CN104350200B - Carbon fiber manufacture acrylic fiber finishing agent and uses thereof - Google Patents

Carbon fiber manufacture acrylic fiber finishing agent and uses thereof Download PDF

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CN104350200B
CN104350200B CN201380026434.2A CN201380026434A CN104350200B CN 104350200 B CN104350200 B CN 104350200B CN 201380026434 A CN201380026434 A CN 201380026434A CN 104350200 B CN104350200 B CN 104350200B
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finishing agent
fiber
carbon fiber
ester
acid
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CN104350200A (en
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菊田俊彦
高谷淳
木户实树子
中川干生
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Matsumoto Yushi Seiyaku Co Ltd
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Matsumoto Yushi Seiyaku Co Ltd
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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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Inorganic Fibers (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Abstract

The object of the invention is to, a kind of carbon fiber manufacture acrylic fiber finishing agent is provided, its interfibrous melting adhesion that can take into account in carbon fiber manufacture prevents and stable operability, and the broken string of fiber, the generation of fine hair can be suppressed, and provide the manufacture method of the carbon fiber manufacture acrylic fiber and manufacture method thereof that employ this finishing agent and the carbon fiber employing this finishing agent.The present invention is the carbon fiber manufacture acrylic fiber finishing agent containing thioester compound (A1), surfactant and water containing representing with following general formula (1).R 2oOC-(CH 2) n-S-(CH 2) m-COOR 1(1), in formula, m and n is the integer of 1 ~ 4 independently of one another, R 1and R 2be the alkyl of carbon number 12 ~ 16 independently of one another.

Description

Carbon fiber manufacture acrylic fiber finishing agent and uses thereof
Technical field
The present invention relates to carbon fiber manufacture acrylic fiber finishing agent and uses thereof.More specifically, relate to finishing agent (hereinafter sometimes referred to as precursor finishing agent), the precursor fiber employing this finishing agent and the manufacture method thereof used when manufacturing carbon fiber manufacture acrylic fiber (hereinafter sometimes referred to as precursor) and employ the manufacture method of carbon fiber of this finishing agent.
Background technology
Utilize the mechanical property of its excellence, carbon fiber as with the reinforcing fiber of composite of plastics being referred to as matrix resin, be widely used in aerospace purposes, Sport Utility, general industry purposes etc.
As the method manufacturing carbon fiber, general method is, in the oxidizing atmosphere of 200 ~ 300 DEG C, change precursor into fire resistance fibre, next in the torpescence atmosphere of 300 ~ 2000 DEG C, carries out carbonization.When these are by the burning till of high heat, the melting adhesion between filament can be there is, thus have the quality of carbon fiber, the problem of grade that reduce gained.
Adhere to prevent this melting, proposed a lot of to precursor give have excellent heat resistance and based on the fissility of the excellence of the flatness between Fiber-Fiber silicone-based finishing agent, particularly cross-linking reaction can be utilized to improve the technology (such as patent document 1 etc.) of the amino modified silicone-based finishing agent of heat resistance further, industrially extensively utilized.
But on the other hand, the silicone-based finishing agent having carried out adhering to process can come off and become adhesion from fiber, it is deposited on the dryer roll or ways etc. in precursor manufacturing process, thus has the problem of reason Filament-wound Machine or broken string etc. being become cause operability to reduce.In addition, in the oxidizing atmosphere of fire-retardant operation, its part can generate silica, use when nitrogen can generate silicon nitride as inactive gas in the torpescence atmosphere of carbonation process, these foulings (scale) are piled up, and have the problem making operability or runnability reduce, cause the damage of firing furnace.
In addition, the fissility of the excellence based on flatness between Fiber-Fiber that silicone-based finishing agent has plays a role effectively for the melting adhesion prevented between filament, but on the other hand, in the firing process that very many fibre bundles are advanced simultaneously abreast, each fibre bundle width broadens because of the flatness of silicone-based finishing agent, thus make the narrower intervals with adjacent fibre bundle, the not good situation producing fine hair according to circumstances can be had because of this interference.
In order to avoid these problems, proposed the finishing agent of the content decreasing silicone compound, do not use the finishing agent etc. of silicone compound.Such as, the combination aromatic compound of bisphenol-A system and amino modified silicone is had and the finishing agent (such as patent document 2 etc.), the finishing agent (such as patent document 3 etc.) using the fatty acid ester of the alkylene oxide adducts of bisphenol-A as principal component that obtain.
But, although these finishing agents have effect in the problems such as the above-mentioned operability suppressing to be caused by silicone compound, but have the shortcoming of the poor stability in following use, namely, in finishing agent composition, be equivalent to the bisphenol-A based compound of the suspicion of endocrine disruptor (so-called Environmental Hormone) containing existence.In addition, if using the fatty acid ester of the alkylene oxide adducts of bisphenol-A as the finishing agent of principal component, then because the friction between fiber metal is too high, thus have the broken string of fiber or produce the problem of fine hair.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2002-371477 publication
Patent document 2: Japanese Unexamined Patent Publication 2005-89884 publication
Patent document 3: Japanese Unexamined Patent Publication 2004-143645 publication
Summary of the invention
Invent problem to be solved
In view of this technical background in the past, the object of the invention is to, a kind of carbon fiber manufacture acrylic fiber finishing agent is provided, it is the finishing agent not using the composition being equivalent to endocrine disruptor or having this suspicion, the interfibrous melting adhesion that can take into account in carbon fiber manufacture prevents and stable operability, and the broken string of fiber, the generation of fine hair can be suppressed, and provide the manufacture method of the carbon fiber manufacture acrylic fiber and manufacture method thereof that employ this finishing agent and the carbon fiber employing this finishing agent.
For the method for dealing with problems
The present inventor etc. conduct in-depth research to solve the problem, result obtains following opinion, that is, if the carbon fiber manufacture acrylic fiber finishing agent containing specific ester compounds, surfactant and water, then can solve the problem, thus reach the present invention.
That is, carbon fiber manufacture of the present invention with acrylic fiber finishing agent contain with following general formula (1) represent containing thioester compound (A1), surfactant and water.
[changing 1]
R 2OOC-(CH 2) n-S-(CH 2) m-COOR 1(1)
In formula, m and n is the integer of 1 ~ 4 independently of one another, R 1and R 2be the alkyl of carbon number 12 ~ 16 independently of one another.
Finishing agent of the present invention preferably also contains thioester compound (A2) containing what represent with following general formula (2).
[changing 2]
R 3OOC-(CH 2) n-S-(CH 2) m-COOH(2)
In formula, m and n is the integer of 1 ~ 4 independently of one another, R 3for the alkyl of carbon number 12 ~ 16.
Described containing thioester compound (A1) and the described weight ratio (A1/A2) containing thioester compound (A2) preferably 99.9/0.1 ~ 50/50.
Shared in the nonvolatile component of finishing agent, the described part by weight containing thioester compound (A1) and the described total containing thioester compound (A2) or not being preferably 30 ~ 98.9 % by weight containing described containing the part by weight containing thioester compound (A1) described thioester compound (A2).Similarly, the part by weight of described surfactant is preferably 1 ~ 40 % by weight.
Finishing agent of the present invention also can also containing the modified silicone (B) with the modification base comprising nitrogen-atoms.
Described containing thioester compound (A1) and described containing the total of thioester compound (A2) and the weight ratio ((A1+A2)/B) of described modified silicone (B) or when not containing described containing described containing weight ratio (A1/B) preferably 99.9/0.1 ~ 50/50 of thioester compound (A1) with described modified silicone (B) thioester compound (A2).
Described modified silicone (B) is preferably amino modified silicone.
Finishing agent of the present invention is preferably formed the emulsion be scattered in water.
Carbon fiber manufacture acrylic fiber of the present invention is the fiber adhering to above-mentioned finishing agent and throwing on the raw material propylene acid fiber of carbon fiber manufacture acrylic fiber.
The raw material propylene acid fiber that the manufacture method of carbon fiber manufacture acrylic fiber of the present invention is included in carbon fiber manufacture acrylic fiber adheres to the silk producing procedures of above-mentioned finishing agent and throwing.
The manufacture method of carbon fiber of the present invention comprises: silk producing procedures, the raw material propylene acid fiber of carbon fiber manufacture acrylic fiber adheres to above-mentioned finishing agent, manufactures carbon fiber manufacture acrylic fiber; Flame treatment operation, makes the carbon fiber manufacture acrylic fiber after attachment process change fire resistance fibre in the oxidizing atmosphere of 200 ~ 300 DEG C; With carbonization treatment operation, make the carbonization in the torpescence atmosphere of 300 ~ 2000 DEG C again of described fire resistance fibre.
The effect of invention
Even if carbon fiber manufacture acrylic fiber finishing agent of the present invention does not use the composition being equivalent to endocrine disruptor or having this suspicion, the interfibrous melting adhesion that also can take into account in carbon fiber manufacture prevents and stable operability, and can suppress the broken string of fiber, the generation of fine hair.
If use the carbon fiber manufacture acrylic fiber obtained in carbon fiber manufacture acrylic fiber of the present invention and manufacture method thereof, the interfibrous melting adhesion that just can take into account in carbon fiber manufacture prevents and stable operability, and can suppress the broken string of fiber, the generation of fine hair.
The manufacture method of carbon fiber of the present invention can be taken into account interfibrous melting adhesion and prevent and stable operability, and can suppress the broken string of fiber, the generation of fine hair.In addition, the carbon fiber of high strength can be manufactured.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the determination method that F/F frictional force is described.
Detailed description of the invention
Carbon fiber manufacture acrylic fiber finishing agent (precursor finishing agent) of the present invention is the finishing agent for the purpose of the upper imparting of acrylic fiber (precursor of carbon fiber) used in manufacturing to carbon fiber, containing specific containing thioester compound (A1), surfactant and water.First, each composition forming precursor finishing agent is described.
(containing thioester compound (A1))
Being the compound represented with above-mentioned general formula (1) containing thioester compound (A1), is the required composition of precursor finishing agent of the present invention.Containing thioester compound (A1) be in the manufacture of carbon fiber can maintain throwing time operability while, improve burn till time operability composition.Containing thioester compound (A1), just should can improve between Fiber-Fiber and rubbing by using, improving the convergence of fibre bundle.Consequently, operability when realizing good burning till.
In the formula of general formula (1), R 1and R 2be the alkyl of carbon number 12 ~ 16 independently of one another.R 1and R 2both can be identical, also can be different.R 1and R 2be straight-chain, branched which kind of can, but from the viewpoint of convergence, burn till time operability, preferred branched.As alkyl, alkyl, thiazolinyl, alkynyl etc. can be enumerated, preferred alkyl.The carbon number of alkyl is 12 ~ 16, is preferably 14 ~ 16.If this carbon number is less than 12, then between fiber metal, friction uprises, and can produce filamentary broken string, fine hair.On the other hand, if carbon number is greater than 16, then can produce carbonizing matter in large quantities when burning till, make melting adhesion between fiber.
In the formula of general formula (1), m and n is the integer of 1 ~ 4 independently of one another, is preferably 2 ~ 3.If m or n is greater than 4, then rub between Fiber-Fiber step-down, produces convergence not enough, thus have the situation that when burning till, operability worsens.
As the concrete example of the alkyl of straight-chain, such as, can enumerate dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl etc.In addition, as the concrete example of the alkyl of branched, such as, can enumerate Permethyl 99A base, isotridecyl, different myristyl, different pentadecyl, isocetyl, 2-hexyl decyl etc.In the middle of them, from the viewpoint of convergence, burn till time operability, preferred dodecyl, 2-hexyl decyl.
As containing thioester compound (A1), such as, can enumerate the thiodiglycolic acid two straight chain type esters such as two (dodecyl) thiodiglycolic acid ester, two (n-tridecane base) thiodiglycolic acid ester, two (n-tetradecane base) thiodiglycolic acid ester, two (n-pentadecane base) thiodiglycolic acid ester, two (n-hexadecyl) thiodiglycolic acid ester; The thiodiglycolic acid two branched chain type esters such as two (Permethyl 99A base) thiodiglycolic acid ester, two (isotridecyl) thiodiglycolic acid ester, two (different myristyl) thiodiglycolic acid ester, two (different pentadecyl) thiodiglycolic acid ester, two (isocetyl) thiodiglycolic acid ester, two (2-hexyl decyl) thiodiglycolic acid ester; The thio-2 acid two straight chain type esters such as two (dodecyl) thiodipropionate, two (n-tridecane base) thiodipropionate, two (n-tetradecane base) thiodipropionate, two (n-pentadecane base) thiodipropionate, two (n-hexadecyl) thiodipropionate; The thio-2 acid two branched chain type ester such as two (Permethyl 99A base) thiodipropionate, two (isotridecyl) thiodipropionate, two (different myristyl) thiodipropionate, two (different pentadecyl) thiodipropionate, two (isocetyl) thiodipropionate, two (2-hexyl decyl) thiodipropionate; The sulfo-two butyric acid two straight chain type esters such as two (dodecyl) sulfo-dibutyrate, two (n-tridecane base) sulfo-dibutyrate, two (n-tetradecane base) sulfo-dibutyrate, two (n-pentadecane base) sulfo-dibutyrate, two (n-hexadecyl) sulfo-dibutyrate; The sulfo-two butyric acid two branched chain type esters such as two (Permethyl 99A base) sulfo-dibutyrate, two (isotridecyl) sulfo-dibutyrate, two (different myristyl) sulfo-dibutyrate, two (different pentadecyl) sulfo-dibutyrate, two (isocetyl) sulfo-dibutyrate, two (2-hexyl decyl) sulfo-dibutyrate; The sulfo-two valeric acid two straight chain type esters such as two (dodecyl) sulfo-divalerate, two (n-tridecane base) sulfo-divalerate, two (n-tetradecane base) sulfo-divalerate, two (n-pentadecane base) sulfo-divalerate, two (n-hexadecyl) sulfo-divalerate; The sulfo-two valeric acid two branched chain type esters etc. such as two (Permethyl 99A base) sulfo-divalerate, two (isotridecyl) sulfo-divalerate, two (different myristyl) sulfo-divalerate, two (different pentadecyl) sulfo-divalerate, two (isocetyl) sulfo-divalerate, two (2-hexyl decyl) sulfo-divalerate.In the middle of them, from the viewpoint of convergence, burn till time operability, preferred thio-2 acid two straight chain type ester, thio-2 acid two branched chain type ester, more preferably two (dodecyl) thiodipropionate, two (2-hexyl decyl) thiodipropionate.
These can use containing thioester compound (A1) individually or use in combination of two or more.
As the manufacture method containing thioester compound (A1), be not particularly limited, known gimmick can be adopted.Such as can be manufactured by the esterification of carrying out thio-2 acid and aliphatic alcohol.As concrete example, can enumerate with aliphatic alcohol for thio-2 acid is 2 ~ 2.5 times moles adding ratio, discharge the water generated and carry out the method for esterification.
Such as, as enzymatic synthesis condition, as esterification reaction temperature, be generally 120 ~ 250 DEG C, be preferably 130 DEG C ~ 230 DEG C.In addition, as the reaction time, be generally 1 ~ 10 hour, be preferably 2 ~ 8 hours.Reaction both can be carried out catalyst-free, and esterification catalyst described later also can be used to react.
As the concrete example of aliphatic alcohol, n-dodecanol, positive tridecanol, tetradecanol, pentadecanol, positive hexadecanol, different lauryl alcohol, different tridecanol, different tetradecyl alchohol, different pentadecanol, different hexadecanol, 2-hexyl decyl alcohol etc. can be enumerated.In the middle of them, preferred n-dodecanol, 2-hexyl decyl alcohol.
These aliphatic alcohols both can use individually, also can use in combination of two or more.
As esterification catalyst, Louis's acids, sulphonic acids etc. can be enumerated.More specifically, as Louis's acids, aluminium derivative, tin derivative, titanium derivative etc. can be enumerated, in addition as sulphonic acids, p-methyl benzenesulfonic acid, partially sulfonic acid, sulfuric acid etc. can be enumerated.In the middle of them, preferred titanium derivative, sulphonic acids.Its use amount is such as preferably 0.05 ~ 5 about % by weight relative to the gross weight of raw material.
In esterification, as required, also the water generated can be used the band such as benzene,toluene,xylene, cyclohexane water entrainer to azeotropic distillation removing outside system.
After esterification terminates, with reaction under reduced pressure or distill under normal pressure by the aliphatic alcohol of surplus and remove accordingly, in addition, carry out usual method of purification, the adsorbent purifications such as such as washing, decompression distillation, active carbon, just can obtain didodecyl thiodipropionate.
(containing thioester compound (A2))
Precursor finishing agent of the present invention preferably also contains thioester compound (A2) containing what represent with above-mentioned general formula (2).By containing outside thioester compound (A1) aforesaid, also containing containing thioester compound (A2), just while guaranteeing to rub between Fiber-Fiber, effectively can reduce between fiber metal and rub.Consequently, the convergence of fibre bundle can be improved, and suppress the generation of filamentary broken string, fine hair further.In addition, emulsion stability when finishing agent being carried out water system emulsification becomes good, and finishing agent can be made to be attached to equably on fiber.
In the formula of general formula (2), R 3for the alkyl of carbon number 12 ~ 16, although be straight-chain, branched which kind of can, but from the viewpoint of convergence, burn till time operability, preferred branched.As alkyl, alkyl, thiazolinyl, alkynyl etc. can be enumerated, preferred alkyl.The carbon number of alkyl is 12 ~ 16, is preferably 14 ~ 16.If carbon number is less than 12, then between Fiber-Fiber, friction reduces, and produces convergence not enough, thus has the situation that when burning till, operability worsens.On the other hand, if carbon number is greater than 16, then can produce carbonizing matter in large quantities when burning till, thus have the situation of melting adhesion between fiber.
For the concrete example of the alkyl of straight-chain, the alkyl of branched, with aforesaid R 1and R 2project in the example that illustrates identical.
In the formula of general formula (2), m and n is the integer of 1 ~ 4 independently of one another, is preferably 2 ~ 3.If m or n is greater than 4, then between Fiber-Fiber, friction reduces, and produces convergence not enough, thus has the situation that when burning till, operability worsens.
As containing thioester compound (A2), such as, can enumerate the thiodiglycolic acid list straight chain type esters such as thiodiglycolic acid list (dodecyl) ester, thiodiglycolic acid list (n-tridecane base) ester, thiodiglycolic acid list (n-tetradecane base) ester, thiodiglycolic acid list (n-pentadecane base) ester, thiodiglycolic acid list (n-hexadecyl) ester; The thiodiglycolic acid list branched chain type esters such as thiodiglycolic acid list (Permethyl 99A base) ester, thiodiglycolic acid list (isotridecyl) ester, thiodiglycolic acid list (different myristyl) ester, thiodiglycolic acid list (different pentadecyl) ester, thiodiglycolic acid list (isocetyl) ester, thiodiglycolic acid list (2-hexyl decyl) ester; The thio-2 acid list straight chain type esters such as thio-2 acid list (dodecyl) ester, thio-2 acid list (n-tridecane base) ester, thio-2 acid list (n-tetradecane base) ester, thio-2 acid list (n-pentadecane base) ester, thio-2 acid list (n-hexadecyl) ester; The thio-2 acid list branched chain type esters such as thio-2 acid list (Permethyl 99A base) ester, thio-2 acid list (isotridecyl) ester, thio-2 acid list (different myristyl) ester, thio-2 acid list (different pentadecyl) ester, thio-2 acid list (isocetyl) ester, thio-2 acid list (2-hexyl decyl) ester; The sulfo-two butyric acid list straight chain type esters such as sulfo-two butyric acid list (dodecyl) ester, sulfo-two butyric acid list (n-tridecane base) ester, sulfo-two butyric acid list (n-tetradecane base) ester, sulfo-two butyric acid list (n-pentadecane base) ester, sulfo-two butyric acid list (n-hexadecyl) ester; The sulfo-two butyric acid list branched chain type esters such as sulfo-two butyric acid list (Permethyl 99A base) ester, sulfo-two butyric acid list (isotridecyl) ester, sulfo-two butyric acid list (different myristyl) ester, sulfo-two butyric acid list (different pentadecyl) ester, sulfo-two butyric acid list (isocetyl) ester, sulfo-two butyric acid list (2-hexyl decyl) ester; The sulfo-two valeric acid list straight chain type esters such as sulfo-two valeric acid list (dodecyl) ester, sulfo-two valeric acid list (n-tridecane base) ester, sulfo-two valeric acid list (n-tetradecane base) ester, sulfo-two valeric acid list (n-pentadecane base) ester, sulfo-two valeric acid list (n-hexadecyl) ester; The sulfo-two valeric acid list branched chain type esters etc. such as sulfo-two valeric acid list (Permethyl 99A base) ester, sulfo-two valeric acid list (isotridecyl) ester, sulfo-two valeric acid list (different myristyl) ester, sulfo-two valeric acid list (different pentadecyl) ester, sulfo-two valeric acid list (isocetyl) ester, sulfo-two valeric acid list (2-hexyl decyl) ester.In the middle of them, from the viewpoint of convergence, burn till time operability, preferred thio-2 acid list straight chain type ester, thio-2 acid list branched chain type ester, more preferably thio-2 acid list (dodecyl) ester, thio-2 acid list (2-hexyl decyl) ester.
These both can use individually containing thioester compound (A2), also can use in combination of two or more.
As the manufacture method containing thioester compound (A2), be not particularly limited, known gimmick can be adopted.Such as, can be manufactured by the esterification of carrying out thio-2 acid and aliphatic alcohol.As concrete example, can enumerate as inferior method, that is, add aliphatic alcohol relative to thio-2 acid to wait molar degree, the water of generation is discharged while carry out esterification, carries out distilling, purifying.
And the addition of aliphatic alcohol preferably adds 1 ~ 1.2 times mole to add ratiometer relative to thio-2 acid.For the concrete example, esterification catalyst etc. of enzymatic synthesis condition, aliphatic alcohol, identical with the content illustrated in the project of the aforesaid manufacture method containing thioester compound (A1).
Both aforesaid method can have been utilized to prepare ester compounds respectively containing thioester compound (A1) with containing thioester compound (A2) and used, also can carry out the esterification of thio-2 acid and aliphatic alcohol, preparation uses containing containing thioester compound (A1) and containing the ester admixture of thioester compound (A2).
Contain the method for thioester compound (A1) and the ester admixture containing thioester compound (A2) as preparation, such as, can enumerate method below.
1) can enumerating when carrying out the esterification of thio-2 acid and aliphatic alcohol, for the mol ratio of aliphatic alcohol, relative to thio-2 acid, adding 1.5 ~ 1.99 times moles, preferably adding 1.8 ~ 1.9 times moles and carry out the method for esterification.For the concrete example, esterification catalyst etc. of enzymatic synthesis condition, aliphatic alcohol, identical with the content illustrated in the project of the aforesaid manufacture method containing thioester compound (A1).
2) can enumerate in the aforesaid manufacture method containing thioester compound (A1), the method making esterification terminate on the way in the mode making ester admixture reach required total acid number.
And, can profit calculate in the following method containing thioester compound (A1) and the weight ratio containing thioester compound (A2) in ester admixture.Utilize the ester admixture of gas chromatographic analysis to gained to analyze, determine the content of the thio-2 acid as raw material, obtain the acid number coming from thio-2 acid in ester admixture.Then, the total acid number of ester admixture is determined.According to deducting the acid number coming from thio-2 acid and the value obtained and the molecular weight containing thioester compound (A2) from total acid number, just can calculate in ester admixture containing thioester compound (A1) and the weight ratio containing thioester compound (A2).
In order to play effect of the present invention further, not preferably only containing thioester compound (A1) and containing thioester compound (A2) merely and use, but will and thioester compound (A2) will be contained containing thioester compound (A1) and use with specific ratio.99.9/0.1 ~ 50/50 is preferably containing thioester compound (A1) and the weight ratio (A1/A2) containing thioester compound (A2), be more preferably 99.9/0.1 ~ 70/30, more preferably 99/1 ~ 80/20, be particularly preferably 98/2 ~ 90/10.When this part by weight is greater than 99.9/0.1, the friction between fiber metal uprises, thus has the generation broken string of fiber, the situation of fine hair.In addition, the situation that the emulsion stability also having emulsion when carrying out water system emulsification is deteriorated.On the other hand, when this part by weight is less than 50/50, between Fiber-Fiber, friction reduces, and produces convergence not enough, thus has the situation that when burning till, operability worsens.
(surfactant)
Precursor finishing agent of the present invention contains surfactant.Surfactant is used by as emulsifying agent, can make aforesaid containing thioester compound (A1) or containing the emulsification such as thioester compound (A2), modified silicone described later, be dispersed in water.As surfactant, be not particularly limited, can from nonionic surfactant, anionic surfactant, cationic surfactant and amphoteric surfactant the suitably known surfactant of choice for use.Surfactant can be used alone or in combination with two or more kinds.
As nonionic surfactant, such as, can enumerate the polyoxy alkylidene straight chained alkyl ethers such as polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene ether in the last of the ten Heavenly stems, polyoxyethylenelauryl ether, polyoxyethylene cetyl ether; The polyoxy alkylidene branched primary alkyl ethers such as polyoxyethylene 2-ethyl hexyl ether, polyoxyethylene isocetyl ether, polyoxyethylene isooctadecane base ether; The polyoxy alkylidene branched secondary alkyl group ethers such as polyoxyethylene 1-hexyl hexyl ether, polyoxyethylene 1-octyl group hexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-amyl group heptyl ether, polyoxyethylene 1-heptyl amyl ether; The polyoxy alkylidene alkene ethers such as polyoxyethylene oleyl ether; The polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene dodecylphenyl ether; The polyoxyalkylene alkyl aryl phenyl ethers such as polyoxyethylene tristyryl base phenyl ether, polyoxyethylene diphenylethyllene phenyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzylphenyl ether, polyoxyethylene benzyl phenyl ether; The polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monoleate, polyoxyethylene monostearate, polyoxyethylene list myristinate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxyethylene two myristinate, polyoxyethylene distearate; The sorbitan esters such as single palmitic acid sorbitan ester, single oleic acid sorbitan ester; The polyoxy alkylidene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate; The fatty glycerides such as glycerin monostearate, glyceryl monolaurate, monopalmitin; Polyoxyalkylene sorbitan fatty acid ester; Sucrose fatty ester; The castor oil polyoxy alkylidene ethers such as castor oil polyoxyethylene ether; The solidification castor oil polyoxy alkylidene ethers such as solidification castor oil polyoxyethylene ether; The polyoxyalkylene alkyl amino ethers such as polyoxyethylenelauryl base amino ethers, polyoxyethylene stearyl ether; Oxygen ethylidene-oxygen propylidene block or random copolymer; The end alkyl etherate of oxygen ethylidene-oxygen propylidene block or random copolymer; The end sucrose ether compound etc. of oxygen ethylidene-oxygen propylidene block or random copolymer.
In the middle of these nonionic surfactants, based on the reason that the water system emulsifying ability of ester and silicone compounds is excellent especially, preferred polyoxy alkylidene branched primary alkyl ether, polyoxy alkylidene branched secondary alkyl group ether, polyoxy alkylidene alkene ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene fatty acid esters, oxygen ethylidene-oxygen propylidene block copolymer, the end alkyl etherate of oxygen ethylidene-oxygen propylidene block copolymer, in addition based on being difficult to coking on fiber in firing process, fiber is caused to the reason of damage, more preferably oxygen ethylidene-oxygen propylidene block or random copolymer, the end alkyl etherate of oxygen ethylidene-oxygen propylidene block copolymer.
As anionic surfactant, such as, can enumerate the aliphatic acid (salt) such as oleic acid, palmitic acid, Oleic acid sodium salt, palmitic acid sylvite, triethanol amine oleate; The carboxylic acid (salt) containing hydroxyl such as glycolic acid, glycolic acid sylvite, lactic acid, lactic acid sylvite; The polyoxyalkylene alkyl ether acetic acid (salt) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); The salt of the carboxyl Polysubstituted Aromatic Compounds such as trimellitic acid potassium, pyromellitic acid potassium; The alkyl benzene sulphonates (salt) such as DBSA (sodium salt); The polyoxyalkylene alkyl ether sulfonic acid (salt) such as polyoxyethylene 2-ethyl hexyl ether sulfonic acid (sylvite); The higher fatty acid amides sulfonic acid (salt) such as stearyl N-methyltaurine (sodium), lauroyl N-methyltaurine (sodium), myristoyl N-methyltaurine N (sodium), palmityl N-methyltaurine (sodium); The N-acyl group methyl amimoacetic acids (salt) such as lauroyl sarcosine (sodium); The alkyl phosphonic acids (salt) such as octyl phosphonic acid salt (sylvite); The aromatic series phosphonic acids (salt) such as Phenylphosphine hydrochlorate (sylvite); The alkyl phosphonic acid alkyl phosphates (salt) such as 2-ethylhexyl phosphonic acid mono 2-Octyl Nitrite (sylvite); The nitrogenous alkyl phosphonic acids (salt) such as aminoethyl phosphonic acid (diethanolamine salt); The alkyl sulfates (salt) such as 2-ethylhexylsulphate (sodium salt); The polyoxy alkylidene sulfuric esters (salt) such as polyoxyethylene 2-ethylhexyl ether sulfate (sodium salt); The long-chain N-acyl glutamates etc. such as the long-chain sulfosuccinates such as two-2-ethylhexylsulfosuccinate sodium, dioctyl sodium sulphosuccinate, N-lauroyl glutamate list sodium, N-stearyl-Pidolidone disodium.
As cationic surfactant, such as lauryl trimethyl ammonium chloride can be enumerated, myristyl trimonium ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oil base trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, INCROQUAT TMC-80, coco alkyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, Cocoalkyl trimethylammonium bromide, cetyl trimethyl sulfate methyl ammonium, oleyl dimethyl ethyl sulfuric acid ethyl ester ammonium, Quaternium 24, dilauryl ammonium chloride, VARISOFT TA100, the alkyl quaternary ammonium saltss such as octadecyl diethylmethyl ammonium sulfate, (polyoxyethylene) lauryl amino ether lactate, stearyl ether lactate, two (polyoxyethylene) lauryl methyl amino ethers dimethylphosphate, two (polyoxyethylene) lauryl ethyl sulfuric acid ethyl ester ammonium, two (polyoxyethylene) solidify (polyoxy alkylidene) alkyl amino ether salt such as tallow alkyl ethyl sulfuric acid ethyl ester amine, two (polyoxyethylene) lauryl methyl dimethyl ammonium phosphate, two (polyoxyethylene) stearic amine lactate, the acylamide alkyl quaternary ammonium saltss such as N-(2-hydroxyethyl)-N, N-dimethyl-N-stearyl amido propyl ammonium nitrate, lanolin fatty acid amide ethyl dimethyl disulfide acetoacetic ester ammonium, lauroyl acid amides ethyl-methyl diethyl sulfide acetoacetic ester ammonium, the alkyl oxygen ethylidene quaternary ammonium salts such as two palmityl polyoxyethylene ethyl ammonium chlorides, distearyl polyoxyethylene ammonio methacrylate, the alkyl isoquinolinium salts such as lauryl isoquinolin chloride, the zephiran such as lauryl dimethyl benzyl ammonium chloride, stearalkonium chloride salt, the Benzethonium salt such as benzyl dimethyl { 2-[2-(p-1,1,3,3-tetramethyl butyl phenoxy group) ethyoxyl] ethyl } ammonium chloride, the pyridinium salt such as pyrisept, the imidazole salts such as oil base hydroxyethyl imidazoles ethyl-sulfate salt, lauryl hydroxyethyl imidazoles ethyl-sulfate salt, the acyl group basic amino acid alkyl ester salts such as N-cocoyl arginine ethyl ester pyrrolidone carboxylic acid salt, N-lauroyl lysine diethyl acetamidomalonate chloride, the primary amine salt such as lauryl amine chloride, stearic amine bromide, solidification tallow alkyl amine chloride, rosin amine acetate, the secondary amine salt such as cetyl methyl amine sulfate, lauryl methyl amine chloride, dilauryl amine acetate, stearyl ethylamine bromide, lauryl propyl group amine acetate, dioctylamine chloride, octadecyl ethylamine hydroxide, the tertiary ammonium salts such as dilauryl methyl amine sulfate, lauryl diethylamide chloride, lauryl ethylmethylamine bromide, diethanol stearyl amido-propyl ethylamine trihydroxy ethyl phosphate, stearyl amido-propyl ehtylethanolamine urea condensation polymer acetate, fatty acid amide guanidinesalt, the alkyl three aklylene glycol ammonium salts etc. such as lauryl triethylene glycol ammonium hydroxide.
As amphoteric surfactant, such as, can enumerate 2-undecyl-N, the imidazoline system amphoteric surfactantes such as N-(hydroxyethyl carboxymethyl group)-2-imidazoline sodium, 2-cocoyl-2-imidazoline hydroxide-1-Carboxyethoxy 2 sodium salt; The betaine system amphoteric surfactantes such as 2-heptadecyl-N-carboxymethyl group-N-hydroxyethyl imidazolines betaine, lauryl dimethyl oxyneurine, alkyl betaine, amide betaine, DMPT; The amino acid type amphoteric surfactants etc. such as N-lauryl glycine, N-lauryl Beta-alanine, N-stearyl Beta-alanine.
In the middle of these surfactants, from ageing stability excellence and containing thioester compound (A1), consider containing the reason that the emulsifying ability of thioester compound (A2), modified silicone is also excellent, preferred nonionic surfactant.Ionic surfactant, compared with nonionic surfactant, has the advantage that can suppress the excellent antistatic property being produced the loose hair of the fibre bundle caused by electrostatic, therefore preferably and non-ionic surface active agent using.As ionic surfactant; above-mentioned anionic surfactant, cationic surfactant, amphoteric surfactant can be enumerated; but in the middle of them preferred cationic surfactant; in the middle of cationic surfactant, more preferably alkyl quaternary ammonium salts, (polyoxy alkylidene) alkyl amino ether salt, acylaminoalkyl quaternary ammonium salt, alkyl oxygen ethylidene quaternary ammonium salt, primary amine salt, secondary amine salt, tertiary ammonium salt etc.
(there is the modified silicone (B) of the modification base comprising nitrogen-atoms)
Precursor finishing agent of the present invention can also containing the modified silicone (B) with the modification base comprising nitrogen-atoms.Precursor finishing agent of the present invention is owing to containing thioester compound (A1) containing aforesaid, therefore can not improve frictionally to improve between Fiber-Fiber between fiber metal and rub, in firing process, prevent the expansion of fibre bundle width, effectively can reduce the generation of the fine hair caused by the interference of fibre bundle thus.That is, containing the not good situation that can suppress containing the precursor finishing agent of the present invention of thioester compound (A1) to be caused by modified silicone (B), thus modified silicone (B) can be used.
In order to play this kind of effect further, not preferably only simply also with modified silicone (B), but use above-mentioned with specific ratio containing thioester compound (A1) and containing the total of thioester compound (A2) and modified silicone (B), or when not containing described containing thioester compound (A2), will describedly use with specific ratio containing thioester compound (A1) and described modified silicone (B).For containing thioester compound (A1) and containing the total of thioester compound (A2) and the weight ratio ((A1+A2)/B) of modified silicone (B), or when not containing described containing thioester compound (A2), for described containing the weight ratio (A1/B) of thioester compound (A1) with described modified silicone (B), be preferably 99.9/0.1 ~ 50/50, be more preferably 95/5 ~ 60/40, more preferably 90/12 ~ 70/30.When this part by weight is greater than 99.9/0.1, the friction between fiber metal uprises, thus has the generation broken string of fiber, the situation of fine hair.In addition, the situation that the emulsion stability also having emulsion when carrying out water system emulsification is deteriorated.On the other hand, when this part by weight is less than 50/50, because between Fiber-Fiber, friction reduces, and produces convergence deficiency, thus have the situation that when burning till, operability worsens.
As long as modified silicone (B) is the modification base comprising nitrogen-atoms, then the kind of modification base is just not particularly limited.As the modification base comprising nitrogen-atoms, can enumerate containing amino key or the modification base (namely amino) of imido base key, the modification base (i.e. amide groups) etc. containing amido link, also can be the modification base having the different key such as multiple amino key and amido link.The modification base comprising nitrogen-atoms both can with the side chain bonding of the silicone as main chain, also can with end bonding, in addition can also with both bondings.In addition, polyoxy alkylidene (such as polyoxyethylene, polyoxypropylene, polyoxy butylidene etc.) can also be had in the molecule.
As the modified silicone (B) with the modification base comprising nitrogen-atoms, such as can enumerate amino modified silicone, amino-polyether modified silicone, amide modifications silicone, acid amides polyether modified silicone etc., both can use a kind of modified silicone, also can be used together multiple modified silicone.
In addition, the content of the nitrogen-atoms in modified silicone (B) is preferably 0.35 ~ 3.2 % by weight, is more preferably 0.37 ~ 2.2 % by weight, and more preferably 0.40 ~ 1.3 % by weight.When nitrogen-atoms content lower than 0.35 % by weight, have when carrying out water system emulsification emulsion emulsion stability be deteriorated situation.On the other hand, when nitrogen-atoms content higher than 3.2 % by weight, the adhesiveness of modified silicone (B) raises because of heat cross-linking, becomes the reason causing viscose glue (gumup).
From the viewpoint of the emulsion stability of emulsion when carrying out water system emulsification excellent and also by with containing thioester compound (A1) and with the excellent effect brought, in the middle of these modified silicones (B), preferred amino modified silicone.
When modified silicone (B) is for amino modified silicone, the structure of this amino modified silicone is not particularly limited.That is, as modification base amino both can with the side chain bonding of the silicone as main chain, also can with end bonding, in addition can also with both bondings.In addition, this amino both can be monoamine type also can be polyamine type, can also in 1 molecule both and deposit.
Amino (NH in amino modified silicone 2) content (hereinafter referred to as " amino % by weight ") be preferably 0.4 ~ 3.7 % by weight, be more preferably 0.42 ~ 2.5 % by weight, more preferably 0.46 ~ 1.5 % by weight.If amino % by weight lower than 0.4 % by weight, then the situation that the emulsion stability having emulsion when carrying out water system emulsification is deteriorated.On the other hand, when higher than 3.7 % by weight, the adhesiveness of amino modified silicone can raise because of heat cross-linking, becomes the reason causing viscose glue.
For the viscosity of 25 DEG C of amino modified silicone, be not particularly limited, but if too low viscosity, then finishing agent easily splashes, when carrying out water system emulsification, the emulsion stability of emulsion is deteriorated in addition, finishing agent cannot be given equably to fiber.Consequently, the situation that cannot prevent the melting of fiber from adhering is had.If be too high viscosity in addition conversely, then have the situation that the viscose glue caused by adhesiveness becomes problem.From the viewpoint of preventing these problems, the viscosity of 25 DEG C of amino modified silicone is preferably 100 ~ 15,000mm 2/ s, is more preferably 500 ~ 10,000mm 2/ s, more preferably 1,000 ~ 5,000mm 2/ s.
(other compositions)
Precursor finishing agent of the present invention also can in the scope not hindering effect of the present invention, the composition containing other beyond above-mentioned composition.As other composition, the antioxidants such as acid phosphoric acid ester, phenol system, amine system, sulphur system, phosphorus system, quinone system can be enumerated; The antistatic additive such as phosphate ester salt, quaternary ammonium salt cationic system surfactant, amine salt type CATION system surfactant of the sulfuric acid of the senior alcohol ether of higher alcohol, sulfonate, the senior alcohol ether of higher alcohol; The smooth agents such as the Arrcostab of higher alcohol, senior alcohol ether, paraffin class; Antiseptic; Preservative agent; Rust inhibitor; And hygroscopic agent etc.
The composition that antioxidant is the thermal decomposition of the precursor finishing agent caused by heating effectively suppressed in flame treatment operation, preventing effectiveness is adhered in the melting improved between Fiber-Fiber.
As antioxidant, be not particularly limited, but from the viewpoint of preventing firing furnace from polluting, preferred organic antioxidant.As organic oxidation-resistant agent, such as can enumerate 4,4 '-butylidene two (3 methy 6 tert butyl phenol, tricresyl phosphite (octadecyl) ester, N, N '-diphenyl-p-phenylenediamine, triethylene glycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], two oil bases-thiodipropionate etc.These organic oxidation-resistant agent can be used alone or in combination with two or more kinds.
In addition, precursor finishing agent of the present invention also can containing the silicone composition beyond the modified silicone (B) with the modification base comprising nitrogen-atoms in the scope not hindering effect of the present invention.Specifically, dimethyl silscone, epoxy-modified silicone, epoxyalkane modified silicone (polyether modified silicone), epoxy radicals polyether modified silicone (such as with reference to No. 4616934, Japan Patent), carboxy-modified silicone, carbinol-modified silicone, alkyl-modified silicone, phenol-modified silicone, methacrylate modified silicone, alkoxy-modified silicone, fluorine richness silicone etc. can be enumerated.
(precursor finishing agent)
Precursor finishing agent of the present invention is must containing aforesaid containing thioester compound (A1), surfactant and water and as required containing the finishing agent containing thioester compound (A2).For the part by weight containing thioester compound (A1) and the total containing thioester compound (A2) shared in the nonvolatile component of finishing agent, or when not containing described containing the part by weight containing thioester compound (A1) described thioester compound (A2), be preferably 30 ~ 98.9 % by weight.Be more preferably 45 ~ 95 % by weight, more preferably 55 ~ 85 % by weight, be particularly preferably 65 ~ 75 % by weight.When this part by weight is less than 30 % by weight, rub between Fiber-Fiber step-down, produces convergence not enough, thus have the situation that when burning till, operability worsens.On the other hand, when being greater than 98.9 % by weight, the situation that the emulsion stability having emulsion when carrying out water system emulsification is deteriorated.
The part by weight of surfactant shared in the nonvolatile component of finishing agent is preferably 1 ~ 40 % by weight, is more preferably 5 ~ 30 % by weight, and more preferably 8 ~ 25 % by weight.If this part by weight is less than 1 % by weight, then have the situation being difficult to obtain good emulsion stability.In addition, if this part by weight is greater than 40 % by weight, then the heat resistance of finishing agent reduces, and has the situation of the melting adhesion of the carbon fiber that cannot suppress in firing process.
When precursor finishing agent of the present invention contains modified silicone (B), the part by weight of modified silicone (B) shared in the nonvolatile component of finishing agent is more preferably 5 ~ 40 % by weight, more preferably 10 ~ 30 % by weight, be particularly preferably 15 ~ 25 % by weight.
Precursor finishing agent of the present invention preferably contains surfactant as emulsifying agent, make containing thioester compound (A1), use as required containing thioester compound (A2), modified silicone emulsification or be dispersed in water, form the state of the emulsion be scattered in water.
For the part by weight of water, the part by weight of nonvolatile component shared in precursor finishing agent entirety, be not particularly limited.Such as, if consider transport precursor finishing agent of the present invention time cost of transportation, suitably determine based on the disposal etc. of emulsion viscosity.The part by weight of water shared in precursor finishing agent entirety is preferably 0.1 ~ 99.9 % by weight, is more preferably 10 ~ 99.5 % by weight, is particularly preferably 50 ~ 99 % by weight.The part by weight (concentration) of nonvolatile component shared in precursor finishing agent entirety is preferably 0.01 ~ 99.9 % by weight, is more preferably 0.5 ~ 90 % by weight, is particularly preferably 1 ~ 50 % by weight.
The average grain diameter of the emulsion in precursor finishing agent is preferably 0.05 ~ 0.30 μm, is more preferably 0.06 ~ 0.20 μm, more preferably 0.07 ~ 0.10 μm.When this average grain diameter is less than 0.05 μm, finishing agent easily to fibrous inside infiltration, thus can rewarding carbon fiber intensity reduce situation.On the other hand, when this average grain diameter is greater than 0.30 μm, finishing agent cannot be attached to fiber surface equably, thus can rewarding carbon fiber intensity reduce situation.And so-called average grain diameter in the present invention, refers to the mean value calculated according to the size distribution measured with laser diffraction/diffuse transmission type particle size distribution device (hole field LA-910).
Precursor finishing agent of the present invention can by manufacturing the mixing of the composition of above-mentioned explanation.For making the composition emulsification of above-mentioned explanation, the method for dispersion is not particularly limited, and can adopt known gimmick.As this kind of method, such as, can enumerate and each composition forming precursor finishing agent is dropped into the method for carrying out emulsion dispersion in the warm water under stirring; The each composition forming precursor finishing agent mix and uses homogenizer, mixer for well-distribution, ball mill etc. to apply mechanical shear stress while input water and carry out the method etc. of Phase inversion emulsification at leisure.
In addition, precursor finishing agent of the present invention can be used to manufacture precursor and carbon fiber.Employ the precursor of precursor finishing agent of the present invention and the manufacture method of carbon fiber is not particularly limited, but such as can enumerate following manufacture method.
(manufacture method of precursor and manufacture method and carbon fiber)
Carbon fiber manufacture acrylic fiber (precursor) of the present invention be make above-mentioned precursor finishing agent be attached to precursor raw material propylene acid fiber on and fiber that throwing obtains.The manufacture method of precursor of the present invention comprise make above-mentioned precursor finishing agent be attached to precursor raw material propylene acid fiber on and the silk producing procedures of throwing.
The manufacture method of carbon fiber of the present invention comprises: silk producing procedures, make above-mentioned precursor finishing agent be attached to precursor raw material propylene acid fiber on and by precursor throwing; Flame treatment operation, changes the precursor manufactured in this silk producing procedures into fire resistance fibre in the oxidizing atmosphere of 200 ~ 300 DEG C; With carbonization treatment operation, make the carbonization in the torpescence atmosphere of 300 ~ 2000 DEG C again of described fire resistance fibre.
Silk producing procedures be make precursor finishing agent be attached to precursor raw material propylene acid fiber on and by the operation of precursor throwing, comprise attachment treatment process and stretching process.
Attachment treatment process be after by the raw material propylene of precursor acid fibre spinning, operation that precursor finishing agent is adhered to.That is, in attachment treatment process, precursor finishing agent is made to be attached on the raw material propylene acid fiber of precursor.Although the raw material propylene acid fiber of this precursor is stretched immediately after spinning in addition, but the high magnification stretching after attachment treatment process is called especially " stretching process ".Stretching process both can be the use of the damp and hot extension of high-temperature vapor, also can be the use of the xeothermic extension of hot-rolling.
Precursor is made up of the acrylic fiber of the polyacrylonitrile obtained to make the fire-retardant promotion composition copolymerization of the acrylonitrile of more than at least 95 % by mole and less than 5 % by mole as principal component.As fire-retardant promotion composition, the compound containing vinyl relative to acrylonitrile with copolymerizable can be used suitably.For the filament denier of precursor, be not particularly limited, but consider from the balance of performance and manufacturing cost, be preferably 0.1 ~ 2.0dTex.In addition, the filamentary radical for the fibre bundle forming precursor is also not particularly limited, but considers from the balance of performance and manufacturing cost, is preferably 1,000 ~ 96,000.
Although on the raw material propylene acid fiber which of silk producing procedures makes precursor finishing agent be attached to precursor in stage can, but preferably make it to adhere to once before stretching process.As long as the stage before stretching process, be no matter which in stage can, such as also can make it attachment after just spinning.In addition also which after stretching process can make it again to adhere in stage, such as, can make it immediately again to adhere to after stretching process, also can make it again to adhere at winding portion, can also flame treatment operation not long ago make it again adhere to.About its adherence method, roller etc. both can be used to adhere to, infusion process, spray-on process etc. also can be utilized to adhere to.
In attachment treatment process, for the imparting rate of precursor finishing agent, from the deadlocked preventing effectiveness obtained between Fiber-Fiber, melting adhesion preventing effectiveness, with carbonization treatment operation prevent the quality making carbon fiber because of the carbonizing matter of finishing agent from reducing balance consider, be preferably 0.1 ~ 2 % by weight relative to the weight of precursor, be more preferably 0.3 ~ 1.5 % by weight.If the imparting rate of precursor finishing agent is less than 0.1 % by weight, then cannot prevent deadlocked, the melting adhesion between filament fully, the situation of the intensity reduction of the rewarding carbon fiber of meeting.On the other hand, if the imparting rate of precursor finishing agent is greater than 2 % by weight, then because precursor finishing agent is by covering more than required degree between filament, oxygen therefore can be hindered in flame treatment operation to the supply of fiber, the situation of the intensity reduction of the rewarding carbon fiber of meeting.And the imparting rate of so-called precursor finishing agent is defined relative to the percentage of front body weight by the nonvolatile component weight of the precursor finishing agent adhered to herein.
Flame treatment operation is the operation precursor that attached to precursor finishing agent being changed in the oxidizing atmosphere of 200 ~ 300 DEG C into fire resistance fibre.So-called oxidizing atmosphere, as long as usual air atmosphere.The temperature of oxidizing atmosphere is preferably 230 ~ 280 DEG C.In flame treatment operation, relative to the acrylic fiber after attachment process, apply the tension force of draw ratio 0.90 ~ 1.10 (being preferably 0.95 ~ 1.05), while carry out the heat treatment of 20 ~ 100 minutes (being preferably 30 ~ 60 minutes).In this flame treatment, through intramolecular cyclization and the oxygen addition to ring, and produce the fire resistance fibre with flame retarding construction.
Carbonization treatment operation is the operation making fire resistance fibre carbonization in the torpescence atmosphere of 300 ~ 2000 DEG C again.In carbonization treatment operation, first, preferably in the torpescence such as nitrogen, argon gas atmosphere, have in the firing furnace of thermograde from 300 DEG C to 800 DEG C, to fire resistance fibre while apply the tension force of draw ratio 0.95 ~ 1.15, the number minute of heat treatment on one side, carries out pre-carbonization treatment operation (the first carbonization treatment operation).Thereafter, in order to make carbonization carry out further, and make it to carry out graphitization, in the torpescence such as nitrogen, argon gas atmosphere, apply the tension force of draw ratio 0.95 ~ 1.05 relative to the first carbonization treatment operation, the number minute of heat treatment on one side, carry out the second carbonization treatment operation, by fire resistance fibre carbonization.For the control of the heat treatment temperature in the second carbonization treatment operation, while applying thermograde, maximum temperature can be set to more than 1000 DEG C (being preferably 1000 ~ 2000 DEG C).This maximum temperature suitably can be selected to determine according to the requirement characteristic (TENSILE STRENGTH, elastic modelling quantity etc.) of required carbon fiber.
In the manufacture method of carbon fiber of the present invention, when the carbon fiber needing elastic modelling quantity higher, after also can being connected on carbonization treatment operation, carry out graphitization processing operation.Graphitization processing operation normally, in the torpescence such as nitrogen, argon gas atmosphere, applies tension force to the fiber obtained in carbonization treatment operation, while carry out at the temperature of 2000 ~ 3000 DEG C.
To the carbon fiber so obtained, can according to object, carry out for improve when making composite with the surface treatment of the adhesive strength of matrix resin.As surface treatment method, gas phase or liquid phase process can be adopted, consider from productive viewpoint, preferably by the liquid phase process of the electrolyte such as acid, alkali.In addition, in order to improve the processability of carbon fiber, the property disposed, the various upper oar agent of intermiscibility excellence can also be given to matrix resin.
Embodiment
Below, utilize embodiment to be specifically described the present invention, but be not limited to the embodiment recorded herein.And the percentage (%) shown in following embodiment, part, as long as no being particularly limited to, are exactly represent " % by weight ", " weight portion ".The mensuration of each characteristic value is carried out based on method shown below.
The calculation method > containing thioester compound (A1) and the weight ratio containing thioester compound (A2) in < ester admixture
(1) gas chromatographic analysis
Utilize internal standard method that the thio-2 acid content (S (g)) in ester admixture 1g is quantitative.The analysis condition of gas chromatographic analysis is expressed as follows.
Equipment: Shimadzu Seisakusho Ltd. GC-2010
Chromatographic column: J & W TC-530m × 0.25m
Column temperature: 80 ~ 300 DEG C (programming rate 10 DEG C/min)
Injection temperature/detector temperature: 300 DEG C/300 DEG C
Detector: FID
Carrier gas: helium
(2) acid number (T (mgKOH/g)) of the thio-2 acid in ester admixture
S×112220/178.21＝T
S: thio-2 acid content (g) in the ester admixture 1g utilizing gas chromatographic analysis to obtain
(3) total acid number
Ester admixture is measured according to JISK2501 (2003).
(4) computational methods of weight ratio
Containing thioester compound (A1): containing thioester compound (A2)
＝(100-X)∶X
X：(A-T)×M/561.1
A: the total acid number (mgKOH/g) of ester admixture
T: the acid number (mgKOH/g) of the thio-2 acid in ester admixture
M: containing the molecular weight of thioester compound (A2)
< average grain diameter (emulsion stability) >
By precursor finishing agent with make transmitance be more than 90% mode dilute with water, the size distribution according to measuring with laser diffraction/diffuse transmission type particle size distribution device (hole field LA-910) calculates mean value.
The imparting rate > of < finishing agent
The ethanol extraction method by soxhlet's extractor is utilized to calculate the imparting rate of precursor finishing agent.But, for the embodiment 11 ~ 16 containing silicone compound, comparative example 1, utilize following method to calculate imparting rate.
After precursor potassium hydroxide/sodium butyrate after imparting finishing agent is carried out alkali fusion, be dissolved in the water and be adjusted to pH1 with hydrochloric acid.Add sodium sulfite and ammonium molybdate and make it color development, carrying out the colorimetric assay (wavelength 815 μm) of silicon molybdenum blue, obtain the content of silicon.Use the value of the silicone content in the silicone content obtained and the finishing agent utilizing same procedure to obtain in advance herein, calculate the imparting rate (% by weight) of precursor finishing agent.
Friction > between < Fiber-Fiber
Carbon fiber bundle is arranged in the Fiber-Fiber friction analyzer shown in Fig. 1, will (twisting number of times 2 times) will utilize load to apply the initial tension of 50g using the tension force (g) during the speed tractive of 30cm/ minute as Fiber-Fiber frictional force under twisting exists.
Friction > between < fiber metal
After by carbon fiber bundle degreasing, with make finishing agent imparting amount (OPU) be 1.0 % by weight mode give each finishing agent, using use wire method friction analyzer to determine tension force (g) as fiber metal frictional force.
< condition determination >
Silk speed: 50m/min
Load: 50g
Friction piece: pears surface chromium is followed closely
< scratch resistance >
Utilize TM formula friction cohesive force testing machine TM-200 (Daiei science Jing Ji Inc.), by 3 minute surface chromium plating stainless pins configured with zigzag with the tension force of 50g scraping carbon fiber bundle 1000 times (reciprocating motion speed 300 beats/min), following benchmark is utilized to carry out visual judgement to the state of the fluffing of carbon fiber bundle.
◎: produce with identical fine hair of can't see completely before scraping
Zero: although see several fine hair but scratch resistance is good
△: fluffing is slightly many, scratch resistance is slightly poor
×: fluff many, can see that obvious single wire fracture scratch resistance is bad
< throwing operability (roller pollution) >
Following metewand is utilized to determined the pollution level (viscose glue) of precursor 50kg being given to the dryer roll after finishing agent.
◎: the roller do not caused by viscose glue pollutes, and does not have throwing operational problem
Zero: the roller caused by viscose glue pollutes few, does not have throwing operational problem
△: have the roller caused by viscose glue to pollute, throwing operability is slightly poor
×: the roller caused by viscose glue pollutes obviously, by monofilament filature during throwing, has winding
< melting adhesion preventive >
From carbon fiber, choose 20 randomly, from the staple fibre wherein cutting out long 10mm, observe its melting tacky state, utilize following metewand to judge.
◎: do not have melting to adhere
Zero: there is no that melting is adhered
△: melting adhesion is few
×: melting adhesion is many
< carbon fiber strength >
Measure according to the epoxy resin infiltration tow method specified in JIS-R-7601, will the mean value of number of times 10 times be measured as carbon fiber strength (GPa).
(embodiment 1)
Nonionic surfactant (polyoxyethylene 7mol addition alkyl ether (carbon number of alkyl is 12 ~ 14), the tristyrenated phenyl ether of polyoxyethylene 12mol addition and ethylene oxide/propylene oxide (50/50) block copolymer) is utilized to carry out water system emulsification by as the following ester compounds a1 containing thioester compound (A1), as finishing agent nonvolatile component composition, obtain the finishing agent emulsion (precursor finishing agent) be made up of the weight rate of ester compounds a1/ nonionic surfactant=70/30.And, finishing agent nonvolatile component concentration is set to 3.0 % by weight.
By this finishing agent emulsion with make imparting rate be 1.0 % by weight mode be attached on precursor (filament denier 0.8dtex, 24,000 long filament), dry and remove moisture at 100 ~ 140 DEG C.By the flame treatment 60 minutes in the fire-retardant stove of 250 DEG C of the precursor after this attachment finishing agent, then under nitrogen atmosphere have 300 ~ 1400 DEG C thermograde carbonization kiln roasting and change carbon fiber into.The evaluation result of each characteristic value is shown in table 1.
(embodiment 2 ~ 10 and comparative example 1 ~ 7)
Except in embodiment 1, to reach the mode of finishing agent nonvolatile component composition (% by weight) shown in table 1,2,4 respectively, prepare beyond finishing agent emulsion, identical with embodiment 1.Its evaluation result is shown in table 1,2,4.
(embodiment 11)
Will as the following ester admixture a5 containing thioester compound (A1) and the ester admixture containing thioester compound (A2), following silicone compound b1 utilizes nonionic surfactant (polyoxyethylene 7mol addition alkyl ether (carbon number of alkyl is 12 ~ 14), the tristyrenated phenyl ether of polyoxyethylene 12mol addition and ethylene oxide/propylene oxide (50/50) block copolymer) carry out water system emulsification, form as finishing agent nonvolatile component, obtain the finishing agent emulsion (precursor finishing agent) be made up of the weight rate of ester admixture a5/ silicone compound b1/ nonionic surfactant=50/20/30.And finishing agent nonvolatile component concentration is set to 3.0 % by weight.
This finishing agent emulsion is attached on precursor (filament denier 0.8dtex, 24,000 long filament) in the mode reaching imparting rate 1.0 % by weight, dry and remove moisture at 100 ~ 140 DEG C.By the flame treatment 60 minutes in the fire-retardant stove of 250 DEG C of the precursor after this attachment finishing agent, then under nitrogen atmosphere have 300 ~ 1400 DEG C thermograde carbonization kiln roasting and change carbon fiber into.The evaluation result of each characteristic value is shown in table 3.
(embodiment 12 ~ 16)
Except in embodiment 11, respectively to reach the mode of finishing agent nonvolatile component composition (% by weight) shown in table 3, prepare beyond finishing agent emulsion, identical with embodiment 11.Its evaluation result is shown in table 3.
And, in the illustration and table 1 ~ 4 of following ester admixture, " A1: A2 " represents that, containing thioester compound (A1) and the weight ratio (A1: A2) containing thioester compound (A2), " (A1+A2): B " represents containing thioester compound (A1) and containing the total of thioester compound (A2) and the weight ratio ((A1+A2): B) of modified silicone (B).
(containing thioester compound (A1))
A1: thio-2 acid two (dodecyl) ester
A2: thio-2 acid two (2-hexyl decyl) ester
And, in table 1 ~ 4, represent ester compounds A1 containing thioester compound (A1).
(containing thioester compound (A1) and the ester admixture containing thioester compound (A2))
A3: the mixture (A1: A2=95: 5) of thio-2 acid two (dodecyl) ester and thio-2 acid list (dodecyl) ester
A4: the mixture (A1: A2=99.6: 0.4) of thio-2 acid two (2-hexyl decyl) ester and thio-2 acid list (2-hexyl decyl) ester
A5: the mixture (A1: A2=95: 5) of thio-2 acid two (2-hexyl decyl) ester and thio-2 acid list (2-hexyl decyl) ester
A6: the mixture (A1: A2=85: 15) of thio-2 acid two (2-hexyl decyl) ester and thio-2 acid list (2-hexyl decyl) ester
A7: the mixture (A1: A2=75: 25) of thio-2 acid two (2-hexyl decyl) ester and thio-2 acid list (2-hexyl decyl) ester
And, in table 1 ~ 4, be expressed as ester admixture A1A2 simply by containing thioester compound (A1) and the ester admixture containing thioester compound (A2).
(modified silicone (B))
B1: amino modified silicone (25 DEG C of viscosity: 1300mm 2/ s, amino equivalent: 2000g/mol, modification type: diamines)
B2: amino modified silicone (25 DEG C of viscosity: 4500mm 2/ s, amino equivalent: 1000g/mol, modification type: diamines)
B3: amino modified silicone (25 DEG C of viscosity: 120mm 2/ s, amino equivalent: 5000g/mol, modification type: monoamine)
(ester compounds (C))
C1: the dilauryl ester of oxirane 2 moles of addition products of bisphenol-A
C2: the mixture (weight ratio of diester and monoesters is 95: 5) of thio-2 acid two (n-octyl) ester and thio-2 acid list (n-octyl) ester
C3: the mixture (weight ratio of diester and monoesters is 95: 5) of thio-2 acid two oil base ester and thio-2 acid list oil base ester
C4: thio-2 acid two (n-octyl) ester
C5: thio-2 acid two oil base ester
C6: thio-2 acid list (2-hexyl decyl) ester
[table 1]
[table 2]
[table 3]
[table 4]
As shown in table 1 ~ 4, interfibrous melting adhesion can be taken into account with the carbon fiber that the precursor finishing agent of embodiment processes to prevent and stable operability, in addition, the broken string of fiber, the generation of fine hair can also be suppressed, also can obtain very good result for carbon fiber strength.
And it is known on the other hand, the carbon fiber processed with the precursor finishing agent of comparative example is sometimes as shown in comparative example 1, although carbon fiber strength is comparatively good, but produce roller pollution, cannot obtain stable operability, or as shown in comparative example 2,3,5, fiber metal friction is high, scratch resistance worsens, and carbon fiber strength is poor.Particularly in comparative example 2,5, because average grain diameter is bigger, finishing agent therefore cannot be made to be attached to equably on fiber, can think the performance that cannot play finishing agent.In addition, the ester composition coking of comparative example 4,6,7, produces the melting adhesion of a lot of fiber, causes the result of carbon fiber strength difference.Particularly rub between Fiber-Fiber in comparative example 7 step-down, produces convergence not enough, can think the performance that cannot play finishing agent.
Utilizability in industry
The finishing agent that carbon fiber manufacture acrylic fiber finishing agent of the present invention uses when being and manufacturing carbon fiber manufacture acrylic fiber, useful for the high-grade carbon fiber of manufacture.Carbon fiber manufacture acrylic fiber of the present invention is by with finishing agent process of the present invention, useful for the high-grade carbon fiber of manufacture.Utilize the manufacture method of carbon fiber of the present invention, high-grade carbon fiber can be obtained.
The explanation of symbol
1 tension draftomter
2 deflector rolls
3 loads
4 carbon fiber bundles

Claims (11)

1. a carbon fiber manufacture acrylic fiber finishing agent, its contain with following general formula (1) represent containing thioester compound (A1), surfactant and water,
Also contain thioester compound (A2) containing what represent with following general formula (2),
R 2OOC-(CH 2) n-S-(CH 2) m-COOR 1(1)
In formula, m and n is the integer of 1 ~ 4 independently of one another, R 1and R 2be the alkyl of carbon number 12 ~ 16 independently of one another,
R 3OOC-(CH 2) n-S-(CH 2) m-COOH(2)
In formula, m and n is the integer of 1 ~ 4 independently of one another, R 3for the alkyl of carbon number 12 ~ 16.
2. finishing agent according to claim 1, wherein,
Described is 99.9/0.1 ~ 50/50 containing thioester compound (A1) and the described weight ratio (A1/A2) containing thioester compound (A2).
3. finishing agent according to claim 1 and 2, wherein,
The part by weight containing thioester compound (A1) and the described total containing thioester compound (A2) described in shared in the nonvolatile component of finishing agent is 30 ~ 98.9 % by weight, and the part by weight of described surfactant is 1 ~ 40 % by weight.
4. finishing agent according to claim 1 and 2, wherein,
Also containing modified silicone (B), it has the modification base comprising nitrogen-atoms.
5. finishing agent according to claim 4, wherein,
Described containing thioester compound (A1) and described be 99.9/0.1 ~ 50/50 containing the total of thioester compound (A2) and weight ratio (the A1+A2)/B of described modified silicone (B).
6. finishing agent according to claim 4, wherein,
Described modified silicone (B) is amino modified silicone.
7. finishing agent according to claim 5, wherein,
Described modified silicone (B) is amino modified silicone.
8. finishing agent according to claim 1 and 2,
It forms the emulsion be scattered in water.
9. a carbon fiber manufacture acrylic fiber, its for make the finishing agent according to any one of claim 1 ~ 8 be attached to carbon fiber manufacture acrylic fiber raw material propylene acid fiber on throwing and obtaining.
10. a manufacture method for carbon fiber manufacture acrylic fiber, it comprise make the finishing agent according to any one of claim 1 ~ 8 be attached to carbon fiber manufacture acrylic fiber raw material propylene acid fiber on and the silk producing procedures of throwing.
The manufacture method of 11. 1 kinds of carbon fibers, it comprises:
Silk producing procedures, makes the finishing agent according to any one of claim 1 ~ 8 be attached on the raw material propylene acid fiber of carbon fiber manufacture acrylic fiber, by carbon fiber manufacture acrylic fiber throwing;
Flame treatment operation, changes the carbon fiber manufacture acrylic fiber manufactured in this silk producing procedures into fire resistance fibre in the oxidizing atmosphere of 200 ~ 300 DEG C; With
Carbonization treatment operation, makes the carbonization in the torpescence atmosphere of 300 ~ 2000 DEG C further of described fire resistance fibre.
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