KR20190119063A - Acrylic Fiber Treatment Agents And Their Uses - Google Patents

Abstract

When the acrylic fiber for producing carbon fiber prepared by applying a treating agent is stored for a long time, an acrylic fiber treating agent capable of suppressing deterioration of the acrylic fiber for producing carbon fiber, an acrylic fiber for producing carbon fiber using the treating agent, and a carbon fiber using the treating agent It provides a method for producing. The acrylic fiber processing agent of this invention contains an amino modified silicone (A), Bronsted acid compound (B), and an acetylene type surfactant (C). The acrylic fiber for carbon fiber manufacture of this invention attaches the acrylic fiber processing agent of this invention to the raw material acrylic fiber of the acrylic fiber for carbon fiber manufacture.

Description

Acrylic Fiber Treatment Agents And Their Uses

This invention relates to an acrylic fiber processing agent and its use. In more detail, the processing agent used when manufacturing an acrylic fiber, the acrylic fiber for carbon fiber manufacture using the said processing agent (henceforth a precursor), and the manufacturing method of the carbon fiber using the said processing agent will be.

Carbon fiber is widely used for aerospace, sports, general industrial use, and the like as a reinforcing fiber for composite materials with plastics called matrix resins by utilizing its excellent mechanical properties.

As a method of manufacturing carbon fiber, first, acrylic fiber (also called a precursor) for carbon fiber production is manufactured (the manufacturing process of this precursor is also called a weaving process). The precursor is converted into a flame resistant fiber in an oxidizing atmosphere of 200 to 300 ° C (hereinafter, also referred to as a flameproofing step), followed by carbonization in an inert atmosphere of 300 to 2,000 ° C. (This step is hereinafter also referred to as a carbonization treatment step.) A method is generally used (hereinafter also referred to as a calcination step in which the flameproof treatment step and the carbonization treatment step are combined). In the production of this precursor, the stretching step is performed at a high magnification even when compared with normal acrylic fibers. In that case, it becomes easy to produce the crosslinking of fibers, and since high magnification extending | stretching is not performed uniformly, it becomes a nonuniform precursor. The carbon fiber obtained by baking such a precursor has a problem that sufficient strength cannot be obtained. Moreover, at the time of baking of a precursor, fusion of short fibers generate | occur | produces, and there exists a problem of reducing the quality and quality of the obtained carbon fiber.

As a treatment agent applied to the precursor for preventing the sticking of the precursor and preventing the fusion of the carbon fibers, a silicone-based treatment agent having a low friction between the fibers and fibers and excellent peeling property, especially due to heat, when wet and under a high temperature environment. Numerous techniques have been proposed to impart an amino-modified silicone treatment agent capable of further improving heat resistance by a crosslinking reaction to a precursor (see Patent Documents 1 and 2).

When the precursor prepared by applying such a treatment agent is stored for a long time, there is a problem of deterioration of the precursor over time. For this reason, when carbon fiber is manufactured by baking the precursor preserve | saved for a long time, there existed a problem, such as fluff generate | occur | produced in the baking process and the carbon fiber strength after baking falls.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-172879 Patent Document 2: Japanese Patent Application Laid-Open No. 2002-129481

In view of such a conventional technical background, an object of the present invention is to provide an acrylic fiber treatment agent capable of suppressing deterioration of acrylic fiber for carbon fiber production when the acrylic fiber for carbon fiber production produced by imparting a treatment agent is stored for a long time. It is providing the manufacturing method of the carbon fiber which used the acrylic fiber for carbon fiber manufacture which used, and the said processing agent.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, when the long term storage of the precursor manufactured by giving a process agent was carried out, the present inventors attributed to the amino group of the amino modified silicone contained in a process agent, and amino modification. It has been found that the penetration of the emulsifier used to emulsify silicone into the fiber is caused. And when amino modified silicone (A), Bronsted acid compound (B), and an acetylene surfactant (C) are used together, deterioration of the precursor resulting from deterioration of the precursor resulting from an amino group, and penetration of the emulsifier into the fiber inside It was found that it can be suppressed, the present invention was reached.

In other words. The acrylic fiber processing agent of this invention contains an amino modified silicone (A), Bronsted acid compound (B), and an acetylene type surfactant (C).

It is preferable that the ratio of Bronsted-acid compound (B) is 0.01-2.5 mol equivalent with respect to 1 mol of amino groups of the said amino modified silicone (A).

It is preferable that the ratio of the said acetylene type surfactant (C) is 0.1-12 weight part with respect to 100 weight part of said amino modified silicone (A).

The acetylene surfactant (C) is selected from acetylene alcohol (C1), acetylene diol (C2), a compound (C3) to which alkylene oxide is added to acetylene alcohol, and a compound (C4) to which alkylene oxide is added to acetylene diol. It is preferable that it is at least 1 sort.

It is preferable that the said acetylene alcohol (C1) is a compound represented by following General formula (1). It is preferable that the said acetylene diol (C2) is a compound represented by following General formula (2). It is preferable that the compound (C3) which added the alkylene oxide to the said acetylene alcohol is a compound represented by following General formula (3). It is preferable that the compound (C4) which added the alkylene oxide to the said acetylene diol is a compound represented by following General formula (4).

[Formula 1]

(In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms.)

[Formula 2]

(In Formula (2), R <^3> , R <^4> , R <^5> and R <^6> are respectively independently and a C1-C8 alkyl group.)

[Formula 3]

(In formula (3), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms. R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. AO is an oxyalkylene group having 2 to 4 carbon atoms. N is a number from 1 to 50.

[Formula 4]

(In formula (4), R <^3> , R <^4> , R <^5> and R <^6> are respectively independently and a C1-C8 alkyl group. R <^7> is a hydrogen atom or a C1-C5 alkyl group. ) is a plurality of R ⁷ may be the same or different from. AO represents an oxyalkylene group of a carbon number of 2 ~ 4. m, n are each independently a number from 1 to 50.)

It is preferable that the weight ratio of the said amino modified silicone (A) to the non volatile matter of a processing agent is 40 to 95 weight%.

It is preferable that the processing agent for acrylic fibers of this invention contains a polyoxyalkylene alkyl ether (D) further.

It is preferable that the said polyoxyalkylene alkyl ether (D) contains the compound represented by following General formula (5).

[Formula 5]

(In General Formula (5), R ⁸ represents an alkyl group having 6 to 22 carbon atoms. AO represents an oxyalkylene group having 2 to 4 carbon atoms. J is each independently a number of 1 to 50.)

It is preferable that the ratio of the sum total of the said acetylene type surfactant (C) and the said polyoxyalkylene alkyl ether (D) with respect to 100 weight part of said amino modified silicones (A) is 5-50 weight part.

The acrylic fiber for carbon fiber manufacture of this invention attaches the said acrylic fiber processing agent to the raw material acrylic fiber of the acrylic fiber for carbon fiber manufacture.

The manufacturing method of the carbon fiber of this invention is a manufacturing process which affixes and manufactures the said fiber processing agent to the raw material acrylic fiber of the acrylic fiber for carbon fiber manufacture, and flameproofing process which switches to flame-resistant fiber in the oxidizing atmosphere of 200-300 degreeC. Process and the carbonization treatment process which carbonizes the said flame resistant fiber further in inert atmosphere of 300-2,000 degreeC.

The acrylic fiber processing agent of this invention can suppress deterioration of the acrylic fiber for carbon fiber manufacture, when storing the acrylic fiber for carbon fiber manufacture manufactured by providing a processing agent for a long time. When the acrylic fiber for carbon fiber production of this invention is used, even if it uses the acrylic fiber bundle preserve | saved for a long time, generation | occurrence | production of fluff in a baking process can be suppressed and a high strength and high quality carbon fiber can be obtained. According to the manufacturing method of the carbon fiber of this invention, even if it uses the acrylic fiber bundle preserve | saved for a long time, generation | occurrence | production of fluff in a baking process can be suppressed and a high strength and high quality carbon fiber can be obtained.

(Amino modified silicone (A))

The treatment agent of the present invention essentially contains an amino modified silicone (A). The amino group (including the organic group having an amino group), which is a modified group of the amino-modified silicone, may be bonded to the side chain of the main silicone, may be bonded to the terminal, or may be bonded to both. From the viewpoint of fiber protection in the treatment step, it is more preferable to be bonded to the side chain (having an amino group in the side chain). In addition, the amino group may be any of monoamine type, diamine type, and polyamine type, and both may coexist in one molecule. However, the treating agent is uniformly applied to the inside of the fiber bundle in the flameproofing treatment step, and the treating agent is further added. In view of protecting the fibers by forming a film, a monoamine type or a diamine type is preferable. The amino modified silicone (A) may be used singly or in combination of two or more kinds thereof.

As for the kinematic viscosity in 25 degreeC of an amino modified silicone (A), 50-30,000 mm <^2> / s is preferable from a viewpoint of exhibiting this effect. When the kinematic viscosity is less than 50 mm ² / s, the treatment agent may easily scatter, and the aqueous solution may have poor solution stability when emulsified in water, and the treatment agent may not be uniformly applied to the fibers. As a result, fusion of fibers may not be prevented. When kinematic viscosity exceeds 30,000 mm <^2> / s, gum up resulting from adhesiveness may become a problem. The upper limit of the kinematic viscosity is ^{25,000mm 2 / s, 20,000mm 2 /} s, 10,000mm 2 / s, 5,000mm 2 / s, 4,000mm 2 / s, 3,000mm 2 / s, 2,500mm in order preferably to the ² / s Do.

As for the amino equivalent of amino-modified silicone (A), 300-10,000 g / mol is preferable, 500-10,000 g / mol is more preferable, and 1,000-1,000 g / mol from a viewpoint of preventing the interlocking and fusion between fibers. This is more preferable. When the amino equivalent is less than 300 g / mol, the treating agent may not be uniformly applied to the inside of the fiber bundle because the treating agent is thermally crosslinked at the initial stage of the flameproof treatment step. Moreover, when the said amino equivalent weight is 10,000 g / mol or more, fiber protection may not be performed because heat crosslinking of a processing agent does not occur in the latter stage of a flameproofing process. Here, amino equivalent means the mass of the siloxane skeleton per amino group or ammonium group. G / mol of a marking unit is the value converted into 1 mol of amino groups or ammonium groups. Therefore, the smaller the value of amino equivalent, the higher the proportion of amino group or ammonium group in the molecule.

An amino modified silicone (A) may use together several amino modified silicone in which an amino equivalent and kinematic viscosity (25 degreeC) differ. When two or more amino modified silicones are used, the amino equivalents refer to amino equivalents of the entire amino modified silicone (mixture), and the kinematic viscosity at 25 ° C refers to the kinematic viscosity of the entire amino modified silicone (mixture).

As said amino modified silicone, the compound represented by following General formula (6) is mentioned, for example.

[Formula 6]

(In formula (6), R ⁹ represents an alkyl group or an aryl group having 1 to 20 carbon atoms. R ¹⁰ is a group represented by the following formula (7). R ¹¹ is R ⁹ , R ¹⁰ or —OR ¹⁷ (R ¹⁷ Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, p is 10 ≦ p ≦ 10,000, and q is 0.1 ≦ q ≦ 1,000.)

In Formula (6), R <^9> represents a C1-C20 alkyl group or aryl group. R ⁹ is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group. In addition, some R <^9> in Formula (6) may be same or different. R <^10> is group represented by following General formula (7). R11 is a group represented by R ⁹ , R ¹⁰ or -OR ¹⁷ , preferably R ⁹ . In addition, some R <^11> in Formula (6) may be same or different.

R ¹⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group. p is a number of 10-10,000, Preferably it is 50-5,000, More preferably, it is 100-2,000. q is a number of 0.1-1,000, Preferably it is 0.5-500, More preferably, it is 1-100.

[Formula 7]

In Formula (7), R <^12> and R <^14> is respectively independently, a C1-C6 alkylene group, Preferably it is a C1-C3 alkylene group. R ¹³ , R ¹⁵ and R ¹⁶ are each independently, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom. r is a number of 0-6, Preferably it is 0-3, More preferably, it is 0-1.

(Brooked Acid Compound (B))

The fiber treating agent of the present invention essentially contains the Bronsted Acid Compound (B). When Bronsted acid (B) is not used, even when the acetylene-based surfactant (C) which is an essential component is used, it is not possible to suppress the crosslinking with time due to the amino group of the amino-modified silicone. The Bronsted Acid Compound (B) refers to a proton donor, and examples thereof include a carboxylic acid compound, an inorganic acid, a sulfonic acid compound, and a phosphonic acid compound. Bronsted acid compound (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

A carboxylic acid compound refers to the compound containing a carboxyl group in molecular structure. Although there is no limitation in particular as a carboxylic acid compound, Aliphatic monocarboxylic acid, aliphatic polycarboxylic acid, aromatic carboxylic acid, aromatic polycarboxylic acid, an amino acid, etc. are mentioned.

Examples of the aliphatic monocarboxylic acids include acetic acid, lactic acid, butanoic acid, crotonic acid, citric acid, caproic acid, enanthic acid, caprylic acid, pelagonic acid, capric acid, lauric acid, myristic acid, myristic acid and penta. Decanoic acid, palmitic acid, palmitoleic acid, isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elideic acid, bacenic acid, linoleic acid, linolenic acid, arachidic acid, isoeic acid, gadolic acid, eicosane Sen acid, docoic acid, isodocoic acid, erucic acid, tetracoic acid, isotetracoic acid, nerbonic acid, sertinic acid, montanic acid, melic acid, polyoxyalkylene monocarboxylic acid, polyoxyalkylene alkyl ether monocar Main acid etc. are mentioned.

As the aliphatic polycarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suveric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetra Decanedioic acid, pentadecanedioic acid, polyoxyalkylene dicarboxylic acid, polyoxyalkylene alkyl ether dicarboxylic acid, and derivatives thereof are mentioned.

Examples of the aromatic monocarboxylic acid include benzoic acid, cinnamic acid, naphthoic acid, toluic acid, and derivatives thereof.

Examples of the aromatic polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, and derivatives thereof.

An amino acid is a compound which has both an amino group and a carboxyl group in a molecular structure, and alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, methionine, proline, glycine, tyrosine, serine, threonine, cysteine, asparagine, glutamine, lysine, and arginine , Histidine, aspartic acid, glutamic acid and the like.

An inorganic acid refers to the acid which has a nonmetallic atom as a component. Examples of the inorganic acid include sulfuric acid, nitric acid, phosphoric acid and hydrochloric acid.

Examples of the sulfonic acid compound include alkylbenzene sulfonic acid, polyoxyalkylene alkyl ether sulfonic acid, higher fatty acid amide sulfonic acid, alkyl sulfate monoester, polyoxyalkylene sulfate monoester, and the like.

Examples of the phosphonic acid compound include alkyl phosphonic acid, aromatic phosphonic acid, polyoxyalkylene alkyl ether phosphonic acid, alkyl phosphonic acid alkyl phosphonic acid monoester and the like.

The pKa of the Bronsted Compound (B) is preferably 0 to 7, more preferably 1 to 6.5, from the viewpoint of corrosion and safety of the equipment and the suppression of crosslinking over time due to the amino group of the amino-modified silicone. , 2 to 6 are more preferable.

(Acetylene-based surfactant (C))

The acrylic fiber processing agent of this invention contains an acetylene type surfactant (C) as essential. By using together a Bronsted acid compound (B) and an acetylene type surfactant (C) with respect to an amino modified silicone, water-based emulsification of amino modified silicone and suppression of the crosslinking | temporality resulting from the amino group of an amino modified silicone can be carried out. It is estimated that the emulsifier at the time can be suppressed from penetrating into the fiber structure, and as a result, the degradation of the precursor fiber when the precursor fiber is stored for a long time can be suppressed. Even when an acetylene-based surfactant (C) is used and another surfactant is used, even when the bransted acid compound (B) is used, the penetration of the emulsifier into the fiber structure is not suppressed, and as a result, the precursor fiber It is guessed that the strength will fall when carbon fiber is manufactured using the precursor fiber at the time of storing it for a long time. In addition, an acetylene surfactant refers to the compound which has hydrophilic groups, such as an acetylene group and a hydroxyl group, in a molecular structure. An acetylene type surfactant (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

The acetylene-based surfactant (C) is selected from acetylene alcohol (C1), acetylene diol (C2), compound (C3) in which alkylene oxide is added to acetylene alcohol, and compound (C4) in which alkylene oxide is added to acetylene diol. It is preferable that it is at least 1 sort. Among these, compound (C3) which added alkylene oxide to acetylene alcohol, and compound (C4) which added alkylene oxide to acetylene diol are preferable, and compound (C4) which added alkylene oxide to acetylene diol is more preferable. .

Acetylene alcohol (C1) is a compound which has an acetylene group and one hydroxyl group in molecular structure.

It is preferable that acetylene alcohol (C1) is a compound represented by the said General formula (1).

Acetylenediol (C2) is a compound which has an acetylene group and two hydroxyl groups in molecular structure.

It is preferable that acetylene diol (C2) is a compound represented by the said General formula (2).

The compound (C3) which added the alkylene oxide to acetylene alcohol is a compound which added the alkylene oxide to the hydroxyl group of acetylene alcohol.

It is preferable that the compound (C3) which added the alkylene oxide to acetylene alcohol is a compound represented by the said General formula (3).

The compound (C4) which added the alkylene oxide to acetylene diol is a compound which added the alkylene oxide to at least one hydroxyl group of acetylene diol.

It is preferable that the compound (C4) which added the alkylene oxide to acetylene diol is a compound represented by the said General formula (4).

In formula (1) and formula (3), R <^1> and R <^2> is respectively independently and is a C1-C8 alkyl group. The alkyl group may be linear or may have a branched structure. Carbon number of the said alkyl group becomes like this. Preferably it is 1-7, More preferably, it is 1-6, More preferably, it is 1-5.

In formula (2) and (4), R <^3> , R <^4> , R <^5> and R <^6> are respectively independently and a C1-C8 alkyl group. The alkyl group may be linear or may have a branched structure. Carbon number of the said alkyl group becomes like this. Preferably it is 1-7, More preferably, it is 1-6, More preferably, it is 1-5.

In formula (3) and formula (4), R <^7> is a hydrogen atom or a C1-C5 alkyl group. Carbon number of the said alkyl group becomes like this. Preferably it is 1-4, More preferably, it is 1-3, More preferably, it is 1-2.

In Formulas (3) and (4), AO represents an oxyalkylene group having 2 to 4 carbon atoms. That is, an oxyethylene group, an oxypropylene group, or an oxybutylene group is represented. As an oxyalkylene group, an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is more preferable. 1 type may be sufficient as AO which comprises (AO) _n or (AO) _m , and 2 or more types may be sufficient as it. In the case of two or more kinds, any of a block adduct, an alternating adduct, and a random adduct may be used.

In formula (3), n is a number of 1-50. 1-45 are preferable, as for n, 1-40 are more preferable, and 1-35 are more preferable.

In formula (4), m and n are each independent and a number of 1-50. m and n are each independently, 1-45 are preferable, 1-40 are more preferable, and 1-35 are more preferable.

4-25 are preferable from a viewpoint of emulsification, 5-20 are more preferable, and, as for HLB of an acetylene type surfactant (C), 6-18 are more preferable. HLB in this invention can be experimentally calculated | required by the Atlas method by Griffin et al.

An acetylene surfactant (C) is a well-known compound, and can be easily manufactured by a well-known method. For example, such a compound can be obtained by a method of reacting a ketone or an aldehyde with acetylene in the presence of a catalyst such as an alkali or a metal compound under pressure, called a repe reaction.

In addition, the compound (C3) or the compound (C4) is an alkylene oxide (for example, ethylene oxide and / or propylene oxide) to acetylene alcohol (C1) or acetylene diol (C2), respectively, as a catalyst such as an alkali or a metal compound. It can be obtained by addition polymerization in the presence of.

[Acrylic Fiber Treatment Agent]

The processing agent for acrylic fibers of this invention contains the said amino modified silicone (A), Bronsted acid compound (B), and an acetylene type surfactant (C).

The weight ratio of amino-modified silicone (A) in the nonvolatile content of the treatment agent is preferably 40 to 95% by weight, more preferably 45 to 94% by weight, still more preferably 50 to 92% by weight, particularly preferably 55 to 90% by weight. When the said weight ratio is less than 40 weight%, the heat resistance of a processing agent may be insufficient in a salt-proofing process. On the other hand, when the said weight ratio is more than 95 weight%, a stable aqueous emulsion may not be obtained when the processing agent is emulsified aqueously.

The weight ratio of the acetylene-based surfactant (C) to the nonvolatile content of the treatment agent is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight, still more preferably 0.3 to 13% by weight, particularly preferably Is 0.5 to 10% by weight. When the said weight ratio is less than 0.1 weight%, the penetration of an emulsifier into the fiber structure inside may not be suppressed. On the other hand, when the said weight ratio is more than 20 weight%, stable operation property may not be obtained.

From the viewpoint of achieving both stable operation and storage stability of the precursor, the ratio of the acetylene-based surfactant (C) is preferably 0.1 to 12 parts by weight with respect to 100 parts by weight of the amino modified silicone (A). The said ratio becomes like this. Preferably it is 0.2-11 weight part, More preferably, it is 0.2-10 weight part, More preferably, it is 0.5-8 weight part. When the said ratio is less than 0.1 weight part, penetration of an emulsifier into the fiber structure inside may not be suppressed. On the other hand, when the said ratio is more than 12 weight part, stable operation property may not be acquired.

It is preferable that the ratio of Bronsted acid compound (B) is 0.01-2.5 mol equivalent with respect to 1 mol of amino groups of an amino-modified silicone (A) from a viewpoint of suppressing crosslinking with time resulting from the amino group of amino-modified silicone. Do. The ratio is preferably 0.05 to 2.25 molar equivalents, more preferably 0.1 to 2.0 molar equivalents, still more preferably 0.12 to 1.5 molar equivalents. When the said ratio is less than 0.01 equivalent, the suppression of crosslinking with time resulting from the amino group of amino modified silicone may not be performed. On the other hand, when the said ratio is more than 2.5 equivalent, gum up may be promoted in a process and stable operation property may not be obtained.

(Polyoxyalkylene Alkyl Ether (D))

It is preferable that the processing agent of this invention contains a polyoxyalkylene alkyl ether (D) from a viewpoint which can improve emulsification property. And polyoxyalkylene alkyl ether is a compound which has a structure which the alkylene oxide added to the saturated aliphatic alcohol, In said General formula (5), R <^8> is an alkyl group and AO is a C2-C4 oxyalkylene group, j is a number of 1 or more. Polyoxyalkylene alkyl ether (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

As polyoxyalkylene alkyl ether, For example, polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, Polyoxyalkylene straight chain alkyl ethers such as polyoxyethylene tetradecyl ether and polyoxyethylene cetyl ether; Polyoxyalkylene branched primary alkyl ethers such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether and polyoxyethylene isostearyl ether; Polyoxyethylene 1-hexylhexyl ether, polyoxyethylene 1-octylhexyl ether, polyoxyethylene 1-hexyl octyl ether, polyoxyethylene 1-pentylheptyl ether, polyoxyethylene 1-heptylpentyl ether, polyoxyethylene 1 And polyoxyalkylene branched secondary alkyl ethers such as -hexylheptyl ether, polyoxyethylene 1-heptyl hexyl ether, polyoxyethylene 1-pentyl captyl ether, and polyoxyethylene 1-captylpentyl ether. .

It is preferable that a polyoxyalkylene alkyl ether (D) essentially contains the compound represented by the said General formula (5) from a viewpoint of exhibiting this effect. In General formula (5), R <^8> is a C6-C22 alkyl group. When R ⁸ is a hydrocarbon group other than an alkyl group and the carbon number of R ⁸ is more than 22, a disadvantage in converting the precursor into the flame resistant structure is that the polyoxyalkylene alkyl ether is tarized in the flameproofing process. This may cause a decrease in strength of the carbon fiber. On the other hand, when carbon number of R <^8> is less than 6, the solution stability of the emulsion at the time of water-emulsifying a processing agent may deteriorate. 8-20 are preferable, as for carbon number of R <^8> , 10-18 are more preferable, and 10-16 are more preferable. There may be distribution in carbon number of R <^8> , and R <^8> may be linear or may have a branch.

A represents a C2-C4 alkylene group and AO represents an oxyalkylene group. That is, an oxyethylene group, an oxypropylene group, or an oxybutylene group is represented. As an oxyalkylene group, an oxyethylene group and an oxypropylene group are preferable, and an oxyethylene group is more preferable. J which is the repeating number of an oxyalkylene group is the number of 1-50, 2-40 are preferable and 3-30 are more preferable. When n is more than 30, when used together with the amino-modified silicone, fusion may occur because the treatment agent cannot be uniformly applied to the inside of the fiber bundle in the flameproofing treatment step. As AO which comprises polyoxyalkylene group (AO) _j , 1 type may be sufficient and 2 or more types may be sufficient as it. In the case of two or more kinds, any of a block adduct, an alternating adduct, and a random adduct may be used. J of AO is the added mole number of an oxyalkylene group.

When a processing agent contains a polyoxyalkylene alkyl ether (D), it is preferable that the weight ratio of the polyoxyalkylene alkyl ether (D) which occupies for the non volatile matter of a processing agent is 2-25 weight%, and it is 5-20 weight % Is more preferable, and 10-20 weight% is further more preferable. When the said weight ratio is less than 2 weight%, a stable aqueous emulsion may not be obtained when water-emulsifying a processing agent. On the other hand, when the said weight ratio is more than 25 weight%, the heat resistance of a processing agent may be insufficient in a salt-proofing process.

From the viewpoint of improving the long-term storage stability of the precursor, the ratio of the total of the acetylene-based surfactant (C) and the polyoxyalkylene alkyl ether (D) is 5 to 50 parts by weight based on 100 parts by weight of the amino modified silicone (A). It is preferable. When the said ratio is less than 5 weight part, emulsion stability may worsen. On the other hand, when the said weight part is more than 50 weight part, stable operation property may not be obtained.

(Other surfactant)

The acrylic fiber processing agent of this invention may contain surfactant other than the said acetylene type surfactant (C) and polyoxyalkylene alkyl ether (D) in the range which does not impair the effect of this invention. Surfactant is used as an emulsifier, an antistatic agent, etc. There is no restriction | limiting in particular as surfactant, Nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant other than the said acetylene type surfactant (C) and polyoxyalkylene alkyl ether (D) A well-known thing can be suitably selected and used from the. 1 type may be sufficient as surfactant and it may use 2 or more types together.

As nonionic surfactants other than the said acetylene type surfactant (C) and polyoxyalkylene alkyl ether (D), For example, Polyoxyalkylene alkenyl ether, such as polyoxyethylene oleyl ether; Polyoxyalkylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and polyoxyethylene dodecylphenyl ether; Poly such as polyoxyethylene tristyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene benzyl phenyl ether Oxyalkylene alkylaryl phenyl ether; Polyoxyethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristylate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxyethylene dimyrilate, Polyoxyalkylene fatty acid esters such as polyoxyethylene distearate; Sorbitan esters such as sorbitan monopalmitate and sorbitan monooleate; Polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; Glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, and glycerin monopalmitate; Polyoxyalkylene sorbitol fatty acid esters; Sucrose fatty acid esters; Polyoxyalkylene castor oil ethers such as polyoxyethylene castor oil ether; Polyoxyalkylene hardened castor oil ethers such as polyoxyethylene hardened castor oil ether; Oxyethylene-oxypropylene block or random copolymer; Terminal sucrose etherates of oxyethylene-oxypropylene blocks or random copolymers; Etc. can be mentioned. 2,000 or less are preferable, as for the weight average molecular weight of a nonionic surfactant, 200-1,800 are more preferable, 300-1,500 are more preferable, 500-1,000 are still more preferable.

As anionic surfactant, For example, Fatty acid salts, such as a sodium oleate salt, a palmitic-acid potassium salt, and a oleic acid triethanol amine salt; Hydroxyl group-containing carboxylates such as hydroxy potassium acetate and potassium lactate salt; Polyoxyalkylene alkyl ether acetates such as polyoxyethylene tridecyl ether sodium acetate; Salts of carboxyl group polysubstituted aromatic compounds such as potassium trimellitate and potassium pyromellitate; Alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate; Polyoxyalkylene alkyl ether sulfonates such as polyoxyethylene 2-ethylhexyl ether sulfonic acid potassium salt; Higher fatty acid amide sulfonates such as sodium stearoyl methyl taurine, sodium lauroyl methyl taurine, sodium myristic yl taurine, and sodium palmitoylmethyl taurine; N-acyl sarcosinates, such as sodium lauroyl sarcosinate; Alkyl phosphonates, such as an octyl phosphonate potassium salt; Aromatic phosphonates such as phenyl phosphonate potassium salt; Alkyl phosphonic acid alkyl phosphate ester salts such as 2-ethylhexyl phosphonate mono2-ethylhexyl ester potassium salt; Nitrogen-containing alkyl phosphonates such as aminoethylphosphonic acid diethanolamine salts; Alkyl sulfate ester salts, such as 2-ethylhexyl sulfate sodium salt; Polyoxyalkylene sulfate ester salts such as polyoxyethylene 2-ethylhexyl ether sulfate sodium salt; Long-chain sulfosuccinates such as sodium di-2-ethylhexylsulfosuccinate, sodium dioctylsulfosuccinate, monosodium N-lauroyl glutamate, and disodium N-stearoyl-L-glutamate -Acyl glutamate, etc. are mentioned.

As the cationic surfactant, for example, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride, palmityltrimethylammonium chloride, stearyltrimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride , Palm oil alkyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, palm oil alkyltrimethylammonium bromide, cetyltrimethylammonium sulfate, oleyldimethylethylammonium sulfate, dioctyldimethylammonium Alkyl quaternary ammonium salts such as chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride and octadecyldiethylmethylammonium sulfate; (Polyoxyethylene) lauryl amino ether lactate, stearylamino ether lactate, di (polyoxyethylene) lauryl methyl amino ether dimethyl phosphate, di (polyoxyethylene) lauryl ethyl ammonium sulphate, di (polyoxy (Polyoxyalkylene) alkylamino ether salts such as ethylene) cured tallow alkylethylamine acetate sulfate, di (polyoxyethylene) laurylmethylammonium dimethyl phosphate, di (polyoxyethylene) stearylamine lactate; N- (2-hydroxyethyl) -N, N-dimethyl-N-stearoylamide propyl ammonium nitrate, lanolin fatty acid amide propyl ethyl dimethyl ammonium sulfate, lauroyl amide ethyl methyl diethyl ammonium methosulfate, etc. Acylamide alkyl quaternary ammonium salts; Alkylethenoxy quaternary ammonium salts such as dipalmityl polyethenoxyethylammonium chloride and distearylpolyethenoxymethylammonium chloride; Alkyl isoquinolinium salts such as lauryl isoquinolinium chloride; Benzaconium salts such as lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride; Benzetium salts such as benzyldimethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl} ammonium chloride; Pyridinium salts such as cetylpyridinium chloride; Imidazolinium salts, such as oleyl hydroxyethyl imidazolinium eosulfate and lauryl hydroxyethyl imidazolinium eosulfate; Acyl basic amino acid alkyl ester salts such as N-cocoyl arginine ethyl ester pyrrolidone carbonate and N-laurolysine ethyl ethyl ester chloride; Primary amine salts such as laurylamine chloride, stearylamine bromide, cured tallow alkylamine chloride and rosin amine acetate; Secondary amine salts such as cetylmethylamine sulfate, laurylmethylamine chloride, dilaurylamine acetate, stearylethylamine bromide, laurylpropylamine acetate, dioctylamine chloride and octadecylethylamine hydrooxide; Dilaurylmethylamine sulfate, lauryldiethylamine chloride, laurylethylmethylamine bromide, diethanol stearylamide ethylamine trihydroxyethyl phosphate salt, stearylamide ethyl ethanolamine urea polycondensate acetate salt Tertiary amine salts such as these; Fatty acid amideguanidinium salts; Alkyl trialkylene glycol ammonium salts, such as lauryl triethylene glycol ammonium hydrooxide, etc. are mentioned.

As the amphoteric surfactant, for example, 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxy Imidazoline type amphoteric surfactants such as ethyloxy disodium salt; Betaine-based amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine and sulfobetaine; And amino acid type amphoteric surfactants such as N-laurylglycine, N-lauryl β-alanine, and N-stearyl β-alanine.

(Other ingredients)

The acrylic fiber processing agent of this invention may contain other components other than the component mentioned above in the range which does not impair the effect of this invention. As another component, Antioxidants, such as an acidic phosphate ester, a phenol type, an amine type, a sulfur type, phosphorus type, a quinone type; Antistatic agents such as sulfate ester salts of higher alcohols and higher alcohol ethers, sulfonates, phosphate ester salts of higher alcohols and higher alcohol ethers, quaternary ammonium salt type cationic surfactants, and amine salt type cationic surfactants; Leveling agents such as alkyl esters of higher alcohols, higher alcohol ethers and wax types; Antibacterial agents; antiseptic; Rustproof agent; And a moisture absorbent.

Moreover, the processing agent of this invention may contain modified silicones other than said amino modified silicone in the range which does not impair the effect of this invention. Examples of the modified silicone include amino polyether modified silicone, amide modified silicone, amide polyether modified silicone, epoxy modified silicone, polyether modified silicone, epoxy polyether modified silicone (see, for example, Japanese Patent No. 4616934) Binol modified silicone, alkyl modified silicone, phenol modified silicone, methacrylate modified silicone, alkoxy modified silicone, fluorine modified silicone, etc. are mentioned, One type of modified silicone may be used, and several modified silicone may be used together.

The acrylic fiber treatment agent of the present invention is an amino-modified silicone (A), Bronsted acid compound (B) and an acetylene-based surfactant (C), if necessary, polyoxyalkylene alkyl ether (D) is dissolved in water, solubilized, It is preferably in an emulsified or dispersed state.

It does not specifically limit about the weight ratio of the water which occupies for the whole acrylic fiber processing agent, and the weight ratio of a non volatile matter. For example, what is necessary is just to determine suitably in consideration of the transport cost at the time of transporting the acrylic fiber processing agent of this invention, the handleability by emulsion viscosity, etc. 0.1-99.9 weight% is preferable, as for the weight ratio of the water to the whole acrylic fiber processing agent, 10-99.5 weight% is more preferable, 50-99 weight% is especially preferable. 0.01-99.9 weight% is preferable, as for the weight ratio (concentration) of the non volatile matter to the whole acrylic fiber processing agent, 0.5-90 weight% is more preferable, 1-50 weight% is especially preferable.

The acrylic fiber processing agent of this invention can be manufactured by mixing the above-mentioned component. It does not specifically limit about the method of emulsifying and disperse | distributing the above-mentioned component, A well-known method is employable. As such a method, for example, each component constituting the acrylic fiber treatment agent is added to hot water under stirring to disperse and emulsion, or each component constituting the acrylic fiber treatment agent is mixed, and a homogenizer and a homomixer are mixed. And a method of gradually injecting water while applying a mechanical shearing force using a ball mill or the like to phase-phase emulsification.

The acrylic fiber processing agent of this invention can be used suitably as a processing agent (precursor processing agent) of the acrylic fiber (precursor) for carbon fiber manufacture. You may use as a spinning oil agent of acrylic fiber other than a precursor.

From a viewpoint of providing the favorable fiber bundle focusing property in a precursor manufacturing process and a flameproofing process, as for the viscosity at 25 degrees C of the non volatile matter of the acrylic fiber processing agent of this invention, 10-50,000 mPa * s is preferable, The said viscosity When the ratio is less than 10 mPa · s, the bundle concentration of the fiber bundle may be deteriorated in the precursor weaving step or the flameproofing step. Moreover, when the said viscosity exceeds 50,000 mPa * s, even if it can provide favorable fiber bundle focusing property in a precursor manufacturing process and a flameproofing process, the viscosity of a processing agent may become high too much and the handleability of a processing agent may deteriorate. The said viscosity is preferable in order of 10-25,000 mPa * s, 10-15,000 mPa * s, 10-10,000 mPa * s, 10-5,000 mPa * s, and 50-1,000 mPa * s.

ACRYLIC FIBER FOR CARBON FIBER MANUFACTURE, THE MANUFACTURING METHOD AND THE MANUFACTURING METHOD OF CARBON FIBER

The acrylic fiber (precursor) for carbon fiber manufacture of this invention attaches and manufactures the above-mentioned acrylic fiber processing agent to the raw material acrylic fiber of a precursor, and is manufactured. The manufacturing method of the precursor of this invention includes the manufacturing process which affixes the above-mentioned acrylic fiber processing agent to the raw material acrylic fiber of a precursor, and is manufactured.

The manufacturing method of the carbon fiber of this invention attaches the acrylic fiber processing agent mentioned above to the raw material acrylic fiber of a precursor, and manufactures a precursor, and flame-proofs the precursor manufactured by the said manufacturing process in 200-300 degreeC oxidizing atmosphere. It comprises a carbonization treatment step of carbonizing the flame resistant treatment step of converting the fiber into an inert atmosphere at 300 to 2,000 ° C.

According to the manufacturing method of the carbon fiber of this invention, since the acrylic fiber processing agent of this invention is used, a processing agent can be uniformly provided from the initial stage of a flameproofing process to the inside of a fiber bundle, and a processing agent is mentioned later in a flameproofing process Since the film can be formed into a film to protect the fiber, fusion between the fibers and the occurrence of fluff can be suppressed and a high quality carbon fiber can be produced.

A weaving process is a process of sticking an acrylic fiber processing agent to the raw material acrylic fiber of a precursor, and manufacturing a precursor, and includes an adhesion process process and an extending process.

An adhesion treatment process is a process of sticking an acrylic fiber processing agent, after spinning the raw material acrylic fiber of a precursor. That is, an acrylic fiber processing agent is made to adhere to the raw material acrylic fiber of a precursor in an adhesion | attachment process. Moreover, although the raw material acrylic fiber of this precursor extends immediately after spinning, the high magnification extending | stretching after an adhesion treatment process is called especially a "stretching process." The stretching step may be a wet heat stretching method using high temperature steam or a dry heat stretching method using a heat roller.

The precursor is composed of acrylic fibers composed mainly of polyacrylonitrile obtained by copolymerizing at least 95 mol% or more of acrylonitrile and 5 mol% or less of a flameproofing promoting component. As a flameproofing promotion component, the vinyl group containing compound which has copolymerization property with respect to acrylonitrile can be used preferably. Although there is no limitation in particular about the short fiber fineness of a precursor, Preferably it is 0.1-2.0 dTex from the balance of a performance and manufacturing cost. Moreover, there is no restriction | limiting in particular also about the number of the short fibers which comprise the fiber bundle of precursor, In consideration of the balance of performance and manufacturing cost, Preferably it is 1,000-96,000 pieces.

The acrylic fiber treating agent may be attached to the raw material acrylic fiber of the precursor at any stage of the weaving step, but is preferably attached once before the stretching step. As long as it is a step before an extending process, you may adhere, for example immediately after spinning. Moreover, it may be made to adhere again at any stage after an extending process, for example, may be made to attach again immediately after an extending process, may be made to attach again at a winding stage, and may be made to attach again just before a flameproofing process. About the attachment method, you may adhere using a roller etc., and you may adhere by an immersion method, a spray method, etc.

In the adhesion treatment step, the provision rate of the acrylic fiber treatment agent is a balance between obtaining the anti-adhesion effect or the fusion prevention effect between the fibers and the fibers, and preventing the deterioration of the carbon fiber by the tar cargo of the treatment agent in the carbonization treatment process. In consideration, the weight of the precursor is preferably 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight. When the provision rate of the acrylic fiber treatment agent is less than 0.1% by weight, the interlocking and fusion between the short fibers cannot be sufficiently prevented, and the strength of the carbon fiber obtained may be lowered. On the other hand, when the provision rate of the acrylic fiber treatment agent exceeds 2% by weight, since the acrylic fiber treatment agent covers more than necessary between the short fibers, when the supply of oxygen to the fiber is hindered in the flameproofing treatment step, the strength of the carbon fiber obtained is lowered. There is. In addition, the provision rate of the acrylic fiber processing agent here is defined as the percentage of the weight of the attached non volatile matter of the acrylic fiber processing agent with respect to the precursor weight.

The flameproofing process is a process of converting the precursor with an acrylic fiber treatment agent into flameproof fiber in 200-300 degreeC oxidizing atmosphere. An oxidizing atmosphere should just be an air atmosphere normally. The temperature of an oxidative atmosphere becomes like this. Preferably it is 230-280 degreeC. In the flameproofing process, heat treatment is performed for 20 to 100 minutes (preferably 30 to 60 minutes) while applying a tension of the stretching ratio of 0.90 to 1.10 (preferably 0.95 to 1.05) to the acrylic fiber after the adhesion treatment. In this flameproofing process, flameproof fiber which has a flameproof structure is manufactured through molecular cyclization and oxygen addition to a ring.

The carbonization treatment step is a step of carbonizing the flame resistant fiber in an inert atmosphere at 300 to 2,000 ° C. In the carbonization process, first, a tension ratio of 0.95 to 1.15 is applied to the flame resistant fiber in a kiln having a temperature gradient from 300 ° C to 800 ° C in an inert atmosphere such as nitrogen and argon. It is preferable to heat-process for several minutes, and to perform a preliminary carbonation process process (1st carbonation process process). Thereafter, in order to further advance the carbonization and to proceed with the graphite, heat treatment is performed for several minutes while applying a tension of 0.95 to 1.05 to the first carbonation treatment process in an inert atmosphere such as nitrogen and argon. A carbonation treatment process is performed to carbonize the flame resistant fiber. About control of the heat processing temperature in a 2nd carbonation process process, it is good to set the maximum temperature to 1,000 degreeC or more (preferably 1,000-2,000 degreeC), putting a temperature gradient. This maximum temperature is appropriately selected and determined according to the required properties (tensile strength, elastic modulus, etc.) of the desired carbon fiber.

In the manufacturing method of the carbon fiber of this invention, when carbon fiber with a higher modulus of elasticity is desired, it can also perform a graphitization process process following a carbonization process process. The graphitization treatment step is usually performed at a temperature of 2,000 to 3,000 ° C while applying tension to the fiber obtained in the carbonization treatment step in an inert atmosphere such as nitrogen and argon.

The carbon fiber thus obtained can be subjected to surface treatment for increasing the adhesive strength with the matrix resin in the case of using a composite material according to the purpose. As the surface treatment method, a gaseous phase or a liquid phase treatment can be employed, and a liquid phase treatment with an electrolyte solution such as an acid or an alkali is preferable from the viewpoint of productivity. Moreover, in order to improve the workability and handleability of carbon fiber, you may provide the various sizing agent excellent in compatibility with respect to matrix resin.

Example

Hereinafter, although an Example demonstrates this invention concretely, it is not limited to the Example described here. In addition, the percent (%) and parts shown in the following examples represent "weight%" and "weight part" unless there is particular limitation. The measurement of each characteristic value is performed based on the method shown below.

<Treatment rate of treatment agent>

The precursor after applying the treating agent was alkali melted with potassium hydroxide / sodium butyrate, dissolved in water, and adjusted to pH 1 with hydrochloric acid. This was colored by adding sodium sulfite and ammonium molybdate, and colorimetric determination (wavelength 815 mμ) of silica molybdenum blue was carried out to obtain silicon content. The provision rate (weight%) of the acrylic fiber processing agent was computed using the value of the silicon content in the processing agent calculated | required in the same way as the silicon content calculated | required here.

<Anti-fusion>

Twenty places were randomly selected from the carbon fibers, short fibers 10 mm in length were cut therefrom, the fusion state was observed, and the following evaluation criteria were determined.

◎: no fusion

○: almost no fusion

△: less welding

×: fusion

<Strand hardness of precursor>

The hardness of the precursor strand (length: about 50 cm) was measured by a texture tester (manufactured by HANDLE-O-METERHOM-2 Daiei Kagaku Seiki Seisakusho Co., Ltd., slit width 5 mm). And the measurement was performed 10 times, and it judged that precursor strands were flexible, so that the average value was small. At the time of evaluation, the precursor immediately after manufacture (within 7 days after manufacture) and the precursor stored 12 months at room temperature after manufacture (it shows after storage in the table) were used.

<Abrasion resistance>

Precursor strand 12K was rubbed 1,000 times with 50 g of tension by three mirror chromium-plated stainless steel needles arranged in a zigzag by TM-type friction bonding tester TM-200 (manufactured by Daiei Chemical Co., Ltd.). Movement speed 300 times / min) and the fluff occurrence state of the precursor strands were visually determined based on the following criteria. At the time of evaluation, the precursor immediately after manufacture (within 7 days after manufacture), and the precursor stored for 12 months at normal temperature after manufacture were used.

(Double-circle): No fluff occurrence is seen like abrasion before

○: Some fluff is visible but scratch resistance is good

(Triangle | delta): Slightly fluffy and abrasion resistance deteriorates slightly

X: Lint-free and marked short fiber breakage is seen. Poor abrasion resistance

<Carbon fiber strength>

It measured according to the epoxy resin impregnation strand method prescribed | regulated to JIS-R-7601, and made the average value of ten times of measurement into carbon fiber strength (GPa). At the time of evaluation, the precursor immediately after manufacture (within 7 days after manufacture), and the precursor stored for 12 months at room temperature after manufacture were used.

Example 1

An acetylene-based surfactant was added to an amino-modified silicone aqueous emulsion obtained by mixing the amino-modified silicone A1, the Bronsted Acid Compound B1, the polyoxyethylene alkyl ether D1, and water so as to obtain a nonvolatile content of the treatment agent shown in Table 1. C1 was added, the weight ratio of amino-modified silicone A1 in the nonvolatile content of the treatment agent was 80% by weight, the weight ratio of Bronsted acid compound B1 was 0.7% by weight, the weight ratio of acetylene surfactant C1 was 2% by weight, A treating agent (precursor treating agent) having a weight ratio of polyoxyethylene alkyl ether D1 of 17.3 wt% was prepared. And the non volatile matter concentration of the treatment agent was 20% by weight.

Subsequently, the adjusted treatment agent was further diluted with water to obtain a treatment liquid having a nonvolatile content of 3.0% by weight.

The treatment solution is attached to the raw material acrylic fiber of the precursor obtained by copolymerizing 97 mol% acrylonitrile and 3 mol% itaconic acid so as to have a provision rate of 1.0%, and the precursor is subjected to a stretching step (steam stretching, stretching ratio 2.1 times). Was prepared (single fiber fineness 0.8 dtex, 24,000 filaments). This precursor was flameproofed for 60 minutes in the flameproof furnace at 250 degreeC, and then baked in the carbonization furnace which has a temperature gradient of 300-1,400 degreeC under nitrogen atmosphere, and was converted into carbon fiber. Table 1 shows the evaluation results of each characteristic value.

Examples 2 to 22 and Comparative Examples 1 to 17

Except having adjusted the process liquid so that it might become the non volatile matter composition of the process agents shown in Tables 2-4 in Example 1, it carried out similarly to Example 1, and obtained the precursor and carbon fiber after a process agent adhesion. The evaluation result of each characteristic value is shown to Tables 1-4.

In addition, the detail of the non volatile matter composition of Tables 1-4 is as follows.

<Amino modified silicone (A)>

Amino modified silicone A1 (25 degreeC viscosity: 250mm ² / s, amino equivalent: 7,600 g / mol, diamine type)

Amino-modified silicone A2 (25 ℃ viscosity: 1,300mm ² / s, amino equivalent weight: 1.700g / mol, a diamine-type)

Amino modified silicone A3 (25 degreeC viscosity: 1,700 mm ² / s, amino equivalent: 3,800 g / mol, monoamine type)

Amino-modified silicone A4 (25 ℃ viscosity: 20,000mm ² / s, amino equivalence: 1,800g / mol, a diamine-type)

Amino modified silicone A5 (25 degreeC viscosity: 1500 mm ² / s, amino equivalent: 3,800 g / mol, diamine type)

<Bronsted Acid Compound (B)>

Carboxylic acid compound B1: acetic acid

Carboxylic Acid Compound B2: Benzoic Acid

Carboxylic Acid Compound B3: Arginine

Carbonic Acid Compound B4: Phosphoric Acid

<Acetylene Surfactant (C)>

Acetylene surfactant C1: 20 mole adduct of ethylene oxide of 2,4,7,9-tetramethyl-5-decine-4,7-diol (in formula (4), R ³ , R ⁵ are both methyl groups, R ⁴ , R ⁶ is an isobutyl group, R ⁷ is a hydrogen atom, AO is ethylene oxide, and n + m = 20.)

Acetylene-based surfactant C2: 5 mole adduct of ethylene oxide of 2,4,7,9-tetramethyl-5-decine-4,7-diol (in formula (4), R ³ and R ⁵ are both methyl groups, R ⁴ , R ⁶ is an isobutyl group, R ⁷ is a hydrogen atom, AO is ethylene oxide, and n + m = 5.)

Acetylene surfactant C3: 3,6-dimethyl-4-octyne-3,6-diol (In formula (2), R ³ and R ⁵ are all methyl groups, R ⁴ and R ⁶ are all ethyl groups, and R ⁷ is hydrogen. Is an atom.)

Acetylene-based surfactant C4: 2,4,7,9-tetramethyl-5-decine-4,7-diol (In formula (2), R ³ and R ⁵ are all methyl groups, R ⁴ and R ⁶ are all iso Butyl group, R ⁷ is a hydrogen atom.)

<Polyoxyalkylene alkyl ether (D)>

Polyoxyethylene alkyl ether D1: Alkyl ether of 12-14 carbon atoms to which 5 mol of oxyethylene groups were added

Polyoxyethylene alkyl ether D2: Alkyl ether of 12-14 carbon atoms to which 7 mol of oxyethylene groups were added

Polyoxyethylene alkyl ether D3: alkyl ether having 12 to 14 carbon atoms to which 9 mol of an oxyethylene group is added

In addition, in Tables 1-4, the numerical value in the parentheses of Bronsted-acid compound (B) shows the molar equivalent of Bronsted-acid compound (B) with respect to 1 mol of amino groups of an amino modified silicone (A). In addition, the numerical value in the parentheses of an acetylene type surfactant (C) shows the weight ratio of the acetylene type surfactant (C) at the time of making an amino modified silicone (A) 100 weight part. In addition, the numerical value indicated by the parenthesis after strand hardness and carbon fiber strength storage shows the change rate with respect to the numerical value immediately after manufacture.

As apparent from Tables 1 to 4, the acrylic fiber treating agent of the example is used for producing carbon fibers, compared to the acrylic fiber treating agent of the comparative example which does not contain the Bronsted acid compound (B) and / or the acetylene surfactant (C). It turns out that the deterioration suppression of an acrylic fiber with time is excellent.

Industrial availability

The acrylic fiber treating agent of the present invention is a treatment agent used when producing acrylic fibers for producing carbon fibers, and is useful for producing high quality carbon fibers. The acrylic fiber for carbon fiber manufacture of this invention is useful in order to process the processing agent of this invention, and to manufacture high quality carbon fiber. The high quality carbon fiber can be obtained by the manufacturing method of the carbon fiber of this invention.

Claims (11)

The processing agent for acrylic fibers containing an amino modified silicone (A), Bronsted acid compound (B), and an acetylene type surfactant (C). The method of claim 1,
The processing agent for acrylic fibers whose ratio of Bronsted-acid compound (B) is 0.01-2.5 mol equivalent with respect to 1 mol of amino groups of the said amino modified silicone (A). The method according to claim 1 or 2,
The processing agent for acrylic fibers whose ratio of the said acetylene type surfactant (C) is 0.1-12 weight part with respect to 100 weight part of said amino modified silicone (A). The method according to any one of claims 1 to 3,
The acetylene surfactant (C) is selected from acetylene alcohol (C1), acetylene diol (C2), compound (C3) in which alkylene oxide is added to acetylene alcohol, and compound (C4) in which alkylene oxide is added to acetylene diol At least 1 sort (s), the processing agent for acrylic fibers. The method of claim 4, wherein
The said acetylene alcohol (C1) is a compound represented by following General formula (1), The said acetylene diol (C2) is a compound represented by following General formula (2), The compound (C3) which added the alkylene oxide to the said acetylene alcohol. The processing agent for acrylic fibers which is a compound represented by following General formula (3), and the compound (C4) which added the alkylene oxide to the said acetylene diol is a compound represented by following General formula (4).
[Formula 1]

(In formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms.)
[Formula 2]

(In Formula (2), R <^3> , R <^4> , R <^5> and R <^6> are respectively independently and a C1-C8 alkyl group.)
[Formula 3]

(In formula (3), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms. R ⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. AO is an oxyalkylene group having 2 to 4 carbon atoms. N is a number from 1 to 50.
[Formula 4]

(In formula (4), R <^3> , R <^4> , R <^5> and R <^6> are respectively independently and a C1-C8 alkyl group. R <^7> is a hydrogen atom or a C1-C5 alkyl group. ) is a plurality of R ⁷ may be the same or different from. AO represents an oxyalkylene group of a carbon number of 2 ~ 4. m, n are each independently a number from 1 to 50.) The method according to any one of claims 1 to 5,
The processing agent for acrylic fibers whose weight ratio of the said amino modified silicone (A) to a non volatile matter of a processing agent is 40 to 95 weight%. The method according to any one of claims 1 to 6,
The processing agent for acrylic fibers which further contains polyoxyalkylene alkyl ether (D). The method of claim 7, wherein
The processing agent for acrylic fibers in which the said polyoxyalkylene alkyl ether (D) contains the compound represented by following General formula (5).
[Formula 5]

(In General Formula (5), R ⁸ represents an alkyl group having 6 to 22 carbon atoms. AO represents an oxyalkylene group having 2 to 4 carbon atoms. J is each independently a number of 1 to 50.) The method according to claim 7 or 8,
The processing agent for acrylic fibers whose ratio of the sum total of the said acetylene type surfactant (C) and the said polyoxyalkylene alkyl ether (D) is 5-50 weight part with respect to 100 weight part of said amino modified silicone (A). The acrylic fiber for carbon fiber manufacture which adhere | attaches the acrylic fiber processing agent in any one of Claims 1-9 to the raw material acrylic fiber of the acrylic fiber for carbon fiber manufacture. A salt-proofing fiber in the oxidizing atmosphere of 200-300 degreeC, the spinning process which affixes the fiber processing agent of any one of Claims 1-9 to the raw material acrylic fiber of the acrylic fiber for carbon fiber manufacture, and is manufactured. A method of producing carbon fiber, comprising a carbonization treatment step of carbonizing the flame resistant treatment step to be converted to the flame resistant fiber in an inert atmosphere at 300 to 2,000 ° C.