JPWO2018003347A1 - Textile treatment agent and its use - Google Patents

Abstract

Provided is a fiber treatment agent that has high permeability to fibers and suppresses gelation of amino-modified silicone. An amino-modified silicone (A), a surfactant (B), and a compound (C) that is at least one selected from the following compound (C1) and the following compound (C2) represented by the following chemical formula (1): Fiber treatment agent. (In formula (1), R1 represents an organic group, R2 represents an organic group, A1O represents an oxyalkylene group having 2 to 4 carbon atoms, and m represents a number of 1 to 50.) Compound (C2 ): Amine compound having a polyoxyalkylene group and two or more primary amine groups in the molecule

Description

  The present invention relates to a fiber treatment agent and use thereof.

  In producing fibers, it is well known that amino-modified silicone is attached to the fibers to improve process passability and texture because of low frictional resistance and high affinity for the fibers. 1). As a method for attaching such amino-modified silicone, it is generally necessary to immerse the fiber in an aqueous emulsion of amino-modified silicone oil, and then pass through a drying step in which moisture is removed by heat. In these heat treatment processes, amino-modified silicone-based treatment agents with high heat-crosslinkability tend to form a film or a pressure-sensitive adhesive on the fiber or on the drying roller, and the treatment agent cannot move into the fiber bundle. Problems such as a decrease in texture and a decrease in process passability occur. Moreover, since the time to immerse is very short, when the permeability of the amino-modified silicone emulsion to the fiber is low, there is a problem that the amino-modified silicone-based treatment agent cannot uniformly adhere to the fiber.

  In particular, when carbon fibers are produced, the above-mentioned film formation by cross-linking and fiber permeability are important. As a method for producing carbon fiber, a precursor is first produced (this precursor production process may be referred to as a yarn-making process). This precursor is converted to flame-resistant fibers in an oxidizing atmosphere at 200 to 300 ° C. (this process may be referred to as a flame-resistant treatment process hereinafter), followed by carbonization in an inert atmosphere at 300 to 2000 ° C. (This process may hereinafter be referred to as a carbonization treatment process) is generally used (hereinafter, the flameproofing treatment process and the carbonization treatment process may be collectively referred to as a firing process). The precursor is manufactured through a drawing process that is drawn at a high magnification even when compared with a normal acrylic fiber. Therefore, if amino-modified silicone is not adhered, the fibers tend to stick together and are not uniformly stretched at a high magnification, resulting in a non-uniform precursor, and the carbon fiber obtained by firing has sufficient strength. There is a problem that it cannot be obtained. Further, when the precursor is fired, there is a problem that the single fibers are fused with each other, and the quality and quality of the obtained carbon fibers are deteriorated. In order to solve such problems, many techniques for applying an amino-modified silicone-based treatment agent to a precursor have been proposed (see Patent Documents 1 and 2), but the above-mentioned amino-modified silicone has good coating and permeability. If not, the problem of insufficient carbon fiber strength after firing occurs.

Japanese Unexamined Patent Publication No. 2001-271477 Japanese Patent Laid-Open No. 2002-129482

  In view of the conventional technical background, an object of the present invention is to provide a fiber treatment agent that has high permeability to fibers and suppresses gelation of amino-modified silicone.

（式（１）中、Ｒ^１は有機基、Ｒ^２は有機基、Ａ^１Ｏは、炭素数２〜４のオキシアルキレン基を示す。ｍは１〜５０の数を示す。）
化合物（Ｃ２）：分子内にポリオキシアルキレン基及び２つ以上の１級アミン基を有するアミン化合物As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a compound having an amino-modified silicone, a primary amino group, and an oxyalkylene group, and a surfactant in combination, so that the permeability to fibers can be improved. The inventors have found that the gelation of amino-modified silicone can be suppressed and have reached the present invention.
That is, the fiber treatment agent of the present invention is at least one selected from the amino-modified silicone (A), the surfactant (B), the compound (C1) represented by the following chemical formula (1), and the following compound (C2). It is a fiber processing agent containing the compound (C) which is.

(In the formula (1), ^{R 1} represents an organic group, ^{R 2} is an organic group, ^{A 1} O is, .m showing an oxyalkylene group having 2 to 4 carbon atoms is a number of 1 to 50.)
Compound (C2): amine compound having a polyoxyalkylene group and two or more primary amine groups in the molecule

It is preferable to further contain a carboxylic acid compound (D).
The A ¹ O is preferably an oxyethylene group.
It is preferable that the weight ratio of the compound (C) in the nonvolatile content of the treatment agent is 0.1 to 15% by weight.
It is preferable that the surfactant (B) has a polyoxyethylene skeleton.
It is preferable for acrylic fibers.

  The acrylic fiber for carbon fiber production of the present invention is obtained by adhering the fiber treatment agent to the raw acrylic fiber of the acrylic fiber for carbon fiber production.

  The carbon fiber production method of the present invention includes a yarn production process in which the fiber treatment agent is attached to a raw acrylic fiber for producing carbon fiber, and a flame resistant fiber in an oxidizing atmosphere at 200 to 300 ° C. It includes a flameproofing treatment step to be converted, and a carbonization treatment step of carbonizing the flameproofed fiber in an inert atmosphere at 300 to 2000 ° C.

  The fiber treatment agent of the present invention contains an amino-modified silicone (A), a surfactant (B), and a compound (C). Each component will be described in detail.

(Amino-modified silicone (A))
The treatment agent of the present invention essentially contains an amino-modified silicone (A). The amino group (including an organic group having an amino group) that is a modified group of the amino-modified silicone may be bonded to the side chain of the silicone that is the main chain, or may be bonded to the terminal. It may be bonded to both, but is preferably bonded to a side chain (having an amino group in the side chain) from the viewpoint of fiber protection in the flameproofing treatment step. Further, the amino group may be any of monoamine type, diamine type, and polyamine type, and both may coexist in one molecule. A monoamine type or a diamine type is preferable from the viewpoints of imparting it uniformly and protecting the fiber by forming a film of the treatment agent.

The kinematic viscosity at 25 ° C. of the amino-modified silicone (A) is preferably 50 to 5000 mm ² / s, more preferably 50 to 4000 mm ² / s, and even more preferably 50 to 3000 mm ² / s from the point of exerting the effect of the present application. 50 to 2500 mm ² / s is particularly preferable. When the kinematic viscosity is less than 50 mm ² / s, the treatment agent is likely to be scattered, and when the aqueous emulsification is performed, the solution stability of the emulsion is deteriorated, and the treatment agent may not be uniformly applied to the fibers. . As a result, fiber fusion may not be prevented. When the kinematic viscosity is more than 5000 mm ² / s, gum-up due to adhesiveness may be a problem.

  The amino equivalent of the amino-modified silicone (A) is preferably from 300 to 10,000 g / mol, more preferably from 500 to 10,000 g / mol, and even more preferably from 1,000 to 9000 g / mol from the viewpoint of preventing sticking and fusion between fibers. When the amino equivalent is less than 300 g / mol, the treatment agent is thermally crosslinked at the initial stage of the flameproofing treatment step, and thus the treatment agent may not be uniformly applied to the inside of the fiber bundle. Further, when the amino equivalent is 10,000 g / mol or more, the fiber may not be protected because thermal crosslinking of the treatment agent does not occur later in the flameproofing treatment step.

  As the amino-modified silicone (A), a plurality of amino-modified silicones having different amino equivalents and different kinematic viscosities (25 ° C.) may be used in combination. When two or more amino-modified silicones are used, the amino equivalent means the amino equivalent of the whole amino-modified silicone (mixture), and the kinematic viscosity at 25 ° C. means the kinematic viscosity of the whole amino-modified silicone (mixture). .

（式（２）中、Ｒ^３は炭素数が１〜２０のアルキル基又はアリール基を示す。Ｒ^４は下記化学式（３）で示される基である。Ｒ^５は、Ｒ^３、Ｒ^４又は−ＯＲ^１１（Ｒ^１１は水素原子又は炭素数が１〜６のアルキル基）である。ｐは１０≦ｐ≦１００００、ｑは０．１≦ｑ≦１０００である。）As said amino modified silicone, the compound shown by following General formula (2) can be mentioned, for example.

(In formula (2), R ³ represents an alkyl group or aryl group having 1 to 20 carbon atoms. R ⁴ is a group represented by the following chemical formula (3). R ⁵ represents R ³ , R ⁴ or -OR ¹¹ (R ¹¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P is 10 ≦ p ≦ 10000, and q is 0.1 ≦ q ≦ 1000.)

In formula (2), R ³ represents an alkyl group or aryl group having 1 to 20 carbon atoms. R ³ 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, and further preferably a methyl group. In addition, several R < ³ > in Formula (2) may be the same, and may differ. R ⁴ is a group represented by the following general formula (3). R ⁵ is a group represented by R ³ , R ⁴ or —OR ¹¹ , and preferably R ³ . In addition, several R < ⁵ > in Formula (2) may be the same, and may differ.
R ¹¹ 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 to 10000, preferably 50 to 5000, and more preferably 100 to 2000. q is a number of 0.1 to 1000, preferably 0.5 to 500, and more preferably 1 to 100.

In formula (3), R ⁶ and R ⁸ are each independently an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms. R ⁷ , R ⁹ and R ¹⁰ 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, Preferably it is a hydrogen atom. r is a number of 0-6, preferably 0-3, more preferably 0-1.

  The weight ratio of the amino-modified silicone (A) in the nonvolatile content of the treatment agent is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, and still more preferably 65 to 90% by weight. When the weight ratio is less than 50% by weight, the heat resistance of the treatment agent may be insufficient in the flameproofing treatment step. On the other hand, when the weight ratio exceeds 95% by weight, a stable aqueous emulsion may not be obtained when the treatment agent is water-based emulsified.

[Surfactant (B)]
The acrylic fiber treatment agent of the present invention essentially contains a surfactant (B). Surfactants are used as emulsifiers, antistatic agents and the like. The surfactant is not particularly limited, and a known one can be appropriately selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. One type of surfactant may be used, or two or more types may be used in combination.

  Examples of the nonionic surfactant include polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene Polyoxyalkylene linear alkyl ethers such as ethylene tetradecyl ether and polyoxyethylene cetyl ether; polyoxyalkylene branched primary such as polyoxyethylene 2-ethylhexyl ether, polyoxyethylene isocetyl ether and polyoxyethylene isostearyl ether Alkyl ether; polyoxyethylene 1-hexyl hexyl ether, polyoxyethylene 1-octyl hexyl ether, polyoxyethylene 1- Xyloctyl ether, polyoxyethylene 1-pentyl heptyl ether, polyoxyethylene 1-heptyl pentyl ether, polyoxyethylene 1-hexyl heptyl ether, polyoxyethylene 1-heptyl hexyl ether, polyoxyethylene 1-pentyl captil ether Polyoxyalkylene branched secondary alkyl ethers such as polyoxyethylene 1-captylpentyl ether; polyoxyalkylene alkenyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Polyoxyalkylene alkyl phenyl ethers such as oxyethylene dodecyl phenyl ether; polyoxyethylene tristyryl phenyl ether Polyoxyalkylene alkyl aryl phenyl ethers such as polyoxyethylene distyryl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene benzyl phenyl ether; polyoxyethylene Monolaurate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monomyristate, polyoxyethylene dilaurate, polyoxyethylene dioleate, polyoxyethylene dimyristate, polyoxyethylene distearate Polyoxyalkylene fatty acid esters such as sorbitan monopalmitate, sorbitan esters such as 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 ester; polyoxyalkylene castor oil ether such as polyoxyethylene castor oil ether; polyoxyalkylene cured castor oil ether such as polyoxyethylene hydrogenated castor oil ether; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether and other poly Oxyalkylene alkylamino ether; oxyethylene-oxypropylene block or random copolymer Coalescing; oxyethylene - terminus sucrose ethers of polyoxypropylene block or random copolymer; polyoxyethylene lauryl amide, polyoxyalkylene alkylamide such as polyoxyethylene stearyl amide; and the like can be given. The weight average molecular weight of the nonionic surfactant is preferably 2000 or less, more preferably 200 to 1800, more preferably 300 to 1500, and still more preferably 500 to 1000.

  Examples of the anionic surfactant include fatty acids (salts) such as oleic acid, palmitic acid, sodium oleate, potassium palmitate, triethanolamine oleate; hydroxyacetic acid, potassium potassium hydroxyacetate, lactic acid, lactic acid Hydroxyl group-containing carboxylic acid (salt) such as potassium salt; polyoxyalkylene alkyl ether acetic acid (salt) such as polyoxyethylene tridecyl ether acetic acid (sodium salt); and many carboxyl groups such as potassium trimellitic acid and potassium pyromellitic acid Substituted aromatic compound salts; alkylbenzene sulfonic acid (salt) such as dodecylbenzene sulfonic acid (sodium salt); polyoxyalkylene alkyl ether sulfonic acid (salt) such as polyoxyethylene 2-ethylhexyl ether sulfonic acid (potassium salt); Higher fatty acid amide sulfonic acid (salt) such as theauroylmethyl taurine (sodium), lauroyl methyl taurine (sodium), myristoyl methyl taurine (sodium), palmitoyl methyl taurine (sodium); N-acyl such as lauroyl sarcosine acid (sodium) Sarcosine acid (salt); alkyl phosphonic acid (salt) such as octyl phosphonate (potassium salt); aromatic phosphonic acid (salt) such as phenyl phosphonate (potassium salt); 2-ethylhexyl phosphonate mono 2-ethylhexyl ester (potassium salt) Alkylphosphonic acid esters (salts) such as alkylphosphonic acid; nitrogen-containing alkylphosphonic acid (salt) such as aminoethylphosphonic acid (diethanolamine salt); alkylsulfuric acid such as 2-ethylhexyl sulfate (sodium salt) Esters (salts); polyoxyalkylene sulfate esters (salts) such as polyoxyethylene 2-ethylhexyl ether sulfate (sodium salt); long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate and sodium dioctyl sulfosuccinate; N -Long-chain N-acyl glutamates such as monosodium lauroyl glutamate and disodium N-stearoyl-L-glutamate;

  Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, oleyl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, coconut oil alkyl trimethyl. Ammonium chloride, tallow alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methosulfate, oleyldimethylethylammonium ethosulphate, dioctyldimethylammonium chloride, dill Alkyl quaternary ammonium salts such as ril dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, octadecyl diethyl methyl ammonium sulfate; (polyoxyethylene) lauryl amino ether lactate, stearyl amino ether lactate, di (polyoxyethylene) lauryl Methylaminoether dimethyl phosphate, di (polyoxyethylene) laurylethylammonium ethosulphate, di (polyoxyethylene) -cured tallow alkylethylamine ethosulphate, di (polyoxyethylene) laurylmethylammonium dimethylphosphate, di (polyoxyethylene) stearyl (Polyoxyalkylene) alkylamino ether salts such as amine lactate; N- (2-hydroxyethyl)- Acylamide alkyl quaternary ammonium salts such as N, N-dimethyl-N-stearoylamidopropylammonium nitrate, lanolin fatty acid amidopropylethyldimethylammonium etosulphate, lauroylamidoethylmethyldiethylammonium methosulfate; Alkylethenoxy quaternary ammonium salts such as ammonium chloride and distearyl polyethenoxymethylammonium chloride; alkylisoquinolinium salts such as laurylisoquinolinium chloride; lauryldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride and the like Benzalkonium salt; benzyldimethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenol) Benzethonium salts such as nooxy) ethoxy] ethyl} ammonium chloride; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts such as oleyl hydroxyethyl imidazolinium etsulfate, lauryl hydroxyethyl imidazolinium etsulfate; N-cocoyl arginine ethyl Acyl basic amino acid alkyl ester salts such as ester pyrrolidone carboxylate and N-lauroyllysine ethyl ethyl ester chloride; Primary amine salts such as laurylamine chloride, stearylamine bromide, hardened beef tallow alkylamine chloride, rosinamine acetate; cetyl Methylamine sulfate, laurylmethylamine chloride, dilaurylamine acetate, stearylethylamine bromide, laur Secondary amine salts such as rupropylamine acetate, dioctylamine chloride, octadecylethylamine hydroxide; dilaurylmethylamine sulfate, lauryldiethylamine chloride, laurylethylmethylamine bromide, diethanol stearylamide ethylamine trihydroxyethyl phosphate salt, stearylamide Examples include tertiary amine salts such as ethyl ethanolamine urea polycondensate acetate; fatty acid amidoguanidinium salts; alkyltrialkylene glycol ammonium salts such as lauryl triethylene glycol ammonium hydroxide.

  Examples of amphoteric surfactants include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, and the like. Imidazoline-based amphoteric surfactants; 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaines, amide betaines, sulfobetaine, and other betaine-based amphoteric surfactants; N- Amino acid type amphoteric surfactants such as lauryl glycine, N-lauryl β-alanine, N-stearyl β-alanine and the like can be mentioned.

  The weight ratio of the surfactant (B) in the nonvolatile content of the treatment agent is preferably 2 to 25% by weight, more preferably 5 to 20% by weight, and still more preferably 10 to 20% by weight. When the weight ratio is less than 2% by weight, a stable aqueous emulsion may not be obtained when the treatment agent is water-based emulsified. On the other hand, when the weight ratio exceeds 25% by weight, the heat resistance of the treatment agent may be insufficient in the flameproofing treatment step.

  The weight ratio of amino-modified silicone (A) and surfactant (B) (amino-modified silicone (A) / surfactant (B)) in the nonvolatile content of the treatment agent of the present invention is preferably 75/25 to 98/2. 80/20 to 95/5 is more preferable, and 80/20 to 90/10 is still more preferable. When the weight ratio is more than 98/2, a stable aqueous emulsion may not be obtained when the treatment agent is aqueous-emulsified. On the other hand, if it is less than 75/25, the heat resistance of the treating agent may be insufficient in the flameproofing treatment step.

[Compound (C)]
The fiber treatment agent of the present invention essentially contains at least one compound (C) selected from the compound (C1) represented by the chemical formula (1) and the compound (C2).
The compound (C) is a component that suppresses gelation of the amino-modified silicone (A).

(Compound (C1))
Compound (C1) is a compound represented by the above chemical formula (1).
In the above formula (1), R ¹ represents an organic group, R ² represents an organic group, and A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms. m shows the number of 0-50.
R ¹ is not particularly limited as long as it is an organic group, but is preferably an ethylene group or a propylene group from the viewpoint of suppressing gelation of the amino-modified silicone (A).
R ² is not particularly limited as long as it is an organic group, but is preferably an ethylene group or a propylene group from the viewpoint of suppressing gelation of the amino-modified silicone (A).

A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and among them, an oxyethylene group having 2 carbon atoms is preferable from the viewpoint of suppressing gelation of the amino-modified silicone (A).
m represents an average addition number of moles of ^{A 1} O, is a number from 1 to 50, 1 to 40, more preferably 2 to 30, more preferably 3 to 20, particularly preferably from 4 to 15. If it exceeds 50, the effect of suppressing the gelation of the amino-modified silicone (A) is weak.
(A ¹ O) m represents a polyoxyalkylene group obtained by adding n moles of an oxyalkylene group having 2 to 4 carbon atoms. A ¹ O may be one or two or more. In the case of two or more types, any of a block adduct, an alternating adduct, or a random adduct may be configured. A ¹ O preferably contains an oxyethylene group essentially from the viewpoint of suppressing the gelation of the amino-modified silicone (A). The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, further preferably 60 mol% or more, and particularly preferably 80 mol% or more.

Ｒ^ａは有機基であれば、特に限定されないが、アミノ変性シリコーン（Ａ）のゲル化を抑える観点から、エチレン基またはプロピレン基が好ましい。
Ｒ^ｂ有機基であれば、特に限定されないが、アミノ変性シリコーン（Ａ）のゲル化を抑える観点から、エチレン基またはプロピレン基が好ましい。
ｎはＡ^２Ｏの平均付加モル数を示し、１〜５０の数であり、１〜４０が好ましく、２〜３０がより好ましく、３〜２０がさらに好ましく、４〜１５が特に好ましい。５０を超えると、アミノ変性シリコーン（Ａ）のゲル化の抑制効果が弱い。
（Ａ^２Ｏ）ｎは、炭素数２〜４のオキシアルキレン基がｎモル付加したポリオキシアルキレン基を示す。Ａ^２Ｏは、１種又は２種以上であってもよい。２種以上の場合、ブロック付加体、交互付加体、またはランダム付加体のいずれを構成してもよい。Ａ^２Ｏは、アミノ変性シリコーン（Ａ）のゲル化を抑える観点から、オキシエチレン基を必須に含有することが好ましい。オキシアルキレン基全体に占めるオキシエチレン基の割合は、４０モル％以上が好ましく、５０モル％がより好ましく、６０モル％以上がさらに好ましく、８０モル％以上が特に好ましい。(Compound (C2))
The compound (C2) is an amine compound having a polyoxyalkylene group and two or more primary amine groups in the molecule.
Although it will not specifically limit if a compound (C2) is an amine compound which has a polyoxyalkylene group and two or more primary amine groups in a molecule | numerator, from a viewpoint of suppressing gelatinization of amino modified silicone (A), it is the following. It is preferable to have the structure of formula (4).
Compound (C2) has two or more primary amines, preferably 2 to 4, more preferably 2 or 3, and particularly preferably 2.

^Ra is not particularly limited as long as it is an organic group, but is preferably an ethylene group or a propylene group from the viewpoint of suppressing gelation of the amino-modified silicone (A).
Although it will not specifically limit if it is ^Rb organic group, From a viewpoint of suppressing gelatinization of amino modified silicone (A), an ethylene group or a propylene group is preferable.
n represents an average addition number of moles of ^{A 2} O, is a number from 1 to 50, 1 to 40, more preferably 2 to 30, more preferably 3 to 20, particularly preferably from 4 to 15. If it exceeds 50, the effect of suppressing the gelation of the amino-modified silicone (A) is weak.
(A ² O) n represents a polyoxyalkylene group obtained by adding n moles of an oxyalkylene group having 2 to 4 carbon atoms. A ² O may also be one or more. In the case of two or more types, any of a block adduct, an alternating adduct, or a random adduct may be configured. A ² O preferably contains an oxyethylene group essentially from the viewpoint of suppressing the gelation of the amino-modified silicone (A). The proportion of the oxyethylene group in the entire oxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, further preferably 60 mol% or more, and particularly preferably 80 mol% or more.

  The weight ratio of the amino-modified silicone (A) to the compound (C) (amino-modified silicone (A) / compound (C)) in the nonvolatile content of the treatment agent of the present invention is preferably 75/25 to 99.9 / 0.1. 80/20 to 99.5 / 0.5 is more preferable, and 80/20 to 99/1 is still more preferable. When the weight ratio is more than 75/25, a stable aqueous emulsion may not be obtained when the treatment agent is water-based emulsified. On the other hand, if it is less than 99.9 / 0.1, the gelation suppressing function may be insufficient.

[Carboxylic acid compound (D)]
When the fiber treatment agent of the present invention contains a carboxylic acid compound (D), it is preferable from the viewpoint of suppressing gelation and improving the stability of the emulsion.
Although it will not specifically limit if it is a compound which has carboxylic acid as a carboxylic acid compound (D), Aliphatic monocarboxylic acid, aliphatic polycarboxylic acid, aromatic carboxylic acid, aromatic polycarboxylic acid, etc. are mentioned.
Aliphatic monocarboxylic acids include butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, Isocetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, isoeicosaic acid, gadoleic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid , Isotetracosanoic acid, nervonic acid, serotic acid, montanic acid, melicic acid and the like.

  Aliphatic polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, undencanic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid , Pentadecanedioic acid, and derivatives thereof.

  Aromatic monocarboxylic acids 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.

(Other ingredients)
The fiber treatment agent of the present invention may contain other components in addition to the components described above as long as the effects of the present invention are not impaired. Other components include acid phosphate esters, phenolic, amine-based, sulfur-based, phosphorus-based and quinone-based antioxidants; sulfates of higher alcohols and higher alcohol ethers, sulfonates, higher alcohols and higher alcohols Antistatic agents such as phosphate salts of alcohol ethers, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants; smoothing agents such as alkyl esters of higher alcohols, higher alcohol ethers, waxes, etc. Antibacterial agents; antiseptics; antifungal agents; and hygroscopic agents.

  Moreover, the fiber treatment agent of this invention may contain modified silicones other than said amino modified silicone in the range which does not inhibit 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), carbinol-modified silicone. Alkyl-modified silicone, phenol-modified silicone, methacrylate-modified silicone, alkoxy-modified silicone, fluorine-modified silicone, and the like. One type of modified silicone may be used, or a plurality of modified silicones may be used in combination.

  Moreover, the fiber treatment agent of this invention may contain an ester compound in the range which does not inhibit the effect of this invention. Examples of ester compounds include ester compounds having 3 or more ester groups in the molecule described in republished WO 2007/066517, and sulfur-containing esters described in international application PCT / JP2013 / 75081. A compound etc. can be mentioned.

The fiber treatment agent of the present invention is preferably in a state in which amino-modified silicone and polyoxyalkylene alkyl ether are dissolved, solubilized, emulsified or dispersed in water.
There is no particular limitation on the weight ratio of water and the weight ratio of non-volatile content in the entire fiber treatment agent. 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 etc. resulting from emulsion viscosity, etc. The weight ratio of water in the entire fiber treatment agent is preferably 0.1 to 99.9% by weight, more preferably 10 to 99.5% by weight, and particularly preferably 50 to 99% by weight. The weight ratio (concentration) of the non-volatile content in the entire fiber treatment agent is preferably 0.01 to 99.9% by weight, more preferably 0.5 to 90% by weight, and particularly preferably 1 to 50% by weight.

  The fiber treatment agent of the present invention can be produced by mixing the components described above. The method for emulsifying and dispersing the components described above is not particularly limited, and a known method can be employed. As such a method, for example, each component constituting the fiber treatment agent is poured into warm water under stirring and emulsified and dispersed, and each component constituting the fiber treatment agent is mixed, a homogenizer, a homomixer, Examples of the method include phase inversion emulsification by gradually adding water while applying a mechanical shearing force using a ball mill or the like.

  The fiber treatment agent of the present invention can be suitably used as a treatment agent (precursor treatment agent) for acrylic fibers (precursor) for producing carbon fibers. You may use it as spinning oil agents other than an acrylic fiber.

  The viscosity at 25 ° C. of the non-volatile content of the fiber treatment agent of the present invention is preferably 10 to 10000 mPa · s, and preferably 10 to 5000 mPa · s, from the viewpoint of imparting good fiber bundle convergence in the precursor yarn making process and flameproofing process. s is more preferable, and 50 to 1000 mPa · s is more preferable. When the viscosity is less than 10 mPa · s, fiber bundles may be deteriorated in the precursor yarn making process or the flameproofing process. Moreover, when the viscosity exceeds 10,000 mPa · s, the viscosity of the treating agent becomes too high and the handling property of the treating agent is deteriorated even if good fiber bundle convergence property can be imparted in the precursor yarn forming process and the flameproofing process. May

[Acrylic fiber for producing carbon fiber, method for producing the same, and method for producing carbon fiber]
The acrylic fiber for carbon fiber production (precursor) of the present invention is produced by attaching the above-mentioned acrylic fiber treatment agent to the precursor acrylic fiber of the precursor. The method for producing a precursor according to the present invention includes a yarn production step in which the acrylic fiber treatment agent is attached to the raw material acrylic fiber of the precursor to produce a yarn.
The carbon fiber production method of the present invention includes a spinning process in which the above acrylic fiber treatment agent is attached to the precursor acrylic fiber to produce the precursor, and the precursor produced in the spinning process is oxidized at 200 to 300 ° C. A flameproofing process for converting to a flameproofed fiber in a neutral atmosphere, and a carbonization process for carbonizing the flameproofed fiber in an inert atmosphere at 300 to 2000 ° C.
According to the carbon fiber production method of the present invention, since the acrylic fiber treatment agent of the present invention is used, the treatment agent can be uniformly applied to the inside of the fiber bundle at the initial stage of the flame resistance treatment step, and the flame resistance is improved. Since the treatment agent can be made into a film at a later stage of the treatment process to protect the fiber, fusion between fibers and generation of fluff can be suppressed, and high-quality carbon fiber can be produced.

The yarn making process is a process of making a precursor by attaching an acrylic fiber treatment agent to the precursor raw acrylic fiber, and includes an adhesion treatment process and a stretching process.
The adhesion treatment process is a process of adhering the acrylic fiber treatment agent after spinning the precursor raw acrylic fiber. That is, the acrylic fiber treatment agent is adhered to the precursor raw acrylic fiber in the adhesion treatment step. The precursor raw acrylic fiber is stretched immediately after spinning, and the high-strength stretching after the adhesion treatment step is particularly called a “stretching step”. The stretching process may be a wet heat stretching method using high temperature steam or a dry heat stretching method using a hot roller.

  A precursor is comprised from the acrylic fiber which has as a main component the polyacrylonitrile obtained by copolymerizing at least 95 mol% or more of acrylonitrile and 5 mol% or less of a flame-resistant acceleration | stimulation component. As the flame resistance promoting component, a vinyl group-containing compound having copolymerizability with acrylonitrile can be suitably used. Although there is no limitation in particular about the single fiber fineness of a precursor, from the balance of a performance and manufacturing cost, Preferably it is 0.1-2.0 dTex. Further, the number of single fibers constituting the precursor fiber bundle is not particularly limited, but is preferably 1,000 to 96,000 from the balance between performance and production cost.

  The acrylic fiber treatment agent may be attached to the precursor raw acrylic fiber at any stage of the yarn production process, but is preferably attached once before the drawing process. It may be attached at any stage before the stretching process, for example, immediately after spinning. Further, it may be reattached at any stage after the stretching process, for example, it may be reattached immediately after the stretching process, it may be reattached at the winding stage, or it may be reattached immediately before the flameproofing process. You may let them. As for the attachment method, it may be attached using a roller or the like, or may be attached by a dipping method, a spray method or the like.

  In the adhesion treatment process, the application rate of the acrylic fiber treatment agent obtains the effect of preventing fiber-to-fiber sticking and the prevention of fusion, and prevents the deterioration of the quality of the carbon fiber due to the tar product of the treatment agent in the carbonization treatment process. From the balance with the content of the precursor, it is preferably 0.1 to 2% by weight, more preferably 0.3 to 1.5% by weight, based on the weight of the precursor. When the application rate of the acrylic fiber treatment agent is less than 0.1% by weight, sticking and fusion between single fibers cannot be sufficiently prevented, and the strength of the obtained carbon fibers may be lowered. On the other hand, when the application rate of the acrylic fiber treatment agent is more than 2% by weight, the acrylic fiber treatment agent covers more than necessary between the single fibers, so that the supply of oxygen to the fibers is hindered in the flameproofing treatment step, and thus obtained. The strength of the carbon fiber may decrease. In addition, the provision rate of an acrylic fiber processing agent here is defined with the percentage of the non volatile matter weight to which the acrylic fiber processing agent adhered with respect to the precursor weight.

  The flameproofing treatment step is a step of converting the precursor with the acrylic fiber treating agent attached thereto into flameproofing fibers in an oxidizing atmosphere at 200 to 300 ° C. The oxidizing atmosphere is usually an air atmosphere. The temperature of the oxidizing atmosphere is preferably 230 to 280 ° C. In the flameproofing treatment step, the acrylic fiber after the adhesion treatment is applied for 20 to 100 minutes (preferably 30) while applying a tension ratio of 0.90 to 1.10 (preferably 0.95 to 1.05). Heat treatment is performed for ˜60 minutes. In this flameproofing treatment, a flameproof fiber having a flameproof structure is produced through intramolecular cyclization and oxygen addition to the ring.

  The carbonization treatment step is a step of carbonizing the flameproof fiber in an inert atmosphere of 300 to 2000 ° C. In the carbonization treatment step, first, in a firing furnace having a temperature gradient from 300 ° C. to 800 ° C. in an inert atmosphere such as nitrogen or argon, a tension ratio of 0.95 to 1.15 is applied to the flameproof fiber. It is preferable to carry out a pre-carbonization treatment step (first carbonization treatment step) by applying heat treatment for several minutes while applying. Thereafter, in order to further promote carbonization and advance graphitization, a tension ratio of 0.95 to 1.05 is applied to the first carbonization treatment step in an inert atmosphere such as nitrogen or argon. While being applied, heat treatment is performed for several minutes to perform the second carbonization treatment step, and the flame resistant fiber is carbonized. About control of the heat processing temperature in a 2nd carbonization process process, it is good to make maximum temperature into 1000 degreeC or more (preferably 1000-2000 degreeC), applying a temperature gradient. This maximum temperature is appropriately selected and determined according to the required characteristics (tensile strength, elastic modulus, etc.) of the desired carbon fiber.

  In the carbon fiber manufacturing method of the present invention, when a carbon fiber having a higher elastic modulus is desired, the graphitization treatment step can be performed subsequent to the carbonization treatment step. The graphitization treatment step is usually performed at a temperature of 2000 to 3000 ° C. while applying tension to the fiber obtained in the carbonization treatment step in an inert atmosphere such as nitrogen or argon.

  The carbon fiber thus obtained can be subjected to a surface treatment for increasing the adhesive strength with the matrix resin when made into a composite material, depending on the purpose. As the surface treatment method, gas phase or liquid phase treatment can be adopted, and from the viewpoint of productivity, liquid phase treatment with an electrolytic solution of acid, alkali or the like is preferable. Furthermore, various sizing agents having excellent compatibility with the matrix resin can be added to improve the processability and handleability of the carbon fiber.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to the Example described here. In addition, the percentage (%) and part shown in the following examples indicate “% by weight” and “part by weight” unless otherwise specified. Each characteristic value was measured based on the following method.

Using each component of the following (A-1 to E-1), mixing is performed at the ratio (parts by weight) described in Tables 1 and 2, and the fiber treatment agents according to Examples 1 to 12 and Comparative Examples 1 to 6 are used. I got each.
POE (10) means 10 moles of ethylene oxide addition, PEG means polyethylene glycol, and PPG means polypropylene glycol.
A-1: Diamine-modified silicone Viscosity: 1,200 mm ² / s, amine equivalent: 1,750 g / mol
A-2: Monoamine-modified silicone Viscosity: 1,700 mm ² / s, amine equivalent: 3,800 g / mol
B-1 POE (3-12) alkyl ether having 8 to 16 carbon atoms C1-1: PEG / PPG block (molecular weight 1000) with one end added with 2-aminopropyl group C2-1: PEG (molecular weight 600) with 3-aminopropyl groups added to both ends of PEG.
C2-2: PEG (molecular weight 1000) with 3-aminopropyl groups added to both ends of PEG.
C2-3: A compound in which 3-aminopropyl groups are added to both ends of PEG (molecular weight 400).
C2-4: A PEG (molecular weight of 200) with both amino acid groups added with 3-aminopropyl groups.
C2-5: A compound in which 2-aminopropyl groups are added to both ends of PPG (molecular weight 400).
C2-6: A PPG / PEG / PPG block (molecular weight 2300) with 2-aminopropyl groups added to both ends.
D-1: Acetic acid E-1: Water X-1: Diethanolamine X-2: Diethylenetriamine X-3: POE (10) stearylaminoether

(Permeability evaluation)
The permeability was evaluated by the following felt sedimentation test.
Nikke Orifelt S20 (No. 103) cut to 2 cm x 2 cm is floated on 100 mL of each emulsion diluted to 2% active ingredient, and the time (seconds) until settling is measured to evaluate permeability. It was. Temperature: 23 ° C. The shorter the time until settling, the better the permeability.
The indicators are as follows, and ◎ and ○ are acceptable.
Very good (◎): 7 seconds or less Good (○): Over 7 seconds to 13 seconds or less Somewhat bad (△): Over 13 seconds to 14 seconds or less Poor (×): Over 14 seconds

(Gelability)
The stainless steel plate was heated to 160 ° C., and two drops of each emulsion were dropped on it, and it was confirmed whether it was liquid or gel every predetermined time. When it becomes a gel, stickiness is expressed, and thread breakage or the like occurs.
The indicators are as follows, and ◎ and ○ are acceptable.
Very good (◎): liquid at 160 ° C for 30 minutes Good (○): liquid at 160 ° C for 20 minutes and partial gel or gel at 160 ° C for 30 minutes Poor (X): gel or partial gel at 160 ° C for 20 minutes

(Stability)
Each emulsion was placed in a closed container and allowed to stand at 50 ° C. for 1 week. At that time, if separation or the like accompanying emulsion collapse was observed, it was judged as unacceptable (x), and if there was no separation, it was judged as acceptable (◯).

As described above, as can be seen from Tables 1 and 2, the fiber treatment agent according to the examples includes the amino-modified silicone (A), the surfactant (B), the compound (C1) represented by the chemical formula (1), and Since it contains the compound (C) which is at least 1 sort (s) chosen from the said compound (C2), it turns out that all have suppressed the gelatinization of amino-modified silicone.
On the other hand, a polyoxyalkylene derivative having no amino group (Comparative Example 2), an amine compound having no polyoxyalkylene structure (Comparative Examples 3 and 4), and a polyoxyalkylene compound having one amino group at a non-terminal portion Since (Comparative Example 5) does not correspond to the compound (C), gelation of the amino-modified silicone that is the subject of the present application cannot be suppressed.

Claims (8)

An amino-modified silicone (A), a surfactant (B), and a compound (C) that is at least one selected from the following compound (C1) and the following compound (C2) represented by the following chemical formula (1): Fiber treatment agent.

(In the formula (1), ^{R 1} represents an organic group, ^{R 2} is an organic group, ^{A 1} O is, .m showing an oxyalkylene group having 2 to 4 carbon atoms is a number of 1 to 50.)
Compound (C2): amine compound having a polyoxyalkylene group and two or more primary amine groups in the molecule   The fiber treatment agent according to claim 1, further comprising a carboxylic acid compound (D). The fiber treatment agent according to claim 1 or 2, wherein the A ¹ O is an oxyethylene group.   The fiber processing agent in any one of Claims 1-3 whose weight ratio of the said compound (C) to the non volatile matter of the said processing agent is 0.1 to 15 weight%.   The fiber treatment agent according to any one of claims 1 to 4, wherein the surfactant has a polyoxyethylene skeleton.   The fiber treatment agent according to any one of claims 1 to 5, which is used for acrylic fibers.   The acrylic fiber for carbon fiber manufacture formed by making the fiber treatment agent in any one of Claims 1-6 adhere to the raw material acrylic fiber of the acrylic fiber for carbon fiber manufacture.   A yarn-making process in which the fiber treatment agent according to any one of claims 1 to 6 is attached to a raw acrylic fiber for acrylic fiber for carbon fiber production, and a flame-resistant fiber in an oxidizing atmosphere at 200 to 300 ° C. A method for producing carbon fiber, comprising: a flameproofing treatment step to be converted; and a carbonization treatment step of carbonizing the flameproofed fiber in an inert atmosphere at 300 to 2000 ° C.