and particularly preferably m is 0 namely not containing the situation of polyoxy alkylidene.(A 1o) mthe polyoxy alkylidene of aerobic ethylidene more than 50 % by mole is preferably contained as oxygen alkylene unit.
N is the integer of 1 ~ 2.When n=2, form 2 organic group " R of the compound represented by above-mentioned general formula (2) 1o (A 1o) m" can be identical, also can be different.
In addition, at Q=R 1o (A 1o) mwhen, form 2 organic group " R of the compound represented by general formula (3) 1o (A 1o) m" can be identical, also can be different.
M 1for hydrogen atom, alkali metal, ammonium or organic amino group.As alkali metal, such as, can enumerate: lithium, sodium, potassium etc.As ammonium and organic amino group, can enumerate: by NR ar br cr dthe group represented.By NR ar br cr dthe group represented is identical with the M that organic sulfonic acid compound (B) place illustrates.
The mixture of the organophosphorus compounds (C2) represented during n=2 in the organophosphorus compounds (C1) that organophosphorus compounds (C) represents when preferably including n=1 in general formula (2) and general formula (2) or comprise organophosphorus compounds (C1), (C2) and general formula (3) middle Y=1, Q=R 1o (A 1o) mtime the mixture of organophosphorus compounds (C3) that represents.In these mixtures, the organophosphorus compounds (C4) represented when can contain Y=1, Q=hydrogen atom in general formula (3).
P core integration ratio (%) of organophosphorus compounds (C1), (C2), (C3) and (C4) and inorganic phosphate can basis 31calculate from the integrated value at the peak of each phosphorus atoms in P-NMR.It should be noted that, P core integration ratio (%) refers to the value total of the integrated value of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate calculated as 100%.About inorganic phosphate, aftermentioned.
P core integration ratio (%) of organophosphorus compounds (C1) is preferably 25 ~ 82%, and more preferably 35 ~ 80%, further preferably 40 ~ 70%.P core integration ratio (%) of organophosphorus compounds (C2) is preferably 15 ~ 65%, is more preferably 20 ~ 60%, and more preferably 25 ~ 55%.P core integration ratio (%) of organophosphorus compounds (C3) is preferably 0 ~ 50%, is more preferably 0 ~ 45%, and more preferably 0 ~ 40%.P core integration ratio (%) of organophosphorus compounds (C4) is preferably 0 ~ 7%, is more preferably 0 ~ 6%, and more preferably 0 ~ 5%.P core integration ratio (%) of inorganic phosphate is preferably 0 ~ 10%, is more preferably 0 ~ 9%, and more preferably 0 ~ 8%.
As the manufacture method of organophosphorus compounds (C), be not particularly limited, known method can be adopted.Such as, the manufacture method of organophosphorus compounds (C) comprises and making by R 1o (A 1o) mthe organic hydroxy compounds that H represents and phosphoric anhydride P 2o 5react, obtain the operation (I) of reactant.In addition, in operation (I), also can add inorganic phosphate, water, react.The manufacture method of organophosphorus compounds (C) is added water after can being included in operation (I) and carries out the operation (II) of hydrolyzable in above-mentioned reactant.By comprising operation (II) thus organophosphorus compounds (C3) contained in organophosphorus compounds (C), the ratio of (C4) can being adjusted.Relative to above-mentioned organophosphorus compounds (C), the amount of adding the water in above-mentioned reactant to is preferably 0.01 ~ 5 % by weight, and more preferably 0.05 ~ 4 % by weight, further preferably 0.1 ~ 3 % by weight.If the addition of water is less than 0.01 % by weight or more than 5 % by weight, then have the situation of amount that may be difficult to regulate organophosphorus compounds (C3), (C4).As the manufacture method of organophosphorus compounds (C), also can comprise with having M after operation (I) or operation (II) 1alkali cpd carry out the operation (III) that neutralizes.
The heavy metal compound of the arsenic of originating as the impurity in phosphoric anhydride or Phos etc. is comprised in organophosphorus compounds (C).Finishing agent of the present invention also can contain the heavy metal compound of arsenic etc.Consider from the point of the impact on human body or the security to environment, the part by weight of heavy metal compound shared by the nonvolatile component of finishing agent is preferably less than 0.01 % by weight, be more preferably less than 0.005 % by weight, more preferably less than 0.001 % by weight.
When manufacturing organophosphorus compounds (C), produce inorganic phosphate and/or its salt.Therefore, comprise in the raw material (hereinafter referred to as raw material Z) of organophosphorus compounds (C) containing inorganic phosphate and/or its salt.The ratio of inorganic phosphate and/or its salt can by organic hydroxy compounds and phosphoric anhydride P 2o 5ratio, reaction condition etc. adjust.
[non-ionic surface active agent (D)]
Finishing agent of the present invention, from giving precursor film strength, convergence improve the some consideration of yarn processed, preferably except above-mentioned level and smooth composition (A), organic sulfonic acid compound (B), also containing non-ionic surface active agent (D).It should be noted that, non-ionic surface active agent (D) refers to the material except above-mentioned level and smooth composition (A).Non-ionic surface active agent (D) can use a kind or two or more.
As non-ionic surface active agent (D), can enumerate: the fatty acid ester, polyol fatty acid ester etc. of the hydroxy aliphatic acid polyol ester (following, to be sometimes referred to as poly-hydroxy ester) containing polyoxy alkylidene, the ester by after at least one hydroxyl aliphatic acid end-blocking of poly-hydroxy ester, polyalkylene oxide polyol ethers, polyalkylene oxide polyol fatty acid ester, polyalkylene oxide aliphatic alcohol ether, poly alkylene glycol.
(gathering hydroxy ester, by the ester after at least one hydroxyl aliphatic acid end-blocking of poly-hydroxy ester)
Poly-hydroxy ester is structurally preferably the ester of hydroxy fatty acid containing polyoxy alkylidene and polyalcohol, and the hydroxyl of more than 2 in the hydroxyl of polyalcohol is esterified.Therefore, the hydroxy aliphatic acid polyol ester containing polyoxy alkylidene is the ester with multiple hydroxyl.
Hydroxy fatty acid containing polyoxy alkylidene has the structure being combined with polyoxy alkylidene on the alkyl of aliphatic acid by oxygen atom, and the end be not combined with the alkyl of aliphatic acid of polyoxy alkylidene becomes hydroxyl.
As poly-hydroxy ester, such as, can enumerate: the alkylene oxide addition product of the hydroxy fatty acid of carbon number 6 ~ 22 (being preferably 16 ~ 20) and the carboxylate of polyalcohol.
As the hydroxy fatty acid of carbon number 6 ~ 22, such as, can enumerate: Hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric acid, hydroxy stearic acid, ricinoleic acid, preferred hydroxyoctadecanoic base acid, ricinoleic acid.As polyalcohol, such as, can enumerate: ethylene glycol, glycerine, D-sorbite, sorbitan, trimethylolpropane, pentaerythrite etc., preferably glycerine.As alkylene oxide, can enumerate: the carbon numbers such as oxirane, expoxy propane, epoxy butane are the alkylene oxide of 2 ~ 4.
The addition molal quantity of alkylene oxide is preferably 3 ~ 60, and more preferably 8 ~ 50.The ratio of oxirane shared by alkylene oxide is preferably 50 % by mole, more preferably 80 % by mole.
When two or more alkylene oxide of addition, their addition order is not particularly limited, and addition form can be any in block-wise, random shape.The addition of alkylene oxide can be undertaken by known method, but usually carries out under the existence of base catalyst.
Poly-hydroxy ester such as can manufacture as follows, that is: at typical condition, by polyalcohol and hydroxy fatty acid (hydroxy monocarboxylic acids) esterification, obtains carboxylate, then, makes alkylene oxide and this carboxylate carry out addition reaction and manufacture.Poly-hydroxy ester also can suitably manufacture by the following method, that is: use the natural grease obtained of castor-oil plant wet goods or the rilanit special adding hydrogen wherein and obtain, then carry out addition reaction with alkylene oxide and obtain.
In non-ionic surface active agent (D) also containing above-mentioned by the ester after at least one hydroxyl aliphatic acid end-blocking of poly-hydroxy ester.The carbon number of the aliphatic acid of end-blocking is preferably 6 ~ 24, is more preferably 12 ~ 18.The carbon number of the alkyl in aliphatic acid can have distribution, and alkyl can be straight-chain, also can have side chain, can be saturated, also can be undersaturated, also can have the structure of many rings.As such aliphatic acid, such as, can enumerate: laurate, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, 20 carbonic acid, behenic acid, lignoceric acid etc.Method, reaction condition etc. for esterification are not particularly limited, and can use known method, common condition.
As poly-hydroxy ester with by the ester after at least one hydroxyl aliphatic acid end-blocking of poly-hydroxy ester, it is such as rilanit special ethylene oxide adduct, castor oil ethylene oxide adduct, rilanit special ethylene oxide adduct monoleate, rilanit special ethylene oxide adduct dioleate, rilanit special ethylene oxide adduct trioleate, castor oil ethylene oxide adduct trioleate, rilanit special ethylene oxide adduct tristearate, castor oil ethylene oxide adduct tristearate, wherein, from the intermiscibility of finishing agent, film strength, the point that fine hair reduces is considered, preferred rilanit special ethylene oxide adduct, rilanit special ethylene oxide adduct trioleate, rilanit special ethylene oxide adduct tristearate.
(polyalkylene oxide polyol ethers)
Polyalkylene oxide polyol ethers refers to the compound of the structure with on the polyalcohol addition alkylene oxides such as oxirane, expoxy propane, epoxy butane.
As polyalcohol, can enumerate: ethylene glycol, glycerine, trimethylolpropane, pentaerythrite, two glycerine, sorbitan, D-sorbite, two trimethylolpropanes, dipentaerythritol, sucrose etc.In these, preferably glycerine, trimethylolpropane, sucrose.
As the addition molal quantity of alkylene oxide, be preferably 3 ~ 100, be more preferably 4 ~ 70, more preferably 5 ~ 50.In addition, the ratio that oxirane is shared in alkylene oxide is preferably more than 50 % by mole, more preferably more than 80 % by mole.
The weight average molecular weight of polyalkylene oxide polyol ethers is preferably 300 ~ 10000, is more preferably 400 ~ 8000, and more preferably 500 ~ 5000.When this molecular weight is less than 300, the generation of fine hair, broken yarn can not be reduced.On the other hand, if this molecular weight is more than 10000, then the friction of finishing agent uprises, and not only can not reduce the generation of fine hair, broken yarn, but also it can be made to worsen.
As polyalkylene oxide polyol ethers, can enumerate: polyethylene glycol, glycerol epoxy ethane additive product, trimethylolpropane ethylene oxide adduct, pentaerythrite ethylene oxide adduct, two glycerol epoxy ethane additive products, sorbitan ethylene oxide adduct, sorbitan ethylene oxide propylene oxide addition product, D-sorbite ethylene oxide adduct, D-sorbite ethylene oxide propylene oxide addition product, two trimethylolpropane ethylene oxide adducts, dipentaerythritol ethylene oxide adduct, sucrose ethylene oxide adduct etc., but be not limited to these.
(polyalkylene oxide polyol fatty acid ester)
Polyalkylene oxide polyol fatty acid ester has on the polyalcohol addition alkylene oxides such as oxirane, expoxy propane, epoxy butane and the compound of ester bond structure that formed of the compound obtained and aliphatic acid.
As polyalcohol, can enumerate: glycerine, trimethylolpropane, pentaerythrite, erythrite, two glycerine, sorbitan, D-sorbite, two trimethylolpropanes, dipentaerythritol, sucrose etc.In these, preferably glycerine, two glycerine, sorbitan, D-sorbite.
As aliphatic acid, can enumerate: the acid of laurate, myristic acid, nutmeg oleic acid, palmitic acid, palmitoleic acid, isocetic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidic acid, 20 carbonic acid, behenic acid, isobehenic acid, erucic acid, tetracosa carbon, the acid of different tetracosa carbon etc.
As the addition molal quantity of alkylene oxide, be preferably 3 ~ 100, be more preferably 5 ~ 70, more preferably 10 ~ 50.In addition, the ratio that oxirane is shared in alkylene oxide is preferably more than 50 % by mole, more preferably more than 80 % by mole.
The weight average molecular weight of polyalkylene oxide polyol fatty acid ester is preferably 300 ~ 7000, is more preferably 500 ~ 5000, and more preferably 700 ~ 3000.When this molecular weight is less than 300, the situation of ecological deterioration of smoldering in heat treatment step, make.In addition, the generation of broken yarn can not be reduced.On the other hand, if this molecular weight is more than 7000, then the friction of finishing agent increases, and not only can not reduce the generation of fine hair, broken yarn, it can be made on the contrary to worsen.
As polyalkylene oxide polyol fatty acid ester, can enumerate: glycerol epoxy ethane additive product monolaurate, glycerol epoxy ethane additive product dilaurate, glycerol epoxy ethane additive product trilaurin, trimethylolpropane ethylene oxide adduct trilaurin, sorbitan ethylene oxide adduct monoleate, sorbitan ethylene oxide adduct dioleate, sorbitan ethylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide addition product monoleate, sorbitan ethylene oxide propylene oxide addition product dioleate, sorbitan ethylene oxide propylene oxide addition product trioleate, sorbitan ethylene oxide propylene oxide addition product trilaurin, sucrose ethylene oxide adduct trilaurin etc., but be not limited to these.
(polyalkylene oxide aliphatic alcohol ether)
Polyalkylene oxide aliphatic alcohol ether to have on aliphatic monobasic alcohol the addition alkylene oxides such as oxirane, expoxy propane, epoxy butane and the compound of the structure obtained.
As polyalkylene oxide aliphatic alcohol ether, such as, can enumerate: the alkylene oxide addition product of the aliphatic alcohols such as octanol, 2-Ethylhexyl Alcohol, decyl alcohol, laruyl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol.
As the addition molal quantity of alkylene oxide, be preferably 1 ~ 100 mole, be more preferably 2 ~ 70 moles, more preferably 3 ~ 50 moles.In addition, oxirane is preferably more than 20 % by mole relative to the ratio of alkylene oxide entirety, is more preferably more than 30 % by mole, more preferably more than 40 % by mole.
(fatty acid ester of poly alkylene glycol)
The fatty acid ester of poly alkylene glycol refers to the compound with the ester bond structure that polyoxyethylene glycol (polyoxyethyleneglycol), polyoxyethylene polyoxypropylene glycol and aliphatic acid are formed.The weight average molecular weight of poly alkylene glycol is preferably 100 ~ 1000, is more preferably 150 ~ 800, and more preferably 200 ~ 700.
As polyalkylene glycol fatty acid esters, can enumerate: polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monooleate, glycol dioleate, polyethylene glycol mono stearate, polyglycol distearate, polyethylene polypropylene glycol monolaurate, polyethylene polypropylene glycol dilaurate, polyethylene polypropylene glycol monoleate, polyethylene polypropylene glycol dioleate etc., but be not limited thereto.
(polyol fatty acid ester)
Polyol fatty acid ester is the compound with the ester bond structure that polyalcohol and aliphatic acid are formed, and is the compound except above-mentioned level and smooth composition (A).
As polyalcohol, can enumerate: ethylene glycol, trimethylolpropane, pentaerythrite, erythrite, diethylene glycol, two glycerine, sorbitan, D-sorbite, two trimethylolpropanes, sucrose etc.In these, preferred ethylene glycol, glycerine, two glycerine, sorbitan, D-sorbite.
As aliphatic acid, can enumerate: laurate, myristic acid, nutmeg oleic acid, palmitic acid, palmitoleic acid, isocetic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid (gadoleicacid), arachidonic acid (eicosenoicacid), behenic acid, isobehenic acid, erucic acid, tetracosa carbon acid etc.
And this polyol fatty acid ester at least has the hydroxyl of more than 1 or 2.
The weight average molecular weight of polyol fatty acid ester is preferably 100 ~ 1000, is more preferably 200 ~ 800, and more preferably 300 ~ 600.
As fatty acid ester, can enumerate: glyceryl monolaurate, dilaurin, glycerin mono-fatty acid ester, diolein, sorbitan monooleate, sorbitan dioleate, sucrose monolaurate, sucrose dilaurate etc., but be not limited to these.
As non-ionic surface active agent (D), from the some consideration of raising heat resistance, the material after preferably using removing catalyst etc. also to refine.
[synthetic fiber finishing agent]
Finishing agent of the present invention is containing level and smooth composition (A) and the finishing agent of organic sulfonic acid compound (B) that represented by above-mentioned general formula (1).Further, by sulfate ion (SO that the chromatography of ions detects from the nonvolatile component of finishing agent 4 2-) part by weight be below 200ppm, and chlorion (Cl -) part by weight be below 200ppm.Like this, by the sulfate ion detected from the nonvolatile component of finishing agent and chlorion are set as specify part by weight below, thus can sharply reduce fine hair, broken yarn, roller pollute.
This sulfate ion part by weight more than during 200ppm or the part by weight of this chlorion more than 200ppm time, sodium sulphate, sodium chloride come off when spinning and accumulate on draw roll, cause the increase of broken string broken yarn, for the roller carrying out hot-stretch, accelerate the accumulation of tar, cause roller to pollute.
It should be noted that, of the present invention carry out based on the chromatography of ions sulfate ion, chlorion analytical method according to the content recorded in embodiment.In addition, the nonvolatile component in the present invention refers to, heat-treats finishing agent with 105 DEG C, and except desolventizing etc., adiabatic drying when reaching constant becomes powder.
Consider from the better point playing effect of the present invention, the part by weight of this sulfate ion is preferably below 200ppm, is more preferably below 150ppm, more preferably below 100ppm.Equally, the part by weight of this chlorion is preferably below 200ppm, is more preferably below 150ppm, more preferably below 100ppm.
As the method for adjustment of the part by weight of sulfate ion and chlorion, as previously mentioned, comprise the sodium sulphate, the sodium chloride that contain in the raw material X of organic sulfoacid compound (B) realize by being reduced in.
The part by weight shared in the nonvolatile component of finishing agent of level and smooth composition (A) is preferably 20 ~ 70 % by weight, is more preferably 30 ~ 65 % by weight, and more preferably 40 ~ 65 % by weight, be particularly preferably 40 ~ 60 % by weight.When this part by weight is less than 20 % by weight, flatness is not enough sometimes, causes fine hair to increase.On the other hand, when this part by weight is more than 70 % by weight, convergence is not enough, and when emulsification uses, likely emulsion stability is deteriorated and can not uses.
The part by weight of organic sulfonic acid compound (B) shared by the nonvolatile component of finishing agent is 1.25 ~ 12 % by weight, be preferably 1.25 ~ 10 % by weight, be more preferably 1.25 ~ 8 % by weight, more preferably 1.25 ~ 7 % by weight, be particularly preferably 1.5 ~ 6 % by weight.When this part by weight is less than 1.25 % by weight, sometimes can not reduces roller and pollute.On the other hand, when this part by weight is more than 12 % by weight, friction increases, and fine hair increases.
When finishing agent of the present invention contains organophosphorus compounds (C), the phosphate anion (PO detected from the nonvolatile component of finishing agent by the chromatography of ions 4 3-) part by weight be preferably below 500ppm.When the part by weight of this phosphate anion is more than 500ppm, likely comes off on draw roll, cause the increase of broken string broken yarn.The part by weight of this phosphate anion is more preferably below 400ppm, more preferably below 300ppm, is particularly preferably below 200ppm.It should be noted that, sometimes by phosphate anion (PO 4 3-) referred to as phosphate anion.
As the method for adjustment of the part by weight of phosphate anion, as previously mentioned, by being reduced in the use level of the inorganic phosphate that comprises and contain in the raw material Z of organophosphorus compounds (C) and/or its salt, adjustment raw material Z, the filtration adjuvants such as diatomite can being used to filter finishing agent and to realize.
When finishing agent of the present invention contains organophosphorus compounds (C), the part by weight of organophosphorus compounds (C) shared by the nonvolatile component of finishing agent is preferably 0.05 ~ 10 % by weight, be more preferably 0.08 ~ 8 % by weight, more preferably 0.1 ~ 7 % by weight.
When finishing agent of the present invention contains non-ionic surface active agent (D), the part by weight of non-ionic surface active agent (D) shared by the nonvolatile component of finishing agent is preferably 20 ~ 70 % by weight, be more preferably 25 ~ 65 % by weight, more preferably 30 ~ 65 % by weight, be particularly preferably 30 ~ 60 % by weight.
(other compositions)
In order to realize finishing agent emulsification, the tack of fiber is assisted, from the washing of the finishing agent of fiber, fiber given system electrically, lubricity, convergence etc., synthetic fiber finishing agent of the present invention also can contain the surfactant beyond above-mentioned organic sulfonic acid compound (B), organophosphorus compounds (C) and non-ionic surface active agent (D).As such surfactant, the anion surfactants such as fatty acid soaps can be enumerated; The cationic surfactants such as alkylamine salt, alkyl imidazole salt, quaternary ammonium salt; The amphoteric surfactant such as Empigen, stearyl dimethyl betaine; Dimethyl lauryl amine oxide etc.These surfactants can use a kind or two or more.The part by weight shared in the nonvolatile component of finishing agent containing this surfactant when these surfactants is not particularly limited, and is preferably 0.01 ~ 15 % by weight, is more preferably 0.1 ~ 10 % by weight.Surfactant mentioned here refers to the surfactant that weight average molecular weight is less than 1000.
In addition, in order to give heat resistance, synthetic fiber finishing agent of the present invention can also contain antioxidant.As antioxidant, can enumerate: the known antioxidants such as phenol system, sulphur system, phosphite ester system.Antioxidant can use a kind or two or more.Shared part by weight is not particularly limited in containing the nonvolatile component of antioxidant when antioxidant at finishing agent, is preferably 0.1 ~ 5 % by weight, is preferably 0.1 ~ 3 % by weight.
In addition, synthetic fiber finishing agent of the present invention can also contain stoste stabilizing agent (such as, water, ethylene glycol, propylene glycol).The part by weight shared in finishing agent of stoste stabilizing agent is preferably 0.1 ~ 30 % by weight, and more preferably 1 ~ 20 % by weight.
Synthetic fiber finishing agent of the present invention can be made up of the mentioned component only comprising nonvolatile component, also can be made up of nonvolatile component and stoste stabilizing agent, also can be by low viscosity mineral oil dilution nonvolatile component after finishing agent, also can for by nonvolatile component emulsification and water serial emulsion of obtaining in water.When synthetic fiber finishing agent of the present invention be by nonvolatile component in water emulsification and the water serial emulsion obtained, the concentration of nonvolatile component is preferably 5 ~ 35 % by weight, is more preferably 6 ~ 30 % by weight.Consider from the point being evenly imparted to fibrous material, be preferably 3 ~ 120mm by the viscosity (30 DEG C) of the finishing agent after low viscosity mineral oil dilution nonvolatile component 2/ s, more preferably 5 ~ 100mm 2/ s.
The manufacture method of synthetic fiber finishing agent of the present invention is not particularly limited, and can adopt known method.Synthetic fiber finishing agent can arbitrarily or add with specific order above-mentioned each composition that mixing formed and manufacture.Consider from the point improving heat resistance, the material after each composition can use removing catalyst etc. also to refine.Particularly, in the level and smooth composition (A) used in the present invention, non-ionic surface active agent (D), there is the situation containing organic/inorganic substance, when making Be very effective of the present invention reduce, then preferably remove inorganic matter and refine.As the method that removing inorganic matter carrying out is refined, can be undertaken by known method, such as, if level and smooth composition (A), then can by using diatomaceous filtration thus removing, if be non-ionic surface active agent (D), then can by using the absorption of Inorganic synthese adsorbent removing thus refining.
[manufacture method of synthetic fiber filament yarn line and fiber structure]
The manufacture method of synthetic fiber filament yarn line of the present invention comprises the operation of Material synthesis fiber filament yarn being given to synthetic fiber finishing agent of the present invention.According to the manufacture method of invention, the generation of scum silica frost or broken yarn can be reduced, the synthetic fiber filament yarn line of yarn excellent quality can be obtained.It should be noted that, the Material synthesis fiber filament yarn in the present invention refers to the synthetic fiber filament yarn line not giving finishing agent.
As the operation of giving synthetic fiber finishing agent, be not particularly limited, known method can be adopted.Usually, in the spinning process of Material synthesis fiber filament yarn, synthetic fiber finishing agent is given.After imparting finishing agent, stretched by hot-rolling, carry out thermmohardening (thermosetting), batch.Like this, when temporarily not batching but carry out the operation of hot-stretch after there is imparting finishing agent, can be suitable for using synthetic fiber finishing agent of the present invention.As temperature during hot-stretch, an example can be enumerated, for polyester, nylon, if industrial goods and materials use, be then envisioned for 210 ~ 260 DEG C, if dress material, be then envisioned for 110 ~ 220 DEG C.
Synthetic fibre treating agent when being imparted to Material synthesis fiber filament yarn as previously mentioned, can be enumerated: the finishing agent be only made up of nonvolatile component, the finishing agent crossed by low viscosity mineral oil dilution nonvolatile component or in water by the water serial emulsion finishing agent etc. after nonvolatile component emulsification.As adding method, be not particularly limited, can enumerate: guide oil supply, roller oil supply, dipping oil supply, spray to wet goods.In these, the point easily carried out from the management of imparting amount is considered, preferably guides oil supply, roller oil supply.
Relative to Material synthesis fiber filament yarn, the imparting amount of the nonvolatile component of synthetic fiber finishing agent is preferably 0.05 ~ 5 % by weight, is more preferably 0.1 ~ 3 % by weight, and more preferably 0.1 ~ 2 % by weight.When being less than 0.05 % by weight, there is the situation that can not play effect of the present invention.On the other hand, when more than 5 % by weight, the nonvolatile component of finishing agent easily comes off in yarn road, and the tar on hot-rolling significantly increases, and there is the situation with fine hair, broken yarn winding.
As (raw material) synthetic fiber filament yarn line, can enumerate: the filament yarn of the synthetic fiber such as polyester fiber, polyamide fiber, polyamide fiber.Synthetic fiber finishing agent of the present invention is applicable to the synthetic fiber such as polyester fiber, polyamide fiber, polyamide fiber.As polyester fiber, can enumerate: take ethylene glycol terephthalate as the polyester (PET) of main composition unit, with the trimethylene ethylene glycol terephthalate polyester (PTT) that is main composition unit, with the butylidene ethylene glycol terephthalate polyester (PBT) that is primary structure unit, take lactic acid as the polyester (PLA) etc. of main composition unit, as polyurethane fiber, can enumerate: nylon 6, nylon66 fiber etc., as polyamide fiber, can enumerate: polypropylene, polyethylene etc.As the manufacture method of synthetic fiber filament yarn line, be not particularly limited, known method can be adopted.
(fiber structure)
Fiber structure of the present invention is the material containing the synthetic fiber filament yarn line obtained by above-mentioned manufacture method of the present invention.Specifically, be use the volume thing imparting the synthetic fiber filament yarn line of synthetic fiber finishing agent of the present invention, the fabric utilizing water jet looms, air-jet loom or Rapier looms to weave and utilize circular knitting machine, vertical braiding machine or flat braiding machine to be compiled into.In addition, as the purposes of fiber structure, can enumerate: the industrial materials such as tire cord, safety belt, airbag, fishing net, rope, dress material are used.As manufacturing fabric, compiling the method for thing, be not particularly limited, known method can be adopted.
Embodiment
Below, by embodiment, the present invention is described, the invention is not restricted to the embodiment recorded at this.It should be noted that, " % " in literary composition neutralization table means " % by weight ".
[the raw material X containing organic sulfonic acid compound (B)]
(raw material X-1)
As the raw material X-1 containing organic sulfonic acid compound (B), employ HOSTAPURSAS93 (Hoechst company manufactures, organic sulfonic acid compound (B) 93 % by weight).Containing a large amount of saltcake in raw material X-1.By the chromatography of ions to the sulfate ion (SO comprised in raw material X-1 4 2-) and chlorion (Cl -) content (part by weight) measure, as a result, relative to organic sulfonic acid compound (B), sulfate ion is 25950ppm, and chlorion is 62ppm.
(raw material X-2)
As the raw material X-2 containing organic sulfonic acid compound (B), employ MersolatH95 (Beyer Co., Ltd's manufacture, organic sulfonic acid compound (B)) 95 % by weight).Containing a large amount of sodium chloride in raw material X-2.By the chromatography of ions to the sulfate ion (SO comprised in raw material X-2 4 2-) and chlorion (Cl -) content (part by weight) measure, as a result, relative to organic sulfonic acid compound (B), sulfate ion is 820ppm, and chlorion is 30170ppm.
[preparation of the raw material Y containing organic sulfonic acid compound (B)]
Raw material Y-1, Y-2 containing organic sulfonic acid compound (B) can by refining raw material X-1, the X-2 containing above-mentioned organic sulfonic acid compound (B), remove inorganic matter and obtain.The removing method of inorganic matter can use known method, is not limited to the process for purification shown in embodiment.
(preparation of raw material Y-1)
By methyl alcohol 550 parts and ion exchange water 400 parts mixing, carry out temperature adjustment with 45 ± 5 DEG C, while stirring, slowly drop into the above-mentioned raw materials X-1 of 700 parts, make it dissolve completely.Then, this lysate is at room temperature left standstill 20 hours, saltcake is precipitated.Take out not containing the supernatant of saltcake, at 60 ~ 80 DEG C, carry out decompression distillation, a part for removing first alcohol and water, obtains the raw material Y-1 containing 70 % by weight organic sulfonic acid compounds (B).
By the chromatography of ions to sulfate ion (SO contained in raw material Y-1 4 2-) and chlorion (Cl -) content (part by weight) measure, as a result, relative to organic sulfonic acid compound (B), sulfate ion is 1085ppm, and chlorion is 60ppm.
(preparation of raw material Y-2)
Ion exchange water 600 parts is warmed to 80 ± 5 DEG C, and slowly drops into 400 parts of above-mentioned raw materials X-2 while stirring, make it dissolve completely.Then, after this lysate is cooled to 40 DEG C, make spent ion exchange resin, removing sodium chloride, obtains the raw material Y-2 containing 40 % by weight organic sulfonic acid compounds (B).
By the chromatography of ions to the sulfate ion (SO contained by raw material Y-2 4 2-) and chlorion (Cl -) content (part by weight) measure, as a result, relative to organic sulfonic acid compound (B), sulfate ion is 105ppm, and chlorion is 2115ppm.
[preparation of the raw material Z-1 ~ Z-6 containing organophosphorus compounds (C)]
(preparation of raw material Z-1)
In reaction vessel, drop into different cetanol 820 parts, while stirring, notice that phosphorus pentoxide 180 parts is dropped at every turn a small amount of mode in reaction temperature limit below at 60 ± 5 DEG C.Thereafter, maturation 3 hours at 75 ± 5 DEG C, preparation is the raw material Z-1 of the organophosphorus compounds (C) of 100 amount % containing nonvolatile component.
The P core integration ratio of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate is respectively 33.05%, 29.81%, 33.82%, 2.76%, 0.56%.
(preparation of raw material Z-2)
In reactor, add the alcohol 800 parts of C11 ~ 15, while stirring, notice that phosphorus pentoxide 200 parts is dropped at every turn a small amount of mode in reaction temperature limit below at 60 ± 5 DEG C.Thereafter, maturation 3 hours at 75 ± 5 DEG C, the raw material Z-2 of preparation containing organophosphorus compounds (C).
The P core integration ratio of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate is respectively 44.23%, 40.31%, 13.79%, 1.09%, 0.58%.
(preparation of raw material Z-3)
In the above-mentioned 997 parts of raw material Z-2 be prepared into, drop into ion exchange water 3 parts, carry out at 90 DEG C 3 hours add water treatment.Thereafter, at 115 DEG C, carry out the processed of 3 hours, the raw material Z-3 of preparation containing organophosphorus compounds (C).
The P core integration ratio of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate is respectively 56.72%, 40.49%, 0.00%, 0.00%, 2.78%.
(preparation of raw material Z-4)
In reaction vessel, add oleyl alcohol 600 parts, while stirring, notice that phosphorus pentoxide 110 parts is dropped at every turn a small amount of mode in reaction temperature limit below at 70 ± 5 DEG C.Thereafter, maturation 3 hours at 75 ± 5 DEG C, the raw material Z-4 of preparation containing organophosphorus compounds (C).
The P core integration ratio of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate is respectively 57.65%, 35.26%, 4.57%, 0.44%, 2.07%.
(preparation of raw material Z-5)
In reaction vessel, add 600 parts of oleyl alcohol, while stirring, notice that phosphorus pentoxide 110 parts is dropped at every turn a small amount of mode in reaction temperature limit below at 70 ± 5 DEG C.Thereafter, at 70 ± 5 DEG C ripe 3 hours.Then, drop into 15 parts of ion exchange waters, carry out at 90 DEG C 3 hours add water treatment, then, slowly drop into dibutylethanolamine 200 parts, neutralize, preparation is containing the raw material Z-5 of organophosphorus compounds (C).
The P core integration ratio of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate is respectively 55.18%, 35.38%, 2.43%, 0.00%, 7.01%.
(preparation of raw material Z-6)
In the above-mentioned 970 parts of raw material Z-1 be prepared into drop into 30 parts of ion exchange waters, carry out at 90 DEG C 3 hours add water treatment.Thereafter, at 115 DEG C, carry out the processed of 3 hours, the raw material Z-3 of preparation containing organophosphorus compounds (C).
The P core integration ratio of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate is respectively 65.43%, 31.74%, 0.00%, 0.00%, 2.83%.
It should be noted that, organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate P core integration ratio use 31p-NMR calculates by the following method.
In the NMR developmental tube of diameter 5mm, weigh the nonvolatile component measuring sample be about 30mg, as deuterated solvents, add the heavy water (D of about 0.5ml 2o), make it dissolve, use 31p-NMR determinator (BRUKER company manufactures AVANCE400,162MHz) measures.
[embodiment 1 ~ 11, comparative example 1 ~ 9]
The composition that his-and-hers watches 2,3 are recorded mixes, and is stirred to evenly, prepares finishing agent.Use each finishing agent be prepared into, use the pollution accumulation of following method evaluation pole (pin), the pollution wiping of pole, tension change.The results are shown in table 2,3.
It should be noted that, table 2,3 the part by weight shared in the nonvolatile component of finishing agent of each composition of numeral (raw material X, Y, Z, these nonvolatile component) of non-volatile composition of finishing agent.In addition, table 2,3 the illustrating in Table 1 in detail of finishing agent composition.
(sulfate ion (SO 4 2-), chlorion (Cl -), phosphate anion (PO 4 3-) assay method)
Precise sample (nonvolatile component of finishing agent or the nonvolatile component of raw material X, Y, Z) 5g, adds ultra-pure water 95g at every turn a small amount of mode while stirring, makes the aqueous solution, carries out constant volume with the volumetric flask of 100ml.By the aqueous solution 2ml be made into by ODS (making after octadecyl and silica dioxide gel chemical bond) pre-treatment tubing string, by the liquid after removing lipophilicity substance for ion chromatography.Detect under following ion chromatography condition.Utilize and measure detection limit relative to the peak area ratio of the titer of concentration known, and the sulfate ion (SO that converts 4 2-), phosphate anion (PO 4 3-), chlorion (Cl -) amount.It should be noted that, detection limit (determinationlimit) is, sulfate ion (SO 4 2-) be below 0.6ppm, chlorion (Cl -) be below 1.0ppm, phosphate anion (PO 4 3-) for below 0.3ppm.* in table 2,3 represents below detection limit.
< chromatography of ions condition >
Device: Dionex manufactures ICS-1500 and uses TVS
Analytical column: DionexIonPacAS14 internal diameter 4.0mm × length 50mm
Guard column: DionexIonPacAG14 internal diameter 4.0mm × length 250mm
Eluent: 3.5mmolNa 2cO 3, 1.0mmolNaHCO 3
Flow: 1.5ml/min
(the pollution accumulation of pole, the pollution wiping of pole, the evaluation of tension change)
By the above-mentioned finishing agent be prepared into the quantitative mode of 20 % by weight be imparted to 1000 dawn, 96 without oil supply polyester filament, by sweeping yarn method friction measuring machine through the roller being heated to 150 DEG C, removing volatile ingredient, afterwards, contact with the dumb light chromium pole being warmed to 250 DEG C, in the early stage tension force 500g, with sweep within yarn speed 2m/ minute, carry out 4 hours scanning, evaluate pole pollution accumulate degree, the pollution wiping of pole, tension change.It should be noted that, in order to carry out stricter evaluation, imparting 20 % by weight finishing agents.
The degree that the pollution of pole is accumulated is evaluated by following benchmark.
◎: confirm almost not pollute
Zero: confirm reluctantly to pollute
×: obviously accumulate pollution
Tension change value utilizes following formula to calculate.
The tension force (g) at tension change value (g)=the sweep yarn tension force (g) after 4 hours-initial stage
In addition, following benchmark evaluation tension change is utilized according to tension change value.
◎: 0g to being less than 30g
Zero: 30g to being less than 50g
×: more than 50g
With the pollution wiping of following method evaluation pole.
Make to have dissolved NaOH in water and glycerine and the solution that obtains immerses in rag, and wiping is carried out to the pollution occurred on dumb light chromium pole.By until wipe required number of times, evaluate wiping.
◎: the wiping being less than 5 times just can wipe pollution
The wiping being less than 20 times for more than zero: 5 time can wipe pollution
×: the wiping of more than 20 times is wiped not yet
Table 1
Table 2
Table 3
From table 2,3, in embodiment, use the finishing agent sulfate ion detected from the nonvolatile component of finishing agent and chlorion being defined as below predetermined ratio, therefore almost do not have the pollution of pole to accumulate, wiping is fabulous.That is, the roller that can reduce when manufacturing synthetic fiber pollutes, and the cleaning interval of roller can be made elongated, reduces its cleaning number of times.In addition, tension change value is minimum, can sharply reduce fine hair, broken yarn.
On the other hand, in comparative example, the sulfate ion detected from the nonvolatile component of finishing agent or the ratio of chlorion high, therefore, the pollution of pole is accumulated many, and wiping is bad.In addition, known tension change value is very big, and fine hair, broken yarn are multiple.
Industrial applicibility
Synthetic fibre treating agent of the present invention is adapted at the industrial materials such as Tarpauling, tire cord, safety belt, air bag, fishing net, rope, hoist cable, fabric or compiles the middle synthetic fiber filament yarn lines used such as dress material use such as thing.

Claims (11)

1. a synthetic fiber finishing agent is containing level and smooth composition (A) and the synthetic fiber finishing agent of organic sulfonic acid compound (B) that represented by following general formula (1), wherein,
The part by weight that described organic sulfonic acid compound (B) is shared in the nonvolatile component of finishing agent is 1.25 ~ 12 % by weight,
Sulfate ion (the SO detected from the nonvolatile component of finishing agent by the chromatography of ions 4 2-) part by weight be below 200ppm, chlorion (Cl -) part by weight be below 200ppm,
In formula (1), a and b is the integer of more than 0 and is the integer meeting a+b=5 ~ 17, and M is hydrogen atom, alkali metal, ammonium or organic amino group.
2. finishing agent according to claim 1, wherein, the part by weight that described level and smooth composition (A) is shared in finishing agent is 20 ~ 70 % by weight.
3. finishing agent according to claim 1 and 2, wherein, the part by weight that described organic sulfonic acid compound (B) is shared in the nonvolatile component of finishing agent is 1.25 ~ 7 % by weight.
4. the finishing agent according to any one of claims 1 to 3, it is also containing organophosphorus compounds (C),
Phosphate anion (the PO detected from the nonvolatile component of finishing agent by the chromatography of ions 4 3-) part by weight be below 500ppm.
5. finishing agent according to claim 4, wherein, the part by weight of described organophosphorus compounds (C) shared by the nonvolatile component of finishing agent is 0.05 ~ 5 % by weight.
6. the finishing agent according to claim 4 or 5, wherein, described organophosphorus compounds (C) is at least one selected from the compound represented by following general formula (2) and the compound represented by following general formula (3),
In formula (2), R 1for the alkyl of carbon number 6 ~ 24, A 1o is the oxyalkylene of carbon number 2 ~ 4, and m is the integer of 0 ~ 15, and n is the integer of 1 ~ 2, M 1for hydrogen atom, alkali metal, ammonium or organic amino group,
In formula (3), R 1for the alkyl of carbon number 6 ~ 24, A 1o is the oxyalkylene of carbon number 2 ~ 4, and m is the integer of 0 ~ 15, M 1for hydrogen atom, alkali metal, ammonium or organic amino group, Q 1for M 1or R 1o (A 1o) m, Y is 1 or 2.
7. the finishing agent according to any one of claim 1 ~ 6, wherein, also containing non-ionic surface active agent (D).
8. finishing agent according to claim 7, wherein, the part by weight of described non-ionic surface active agent (D) shared by the nonvolatile component of finishing agent is 20 ~ 70 % by weight.
9. a synthetic fiber filament yarn line is the synthetic fiber filament yarn line after imparting according to any one of claim 1 ~ 8 finishing agent to Material synthesis fiber filament yarn.
10. a manufacture method for synthetic fiber filament yarn line, wherein, comprises operation Material synthesis fiber filament yarn entitle being required to the finishing agent according to any one of 1 ~ 8.
11. 1 kinds of fiber structures, it synthetic fiber filament yarn line comprising synthetic fiber filament yarn line according to claim 9 and/or obtain by the manufacture method of claim 10.
CN201580000248.0A 2014-08-05 2015-01-20 Treatment agent for synthetic fibers and use thereof Active CN105492688B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014159470A JP5668170B1 (en) 2014-08-05 2014-08-05 Treatment agent for synthetic fibers and use thereof
JP2014-159470 2014-08-05
PCT/JP2015/051291 WO2016021211A1 (en) 2014-08-05 2015-01-20 Treatment agent for synthetic fibers and use thereof

Publications (2)

Publication Number Publication Date
CN105492688A true CN105492688A (en) 2016-04-13
CN105492688B CN105492688B (en) 2017-05-24

Family

ID=52569529

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580000248.0A Active CN105492688B (en) 2014-08-05 2015-01-20 Treatment agent for synthetic fibers and use thereof

Country Status (5)

Country Link
JP (1) JP5668170B1 (en)
KR (1) KR101896536B1 (en)
CN (1) CN105492688B (en)
TW (1) TWI678445B (en)
WO (1) WO2016021211A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107002348A (en) * 2014-10-29 2017-08-01 松本油脂制药株式会社 Synthetic fibers inorganic agent and its utilization
TWI679325B (en) * 2018-04-16 2019-12-11 日商竹本油脂股份有限公司 Synthetic fiber treatment agent and synthetic fiber
TWI689646B (en) * 2018-04-16 2020-04-01 日商竹本油脂股份有限公司 Synthetic fiber treatment agent and synthetic fiber
CN111479962A (en) * 2018-07-26 2020-07-31 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber
CN113677849A (en) * 2020-06-11 2021-11-19 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber
CN115298388A (en) * 2020-03-27 2022-11-04 松本油脂制药株式会社 Treatment agent for synthetic fiber and use thereof

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6082854B2 (en) * 2015-02-06 2017-02-15 松本油脂製薬株式会社 Treatment agent for synthetic fiber and its use
JP5892714B1 (en) * 2015-04-21 2016-03-23 竹本油脂株式会社 Polyamide-based synthetic fiber treatment agent and method for treating polyamide-based synthetic fiber
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
JP5960885B1 (en) * 2015-06-30 2016-08-02 松本油脂製薬株式会社 Treatment agent for synthetic fibers and use thereof
JP5967852B1 (en) * 2015-07-27 2016-08-10 竹本油脂株式会社 Synthetic fiber treatment agent aqueous liquid, synthetic fiber treatment agent emulsion, and synthetic fiber treatment method
JP6552945B2 (en) * 2015-11-20 2019-07-31 竹本油脂株式会社 Polyamide-based synthetic fiber treatment agent and method for treating polyamide-based synthetic fiber
JP6057489B1 (en) * 2016-05-25 2017-01-11 竹本油脂株式会社 Polyolefin synthetic fiber treatment agent, aqueous solution thereof, polyolefin synthetic fiber treatment method, polyolefin synthetic fiber, and thermal bond nonwoven fabric
JP6345846B1 (en) * 2017-05-26 2018-06-20 竹本油脂株式会社 Treatment agent for elastic fiber and method for producing elastic fiber
JP6328836B1 (en) * 2017-09-15 2018-05-23 竹本油脂株式会社 Elastic fiber treatment agent and elastic fiber
JP6345897B1 (en) * 2018-04-16 2018-06-20 竹本油脂株式会社 Method for producing organophosphate compound
JP6533002B1 (en) * 2018-12-13 2019-06-19 竹本油脂株式会社 Treatment agent for synthetic fiber and method for producing synthetic fiber
JP6530129B1 (en) * 2018-12-13 2019-06-12 竹本油脂株式会社 Processing agents for synthetic fibers and synthetic fibers
JP6553317B2 (en) * 2019-03-04 2019-07-31 竹本油脂株式会社 Polyamide-based synthetic fiber treatment agent and method for treating polyamide-based synthetic fiber
JP6587272B1 (en) * 2019-07-05 2019-10-09 竹本油脂株式会社 Carbon fiber precursor treatment agent and carbon fiber precursor
JP7374643B2 (en) * 2019-07-26 2023-11-07 松本油脂製薬株式会社 Water permeability imparting agent and its use
JP6777347B1 (en) * 2019-09-13 2020-10-28 竹本油脂株式会社 Synthetic fiber processing agent for spinning process and synthetic fiber
JP6781490B1 (en) * 2019-09-13 2020-11-04 竹本油脂株式会社 Synthetic fiber processing agent for spinning process and synthetic fiber
JP6745564B1 (en) * 2020-06-11 2020-08-26 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber
EP4159914A4 (en) * 2020-06-11 2023-11-08 Takemoto Yushi Kabushiki Kaisha Synthetic fiber treatment agent and synthetic fibers
JP6745563B1 (en) * 2020-06-11 2020-08-26 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101058944A (en) * 2007-06-01 2007-10-24 徐元萍 Vinylon pure-spinning fibre oil solution and preparing method thereof
JP4217748B2 (en) * 2005-12-09 2009-02-04 松本油脂製薬株式会社 Acrylic fiber oil for carbon fiber production and method for producing carbon fiber using the same
CN101392458A (en) * 2008-01-30 2009-03-25 浙江传化股份有限公司 Terylene FDY oil and preparation method thereof
CN101906714A (en) * 2010-08-01 2010-12-08 张中法 Environment-friendly polypropylene filament yarn oil agent and production method thereof
CN102965920A (en) * 2012-11-21 2013-03-13 吴江市得可利纺织品有限公司 Oiling agent for synthetic fiber, and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59211680A (en) 1984-04-24 1984-11-30 松本油脂製薬株式会社 Oil agent composition for synthetic fiber
JP3366747B2 (en) * 1994-10-26 2003-01-14 松本油脂製薬株式会社 Synthetic fiber treatment agent
JP4236417B2 (en) * 2001-04-26 2009-03-11 オペロンテックス株式会社 Treatment agent for synthetic fibers
JP3904514B2 (en) * 2002-12-25 2007-04-11 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber treatment method
JP4097266B2 (en) * 2003-08-07 2008-06-11 竹本油脂株式会社 Method for preparing low-concentration aqueous liquid of synthetic fiber treating agent, low-concentration aqueous liquid of synthetic fiber treating agent and method for treating synthetic fiber
JP5730144B2 (en) * 2011-06-27 2015-06-03 松本油脂製薬株式会社 Treatment agent for synthetic fibers and use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4217748B2 (en) * 2005-12-09 2009-02-04 松本油脂製薬株式会社 Acrylic fiber oil for carbon fiber production and method for producing carbon fiber using the same
CN101058944A (en) * 2007-06-01 2007-10-24 徐元萍 Vinylon pure-spinning fibre oil solution and preparing method thereof
CN101392458A (en) * 2008-01-30 2009-03-25 浙江传化股份有限公司 Terylene FDY oil and preparation method thereof
CN101906714A (en) * 2010-08-01 2010-12-08 张中法 Environment-friendly polypropylene filament yarn oil agent and production method thereof
CN102965920A (en) * 2012-11-21 2013-03-13 吴江市得可利纺织品有限公司 Oiling agent for synthetic fiber, and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107002348A (en) * 2014-10-29 2017-08-01 松本油脂制药株式会社 Synthetic fibers inorganic agent and its utilization
TWI679325B (en) * 2018-04-16 2019-12-11 日商竹本油脂股份有限公司 Synthetic fiber treatment agent and synthetic fiber
TWI689646B (en) * 2018-04-16 2020-04-01 日商竹本油脂股份有限公司 Synthetic fiber treatment agent and synthetic fiber
CN111247287A (en) * 2018-04-16 2020-06-05 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber
CN111247287B (en) * 2018-04-16 2021-01-22 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber
CN111479962A (en) * 2018-07-26 2020-07-31 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber
CN111479962B (en) * 2018-07-26 2021-08-03 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber
CN115298388A (en) * 2020-03-27 2022-11-04 松本油脂制药株式会社 Treatment agent for synthetic fiber and use thereof
CN115298388B (en) * 2020-03-27 2023-07-07 松本油脂制药株式会社 Treating agent for synthetic fiber and use thereof
CN113677849A (en) * 2020-06-11 2021-11-19 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber

Also Published As

Publication number Publication date
KR20170039549A (en) 2017-04-11
TWI678445B (en) 2019-12-01
TW201610262A (en) 2016-03-16
KR101896536B1 (en) 2018-09-07
JP5668170B1 (en) 2015-02-12
CN105492688B (en) 2017-05-24
WO2016021211A1 (en) 2016-02-11
JP2016065324A (en) 2016-04-28

Similar Documents

Publication Publication Date Title
CN105492688A (en) Treatment agent for synthetic fibers and use thereof
CN107002348A (en) Synthetic fibers inorganic agent and its utilization
KR102095920B1 (en) Treatment agent for synthetic fibers and use of same
KR102232594B1 (en) Finish for synthetic fibers and application thereof
JP6619336B2 (en) Treatment agent for synthetic fibers and use thereof
WO2016017336A1 (en) Elastic fiber treatment agent, and elastic fibers
JP5730144B2 (en) Treatment agent for synthetic fibers and use thereof
JP6676049B2 (en) Synthetic fiber treatment agent and its use
JP2016089324A (en) Treatment agent for synthetic fibers and use thereof
WO2015068671A1 (en) Synthetic fiber treatment agent and use for same
JP6482945B2 (en) Treatment agent for synthetic fibers and use thereof
KR102308008B1 (en) Synthetic fibre treatment agent, and use thereof
JP6643838B2 (en) Synthetic fiber treatment agent and its use

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant