JP2021046648A - Treatment agent for synthetic fiber spinning process and synthetic fiber - Google Patents

Abstract

To provide a treatment agent for synthetic fiber that reduces the generation of fuzz in a spinning process and can suppress a deterioration of yarn quality due to long-term operation in the spinning process, and provide a synthetic fiber.SOLUTION: A treatment agent for synthetic fiber contains an alkenesulfonic acid compound represented by formula (1).SELECTED DRAWING: None

Description

The present invention relates to a treatment agent for synthetic fibers capable of improving the quality of yarn wound by spinning and further suppressing deterioration of yarn quality due to long-term operation, and synthetic fibers to which such treatment agents are attached.

Generally, in the synthetic fiber spinning process, a treatment for adhering a synthetic fiber treatment agent to the surface of the filament yarn of the synthetic fiber is performed from the viewpoint of reducing friction and preventing fiber damage such as yarn breakage. is there. In order to reduce the number of fluffs that may occur in the spinning process, it is preferable that the friction of the synthetic fiber treatment agent is as low as possible. On the other hand, in the spinning process, the frictional resistance between the fiber and the godet roller increases with time during a long operation, which causes a deterioration in yarn quality.

Conventionally, treatment agents for synthetic fibers disclosed in Patent Documents 1 to 3 are known. Patent Document 1 discloses a treatment agent for synthetic fibers containing 1 to 50% of a cured castor oil derivative. Patent Document 2 discloses a treatment agent for synthetic fibers containing a thiodipropionic acid ester, a secondary alkyl sulfonic acid compound, and a phosphoric acid ester in a specific ratio. Patent Document 3 discloses a treatment agent for synthetic fibers containing an esterified product of a sulfur-containing compound and a gelber alcohol.

Japanese Unexamined Patent Publication No. 2006-307352 Japanese Unexamined Patent Publication No. 08-120564 Japanese Patent No. 6530129

However, these conventional treatment agents for synthetic fibers have not been able to sufficiently cope with suppressing the generation of fluff caused by the large friction between the high temperature roller and the yarn to which the treatment agent is applied. In addition, it has not been possible to sufficiently cope with the deterioration of yarn quality due to rubbing with a high temperature roller for a long time in the spinning process.
The problem to be solved by the present invention is for synthetic fibers capable of reducing fluff generated due to high friction in the spinning process and further suppressing deterioration of yarn quality due to long-term operation in the spinning process. It is in the place of providing treatment agents and synthetic fibers.

As a result of intensive research to solve the above problems, the present inventor reduces fluff generated due to high friction in the spinning process, and reduces yarn quality due to long-term operation in the spinning process. It has been found that an alkene sulfonic acid compound having a specific chemical structure is largely involved in the suppression, and the above-mentioned problems have been solved.

（式（１）中において、
Ｒ^１：炭素数３〜２１の炭化水素基。
Ｍ^１：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）
２．前記式（１）のＲ^１が、炭素数７〜１７の炭化水素基である、１．に記載の合成繊維用処理剤。
３．平滑剤、ノニオン界面活性剤及び前記アルケンスルホン酸化合物を含む合成繊維用処理剤であって、前記平滑剤、前記ノニオン界面活性剤及び前記アルケンスルホン酸化合物の含有割合の合計を１００質量％とすると、前記アルケンスルホン酸化合物を０．０１〜１０質量％の割合で含有するものである、１．又は２．に記載の合成繊維用処理剤。
４．さらに、リン酸エステル化合物を含有する合成繊維用処理剤であって、前記リン酸エステル化合物が下記式（２）に示されるリン酸エステルＱ１と、下記式（３）に示されるリン酸エステルＱ２及び下記式（４）に示されるリン酸エステルＱ３から選ばれる少なくとも１つ以上とを含み、アルカリ過中和前処理された前記合成繊維用処理剤のＰ核ＮＭＲ測定において、前記リン酸エステルＱ１、前記リン酸エステルＱ２、前記リン酸エステルＱ３、リン酸及びその塩に帰属されるＰ核ＮＭＲ積分比率の合計を１００％としたとき、前記リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分比率が１５％以上である、１．〜３．のいずれか一項に記載の合成繊維用処理剤。

（式（２）中において、
Ｒ^２：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^３：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^２：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（３）中において、
Ｒ^４：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^５：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^３：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^４：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（４）中において、
Ｒ^６：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^５：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^６：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）
５．前記リン酸エステル化合物が前記リン酸エステルＱ１と前記リン酸エステルＱ２とを含み、前記リン酸エステルＱ１、前記リン酸エステルＱ２、前記リン酸エステルＱ３、前記リン酸及びその塩に帰属されるＰ核ＮＭＲ積分比率の合計を１００％としたとき、前記リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分比率が５〜５０％である、４．に記載の合成繊維用処理剤。
６．前記平滑剤が、分岐鎖を有するエステル化合物を含有する、３．〜５．のいずれか一項に記載の合成繊維用処理剤。
７．さらに、下記の式（５）に示されるヒドロキシアルカンスルホン酸化合物を含む、１．〜６．のいずれか一項に記載の合成繊維用処理剤。

（式（５）において、
Ｒ^７：炭素数５〜２３のヒドロキシアルキル基。
Ｍ^７：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）
８．前記アルケンスルホン酸化合物及び前記ヒドロキシアルカンスルホン酸化合物の含有割合の合計を１００質量部とすると、前記アルケンスルホン酸化合物を４０〜７５質量部及び前記ヒドロキシアルカンスルホン酸化合物を２５〜６０質量部の割合で含む、７．に記載の合成繊維用処理剤。
９．前記平滑剤、前記ノニオン界面活性剤、及びイオン界面活性剤を含有する合成繊維用処理剤であって、前記イオン界面活性剤が前記アルケンスルホン酸化合物、前記リン酸エステル化合物及び前記ヒドロキシアルカンスルホン酸化合物を含み、前記平滑剤、前記ノニオン界面活性剤及び前記イオン界面活性剤の含有割合の合計を１００質量％とすると、前記アルケンスルホン酸化合物を０．０１〜１０質量％の割合で含有する、７．又は８．に記載の合成繊維用処理剤。
１０．１．〜９．のいずれか一項に記載の合成繊維用処理剤が付着していることを特徴とする合成繊維。 Specifically, the gist of the present invention is as follows.
1. 1. A treatment agent for synthetic fibers, which comprises an alkene sulfonic acid compound represented by the following formula (1).

(In equation (1)
R ¹ : Hydrocarbon group having 3 to 21 carbon atoms.
M ¹ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )
2. ^{1. R 1 of the} formula (1) is a hydrocarbon group having 7 to 17 carbon atoms. The treatment agent for synthetic fibers described in 1.
3. 3. A treatment agent for synthetic fibers containing a smoothing agent, a nonionic surfactant and the alkene sulfonic acid compound, wherein the total content of the smoothing agent, the nonionic surfactant and the alkene sulfonic acid compound is 100% by mass. The alkene sulfonic acid compound is contained in a proportion of 0.01 to 10% by mass. Or 2. The treatment agent for synthetic fibers described in 1.
4. Further, a treatment agent for synthetic fibers containing a phosphoric acid ester compound, wherein the phosphoric acid ester compound is a phosphoric acid ester Q1 represented by the following formula (2) and a phosphoric acid ester Q2 represented by the following formula (3). In the P-nuclear NMR measurement of the synthetic fiber treatment agent containing at least one selected from the phosphoric acid ester Q3 represented by the following formula (4) and pretreated with alkali overneutralization, the phosphoric acid ester Q1 , The P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q1 when the total of the P-nuclear NMR integration ratios attributed to the phosphoric acid ester Q2, the phosphoric acid ester Q3, phosphoric acid and its salts is 100%. Is 15% or more. ~ 3. The treatment agent for synthetic fibers according to any one of the above.

(In equation (2)
R ² : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ³ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ² : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )

(In equation (3)
R ^{4: Alkyl group having 4 to} 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ⁵ : An alkyl group having 4 to 24 carbon atoms or an alkenyl group having 4 to 24 carbon atoms.
M ³ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt.
M ⁴ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )

(In equation (4)
R ⁶ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ⁵ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt.
M ⁶ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )
5. The phosphoric acid ester compound contains the phosphoric acid ester Q1 and the phosphoric acid ester Q2, and is attributed to the phosphoric acid ester Q1, the phosphoric acid ester Q2, the phosphoric acid ester Q3, the phosphoric acid and a salt thereof. 4. When the total nuclear NMR integration ratio is 100%, the P nuclear NMR integration ratio attributed to the phosphoric acid ester Q2 is 5 to 50%. The treatment agent for synthetic fibers described in 1.
6. 3. The smoothing agent contains an ester compound having a branched chain. ~ 5. The treatment agent for synthetic fibers according to any one of the above.
7. Further, 1. The hydroxyalkane sulfonic acid compound represented by the following formula (5) is contained. ~ 6. The treatment agent for synthetic fibers according to any one of the above.

(In equation (5)
R ⁷ : Hydroxyalkyl group having 5 to 23 carbon atoms.
M ⁷ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )
8. Assuming that the total content of the alkene sulfonic acid compound and the hydroxyalcan sulfonic acid compound is 100 parts by mass, the ratio of the alkene sulfonic acid compound is 40 to 75 parts by mass and the content ratio of the hydroxyalcan sulfonic acid compound is 25 to 60 parts by mass. Including in 7. The treatment agent for synthetic fibers described in 1.
9. A processing agent for synthetic fibers containing the smoothing agent, the nonionic surfactant, and an ionic surfactant, wherein the ionic surfactant is the alkene sulfonic acid compound, the phosphoric acid ester compound, and the hydroxyalcan sulfonic acid. Assuming that the total content of the smoothing agent, the nonionic surfactant and the ionic surfactant is 100% by mass, the alkene sulfonic acid compound is contained in a ratio of 0.01 to 10% by mass. 7. 7. Or 8. The treatment agent for synthetic fibers described in 1.
10.1. ~ 9. A synthetic fiber to which the treatment agent for synthetic fiber according to any one of the above items is attached.

According to the present invention, in the spinning process, the generation of fluff due to the high friction between the high temperature roller and the yarn to which the treatment agent is applied is reduced, and further, the yarn quality due to the long operation in the spinning process is reduced. It is possible to suppress the decrease of.

The present invention relates to a synthetic fiber treatment agent containing the alkene sulfonic acid compound represented by the above formula (1), and a synthetic fiber to which the synthetic fiber treatment agent is attached.
Hereinafter, the present invention will be described in detail.

（式（１）中において、
Ｒ^１：炭素数３〜２１の炭化水素基。
Ｍ^１：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）
本発明におけるアルケンスルホン酸化合物は、式（１）中のＲ^１で示される炭化水素基は、分岐鎖を有していてもよく、式（１）に示されるアルケンスルホン酸化合物は、シス−トランス異性体を有するが、シス体であっても、トランス体であってもよい。
本発明において、上記式（１）中のＲ^１が、炭素数７〜１７のアルキル基であるアルケンスルホン酸化合物が好ましく、炭素数９〜１６がさらに好ましく、炭素数１１〜１５が特に好ましい。
本発明における式（１）に示されるアルケンスルホン酸化合物は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 <Alkene sulfonic acid compound represented by the formula (1)>
The treatment agent for synthetic fibers of the present invention contains an alkene sulfonic acid compound represented by the following formula (1) as an essential component.

(In equation (1)
R ¹ : Hydrocarbon group having 3 to 21 carbon atoms.
M ¹ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )
Alkene sulfonic acid compound in the present invention, the hydrocarbon group represented by R ¹ in the formula (1) may have a branched chain, alkene sulfonic acid compound represented by formula (1) cis - It has a trans isomer, but may be a cis form or a trans form.
^{In the present invention, R 1} in the above formula (1) is preferably an alkene sulfonic acid compound which is an alkyl group having 7 to 17 carbon atoms, more preferably 9 to 16 carbon atoms, and particularly preferably 11 to 15 carbon atoms.
The alkene sulfonic acid compound represented by the formula (1) in the present invention may be used alone or in combination of two or more.

When the treatment agent for synthetic fibers in the present invention contains a smoothing agent, a nonionic surfactant and the alkene sulfonic acid compound, the total content of the smoothing agent, the nonionic surfactant and the alkene sulfonic acid compound is 100. In terms of mass%, the alkene sulfonic acid compound is preferably contained in a proportion of 0.01 to 10% by mass, more preferably in a proportion of 0.05 to 8% by mass, and 0.1 to 6% by mass. It is more preferable to contain it in a proportion of%.

<Smoothing agent>
The smoothing agent used for the synthetic fiber treatment agent in the present invention includes (1) monoester compounds such as octyl steerert, lauryl palmitate, oleyl oleate, and oleyl ercinato, and (2) diorail adipate, 1, Diester compounds such as 4-butane diolate, dilauryl sebatate, diolayl fumarate, etc., (3) lauryl mercaptopropionate, octyl mercaptopropionate, dilauryl thiodipropionate, diorail thiodipropionate, etc. Examples of the sulfur-containing ester compound (4) mineral oil composed of paraffin, olefin, naphthene and the like. Of these, those containing an ester compound having a branched structure in the molecule are preferable. Examples of the ester compound having a branched structure in the molecule include (5) branched monoester compounds such as (5) isobutyl steerate, 2-ethylhexyl oleic acid ester, 2-ethylhexyl erucic acid ester, isostearyl oleate, and isotetracosyl ersinato. , (6) Branched diesters such as diisolauryl sebatate, diisostearyl adipate, diisotetracosyl adipate, di-2-ethylhexyl maleic acid ester, neopentyl glycol dioleic acid ester, 2-ethylhexyl adipate, etc. (7) Polyhydric alcohol esters such as glycerin trioleate, glycerin trilaurate, trimethylolpropane trioleate, trimethylolpropane soybean fatty acid ester, pentaerythritol tetraoctanoate, (8) trioctyl limerite, triethyl citrate Polyvalent carboxylic acid esters such as (9) natural fats and oils such as soybean oil, palm oil, castor oil, palm oil, rapeseed oil, (10) 2-ethylhexyl mercaptopropionate, isolauryl mercaptopropionate, diisolauryl Examples thereof include sulfur-containing branched esters such as thiodipropionate, diisostearylthiodipropionate, diisopalmityl dithiopropionate, and trimethylpropanthris mercaptopropionate. Of these, 2-ethylhexyl adipate, isostearyl oleate, rapeseed oil, trimethylolpropane trioleate, diisostearylthiodipropionate, and diisolaurylthiodipropionate are more preferable. These smoothing agent components may be used alone or in combination of two or more.

<Nonion surfactant>
The nonionic surfactant used in the synthetic fiber treatment agent in the present invention is not particularly limited, and for example, (1) at least one selected from (1) organic acids, organic alcohols, organic amines, and organic amides has 2 to 4 carbon atoms. Polyoxyethylene lauric acid ester, polyoxyethylene oleic acid ester, polyoxyethylene lauric acid ester methyl ether, polyoxyethylene octyl ether, polyoxypropylene lauryl ether methyl ether, polyoxybutylene oleyl Ether-type nonionic surfactants such as ethers, polyoxyethylene polyoxypropylene lauryl ethers, polyoxyethylene polyoxypropylene nonylphenyl ethers, polyoxyethylene lauryl amino ethers, and polyoxyethylene lauroamide ethers, (2) sorbitan monooleate , Solbitan trioleate, polyhydric alcohol partial ester type nonionic surfactant such as glycerin monolaurate, (3) polyethylene glycol dioleate, polyoxyethylene sorbitan monooleate, polyoxybutylene sorbitan trioleate, polyoxypropylene castor oil , Polyoxyethylene hydrogenated castor oil, polyoxyethylene propylene cured castor oil trioleate, polyoxyethylene cured castor oil trilaurate, ethylene oxide (hereinafter referred to as EO) additive of castor oil and at least one compound selected from EO adduct of cured castor oil. And polyoxyalkylene polyhydric alcohol fatty acid ester type nonionic surfactant such as ether ester compound condensed with monocarboxylic acid and dicarboxylic acid, (4) alkylamide type nonionic surfactant such as diethanolamine monolauroamide and the like. Can be mentioned. These nonionic surfactants may be used alone or in combination of two or more. In the present invention, EO and PO at the end of the compound name mean an adduct of ethylene oxide and propylene oxide, respectively, and the number following the compound indicates the number of adducts thereof.

（式（２）中において、
Ｒ^２：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^３：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^２：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（３）中において、
Ｒ^４：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^５：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^３：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^４：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（４）中において、
Ｒ^６：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^５：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^６：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。） <Phosphate ester>
The treatment agent for synthetic fibers in the present invention is at least selected from the phosphoric acid ester Q1 represented by the following formula (2), the phosphoric acid ester Q2 represented by the following formula (3), and the phosphoric acid ester Q3 represented by the following formula (4). It may contain one or more.

(In equation (2)
R ² : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ³ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ² : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )

(In equation (3)
R ^{4: Alkyl group having 4 to} 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ⁵ : An alkyl group having 4 to 24 carbon atoms or an alkenyl group having 4 to 24 carbon atoms.
M ³ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt.
M ⁴ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )

(In equation (4)
R ⁶ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ⁵ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt.
M ⁶ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )

Here, in the P-nuclear NMR measurement of the treatment agent for synthetic fibers that has been pretreated with alkali overneutration, P belonging to the phosphoric acid ester Q1, the phosphoric acid ester Q2, the phosphoric acid ester Q3, the phosphoric acid and a salt thereof. When the total nuclear NMR integration ratio is 100%, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is preferably 15% or more, more preferably 17% or more, and more preferably 20% or more. Is more preferable. Similarly, the P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q2 is preferably 5 to 50%, more preferably 6 to 45%, and further preferably 7 to 40%. preferable. Further, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is 15 to 80%, and the P-nuclear NMR integration ratio attributable to the phosphate ester Q2 is 5 to 50%. Preferably, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is 17 to 70%, and the P-nuclear NMR integration ratio attributable to the phosphate ester Q2 is 6 to 45%. Preferably, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is 20 to 60%, and the P-nuclear NMR integration ratio attributable to the phosphate ester Q2 is 7 to 40%. preferable.
The "alkali overneutralization pretreatment" in the present invention means a pretreatment in which an excess amount of alkali (for example, sodium hydroxide, potassium hydroxide, laurylamine) is added to a treatment agent for synthetic fibers. ^{31 In} the measurement of P-NMR, by performing this "alkaline overneutralization pretreatment", the peaks attributed to phosphoric acid ester Q1, phosphoric acid ester Q2, phosphoric acid ester Q3, phosphoric acid and its salts can be clarified. It can be divided, and the P nuclear integral ratio attributed to each compound can be calculated by the following formulas (1) to (4). ^{In the measurement of 31} P-NMR in the present invention, an alkali overneutralization pretreatment was performed by adding an alkali to which the observed peaks were separated to the synthetic fiber treatment agent.
The P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q1 is the following formula (1), and the P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q2 is the following formula (2). The P-nuclear NMR integration ratio attributed to Q3 is shown in the following formula (3), and the P-nuclear NMR integration ratio attributed to the phosphoric acid and its salt is shown in the following formula (4).

（数式（１）において、
Ｑ１＿Ｐ％：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

（数式（２）において、
Ｑ２＿Ｐ％：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

（数式（３）において、
Ｑ３＿Ｐ％：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

（数式（４）において、
リン酸＿Ｐ％：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

(In formula (1)
Q1_P%: P-nuclear NMR integration ratio attributed to phosphate ester Q1,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

(In formula (2)
Q2_P%: P-nuclear NMR integration ratio attributed to phosphate ester Q2,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

(In formula (3)
Q3_P%: P-nuclear NMR integration ratio attributed to phosphate ester Q3,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

(In formula (4)
Phosphoric acid_P%: P-nuclear NMR integration ratio attributed to phosphoric acid and its salts,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

The formula (2) to the phosphoric acid ester Q1~Q3 shown in (4), the ^{R 2, R 3, R 4} , R 5, R 6 in the formula (2) to (4), for example, butanol Residues without hydroxyl groups, hexanols with hydroxyl groups, heptanols with hydroxyl groups, octanols with hydroxyl groups, nonanols with hydroxyl groups, decanols with hydroxyl groups Residues, lauryl alcohol with hydroxyl groups removed, myristyl alcohols with hydroxyl groups removed, palmityl alcohols with hydroxyl groups removed, oleyl alcohols with hydroxyl groups removed, stearyl alcohols with hydroxyl groups removed Residues, Eikosanol minus hydroxyl groups, Tetracosanol without hydroxyl groups, 2-Ethylhexanol without hydroxyl groups, 2-decyl-1-tetradecanol without hydroxyl groups Examples thereof include residues, residues obtained by removing hydroxyl groups from isocetyl alcohol, residues obtained by removing hydroxyl groups from 2-butyl-1-octanol, and the like. Of these, residues obtained by removing hydroxyl groups from 2-ethylhexanol, oleyl alcohol, 2-decyl-1-tetradecanol, isosetyl alcohol, and 2-butyl-1-octanol are preferable.
The counter ion for the phosphoric acid ester in the phosphoric acid esters Q1 to Q3 represented by the above formulas (2) to (4) is not particularly limited, but for example, hydrogen, alkali metal, alkaline earth metal, ammonium, organic amine, and the like. Examples include phosphonium. Of these, dibutylethanolamine, polyoxyethylene laurylamino ether, polyoxyethylene octylamino ether, sodium hydroxide, and potassium hydroxide are preferable.
These phosphoric acid esters may be used alone or in combination of two or more.

（式（５）において、
Ｒ^７：炭素数５〜２３のヒドロキシアルキル基。
Ｍ^７：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、ホスホニウム又は有機アミン塩。）
上記式（５）中のヒドロキシアルキル基は分岐鎖であってもよく、ヒドロキシ基の位置は、式（５）中のスルホ基に結合した炭素を１位としたとき、２位、３位、４位の少なくとも１か所にあることが好ましい。また、炭素数９〜１９のヒドロキシアルキル基であることが好ましい。
上記式（５）に示すヒドロキシアルカンスルホン酸化合物は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The treatment agent for synthetic fibers in the present invention preferably contains a hydroxyalkane sulfonic acid compound represented by the following formula (5).

(In equation (5)
R ⁷ : Hydroxyalkyl group having 5 to 23 carbon atoms.
M ⁷ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )
The hydroxyalkyl group in the above formula (5) may be a branched chain, and the positions of the hydroxy groups are at the 2nd and 3rd positions when the carbon bonded to the sulfo group in the formula (5) is at the 1st position. It is preferably in at least one of the 4th positions. Further, it is preferably a hydroxyalkyl group having 9 to 19 carbon atoms.
The hydroxyalkane sulfonic acid compound represented by the above formula (5) may be used alone or in combination of two or more.

Assuming that the total content of the alkene sulfonic acid compound represented by the formula (1) and the hydroxyalcan sulfonic acid compound represented by the formula (5) is 100 parts by mass, the alkene sulfonic acid compound is 40 to 75 parts by mass and The hydroxyalkane sulfonic acid compound is preferably contained in a proportion of 25 to 60 parts by mass, and the alken sulfonic acid compound may be contained in a proportion of 40 to 71 parts by mass and the hydroxyalcan sulfonic acid compound may be contained in a proportion of 29 to 60 parts by mass. More preferred.

The treatment agent for synthetic fibers in the present invention may further contain other ionic surfactants, and specifically, for example, (1) potassium acetate, potassium octanoate, potassium oleate, sodium oleate. Carboxylate soap-type ionic surfactants such as salts and potassium alkenyl succinate, (2) Sulfate-type ionic surfactants such as secondary alkane sulfonic acid sodium salt, dodecylbenzene sulfonic acid sodium salt, dioctyl sulfosuccinate sodium salt Agents, (3) Sulfate-type ion surfactants such as polyoxyethylene lauryl sulfate sodium salt, hexadecyl sulfate potassium salt, beef fat sulfide oil, castor oil sulfide oil and the like can be mentioned. These components may be used alone or in combination of two or more.

When the treatment agent for synthetic fibers in the present invention contains the above-mentioned smoothing agent, nonionic surfactant, and ionic surfactant, the ionic surfactant is the alkene sulfonic acid compound, the phosphoric acid ester compound, and the above. Assuming that the total content of the smoothing agent, the nonionic surfactant and the ionic surfactant is 100% by mass, the alkene sulfonic acid compound is contained in an amount of 0.01 to 10% by mass. It is preferably contained in a proportion of 0.05 to 8% by mass, more preferably 0.1 to 6% by mass, and further preferably in a proportion of 0.1 to 6% by mass. By containing the alkene sulfonic acid compound represented by the formula (1) in such a blending amount range, the effect of the present invention can be further improved, which is caused by high friction during spinning. It is possible to reduce fluff and suppress deterioration of yarn quality due to long-term operation in the spinning process.

<Other ingredients>
The treatment agent for synthetic fibers of the present invention is usually used as a stabilizer, antistatic agent, binder, antioxidant, ultraviolet absorber, etc. for maintaining the quality of the treatment agent within a range that does not impair the effects of the present invention. Ingredients used in the synthetic fiber treatment agent may be further blended.

<Synthetic fiber>
The synthetic fiber of the present invention is a synthetic fiber to which the treatment agent for synthetic fiber of the present invention is attached. The synthetic fiber to which the treatment agent for synthetic fibers of the present invention is attached is not particularly limited, and for example, (1) polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polylactic acid ester, (2) nylon 6, nylon. Examples thereof include polyamide fibers such as 66, (3) polyacrylic fibers such as polyacrylic and moda acrylic, and (4) polyolefin fibers such as polyethylene and polypropylene. The fineness of the synthetic fiber to be produced is not particularly limited, but is preferably 150 decitex or more, more preferably 500 decitex or more, and particularly preferably 1000 decitex or more. The strength of the synthetic fiber to be produced is not particularly limited, but is preferably 5.0 cN / dtex or more, more preferably 6.0 cN / dtex or more, and particularly preferably 7.0 cN / dtex or more.
The ratio of the synthetic fiber treatment agent (solvent-free) of the present invention to be attached to the synthetic fiber is not particularly limited, but the synthetic fiber treatment agent of the present invention is 0.1 to 3% by mass (1 to 3% by mass) based on the synthetic fiber. It is preferable to attach the fibers in a ratio of (not containing the diluent and water). With such a configuration, the effect of the present invention is further improved.
The method for adhering the synthetic fiber treatment agent of the present invention is not particularly limited, and for example, a known method such as a roller refueling method, a guide refueling method using a measuring pump, an immersion refueling method, or a spray refueling method is adopted. be able to.

By containing the alkene sulfonic acid compound represented by the above formula (1) as an essential component, the treatment agent for synthetic fibers in the present invention can reduce fluff generated due to high friction in the spinning process. Furthermore, deterioration of yarn quality due to long-term operation in the spinning process of synthetic fibers can be suppressed. As a result, the synthetic fiber of the present embodiment can exhibit excellent process passability.

Hereinafter, the present invention will be described with reference to examples, but the technical scope of the present invention is not limited thereto. In the following Examples and Comparative Examples, "parts" means "parts by mass" and "%" means "% by mass".

<Test Category 1 (Sulfonic Acid Compounds Represented in Formulas (1) and (5))>
-Synthesis of sulfonic acid compounds (S1-1 and S2-1) Sulfur trioxide was added to 1-tetradecene and sulfonated at 50 ° C. or lower. An excess amount of an aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 1 hour and then heated at 150 ° C. for 1 hour in an autoclave. Petroleum ether and ethanol were added thereto, and the mixture was stirred and allowed to stand, and then the oil phase was removed to extract and remove oil-soluble impurities. The remaining aqueous phase was evaporated to dryness. This was chromatographically separated into S1-1 and S2-1 whose counterions are hydrogen, respectively. Then, sodium hydroxide was added to each of them so that the pH became 9, and the mixture was stirred well and then evaporated to dryness to obtain S1-1 and S2-1.
The contents of the alkene sulfonic acid compounds (S1-1 to S1-5, rS1-1) represented by the above formula (1) used in this example and the comparative example are shown in Table 1 and in the above formula (5). The contents of the hydroxyalkane sulfonic acid compounds (S2-1 to S2-5) are shown in Table 2.

<Test Category 2 (Phosphate Ester Compound)>
-Synthesis of Phosphate Ester Compound (P-1) Diphosphorus pentoxide was charged into 2-ethylhexanol under stirring in a four-necked flask and reacted at 70 ± 5 ° C. for 3 hours. Then, dibutylethanolamine was charged as a neutralizing agent, and the mixture was stirred at 50 ° C. for 1 hour. (P-2 to P-5) were synthesized by the same method as P-1 using the raw materials shown in Table 3 below. In the neutralization of P-2 and P-5, phosphorylation was added to an aqueous sodium hydroxide solution and stirred to neutralize.
-Synthesis of phosphoric acid ester compound (rP-1) Diphosphoric pentoxide and polyphosphoric acid were charged into oleyl alcohol under stirring in a four-necked flask and reacted at 60 ± 5 ° C. for 3 hours. Next, this was charged into an aqueous solution of potassium hydroxide as a neutralizing agent, and the mixture was stirred at 50 ° C. for 1 hour.

<Test Category 3 (Preparation of Synthetic Fiber Treatment Agent)>
-Preparation of treatment agent for synthetic fibers (Example 1) As a smoothing agent, 20 parts of dioleyl adipate (A-1), 35 parts of oleyl oleate (A-2), and diisostearylthiodipropionate (bSA) -1) is 5 parts, esterified compound (B-4) of polyethylene glycol (molecular weight 600) and 2 mol of oleic acid as a nonionic surfactant is 10 parts, sorbitan monooleate (B-5) is 8 parts, and castor oil. Alken sulfonic acid represented by the above formula (1) using 10 parts of −EO8 (B-8), 8 parts of an esterified compound (B-11) of 1 mol of castor oil −EO20 and 3 mol of oleic acid, and an ionic surfactant. 0.55 parts of the compound (S1-1), 0.4 parts of the hydroxyalcan sulfonic acid compound (S2-1) represented by the above formula (5), and 2 parts of the phosphoric acid ester compound (P-1). .9 parts and 0.15 parts of potassium oleate (D-1) as other components were uniformly mixed to prepare a treatment agent for synthetic fibers of Example 1.

-Preparation of treatment agents for synthetic fibers (Examples 2 to 11 and Comparative Examples 1 to 4) Synthetic fibers of Examples 2 to 11 and Comparative Examples 1 to 4 in the same manner as the preparation of the treatment agent for synthetic fibers of Example 1. The treatment agents for use were prepared, and the compositions of Examples 1 to 11 are shown in Table 4, and the compositions of Comparative Examples 1 to 4 are shown in Table 5.
However, in Example 2, in addition to the raw materials shown in Table 4, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2 was used as an antioxidant. , 4, 6 (1H, 3H, 5H) -trione was added at a ratio of 0.8 parts to 100 parts of the treatment agent.

0.15 g of laurylamine was added to 0.10 g of the prepared synthetic fiber treatment agent, and the mixture was thoroughly stirred. Using deuterated chloroform as the solvent, ³¹ P-NMR of this was measured. The P-nuclear integration ratio of the phosphoric acid ester compound is ^{calculated from the above formulas (1) to (4) using the measured values subjected to 31} P-NMR (trade name: MERCURY plus NMR Spectrometer System, 300 MHz manufactured by VARIAN). ), And are shown in Tables 4 and 5 below.

In Tables 4 and 5,
A-1: Georail Ajipart A-2: Oleyl Oleart A-3: 1,4-Butane Dioreart A-4: Mineral oil (Redwood seconds 120)
bA-1: Di (2-ethylhexyl) adipate bA-2: Isostearyl oleate bA-3: Rapeseed oil bA-4: Trimethylolpropane Trioleate SA-1: Diorylthiodipropionate bSA-1: Diiso Stearylthiodipropionate bSA-2: Diisododecylthiodipropionate B-1: Palm fatty acid-EO12
B-2: Oleyl alcohol-EO15
B-3: Isostearyl alcohol-EO8PO10
B-4: Esterate of polyethylene glycol (molecular weight 600) and 2 mol of oleic acid B-5: Sorbitan monooleate B-6: Laurylamine-EO6
B-7: Diethanolamine Oleic acid amide B-8: Castor oil-EO8
B-9: Hardened castor oil-EO12
B-10: Hardened castor oil-EO10PO15
B-11: Castor oil-EO20 1 mol and oleic acid 3 mol esterified B-12: Hardened castor oil-EO25 1 mol and lauric acid 2 mol esterified B-13: Hardened castor oil-EO15, adipic acid and stearic acid Polycondensate (molecular weight 6000)
D-1: Potassium oleate D-2: Sodium octylate SD-1: Sodium secondary alkylsulfonate (14-18 carbon atoms) SD-2: Sodium dioctylsulfosuccinate

<Test Category 4 (Evaluation of Synthetic Fiber Treatment Agent)>
-Evaluation of tension value Each synthetic fiber treatment agent prepared in Test Category 3 was uniformly diluted with ion-exchanged water or a diluent of an organic solvent as necessary to prepare a 15% solution. The above solution was applied to 1100 decitex, 192 filaments, and non-lubricated polyethylene terephthalate fiber having an intrinsic viscosity of 0.93 by the oiling roller lubrication method so as to give 0.6% by mass as a non-volatile content, and diluted. The agent was dried to obtain a test yarn. The test yarn was run in contact with a satin chrome pin having a surface temperature of 240 ° C. at an initial tension of 1.5 kg and a yarn speed of 1.0 m / min, and the tension value of the yarn after contact with the satin chrome pin was measured. The results are shown in Table 6.

・ Evaluation criteria for tension value ◎ ◎: less than 1.9 kg ◎ ○: 1.9 kg or more and less than 2.0 kg ○ ○: 2.0 kg or more and less than 2.1 kg ○: 2.1 kg or more and less than 2.2 kg ×: 2.2 kg that's all

-Evaluation of tension over time under high temperature conditions Each synthetic fiber treatment agent prepared in Test Category 3 was uniformly diluted with ion-exchanged water or a diluent of an organic solvent as necessary to prepare a 15% solution. The above solution was applied to 1670 decitex, 288 filaments, and non-lubricated polyethylene terephthalate fiber having an intrinsic viscosity of 0.93 by the oiling roller lubrication method so as to give a non-volatile content of 0.6% by mass, and diluted. The agent was dried to obtain a test yarn. The test yarn was run in contact with a satin chrome pin having a surface temperature of 250 ° C. at an initial tension of 1.5 kg and a yarn speed of 1.0 m / min, and the tension value of the yarn after contact with the satin chrome pin was measured. The running time at the time when the tension value increased by 10% from the tension value after 20 minutes of running was recorded and evaluated according to the following criteria. The results are shown in Table 6.

・ Evaluation criteria for tension increase ◎ ◎: 8 hours or more ◎ ○: 6 hours or more and less than 8 hours ○ ○: 4 hours or more and less than 6 hours ○: 2 hours or more and less than 4 hours ×: less than 2 hours

As is clear from the results in Table 6, the synthetic fiber treatment agents of each example had good evaluations of tension value and tension increase. According to the present invention, there is an effect of reducing fluff generated due to high friction in the spinning process and suppressing deterioration of yarn quality due to long-term operation.

The synthetic fiber treatment agent of the present invention and the synthetic fiber to which the synthetic fiber treatment agent is attached have fluff caused by the high friction between the high temperature roller and the yarn to which the treatment agent is applied in the spinning process. It is very useful because it can reduce the occurrence and further suppress the deterioration of yarn quality due to long-term operation in the spinning process.

The present invention relates to a synthetic fiber spinning process treatment agent capable of improving the quality of yarn wound by spinning and further suppressing deterioration of yarn quality due to long-term operation, and a synthetic fiber to which such a treatment agent is attached.

Generally, in the synthetic fiber spinning process, a treatment for adhering a synthetic fiber treatment agent to the surface of the filament yarn of the synthetic fiber is performed from the viewpoint of reducing friction and preventing fiber damage such as yarn breakage. is there. In order to reduce the number of fluffs that may occur in the spinning process, it is preferable that the friction of the synthetic fiber treatment agent is as low as possible. On the other hand, in the spinning process, the frictional resistance between the fiber and the godet roller increases with time during a long operation, which causes a deterioration in yarn quality.

Conventionally, treatment agents for synthetic fibers disclosed in Patent Documents 1 to 3 are known. Patent Document 1 discloses a treatment agent for synthetic fibers containing 1 to 50% of a cured castor oil derivative. Patent Document 2 discloses a treatment agent for synthetic fibers containing a thiodipropionic acid ester, a secondary alkyl sulfonic acid compound, and a phosphoric acid ester in a specific ratio. Patent Document 3 discloses a treatment agent for synthetic fibers containing an esterified product of a sulfur-containing compound and a gelber alcohol.

Japanese Unexamined Patent Publication No. 2006-307352 Japanese Unexamined Patent Publication No. 08-120564 Japanese Patent No. 6530129

However, these conventional treatment agents for synthetic fibers have not been able to sufficiently cope with suppressing the generation of fluff caused by the large friction between the high temperature roller and the yarn to which the treatment agent is applied. In addition, it has not been possible to sufficiently cope with the deterioration of yarn quality due to rubbing with a high temperature roller for a long time in the spinning process.
The problem to be solved by the present invention is synthetic fiber spinning that can reduce fluff generated due to high friction in the spinning process and further suppress deterioration of yarn quality due to long-term operation in the spinning process. in processing to provide a process for processing agents and synthetic fibers.

As a result of intensive research to solve the above problems, the present inventor reduces fluff generated due to high friction in the spinning process, and reduces yarn quality due to long-term operation in the spinning process. It has been found that an alkene sulfonic acid compound having a specific chemical structure is largely involved in the suppression, and the above-mentioned problems have been solved.

（式（１）中において、
Ｒ^１：炭素数３〜２１の炭化水素基。
Ｍ^１：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）
２．前記式（１）のＲ^１が、炭素数７〜１７の炭化水素基である、１．に記載の合成繊維紡糸工程用処理剤。
３．平滑剤、ノニオン界面活性剤及び前記アルケンスルホン酸化合物を含む合成繊維紡糸工程用処理剤であって、前記平滑剤、前記ノニオン界面活性剤及び前記アルケンスルホン酸化合物の含有割合の合計を１００質量％とすると、前記アルケンスルホン酸化合物を０．０１〜１０質量％の割合で含有するものである、１．又は２．に記載の合成繊維紡糸工程用処理剤。
４．さらに、リン酸エステル化合物を含有する合成繊維紡糸工程用処理剤であって、前記リン酸エステル化合物が下記式（２）に示されるリン酸エステルＱ１と、下記式（３）に示されるリン酸エステルＱ２及び下記式（４）に示されるリン酸エステルＱ３から選ばれる少なくとも１つ以上とを含み、アルカリ過中和前処理された前記合成繊維紡糸工程用処理剤のＰ核ＮＭＲ測定において、前記リン酸エステルＱ１、前記リン酸エステルＱ２、前記リン酸エステルＱ３、リン酸及びその塩に帰属されるＰ核ＮＭＲ積分比率の合計を１００％としたとき、前記リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分比率が１５％以上である、３．に記載の合成繊維紡糸工程用処理剤。

（式（２）中において、
Ｒ^２：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^３：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^２：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（３）中において、
Ｒ^４：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^５：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^３：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^４：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（４）中において、
Ｒ^６：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^５：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^６：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）
５．前記リン酸エステル化合物が前記リン酸エステルＱ１と前記リン酸エステルＱ２とを含み、前記リン酸エステルＱ１、前記リン酸エステルＱ２、前記リン酸エステルＱ３、前記リン酸及びその塩に帰属されるＰ核ＮＭＲ積分比率の合計を１００％としたとき、前記リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分比率が５〜５０％である、４．に記載の合成繊維紡糸工程用処理剤。
６．前記平滑剤が、分岐鎖を有するエステル化合物を含有する、４．又は５．に記載の合成繊維紡糸工程用処理剤。
７．さらに、下記の式（５）に示されるヒドロキシアルカンスルホン酸化合物を含む、４．〜６．のいずれか一項に記載の合成繊維紡糸工程用処理剤。

（式（５）において、
Ｒ^７：炭素数５〜２３のヒドロキシアルキル基。
Ｍ^７：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）
８．前記アルケンスルホン酸化合物及び前記ヒドロキシアルカンスルホン酸化合物の含有割合の合計を１００質量部とすると、前記アルケンスルホン酸化合物を４０〜７５質量部及び前記ヒドロキシアルカンスルホン酸化合物を２５〜６０質量部の割合で含む、７．に記載の合成繊維紡糸工程用処理剤。
９．前記平滑剤、前記ノニオン界面活性剤、及びイオン界面活性剤を含有する合成繊維紡糸工程用処理剤であって、前記イオン界面活性剤が前記アルケンスルホン酸化合物、前記リン酸エステル化合物及び前記ヒドロキシアルカンスルホン酸化合物を含み、前記平滑剤、前記ノニオン界面活性剤及び前記イオン界面活性剤の含有割合の合計を１００質量％とすると、前記アルケンスルホン酸化合物を０．０１〜１０質量％の割合で含有する、７．又は８．に記載の合成繊維紡糸工程用処理剤。
１０．１．〜９．のいずれか一項に記載の合成繊維紡糸工程用処理剤が、合成繊維に対し０．１〜３質量％（希釈剤と水を含まない）で付着していることを特徴とする合成繊維。 Specifically, the gist of the present invention is as follows.
1. 1. A treatment agent for a synthetic fiber spinning process , which comprises an alkene sulfonic acid compound represented by the following formula (1).

(In equation (1)
R ¹ : Hydrocarbon group having 3 to 21 carbon atoms.
M ^1: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )
2. ^{1. R 1 of the} formula (1) is a hydrocarbon group having 7 to 17 carbon atoms. The treatment agent for the synthetic fiber spinning process described in 1.
3. 3. A treatment agent for a synthetic fiber spinning process containing a smoothing agent, a nonionic surfactant and the alkene sulfonic acid compound, and the total content of the smoothing agent, the nonionic surfactant and the alkene sulfonic acid compound is 100% by mass. Then, the alkene sulfonic acid compound is contained in a ratio of 0.01 to 10% by mass. Or 2. The treatment agent for the synthetic fiber spinning process described in 1.
4. Further, a treatment agent for a synthetic fiber spinning process containing a phosphoric acid ester compound, wherein the phosphoric acid ester compound is a phosphoric acid ester Q1 represented by the following formula (2) and a phosphoric acid represented by the following formula (3). In the P-nuclear NMR measurement of the synthetic fiber spinning process treatment agent containing at least one selected from the ester Q2 and the phosphoric acid ester Q3 represented by the following formula (4) and pretreated with alkali overneutralization, the above. When the total of the P-nuclear NMR integration ratios attributed to the phosphoric acid ester Q1, the phosphoric acid ester Q2, the phosphoric acid ester Q3, the phosphoric acid and its salt is 100%, the P assigned to the phosphoric acid ester Q1. 2. The nuclear NMR integration ratio is 15% or more . The treatment agent for the synthetic fiber spinning process described in 1.

(In equation (2)
R ² : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ³ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ^2: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )

(In equation (3)
R ^{4: Alkyl group having 4 to} 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ⁵ : An alkyl group having 4 to 24 carbon atoms or an alkenyl group having 4 to 24 carbon atoms.
M ^3: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts.
M ^4: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )

(In equation (4)
R ⁶ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ^5: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts.
M ^6: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )
5. The phosphoric acid ester compound contains the phosphoric acid ester Q1 and the phosphoric acid ester Q2, and is attributed to the phosphoric acid ester Q1, the phosphoric acid ester Q2, the phosphoric acid ester Q3, the phosphoric acid and a salt thereof. 4. When the total nuclear NMR integration ratio is 100%, the P nuclear NMR integration ratio attributed to the phosphoric acid ester Q2 is 5 to 50%. The treatment agent for the synthetic fiber spinning process described in 1.
6. 4. The smoothing agent contains an ester compound having a branched chain . Or 5. The treatment agent for the synthetic fiber spinning process described in 1.
7. Further, it contains a hydroxyalkane sulfonic acid compound represented by the following formula (5), 4 . ~ 6. The treatment agent for the synthetic fiber spinning process according to any one of the above.

(In equation (5)
R ⁷ : Hydroxyalkyl group having 5 to 23 carbon atoms.
M ^7: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )
8. Assuming that the total content of the alkene sulfonic acid compound and the hydroxyalcan sulfonic acid compound is 100 parts by mass, the ratio of the alkene sulfonic acid compound is 40 to 75 parts by mass and the content ratio of the hydroxyalcan sulfonic acid compound is 25 to 60 parts by mass. Including in 7. The treatment agent for the synthetic fiber spinning process described in 1.
9. A processing agent for a synthetic fiber spinning process containing the smoothing agent, the nonionic surfactant, and an ionic surfactant, wherein the ionic surfactant is the alkene sulfonic acid compound, the phosphoric acid ester compound, and the hydroxyalkane. It contains a sulfonic acid compound, and if the total content of the smoothing agent, the nonionic surfactant and the ionic surfactant is 100% by mass, the alkene sulfonic acid compound is contained in a ratio of 0.01 to 10% by mass. Yes, 7. Or 8. The treatment agent for the synthetic fiber spinning process described in 1.
10.1. ~ 9. The synthetic fiber according to any one of the above items, wherein the treatment agent for the synthetic fiber spinning process is attached to the synthetic fiber in an amount of 0.1 to 3% by mass (excluding a diluent and water).

According to the present invention, in the spinning process, the generation of fluff due to the high friction between the high temperature roller and the yarn to which the treatment agent is applied is reduced, and further, the yarn quality due to the long operation in the spinning process is reduced. It is possible to suppress the decrease of.

In the present invention, the synthetic fiber spinning process treatment agent containing the alkene sulfonic acid compound represented by the above formula (1) and the synthetic fiber spinning process treatment agent contain 0.1 to 3% by mass (1 to 3% by mass) of the synthetic fiber. It relates to synthetic fibers attached with ( without diluent and water).
Hereinafter, the present invention will be described in detail.

（式（１）中において、
Ｒ^１：炭素数３〜２１の炭化水素基。
Ｍ^１：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）
本発明におけるアルケンスルホン酸化合物は、式（１）中のＲ^１で示される炭化水素基は、分岐鎖を有していてもよく、式（１）に示されるアルケンスルホン酸化合物は、シス−トランス異性体を有するが、シス体であっても、トランス体であってもよい。
本発明において、上記式（１）中のＲ^１が、炭素数７〜１７のアルキル基であるアルケンスルホン酸化合物が好ましく、炭素数９〜１６がさらに好ましく、炭素数１１〜１５が特に好ましい。
本発明における式（１）に示されるアルケンスルホン酸化合物は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 <Alkene sulfonic acid compound represented by the formula (1)>
The treatment agent for the synthetic fiber spinning process of the present invention contains an alkene sulfonic acid compound represented by the following formula (1) as an essential component.

(In equation (1)
R ¹ : Hydrocarbon group having 3 to 21 carbon atoms.
M ^1: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )
Alkene sulfonic acid compound in the present invention, the hydrocarbon group represented by R ¹ in the formula (1) may have a branched chain, alkene sulfonic acid compound represented by formula (1) cis - It has a trans isomer, but may be a cis form or a trans form.
^{In the present invention, R 1} in the above formula (1) is preferably an alkene sulfonic acid compound which is an alkyl group having 7 to 17 carbon atoms, more preferably 9 to 16 carbon atoms, and particularly preferably 11 to 15 carbon atoms.
The alkene sulfonic acid compound represented by the formula (1) in the present invention may be used alone or in combination of two or more.

When the treatment agent for the synthetic fiber spinning process in the present invention contains a smoothing agent, a nonionic surfactant and the alkene sulfonic acid compound, the total content of the smoothing agent, the nonionic surfactant and the alkene sulfonic acid compound. Is 100% by mass, the alkene sulfonic acid compound is preferably contained in a proportion of 0.01 to 10% by mass, more preferably in a proportion of 0.05 to 8% by mass, and 0.1 to 1% by mass. It is more preferably contained in a proportion of 6% by mass.

<Smoothing agent>
Examples of the smoothing agent used in the treatment agent for the synthetic fiber spinning process in the present invention include (1) monoester compounds such as octyl steerert, lauryl palmitate, oleyl oleate, and oleyl ercinato, and (2) dioleyl adipate. Diester compounds such as 1,4-butane dioleate, dilauryl sebatate, and diolayl fumarate, (3) lauryl mercaptopropionate, octyl mercaptopropionate, dilauryl thiodipropionate, diorail thiodipropio Examples thereof include sulfur-containing ester compounds such as nat, and (4) mineral oils composed of paraffin, olefin, naphthene and the like. Of these, those containing an ester compound having a branched structure in the molecule are preferable. Examples of the ester compound having a branched structure in the molecule include (5) branched monoester compounds such as (5) isobutyl steerate, 2-ethylhexyl oleic acid ester, 2-ethylhexyl erucic acid ester, isostearyl oleate, and isotetracosyl ersinato. , (6) Branched diesters such as diisolauryl sebatate, diisostearyl adipate, diisotetracosyl adipate, di-2-ethylhexyl maleic acid ester, neopentyl glycol dioleic acid ester, 2-ethylhexyl adipate, etc. (7) Polyhydric alcohol esters such as glycerin trioleate, glycerin trilaurate, trimethylolpropane trioleate, trimethylolpropane soybean fatty acid ester, pentaerythritol tetraoctanoate, (8) trioctyl limerite, triethyl citrate Polyvalent carboxylic acid esters such as (9) natural fats and oils such as soybean oil, palm oil, castor oil, palm oil, rapeseed oil, (10) 2-ethylhexyl mercaptopropionate, isolauryl mercaptopropionate, diisolauryl Examples thereof include sulfur-containing branched esters such as thiodipropionate, diisostearylthiodipropionate, diisopalmityl dithiopropionate, and trimethylpropanthris mercaptopropionate. Of these, 2-ethylhexyl adipate, isostearyl oleate, rapeseed oil, trimethylolpropane trioleate, diisostearylthiodipropionate, and diisolaurylthiodipropionate are more preferable. These smoothing agent components may be used alone or in combination of two or more.

<Nonion surfactant>
The nonionic surfactant used in the treatment agent for the synthetic fiber spinning process in the present invention is not particularly limited, and for example, (1) at least one selected from (1) organic acids, organic alcohols, organic amines, and organic amides has 2 carbon atoms. Compounds to which ~ 4 alkylene oxides are added, such as polyoxyethylene lauric acid ester, polyoxyethylene oleic acid ester, polyoxyethylene lauric acid ester methyl ether, polyoxyethylene octyl ether, polyoxypropylene lauryl ether methyl ether, polyoxy Ether-type nonionic surfactants such as butylene oleyl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene nonylphenyl ether, polyoxyethylene lauryl amino ether, and polyoxyethylene lauroamide ether, (2) sorbitan mono Polyhydric alcohol partially esterified nonionic surfactants such as oleart, sorbitan trioleate, glycerin monolaurate, (3) polyethylene glycol dioleate, polyoxyethylene sorbitan monooleate, polyoxybutylene sorbitan trioleate, polyoxy At least one selected from propylene castor oil, polyoxyethylene cured castor oil, polyoxyethylene propylene cured castor oil trioleate, polyoxyethylene cured castor oil trilaurate, ethylene oxide (hereinafter referred to as EO) additive of castor oil and EO adduct of cured castor oil. Polyoxyalkylene polyhydric alcohol fatty acid ester type nonionic surfactant such as ether ester compound obtained by condensing the compound with monocarboxylic acid and dicarboxylic acid, (4) Alkylamide type nonionic surfactant such as diethanolamine monolauroamide. And so on. These nonionic surfactants may be used alone or in combination of two or more. In the present invention, EO and PO at the end of the compound name mean an adduct of ethylene oxide and propylene oxide, respectively, and the number following the compound indicates the number of adducts thereof.

（式（２）中において、
Ｒ^２：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^３：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^２：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（３）中において、
Ｒ^４：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｒ^５：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^３：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^４：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）

（式（４）中において、
Ｒ^６：炭素数４〜２４のアルキル基、又は炭素数４〜２４のアルケニル基。
Ｍ^５：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。
Ｍ^６：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。） <Phosphate ester>
The treatment agent for the synthetic fiber spinning process in the present invention is selected from the phosphoric acid ester Q1 represented by the following formula (2), the phosphoric acid ester Q2 represented by the following formula (3), and the phosphoric acid ester Q3 represented by the following formula (4). It may contain at least one or more esters.

(In equation (2)
R ² : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ³ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ^2: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )

(In equation (3)
R ^{4: Alkyl group having 4 to} 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ⁵ : An alkyl group having 4 to 24 carbon atoms or an alkenyl group having 4 to 24 carbon atoms.
M ^3: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts.
M ^4: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )

(In equation (4)
R ⁶ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ^5: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts.
M ^6: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )

Here, in the P-nuclear NMR measurement of the treatment agent for the synthetic fiber spinning process that has been pretreated with alkali overneutralization, it is attributed to the above-mentioned phosphoric acid ester Q1, phosphoric acid ester Q2, phosphoric acid ester Q3, phosphoric acid and salts thereof. When the total P-nuclear NMR integration ratio is 100%, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is preferably 15% or more, more preferably 17% or more, 20 It is more preferably% or more. Similarly, the P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q2 is preferably 5 to 50%, more preferably 6 to 45%, and further preferably 7 to 40%. preferable. Further, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is 15 to 80%, and the P-nuclear NMR integration ratio attributable to the phosphate ester Q2 is 5 to 50%. Preferably, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is 17 to 70%, and the P-nuclear NMR integration ratio attributable to the phosphate ester Q2 is 6 to 45%. Preferably, the P-nuclear NMR integration ratio attributable to the phosphate ester Q1 is 20 to 60%, and the P-nuclear NMR integration ratio attributable to the phosphate ester Q2 is 7 to 40%. preferable.
The "alkali overneutralization pretreatment" in the present invention means a pretreatment in which an excess amount of alkali (for example, sodium hydroxide, potassium hydroxide, laurylamine) is added to a treatment agent for a synthetic fiber spinning process. .. ^{31 In} the measurement of P-NMR, by performing this "alkaline overneutralization pretreatment", the peaks attributed to phosphoric acid ester Q1, phosphoric acid ester Q2, phosphoric acid ester Q3, phosphoric acid and its salts can be clarified. It can be divided, and the P nuclear integral ratio attributed to each compound can be calculated by the following formulas (1) to (4). ^{In the measurement of 31} P-NMR in the present invention, an alkali overneutralization pretreatment was performed by adding an alkali to which the observed peaks were separated to the treatment agent for the synthetic fiber spinning process.
The P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q1 is the following formula (1), and the P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q2 is the following formula (2). The P-nuclear NMR integration ratio attributed to Q3 is shown in the following formula (3), and the P-nuclear NMR integration ratio attributed to the phosphoric acid and its salt is shown in the following formula (4).

（数式（１）において、
Ｑ１＿Ｐ％：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

（数式（２）において、
Ｑ２＿Ｐ％：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

（数式（３）において、
Ｑ３＿Ｐ％：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

（数式（４）において、
リン酸＿Ｐ％：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分比率、
Ｑ１＿Ｐ：リン酸エステルＱ１に帰属されるＰ核ＮＭＲ積分値、
Ｑ２＿Ｐ：リン酸エステルＱ２に帰属されるＰ核ＮＭＲ積分値、
Ｑ３＿Ｐ：リン酸エステルＱ３に帰属されるＰ核ＮＭＲ積分値、
リン酸＿Ｐ：リン酸及びその塩に帰属されるＰ核ＮＭＲ積分値。）

(In formula (1)
Q1_P%: P-nuclear NMR integration ratio attributed to phosphate ester Q1,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

(In formula (2)
Q2_P%: P-nuclear NMR integration ratio attributed to phosphate ester Q2,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

(In formula (3)
Q3_P%: P-nuclear NMR integration ratio attributed to phosphate ester Q3,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

(In formula (4)
Phosphoric acid_P%: P-nuclear NMR integration ratio attributed to phosphoric acid and its salts,
Q1_P: P-nuclear NMR integral value attributed to phosphate ester Q1,
Q2_P: P-nuclear NMR integral value attributed to phosphate ester Q2,
Q3_P: P-nuclear NMR integral value attributed to phosphate ester Q3,
Phosphoric acid_P: P-nuclear NMR integral value attributed to phosphoric acid and its salt. )

The formula (2) to the phosphoric acid ester Q1~Q3 shown in (4), the ^{R 2, R 3, R 4} , R 5, R 6 in the formula (2) to (4), for example, butanol Residues without hydroxyl groups, hexanols with hydroxyl groups, heptanols with hydroxyl groups, octanols with hydroxyl groups, nonanols with hydroxyl groups, decanols with hydroxyl groups Residues, lauryl alcohol with hydroxyl groups removed, myristyl alcohols with hydroxyl groups removed, palmityl alcohols with hydroxyl groups removed, oleyl alcohols with hydroxyl groups removed, stearyl alcohols with hydroxyl groups removed Residues, Eikosanol minus hydroxyl groups, Tetracosanol without hydroxyl groups, 2-Ethylhexanol without hydroxyl groups, 2-decyl-1-tetradecanol without hydroxyl groups Examples thereof include residues, residues obtained by removing hydroxyl groups from isocetyl alcohol, residues obtained by removing hydroxyl groups from 2-butyl-1-octanol, and the like. Of these, residues obtained by removing hydroxyl groups from 2-ethylhexanol, oleyl alcohol, 2-decyl-1-tetradecanol, isosetyl alcohol, and 2-butyl-1-octanol are preferable.
The formula (2) to pairs for phosphate ester in the phosphate ester Q1~Q3 shown in (4) ion is not particularly limited, for example, hydrogen, an alkali metal, of ammonium, organic amines, phosphonium or the like can be mentioned Be done. Of these, dibutylethanolamine, polyoxyethylene laurylamino ether, polyoxyethylene octylamino ether, sodium hydroxide, and potassium hydroxide are preferable.
These phosphoric acid esters may be used alone or in combination of two or more.

（式（５）において、
Ｒ^７：炭素数５〜２３のヒドロキシアルキル基。
Ｍ^７：水素原子、アルカリ金属、アンモニウム、ホスホニウム又は有機アミン塩。）
上記式（５）中のヒドロキシアルキル基は分岐鎖であってもよく、ヒドロキシ基の位置は、式（５）中のスルホ基に結合した炭素を１位としたとき、２位、３位、４位の少なくとも１か所にあることが好ましい。また、炭素数９〜１９のヒドロキシアルキル基であることが好ましい。
上記式（５）に示すヒドロキシアルカンスルホン酸化合物は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The treatment agent for the synthetic fiber spinning process in the present invention preferably contains a hydroxyalkane sulfonic acid compound represented by the following formula (5).

(In equation (5)
R ⁷ : Hydroxyalkyl group having 5 to 23 carbon atoms.
M ^7: a hydrogen atom, an alkali metal, of ammonium, phosphonium or organic amine salts. )
The hydroxyalkyl group in the above formula (5) may be a branched chain, and the positions of the hydroxy groups are at the 2nd and 3rd positions when the carbon bonded to the sulfo group in the formula (5) is at the 1st position. It is preferably in at least one of the 4th positions. Further, it is preferably a hydroxyalkyl group having 9 to 19 carbon atoms.
The hydroxyalkane sulfonic acid compound represented by the above formula (5) may be used alone or in combination of two or more.

Assuming that the total content of the alkene sulfonic acid compound represented by the formula (1) and the hydroxyalcan sulfonic acid compound represented by the formula (5) is 100 parts by mass, the alkene sulfonic acid compound is 40 to 75 parts by mass and The hydroxyalkane sulfonic acid compound is preferably contained in a proportion of 25 to 60 parts by mass, and the alken sulfonic acid compound may be contained in a proportion of 40 to 71 parts by mass and the hydroxyalcan sulfonic acid compound may be contained in a proportion of 29 to 60 parts by mass. More preferred.

The treatment agent for the synthetic fiber spinning process in the present invention may further contain other ionic surfactants, and specifically, for example, (1) potassium acetate, potassium octanoate, potassium oleate, olein. Carboxylate soap-type ion surfactants such as sodium acid salt and potassium alkenyl succinate, (2) Sulfate-type ions such as secondary alkane sulfonic acid sodium salt, dodecylbenzene sulfonic acid sodium salt, and dioctyl sulfosuccinate sodium salt. Examples thereof include surfactants, (3) sulfate ester-type ionized surfactants such as polyoxyethylene lauryl sulfate sodium salt, hexadecyl sulfate potassium salt, beef fat sulfide oil, and castor oil sulfide oil. These components may be used alone or in combination of two or more.

When the treatment agent for the synthetic fiber spinning process in the present invention contains the above-mentioned smoothing agent, nonionic surfactant, and ionic surfactant, the ionic surfactant is the alkene sulfonic acid compound and the phosphoric acid ester compound. And the hydroxyalkane sulfonic acid compound, and the total content of the smoothing agent, the nonionic surfactant and the ionic surfactant is 100% by mass, the alkene sulfonic acid compound is 0.01 to 10% by mass. It is preferably contained in a proportion of, more preferably 0.05 to 8% by mass, and even more preferably 0.1 to 6% by mass. By containing the alkene sulfonic acid compound represented by the formula (1) in such a blending amount range, the effect of the present invention can be further improved, which is caused by high friction during spinning. It is possible to reduce fluff and suppress deterioration of yarn quality due to long-term operation in the spinning process.

<Other ingredients>
The treatment agent for the synthetic fiber spinning process of the present invention is a stabilizer, an antistatic agent, a binder, an antioxidant, an ultraviolet absorber, etc. for maintaining the quality of the treatment agent within a range that does not impair the effect of the present invention. Ingredients usually used in the treatment agent for synthetic fibers may be further blended.

<Synthetic fiber>
The synthetic fiber of the present invention is a synthetic fiber in which the treatment agent for the synthetic fiber spinning process of the present invention is attached in an amount of 0.1 to 3% by mass (excluding a diluent and water) to the synthetic fiber. The synthetic fiber to which the treatment agent for the synthetic fiber spinning process of the present invention is attached is not particularly limited, and is, for example, (1) polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polylactic acid ester, and (2) nylon 6. , Polyacrylate-based fibers such as nylon 66, (3) Polyacrylic fibers such as polyacrylic and moda acrylic, and (4) Polyethylene fibers such as polyethylene and polypropylene. The fineness of the synthetic fiber to be produced is not particularly limited, but is preferably 150 decitex or more, more preferably 500 decitex or more, and particularly preferably 1000 decitex or more. The strength of the synthetic fiber to be produced is not particularly limited, but is preferably 5.0 cN / dtex or more, more preferably 6.0 cN / dtex or more, and particularly preferably 7.0 cN / dtex or more.
Proportion of attaching the synthetic fiber spinning process維用treatment agent of the present invention (without solvent) in the synthetic fibers, 0.1 to 3 wt% with respect to the synthetic fiber synthetic fiber spinning process for the treatment agent of the present invention (diluted Ru is deposited so that the ratio of the agent and water does not contain). With such a configuration, the effect of the present invention is further improved.
The method for adhering the treatment agent for the synthetic fiber spinning process of the present invention is not particularly limited, and known methods such as a roller refueling method, a guide refueling method using a measuring pump, a dipping refueling method, and a spray refueling method can be used. Can be adopted.

The treatment agent for the synthetic fiber spinning process in the present invention contains the alken sulfonic acid compound represented by the above formula (1) as an essential component, thereby reducing fluff generated due to high friction in the spinning process. Furthermore, it is possible to suppress deterioration of yarn quality due to long-term operation in the spinning process of synthetic fibers. As a result, the synthetic fiber of the present embodiment can exhibit excellent process passability.

Hereinafter, the present invention will be described with reference to examples, but the technical scope of the present invention is not limited thereto. In the following Examples and Comparative Examples, "parts" means "parts by mass" and "%" means "% by mass".

<Test Category 1 (Sulfonic Acid Compounds Represented in Formulas (1) and (5))>
-Synthesis of sulfonic acid compounds (S1-1 and S2-1) Sulfur trioxide was added to 1-tetradecene and sulfonated at 50 ° C. or lower. An excess amount of an aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 1 hour and then heated at 150 ° C. for 1 hour in an autoclave. Petroleum ether and ethanol were added thereto, and the mixture was stirred and allowed to stand, and then the oil phase was removed to extract and remove oil-soluble impurities. The remaining aqueous phase was evaporated to dryness. This was chromatographically separated into S1-1 and S2-1 whose counterions are hydrogen, respectively. Then, sodium hydroxide was added to each of them so that the pH became 9, and the mixture was stirred well and then evaporated to dryness to obtain S1-1 and S2-1.
The contents of the alkene sulfonic acid compounds (S1-1 to S1-5, rS1-1) represented by the above formula (1) used in this example and the comparative example are shown in Table 1 and in the above formula (5). The contents of the hydroxyalkane sulfonic acid compounds (S2-1 to S2-5) are shown in Table 2.

<Test Category 2 (Phosphate Ester Compound)>
-Synthesis of Phosphate Ester Compound (P-1) Diphosphorus pentoxide was charged into 2-ethylhexanol under stirring in a four-necked flask and reacted at 70 ± 5 ° C. for 3 hours. Then, dibutylethanolamine was charged as a neutralizing agent, and the mixture was stirred at 50 ° C. for 1 hour. (P-2 to P-5) were synthesized by the same method as P-1 using the raw materials shown in Table 3 below. In the neutralization of P-2 and P-5, phosphorylation was added to an aqueous sodium hydroxide solution and stirred to neutralize.
-Synthesis of phosphoric acid ester compound (rP-1) Diphosphoric pentoxide and polyphosphoric acid were charged into oleyl alcohol under stirring in a four-necked flask and reacted at 60 ± 5 ° C. for 3 hours. Next, this was charged into an aqueous solution of potassium hydroxide as a neutralizing agent, and the mixture was stirred at 50 ° C. for 1 hour.

<Test Category 3 (Preparation of Treatment Agent for Synthetic Fiber Spinning Process)>
-Preparation of treatment agent for synthetic fiber spinning process (Example 1) As a smoothing agent, 20 parts of dioleyl adipate (A-1), 35 parts of oleyl oleate (A-2), diisostearylthiodipropionate (BSA-1) 5 parts, esterified compound (B-4) of polyethylene glycol (molecular weight 600) and 2 mol of oleic acid as a nonionic surfactant, 10 parts, sorbitan monooleate (B-5) 8 parts , 10 parts of castor oil-EO8 (B-8), 8 parts of esterified compound (B-11) of 1 mol of castor oil-EO20 and 3 mol of oleic acid, as an ionic surfactant, the arcene represented by the above formula (1). 0.55 parts of the sulfonic acid compound (S1-1), 0.4 parts of the hydroxyalcan sulfonic acid compound (S2-1) represented by the above formula (5), and (P-1) of the phosphoric acid ester compound. 2.9 parts and 0.15 parts of potassium oleate (D-1) as other components were uniformly mixed to prepare a treatment agent for the synthetic fiber spinning process of Example 1.

-Preparation of treatment agents for synthetic fiber spinning process (Examples 2 to 11 and Comparative Examples 1 to 4) Examples 2 to 11 and Comparative Examples 1 to 1 are the same as the preparation of the treatment agent for the synthetic fiber spinning process of Example 1. The treatment agent for the synthetic fiber spinning process of No. 4 was prepared, and the compositions of Examples 1 to 11 are shown in Table 4, and the compositions of Comparative Examples 1 to 4 are shown in Table 5.
However, in Example 2, in addition to the raw materials shown in Table 4, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2 was used as an antioxidant. , 4, 6 (1H, 3H, 5H) -trione was added at a ratio of 0.8 parts to 100 parts of the treatment agent.

0.15 g of laurylamine was added to 0.10 g of the prepared synthetic fiber spinning process treatment agent, and the mixture was thoroughly stirred. Using deuterated chloroform as the solvent, ³¹ P-NMR of this was measured. The P-nuclear integration ratio of the phosphoric acid ester compound is ^{calculated from the above formulas (1) to (4) using the measured values subjected to 31} P-NMR (trade name: MERCURY plus NMR Spectrometer System, 300 MHz manufactured by VARIAN). ), And are shown in Tables 4 and 5 below.

In Tables 4 and 5,
A-1: Georail Ajipart A-2: Oleyl Oleart A-3: 1,4-Butane Dioreart A-4: Mineral oil (Redwood seconds 120)
bA-1: Di (2-ethylhexyl) adipate bA-2: Isostearyl oleate bA-3: Rapeseed oil bA-4: Trimethylolpropane Trioleate SA-1: Diorylthiodipropionate bSA-1: Diiso Stearylthiodipropionate bSA-2: Diisododecylthiodipropionate B-1: Palm fatty acid-EO12
B-2: Oleyl alcohol-EO15
B-3: Isostearyl alcohol-EO8PO10
B-4: Esterate of polyethylene glycol (molecular weight 600) and 2 mol of oleic acid B-5: Sorbitan monooleate B-6: Laurylamine-EO6
B-7: Diethanolamine Oleic acid amide B-8: Castor oil-EO8
B-9: Hardened castor oil-EO12
B-10: Hardened castor oil-EO10PO15
B-11: Castor oil-EO20 1 mol and oleic acid 3 mol esterified B-12: Hardened castor oil-EO25 1 mol and lauric acid 2 mol esterified B-13: Hardened castor oil-EO15, adipic acid and stearic acid Polycondensate (molecular weight 6000)
D-1: Potassium oleate D-2: Sodium octylate SD-1: Sodium secondary alkylsulfonate (14-18 carbon atoms) SD-2: Sodium dioctylsulfosuccinate

<Test Category 4 (Evaluation of Treatment Agent for Synthetic Fiber Spinning Process)>
-Evaluation of tension value Each synthetic fiber spinning process treatment agent prepared in Test Category 3 was uniformly diluted with ion-exchanged water or a diluent of an organic solvent as necessary to prepare a 15% solution. The above solution was applied to 1100 decitex, 192 filaments, and non-lubricated polyethylene terephthalate fiber having an intrinsic viscosity of 0.93 by the oiling roller lubrication method so as to give 0.6% by mass as a non-volatile content, and diluted. The agent was dried to obtain a test yarn. The test yarn was run in contact with a satin chrome pin having a surface temperature of 240 ° C. at an initial tension of 1.5 kg and a yarn speed of 1.0 m / min, and the tension value of the yarn after contact with the satin chrome pin was measured. The results are shown in Table 6.

・ Evaluation criteria for tension value ◎ ◎: less than 1.9 kg ◎ ○: 1.9 kg or more and less than 2.0 kg ○ ○: 2.0 kg or more and less than 2.1 kg ○: 2.1 kg or more and less than 2.2 kg ×: 2.2 kg that's all

-Evaluation of tension over time under high temperature conditions Each synthetic fiber spinning process treatment agent prepared in Test Category 3 was uniformly diluted with ion-exchanged water or a diluent of an organic solvent as necessary to prepare a 15% solution. The above solution was applied to 1670 decitex, 288 filaments, and non-lubricated polyethylene terephthalate fiber having an intrinsic viscosity of 0.93 by the oiling roller lubrication method so as to give a non-volatile content of 0.6% by mass, and diluted. The agent was dried to obtain a test yarn. The test yarn was run in contact with a satin chrome pin having a surface temperature of 250 ° C. at an initial tension of 1.5 kg and a yarn speed of 1.0 m / min, and the tension value of the yarn after contact with the satin chrome pin was measured. The running time at the time when the tension value increased by 10% from the tension value after 20 minutes of running was recorded and evaluated according to the following criteria. The results are shown in Table 6.

・ Evaluation criteria for tension increase ◎ ◎: 8 hours or more ◎ ○: 6 hours or more and less than 8 hours ○ ○: 4 hours or more and less than 6 hours ○: 2 hours or more and less than 4 hours ×: less than 2 hours

As is clear from the results in Table 6, the treatment agents for the synthetic fiber spinning process of each example had good evaluations of the tension value and the evaluation of the tension increase. According to the present invention, there is an effect of reducing fluff generated due to high friction in the spinning process and suppressing deterioration of yarn quality due to long-term operation.

And synthetic fiber spinning process for the treatment agent of the present invention, synthetic fibers adhered with the synthetic fiber spinning process for processing agents, 0.1 to 3 wt% with respect to the synthetic fibers (not including the diluent and water), spinning In the process, it is possible to reduce the generation of fluff caused by the high friction between the high temperature roller and the thread to which the treatment agent is applied, and further to suppress the deterioration of yarn quality due to long-term operation in the spinning process. It can be and is very useful.

Claims (10)

A treatment agent for synthetic fibers, which comprises an alkene sulfonic acid compound represented by the following formula (1).

(In equation (1)
R ¹ : Hydrocarbon group having 3 to 21 carbon atoms.
M ¹ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. ) The treatment agent for synthetic fibers according to claim 1, ^{wherein R 1 of the} formula (1) is a hydrocarbon group having 7 to 17 carbon atoms. A treatment agent for synthetic fibers containing a smoothing agent, a nonionic surfactant and the alkene sulfonic acid compound, wherein the total content of the smoothing agent, the nonionic surfactant and the alkene sulfonic acid compound is 100% by mass. The treatment agent for synthetic fibers according to claim 1 or 2, which contains the alkene sulfonic acid compound in a proportion of 0.01 to 10% by mass. Further, a treatment agent for synthetic fibers containing a phosphoric acid ester compound, wherein the phosphoric acid ester compound is a phosphoric acid ester Q1 represented by the following formula (2) and a phosphoric acid ester Q2 represented by the following formula (3). In the P-nuclear NMR measurement of the synthetic fiber treatment agent containing at least one selected from the phosphoric acid ester Q3 represented by the following formula (4) and pretreated with alkali overneutralization, the phosphoric acid ester Q1 , The P-nuclear NMR integration ratio attributed to the phosphoric acid ester Q1 when the total of the P-nuclear NMR integration ratios attributed to the phosphoric acid ester Q2, the phosphoric acid ester Q3, phosphoric acid and its salts is 100%. The synthetic fiber treatment agent according to any one of claims 1 to 3, wherein the content is 15% or more.

(In equation (2)
R ² : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ³ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ² : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )

(In equation (3)
R ^{4: Alkyl group having 4 to} 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
R ⁵ : An alkyl group having 4 to 24 carbon atoms or an alkenyl group having 4 to 24 carbon atoms.
M ³ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt.
M ⁴ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. )

(In equation (4)
R ⁶ : Alkyl group having 4 to 24 carbon atoms or alkenyl group having 4 to 24 carbon atoms.
M ⁵ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt.
M ⁶ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. ) The phosphoric acid ester compound contains the phosphoric acid ester Q1 and the phosphoric acid ester Q2, and is attributed to the phosphoric acid ester Q1, the phosphoric acid ester Q2, the phosphoric acid ester Q3, the phosphoric acid and a salt thereof. The treatment agent for synthetic fibers according to claim 4, wherein the P nuclear NMR integration ratio attributed to the phosphoric acid ester Q2 is 5 to 50% when the total nuclear NMR integration ratio is 100%. The treatment agent for synthetic fibers according to any one of claims 3 to 5, wherein the smoothing agent contains an ester compound having a branched chain. The treatment agent for synthetic fibers according to any one of claims 1 to 6, further comprising a hydroxyalkane sulfonic acid compound represented by the following formula (5).

(In equation (5)
R ⁷ : Hydroxyalkyl group having 5 to 23 carbon atoms.
M ⁷ : Hydrogen atom, alkali metal, alkaline earth metal, ammonium, phosphonium or organic amine salt. ) Assuming that the total content of the alkene sulfonic acid compound and the hydroxyalcan sulfonic acid compound is 100 parts by mass, the ratio of the alkene sulfonic acid compound is 40 to 75 parts by mass and the content ratio of the hydroxyalcan sulfonic acid compound is 25 to 60 parts by mass. 7. The treatment agent for synthetic fibers according to claim 7. A processing agent for synthetic fibers containing the smoothing agent, the nonionic surfactant and the ionic surfactant, wherein the ionic surfactant is the alkene sulfonic acid compound, the phosphoric acid ester compound and the hydroxyalcan sulfonic acid compound. The alkene sulfonic acid compound is contained in a ratio of 0.01 to 10% by mass, assuming that the total content of the smoothing agent, the nonionic surfactant and the ionic surfactant is 100% by mass. Item 7. The treatment agent for synthetic fibers according to Item 7. A synthetic fiber to which the treatment agent for synthetic fibers according to any one of claims 1 to 9 is attached.