CN105492688B - Treatment agent for synthetic fibers and use thereof - Google Patents

Treatment agent for synthetic fibers and use thereof Download PDF

Info

Publication number
CN105492688B
CN105492688B CN201580000248.0A CN201580000248A CN105492688B CN 105492688 B CN105492688 B CN 105492688B CN 201580000248 A CN201580000248 A CN 201580000248A CN 105492688 B CN105492688 B CN 105492688B
Authority
CN
China
Prior art keywords
acid
inorganic 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.)
Active
Application number
CN201580000248.0A
Other languages
Chinese (zh)
Other versions
CN105492688A (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

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties

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 fibers inorganic agent and its utilization
Technical field
The present invention relates to synthetic fibers inorganic agent and its utilization.In more detail, when being related to manufacture synthetic fibers resin The synthetic fibers inorganic agent for using, the manufacture method of the synthetic fiber filament yarn line for having used the inorganic agent and comprising the synthesis The fiber structure of fiber filament yarn.
Background technology
All the time, the fiber for being treated with fibre finishing is temporarily crimped, and is used in stretching process, but contracting recently The short operation, employs the method that oil supply (oiling) yarn is used directly in into stretching process.
In the method, in stretching process, once the problems such as broken yarn occurs, can cause substantial amounts of fiber loss, therefore, need Strongly to avoid producing problem in stretching process.The main cause of the generation of problem is the fibre damage of yarn breakage etc., is This problem is prevented, it is necessary to the synthetic fibers inorganic agent of lubricity and excellent heat resistance.
Furthermore, realize multiterminal (he when physical property as high-tenacity, the low-shrinkage of fiber is improved, produced エ Application De), the so so-called productive raising of high speed, so far will not turn into problem roller pollution cause to generate The increased problem of fine hair, broken yarn.Therefore it is noted：In order to roller is remained into clean conditions, the cleaning interval of roller is shortened, and cleans secondary Number increases, productivity reduction.
For the problem, propose have and with phosphate series anion surfactant and sulphonic acid ester system in patent document 1 The synthetic fibers inorganic agent of anion surfactant.But, the inorganic agent exists when being used in spindle (spindle) mode Following shortcoming：Heat resistance and lubricity are insufficient, and finish composition after heat deterioration etc. lodges in draw roll, friction through when rise, Broken yarn, fiber quality deterioration are produced in stretching process.
Additionally, in patent document 1, it is also proposed that have in above-mentioned anion surfactant and used specific ester and antioxygen The inorganic agent of agent.But, even such inorganic agent, cannot also be met the heat resistance of strict sliver part processed.
Furthermore, regarding to the issue above, proposed in patent document 2 and with the ester of polyalcohol, the carboxylic acid with thioether group with The ester of alcohol, two grades of sulphonic acid esters, alkyl phosphate, inorganic agents obtained from hindered phenol series antioxidant.But, it is high-strength for realizing It is productive as power, low-shrinkage, high speed to improve so as to the roller pollution so far not as problem is led The fine hair of cause, broken yarn, even with the inorganic agent, can not be improved.Additionally, using described in patent document 2 Antioxidant in the case of, also have the shortcomings that fiber can change colour gradually in the keeping of fiber.
Therefore, it is desirable to obtain suppressing the cleaning interval shortening due to roller, clean number of times increase and cause productive Reduction, the inorganic agent of excellent heat resistance.
Citation
Patent document
Patent document 1：Japanese Unexamined Patent Application 59-211680 publications
Patent document 2：Japanese Unexamined Patent Publication 8-120563 publications
The content of the invention
The invention technical problem to be solved
It is an object of the invention to provide it is a kind of it is being used when synthetic resin is manufactured, roller pollution can be reduced, its is heat-resisting The excellent synthetic fibers inorganic agent of property, used the inorganic agent synthetic fiber filament yarn line manufacture method, comprising with this The fiber structure of the synthetic fiber filament yarn line that manufacture method is obtained.
For the technological means of solve problem
Present inventor has performed the result of further investigation, find first：1) organic sulfonic acid represented by formula (1) is being contained Largely contain sodium sulphate, sodium chloride in the raw material of compound；2) sodium sulphate or sodium chloride for containing in inorganic agent are de- in spinning Fall, accumulate on draw roll, so as to the increase for causing broken yarn to break and for carrying out the roller of hot-stretch, accelerate to accumulate Tar, causes roller to pollute.Therefore, the 3) sulfate ion (SO by will be detected from the nonvolatile component of inorganic agent4 2-) and Chlorion (Cl-) be set in below the ratio of regulation, roller pollution can be drastically reduced, thus so far complete the present invention.
That is, synthetic fibers inorganic agent of the invention contains smooth composition (A) and the organic sulphur represented by following formulas (1) Acid compound (B), also, the shared part by weight in the nonvolatile component of inorganic agent of the organic sulfonic acid compound (B) is 1.25~12 weight %, the sulfate ion (SO detected from the nonvolatile component of inorganic agent by the chromatography of ions4 2-) Part by weight is below 200ppm, chlorion (Cl-) part by weight be below 200ppm.
[changing 1]
(in formula (1), a and b is more than 0 integer and is the integer for meeting a+b=5~17.M be hydrogen atom, alkali metal, Ammonium or organic amino group).
It is preferred that the shared part by weight in inorganic agent of the smooth composition (A) is 20~70 weight %.
It is preferred that the shared part by weight in the nonvolatile component of inorganic agent of the organic sulfonic acid compound (B) be 1.25~ 7 weight %.
It is preferred that inorganic agent of the invention also contains organophosphorus compounds (C), and by the chromatography of ions from treatment Phosphate anion (the PO detected in the nonvolatile component of agent4 3-) part by weight be below 500ppm.
It is preferred that the shared part by weight in the nonvolatile component of inorganic agent of the organophosphorus compounds (C) is 0.05 ~5 weight %.
It is preferred that the organophosphorus compounds (C) is from the compound represented by following formulas (2) and by following formulas (3) at least one selected in the compound for representing.
[changing 2]
(in formula (2), R1It is the alkyl of carbon number 6~24.A1O is the oxyalkylene of carbon number 2~4, and m is 0~15 Integer, n is 1~2 integer.M1It is hydrogen atom, alkali metal, ammonium or organic amino group).
[changing 3]
(in formula (3), R1It is the alkyl of carbon number 6~24.A1O is the oxyalkylene of carbon number 2~4, and m is 0~15 Integer.M1It is hydrogen atom, alkali metal, ammonium or organic amino group.Q1It is M1Or R1O(A1O)m.Y is 1 or 2).
It is preferred that inorganic agent of the invention also contains nonionic surfactant (D).
It is preferred that the shared part by weight in the nonvolatile component of inorganic agent of the nonionic surfactant (D) be 20~ 70 weight %.
Synthetic fiber filament yarn line of the invention is after imparting above-mentioned inorganic agent to Material synthesis fiber filament yarn Synthetic fiber filament yarn line.
The manufacture method of synthetic fiber filament yarn line of the invention includes above-mentioned to the imparting of Material synthesis fiber filament yarn The manufacture method of the operation of inorganic agent.
Fiber structure of the invention is obtained including above-mentioned synthetic fiber filament yarn line and/or with above-mentioned manufacture method The fiber structure of synthetic fiber filament yarn line.
Invention effect
In the case of using synthetic fibers inorganic agent of the invention, roller pollution during manufacture synthetic fibers can be reduced, Excellent heat resistance.As a result, the cleaning interval of roller is elongated, the cleaning number of times can be reduced, the productivity of synthetic fibers can be realized Improve.
Manufacturing method according to the invention, can reduce the generation of scum silica frost or broken yarn, can obtain the synthesis of yarn excellent quality Fiber filament yarn.Fiber structure excellent quality of the invention.
Specific embodiment
Synthetic fibers inorganic agent of the invention contains smooth composition (A) and the organic sulfonic acid represented by above-mentioned formula (1) Compound (B), and make the sulfate ion and chlorion that are detected from the nonvolatile component of inorganic agent using the chromatography of ions Below normal concentration.Hereinafter, it is described in detail.
[smooth composition (A)]
Smooth composition (A) is the required composition of inorganic agent of the invention.As smooth composition (A), can enumerate：1) have Ester compounds (A1), 2 of the ester bond structure that aliphatic monobasic alcohol is formed with aliphatic acid) with aliphatic polyol and aliphatic acid Ester compounds (A2), 3 of the ester bond structure for being formed) ester bond that is formed with aliphatic monobasic alcohol and aliphatic polycarboxylic acid Ester compounds (A3), 4 of structure) intramolecular has aromatic ester compound (A4), 5 of aromatic rings) ester compounds of sulfur-bearing (A5), 6) mineral oil (A6) etc. is typically used for the known smooth composition of synthetic fibre treating agent.Smooth composition (A) can make With one kind or two or more.
1) ester compounds (A1)
Ester compounds (A1) are the ester bond knots formed with aliphatic monobasic alcohol and aliphatic acid (aliphatic monocarboxylic acid) The compound of structure, and be the compound without polyoxy alkylidene in intramolecular.Ester compounds (A1) can using a kind or 2 kinds.
As ester compounds (A1), the compound for preferably being represented by following formulas (4).
[changing 4]
R2-COO-R3 (4)
(in formula, R2Represent the alkyl or alkenyl of carbon number 4~24, R3Represent carbon number 6~24 alkyl or Alkenyl.)
R2Carbon number be preferably 6~22, more preferably 8~20, more preferably 10~18.If the carbon atom Number is less than 4, then oil film dies down, it is possible to cause the fine hair to increase.On the other hand, if the carbon number is more than 24, fibers gold Friction between category is increased, it is also possible to cause the fine hair to increase.R2Can be any in alkyl or alkenyl, but from excellent heat resistance Point consider, preferred alkyl.
R3Carbon number be preferably 6~22, more preferably 8~20, more preferably 10~18.If the carbon atom Number is less than 6, then oil film dies down, it is therefore possible to cause fine hair to increase.On the other hand, it is fine if the carbon number is more than 24 The intermetallic friction of dimension is increased, it is possible to cause the fine hair to increase.R3Can be any in alkyl or alkenyl, but from film strength Point consideration high, being not likely to produce fine hair, preferably alkenyl.
As ester compounds (A1), it is not particularly limited, for example, can enumerates：The capryl erucic acid ester of 2- decyls four, The capryl oleate of 2- decyls four, 2- octyldodecyls stearate, palmitic acid isooctyl acrylate, stearic acid isooctyl acrylate, palm fibre Palmitic acid acid butyl ester, stearic acid butyl ester, oleic acid butyl ester, oleic acid isooctyl acrylate, oleic acid Lauryl Ester, stearic acid isotridecyl The different spermaceti base ester of ester, stearic acid, oleic acid iso stearyl ester, sad oil base ester, lauric acid oil base ester, oleyl palmitate, tristearin Sour oil base ester, oleic oil base ester etc..In these, preferably the capryl oleate of 2- decyls four, 2- octyldodecyls stearate, Palmitic acid isooctyl acrylate, stearic acid isooctyl acrylate, oleic acid Lauryl Ester, stearic acid isotridecyl ester, the different cetyl of stearic acid Ester, oleic acid iso stearyl ester, oleic oil base ester.
Ester compounds (A1) can pass through known method and synthesize using generally commercially available aliphatic acid and aliphatic monobasic alcohol Obtain.
2) ester compounds (A2)
Ester compounds (A2) are the ester bond knots formed with aliphatic polyol and aliphatic acid (aliphatic monocarboxylic acid) The compound of structure, and be compound of the intramolecular without polyoxy alkylidene.Ester compounds (A2) can use a kind or 2 More than kind.
Constitute ester compounds (A2) as long as aliphatic polyol binary more than be just not particularly limited, it is possible to use 1 Plant or two or more.Consider that polyalcohol is preferably more than ternary, more preferably ternary~quaternary, further from the point of film strength It is preferred that ternary.
As aliphatic polyol, for example, can enumerate：Ethylene glycol, diethylene glycol, triethylene glycol, propane diols, dipropyl two Alcohol, tripropylene glycol, 2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 2- methyl-1,3-propanediols, 1,5- pentanediols, 1,6- It is hexylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, glycerine, trimethylolpropane, pentaerythrite, erythrite, two sweet Oil, sorbitan, D-sorbite, two trimethylolpropanes, dipentaerythritol, triglycerin, four glycerine, sucrose etc..Wherein, Preferably glycerine, trimethylolpropane, pentaerythrite, erythrite, two glycerine, sorbitan, D-sorbite, two trihydroxy methyls Propane, dipentaerythritol, sucrose, more preferably glycerine, trimethylolpropane, pentaerythrite, erythrite, two glycerine, anhydrosorbitol Sugar alcohol, further preferred glycerine, trimethylolpropane.
The aliphatic acid for constituting ester compounds (A2) can be with saturation, it is also possible to unsaturated.The quantity of unsaturated bond is without special Limit, but when with more than 3, oxidation causes more to deteriorate, inorganic agent thickening, destroys lubricity, therefore preferably 1 or 2 It is individual.As the carbon number of aliphatic acid, consider from the point for taking into account film strength and lubricity, preferably 8~24, more preferably 10~ 20, further preferred 12~18.Aliphatic acid can using a kind or two or more, it is also possible to and with saturated fatty acid and unsaturation Aliphatic acid.
As aliphatic acid, can enumerate：Butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, 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, different tristearin Acid, oleic acid, antiform oleic acid, vaccenic acid, linoleic acid, leukotrienes, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid (gadoleic acid), arachidonic acid (eicosenoic acid), behenic acid, isobehenic acid, erucic acid, 24 Carbonic acid, the acid of different tetracosa carbon, 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, flax Acid, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid, arachidonic acid, behenic acid, isobehenic acid, erucic acid, two Ten tetra-carbonics, 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, sub- oil Acid, leukotrienes, tuberlostearic acid, arachidic acid, 20 carbonic acid, gadoleic acid, arachidonic acid, further preferred laurate, nutmeg Acid, nutmeg oleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isocetic acid, Heptadecanoic acide, stearic acid, isostearic acid, oil Acid, antiform oleic acid, vaccenic acid, linoleic acid, leukotrienes.
Ester compounds (A2) are the compounds of the ester bond that intramolecular has more than 2, but are considered from the point of yarn processed, preferably It is the compound of the ester bond that intramolecular has more than 3, is further preferred that intramolecular has 3 compounds of ester bond.
The iodine value of ester compounds (A2) is not particularly limited.
The weight average molecular weight of ester compounds (A2) is preferably 300~1200, more preferably 300~1000, further preferably It is 500~1000.When the weight average molecular weight is less than 300, there is film strength deficiency, at the increased situation of fine hair, and heat The increased situation of smoke during reason.On the other hand, when the weight average molecular weight is more than 1200, more than flatness is not enough, fine hair It is multiple, the fiber of high-quality can't be obtained, and there is the situation of the quality deterioration of weaving or knitting process.Need explanation It is that weight average molecular weight of the invention is the high speed gel permeation chromatography subtraction unit HLC-8220GPC using Tosoh (strain) manufactures, Under sample solution concentration 3mg/cc, splitter KF-402HQ, KF-403HQ of injection Showa electrician (strain) manufacture, and by by differential The peak that RI-detector is determined is calculated.
As ester compounds (A2), for example, can enumerate：Trimethylolpropane tris caprylate, trimethylolpropane tris capric acid Ester, trimethylolpropane trilaurate, trimethylolpropane tris oleate, trimethylolpropane (laurate, myristic acid Ester, palmitate), trimethylolpropane (laurate, myristinate, oleate), trimethylolpropane (three palm kernel fats Fat acid esters), trimethylolpropane (three coconut oil fat acid esters), trimethylolpropane dicaprylate, trimethylolpropane didecyl Acid esters, trimethylolpropane dilaurate, trimethylolpropane dioleate, trimethylolpropane (laurate, nutmeg Acid esters), trimethylolpropane (laurate, oleate), trimethylolpropane (myristinate, oleate), trihydroxy methyl It is propane (two palm kernel fat acid esters), trimethylolpropane (two coconut oil fat acid esters), coconut oil, rapeseed oil, palm oil, sweet Oily trilaurin, glycerol trioleate, glycerol tristearate, diolein, glyceryl monolaurate, two glycerine two Oleate, sorbitan trioleate, sorbitan (laurate, myristinate, oleate), anhydrosorbitol Sugar alcohol dilaurate, dehydrated sorbitol mono-fatty acid ester, the caprylate of pentaerythrite four, the decylate of pentaerythrite four, Ji Wusi The laurate of alcohol four, the laurate of erythrite four, pentaerythrite (four palm kernel fat acid esters), pentaerythrite (four coconut greases Fat acid esters), erythrite trioleate, erythrite dipalmitate, 1,6-HD dioleate etc..
Ester compounds (A2) can be using using generally commercially available aliphatic acid and aliphatic polyol, using known method The material that synthesis is obtained.Or, it is also possible to the natural esters that are directly naturally obtained using natural fruit, seed or flower etc. and should Natural esters meet the structure of ester compounds (A2), or as needed, it is also possible to natural esters are entered using using known method Row is refined, then or can use by known method to refining after ester separated using fusing point difference, re-refined and obtained The ester for arriving.In addition it is also possible to carry out ester obtained from ester exchange using to natural esters of more than two kinds (grease).
3) ester compounds (A3)
Ester compounds (A3) are the chemical combination of the ester bond structure formed with aliphatic monobasic alcohol and aliphatic polycarboxylic acid Thing, and be compound of the intramolecular without polyoxy alkylidene.Ester compounds (A3) can using a kind or two or more.
Constitute ester compounds (A3) aliphatic monobasic alcohol, be not particularly limited, it is possible to use a kind or two or more.Fat Fat race monohydric alcohol can be saturation, or undersaturated.The quantity of unsaturated bond is not particularly limited, when with 2 During the above, oxidation causes more to deteriorate, and inorganic agent thickening, lubricity is destroyed, therefore preferably one.As aliphatic unitary The carbon number of alcohol, considers, preferably 8~24, more preferably 14~24, further preferably from the point of flatness and film strength It is 18~22.Aliphatic monobasic alcohol can using a kind or two or more, it is also possible to and with saturated fatty acid monohydric alcohol and insatiable hunger And aliphatic monobasic alcohol.
As aliphatic monobasic alcohol, can enumerate：Octanol, isooctanol, laruyl alcohol, myristyl alcohol, nutmeg oleyl alcohol, spermaceti Alcohol, 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 alcohol, suitable sinapinic alcohol, tetracosanol, different tetracosanol, nerve Alcohol, ceryl alcohol, montanyl alcohol, melissyl alcohol etc..Wherein, preferably octanol, isooctanol, laruyl alcohol, myristyl alcohol, nutmeg oleyl alcohol, spermaceti Alcohol, 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 alcohol, suitable sinapinic alcohol, tetracosanol, different tetracosanol, nerve 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, suitable sinapinic alcohol.
Constitute ester (A3) as long as aliphatic polycarboxylic acid's binary more than be just not particularly limited, it is possible to use a kind or Person two or more.Sulfur-bearing polybasic carboxylic acid of the aliphatic polycarboxylic acid used in the present invention not including thio-2 acid etc..Aliphatic The valence mumber of polybasic carboxylic acid is preferably binary.Again it is preferred in intramolecular not hydroxyl.
As aliphatic polycarboxylic acid, can enumerate：Citric acid, isocitric acid, malic acid, aconitic acid, oxaloacetic acid, grass Acyl butanedioic acid, butanedioic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid etc..Its In, preferably 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), for example, can enumerate：Adipic acid dibutyl ester, adipic acid dilauryl, the oil of adipic acid two Ester, the different cetyl of adipic acid two, dioctyl sebacate, decanedioic acid dilauryl, the grease of decanedioic acid two, the different cetyl of decanedioic acid two Deng.
Ester compounds (A3) are the compounds of the ester bond for having more than 2 in intramolecular.The iodine value of ester compounds (A3) does not have It is particularly limited to.
The weight average molecular weight of ester compounds (A3) is preferably 500~1000, more preferably 500~800, more preferably 500~700.When the weight average molecular weight is less than 500, having film strength deficiency, fine hair increases, and smoke increasing during heat treatment Plus situation.On the other hand, when the weight average molecular weight is more than 1000, fusing point increases, as weaving or knitting process in it is floating Slag Producing reason, the situation that there is quality deterioration.
Ester compounds (A3) use generally commercially available aliphatic monobasic alcohol and aliphatic polycarboxylic acid, using known method It is synthesized into.
4) aromatic ester compound (A4)
Aromatic ester compound (A4) is that at least have 1 ester compounds of aromatic rings in intramolecular.Specifically, can be with Enumerate：The ester compounds (A4-1) of the ester bond structure formed with aromatic carboxylic acid and alcohol, with aromatic alcohols and carboxylic acid institute The ester compounds (A4-2) of the ester bond structure of formation.Additionally, aromatic ester compound (A4) is sub- without polyoxy in intramolecular The compound of alkyl.Aromatic ester compound (A4) can using a kind or two or more.
The aromatic carboxylic acid for constituting ester compounds (A4-1) can be monocarboxylic acid, or polybasic carboxylic acid.Can make With 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, PMA etc..Wherein, preferably inclined benzene Three acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), further preferred trimellitic acid.
The alcohol for constituting ester compounds (A4-1) can be monohydric alcohol, or polyalcohol.In addition it is also possible to be aliphatic It is any in alcohol, alicyclic alcohol, aromatic alcohols.Monohydric alcohol can using a kind or two or more.Wherein, preferred monohydric alcohol, enters One step preferred aliphat monohydric alcohol.
Can be enumerated as monohydric alcohol：Alkylbenzene alcohol, dialkyl benzene alcohol, octanol, isooctanol, laruyl alcohol, myristyl alcohol, meat Cardamom oleyl alcohol, cetanol, different cetanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, anti-oleyl alcohol, different oleyl alcohol, eicosylene Alcohol, arachidic alcohol, Isoeicosane alcohol, tadenan, docosyl alcohol, different two lanolin alcohol, suitable sinapinic alcohol, tetracosanol, different two Tetradecyl alchohol, neural alcohol, ceryl alcohol, montanyl alcohol, melissyl alcohol etc..
As polyalcohol, can enumerate：In the middle aliphatic polyol for illustrating of ester compounds (A2), in ester compounds (A4- 2) aromatic polyol of explanation etc. in.
Constitute ester compounds (A4-2) aromatic alcohols can using a kind or two or more.It is excellent as fragrant family alcohol Select aromatic polyol, further preferred aromatic series trihydroxylic alcohol.
As aromatic alcohols, can enumerate：The aromatic monoalcohols such as alkylbenzene alcohol, dialkyl benzene alcohol, bisphenol-A, bisphenol Z, Aromatic polyols such as 1,3,5- trihydroxy methyl benzene etc..Wherein, preferably bisphenol-A, bisphenol Z, 1,3,5- trihydroxy methyl benzene, more It is preferred that 1,3,5- trihydroxy methyl benzene.
The carboxylic acid for constituting ester compounds (A4-2) can be any in aliphatic carboxylic acid, aromatic carboxylic acid.Furthermore, it is possible to It is any in for monocarboxylic acid, polybasic carboxylic acid.Can using a kind or two or more.Wherein, preferred monocarboxylic acid, it is further excellent Select aliphatic acid.Consider that aliphatic acid is preferably saturation from the point of residual.Aliphatic acid can be straight-chain, it is possible to have branch Chain.
As monocarboxylic acid, can enumerate：Alkyl benzene carboxylic acid, dialkyl benzene carboxylic acid, butyric acid, crotonic acid, valeric acid, caproic acid, Enanthic acid, octanoic acid, n-nonanoic acid, capric acid, laurate, myristic acid, nutmeg oleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, different whale Cerinic acid, Heptadecanoic acide, stearic acid, isostearic acid, oleic acid, antiform oleic acid, vaccenic acid, linoleic acid, leukotrienes, tuberlostearic acid, Arachidic acid, 20 carbonic acid, gadoleic acid (gadoleic acid), arachidonic acid (eicosenoic acid), behenic acid, different 20 Diacid, erucic acid, tetracosa carbon are sour, different tetracosa carbon acid, nervonic acid, cerinic acid, montanic acid, melissic acid etc..
As polybasic carboxylic acid, can enumerate：In the middle aliphatic polycarboxylic acid for illustrating of ester compounds (A3), in ester compounds (A4-1) aromatic polycarboxylic acid of explanation etc. in.
5) ester compounds (A5) of sulfur-bearing
The ester compounds of sulfur-bearing are the diester compound and thio-2 acid and fat from thio-2 acid and aliphatic alcohol At least one selected in the monoester compound of fat race alcohol.
The ester compounds of sulfur-bearing are the compositions with oxidation resistance.By using the ester compounds of the sulfur-bearing, Neng Gouti The heat resistance of high disposal agent.The ester compounds of sulfur-bearing can using a kind or two or more.Constitute the ester compounds of the sulfur-bearing The molecular weight of thio-2 acid is preferably 400~1000, more preferably 500~900, more preferably 600~800.Constitute The aliphatic alcohol of the ester compounds of the sulfur-bearing can be saturation, or undersaturated.Additionally, aliphatic alcohol can be straight Chain, it is possible to have branched structure, it is preferred that having branched structure.The carbon number of aliphatic alcohol is preferably 8~24, more Preferably 12~24, more preferably 16~24.As aliphatic alcohol, for example, can enumerate：Octanol, 2- ethylhexyl alcohols, Decyl alcohol, laruyl alcohol, myristyl alcohol, different cetanol, oleyl alcohol and isooctadecanol etc., in these, preferably oleyl alcohol and isooctadecanol.
The ester compounds of sulfur-bearing can be for the diester compound of thio-2 acid and aliphatic alcohol (in this paragraph, referred to as Diester) and thio-2 acid and aliphatic alcohol monoester compound (in this paragraph, referred to as monoesters) mixture.Now, two The mol ratio of ester and monoesters is preferably 100/0~70/30, more preferably 100/0~75/25, more preferably 100/0~ 80/20。
6) mineral oil (A6)
Additionally, in synthetic fibers inorganic agent of the invention, as smooth composition other than the above, mineral can also be contained Oil.Mineral oil referred to herein is not configured to dilute inorganic agent and the low viscosity diluent that uses, and be included in it is non-volatile into In point.As mineral oil, it is not particularly limited, can enumerates：Machine oil, bobbin oil, atoleine etc..Mineral oil can use 1 Plant or two or more.Viscosity of the mineral oil at 30 DEG C is preferably 100~500 seconds.
As smooth composition (A), consider from the point for improving heat resistance, preferably use removing catalyst etc. and refined thing Matter.
[organic sulfonic acid compound (B)]
The organic sulfonic acid compound (B) represented by above-mentioned formula (1) is the neccessary composition of inorganic agent of the invention.By containing There are smooth composition (A) and organic sulfonic acid compound (B) and make to be examined from the nonvolatile component of inorganic agent by the chromatography of ions Sulfate ion (the SO for measuring4 2-) part by weight for below 200ppm, make chlorion (Cl-) part by weight be 200ppm Below such that it is able to drastically reduce fine hair, broken yarn, roller pollution.It should be noted that by sulfate ion (SO4 2-) it is referred to as sulphur Acid ion, chlorion (Cl-) it is referred to as chlorion.
In formula (1), a and b is more than 0 integer and is the integer for meeting a+b=5~17.When a+b is less than 5, reduce The effect of roller pollution diminishes.On the other hand, when a+b is more than 17, fusing point is high, the compatibility poor in inorganic agent, it is impossible to use. A+b is preferably 7~17, more preferably 10~15.
M is hydrogen atom, alkali metal, ammonium or organic amino group.As alkali metal, for example, can enumerate：Lithium, sodium, potassium Deng.As ammonium and organic amino group, can enumerate：By NRaRbRcRdThe group of expression.Ra、Rb、Rc、RdIndependently and for hydrogen is former Son, alkyl, alkenyl, polyoxy alkylidene.The carbon number of alkyl and alkenyl is preferably 1~24, more preferably 1~20, further Preferably 1~18.Polyoxy alkylidene [- (A1O)mH] represent, (A1O)mIt is same with the material represented by formula (2).
As by NRaRbRcRdThe group of expression, for example, can enumerate：Ammonium, methyl ammonium, ethyl ammonium, propyl ammonium Base, butyl ammonium, hexyl ammonium, octyl group ammonium, dimethylammonio, diethyl ammonium, dipropyl ammonium, dibutyl ammonium, two Hexyl ammonium, dioctyl ammonium, trimethyl ammonium, triethyl group ammonium, tripropyl ammonium, tributyl ammonium, three hexyl ammoniums, three Octyl group ammonium, tetramethyl ammonium, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl ammonium, tetrahexyl ammonium base, four octyl group ammoniums, second Base trimethyl ammonium, oxypropyl trimethyl ammonium, butyl trimethyl ammonium, hexyl trimethyl ammonium, octyl trimethyl ammonium, methyl alcohol Ammonium, ethanol ammonium, propyl alcohol ammonium, butanol ammonium, hexanol ammonium, octanol ammonium, dimethanol ammonium, diethanolammonium group, dipropyl Alcohol ammonium, two butanol ammoniums, two hexanol ammoniums, two octanol ammoniums, three methyl alcohol ammoniums, triethanol ammonium base, three propyl alcohol ammoniums, three fourths Alcohol ammonium, three hexanol ammoniums, three octanol ammoniums, (EO6) butylamino ether, (EO6) hexylamino ether, (EO6) octyl group ammonia Base ether, (EO6) Decylamino ether, (EO6) lauryl amino ether, (EO6) tetradecyl amino ether, (EO6) different spermaceti Base amino ether, (EO6) oil base amino ether, (EO6) stearyl ether, (EO6) cod oil base amino ether, (EO6) two Tetradecyl amino ether, (EO10) oil base amino ether, (EO10) oil base amino ether/erucic acid salt, (EO3) lauryl ammonia Base ether, (EO3) lauryl amino ether, (EO7) lauryl amino ether, (EO15) oil base amino ether, (PO3, EO5) are hard Aliphatic radical amino 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.Sodium sulphate that raw material X is included, the ratio of sodium chloride can utilize the chromatography of ions, according to original The sulfate ion that is detected in material X, the part by weight of chlorion are calculated.
In the case where raw material X contains sodium sulphate, the part by weight of the sulfate ion detected from raw material X is, phase It is more than 20000ppm for organic sulfonic acid compound (B).Additionally, in the case where raw material X contains sodium chloride, from raw material X The part by weight of the chlorion for detecting is, is more than 20000ppm relative to organic sulfonic acid compound (B).
When such raw material X is used as into inorganic agent, as it was previously stated, sodium sulphate, sodium chloride can come off and product in spinning Exist on draw roll, the increase for causing broken yarn to break.Additionally, the roller for carrying out hot-stretch, sodium sulphate, sodium chloride can accelerate product Tar is deposited, causes roller to pollute.As such raw material X, can enumerate：HOSTAPUR SAS (manufacture of Hoechst companies), Mersolat H (Beyer Co., Ltd's manufacture) etc..
Consider from the point for playing effect of the invention, for inorganic agent of the invention, using containing reducing from raw material X Sodium sulphate, the raw material (hereinafter referred to as raw material Y) of the organic sulfonic acid compound (B) of sodium chloride be important.Specifically, it is excellent Choosing, the part by weight of the sulfate ion detected from raw material Y by the chromatography of ions is relative to organic sulfonic acid Compound (B) is below 5000ppm, and it relative to organic sulfonic acid compound (B) is below 5000ppm that the part by weight of chlorion is.
Consider from the point of the effect for more preferably playing the application, relative to organic sulfonic acid compound, detected from raw material Y The part by weight of the sulfate ion is more preferably below 4000ppm, more preferably below 3000ppm, 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, more preferably below 2000ppm.
It should be noted that the sulfate ion carried out by the chromatography of ions, the analysis side of chlorion in the present invention Method is according to the method described in embodiment.
As the method for reduction sodium sulphate or sodium chloride from the raw material X containing organic sulfonic acid compound (B), without special Limit, can be using known method.For example, can enumerate：In the case where raw material X includes sodium sulphate, added in raw material X Methyl alcohol, water equal solvent, and make the inorganic matter such as sodium sulphate Precipitation, separate method etc..Additionally, including sodium chloride in raw material X In the case of, can enumerate：The method of the sodium chloride included in raw material X is removed by amberplex, by amberlite Method that fat is adsorbed etc..
Above-mentioned organic sulfonic acid compound (B) is that have a sulfonic single sulfoacid compound.Inorganic agent of the invention is removed Single sulfoacid compound, can also contain the disulfonic acid compound represented by following formulas (5).
[changing 5]
In formula (5), c, d and e are more than 0 integer, and are the integers for meeting c+d+e=4~16.4 are less than in c+d+e When, the effect that roller pollution is reduced sometimes diminishes.On the other hand, when c+d+e is more than 17, the compatibility poor in inorganic agent has Shi Buneng is used.C+d+e is preferably 6~16, 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 formula (1) place illustrates.
In the case of containing above-mentioned disulfonic acid compound, as organic sulfonic acid compound (B) single sulfoacid compound with The part by weight (single sulfoacid compound/disulfonic acid compound) of the disulfonic acid compound represented by formula (5) is preferably 50/50~ 99/1, more preferably 70/30~99/1, more preferably 80/20~98/2.
[organophosphorus compounds (C)]
In inorganic agent of the invention, consider from the point for reducing fine hair, except above-mentioned smooth composition (A), organic sulfonic acid chemical combination Thing (B) preferably also contains organophosphorus compounds (C).As organophosphorus compounds (C), preferably from by above-mentioned formula (2) compound for representing and at least one by being selected in the compound of above-mentioned formula (3) expression.
In formula (2) and (3), R1It is the alkyl of carbon number 6~24.A1O is the oxyalkylene of carbon number 2~4, and m is 0~15 integer.N is 1~2 integer.M1It is hydrogen atom, alkali metal, ammonium or organic amino group.Q1It is M1Or R1O(A1O)m。 Y is 1 or 2.
As R1Alkyl, can enumerate：Alkyl, alkenyl etc..R1Carbon number be preferably 8~24, more preferably 12~24.R1Carbon atom can have distribution, R1Can be straight-chain, it is possible to have side chain, can be saturation or insatiable hunger With.
A1O is the oxyalkylene of carbon number 2~4.The repeat number m of oxygen alkylene unit is 0~15 integer, preferably 0 ~10, more preferably 0~3, particularly preferred m are the 0 i.e. situation without polyoxy alkylidene.(A1O)mIt is sub- preferably as oxygen Alkane unit and contain 50 moles of polyoxy alkylidenes of more than % of aerobic ethylidene.
N is 1~2 integer.In the case of n=2,2 organic groups of the compound represented by above-mentioned formula (2) are constituted Group " R1O(A1O)m" can be with identical, it is also possible to it is different.
In addition, in Q=R1O(A1O)mIn the case of, constitute 2 organic group " R of the compound represented by formula (3)1O (A1O)m" can be with identical, it is also possible to it is different.
M1It is hydrogen atom, alkali metal, ammonium or organic amino group.As alkali metal, for example, can enumerate：Lithium, sodium, potassium Deng.As ammonium and organic amino group, can enumerate：By NRaRbRcRdThe group of expression.By NRaRbRcRdThe group of expression with it is organic The M of sulfoacid compound (B) place explanation is identical.
Organophosphorus compounds (C) preferably includes the organophosphorus compounds represented during n=1 in formula (2) (C1) mixture of the organophosphorus compounds (C2) for and in formula (2) being represented during n=2 or including organic Phosphation Y=1, Q=R in compound (C1), (C2) and formula (3)1O(A1O)mWhen the mixture of organophosphorus compounds (C3) that represents. In these mixtures, the organophosphorus compounds (C4) represented when Y=1, Q=hydrogen atom in formula (3) can be contained.
The P cores of organophosphorus compounds (C1), (C2), (C3) and (C4) and inorganic phosphate integrate ratio (%) can According to31The integrated value at the peak from each phosphorus atoms in P-NMR is calculated.It should be noted that P cores integrate ratio (%) referring to Total using the integrated value of organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate calculates as 100% Value.On inorganic phosphate, aftermentioned.
The P cores of organophosphorus compounds (C1) integrate ratio (%) and are preferably 25~82%, more preferably 35~80%, enter One step preferably 40~70%.The P cores of organophosphorus compounds (C2) integrate ratio (%) and are preferably 15~65%, more preferably 20~60%, more preferably 25~55%.The P cores of organophosphorus compounds (C3) integrate ratio (%) be preferably 0~ 50%, more preferably 0~45%, more preferably 0~40%.The P cores integration ratio of organophosphorus compounds (C4) (%) is preferably 0~7%, more preferably 0~6%, more preferably 0~5%.The P cores of inorganic phosphate integrate ratio (%) Preferably 0~10%, more preferably 0~9%, more preferably 0~8%.
As the manufacture method of organophosphorus compounds (C), it is not particularly limited, can be using known method.Example Such as, the manufacture method of organophosphorus compounds (C) includes making by R1O(A1O)mOrganic hydroxy compounds and phosphoric anhydride that H is represented P2O5React, obtain the operation (I) of reactant.Additionally, in operation (I), it is also possible to add inorganic phosphate, water, reacted. The manufacture method of organophosphorus compounds (C) is carried out after may be embodied in operation (I) to water is added in above-mentioned reactant The operation (II) of hydrolyzable.By contained in organophosphorus compounds (C) so as to adjust including operation (II) Organophosphorus compounds (C3), the ratio of (C4).Relative to above-mentioned organophosphorus compounds (C), it is added to above-mentioned reaction The amount of the water in thing is preferably 0.01~5 weight %, more preferably 0.05~4 weight %, further preferred 0.1~3 weight %.Such as The addition of fruit water then there are and be likely difficult to adjust organophosphorus ester chemical combination less than 0.01 weight % or more than 5 weight % Thing (C3), the situation of the amount of (C4).As the manufacture method of organophosphorus compounds (C), it is also possible in operation (I) or operation (II) comprising with M after1The operation (III) that is neutralized of alkali cpd.
Comprising the heavy metal of the arsenic originated as the impurity in phosphoric anhydride or Phos etc. in organophosphorus compounds (C) Compound.Inorganic agent of the invention can also contain the heavy metal compound of arsenic etc..From the influence to human body or to environment The point of security considers that the shared part by weight in the nonvolatile component of inorganic agent of heavy metal compound is preferably 0.01 weight Amount below %, more preferably more preferably below 0.005 weight %, below 0.001 weight %.
When organophosphorus compounds (C) is manufactured, inorganic phosphate and/or its salt are produced.Therefore, comprising organophosphorus ester Contain inorganic phosphate and/or its salt in the raw material (hereinafter referred to as raw material Z) of compound (C).The ratio of inorganic phosphate and/or its salt Rate can be by organic hydroxy compounds and phosphoric anhydride P2O5Ratio, reaction condition etc. be adjusted.
[nonionic surfactant (D)]
Inorganic agent of the invention, from assigning precursor film strength, convergence and improving the point consideration of yarn processed, preferably except Outside above-mentioned smooth composition (A), organic sulfonic acid compound (B), also contain nonionic surfactant (D).It should be noted that Nonionic surfactant (D) refers to the material in addition to above-mentioned smooth composition (A).Nonionic surfactant (D) can be with Using a kind or two or more.
As nonionic surfactant (D), can enumerate：Hydroxy aliphatic acid polyol ester containing polyoxy alkylidene It is (below, sometimes referred to as poly- hydroxy ester), ester of at least one hydroxyl of poly- hydroxy ester after fatty acid blocked, polyalkylene oxide is more It is first alcohol ether, polyalkylene oxide polyol fatty acid ester, polyalkylene oxide aliphatic alcohol ether, the fatty acid ester of PAG, polynary Alcohol fatty acid ester etc..
(poly- hydroxy ester, by the ester of at least one hydroxyl of poly- hydroxy ester after fatty acid blocked)
Poly- hydroxy ester is preferably in structure the ester of the hydroxy fatty acid containing polyoxy alkylidene and polyalcohol, polyalcohol The hydroxyl of more than 2 in hydroxyl is esterified.Therefore, the hydroxy aliphatic acid polyol ester containing polyoxy alkylidene is that have multiple The ester of hydroxyl.
Hydroxy fatty acid containing polyoxy alkylidene have polyoxy is combined with by oxygen atom on the alkyl of aliphatic acid The structure of alkylidene, and do not combined with the alkyl of aliphatic acid end of polyoxy alkylidene turns into hydroxyl.
As poly- hydroxy ester, for example, can enumerate：The hydroxy fatty acid of carbon number 6~22 (preferably 16~20) with The alkylene oxide addition product of the carboxylate of polyalcohol.
As the hydroxy fatty acid of carbon number 6~22, for example, can enumerate：Hydroxyoctanoic acid, hydroxydecanoic acid, hydroxylauric The acid of acid, hydroxy stearic acid, ricinoleic acid, preferably hydroxyoctadecanoic base, ricinoleic acid.As polyalcohol, for example, can enumerate：Second 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 2~4 alkylene oxide.
The addition molal quantity of alkylene oxide is preferably 3~60, more preferably 8~50.Oxirane institute in alkylene oxide The ratio for accounting for is preferably 50 moles of %, more preferably 80 moles %.
In the case of addition two or more alkylene oxide, their addition order is not particularly limited, and addition form can be It is any in block-wise, random shape.The addition of alkylene oxide can be carried out by known method, but generally in base catalyst In the presence of carry out.
Poly- hydroxy ester can for example be manufactured as follows, i.e.,：At typical condition, by polyalcohol and hydroxy fatty acid (hydroxyl Monocarboxylic acid) esterification, carboxylate is obtained, then so that alkylene oxide carries out addition reaction and manufactures with the carboxylate.Poly- hydroxy ester Can suitably manufacture by the following method, i.e.,：The grease that is naturally obtained using castor oil etc. or wherein addition hydrogen and obtain Rilanit special, then carry out addition reaction with alkylene oxide and obtain.
Also above-mentioned at least one hydroxyl by poly- hydroxy ester fat acid blocked is contained in nonionic surfactant (D) Ester afterwards.The carbon number of the aliphatic acid of end-blocking is preferably 6~24, more preferably 12~18.The carbon of the alkyl in aliphatic acid is former Subnumber can have distribution, and alkyl can be straight-chain, it is possible to have side chain, can be saturation, or unsaturation , it is possible to have polycyclic structure.As such aliphatic acid, for example, can enumerate：Laurate, myristic acid, palmitic acid, Palmitoleic acid, stearic acid, oleic acid, 20 carbonic acid, behenic acid, lignoceric acid etc..Method, reaction condition for esterification etc. do not have It is particularly limited to, known method, common condition can be used.
As poly- hydroxy ester and by ester of at least one hydroxyl of poly- hydroxy ester after fatty acid blocked, castor is e.g. hydrogenated Sesame oil ethylene oxide adduct, castor oil ethylene oxide adduct, rilanit special ethylene oxide adduct monoleate, hydrogenation Castor oil ethylene oxide adduct dioleate, rilanit special ethylene oxide adduct trioleate, castor oil oxirane Addition product trioleate, rilanit special ethylene oxide adduct tristearate, castor oil ethylene oxide adduct three are stearic Acid esters, wherein, the point that intermiscibility, film strength, fine hair from inorganic agent are reduced considers that preferably rilanit special oxirane adds Into thing, rilanit special ethylene oxide adduct trioleate, rilanit special ethylene oxide adduct tristearate.
(polyalkylene oxide polyol ethers)
Polyalkylene oxide polyol ethers refer to have addition oxirane, expoxy propane, epoxy butane etc. on polyalcohol The compound of the structure of alkylene oxide.
As polyalcohol, can enumerate：Ethylene glycol, glycerine, trimethylolpropane, pentaerythrite, two glycerine, anhydrosorbitol Sugar alcohol, D-sorbite, two trimethylolpropanes, dipentaerythritol, sucrose etc..In these, preferably glycerine, trimethylolpropane, Sucrose.
As the addition molal quantity of alkylene oxide, preferably 3~100, more preferably 4~70, more preferably 5~50. Additionally, the shared ratio in alkylene oxide of oxirane is preferably 50 moles of more than %, more preferably 80 moles more than %.
The weight average molecular weight of polyalkylene oxide polyol ethers is preferably 300~10000, more preferably 400~8000, further Preferably 500~5000.When the molecular weight is less than 300, it is impossible to reduce the generation of fine hair, broken yarn.On the other hand, if this point More than 10000, then the friction of inorganic agent is uprised son amount, can not only reduce the generation of fine hair, broken yarn, but also can dislike it Change.
As polyalkylene oxide polyol ethers, can enumerate：Polyethylene glycol, glycerol epoxy ethane additive product, trihydroxy methyl third Alkane ethylene oxide adduct, pentaerythrite ethylene oxide adduct, two glycerol epoxy ethane additive products, sorbitan epoxy second Alkane addition product, sorbitan ethylene oxide propylene oxide addition product, D-sorbite ethylene oxide adduct, D-sorbite epoxy Ethane epoxy propane addition product, two trimethylolpropane ethylene oxide adducts, dipentaerythritol ethylene oxide adduct, sucrose Ethylene oxide adduct etc., but it is not limited to these.
(polyalkylene oxide polyol fatty acid ester)
Polyalkylene oxide polyol fatty acid ester is that have addition oxirane, expoxy propane, epoxy fourth on polyalcohol The compound of the ester bond structure that compound obtained from the alkylene oxides such as alkane is formed with aliphatic acid.
As polyalcohol, can enumerate：Glycerine, trimethylolpropane, pentaerythrite, erythrite, two glycerine, anhydrosorbitol Sugar alcohol, D-sorbite, two trimethylolpropanes, dipentaerythritol, sucrose etc..In these, preferably glycerine, two glycerine, dehydration mountain Pears sugar alcohol, D-sorbite.
As aliphatic acid, can enumerate：Laurate, myristic acid, nutmeg oleic acid, palmitic acid, palmitoleic acid, different spermaceti Acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, leukotrienes, arachidic acid, 20 carbonic acid, behenic acid, different 22 Carbonic acid, erucic acid, tetracosa carbon are sour, different tetracosa carbon acid etc..
As the addition molal quantity of alkylene oxide, preferably 3~100, more preferably 5~70, more preferably 10~50. Additionally, the shared ratio in alkylene oxide of oxirane is preferably 50 moles of more than %, more preferably 80 moles more than %.
The weight average molecular weight of polyalkylene oxide polyol fatty acid ester is preferably 300~7000, more preferably 500~5000, More preferably 700~3000.When the molecular weight is less than 300, the feelings of environmental degradation of being smoldered in heat treatment step, made Condition.Additionally, the generation of broken yarn can not be reduced.On the other hand, if the molecular weight is more than 7000, the friction of inorganic agent increases Greatly, the generation of fine hair, broken yarn can not be not only reduced, it can on the contrary deteriorates.
As polyalkylene oxide polyol fatty acid ester, can enumerate：Glycerol epoxy ethane additive product monolaurate, glycerine Ethylene oxide adduct dilaurate, glycerol epoxy ethane additive product trilaurin, trimethylolpropane oxirane add Into thing trilaurin, sorbitan ethylene oxide adduct monoleate, the oil of sorbitan ethylene oxide adduct two Acid esters, sorbitan ethylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide addition product list oleic acid Ester, sorbitan ethylene oxide propylene oxide addition product dioleate, sorbitan ethylene oxide propylene oxide addition product Trioleate, sorbitan ethylene oxide propylene oxide addition product trilaurin, the bay of sucrose ethylene oxide adduct three Acid esters etc., but it is not limited to these.
(polyalkylene oxide aliphatic alcohol ether)
Polyalkylene oxide aliphatic alcohol ether is that have addition oxirane, expoxy propane, epoxy on aliphatic monobasic alcohol The compound of structure obtained from the alkylene oxides such as butane.
As polyalkylene oxide aliphatic alcohol ether, for example, can enumerate：Octanol, 2-Ethylhexyl Alcohol, decyl alcohol, laruyl alcohol, 13 The alkylene oxide addition product of the aliphatic alcohols such as alkylol, myristyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol.
As the addition molal quantity of alkylene oxide, preferably 1~100 mole, more preferably 2~70 moles, further preferably It is 3~50 moles.Additionally, the oxirane ratio overall relative to alkylene oxide is preferably 20 moles of more than %, more preferably 30 Mole more than %, more preferably 40 moles more than %.
(fatty acid ester of PAG)
The fatty acid ester of PAG refer to polyoxyethylene glycol (polyoxyethylene glycol), The compound of the ester bond structure that polyoxyethylene polyoxypropylene glycol is formed with aliphatic acid.The Weight-average molecular of PAG Amount is preferably 100~1000, more preferably 150~800, more preferably 200~700.
As polyalkylene glycol fatty acid esters, can enumerate：Polyethylene glycol monolaurate, polyethylene glycol tin dilaurate It is ester, polyethylene glycol monooleate, glycol dioleate, polyethylene glycol mono stearate, polyglycol distearate, poly- Ethene polypropylene glycol monolaurate, polyethylene polypropylene glycol dilaurate, polyethylene polypropylene glycol monoleate, polyethylene Polypropylene glycol dioleate etc., but not limited to this.
(polyol fatty acid ester)
Polyol fatty acid ester is the compound of the ester bond structure formed with polyalcohol and aliphatic acid, is except above-mentioned Compound outside smooth composition (A).
As polyalcohol, can enumerate：It is ethylene glycol, trimethylolpropane, pentaerythrite, erythrite, diethylene glycol, two sweet Oil, sorbitan, D-sorbite, two trimethylolpropanes, sucrose etc..In these, preferably ethylene glycol, glycerine, two glycerine, Sorbitan, D-sorbite.
As aliphatic acid, can enumerate：Laurate, myristic acid, nutmeg oleic acid, palmitic acid, palmitoleic acid, different spermaceti Acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, leukotrienes, tuberlostearic acid, arachidic acid, 20 carbonic acid, cod oil Sour (gadoleic acid), arachidonic acid (eicosenoic acid), behenic acid, isobehenic acid, erucic acid, 20 Tetra-carbonic etc..
And, the polyol fatty acid ester at least has the hydroxyl of 1 or more than 2.
The weight average molecular weight of polyol fatty acid ester is preferably 100~1000, more preferably 200~800, further preferably It is 300~600.
As fatty acid ester, can enumerate：Glyceryl monolaurate, dilaurin, glycerin mono-fatty acid ester, glycerine Dioleate, sorbitan monooleate, sorbitan dioleate, sucrose monolaurate, sucrose dilaurate Deng, but it is not limited to these.
As nonionic surfactant (D), consider from the point for improving heat resistance, preferably use removing catalyst etc. and essence Material after system.
[synthetic fibers inorganic agent]
Inorganic agent of the invention is the organic sulfonic acid compound (B) represented containing smooth composition (A) and by above-mentioned formula (1) Inorganic agent.Also, sulfate ion (the SO detected from the nonvolatile component of inorganic agent by the chromatography of ions4 2-) Part by weight is below 200ppm, and chlorion (Cl-) part by weight be below 200ppm.So, by will be from treatment The sulfate ion and chlorion detected in the nonvolatile component of agent are set as below the part by weight of regulation such that it is able to anxious Fall sharply low fine hair, broken yarn, roller pollution.
When the part by weight of the sulfate ion is more than 200ppm or the chlorion part by weight more than 200ppm When, sodium sulphate, sodium chloride come off and accumulate on draw roll in spinning, cause the increase of broken string broken yarn, for carrying out hot-drawn The roller stretched, accelerates the accumulation of tar, causes roller to pollute.
It should be noted that the sulfate ion carried out based on the chromatography of ions of the invention, the analysis side of chlorion Method is according to the content described in embodiment.Additionally, the nonvolatile component in the present invention refers to, heat is carried out to inorganic agent with 105 DEG C Treatment, removes solvent etc., and adiabatic drying when reaching constant is into powder.
Consider from the point for more preferably playing effect of the invention, the part by weight of the sulfate ion be preferably 200ppm with Under, more preferably below 150ppm, more preferably below 100ppm.Equally, the part by weight of the chlorion is preferably Below 200ppm, more preferably below 150ppm, more preferably below 100ppm.
As sulfate ion and the method for adjustment of the part by weight of chlorion, as it was previously stated, being included by reducing The sodium sulphate that contains in the raw material X of machine sulfoacid compound (B), sodium chloride are realized.
The shared part by weight in the nonvolatile component of inorganic agent of smooth composition (A) is preferably 20~70 weight %, more Preferably 30~65 weight %, more preferably 40~65 weight %, particularly preferably 40~60 weight %.In the weight ratio When example is less than 20 weight %, flatness is not enough sometimes, causes fine hair to increase.On the other hand, in the part by weight more than 70 weights During amount %, convergence is not enough, in the case where use is emulsified, it is possible to which emulsion stability is deteriorated and can not use.
The shared part by weight in the nonvolatile component of inorganic agent of organic sulfonic acid compound (B) is 1.25~12 weights Amount %, more preferably preferably 1.25~10 weight %, more preferably 1.25~8 weight %, 1.25~7 weight %, spy You Xuanwei not 1.5~6 weight %.When the part by weight is less than 1.25 weight %, roller pollution can not be reduced sometimes.The opposing party Face, when the part by weight is more than 12 weight %, friction increases, and fine hair increases.
In the case where inorganic agent of the invention contains organophosphorus compounds (C), by the chromatography of ions from treatment Phosphate anion (the PO detected in the nonvolatile component of agent4 3-) part by weight be preferably below 500ppm.In the phosphate radical When the part by weight of ion is more than 500ppm, it is possible to come off on draw roll and cause the increase of broken string broken yarn.The phosphate radical The part by weight of ion is more preferably below 400ppm, particularly preferably more preferably below 300ppm, below 200ppm. It should be noted that sometimes by phosphate anion (PO4 3-) it is referred to as phosphate anion.
As the method for adjustment of the part by weight of phosphate anion, as it was previously stated, can be by reducing comprising organophosphor The inorganic phosphate contained in the raw material Z of ester compound (C) and/or its salt, the use level of adjustment raw material Z, use diatomite etc. Filtration adjuvant is filtered to realize to inorganic agent.
In the case where inorganic agent of the invention contains organophosphorus compounds (C), organophosphorus compounds (C) exists Shared part by weight is preferably 0.05~10 weight %, more preferably 0.08~8 weight % in the nonvolatile component of inorganic agent, More preferably 0.1~7 weight %.
In the case where inorganic agent of the invention contains nonionic surfactant (D), nonionic surfactant (D) exists Shared part by weight is preferably 20~70 weight %, more preferably 25~65 weight % in the nonvolatile component of inorganic agent, enters One step is preferably 30~65 weight %, particularly preferably 30~60 weight %.
(other compositions)
In order to realize the emulsification of inorganic agent, the tack auxiliary to fiber, the washing of the inorganic agent from fiber, to fiber System electrical, lubricity, convergence etc. are assigned, synthetic fibers inorganic agent of the invention can also contain above-mentioned organic sulfonic acid chemical combination Surfactant beyond thing (B), organophosphorus compounds (C) and nonionic surfactant (D).As such surface Activating agent, can enumerate the anion surfactants such as fatty acid soaps；The sun such as alkylamine salt, alkyl imidazole salt, quaternary ammonium salt Ionic surface active agent；The amphoteric surfactantes such as Empigen, stearyl dimethyl betaine；Dimethyl month Osmanthus base amine oxide etc..These surfactants can using a kind or two or more.Situation containing these surfactants The shared part by weight in the nonvolatile component of inorganic agent of the lower surfactant is not particularly limited, and preferably 0.01~15 Weight %, more preferably 0.1~10 weight %.Surfactant mentioned here refers to surface of the weight average molecular weight less than 1000 Activating agent.
In addition, in order to assign heat resistance, synthetic fibers inorganic agent of the invention can also contain antioxidant.As anti- Oxidant, can enumerate：The known antioxidants such as phenol system, sulphur system, phosphite ester system.Antioxidant can using a kind or Person two or more.The shared part by weight in the nonvolatile component of inorganic agent of antioxidant in the case of containing antioxidant It is not particularly limited, preferably 0.1~5 weight %, preferably 0.1~3 weight %.
Additionally, synthetic fibers inorganic agent of the invention can also be containing stoste stabilizer (for example, water, ethylene glycol, the third two Alcohol).The shared part by weight in inorganic agent of stoste stabilizer is preferably 0.1~30 weight %, more preferably 1~20 weight Amount %.
Synthetic fibers inorganic agent of the invention can be made up of the mentioned component for only including nonvolatile component, it is also possible to by Nonvolatile component and stoste stabilizer are constituted, or dilute the inorganic agent after nonvolatile component with low viscosity mineral oil, It can be water serial emulsion obtained from nonvolatile component is emulsified in water.It is by not in synthetic fibers inorganic agent of the invention In the case of water serial emulsion obtained from emulsification in water, the concentration of nonvolatile component is preferably 5~35 weight % to volatile ingredient, More preferably 6~30 weight %.Consider from the point for being uniformly imparted to fibrous material, nonvolatile component is diluted with low viscosity mineral oil The viscosity (30 DEG C) of inorganic agent afterwards is preferably 3~120mm2/ s, more preferably 5~100mm2/s。
The manufacture method of synthetic fibers inorganic agent of the invention is not particularly limited, can be using known method.Close Above-mentioned each composition for being constituted of mixing can arbitrarily or be in a particular order added with inorganic agent into fiber and is manufactured.From carrying The point of high-fire resistance considers, each composition can use the material for removing catalyst etc. and after refining.Particularly, used in the present invention Smooth composition (A), nonionic surfactant (D) in, there is the situation containing organic/inorganic substance, make effect is significant of the invention It is in the case of reduction, then preferred to remove inorganic matter and refined.Inorganic matter and refined method, Neng Goutong are carried out as removing Crossing known method is carried out, for example, if smooth composition (A), then can be by using diatomaceous filtering so as to remove, such as Fruit is nonionic surfactant (D), then can be removed so as to be refined by using the absorption of Inorganic synthese adsorbent.
[manufacture method and fiber structure of synthetic fiber filament yarn line]
The manufacture method of synthetic fiber filament yarn line of the invention includes assigning this hair to Material synthesis fiber filament yarn The operation of bright synthetic fibers inorganic agent.According to the manufacture method of invention, the generation of scum silica frost or broken yarn can be reduced, can Obtain the synthetic fiber filament yarn line of yarn excellent quality.It should be noted that the Material synthesis fiber filament yarn in the present invention It refer to the synthetic fiber filament yarn line for not assigning inorganic agent.
As the operation for assigning synthetic fibers inorganic agent, it is not particularly limited, can be using known method.Generally, Synthetic fibers inorganic agent is assigned in the spinning process of Material synthesis fiber filament yarn.After inorganic agent is assigned, pass through Hot-rolling is stretched, and carries out thermmohardening (thermosetting), is batched.So, do not rolled up temporarily after with imparting inorganic agent Take but in the case of carrying out the operation of hot-stretch, can suitably use synthetic fibers inorganic agent of the invention.As hot-drawn Temperature when stretching, can arrange as an example, for polyester, nylon, if industrial goods and materials are used, then be envisioned for 210~260 DEG C, such as Fruit is dress material, then be envisioned for 110~220 DEG C.
Synthetic fibre treating agent when being imparted to Material synthesis fiber filament yarn is as it was previously stated, can enumerate：Only by not Inorganic agent that volatile ingredient is constituted, the inorganic agent crossed of nonvolatile component is diluted with low viscosity mineral oil or will not be waved in water Water serial emulsion inorganic agent after hair composition emulsification etc..As adding method, it is not particularly limited, can enumerates：Guiding oil supply, roller Oil supply, dipping oil supply, spraying oil supply etc..In these, the management point consideration easy to perform from imparting amount, preferably guiding oil supply, Roller oil supply.
Relative to Material synthesis fiber filament yarn, the imparting amount of the nonvolatile component of synthetic fibers inorganic agent is preferably 0.05~5 weight %, more preferably 0.1~3 weight %, more preferably 0.1~2 weight %.Less than 0.05 weight % When, there is the situation that can not play effect of the invention.On the other hand, when more than 5 weight %, inorganic agent it is non-volatile into Partial volume is easy to fall off in yarn road, and the tar on hot-rolling is dramatically increased, and there is the situation with fine hair, broken yarn winding.
As (raw material) synthetic fiber filament yarn line, can enumerate：Polyester fiber, Fypro, polyolefine fiber etc. The filament yarn of synthetic fibers.It is fine that synthetic fibers of the invention inorganic agent is applied to polyester fiber, Fypro, polyolefin The synthetic fibers such as dimension.As polyester fiber, can enumerate：With the polyester that ethylene glycol terephthalate is main component unit (PET), with polyester (PTT) that trimethylene ethylene glycol terephthalate is main component unit, with butylidene terephthaldehyde Sour glycol ester is the polyester (PBT) of main structural units, with polyester (PLA) that lactic acid is main component unit etc., as poly- Urethane fiber, can enumerate：Nylon 6, nylon66 fiber etc., as polyolefine fiber, can enumerate：Polypropylene, polyethylene etc..As The manufacture method of synthetic fiber filament yarn line, is not particularly limited, can be using known method.
(fiber structure)
Fiber structure of the invention is to contain the synthetic fiber filament yarn obtained with above-mentioned manufacture method of the invention The material of line.Specifically, it is to use synthetic fiber filament yarn line, the utilization for imparting synthetic fibers inorganic agent of the invention Fabric and utilize circular knitting machine, vertical braider or horizontal braiding that water-jet loom, air-jet loom or rapier loom weave The volume thing that machine is compiled into.Additionally, as the purposes of fiber structure, can enumerate：Tire cord, safety belt, airbag, The industrial materials such as fishing net, rope, dress material use etc..Method as manufacturing fabric, compiling thing, is not particularly limited, can be using public affairs The method known.
Embodiment
Hereinafter, the present invention is illustrated by embodiment, the invention is not restricted to the embodiment recorded herein.It should be noted that " % " that text is neutralized in table means " 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), HOSTAPUR SAS93 (Hoechst company systems have been used Make, the weight % of organic sulfonic acid compound (B) 93).Contain substantial amounts of saltcake in raw material X-1.By the chromatography of ions to raw material Sulfate ion (the SO included in X-14 2-) and chlorion (Cl-) content (part by weight) be measured, as a result, relatively In organic sulfonic acid compound (B), sulfate ion is 25950ppm, and chlorion is 62ppm.
(raw material X-2)
Used as the raw material X-2 containing organic sulfonic acid compound (B), using Mersolat H95, (Beyer Co., Ltd manufactures, has Machine sulfoacid compound (B)) 95 weight %).Contain substantial amounts of sodium chloride in raw material X-2.By the chromatography of ions in raw material X-2 Comprising sulfate ion (SO4 2-) and chlorion (Cl-) content (part by weight) be measured, as a result, relative to organic Sulfoacid 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 be by containing above-mentioned organic sulfonic acid compound (B) Raw material X-1, X-2 refined, remove inorganic matter and obtain.The removing method of inorganic matter can use known method, no It is limited to the process for purification shown in embodiment.
(preparation of raw material Y-1)
By the 400 parts of mixing of 550 parts of methyl alcohol and ion exchange water, temperature adjustment is carried out with 45 ± 5 DEG C, slowly thrown while stirring Enter 700 parts of above-mentioned raw materials X-1, be completely dissolved it.Then, the lysate is stood 20 hours at room temperature so that saltcake Precipitation.The supernatant without saltcake is taken out, vacuum distillation is carried out at 60~80 DEG C, remove a part for first alcohol and water, obtained Raw material Y-1 containing 70 weight % organic sulfonic acids compound (B).
By the chromatography of ions to sulfate ion (SO contained in raw material Y-14 2-) and chlorion (Cl-) content (weight Amount ratio) it is measured, as a result, relative to organic sulfonic acid compound (B), sulfate ion is 1085ppm, and chlorion is 60ppm。
(preparation of raw material Y-2)
By ion exchange water, 600 parts are warmed to 80 ± 5 DEG C, and slowly put into 400 parts of above-mentioned raw materials X- while stirring 2, it is completely dissolved it.Then, after the lysate being cooled into 40 DEG C, using ion exchange resin, sodium chloride is removed, is contained There is the raw material Y-2 of 40 weight % organic sulfonic acids compound (B).
By the chromatography of ions to the sulfate ion (SO contained by raw material Y-24 2-) and chlorion (Cl-) content (weight Amount ratio) it is measured, 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)
To 820 parts of different cetanol is put into reaction vessel, on 60 ± 5 DEG C of following attention reaction temperature sides while stirring 180 parts of phosphorus pentoxide is put into mode a small amount of every time.Thereafter, it is ripe 3 hours at 75 ± 5 DEG C, prepare containing non-volatile Composition is the raw material Z-1 of the organophosphorus compounds (C) of 100 amount %.
Organophosphorus compounds (C1), (C2), (C3), the P cores integration ratio of (C4) and inorganic phosphate are respectively 33.05%th, 29.81%, 33.82%, 2.76%, 0.56%.
(preparation of raw material Z-2)
To 800 parts of the alcohol that C11~15 are added in reactor, in 60 ± 5 DEG C of following attention reaction temperatures while stirring While putting into 200 parts of phosphorus pentoxide in mode a small amount of every time.Thereafter, it is ripe 3 hours at 75 ± 5 DEG C, prepare containing organic The raw material Z-2 of phosphate compound (C).
Organophosphorus compounds (C1), (C2), (C3), the P cores integration ratio of (C4) and inorganic phosphate are respectively 44.23%th, 40.31%, 13.79%, 1.09%, 0.58%.
(preparation of raw material Z-3)
To 3 parts of ion exchange water is put into above-mentioned 997 parts of raw material Z-2 being prepared into, carry out adding water for 3 hours at 90 DEG C Treatment.Thereafter, the dewater treatment of 3 hours is carried out at 115 DEG C, the raw material Z-3 containing organophosphorus compounds (C) is prepared.
Organophosphorus compounds (C1), (C2), (C3), the P cores integration ratio of (C4) and inorganic phosphate are respectively 56.72%th, 40.49%, 0.00%, 0.00%, 2.78%.
(preparation of raw material Z-4)
To 600 parts of oleyl alcohol is added in reaction vessel, on 70 ± 5 DEG C of following attention reaction temperature sides with every while stirring Secondary a small amount of mode puts into 110 parts of phosphorus pentoxide.Thereafter, ripe 3 hours at 75 ± 5 DEG C, preparation contains organophosphorus ester The raw material Z-4 of compound (C).
Organophosphorus compounds (C1), (C2), (C3), the P cores integration ratio of (C4) and inorganic phosphate are respectively 57.65%th, 35.26%, 4.57%, 0.44%, 2.07%.
(preparation of raw material Z-5)
To 600 parts of oleyl alcohol are added in reaction vessel, on 70 ± 5 DEG C of following attention reaction temperature sides with every while stirring Secondary a small amount of mode puts into 110 parts of phosphorus pentoxide.Thereafter, it is ripe 3 hours at 70 ± 5 DEG C.Then, 15 parts of ions are put into hand over Water is changed, the treatment that adds water of 3 hours is carried out at 90 DEG C, then, slowly put into 200 parts of dibutylethanolamine, neutralized, prepared Raw material Z-5 containing organophosphorus compounds (C).
Organophosphorus compounds (C1), (C2), (C3), the P cores integration ratio of (C4) and inorganic phosphate are respectively 55.18%th, 35.38%, 2.43%, 0.00%, 7.01%.
(preparation of raw material Z-6)
To in above-mentioned 970 parts of raw material Z-1 being prepared into put into 30 parts of ion exchange waters, carried out at 90 DEG C 3 hours plus Water process.Thereafter, the dewater treatment of 3 hours is carried out at 115 DEG C, the raw material Z- containing organophosphorus compounds (C) is prepared 3。
Organophosphorus compounds (C1), (C2), (C3), the P cores integration ratio of (C4) and inorganic phosphate are respectively 65.43%th, 31.74%, 0.00%, 0.00%, 2.83%.
It should be noted that organophosphorus compounds (C1), (C2), (C3), (C4) and inorganic phosphate P cores integration ratio Use31P-NMR is calculated by the following method.
The nonvolatile component about 30mg for determining sample is weighed in the NMR developmental tubes of diameter 5mm, as deuterated solvents, Add the heavy water (D of about 0.5ml2O), it is dissolved, is used31P-NMR measure device (BRUKER companies manufacture AVANCE400, 162MHz) it is measured.
[embodiment 1~11, comparative example 1~9]
The composition that table 2,3 is recorded is mixed, is stirred until homogeneous, prepare inorganic agent.Using each inorganic agent being prepared into, Pollution accumulation, the pollution wiping of pole, the tension change of pole (pin) are evaluated using following methods.The results are shown in Table 2,3.
It should be noted that the numeral of the non-volatile composition of the inorganic agent of table 2,3 represent each composition (raw material X, Y, Z, these Nonvolatile component) part by weight shared in the nonvolatile component of inorganic agent.Additionally, the inorganic agent composition of table 2,3 is detailed Carefully shown in table 1.
(sulfate ion (SO4 2-), chlorion (Cl-), phosphate anion (PO4 3-) assay method)
Precise sample (nonvolatile component of inorganic agent or the nonvolatile component of raw material X, Y, Z) 5g, in stirring Ultra-pure water 95g is added in mode a small amount of every time simultaneously, the aqueous solution is made, constant volume is carried out with the volumetric flask of 100ml.To be fabricated to Aqueous solution 2ml by ODS (make octadecyl with silica dioxide gel chemical bond after) pre-treatment tubing string, oleophylic will be removed Liquid after property material is for ion chromatography.Detected under the conditions of following ion chromatography.Using relative to The peak area ratio of the titer of concentration known determines detection limit, and the sulfate ion (SO that converts4 2-), phosphate anion (PO4 3-), chlorion (Cl-) amount.It should be noted that detection limit (determination limit) is, sulfate ion (SO4 2-) it is below 0.6ppm, chlorion (Cl-) it is below 1.0ppm, phosphate anion (PO4 3-) it is below 0.3ppm.Table 2,3 In * represent below detection limit.
<Chromatography of ions condition>
Device：Dionex manufactures ICS-1500 uses suppressor
Analytical column：Dionex IonPac AS14 internal diameters 4.0mm × length 50mm
Guard column：Dionex IonPac AG14 internal diameters 4.0mm × length 250mm
Eluent：3.5mmolNa2CO3、1.0mmolNaHCO3
Flow：1.5ml/min
(the pollution accumulation of pole, the pollution wiping of pole, the evaluation of tension change)
By the above-mentioned inorganic agent being prepared into be imparted in the way of quantitative 20 weight % 1000 denier, 96 without oil supply polyester Long filament, passes through and is heated to 150 DEG C of roller by sweeping the yarn method measuring machine that rubs, and removes volatile ingredient, afterwards, and is warmed to 250 DEG C Dumb light chromium pole contact, in the early stage tension force 500g, with sweep yarn speed carry out within 2m/ minute 4 hours scan, evaluation pole pollution Accumulation degree, the pollution wiping of pole, tension change.It should be noted that in order to carry out tightened up evaluation, imparting 20 Weight % inorganic agents.
The degree that the pollution of pole is accumulated is evaluated by following benchmark.
◎：Confirmation is not almost polluted
○：Pollution is confirmed reluctantly
×：Substantially accumulate pollution
Tension change value is calculated using following formula.
The tension force (g) at tension change value (g)=sweep tension force (g)-initial stage of the yarn after 4 hours
Additionally, utilizing following benchmark evaluation tension changes according to tension change value.
◎：0g is to less than 30g
○：30g is to less than 50g
×：More than 50g
The pollution wiping of pole is evaluated with following methods.
In solution immersion rag obtained from making to have dissolved NaOH in water and glycerine, and on dumb light chromium pole The pollution of generation is wiped.By until wiping required number of times, evaluating wiping.
◎：Wiping less than 5 times can just wipe pollution
○：5 wipings less than 20 times can wipe pollution
×：The wiping of more than 20 times is not wiped yet
Table 1
Table 2
Table 3
Knowable to table 2,3, in embodiment, using the sulfate ion that will be detected from the nonvolatile component of inorganic agent and Chlorion is defined as the inorganic agent below predetermined ratio, therefore almost the pollution without pole is accumulated, and wiping is fabulous.Namely Say, roller pollution during manufacture synthetic fibers can be reduced, the cleaning interval of roller can be made elongated, reduce its and clean number of times.Additionally, Tension change value is minimum, can drastically reduce fine hair, broken yarn.
On the other hand, in comparative example, the sulfate ion or chlorion detected from the nonvolatile component of inorganic agent Ratio it is high, therefore, the pollution of pole accumulates many, and wiping is bad.Additionally, understanding tension change value greatly, fine hair, broken yarn are more Hair.
Industrial applicibility
Synthetic fibre treating agent of the invention is adapted in Tarpauling, tire cord, safety belt, air bag, fishing net, rope The industrial materials such as rope, hoist cable, fabric compile the middle synthetic fiber filament yarn lines for using such as the dress materials such as thing use.

Claims (11)

1. a kind of synthetic fibers inorganic agent, is the organic sulfonic acid chemical combination represented containing smooth composition (A) and by following formulas (1) The synthetic fibers inorganic agent of thing (B), wherein,
The shared part by weight in the nonvolatile component of inorganic agent of the organic sulfonic acid compound (B) is 1.25~12 weights Amount %,
Sulfate ion (the SO detected from the nonvolatile component of inorganic agent by the chromatography of ions4 2-) part by weight be Below 200ppm, chlorion (Cl-) part by weight be below 200ppm,
[changing 1]
In formula (1), a and b is more than 0 integer and is the integer for meeting a+b=5~17, M be hydrogen atom, alkali metal, ammonium or Organic amino group.
2. inorganic agent according to claim 1, wherein, the shared part by weight in inorganic agent of the smooth composition (A) It is 20~70 weight %.
3. inorganic agent according to claim 1 and 2, wherein, the organic sulfonic acid compound (B) is in the non-volatile of inorganic agent Shared part by weight is 1.25~7 weight % in composition.
4. inorganic agent according to claim 1 and 2, it also contains organophosphorus compounds (C),
Phosphate anion (the PO detected from the nonvolatile component of inorganic agent by the chromatography of ions4 3-) part by weight be Below 500ppm.
5. inorganic agent according to claim 4, wherein, the organophosphorus compounds (C) is in the non-volatile of inorganic agent Shared part by weight is 0.05~5 weight % in composition.
6. inorganic agent according to claim 4, wherein, the organophosphorus compounds (C) is from by following formulas (2) The compound of expression and at least one by being selected in the compound of following formulas (3) expression,
[changing 2]
In formula (2), R1It is the alkyl of carbon number 6~24, A1O for carbon number 2~4 oxyalkylene, m be 0~15 it is whole Number, n is 1~2 integer, M1It is hydrogen atom, alkali metal, ammonium or organic amino group,
[changing 3]
In formula (3), R1It is the alkyl of carbon number 6~24, A1O for carbon number 2~4 oxyalkylene, m be 0~15 it is whole Number, M1It is hydrogen atom, alkali metal, ammonium or organic amino group, Q1It is M1Or R1O(A1O)m, Y is 1 or 2.
7. inorganic agent according to claim 1 and 2, wherein, also contain nonionic surfactant (D).
8. inorganic agent according to claim 7, wherein, the nonionic surfactant (D) is in the non-volatile of inorganic agent Shared part by weight is 20~70 weight % in composition.
9. a kind of synthetic fiber filament yarn line, is to impart any one of claim 1~8 to Material synthesis fiber filament yarn Synthetic fiber filament yarn line after described inorganic agent.
10. a kind of manufacture method of synthetic fiber filament yarn line, wherein, including to Material synthesis fiber filament yarn entitle It is required that the operation of the inorganic agent any one of 1~8.
A kind of 11. fiber structures, it includes synthetic fiber filament yarn line described in claim 9 and/or with claim 10 The synthetic fiber filament yarn line that obtains of manufacture method.
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
JP2014-159470 2014-08-05
JP2014159470A JP5668170B1 (en) 2014-08-05 2014-08-05 Treatment agent for synthetic fibers and use thereof
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 CN105492688A (en) 2016-04-13
CN105492688B true 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)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5793607B1 (en) * 2014-10-29 2015-10-14 松本油脂製薬株式会社 Treatment agent for synthetic fibers and use thereof
US10370791B2 (en) 2015-02-06 2019-08-06 Matsumoto Yushi-Seiyaku Co., Ltd. Synthetic fiber finish and application thereof
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
KR102355502B1 (en) * 2018-04-16 2022-02-08 다케모토 유시 가부시키 가이샤 Treatment agent for synthetic fibers and synthetic fibers
JP6405068B1 (en) * 2018-04-16 2018-10-17 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber
JP6579721B1 (en) * 2018-07-26 2019-09-25 竹本油脂株式会社 Synthetic fiber treatment agent and synthetic fiber
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
JP6887039B1 (en) * 2020-03-27 2021-06-16 松本油脂製薬株式会社 Treatment agents for synthetic fibers and their use
JP6745563B1 (en) * 2020-06-11 2020-08-26 竹本油脂株式会社 Synthetic fiber treatment agent 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
CN113677848B (en) * 2020-06-11 2022-10-14 竹本油脂株式会社 Treating agent for synthetic fiber and synthetic fiber
KR102460482B1 (en) * 2020-06-11 2022-10-28 다케모토 유시 가부시키 가이샤 Treatment agents for synthetic fibers and synthetic fibers

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

Also Published As

Publication number Publication date
CN105492688A (en) 2016-04-13
KR20170039549A (en) 2017-04-11
JP2016065324A (en) 2016-04-28
KR101896536B1 (en) 2018-09-07
JP5668170B1 (en) 2015-02-12
TW201610262A (en) 2016-03-16
TWI678445B (en) 2019-12-01
WO2016021211A1 (en) 2016-02-11

Similar Documents

Publication Publication Date Title
CN105492688B (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
JP6203444B1 (en) Synthetic fiber treatment agent, synthetic fiber, and synthetic fiber processed product manufacturing method
JP6619336B2 (en) Treatment agent for synthetic fibers and use thereof
JP5730144B2 (en) Treatment agent for synthetic fibers and use thereof
WO2015068671A1 (en) Synthetic fiber treatment agent and use for same
CN107849801B (en) Synthetic fibers inorganic agent and its application
WO2012081564A1 (en) Fiber-treating agent
JP6643838B2 (en) Synthetic fiber treatment agent and its use
KR102308008B1 (en) Synthetic fibre treatment agent, and use thereof
WO2015166603A1 (en) Agent for treating short-staple fibers and use for said agent
JP6745553B1 (en) Elastic fiber treating agent and elastic fiber
JP7135242B1 (en) Dilution of synthetic fiber treatment agent and its use
WO2022219889A1 (en) Treatment agent for synthetic fibers, synthetic fibers, and treatment method for synthetic fibers
WO2022254904A1 (en) Diluted solution of treatment agent for synthetic fibers and use of same

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