CN106414841B - Acrylic fiber inorganic agent and application thereof - Google Patents

Acrylic fiber inorganic agent and application thereof Download PDF

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Publication number
CN106414841B
CN106414841B CN201580030878.2A CN201580030878A CN106414841B CN 106414841 B CN106414841 B CN 106414841B CN 201580030878 A CN201580030878 A CN 201580030878A CN 106414841 B CN106414841 B CN 106414841B
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inorganic agent
acrylic fiber
fiber
alkyl
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CN106414841A (en
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菊田俊彦
吉田昌彦
中山武圭
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Matsumoto Yushi Seiyaku Co Ltd
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Matsumoto Yushi Seiyaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/18—Ethers, e.g. epoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/16—Ethers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/70—Esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Toxicology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inorganic Fibers (AREA)

Abstract

The purpose of the present invention is to provide the convergence that can take into account the fibre bundle in carbon fiber manufacture, the operational acrylic fiber inorganic agents for preventing interfibrous melting adhesion and stablizing.The acrylic fiber inorganic agent of the present invention contains the following general formula (1) compound represented (A) and weight average molecular weight for 8000~25000 polyether compound (B), and total weight ratio of above compound (A) and above-mentioned polyether compound (B) is 50~99 weight %.(in formula (1), R1And R2It is separately hydrogen atom or alkyl.AO is the oxyalkylene group of carbon number 2~4.M and n is separately 1 or more numerical value.)

Description

Acrylic fiber inorganic agent and application thereof
Technical field
The present invention relates to acrylic fiber inorganic agents and application thereof.More specifically, it is related to when manufacturing acrylic fiber The inorganic agent that uses has used the carbon fiber manufacture acrylic fiber (hereinafter sometimes referred to as precursor) of the inorganic agent and has used The manufacturing method of the carbon fiber of the inorganic agent.
Background technology
Carbon fiber is increased using its excellent mechanical property as with the composite material of the plastics referred to as matrix resin Strong fiber is widely used in aerospace purposes, Sport Utility, general industry purposes etc..
As the method for manufacture carbon fiber, general method is：Precursor is turned in 200~300 DEG C of oxidizing atmosphere Become fire resisting chemical fibre dimension, then, is carbonized in 300~2000 DEG C of torpescence atmosphere.In these firings based on high fever When, it may occur that single fiber mutual melting adhesion, to have the quality for the carbon fiber for making gained, the problem of grade reduces.
The melting is adhered in order to prevent, proposes much to assign using silicone compounds as principal component and with excellent precursor The silicone-based inorganic agent of different heat resistance and the excellent fissility based on the flatness between Fiber-Fiber, particularly can profit The technology (such as patent document 1 etc.) that the amino modified silicone-based inorganic agent of heat resistance is further increased with cross-linking reaction, in work It is utilized extensively in industry.
However, on the other hand, adhesion can be become from fibre shedding by having carried out the silicone-based inorganic agent of attachment processing, it On dryer roll or ways for being deposited in precursor manufacturing process etc., make that fiber is wound or fracture of wire etc. becomes and causes to have The problem of the reason of operability reduces.In addition, in the oxidizing atmosphere of resistance to explosive industry sequence, part of it can generate silica, Silicon nitride can be generated in the case of using nitrogen as inactive gas in the torpescence atmosphere for carbonizing process, these foulings (ス ケ ー Le) it accumulates, having makes operability or runnability reduce or the problem of lead to the damage of firing furnace.
In addition, the excellent fissility based on flatness between Fiber-Fiber is for preventing possessed by silicone-based inorganic agent Melting adhesion between single fiber effectively plays a role, and but then, parallelly advances simultaneously in very more fibre bundles In firing process, each fiber beam width broadens because of the flatness of silicone-based inorganic agent, between adjacent fibre bundle Every narrowing, according to circumstances there can be the undesirable condition for generating villus because it is interfered.
In order to avoid these problems, proposed the inorganic agent for the content for reducing silicone compound, do not use silicone-based The inorganic agent etc. of compound.Such as has using the aliphatic ester of the alkylene oxide addition product of bisphenol-A system as principal component and reduce ammonia The inorganic agent (such as patent document 2 etc.) of the content of base modified silicone, using the aliphatic ester of the alkylene oxide addition product of bisphenol-A as Principal component and the inorganic agent (such as patent document 3 etc.) for not using silicone compound.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-371477 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2005-89884 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2004-143645 bulletins
Invention content
The subject that the invention solves
Although however, these inorganic agents have in terms of the problems such as inhibiting operability above-mentioned caused by silicone compound It is effective, but there are the convergence of fibre bundle when batching and when unwinding in precursor filature process and resistance to explosive industry sequences In resistance to cremator entrance and outlet fibre bundle convergence deficiency disadvantage.
In view of the previous technical background, the purpose of the present invention is to provide the fibre bundles that can be taken into account in carbon fiber manufacture Convergence, prevent it is interfibrous melting adhesion and stablize operability acrylic fiber inorganic agent, used the inorganic agent Carbon fiber manufacture acrylic fiber and used the inorganic agent carbon fiber manufacturing method.
Means for solving the problems
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that：Including the alkylene oxide of bisphenol-A adds At the previous inorganic agent of the aliphatic ester of object, a large amount of non-ionic surface is needed to live to emulsify the ester in water system Property agent (emulsifier), under the influence of a large amount of emulsifier, precursor filature process, fibre bundle in resistance to explosive industry sequence boundling Property be deteriorated.And it finds：If inorganic agent of the specific ingredient as principal component is included, then can reduce as in inorganic agent The content of nonionic surfactant and silicone compound that emulsifier uses, and can take into account in carbon fiber manufacture The convergence of fibre bundle prevents interfibrous operability melting adhesion and stablized, and thus reaches the present invention.
That is, the acrylic fiber inorganic agent of the present invention contains the following general formula (1) compound represented (A) and weight average molecular weight For 8000~25000 polyether compound (B), above compound (A) and above-mentioned polyether compound (B) are aggregated in inorganic agent Shared weight ratio is 50~99 weight % in nonvolatile component.
[changing 1]
(in formula (1), R1And R2It is separately hydrogen atom or alkyl.AO is the oxyalkylene group of carbon number 2~4.M and n points It independently is not 1 or more numerical value.)
Above compound (A) and the weight ratio (A/B) of above-mentioned polyether compound (B) are preferably 90/10~20/80.
The acrylic fiber inorganic agent of the present invention preferably also contains nonionic surfactant shown in the following general formula (2) (C)。
[changing 2]
R3-X-[(EO)a/(PO)b]-R4 (2)
(in formula (2), R3For the alkyl of carbon number 8~20.- X- is-O- ,-COO- or-CONH-.EO is oxidation Vinyl, PO are oxypropylene group.A and b indicates average addition molal quantity, and a is that 3~20, b is 0~6.It should be noted that EO The addition form of group and PO groups can be block, or random.R4For hydrogen atom or the alkyl of carbon number 1~6.)
Above-mentioned nonionic surfactant (C) weight ratio shared in the nonvolatile component of inorganic agent is preferably 0.5~15 weight %.
The acrylic fiber inorganic agent of the present invention preferably also contains modified silicone (D), which, which has, includes nitrogen The modified group of atom.
Above-mentioned modified silicone (D) weight ratio shared in the nonvolatile component of inorganic agent is preferably 5~40 weight %.
The carbon fiber manufacture of the present invention is that above-mentioned acrylic fiber inorganic agent is made to be attached to carbon fiber with acrylic fiber It carries out filature on the raw material propylene acid fiber of manufacture acrylic fiber and obtains.
The manufacturing method of carbon fiber of the present invention includes：Filature process makes above-mentioned acrylic fiber inorganic agent be attached to Filature is carried out on the raw material propylene acid fiber of carbon fiber manufacture acrylic fiber；Resistance to cremate treatment process, at 200~300 DEG C Oxidizing atmosphere in be changed into fire resisting chemical fibre dimension；With charing process process, make above-mentioned fire resisting chemical fibre dimension further 300~ It is carbonized in 2000 DEG C of torpescence atmosphere.
Invention effect
The acrylic fiber inorganic agent of the present invention is by the way that into enforcement, its is attached to the processing on precursor in advance, so as to simultaneous It cares for the convergence of the fibre bundle in carbon fiber manufacture, prevent interfibrous operability melting adhesion and stablized.
If using the carbon fiber manufacture acrylic fiber of the present invention, the fibre bundle in carbon fiber manufacture can be taken into account Convergence prevents interfibrous operability melting adhesion and stablized.In addition, the manufacturing method of carbon fiber according to the present invention, The convergence of the fibre bundle in carbon fiber manufacture can be taken into account, prevent interfibrous operability melting adhesion and stablized, it can be with Manufacture the carbon fiber of high-quality.
Specific implementation mode
The acrylic fiber inorganic agent of the present invention is the acrylic fiber (carbon fiber to be imparted to used in carbon fiber manufacture The precursor of dimension) on for the purpose of inorganic agent, be that specific compound (A) and specific polyether compound are contained with specific quantity (B) as the inorganic agent of principal component.Hereinafter, being described in detail.
(compound (A))
The compound (A) used in the acrylic fiber inorganic agent of the present invention is above-mentioned general formula (1) compound represented, Be with the central part comprising bisphenol type skeleton both ends addition have alkylene oxide structure compound.In this way, by that will change It closes object (A) to be used in combination with aftermentioned polyether compound (B), so as to take into account the convergence of the fibre bundle in carbon fiber manufacture, prevent Only interfibrous operability melting adhesion and stablized.Further, since compound (A) has water solubility, therefore conduct is not used The nonionic surfactant of emulsifier can be mixed with water.Its result can prevent in precursor filature process when batching And the fibre bundle of the convergence deficiency of fibre bundle when unwinding and the entrance and outlet of the resistance to cremator in resistance to explosive industry sequence Such disadvantage caused by being mostly used emulsifier that convergence is insufficient.
In above-mentioned general formula (1), R1And R2It is separately hydrogen atom or alkyl.The carbon number of alkyl is preferably 1~2, into one Step preferably 1.AO is the oxyalkylene group of carbon number 2~4, preferably oxyalkylene group (oxyethylene group, the propylene oxide of carbon number 2~3 Base), the more preferably oxyethylene group of carbon number 2.M and n separately be 1 or more numerical value, preferably 4~20, more preferably It is 4~15, further preferably 4~10.In addition, playing effect aspect of the present invention from further, m and n are preferably full The numerical value of sufficient m+n=8~50.M+n is preferably 8~40, more preferably 8~30, further preferably 8~20, particularly preferably 10~20.
In compound (A), it is not necessarily in the addition amount of the alkylene oxide of the both ends addition of the central part comprising bisphenol type skeleton In the left and right consistent of central part, still, due to above-mentioned compound (A) be usually on bisphenol compound addition alkylene oxide and The compound obtained, therefore, for the addition amount in the alkylene oxide of the both ends addition of the central part comprising bisphenol type skeleton, The left and right addition amount of central part will not differ larger mostly.
[polyether compound (B)]
The compound (B) used in the acrylic fiber inorganic agent of the present invention is that weight average molecular weight is 8000~25000 Polyether compound.In this way, by the way that polyether compound (B) and above compound (A) are used in combination, so as to take into account carbon fiber manufacture In fibre bundle convergence, prevent it is interfibrous melting adhesion and stablize operability.Further, since polyether compound (B) It can be mixed with water with water solubility, therefore without using the nonionic surfactant as emulsifier.As a result, can be to prevent Only the convergence deficiency of fibre bundle when batching and when unwinding in precursor filature process and the fire resisting in resistance to explosive industry sequence Change the insufficient such disadvantage caused by being mostly used emulsifier of convergence of the entrance of stove and the fibre bundle of outlet.
Polyether compound (B) is by making the alkylene oxides such as ethylene oxide (EO), propylene oxide (PO), epoxy butane (BO) (AO) polyalkylene glycol obtained from addition polymerization, wherein propylene oxide (PO) is preferably made to be obtained with ethylene oxide (EO) addition polymerization Polyalkylene glycol copolymers.Polyether compound (B) can use a kind or and have two or more.Polyalkylene glycol copolymers The preferably copolymer of the random of PO, EO or block type.The single end or two ends of polyalkylene glycol copolymers can be with Utilize 1 yuan or more of alcohols or acids (Japanese：Salt base acid Class) etc., it is blocked by ehter bond, ester bond.The polyalkylene glycol PO, EO etc. are copolymerized by using well known method and obtain by copolymer.
The molar ratio of the PO/EO of polyether compound (B) is preferably 20/80~50/50, more preferably 20/80~40/60. The weight average molecular weight of polyether compound (B) is preferably 10000~20000, is more preferably 11000~19000, further preferably 12000~18000.It should be noted that weight average molecular weight described in the present invention refers to being surveyed using gel permeation chromatography (GPC) Determine method and measures and carry out the value that polystyrene converts in following determination conditions.
(GPC determination conditions)
Device：Device name " HPLC LC-6A SYSTEM " (SHIMAZU corporations)
Column：" KF-800P", " KF-804", " KF- 802.5", " KF-801" (being SHODEX corporations above)
Mobile phase：Tetrahydrofuran (THF)
Flow velocity：1.0ml/min
Sample size：100 μ l (100 times of dilutions)
Column temperature：50℃
Make the standard substance of calibration curve：Polystyrene (PSt)
[nonionic surfactant (C)]
The fibre bundle that the acrylic fiber inorganic agent of the present invention preferably also contains in being manufactured to carbon fiber assigns uniformly Nonionic surfactant (C) shown in the above-mentioned general formula (2) of adhesion.
As nonionic surfactant (C), the polyoxyalkylene alkyl for meeting general formula (2), polyoxyalkylene can be enumerated Alkyl phenyl ether, polyoxyalkylene diols aliphatic ester, polyoxyethylene polyoxypropylene block polymer etc..
In formula (2), R3For the alkyl of carbon number 8~20.As alkyl, alkyl, alkenyl, aryl, aralkyl etc. can be enumerated, it is excellent Select alkyl, alkenyl.As the carbon number of alkyl, preferably 10~18, further preferred 12~18.
"-X- " is "-O- ", "-COO- " or "-CONH- ", preferably "-O- " or "-COO- ", into one Step is preferably "-O- ".
EO is oxyethylene group, and PO is oxypropylene group.A and b indicates average addition molal quantity.A is 3~20, preferably 5 ~18, further preferably 7~12.B is 0~6, preferably 0~3, more preferably 0.It should be noted that EO groups and PO groups Addition form can be block, or random.
R4For hydrogen atom or the alkyl of carbon number 1~6.As alkyl, alkyl, alkenyl can be enumerated.As R4, preferably hydrogen is former The alkyl of son or carbon number 1~3, more preferably hydrogen atom.
[modified silicone (D) with the modified group comprising nitrogen-atoms]
The aspect that interfibrous melting from preventing carbon fiber from manufacturing is adhered, acrylic fiber of the invention processing Agent preferably also contains modified silicone (D), and the modified silicone (D) has the modified group comprising nitrogen-atoms.The propylene of the present invention Sour fibre finish due to containing above-mentioned compound (A) and polyether compound (B) it is total be used as principal component, do not use Modified silicone (D) can take into account the convergence of the fibre bundle in carbon fiber manufacture as principal component, prevent interfibrous melting viscous The operability and stablized.
Modified silicone (D) is as long as be the modified group comprising nitrogen-atoms, then the type of modified group is not particularly limited.Make For the modified group comprising nitrogen-atoms, the modified group (i.e. amino) containing amino bond or imino group key can be enumerated, contain amide Modified group (i.e. amide groups) of key etc., or there are the modified groups of the different keys such as multiple amino bonds and amido bond.Packet The modified group of nitrogen atom can be mutually bonded with the side chain of the silicone as main chain, can also be mutually bonded with end, can be with It is mutually bonded with the two.Alternatively, it is also possible in the molecule have polyoxyalkylenes (such as polyethylene oxide base, polypropylene oxide base, Polyoxybutylene base etc.).
As the modified silicone (D) with the modified group comprising nitrogen-atoms, it can be mentioned, for example amino modified silicone, amino Polyether modified silicone, amide modifications silicone, amide polyether modified silicone etc. can use a kind of modified silicone, can also be used in combination A variety of modified silicones.
In addition, the content of the nitrogen-atoms in modified silicone (D) be preferably 0.35~3.2 weight %, more preferably 0.37~ 2.2 weight %, further preferably 0.40~1.3 weight %.In the case where the content of nitrogen-atoms is less than 0.35 weight %, When water system emulsifies, the emulsion stability of lotion is made to be deteriorated sometimes.On the other hand, it is higher than 3.2 weight % in the content of nitrogen-atoms In the case of, the reason of getting higher the adherence of modified silicone (D) because of heat cross-linking, become viscose glue (ガ system ア ッ プ).
The emulsion stability of lotion when being emulsified from water system is excellent and with compound (A) and with caused effect Excellent aspect is set out, in these modified silicones (D), preferably amino modified silicone.
In the case where modified silicone (D) is amino modified silicone, the structure of the amino modified silicone is not particularly limited. That is, the amino as modified group can be mutually bonded with the side chain of the silicone as main chain, it can also mutually be bonded with end, may be used also To be mutually bonded with the two.In addition, the amino can be monoamine type, or Polyamine Type in 1 molecule and can also deposit two Person.
Amino (NH in amino modified silicone2) content (hereinafter referred to as " amino weight % ") be preferably 0.4~3.7 Weight %, more preferably 0.42~2.5 weight %, further preferably 0.46~1.5 weight %.If amino weight % is less than 0.4 weight %, then when water system emulsifies, the emulsion stability of lotion can be deteriorated sometimes.On the other hand, higher than 3.7 weight % In the case of, the reason of getting higher the adherence of amino modified silicone because of heat cross-linking, become viscose glue.
It for amino modified silicone in 25 DEG C of viscosity, is not particularly limited, if viscosity is too low, inorganic agent is easy to fly It dissipates, and when water system emulsifies, the emulsion stability of lotion is deteriorated, and can not equably be imparted to inorganic agent on fiber.It is tied Fruit can prevent the melting of fiber from adhering sometimes.On the contrary, if viscosity is excessively high, occurs the viscose glue caused by adherence sometimes Problem.From the viewpoint of preventing these problems, amino modified silicone is preferably 50~15,000mm in 25 DEG C of viscosity2/s、 More preferably 500~10,000mm2/ s, further preferably 1,000~5,000mm2/s。
[surfactant]
The acrylic fiber inorganic agent of the present invention can contain surfactant in the range of not hindering effect of the present invention. Surfactant can be used as the uses such as emulsifier, antistatic agent.As surfactant, it is not particularly limited, it can be from non- Ionic surfactant's (wherein, except above-mentioned nonionic surfactant (C)), anionic surfactant, sun from Suitably selection uses well known surfactant in sub- property surfactant and amphoteric surfactant.Surfactant can make With a kind or it is used in combination of two or more.
As nonionic surfactant, it can be mentioned, for example：Polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxy The polyoxyalkylenes straight chained alkyl ether such as ethylene decyl ethers, polyoxyethylene lauryl ether, polyoxyethylene cetyl base ether；Polyoxyethylene 2- The polyoxyalkylenes branched primary alkyl moiety ethers such as the different cetyl ether of ethylhexyl ether, polyoxyethylene, polyoxyethylene iso stearyl ether；Polyoxy second Alkene 1- hexyls hexyl ether, polyoxyethylene 1- octyls hexyl ether, polyoxyethylene 1- hexyls Octyl Ether, polyoxyethylene 1- amyl heptan The polyoxyalkylenes branched secondary alkyl group ethers such as base ether, polyoxyethylene 1- heptyl amyl ethers；The polyoxyalkylenes alkenyl such as polyoxyethylene oleyl ether Ether；The polyoxyalkylene alkyls such as NONIN HS 240, ethylene nonyl phenyl ether, polyoxyethylene lauryl base phenyl ether Phenyl ether；Polyoxyethylene tri-styryl base phenyl ether, polyoxyethylene diphenylethyllene phenyl ether, polyoxyethylene styryl phenyl The polyoxyalkylene alkyls such as ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene benzyl phenyl ether Aryl phenyl ether；Vinlub 73, Aceonon 300 MO, polyoxyl 40 stearate, polyoxyethylene list Myristinate, polyoxyethylene dilaurate, polyoxyethylene dioleate, two myristinate of polyoxyethylene, polyoxyethylene The polyoxyalkylene fatty acid esters such as distearate；The sorboses such as sorbitan monopalmitate, sorbitan monooleate Alcohol acid anhydride ester；The polyoxyalkylenes sorb such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Sugar alcohol acid anhydride aliphatic ester；The fatty acid glycerides such as glyceryl monostearate, glyceryl monolaurate, glycerol monopalmitate；It is poly- Oxyalkylene Span；Sucrose fatty ester；The polyoxyalkylenes castor oil ether such as Emulsifier EL-60 ether；Polyoxyethylene The polyoxyalkylene hydrogenated castor oil ether such as rilanit special ether；Polyoxyethylene laural base amino ethers, polyoxyethylene stearyl base amino ethers Equal polyoxyalkylene alkyls amino ethers；Ethylene oxide-propylene oxide block or random copolymer；Ethylene oxide-propylene oxide is embedding The end alkyl etherate of section or random copolymer；The end sucrose ether of ethylene oxide-propylene oxide block or random copolymer Compound；The polyoxyalkylene alkylamides such as polyoxyethylene laural base amide, polyoxyethylene stearyl base amide；Deng.It should be noted that The nonionic surfactant illustrated herein refers to will be except nonionic surfactant (C) shown in above-mentioned general formula (2) Nonionic surfactant.In addition, nonionic surfactant is by the non-ionic surface active except polyether compound (B) Agent.The weight average molecular weight of nonionic surfactant is preferably 2000 or less, more preferably 200~1800, more preferably 300 ~1500, it is more preferably 500~1000.
In these nonionic surfactants, for keeping the water system emulsifying ability of ester and silicone compounds especially excellent Reason, preferably polyoxyalkylene branched primary alkyl moiety ether, polyoxyalkylene branched secondary alkyl group ether, polyoxyalkylene alkenyl ether, polyoxyalkylene alkane Base phenyl ether, polyoxyalkylene fatty acid ester, ethylene oxide-propylene oxide block copolymer, ethylene oxide-propylene oxide block End alkyl ether compound, the polyoxyalkylene alkylamides of copolymer, in addition, for being not easy in firing process in the fiber part of the body cavity above the diaphragm housing the heart and lungs Oiling (タ ー Le) and the reasons why cause damage to fiber, more preferable ethylene oxide-propylene oxide block or random copolymerization End alkyl etherate, the polyoxyalkylene alkylamides of object, ethylene oxide-propylene oxide block copolymer.
Above-mentioned polyoxyalkylene alkylamides are the condensation product i.e. amides for instigating polyoxyalkylene to be added to carboxylic acid and amine compounds Compound obtained by upper.As carboxylic acid, it can be mentioned, for example formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, nonyls Acid, capric acid, lauric acid, myristic acid, palmitic acid, Heptadecanoic acide, stearic acid etc..As amine compounds, it can be mentioned, for example：Single first The alkanolamines such as hydramine, dimethanolamine, monoethanolamine, diethanol amine, single Propanolamine, dipropanolamine, monoisopropanolamine；Diethylidene Polyamines such as triamine, tetren etc..As alkylene oxide, it can be mentioned, for example ethylene oxide (EO), propylene oxide (PO), epoxies Butane (BO) etc..As polyoxyalkylene alkylamides, it can be mentioned, for example the alkylene oxide addition product of carboxylic acid single ethanol amide, carboxylic acids two The alkylene oxide addition product etc. of glycollic amide.These polyoxyalkylene alkylamides can be used alone or be applied in combination two or more. In these polyoxyalkylene alkylamides, for the reason for keeping the water system emulsifying ability of ester and silicone compounds especially excellent, preferably Polyoxyethylene laural base amide, polyoxyethylene stearyl base amide.
As anionic surfactant, it can be mentioned, for example：Oleic acid, palmitic acid, Oleic acid sodium salt, palmitic acid sylvite, oil The aliphatic acid such as triethylenetetraminehexaacetic acid alcohol amine salt (salt)；The hydroxyls carboxylic acid such as hydroxyacetic acid, hydroxyacetic acid sylvite, lactic acid, lactic acid sylvite (salt)； The polyoxyalkylene alkyls acetic acid such as polyoxyethylene tridecyl ether acetic acid (sodium salt) (salt)；Trimellitic acid potassium, pyromellitic acid potassium etc. The salt of carboxyl Polysubstituted Aromatic Compounds；The alkyl benzene sulphonates such as dodecyl benzene sulfonic acid (sodium salt) (salt)；Polyoxyethylene 2- second The polyoxyalkylene alkyls sulfonic acid such as base hexyl ether sulfonic acid (sylvite) (salt)；Stearyl N-methyltaurine (sodium), lauroyl first The higher fatty acid amides such as base taurine (sodium), myristoyl N-methyltaurine (sodium), palmityl N-methyltaurine (sodium) Sulfonic acid (salt)；The N- acyl groups sarcosine such as lauroyl sarcosine (sodium) (salt)；The alkyl phosphonic acids such as octyl phosphonic acid salt (sylvite) (salt)；The aromatic series phosphonic acids such as Phenylphosphine hydrochlorate (sylvite) (salt)；The alkane such as 2- ethylhexyl phosphonic acid mono 2- ethylhexyls (sylvite) Base phosphonic acids alkyl phosphate (salt)；The nitrogenous alkyl phosphonic acid such as aminoethyl phosphonic acid (diethanolamine salt) (salt)；2- ethylhexyl sulphur The alkyl sulfate (salt) of acid esters (sodium salt) etc.；The polyoxyalkylenes sulphur such as polyethylene glycol oxide 2- ethylhexyls ether sulfuric ester (sodium salt) Acid esters (salt)；Long-chains sulfosuccinate, the N- such as two -2- ethylhexylsulfosuccinates sodium, dioctyl sodium sulphosuccinate The long-chains N- acyl glutamates such as lauroyl glutamate list sodium, N- stearyls-Pidolidone disodium；Deng.
As cationic surfactant, it can be mentioned, for example：Lauryl trimethyl ammonium chloride, myristyl trimonium chlorine Change ammonium, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oil base trimethyl ammonium chloride, cetyltrimethylammonium chlorination Ammonium, INCROQUAT TMC-80, coconutalkyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, stearyl Trimethylammonium bromide, coconutalkyl trimethylammonium bromide, cetyltrimethylammonium sulfate methyl ammonium, oleyl dimethyl ethyl sulfuric acid Ethyl ester ammonium, Quaternium 24, dilauryl ammonium chloride, VARISOFT TA100, octadecyl The alkyl quaternary ammonium salts such as diethylmethyl ammonium sulfate；(polyethylene glycol oxide) lauryl amino ether lactate, stearyl ether lactic acid Salt, two (polyethylene glycol oxide) lauryl methyl amino ethers Dimethyl phosphates, two (polyethylene glycol oxide) lauryl ethyl sulfuric acid second Ester ammonium, two (polyethylene glycol oxide) hydrogenated tallow alkyl ethyl sulfuric acid ethyl ester amine, two (polyethylene glycol oxide) lauryl methyl dimethyl (polyoxyalkylene) alkyl amino ether salt such as ammonium phosphate, two (polyethylene glycol oxide) stearic amine lactates；N- (2- hydroxyl second Base)-N, N- dimethyl-N-stearyl amido propyl nitric acid ammonium nitrate, lanolin fatty acid amide ethyl diformazan The acylamides alkyl quaternary ammonium salts such as base ethyl-sulfate ammonium, lauroyl amide ethyl-methyl diethyl sulfate methyl ammonium；Two palms Ethyl polyethylene-oxide base (エ テ ノ キ シ) ethyl ammonium chloride, distearyl polyethylene oxide base (エ テ ノ キ シ) methyl chloride The alkyl ethylene oxides such as ammonium base (エ テ ノ キ シ) quaternary ammonium salt；The alkyl isoquinolinium salts such as lauryl isoquinolin chloride；Month The zephirans such as osmanthus base dimethyl benzyl ammonium chloride, stearalkonium chloride (ベ Application ザ Le U ニ ウ system) salt；Benzyl The benzyloxies second ammonium (ベ such as dimethyl { 2- [2- (p- 1,1,3,3- tetramethyl butyls phenoxy group) ethyoxyl] ethyl } ammonium chloride Application ゼ ト ニ ウ system) salt；The pyridiniujms such as cetyl pyridinium chloride；Oil base hydroxyethyl imidazoles ethyl-sulfate salt, bay The imidazole salts such as base hydroxyethyl imidazoles ethyl-sulfate salt；N- cocoyl arginine ethyl esters pyrrolidone carboxylic acid salt, N- The acyl groups basic amino acid alkyl ester salts such as lauroyl lysine diethyl acetamidomalonate chloride；Lauryl amine chloride, stearic amine The primary amine salts such as bromide, hydrogenated tallow alkyl amine chloride, rosin amine acetate；Cetyl methyl amine sulfate, lauryl first Base amine chloride, dilauryl amine acetate, stearyl ethylamine bromide, lauryl propyl amine acetate, dioctylamine chlorine The secondary amine salts such as compound, octadecyl ethylamine hydroxide；Dilauryl methyl amine sulfate, lauryl diethylamide chlorination Object, lauryl ethylmethylamine bromide, diethanol stearyl amido-propyl ethylamine trihydroxy ethyl phosphate, stearyl amido-propyl second The tertiary ammonium salts such as ethylethanolamine urea condensation polymer acetate；Fatty acid amide guanidine salt；The alkyl three such as lauryl triethylene glycol ammonium hydroxide Aklylene glycol ammonium salt etc..
As amphoteric surfactant, it can be mentioned, for example：2- undecyls-N, N- (hydroxyethyl carboxymethyl group)- The imidazolines system both sexes such as 2- imidazolines sodium, 2- cocoyl -2- imidazolium hydroxide -1- Carboxyethoxy disodium salts Surfactant；2- heptadecyl-N- carboxymethyl group-N- hydroxyethyls imidazolinium betaine, lauryl dimethyl amino The glycine betaines such as acetic acid glycine betaine, alkyl betaine, amide betaine, sulfobetaine system amphoteric surfactant；N- lauryls Amino acid type amphoterics surfactants such as glycine, N- lauryls Beta-alanine, N- stearyl Beta-alanines etc..
In these surfactants, emulsifying ability excellent for ageing stability also excellent reason, preferably nonionic Surfactant.Compared with nonionic surfactant, ionic surfactant has and can inhibit because generating electrostatic institute Discrete, the advantage that electrostatic inhibition is excellent of the fibre bundle of cause, therefore be preferably used in combination with nonionic surfactant.As from Sub- property surfactant, can enumerate above-mentioned anionic surfactant, cationic surfactant, amophoteric surface active Agent, still, in these surfactants, preferred cationic surfactant, in cationic surfactant, further Optimizing alkyl quaternary ammonium salt, (polyoxyalkylene) alkyl amino ether salt, acylaminoalkyl quaternary ammonium salt, alkyl ethylene oxide base (エ テ ノ キ シ) quaternary ammonium salt, primary amine salt, secondary amine salt, tertiary ammonium salt etc..
[other compositions]
The present invention acrylic fiber inorganic agent can not hinder the range of effect of the present invention contain except mentioned component with Outer other compositions.As other compositions, can enumerate：Acid phosphoric acid ester, phenol system, amine system, sulphur system, phosphorus system, quinone system etc. resist Oxidant；Phosphate ester salt, the quaternary of the advanced alcohol ether of sulfuric acid, sulfonate, higher alcohol of the advanced alcohol ether of higher alcohol The antistatic agent of cationic system surfactant, amine salt type cationic system surfactant etc.；Arrcostab, the higher alcohol of higher alcohol The smooth agent of ether, wax class etc.；Antiseptic；Preservative；Antirust agent；And hygroscopic agent etc..
Antioxidant is to effectively inhibit to make acrylic fiber inorganic agent heat point because of the heating in resistance to cremate treatment process Solution and the ingredient for improving the melting adhesion effect between preventing Fiber-Fiber.
As antioxidant, it is not particularly limited, from the viewpoint of preventing firing furnace from polluting, preferred organic oxidation-resistant Agent, acid phosphoric acid ester, further preferred acid phosphoric acid ester.As organic oxidation-resistant agent, it can be mentioned, for example 4,4 '-butylidenebis (3 methy 6 tert butyl phenol, three (octadecyl) phosphite esters, N, N '-diphenyl-para-phenylene diamines, triethylene glycol are double [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester], two oil bases-thiodipropionate etc..These are organic Antioxidant can be used alone or in combination with two or more kinds い.
As acid phosphoric acid ester, it can be mentioned, for example the acid described in the claim of International Publication WO2013/129115 Property phosphate.In addition, acid phosphoric acid ester can as recorded in 0036 paragraph of International Publication WO2013/129115 profit It is manufactured with well known method.For example, by making anhydrous phosphoric acid P2O5After equal inorganic phosphates and alcohol or polyoxyalkylene addition The compound with alcohol hydroxyl group in the molecule (hereinafter sometimes referred to simply as raw alcohol) of alkyl ether etc. is anti-with arbitrary molar ratio It answers and obtains.In the acid phosphoric acid ester of gained, acid pyrophosphate that can be containing by-product (the unneutralized burnt phosphorus of non-forming salt Acid esters), the acid polyphosphate (the unneutralized polyphosphate of non-forming salt) such as acid triguaiacyl phosphate.
In addition, the present invention acrylic fiber inorganic agent can in the range of not hindering effect of the present invention, including in addition to Silicone composition other than the modified silicone (D) of modified group with nitrogen atom.Specifically, can enumerate dimethyl silscone, Epoxy-modified silicone, alkylene oxide modified silicone (polyether modified silicone), epoxidized polyether modified silicone are (referring for example to patent No. 4616934), carboxy-modified silicone, carbinol-modified silicone, alkyl-modified silicone, phenol-modified silicone, methacrylate change Property silicone, alkoxy-modified silicone, fluorine richness silicone etc..
In addition, the acrylic fiber inorganic agent of the present invention can close in the range of not hindering effect of the present invention containing esterification Object.As ester compounds, it can be mentioned, for example：The intramolecular described in public table WO2007/066517 bulletins has 3 or more again Described in the ester compounds of ester group, International Application Serial No. PCT/JP2013/75081 containing thioester compound etc..
[acrylic fiber inorganic agent]
The acrylic fiber inorganic agent of the present invention is must to contain above-mentioned general formula (1) compound represented (A) and divide equally again The acrylic fiber inorganic agent of the polyether compound (B) of son amount 8000~25000.The conjunction of compound (A) and polyether compound (B) It is preferably 50~99 weight %, more preferably 55~95 weights to count shared weight ratio in the nonvolatile component of inorganic agent Measure %, further preferably 60~90 weight %, particularly preferably 65~80 weight %.It should be noted that in the present invention Nonvolatile component refers to parching ingredient when being heat-treated at 105 DEG C by inorganic agent and remove solvent etc. and reaching constant.
From the convergence that can take into account the fibre bundle in carbon fiber manufacture, prevent interfibrous behaviour melting adhesion and stablized It sets out in terms of the property made, the weight ratio (A/B) of compound (A) and polyether compound (B) is preferably 90/10~20/80, more preferably It is 75/25~35/65, further preferably 65/35~45/55.
In the case where the acrylic fiber inorganic agent of the present invention contains nonionic surfactant (C), nonionic Surfactant (C) weight ratio shared in the nonvolatile component of inorganic agent is preferably 0.5~15 weight %, is more preferably 1~10 weight %, further preferably 1~8 weight %, particularly preferably 3~5 weight %.
In the case where the acrylic fiber inorganic agent of the present invention contains modified silicone (D), modified silicone (D) is in inorganic agent Nonvolatile component in shared weight ratio be more preferably 5~40 weight %, further preferably 10~30 weight %, especially Preferably 15~25 weight %.
The acrylic fiber inorganic agent of the present invention can reduce the usage amount of the nonionic surfactant as emulsifier. As a result, the total amount of nonionic surfactant can be reduced.Specifically, nonionic surfactant (total amount) can be made Shared weight ratio is 20 weight % or less, is preferably 15 weight % or less, further in the nonvolatile component of inorganic agent Preferably 10 weight % or less.If the weight ratio is more than 20 weight %, sometimes because of a large amount of nonionic surfactant It influences and the convergence of precursor filature process, fibre bundle in resistance to explosive industry sequence is made to be deteriorated.At the acrylic fiber of the present invention In the case that reason agent contains nonionic surfactant (C), nonionic surfactant (total amount) is not waved inorganic agent In hair ingredient shared weight ratio be preferably 1~20 weight %, more preferably 2~15 weight %, further preferably 3~ 10 weight %.
The acrylic fiber inorganic agent of the present invention is preferably by compound (A), polyether compound (B), as needed non- Ionic surfactant (C), modified silicone (D) dissolving, state that is solubilized, emulsifying or be scattered in water.
The weight ratio of water weight ratio shared in acrylic fiber inorganic agent entirety, nonvolatile component is had no It is particularly limited to.As long as example, considering transportation cost when transport, propylene of the invention is suitably determined in the operability etc. of emulsion viscosity Sour fibre finish.Water weight ratio shared in acrylic fiber inorganic agent entirety is preferably 0.1~99.9 weight Measure %, further preferably 10~99.5 weight %, particularly preferably 50~99 weight %.Nonvolatile component is in acrylic fiber Shared weight ratio (concentration) is preferably 0.01~99.9 weight %, further preferably 0.5~90 in inorganic agent entirety Weight %, particularly preferably 1~50 weight %.
Go out in terms of the effect of the melting adhesion between preventing heat resistance and the Fiber-Fiber in resistance to cremate treatment process Hair, acrylic fiber inorganic agent of the invention in air with 250 DEG C heat treatment 1 hour after weight reduction rates preferably less than 40 weight %, more preferably less than 30 weight %, more preferably less than 25%.The situation for being 40% or more in weight reduction rates Under, the inorganic agent epithelium remained on fiber in resistance to cremate treatment process tails off, and being unable to fully obtain sometimes prevents fiber- The effect of interfibrous melting adhesion.
The acrylic fiber inorganic agent of the present invention can be manufactured by mixing the ingredient of above description.It is above-mentioned for making The method of ingredient emulsification, the dispersion of explanation is not particularly limited, and well known method may be used.As such method, can arrange Citing is such as：The method for emulsion dispersion being carried out in hot water under each ingredient input stirring for constituting acrylic fiber inorganic agent；It will Each ingredient mixing for constituting acrylic fiber inorganic agent, applies mechanical shearing using homogenizer, homogeneous mixer, ball mill etc. Power, and slowly input water carries out the method etc. of Phase inversion emulsification.
The acrylic fiber inorganic agent of the present invention can be suitable as the place of carbon fiber manufacture acrylic fiber (precursor) Manage agent (precursor inorganic agent).The spinning oil of the acrylic fiber in addition to precursor be can also be used as to use.
From the convergence aspect that can assign the good fibre bundle in precursor filature process, resistance to explosive industry sequence, The nonvolatile component of the acrylic fiber inorganic agent of the present invention is preferably 350~25000mPas, more preferably in 50 DEG C of viscosity For 1000~20000mPas, further preferably 1500~15000mPas.If the viscosity has less than 350mPas Shi Qianti filatures process, fibre bundle in resistance to explosive industry sequence convergence be deteriorated.If in addition, the viscosity is more than 25000mPas, Even if can then assign precursor filature process, good fibre bundle in resistance to explosive industry sequence convergence inorganic agent viscosity Become excessively high, the operability of inorganic agent is made to be deteriorated sometimes.It should be noted that remembering in the assay method foundation embodiment of the viscosity The method of load carries out.
[carbon fiber manufactures the manufacturing method with acrylic fiber, its manufacturing method and carbon fiber]
It is that above-mentioned acrylic fiber inorganic agent is made to be attached to that the carbon fiber of the present invention, which is manufactured with acrylic fiber (precursor), The raw material propylene acid fiber of precursor carries out acrylic fiber obtained by filature.The manufacturing method of the precursor of the present invention includes making The acrylic fiber inorganic agent stated is attached on the raw material propylene acid fiber of precursor, carries out the filature process of filature.
The manufacturing method of carbon fiber of the present invention includes：Filature process makes above-mentioned acrylic fiber inorganic agent be attached to Filature is carried out on the raw material propylene acid fiber of precursor, to precursor；Resistance to cremate treatment process, before being manufactured in the filature process Body is changed into fire resisting chemical fibre dimension in 200~300 DEG C of oxidizing atmosphere；With charing process process, above-mentioned fire resisting chemical fibre is made to tie up Further carbonized in 300~2000 DEG C of torpescence atmosphere.
Filature process is that acrylic fiber inorganic agent is made to be attached to the raw material propylene acid fiber of precursor, carry out filature to precursor Process comprising attachment treatment process and stretching process.
It is to make to adhere to it acrylic fiber inorganic agent by after the raw material propylene acid fibre spinning of precursor to adhere to treatment process Process.That is, acrylic fiber inorganic agent is made to be attached on the raw material propylene acid fiber of precursor in adhering to treatment process.Separately Outside, the raw material propylene acid fiber of the precursor is just stretched after rigid spinning, and the high magnification after attachment treatment process is stretched spy Also known as make " stretching process ".Stretching process can be the damp and hot pulling method using high hot steam, or using hot-rolling Xeothermic pulling method.
Precursor by so that the resistance to cremate below of the acrylonitrile and 5 moles of % of at least 95 moles % or more promote ingredient copolymerization and The polyacrylonitrile obtained is that the acrylic fiber of principal component is constituted.Promote ingredient as resistance to cremate, it can be suitable for use to acrylonitrile Contain vinyl compound with copolymerizable.It for the filament denier of precursor, is not particularly limited, from performance and manufacturing cost Balance set out, preferably 0.1~2.0dTex.In addition, also having no spy for the radical of the single fiber of the fibre bundle of composition precursor It does not limit, from the balance of performance and manufacturing cost, preferably 1,000~96,000.
Acrylic fiber inorganic agent can be attached in any stage of filature process on the raw material propylene acid fiber of precursor, It is preferred that it is made disposably to adhere to before stretching process.If the stage before stretching process, then can in any stage, for example just Adhered to after spinning.Any stage that can also be further after stretching process makes it adhere to once again, such as can be rigid So that it is adhered to once again after stretched process, it can also be made to adhere to once again in coil ing one, can also just carry out fire resisting It is set to adhere to once again before changing treatment process.About the adherence method, roller etc. can be used to be adhered to, dipping can also be utilized Method, spray coating method etc. are adhered to.
In adhering to treatment process, from the deadlocked effect for obtaining preventing between Fiber-Fiber, the effect for preventing melting from adhering Fruit sets out with the balance in charing process process reducing because of the carbonizing matter of inorganic agent carbon fiber quality is prevented, acrylic acid The imparting rate of fibre finish is preferably 0.1~2 weight %, further preferably 0.3~1.5 weight relative to the weight of precursor Measure %.If the imparting rate of acrylic fiber inorganic agent less than 0.1 weight %, is unable to fully to prevent deadlocked, molten between single fiber Melt adhesion, makes the strength reduction of the carbon fiber of gained sometimes.On the other hand, if the imparting rate of acrylic fiber inorganic agent is more than 2 Weight %, then acrylic fiber inorganic agent is between the required above covering single fiber, therefore interferes oxygen in resistance to cremate treatment process Supply to fiber makes the strength reduction of the carbon fiber of gained sometimes.It should be noted that at acrylic fiber said here Percentage of the imparting rate of agent with the nonvolatile component weight of the acrylic fiber inorganic agent adhered to relative to preceding body weight is managed to come Definition.
Resistance to cremate treatment process is the oxidisability gas by the precursor accompanying by acrylic fiber inorganic agent at 200~300 DEG C It is changed into the process of fire resisting chemical fibre dimension in atmosphere.As long as oxidizing atmosphere usually air.The temperature of oxidizing atmosphere is preferred It is 230~280 DEG C.In resistance to cremate treatment process, while to attachment treated acrylic fiber apply draw ratio be 0.90~ The tension side of 1.10 (preferably 0.95~1.05) carries out the heat treatment of 20~100 minutes (preferably 30~60 minutes).It is resistance at this In cremate processing, by intramolecular cyclization and to the oxygen addition of ring, to manufacture the fire resisting chemical fibre dimension with resistance to cremate structure.
Charing process process is that fire resisting chemical fibre is made to tie up the work further carbonized in 300~2000 DEG C of torpescence atmosphere Sequence.In charing process process, preferably：First, in the torpescence atmosphere such as nitrogen, argon gas, have at 300 DEG C~800 DEG C Have in the firing furnace of temperature gradient, the tension that draw ratio is 0.95~1.15 is applied to fire resisting chemical fibre dimension side, side carries out several minutes Heat treatment, and carry out pre- charing process process (the first charing process process).Later, in order to make charing further carry out and make stone Inkization carries out, and in the torpescence atmosphere such as nitrogen, argon gas, relative to the first charing process process, side applies draw ratio and is 0.95~1.05 tension, side carries out several minutes of heat treatment, and carries out the second charing process process, and fire resisting chemical fibre is tieed up and is carbonized. Maximum temperature, can be to be set as by the control for the heat treatment temperature in the second charing process process when applying temperature gradient 1000 DEG C or more (preferably 1000~2000 DEG C).The maximum temperature (can stretch strong according to the requirement characteristic of required carbon fiber Degree, elasticity modulus etc.) suitably selection determination.
In the manufacturing method of the carbon fiber of the present invention, in the case where needing the higher carbon fiber of elasticity modulus, after charing After treatment process, graphitization processing process can also be carried out.Usually in the torpescence atmosphere such as nitrogen, argon gas, while to charing Fiber obtained by treatment process applies tension side and carries out graphitization processing process in 2000~3000 DEG C of temperature.
For the carbon fiber obtained in this way, when can carry out being made composite material according to purpose for improving with matrix tree The surface treatment of the adhesive strength of fat.As surface treatment method, gas phase or liquid phase processing may be used, from the viewpoint of productivity It sets out, is preferably based on the liquid phase processing of the electrolyte such as acid, alkali.In addition, in order to improve processability, the operability of carbon fiber, also may be used To assign various sizing agents excellent in compatibility to matrix resin.
Embodiment
Hereinafter, being specifically explained to the present invention using embodiment, still, however it is not limited to the embodiment recorded herein. It should be noted that percentage (%), part shown in embodiment below are as long as no special instructions, " weight % ", " weight are indicated Part ".The measurement of each characteristic value is carried out based on method as shown below.
The imparting rate ＞ of ＜ inorganic agents
The imparting rate of acrylic fiber inorganic agent is calculated using by the ethyl alcohol extraction of soxhlet's extractor.But it is right In the embodiment comprising modified silicone (D), comparative example, imparting rate is calculated using the following method.
After precursor after inorganic agent is assigned carries out alkali fusion with potassium hydroxide/sodium butyrate, it is dissolved in water and with hydrochloric acid tune Section is pH1.Sodium sulfite and ammonium molybdate, which is added, to it makes its colour developing, carries out the colorimetric assay (815 μm of wavelength) of silicon molybdenum blue, acquires The content of silicon.Use the value of the silicone content acquired at this and the silicone content advanced in the inorganic agent that same procedure acquires, meter Calculate the imparting rate (weight %) of acrylic fiber inorganic agent.
＜ viscosity ＞
In diameterAluminium cup on acquire each inorganic agent so that the weight of its nonvolatile component reaches 1g, utilize temperature Wind drying machine carries out processing in 105 DEG C × 3 hours, removes moisture.ICI cone and plate viscometers are used to the sample (1g) of gained (RESEACH EQUIPMENT (LONDON) LTD. systems) carries out viscosimetric analysis.
More specifically, the temperature of plate is set as 50 DEG C, then, the sample input port input examination on being set to plate Sample then after cone-plate is down to sample input port, the switch of engine is touched after 90 seconds, starts to measure.When by numerical stability Value be set as measured value.
＜ filature operability (roller dirt) ＞
The pollution level (viscose glue) of the dryer roll after inorganic agent is assigned to precursor 50kg using following evaluation criteria judgements.
◎：Roller pollution caused by no viscose glue, no filature operational problem
○：Roller pollution caused by viscose glue is few, no filature operational problem
△：There are the roller pollution caused by viscose glue, filature operability slightly poor
×：Roller pollution caused by viscose glue is notable, obtains (Unit yarn takes ら れ) by monofilament when filature, there is winding
The convergence ＞ of ＜ fibre bundles
In when batching of precursor filature process, the entrance of resistance to cremator when unwinding and in resistance to explosive industry sequence, outlet, observation The boundling degree of fibre bundle, and synthesis is visually confirmed according to following evaluation criteria.
◎：The fibre bundle of uniform rugosity and the discrete of single fiber is not observed completely.
○：The fibre bundle of uniform rugosity and the discrete of single fiber is not almost observed.
△：The fibre bundle of uniform rugosity but observe a little discrete single fiber.
×：Discrete single fiber is also more and observes monofilament fracture of wire.
＜ melting preventing property of adhesion ＞
20 positions are arbitrarily chosen from carbon fiber, from this from Cutting Length 10mm staple fiber, observe its melting adhesion shape State is judged according to following evaluation criteria.
◎：It adheres without melting
○：It adheres almost without melting
△：Melting adhesion is few
×：Melting adhesion is more
＜ carbon fiber strengths ＞
It is measured according to epoxy resin impregnation harness method specified in JIS-R-7601, by 10 times put down of measurement number Mean value is set as carbon fiber strength (GPa).
(preparation of modified silicone (D) emulsion)
Following modified silicone D1~D4 are utilized respectively the nonionic surfactant (alkyl of addition polyoxyethylene 7mol Ether (carbon number of alkyl is 12~14), the tristyrenated phenyl ether of addition polyoxyethylene 12mol and ethylene oxide/propylene oxide (50/50) block copolymer) carry out water system emulsification, obtain as nonvolatile component composition by following modified silicones/above-mentioned it is non-from The emulsion of modified silicone that the weight rate of sub- property surfactant=80/20 is constituted, that nonvolatile component is 20 weight %.
D1：Amino modified silicone (25 DEG C of viscosity：1300mm2/ s, amino equivalent：2000g/mol, modified type：Diamines)
D2：Amino modified silicone (25 DEG C of viscosity：90mm2/ s, amino equivalent：2200g/mol, modified type：Two ends)
D3：Amino modified silicone (25 DEG C of viscosity：250mm2/ s, amino equivalent：7600g/mol, modified type：Diamines)
D4：Amino modified silicone (25 DEG C of viscosity：90mm2/ s, amino equivalent：8800g/mol, modified type：Monoamine)
(preparation of ester based compound (E) emulsion)
Following ester based compound E1, E2 are utilized respectively the nonionic surfactant (alkane of addition polyoxyethylene 7mol Base ether (carbon number of alkyl is 12~14), the tristyrenated phenyl ether of addition polyoxyethylene 12mol and ethylene oxide/epoxy third Alkane (50/50) block copolymer) carry out water system emulsification, obtain nonvolatile component composition by following ester based compounds/above-mentioned it is non-from The emulsification of ester based compound that the weight rate of sub- property surfactant=70/30 is constituted, that nonvolatile component is 20 weight % Object.
E1：The dilauryl ester of 2 moles of addition products of ethylene oxide of bisphenol-A
E2：Triisodecyl trimellitate
(Examples 1 to 28, comparative example 1~13)
Use following compound A1~A3, polyether compound B1~B3, nonionic surfactant C1~C3, above-mentioned The water system emulsion of modified silicone D1~D4 of preparation, the water system emulsion and water of ester based compound E1~E2, according to table 1~3 Shown in nonvolatile component composition be mixed, it is 20 weights to prepare nonvolatile component ratio shared in inorganic agent respectively Measure the acrylic fiber inorganic agent of %.It should be noted that the numerical value of table indicates each ingredient in the nonvolatile component of inorganic agent Shared weight ratio.For example, compound A1~A3 of table numerical value indicate compound A1~A3 inorganic agent it is non-volatile at Shared weight ratio in point.In addition, the numerical value of " nonionic surfactant " of table 1~3 indicates that non-ionic surface lives Property agent (total amount) weight ratio (weight %) shared in nonvolatile component.
Then, the inorganic agent of preparation is further diluted with water, respectively obtains a concentration of 3.0 weight %'s of nonvolatile component Treatment fluid.
Each treatment fluid is set to be attached on precursor (filament denier 0.8dtex, 24,000 long filaments) so that imparting rate is 1.0 Weight % removes moisture in 100~140 DEG C of dryings.Precursor after treatment fluid is adhered to carries out in 250 DEG C of resistance to cremator Resistance to cremate processing in 60 minutes, then, is burnt in 300~1400 DEG C of the retort with temperature gradient under nitrogen atmosphere At being changed into carbon fiber.The evaluation result of each characteristic value is as shown in table 1~3.
A1：POE (8) Bisphenol A Ether
A2：POE (10) Bisphenol A Ether
A3：POE (17.5) Bisphenol A Ether
It should be noted that above-mentioned POE (X) Bisphenol A Ether indicates the R in general formula (1)1And R2For hydrogen atom, m+n=X, AO is the oxyethylene group of carbon number 2.
B1：PO/EO=25/75 polyethers (weight average molecular weight 13000)：To diethylene glycol with the weight of PO/EO=25/75 The random addition of ratio has the polyether compound that PO and EO and weight average molecular weight are 12000.
B2：PO/EO=25/75 polyethers (weight average molecular weight 15000)：To diethylene glycol with the weight of PO/EO=25/75 The random addition of ratio has the polyether compound that PO and EO and weight average molecular weight are 15000.
B3：PO/EO=25/75 polyethers (weight average molecular weight 18500)：To diethylene glycol with the weight of PO/EO=25/75 The random addition of ratio has the polyether compound that PO and EO and weight average molecular weight are 18500.
C1：It is averaged nonionic surfactant obtained by 7 moles of EO of addition to the straight chain primary alcohol of carbon number 12~14
C2：It is averaged nonionic surfactant obtained by 7 moles of EO of addition to the secondary alcohol of carbon number 12~14
C3：To the straight chain primary alcohol of carbon number 12~14 with the sequence of the 5 moles of EO that are averaged, average 2 moles of PO, average 3 moles of EO Nonionic surfactant obtained by block addition successively
[table 1]
[table 2]
[table 3]
Shown in table 1~3, it is known that：The boundling of the fibre bundle in carbon fiber manufacture can be taken into account in any embodiment Property, prevent it is interfibrous melting adhesion and stablize operability.
On the other hand, it understands that the convergence of the fibre bundle in carbon fiber manufacture can not be taken into account in a comparative example, prevent fiber Between melting adhesion and stablize operability.Known to：As comparative example 1~3,8~10, there is filature operability better, But the convergence of fibre bundle is deteriorated, to the situation of carbon fiber strength difference or this as comparative example 4~7,11~13, it is anti- It is only better in terms of interfibrous melting adhesion, but filature operability is poor.
Industrial availability
The acrylic fiber inorganic agent of the present invention is the used processing when manufacturing carbon fiber manufacture acrylic fiber Agent on high-grade carbon fiber is being useful for manufacturing.The carbon fiber manufacture acrylic fiber of the present invention is through the present invention Inorganic agent carried out processing, on high-grade carbon fiber be useful for manufacturing.Utilize the system of the carbon fiber of the present invention The method of making obtains high-grade carbon fiber.

Claims (10)

1. a kind of acrylic fiber inorganic agent is 8000 containing the following general formula (1) compound represented (A) and weight average molecular weight ~25000 polyether compound (B),
The compound (A) and the polyether compound (B) are aggregated in weight ratio shared in the nonvolatile component of inorganic agent Example is the 50 weight % of weight %~99,
In formula (1), R1And R2It is separately hydrogen atom or alkyl, AO is the oxyalkylene group of carbon number 2~4, and m and n are independently The numerical value that ground is 1 or more.
2. acrylic fiber inorganic agent according to claim 1, wherein the compound (A) and the polyether compound (B) weight ratio (A/B) is 90/10~20/80.
3. acrylic fiber inorganic agent according to claim 1 also contains nonionic table shown in the following general formula (2) Face activating agent (C),
R3-X-[(EO)a/(PO)b]-R4 (2)
In formula (2), R3For the alkyl of carbon number 8~20 ,-X- is-O- ,-COO- or-CONH-, and EO is oxyethylene group, PO is oxypropylene group, and a and b indicate average addition molal quantity, and a is that 3~20, b is 0~6, it should be noted that EO groups and PO The addition form of group is block or random, R4For hydrogen atom or the alkyl of carbon number 1~6.
4. acrylic fiber inorganic agent according to claim 2 also contains nonionic table shown in the following general formula (2) Face activating agent (C),
R3-X-[(EO)a/(PO)b]-R4 (2)
In formula (2), R3For the alkyl of carbon number 8~20 ,-X- is-O- ,-COO- or-CONH-, and EO is oxyethylene group, PO is oxypropylene group, and a and b indicate average addition molal quantity, and a is that 3~20, b is 0~6, it should be noted that EO groups and PO The addition form of group is block or random, R4For hydrogen atom or the alkyl of carbon number 1~6.
5. acrylic fiber inorganic agent according to claim 3, wherein the nonionic surfactant (C) is being located It is 0.5 weight of weight %~15 % to manage weight ratio shared in the nonvolatile component of agent.
6. acrylic fiber inorganic agent according to claim 4, wherein the nonionic surfactant (C) is being located It is 0.5 weight of weight %~15 % to manage weight ratio shared in the nonvolatile component of agent.
7. according to acrylic fiber inorganic agent according to any one of claims 1 to 6, also contain modified silicone (D), it is described Modified silicone (D) has the modified group comprising nitrogen-atoms.
8. acrylic fiber inorganic agent according to claim 7, wherein modified silicone (D) not the waving in inorganic agent It is 5 weight of weight %~40 % to send out weight ratio shared in ingredient.
9. a kind of carbon fiber manufacture acrylic fiber is made at acrylic fiber according to any one of claims 1 to 8 Reason agent, which is attached on the raw material propylene acid fiber of carbon fiber manufacture acrylic fiber, to be carried out obtained by filature.
10. a kind of manufacturing method of carbon fiber comprising：
Filature process makes acrylic fiber inorganic agent according to any one of claims 1 to 8 be attached to carbon fiber manufacture with third Filature is carried out on the raw material propylene acid fiber of olefin(e) acid fiber；
Resistance to cremate treatment process is changed into fire resisting chemical fibre dimension in 200 DEG C~300 DEG C of oxidizing atmosphere；With
Charing process process makes the fire resisting chemical fibre dimension further be carbonized in 300 DEG C~2000 DEG C of torpescence atmosphere.
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