CN106414841A - Acrylic fiber treatment agent and use thereof - Google Patents
Acrylic fiber treatment agent and use thereof Download PDFInfo
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- CN106414841A CN106414841A CN201580030878.2A CN201580030878A CN106414841A CN 106414841 A CN106414841 A CN 106414841A CN 201580030878 A CN201580030878 A CN 201580030878A CN 106414841 A CN106414841 A CN 106414841A
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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
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- 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
Abstract
The purpose of the present invention is to provide an acrylic fiber treatment agent which, in the production of carbon fibers, makes it possible to achieve bundling properties of fiber bundles, to prevent fusion between the fibers and to provide stable workability. This acrylic fiber treatment agent contains a compound (A) represented by general formula (1), and a polyether compound (B) having a weight average molecular weight of 8000-25000, wherein the total weight ratio of the compound (A) and the polyether compound (B) is 50-99 wt%. In expression (1), R1 and R2 are independently a hydrogen atom or an alkyl group. AO is an oxyalkylene group of 2-4 carbon atoms. m and n are each independently a number greater than or equal to 1.
Description
Technical field
The present invention relates to acrylic fiber inorganic agent and application thereof.More specifically, it is related to when manufacturing acrylic fiber
Use inorganic agent, employ the carbon fiber manufacture acrylic fiber (hereinafter sometimes referred to as precursor) of this inorganic agent and employ
The manufacture method of the carbon fiber of this inorganic agent.
Background technology
Carbon fiber is increased by the use of its excellent mechanical property as the composite with the plastics being 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 by 200～300 DEG C of oxidizing atmosphere
It is changed into fire resisting chemical fibre dimension, then, 300～2000 DEG C of torpescence atmosphere carries out carbonization.In these burning till based on hyperpyrexia
When it may occur that ultimate fibre each other melting adhesion, thus have the quality of the carbon fiber making gained, grade reduce problem.
In order to prevent this melting from adhering, proposed much precursor to be given using silicone compounds as main constituent and have excellent
Different thermostability and based on Fiber-Fiber between the silicone-based inorganic agent of the excellent fissility of flatness, particularly can profit
Improve the technology (such as patent documentation 1 etc.) of the amino modified silicone-based inorganic agent of thermostability with cross-linking reaction further, in work
Extensively utilized in industry.
However, on the other hand, the silicone-based inorganic agent having carried out adhering to process can be changed into adhesion from fibre shedding, it
It is deposited on dryer roll or ways in precursor manufacturing process etc., thus have making fiber be wound around or fracture of wire etc. becomes and causes
The problem of the reason operability reduces.In addition, in the oxidizing atmosphere of resistance to explosive industry sequence, one part can generate silicon oxide,
Be used in the torpescence atmosphere of carbonization operation nitrogen as inactive gas in the case of can generate silicon nitride, these foulings
(ス ケ Le) is piled up, have so that operability or runnability is reduced or the damage that leads to firing furnace problem.
Additionally, silicone-based inorganic agent have based on Fiber-Fiber between flatness excellent fissility for preventing
Melting adhesion between ultimate fibre plays a role effectively, but then, abreast advances in very many fibre bundles simultaneously
In firing process, each fiber beam width broadens because of the flatness of silicone-based inorganic agent, thus between adjacent fibre bundle
Every narrowing, according to circumstances can have, because of its interference, the undesirable condition producing fine hair.
In order to avoid these problems, proposed to reduce the inorganic agent of the content of silicone compound, do not used silicone-based
Inorganic agent of compound etc..For example have and ammonia as main constituent and is reduced using the fatty acid ester of the alkylene oxide addition product of bisphenol-A system
The inorganic agent (such as patent documentation 2 etc.) of the content of base modified silicone, using the fatty acid ester of the alkylene oxide addition product of bisphenol-A as
Main constituent and do not use the inorganic agent (such as patent documentation 3 etc.) of silicone compound.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2002-371477 publication
Patent documentation 2：Japanese Unexamined Patent Publication 2005-89884 publication
Patent documentation 3：Japanese Unexamined Patent Publication 2004-143645 publication
Content of the invention
Invention problem to be solved
Although however, these inorganic agents the problems such as the above-mentioned operability that suppression is caused by silicone compound in terms of have
Effective, but there is the convergence of fibre bundle when batching and when unwinding in precursor filature operation and resistance to explosive industry sequence
In the entrance of resistance to cremator and outlet fibre bundle the not enough shortcoming of convergence.
In view of this conventional technical background, it is an object of the invention to provide the fibre bundle during carbon fiber manufactures can be taken into account
Convergence, prevent interfibrous melting adhesion and the stable acrylic fiber inorganic agent of operability, employ this inorganic agent
Carbon fiber manufacture acrylic fiber and employ this inorganic agent carbon fiber manufacture method.
Means for solving the problems
The present inventor etc. have made intensive studies to solve above-mentioned problem, it is found that：The alkylene oxide comprising bisphenol-A adds
Become the conventional inorganic agent of the fatty acid ester of thing, in order to by this ester in water system emulsifying and need substantial amounts of non-ionic surface to live
Property agent (emulsifying agent), under the influence of this substantial amounts of emulsifying agent, the boundling of the fibre bundle in precursor filature operation, resistance to explosive industry sequence
Property be deteriorated.And find：If comprising specific composition as the inorganic agent of main constituent, then can reduce as in inorganic agent
Nonionic surfactant and the content of silicone compound that emulsifying agent uses, and can take into account in carbon fiber manufacture
The convergence of fibre bundle, prevent interfibrous melting adhesion and stable operability, thus reach the present invention.
That is, the acrylic fiber inorganic agent of the present invention contains compound (A) and weight average molecular weight shown in following formulas (1)
Polyether compound (B) for 8000～25000, above-claimed cpd (A) and above-mentioned polyether compound (B) be aggregated in inorganic agent
In nonvolatile component, shared part by weight is 50～99 weight %.
[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 divides
It independently is not more than 1 numerical value.)
Above-claimed cpd (A) is preferably 90/10～20/80 with weight ratio (A/B) of above-mentioned polyether compound (B).
The acrylic fiber inorganic agent of the present invention preferably also contains the nonionic surfactant shown in following formulas (2)
(C).
[changing 2]
R3-X-[(EO)a/(PO)b]-R4(2)
(in formula (2), R3Alkyl for carbon number 8～20.- X- is-O- ,-COO- or-CONH-.EO is oxidation
Vinyl, PO is oxypropylene group.A and b represents average addition molal quantity, and a is 3～20, b is 0～6.It should be noted that EO
The addition form of group and PO group can for block or randomly.R4Alkyl for hydrogen atom or carbon number 1～6.)
The shared part by weight in the nonvolatile component of inorganic agent of above-mentioned nonionic surfactant (C) is preferably
0.5～15 weight %.
The acrylic fiber inorganic agent of the present invention preferably also contains modified silicone (D), and this modified silicone (D) has and comprises nitrogen
The modified group of atom.
The shared part by weight in the nonvolatile component of inorganic agent of above-mentioned modified silicone (D) is preferably 5～40 weight %.
The carbon fiber manufacture acrylic fiber of the present invention is to make above-mentioned acrylic fiber inorganic agent be attached to carbon fiber
Manufacture is obtained with carrying out filature on the raw material propylene acid fiber of acrylic fiber.
The manufacture method of the carbon fiber of the present invention includes：Filature operation, makes above-mentioned acrylic fiber inorganic agent be attached to
Carbon fiber manufacture is with carrying out filature on the raw material propylene acid fiber of 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 operation, make above-mentioned fire resisting chemical fibre dimension further 300～
Carbonization in 2000 DEG C of torpescence atmosphere.
Invention effect
The acrylic fiber inorganic agent of the present invention passes through the process that it is attached on precursor in advance into enforcement, such that it is able to simultaneous
Turn round and look at the convergence of fibre bundle in carbon fiber manufacture, prevent interfibrous melting adhesion and stable operability.
If using the carbon fiber manufacture acrylic fiber of the present invention, fibre bundle during carbon fiber manufactures can be taken into account
Convergence, prevent interfibrous melting adhesion and stable operability.In addition, the manufacture method of the carbon fiber according to the present invention,
The convergence of the fibre bundle in carbon fiber manufacture can be taken into account, prevent interfibrous melting adhesion and stable operability, permissible
Manufacture the carbon fiber of high-quality.
Specific embodiment
The acrylic fiber inorganic agent of the present invention is to be imparted to acrylic fiber (the carbon fibre used in carbon fiber manufacture
The precursor of dimension) upper for the purpose of inorganic agent, it is to contain specific compound (A) and specific polyether compound with specified quantitative
(B) as the inorganic agent of main constituent.Hereinafter, it is described in detail.
(compound (A))
Used in the acrylic fiber inorganic agent of the present invention, compound (A) is the compound shown in above-mentioned formula (1), its
It is the compound of the structure that the two ends addition having in the central part comprising bisphenol type skeleton has alkylene oxide.So, by changing
Compound (A) is used in combination with polyether compound described later (B), such that it is able to taking into account the convergence of the fibre bundle during carbon fiber manufactures, preventing
Only interfibrous melting adhesion and stable operability.Further, since compound (A) has water solublity, conduct is not therefore used
The nonionic surfactant of emulsifying agent can be mixed with water.Its result can prevent in precursor filature operation when batching
And fibre bundle when unwinding convergence is not enough and resistance to explosive industry sequence in the entrance of resistance to cremator and outlet fibre bundle
Such disadvantage caused by multiplex emulsifying agent that convergence is not enough.
In above-mentioned formula (1), R1And R2It is separately hydrogen atom or alkyl.The carbon number of alkyl is preferably 1～2, enters one
Step is 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 is separately more than 1 numerical value, preferably 4～20, more preferably
For 4～15, more preferably 4～10.Additionally, from the aspect playing effect of the present invention further, m and n is preferably full
The numerical value of sufficient m+n=8～50.M+n is preferably 8～40, more preferably 8～30, more preferably 8～20, particularly preferably
10～20.
In compound (A), need not in the addition amount of the alkylene oxide of the two ends addition of the central part comprising bisphenol type skeleton
Left and right consistent in central part, but, due to above-mentioned compound (A) be usually on bisphenol compound addition alkylene oxide and
The compound obtaining, therefore, for the addition amount in the alkylene oxide of the two 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)]
Used in the acrylic fiber inorganic agent of the present invention compound (B) be weight average molecular weight be 8000～25000
Polyether compound.So, by being used in combination polyether compound (B) with above-claimed cpd (A), such that it is able to take into account carbon fiber manufacture
In the convergence of fibre bundle, prevent interfibrous melting adhesion and stable operability.Further, since polyether compound (B)
There is water solublity, be not therefore used the nonionic surfactant as emulsifying agent can mix with water.As a result, can in case
The only fire resisting in the convergence deficiency and resistance to explosive industry sequence of fibre bundle when batching and when unwinding in precursor filature operation
Change the not enough such disadvantage caused by multiplex emulsifying agent of convergence of the entrance of stove and the fibre bundle of outlet.
Polyether compound (B) is by making the alkylene oxides such as oxirane (EO), expoxy propane (PO), epoxy butane (BO)
(AO) poly alkylene glycol obtained from addition polymerization, wherein, preferably makes expoxy propane (PO) obtain with oxirane (EO) addition polymerization
Polyalkylene glycol copolymers.Polyether compound (B) using a kind or and can have two or more.Polyalkylene glycol copolymers
It is preferably the random of PO, EO or the copolymer of block type.The single end of polyalkylene glycol copolymers or two ends are permissible
Using more than 1 yuan of alcohols or acids (Japanese：Base acid) etc., blocked by ehter bond, ester bond.This poly alkylene glycol
The copolymerization such as PO, EO are obtained by copolymer by using known method.
The mol 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, is more preferably
12000～18000.It should be noted that described weight average molecular weight in the present invention refers to survey using gel permeation chromatography (GPC)
Method of determining measures and carries out, in following condition determinations, the value that polystyrene conversion obtains.
(GPC condition determination)
Device：Device name " HPLC LC-6A SYSTEM " (SHIMAZU company system)
Post：" KF-800P", " KF-804", " KF-
802.5", " KF-801" (above for SHODEX company system)
Mobile phase：Oxolane (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 during carbon fiber can be manufactured gives uniformly
The nonionic surfactant (C) shown in above-mentioned formula (2) of tack.
As nonionic surfactant (C), polyoxyalkylene alkyl, the polyoxyalkylene meeting formula (2) can be enumerated
Alkyl phenyl ether, polyoxyalkylene diols fatty acid ester, polyoxyethylene polyoxypropylene block polymer etc..
In formula (2), R3Alkyl for carbon number 8～20.As alkyl, alkyl, thiazolinyl, aryl, aralkyl etc. can be enumerated, excellent
Select alkyl, thiazolinyl.As the carbon number of alkyl, preferably 10～18, further preferred 12～18.
"-X- " is "-O- ", "-COO- " or "-CONH- ", and preferably "-O- " or "-COO- " enters one
Step is preferably "-O- ".
EO is oxyethylene group, and PO is oxypropylene group.A and b represents average addition molal quantity.A is 3～20, preferably 5
～18, more preferably 7～12.B is 0～6, preferably 0～3, more preferably 0.It should be noted that EO group and PO group
Addition form can be block or random.
R4Alkyl for hydrogen atom or carbon number 1～6.As alkyl, alkyl, thiazolinyl can be enumerated.As R4, preferably hydrogen is former
Son or the alkyl of carbon number 1～3, more preferably hydrogen atom.
[there is the modified silicone (D) of the modified group comprising nitrogen-atoms]
From the aspect of the interfibrous melting adhesion preventing in carbon fiber manufacture, the acrylic fiber of the present invention is processed
Agent preferably also contains modified silicone (D), and this 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) total as main constituent, therefore do not use
Modified silicone (D) can be taken into account the convergence of fibre bundle in carbon fiber manufacture, prevent interfibrous melting viscous as main constituent
And stable operability.
As long as being the modified group comprising nitrogen-atoms, then the species of modified group is not particularly limited modified silicone (D).Make
For comprising the modified group of nitrogen-atoms, the modified group containing amino linkage or imino group key (i.e. amino) can be enumerated, contain amide
Modified group (i.e. amide groups) of key etc. or the modified group that there is the difference key such as multiple amino linkage and amido link.Bag
The modified group of nitrogen atom can be bonded it is also possible to be bonded with end phase with the side chain phase of the silicone as main chain, acceptable
Mutually it is bonded with both.Alternatively, it is also possible to have in the molecule polyoxyalkylenes (for example polyethylene oxide base, polypropylene oxide base,
Polyoxybutylene base etc.).
As the modified silicone (D) with the modified group comprising nitrogen-atoms, for example amino modified silicone, amino can be enumerated
Polyether modified silicone, amide modifications silicone, amide polyether modified silicone etc., it is possible to use a kind of modified silicone is it is also possible to be used in combination
Multiple modified silicones.
In addition, the content of nitrogen-atoms in modified silicone (D) be preferably 0.35～3.2 weight %, more preferably 0.37～
2.2 weight %, more preferably 0.40～1.3 weight %.In the case that the content of nitrogen-atoms is less than 0.35 weight %,
During water system emulsifying, the emulsion stability of emulsion is made to be deteriorated sometimes.On the other hand, the content in nitrogen-atoms is higher than 3.2 weight %
In the case of, so that the cohesiveness of modified silicone (D) is uprised because of heat cross-linking, the reason become viscose glue (ガ system ア ッ プ).
The emulsion stability of emulsion when water system emulsifying excellent and with compound (A) and the effect with being brought
Excellent aspect is set out, in these modified silicones (D), preferably amino modified silicone.
In the case that modified silicone (D) is amino modified silicone, the structure of this amino modified silicone is not particularly limited.
That is, the amino as modified group can be bonded it is also possible to be bonded with end phase with the side chain phase of the silicone as main chain, also may be used
To be mutually bonded with both.In addition, this amino can be monoamine type or Polyamine Type, and two can also be deposited in 1 molecule
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 %, more preferably 0.46～1.5 weight %.If amino weight % is less than
0.4 weight %, then, in water system emulsifying, the emulsion stability of emulsion can be deteriorated sometimes.On the other hand, higher than 3.7 weight %
In the case of, so that the cohesiveness of amino modified silicone is uprised because of heat cross-linking, the reason become viscose glue.
For amino modified silicone in 25 DEG C of viscosity, it is not particularly limited, if viscosity is too low, inorganic agent easily flies
Dissipate, and the emulsion stability of emulsion is deteriorated it is impossible to equably be imparted to inorganic agent on fiber in water system emulsifying.Its knot
Really, the melting that sometimes can prevent fiber is adhered.On the contrary, if viscosity is too high, the viscose glue that sometimes occurs being caused by cohesiveness
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, more preferably 1,000～5,000mm2/s.
[surfactant]
The acrylic fiber inorganic agent of the present invention can contain surfactant not hindering in the range of effect of the present invention.
Surfactant can use as emulsifying agent, antistatic additive etc..As surfactant, it is not particularly limited, can be from non-
Ionic surfactant's (wherein, except above-mentioned nonionic surfactant (C)), anionic surfactant, sun from
Suitably select in sub- property surfactant and amphoteric surfactant to use known surfactant.Surfactant can make
With a kind or and use two or more.
As nonionic surfactant, can enumerate for example：Polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxy
The polyoxyalkylene straight chained alkyl ether such as ethylene decyl ethers, polyoxyethylene lauryl ether, polyoxyethylene cetyl base ether；Polyoxyethylene 2-
The polyoxyalkylene branched primary alkyl moiety ethers such as the different cetyl ether of ethylhexyl ether, polyoxyethylene, polyoxyethylene iso stearyl ether；Polyoxy second
Alkene 1- hexyl hexyl ether, polyoxyethylene 1- octyl group hexyl ether, polyoxyethylene 1- hexyl Octyl Ether, polyoxyethylene 1- amyl group heptan
The polyoxyalkylene branched secondary alkyl group ethers such as base ether, polyoxyethylene 1- heptyl amyl ether；The polyoxyalkylene thiazolinyl such as polyoxyethylene oleyl ether
Ether；The polyoxyalkylene alkyl 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 alkyl such as ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene benzyl phenyl ether
Aryl phenyl ether；Vinlub 73, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene list
Myristinate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxyethylene two myristinate, polyoxyethylene
The polyoxyalkylene fatty acid ester such as distearate；The sorboses such as sorbitan monopalmitate, sorbitan monooleate
Alcohol acid anhydride ester；The polyoxyalkylene Pyrusussuriensiss such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate
Sugar alcohol acid anhydride fatty acid ester；The fatty acid glycerides such as glyceryl monostearate, glyceryl monolaurate, glycerol monopalmitate；Poly-
Oxyalkylene Span；Sucrose fatty acid ester；The polyoxyalkylene Oleum Ricini ether such as polyoxyethylene castor oil ether；Polyoxyethylene
The polyoxyalkylene hydrogenated Oleum Ricini ether such as castor oil hydrogenated ether；Polyoxyethylene laural base amino ethers, polyoxyethylene stearyl base amino ethers
Deng polyoxyalkylene alkyl amino ethers；Ethylene oxide-propylene oxide block or random copolymer；Ethylene oxide-propylene oxide is embedding
Section or the end alkyl etherate of 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 that here illustrates refers to except the nonionic surfactant (C) shown in above-mentioned 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 less than 2000, more preferably 200～1800, more preferably 300
～1500, more preferably 500～1000.
In these nonionic surfactants, especially excellent for the water system emulsifying ability making ester and silicone compounds
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, POLOXAMER, ethylene oxide-propylene oxide block
The end alkyl ether compound of copolymer, polyoxyalkylene alkylamides, additionally, for being difficult in firing process in the fiber part of the body cavity above the diaphragm housing the heart and lungs
Oiling (タ Le) and fiber is caused damage the reasons why, more preferably ethylene oxide-propylene oxide block or random copolymerization
Thing, the end alkyl etherate of POLOXAMER, polyoxyalkylene alkylamides.
Above-mentioned polyoxyalkylene alkylamides are the condensation substances instigating polyoxyalkylene to be added to carboxylic acid and amines is amide
Compound obtained by upper.As carboxylic acid, such as formic acid, acetic acid, propanoic acid, butanoic acid, valeric acid, caproic acid, enanthic acid, octanoic acid, nonyl can be enumerated
Acid, capric acid, lauric acid, myristic acid, Palmic acid, heptadecanoic acid, stearic acid etc..As amines, can enumerate for example：Single first
The alkanolamines such as hydramine, dimethanolamine, monoethanolamine, diethanolamine, single Propanolamine, dipropanolamine, monoisopropanolamine；Diethylidene
Polyamines such as triamine, tetren etc..As alkylene oxide, such as oxirane (EO), expoxy propane (PO), epoxy can be enumerated
Butane (BO) etc..As polyoxyalkylene alkylamides, alkylene oxide addition product, the carboxylic acid two of such as carboxylic acid single ethanol amide can be enumerated
Alkylene oxide addition product of glycollic amide etc..These polyoxyalkylene alkylamides can be used alone or are applied in combination two or more.
In these polyoxyalkylene alkylamides, the reasons why for making the water system emulsifying ability of ester and silicone compounds especially excellent, preferably
Polyoxyethylene laural base amide, polyoxyethylene stearyl base amide.
As anionic surfactant, can enumerate for example：Oleic acid, Palmic acid, Oleic acid sodium salt, Palmic acid potassium salt, oil
The fatty acid such as triethylenetetraminehexaacetic acid alcohol amine salt (salt)；The hydroxyl carboxylic acid such as hydroxyacetic acid, hydroxyacetic acid potassium salt, lactic acid, lactic acid potassium salt (salt)；
The polyoxyalkylene alkyl acetic acid such as polyoxyethylene tridecyl ether acetic acid (sodium salt) (salt)；Trimellitic acid potassium, PMA potassium etc.
The salt of carboxyl Polysubstituted Aromatic Compounds；The alkyl benzene sulphonate such as DBSA (sodium salt) (salt)；Polyoxyethylene 2- second
The polyoxyalkylene alkyl sulfonic acid such as base hexyl ether sulfonic acid (potassium salt) (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)；N- acyl group sarcosine such as lauroyl sarcosine (sodium) (salt)；The alkyl phosphonic acids such as octyl phosphonic acid salt (potassium salt)
(salt)；The aromatic series phosphonic acids such as Phenylphosphine hydrochlorate (potassium salt) (salt)；The alkane such as the own ester of 2-ethylhexyl phosphonic acid single 2-ethyl (potassium salt)
Base phosphonic acids alkyl phosphate (salt)；The nitrogenous alkyl phosphonic acid such as aminoethyl phosphonic acid (diethanolamine salt) (salt)；2- ethylhexyl sulfur
The alkyl sulfate (salt) of acid esters (sodium salt) etc.；The polyoxyalkylene sulfur such as polyethylene glycol oxide 2- ethylhexyl ether sulfuric ester (sodium salt)
Acid esters (salt)；Long-chain sulfosuccinate, the N- such as two -2- ethylhexylsulfosuccinate sodium, dioctyl sodium sulphosuccinate
The long-chain N- acyl glutamates such as lauroyl glutamate list sodium, N- stearyl-L-Glutamic Acid disodium；Deng.
As cationic surfactant, can enumerate 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 ECONOL TM22, 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 saltss 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 phosphate, 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 lactate；N- (2- hydroxyl second
Base)-N, N- dimethyl-N-stearyl amido propyl nitric acid ammonium nitrate, lanolin fatty acid amide ethyl diformazan
The acylamide alkyl quaternary ammonium saltss such as base ethyl-sulfate ammonium, lauroyl amide ethyl-methyl diethyl sulfate methyl ammonium；Two Petiolus Trachycarpis
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 oxide base such as ammonium (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 benzyloxy second ammonium (ベ such as dimethyl { 2- [2- (p- 1,1,3,3- tetramethyl butyl 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, Laurel
The imidazole salts such as base hydroxyethyl imidazoles ethyl-sulfate salt；N- cocoyl arginine ethyl ester pyrrolidone carboxylic acid salt, N-
The acyl group 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, Colophonium amine acetate；Cetyl methyl amine sulfate, lauryl first
Base amine chloride, dilauryl amine acetate, stearyl ethylamine bromide, lauryl propyl group amine acetate, dioctylamine chlorine
The secondary amine salts such as compound, octadecyl ethylamine hydroxide；Dilauryl methyl amine sulfate, lauryl diethylamide chlorination
Thing, 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 guanidinesalt；The alkyl three such as lauryl triethylene glycol ammonium hydroxide
Aklylene glycol ammonium salt etc..
As amphoteric surfactant, can enumerate for example：2- undecyl-N, N- (hydroxyethyl carboxymethyl group)-
The imidazoline system both sexes such as 2- imidazoline sodium, 2- cocoyl -2- imidazolium hydroxide -1- Carboxyethoxy disodium salt
Surfactant；2- heptadecyl-N- carboxymethyl group-N- hydroxyethyl imidazolinium betaine, lauryl dimethyl amino
The glycine betaine such as acetic acid glycine betaine, alkyl betaine, amide betaine, thetine system amphoteric surfactant；N- lauryl
Amino acid type amphoteric surface active agent such as glycine, N- lauryl Beta-alanine, N- stearyl Beta-alanine etc..
In these surfactants, for ageing stability is excellent, emulsifying ability also excellent the reasons why, preferably nonionic
Surfactant.Compared with nonionic surfactant, ionic surfactant have can suppress because produce electrostatic institute
The advantage discrete, that electrostatic inhibition is excellent of the fibre bundle causing, is therefore preferably used in combination with nonionic surfactant.As from
Sub- property surfactant, can enumerate above-mentioned anionic surfactant, cationic surfactant, amophoteric surface active
Agent, but, in these surfactants, preferred cationic surfactant, in cationic surfactant, further
Preferably alkyl quaternary ammonium saltss, (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 acrylic fiber inorganic agent of the present invention can the scope not hindering 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, sulfur system, phosphorus system, quinone system etc. resist
Oxidant；The sulfuric acid of the senior alcohol ether of higher alcohol, sulfonate, the phosphate ester salt of the senior alcohol ether of higher alcohol, quaternary
The antistatic additive of cation system surfactant, amine salt type cation system surfactant etc.；The Arrcostab of higher alcohol, higher alcohol
The smooth agent of ether, wax class etc.；Antibacterial；Preservative；Antirust agent；And hygroscopic agent etc..
Antioxidant is effectively to suppress to make acrylic fiber inorganic agent heat point because of the heating in resistance to cremate treatment process
Solve and improve the composition preventing the melting between Fiber-Fiber from adhering effect.
As antioxidant, it is not particularly limited, from the viewpoint of preventing firing furnace pollution, preferably organic oxidation-resistant
Agent, acid phosphoric acid ester, further preferred acid phosphoric acid ester.As organic oxidation-resistant agent, such as 4 can be enumerated, 4 '-butylidene is double
(3 methy 6 tert butyl phenol, three (octadecyl) phosphite ester, N, N '-diphenyl-para-phenylene diamine, triethylene glycol are double
[3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) 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, the acid described in claim of such as International Publication WO2013/129115 can be enumerated
Property phosphate ester.In addition, acid phosphoric acid ester can as described in 0036 paragraph of International Publication WO2013/129115 profit
Manufactured with known method.For example, by making anhydrous phosphoric acid P2O5After inorganic phosphate and alcohol or polyoxyalkylene addition
Alkyl ether etc. have in the molecule alcohol hydroxyl group compound (hereinafter sometimes referred to simply as raw alcohol) anti-with arbitrary mol ratio
Answer and obtain.In the acid phosphoric acid ester of gained, can (the unneutralized Jiao's phosphorus of non-forming salt of the acid pyrophosphate containing by-product
Acid esters), the acid poly phosphate (the unneutralized poly phosphate of non-forming salt) such as acid triguaiacyl phosphate.
In addition, the acrylic fiber inorganic agent of the present invention can not hindering in the range of effect of the present invention, comprise except
There is the silicone composition beyond the modified silicone (D) of the modified group of nitrogen atom.Specifically, can enumerate dimethyl silscone,
Epoxide 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 contain esterification conjunction not hindering in the range of effect of the present invention
Thing.As ester compounds, can enumerate for example：Intramolecular described in public table WO2007/066517 publication has more than 3 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 divide containing the compound (A) shown in above-mentioned formula (1) and weight average
The acrylic fiber inorganic agent of the polyether compound (B) of son amount 8000～25000.Compound (A) and the conjunction of polyether compound (B)
Count shared part by weight in the nonvolatile component of inorganic agent and be preferably 50～99 weight %, more preferably 55～95 weights
Amount %, more preferably 60～90 weight %, particularly preferably 65～80 weight %.It should be noted that in the present invention
Composition is parched when nonvolatile component refers to for inorganic agent to carry out heat treatment at 105 DEG C and removes solvent etc. and reach constant.
From the convergence of the fibre bundle that can take into account carbon fiber manufacture, prevent interfibrous melting adhesion and stable behaviour
The aspect of the property made is set out, and weight ratio (A/B) of compound (A) and polyether compound (B) is preferably 90/10～20/80, more preferably
For 75/25～35/65, more preferably 65/35～45/55.
In the case that the acrylic fiber inorganic agent of the present invention contains nonionic surfactant (C), nonionic
The shared part by weight in the nonvolatile component of inorganic agent of surfactant (C) is preferably 0.5～15 weight %, is more preferably
1～10 weight %, more preferably 1～8 weight %, particularly preferably 3～5 weight %.
In the case that the acrylic fiber inorganic agent of the present invention contains modified silicone (D), modified silicone (D) is in inorganic agent
Nonvolatile component in shared part by weight be more preferably 5～40 weight %, more preferably 10～30 weight %, especially
It is preferably 15～25 weight %.
The acrylic fiber inorganic agent of the present invention can reduce the usage amount of the nonionic surfactant as emulsifying agent.
As a result, the total amount of nonionic surfactant can be reduced.Specifically, nonionic surfactant (total amount) can be made
In the nonvolatile component of inorganic agent, shared part by weight is below 20 weight %, is preferably below 15 weight %, further
It is preferably below 10 weight %.If this part by weight is more than 20 weight %, sometimes because of substantial amounts of nonionic surfactant
Affect and so that the convergence of the fibre bundle in precursor filature operation, resistance to explosive industry sequence is deteriorated.At the acrylic fiber of the present invention
In the case that reason agent contains nonionic surfactant (C), nonionic surfactant (total amount) not waving in inorganic agent
Send out shared part by weight in composition be preferably 1～20 weight %, more preferably 2～15 weight %, more preferably 3～
10 weight %.
The acrylic fiber inorganic agent of the present invention is preferably compound (A), polyether compound (B), as needed non-
Ionic surfactant (C), modified silicone (D) dissolving, solubilized, emulsifying or the state being scattered in water.
Part by weight for the shared part by weight in acrylic fiber inorganic agent entirety of water, nonvolatile component has no
It is particularly limited to.For example, as long as considering that cost of transportation during transport, operability of emulsion viscosity etc. suitably determine the propylene of the present invention
Sour fibre finish.The shared part by weight in acrylic fiber inorganic agent entirety of water is preferably 0.1～99.9 weight
Amount %, more preferably 10～99.5 weight %, particularly preferably 50～99 weight %.Nonvolatile component is in acrylic fiber
In inorganic agent entirety shared part by weight (concentration) be preferably 0.01～99.9 weight %, more preferably 0.5～90
Weight %, particularly preferably 1～50 weight %.
Go out in terms of the effect that the melting between the thermostability preventing resistance to cremate treatment process and Fiber-Fiber is adhered
Send out, the acrylic fiber inorganic agent of the present invention is in atmosphere with the weight reduction rates after 250 DEG C of heat treated 1 hour preferably less than
40 weight %, more preferably less than 30 weight %, more preferably less than 25%.The situation being more than 40% in weight reduction rates
Under, the inorganic agent epithelium remaining in resistance to cremate treatment process on fiber tails off, sometimes cannot fully obtain preventing fiber-
The effect of interfibrous melting adhesion.
The acrylic fiber inorganic agent of the present invention can be manufactured by mixing the composition of described above.Above-mentioned for making
The composition emulsifying illustrating, scattered method are not particularly limited, and can adopt known method.As such method, can arrange
Citing is such as：The each composition constituting acrylic fiber inorganic agent is put into the method carrying out emulsion dispersion in the hot water under stirring；Will
Constitute each composition mixing of acrylic fiber inorganic agent, apply mechanical shearing using homogenizer, homogeneous mixer, ball mill etc.
Power, and slowly input water carries out method of Phase inversion emulsification etc..
The acrylic fiber inorganic agent of the present invention can be suitable as the place of carbon fiber manufacture acrylic fiber (precursor)
Reason agent (precursor inorganic agent).Can also use as the spinning oil of the acrylic fiber in addition to precursor.
From the aspect of the convergence that can give precursor filature operation, good fibre bundle in resistance to explosive industry sequence,
The nonvolatile component of the acrylic fiber inorganic agent of the present invention is preferably 350～25000mPa s, more preferably in 50 DEG C of viscosity
For 1000～20000mPa s, more preferably 1500～15000mPa s.If this viscosity, less than 350mPa s, has
The convergence of the fibre bundle in Shi Qianti filature operation, resistance to explosive industry sequence is deteriorated.If in addition, this viscosity is more than 25000mPa s,
Even if the convergence of precursor filature operation, good fibre bundle in resistance to explosive industry sequence, the viscosity of inorganic agent then can be given
Become too high, so that the operability of inorganic agent is deteriorated.It should be noted that the assay method of this viscosity is remembered according in embodiment
The method carrying is carried out.
[manufacture method of carbon fiber manufacture acrylic fiber, its manufacture method and carbon fiber]
Carbon fiber manufacture acrylic fiber (precursor) of the present invention is so that above-mentioned acrylic fiber inorganic agent is attached to
Precursor raw material propylene acid fiber, carry out acrylic fiber obtained by filature.The manufacture 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 operation of filature.
The manufacture method of the carbon fiber of the present invention includes：Filature operation, makes above-mentioned acrylic fiber inorganic agent be attached to
On the raw material propylene acid fiber of precursor, filature is carried out to precursor；Resistance to cremate treatment process, before manufacturing in this filature operation
Body is changed into fire resisting chemical fibre dimension in 200～300 DEG C of oxidizing atmosphere；With charing process operation, make above-mentioned fire resisting chemical fibre dimension
Carbonization in 300～2000 DEG C of torpescence atmosphere further.
Filature operation is the sour fiber of the raw material propylene making acrylic fiber inorganic agent be attached to precursor, carries out filature to precursor
Operation, it includes adhering to treatment process and stretching process.
Attachment treatment process is by after the raw material propylene acid fibre spinning of precursor, makes it is adhered to acrylic fiber inorganic agent
Operation.That is, acrylic fiber inorganic agent is made to be attached on the raw material propylene acid fiber of precursor in attachment treatment process.Separately
Outward, the raw material propylene acid fiber of this precursor is just stretched after firm spinning, and will be special for the high magnification stretching after attachment treatment process
Another name makees " stretching process ".Stretching process can be using the damp and hot pulling method of high hot steam or using hot-rolling
Xeothermic pulling method.
Precursor by so that the resistance to cremate of at least acrylonitrile of 95 moles of more than % and 5 moles of below % promote composition copolymerization and
The polyacrylonitrile obtaining is that the acrylic fiber of main constituent is constituted.Promote composition as resistance to cremate, can suitably use to acrylonitrile
Have copolymerizable containing vinyl compound.For the filament denier of precursor, it is not particularly limited, from performance Manufacturing cost
Balance set out, preferably 0.1～2.0dTex.In addition, the filamentary radical for the fibre bundle constituting precursor also has no spy
Do not limit, from the balance of performance Manufacturing cost, preferably 1,000～96,000.
Acrylic fiber inorganic agent can any stage of filature operation be attached to precursor raw material propylene acid fiber on,
It is preferably made disposably to adhere to before stretching process.If the stage before stretching process, then can be in any stage, for example firm
Adhered to after spinning.Further any stage after stretching process it can also be made to adhere to once again, for example can be firm
It is made to adhere to once again after stretched operation it is also possible to make it adhere to once again in coil ing one, can also be in just fire resisting to be carried out
It is made to adhere to once again before changing treatment process.With regard to this adherence method, it is possible to use roller etc. is adhered to it is also possible to be utilized dipping
Method, spraying process etc. are adhered to.
In attachment treatment process, from obtaining preventing the deadlocked effect between Fiber-Fiber, prevent from melting the effect of adhesion
Really set out with the balance preventing from making because of the carbonizing matter of inorganic agent carbon fiber quality to reduce in charing process operation, acrylic acid
The imparting rate of fibre finish is preferably 0.1～2 weight %, more preferably 0.3～1.5 weight with respect to the weight of precursor
Amount %.If the imparting rate of acrylic fiber inorganic agent is less than 0.1 weight %, cannot be substantially prevented from deadlocked, molten between ultimate fibre
Melt adhesion, sometimes make the intensity decreases of the carbon fiber of gained.On the other hand, if the imparting rate of acrylic fiber inorganic agent is more than 2
Weight %, then, between acrylic fiber inorganic agent is with required above covering ultimate fibre, hinder oxygen therefore in resistance to cremate treatment process
To the supply of fiber, sometimes make the intensity decreases of the carbon fiber of gained.It should be noted that at acrylic fiber said here
The nonvolatile component weight of the acrylic fiber inorganic agent to adhere to for the imparting rate of reason agent is come with respect to the percentage rate of front body weight
Definition.
Resistance to cremate treatment process is in 200～300 DEG C of oxidisability gas by the precursor accompanying by acrylic fiber inorganic agent
It is changed into the operation of fire resisting chemical fibre dimension in atmosphere.As long as oxidizing atmosphere generally air.The temperature of oxidizing atmosphere is preferred
For 230～280 DEG C.In resistance to cremate treatment process, while to attachment process after acrylic fiber apply draw ratio be 0.90～
The tension force side of 1.10 (preferably 0.95～1.05) carries out the heat treatment of 20～100 minutes (preferably 30～60 minutes).Resistance at this
During cremate is processed, oxygen addition through intramolecular cyclization and to ring, to manufacture the fire resisting chemical fibre dimension with resistance to cremate structure.
Charing process operation is the work making fire resisting chemical fibre tie up carbonization in 300～2000 DEG C of torpescence atmosphere further
Sequence.In charing process operation, preferably：First, in the torpescence atmosphere such as nitrogen, argon, have at 300 DEG C～800 DEG C
Have in the firing furnace of thermograde, fire resisting chemical fibre is tieed up with side and applies the tension force that draw ratio is 0.95～1.15, while carrying out several minutes
Heat treatment, and carry out pre- charing process operation (the first charing process operation).Afterwards, in order that carbonization carries out further and makes stone
Inkization is carried out, and in the torpescence atmosphere such as nitrogen, argon, with respect to the first charing process operation, side applies draw ratio and is
0.95～1.05 tension force, while carrying out several minutes heat treatment, and carries out the second charing process operation, and fire resisting chemical fibre is tieed up carbonization.
For the control of the heat treatment temperature in the second charing process operation, can be maximum temperature to be set to when applying thermograde
More than 1000 DEG C (preferably 1000～2000 DEG C).This maximum temperature can (stretching be strong according to the requirement characteristic of required carbon fiber
Degree, elastic modelling quantity etc.) suitably select to determine.
In the manufacture method of the carbon fiber of the present invention, in the case of needing the higher carbon fiber of elastic modelling quantity, continue carbonization
It is also possible to carry out graphitization processing operation after treatment process.Generally in the torpescence atmosphere such as nitrogen, argon, while to carbonization
The fiber applying tension force side for the treatment of process gained carries out graphitization processing operation in 2000～3000 DEG C of temperature.
For the carbon fiber so obtaining, can according to purpose carry out for improve make during composite with substrate tree
The surface treatment of the adhesive strength of fat.As surface treatment method, can be processed using gas phase or liquid phase, from the viewpoint of productivity ratio
Set out, the liquid phase being preferably based on the electrolyte such as acid, alkali is processed.Additionally, for the processability, the operability that improve carbon fiber, also may be used
So that matrix resin is given with the various sizing agents of excellent compatibility.
Embodiment
Hereinafter, using embodiment, the present invention is specifically explained, but however it is not limited to the embodiment of here record.
It should be noted that the percentage ratio (%) shown in below example, part are as long as no special instructions, represent " weight % ", " weight
Part ".The mensure of each characteristic value is carried out based on method shown below.
Imparting rate ＞ of ＜ inorganic agent
The imparting rate of acrylic fiber inorganic agent is calculated using the ethanol extraction by soxhlet's extractor.But, right
In the embodiment, the comparative example that comprise modified silicone (D), calculate imparting rate using following method.
Precursor after inorganic agent is given potassium hydroxide/sodium butyrate is carried out after alkali fusion, is dissolved in water and is adjusted with hydrochloric acid
Save as pH1.Add sodium sulfite and ammonium molybdate so that it is developed the color to it, carry out the colorimetric assay (815 μm of wavelength) of silicon molybdenum blue, try to achieve
The content of silicon.The silicone content tried to achieve using here and the value advancing with the silicone content in the inorganic agent that same procedure is tried to achieve, meter
Calculate the imparting rate (weight %) of acrylic fiber inorganic agent.
＜ viscosity ＞
In diameterAluminum cup on gather each inorganic agent so that the weight of its nonvolatile component reaches 1g, using temperature
Wind drying machine carries out the process of 105 DEG C × 3 hours, removes moisture.Sample (1g) to gained uses ICI cone and plate viscometer
(RESEACH EQUIPMENT (LONDON) LTD. system) carries out viscosimetric analysis.
More specifically, the temperature of plate is set as 50 DEG C, then, the sample input port on being arranged at plate puts into examination
Sample, then, cone-plate is down to behind sample input port, touches the switch of electromotor after 90 seconds, starts to measure.During by numerical stability
Value be set to measured value.
＜ filature operability (roller dirt) ＞
Judge precursor 50kg is given the pollution level (viscose glue) of the dryer roll after inorganic agent using following metewands.
◎：Roller pollution no caused by viscose glue, no filature operational problem
○：Roller pollution caused by viscose glue is few, no filature operational problem
△：There is the roller pollution caused by viscose glue, filature operability is slightly poor
×：Roller pollution caused by viscose glue is notable, is obtained (yarn takes ら れ) by monofilament, have winding during filature
The convergence ＞ of ＜ fibre bundle
In entrance, the outlet of resistance to cremator when batching, when unwinding and in resistance to explosive industry sequence for the precursor filature operation, observe
The boundling degree of fibre bundle, and comprehensively visually confirmed according to following metewands.
◎：The fibre bundle of uniform rugosity and do not observe filamentary discrete completely.
○：The fibre bundle of uniform rugosity and almost do not observe filamentary discrete.
△：The fibre bundle of uniform rugosity but observe a little discrete ultimate fibre.
×：Discrete ultimate fibre is also many and observes monofilament fracture of wire.
＜ melts adhesion preventing property ＞
Arbitrarily choose 20 positions, chopped fiber of Cutting Length 10mm at this from carbon fiber, observe its melting adhesion shape
State, is judged according to following metewands.
◎：No melting adhesion
○：Almost without melting adhesion
△：Melting adhesion is few
×：Melting adhesion is many
＜ carbon fiber strength ＞
It is measured according to epoxy resin impregnation wire harness method specified in JIS-R-7601, by 10 times put down of mensure number of times
Average is set to 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 emulsifying, obtain as nonvolatile component composition by following modified silicones/above-mentioned non-from
The weight rate of sub- property surfactant=80/20 is constituted, nonvolatile component is the emulsion of the modified silicone of 20 weight %.
D1：Amino modified silicone (25 DEG C of viscosity：1300mm2/ s, amino equivalent：2000g/mol, modified type：Diamidogen)
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：Diamidogen)
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 oxirane/epoxy third
Alkane (50/50) block copolymer) carry out water system emulsifying, obtain nonvolatile component composition by following ester based compounds/above-mentioned non-from
The weight rate of sub- property surfactant=70/30 is constituted, nonvolatile component is the emulsifying of the ester based compound of 20 weight %
Thing.
E1：The dilauryl ester of 2 moles of addition products of oxirane of bisphenol-A
E2：Triisodecyl trimellitate
(embodiment 1～28, comparative example 1～13)
Using 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 of ester based compound E1～E2 and water, according to table 1～3
Shown nonvolatile component composition carries out mix and blend, and preparing the shared ratio in inorganic agent of nonvolatile component respectively is 20 weights
The acrylic fiber inorganic agent of amount %.It should be noted that the numerical value of table represents each composition in the nonvolatile component of inorganic agent
Shared part by weight.For example, the numerical value of the compound A1～A3 of table represents the non-volatile one-tenth in inorganic agent for the compound A1～A3
Shared part by weight in point.In addition, the numerical value of " nonionic surfactant " of table 1～3 represents that non-ionic surface lives
The shared part by weight (weight %) in nonvolatile component of property agent (total amount).
Then, by the further dilute with water of inorganic agent of preparation, respectively obtaining nonvolatile component concentration is 3.0 weight %
Treatment fluid.
So that each treatment fluid is attached to makes imparting rate be 1.0 on precursor (filament denier is 0.8dtex, 24,000 long filaments)
Weight %, in 100～140 DEG C of dryings, removes moisture.Precursor after treatment fluid is adhered to is carried out in 250 DEG C of resistance to cremator
Resistance to cremate in 60 minutes is processed, and then, is burnt in 300～1400 DEG C have in the retort of thermograde under nitrogen atmosphere
Become, be 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 represents R in 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 is 13000)：To diethylene glycol with the weight of PO/EO=25/75
The random addition of ratio have PO and EO and weight average molecular weight be 12000 polyether compound.
B2：PO/EO=25/75 polyethers (weight average molecular weight is 15000)：To diethylene glycol with the weight of PO/EO=25/75
The random addition of ratio have PO and EO and weight average molecular weight be 15000 polyether compound.
B3：PO/EO=25/75 polyethers (weight average molecular weight is 18500)：To diethylene glycol with the weight of PO/EO=25/75
The random addition of ratio have PO and EO and weight average molecular weight be 18500 polyether compound.
C1：Nonionic surfactant obtained by 7 moles of EO of the average addition of straight chain primary alcohol to carbon number 12～14
C2：Nonionic surfactant obtained by 7 moles of EO of the average addition of secondary alcohol to carbon number 12～14
C3：To the straight chain primary alcohol of carbon number 12～14 with average 5 moles of EO, average 2 moles of PO, average 3 moles of EO order
Nonionic surfactant obtained by block addition successively
[table 1]
[table 2]
[table 3]
By shown in table 1～3 it is known that：The boundling of the fibre bundle during carbon fiber manufactures all can be taken into account in any embodiment
Property, prevent interfibrous melting adhesion and stable operability.
On the other hand, understand in a comparative example to take into account the convergence of fibre bundle in carbon fiber manufacture, prevent fiber
Between melting adhesion and stable operability.Understand：As comparative example 1～3,8～10, there is filature operability better,
But the convergence of fibre bundle is deteriorated, thus the situation of carbon fiber strength difference, or this is as comparative example 4～7,11～13, anti-
Only interfibrous melting adhesion aspect is better, but filature operability is poor.
Industrial applicability
The acrylic fiber inorganic agent of the present invention is by manufacturing the process being used during carbon fiber manufacture acrylic fiber
Agent, is being useful for manufacturing on high-grade carbon fiber.The carbon fiber manufacture acrylic fiber of the present invention is through the present invention
Inorganic agent carried out process, be useful for manufacturing on high-grade carbon fiber.System using the carbon fiber of the present invention
The method of making obtains high-grade carbon fiber.
Claims (8)
1. a kind of acrylic fiber inorganic agent, it contains the compound (A) shown in following formulas (1) and weight average molecular weight is 8000
～25000 polyether compound (B),
Described compound (A) and described polyether compound (B) be aggregated in shared weight ratio in the nonvolatile component of inorganic agent
Example 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 independently
The numerical value for more than 1 for the ground.
2. acrylic fiber inorganic agent according to claim 1, wherein, described compound (A) and described polyether compound
(B) weight ratio (A/B) is 90/10～20/80.
3. acrylic fiber inorganic agent according to claim 1 and 2, it also contains the nonionic shown in following formulas (2)
Property surfactant (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, a and b represents average addition molal quantity, and a is 3～20, b is 0～6, it should be noted that EO group and PO
The addition form of group can be block or random, R4Alkyl for hydrogen atom or carbon number 1～6.
4. acrylic fiber inorganic agent according to claim 3, wherein, described nonionic surfactant (C) is at place
In the nonvolatile component of reason agent, shared part by weight is 0.5～15 weight %.
5. the acrylic fiber inorganic agent according to any one of Claims 1 to 4, it also contains modified silicone (D), described
Modified silicone (D) has the modified group comprising nitrogen-atoms.
6. acrylic fiber inorganic agent according to claim 5, wherein, described modified silicone (D) not waving in inorganic agent
Sending out shared part by weight in composition is 5～40 weight %.
7. a kind of carbon fiber manufacture acrylic fiber, it is at the acrylic fiber making any one of claim 1～6
Reason agent is attached to and carries out obtained by filature on the raw material propylene acid fiber of carbon fiber manufacture acrylic fiber.
8. a kind of manufacture method of carbon fiber, it includes：
Filature operation, makes the acrylic fiber inorganic agent any one of claim 1～6 be attached to carbon fiber manufacture and uses third
Carry out filature 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 200～300 DEG C of oxidizing atmosphere；With
Charing process operation, makes described fire resisting chemical fibre dimension carbonization in 300～2000 DEG C of torpescence atmosphere further.
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| JP2014164045 | 2014-08-12 | ||
| JP2014-164045 | 2014-08-12 | ||
| PCT/JP2015/070131 WO2016024451A1 (en) | 2014-08-12 | 2015-07-14 | Acrylic fiber treatment agent and use thereof |
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| CN109563680B (en) | 2016-12-02 | 2020-09-11 | 竹本油脂株式会社 | Oil for carbon fiber precursor and carbon fiber precursor |
| CN111793986B (en) * | 2019-04-09 | 2022-10-18 | 广东炬盛新材料科技有限公司 | Nylon moisture-absorbing and sweat-releasing finishing agent and preparation method thereof |
| JP7355367B2 (en) * | 2019-07-12 | 2023-10-03 | 竹本油脂株式会社 | Treatment agent for carbon fiber precursor and carbon fiber precursor |
| JP6984930B1 (en) * | 2021-06-23 | 2021-12-22 | 竹本油脂株式会社 | Treatment agents for carbon fiber precursors and carbon fiber precursors |
| WO2023026674A1 (en) * | 2021-08-27 | 2023-03-02 | 松本油脂製薬株式会社 | Sizing agent for reinforcing fibers and use of same |
| JP7214933B1 (en) * | 2021-08-27 | 2023-01-30 | 松本油脂製薬株式会社 | Sizing agent for reinforcing fiber and use thereof |
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| JPWO2016024451A1 (en) | 2017-04-27 |
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| JP5914780B1 (en) | 2016-05-11 |
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