JP6676049B2 - Synthetic fiber treatment agent and its use - Google Patents

Description

  The present invention relates to a synthetic fiber treating agent and its use. More specifically, the present invention relates to a synthetic fiber treating agent used when producing synthetic fibers, a method for producing a synthetic fiber filament yarn using the treating agent, and a fiber structure containing the synthetic fiber filament yarn.

Conventionally, a fiber treated with a fiber oil agent is once wound and then subjected to a drawing step. Recently, however, a method has been adopted in which this step is shortened and an oiling (oiling) yarn is directly subjected to a drawing step.
In this method, once a trouble such as a yarn breakage occurs in the drawing process, a large amount of fibers is lost, and thus it is necessary to avoid the trouble in the drawing process as much as possible. The main cause of trouble is fiber damage such as yarn breakage, and to prevent this, a synthetic fiber treatment agent having excellent lubricity and heat resistance is required.
Furthermore, the improvement of physical properties such as high strength and low shrinkage of fiber, and the improvement of productivity such as multi-end and high speed during production have been attempted, and due to roll contamination which has not been a problem until now, There is a problem that fluff and yarn breakage increase. For this reason, in order to keep the rolls in a clean state, it is pointed out that the cleaning interval of the rolls is short, the number of times of cleaning is increased, and the productivity is reduced.

  In order to solve the above-mentioned problems, Patent Document 1 discloses an ester of a polyhydric alcohol, an ester of a carboxylic acid having a thioether group and an alcohol, a secondary sulfonate, an alkyl phosphate, and a treating agent using a hindered phenol-based antioxidant in combination. Has been proposed. However, this treatment agent is used for fluff and yarn breakage caused by roll contamination, which has not been a problem until now due to productivity improvements such as higher strength, lower shrinkage, and higher speed. Even if there was, it could not be improved.

  For this reason, there is a long-felt need for a treatment agent having excellent heat resistance and capable of suppressing a decrease in productivity due to a short cleaning interval of the roll and an increase in the number of times of cleaning.

JP-A-8-120563

An object of the present invention is a synthetic fiber treating agent which is used when producing a synthetic fiber, can reduce roll contamination, and has excellent heat resistance, a method for producing a synthetic fiber filament yarn using the treating agent, and the production method. To provide a fibrous structure containing the synthetic fiber filament yarn obtained in the above.

The present inventors have conducted intensive studies and as a result, when synthesizing the smoothing component (A) and the nonionic surfactant component (B), which are the main components, are used for shortening the reaction time and improving the reaction efficiency. Above all, the reaction time is short, and the efficient metal catalyst remains on the synthetic fiber treating agent, drops off and accumulates on the drawing roll at the time of spinning, causing an increase in broken yarn, and First, it was found that tar accumulation was accelerated on rolls subjected to hot stretching, causing roll contamination.
The present inventors have found that by reducing the content of metals (excluding alkali metals) detected from the non-volatile components of the treating agent to a predetermined ratio or less, it is possible to dramatically reduce fluff, thread breakage, and roll dirt. Reached.

That is, the synthetic fiber treating agent of the present invention is a synthetic fiber treating agent containing a smooth component (A) and a nonionic surfactant component (B). ,
The component (A) includes an ester compound (A2) having a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded,
The component (B) includes a nonionic surfactant component (B1) having an ester bond in the molecule, and at least one ICP emission spectrometry selected from Zn, Mn, Co , Ti, Sn, Ni, Zr and Hf. And the content of the metal element detected from the nonvolatile components of the treatment agent by ICP emission spectrometry is more than 0 ppm and 10 ppm or less.

The synthetic fiber treating agent of the present invention is a synthetic fiber treating agent when using an ester synthesized using a metal catalyst,
It contains a smoothing component (A) and a nonionic surfactant component (B),
The component (A) includes an ester compound (A2) having a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded,
The component (B) contains a nonionic surfactant component (B1) having an ester bond in the molecule, and the content of the metal element detected from the nonvolatile components of the treatment agent by ICP emission spectrometry is more than 0 ppm and 10 ppm or less. And the metal is at least one selected from Zn, Mn, Co , Ti, Sn, Ni, Zr and Hf.

The synthetic fiber filament yarn of the present invention is obtained by applying the treatment agent to a raw material synthetic fiber filament yarn.
The method for producing a synthetic fiber filament yarn of the present invention includes a step of applying the treatment agent to a raw material synthetic fiber filament yarn.
The fiber structure of the present invention includes the above-mentioned synthetic fiber filament yarn and / or the synthetic fiber filament yarn obtained by the above-mentioned production method.

When the synthetic fiber treating agent of the present invention is used, roll contamination during production of synthetic fibers can be reduced, and heat resistance is excellent. As a result, the cleaning interval of the roll can be lengthened, the number of times of cleaning can be reduced, and the productivity of synthetic fibers can be improved.
ADVANTAGE OF THE INVENTION According to the manufacturing method of this invention, generation | occurrence | production of a scum and a thread break can be reduced, and the synthetic fiber filament thread excellent in thread quality can be obtained. The fiber structure of the present invention is excellent in quality.

  The synthetic fiber treating agent of the present invention contains a smooth component (A) and a nonionic surfactant component (B), and a metal (excluding an alkali metal) measured by ICP emission spectrometry. It should be below the concentration. The details will be described below.

[Smoothing component (A)]
The smoothing component (A) is an essential component of the treatment agent of the present invention. Examples of the smoothing component (A) include 1) an ester compound (A1) having a structure in which an aliphatic monohydric alcohol and a fatty acid are ester-bonded, and 2) a structure in which a trivalent or higher aliphatic polyhydric alcohol and a fatty acid are ester-bonded. (A2), 3) an ester compound having a structure in which an aliphatic monohydric alcohol and an aliphatic polycarboxylic acid are ester-bonded (A3), 4) an aromatic ester compound having an aromatic ring in the molecule ( A4), 5) a sulfur-containing ester compound (A5), 6) an ester compound (A6) having a structure in which an aliphatic dihydric alcohol and a fatty acid are ester-bonded, and the like, which are generally used as synthetic fiber treating agents. Can be mentioned. One or more kinds of the smoothing component (A) can be used.

1) Ester compound (A1)
The ester compound (A1) is a compound having a structure in which an aliphatic monohydric alcohol and a fatty acid (aliphatic monocarboxylic acid) are ester-bonded, and has no polyoxyalkylene group in the molecule. One or more ester compounds (A1) can be used.
The ester compound (A1) is preferably a compound represented by the following general formula (1).

R ¹ -COO-R ² (1)
(In the formula, R ¹ represents an alkyl group or alkenyl group having 4 to 24 carbon atoms, and R ² represents an alkyl group or alkenyl group having 6 to 24 carbon atoms.)

The carbon number of R ¹ is preferably 6 to 22, more preferably 8 to 20, and still more preferably 10 to 18. If the number of carbon atoms is less than 4, fluff may increase due to a weak oil film. On the other hand, when the carbon number exceeds 24, the friction between the fiber metals becomes high, and the fluff may increase. R ¹ may be either an alkyl group or an alkenyl group, but is preferably an alkyl group from the viewpoint of excellent heat resistance.

The carbon number of R ² is preferably 6 to 22, more preferably 8 to 20, and still more preferably 10 to 18. If the number of carbon atoms is less than 6, the fuzz may increase because the oil film is weak. On the other hand, when the carbon number exceeds 24, the friction between the fiber metals becomes high, and the fluff may increase. R ² may be either an alkyl group or an alkenyl group, but is preferably an alkenyl group from the viewpoint that the oil film strength is high and fluff is not easily generated.

  Although it does not specifically limit as an ester compound (A1), For example, 2-decyltetradecanoyl ercinate, 2-decyltetradecanoyl oleate, 2-octyl dodecyl stearate, isooctyl palmitate, isooctyl stearate, Butyl palmitate, butyl stearate, butyl oleate, isooctyl oleate, lauryl oleate, isotridecyl stearate, hexadecyl stearate, isostearyl oleate, oleyl octanoate, oleyl laurate, oleyl palmitate, oleyl stearate And oleyl oleate. Among these, 2-decyltetradecanoyl oleate, 2-octyldodecyl stearate, isooctyl palmitate, isooctyl stearate, lauryl oleate, isotridecyl stearate, hexadecyl stearate, isostearyl oleate, Oleyl oleate is preferred.

  The ester compound (A1) can be synthesized and obtained by a known method using a commercially available fatty acid and an aliphatic monohydric alcohol.

2) Ester compound (A2)
The ester compound (A2) is a compound having a structure in which a fatty acid (aliphatic monohydric carboxylic acid) and a trihydric or higher aliphatic polyhydric alcohol are ester-bonded, and is essential to the synthetic fiber treating agent of the present invention. It is a compound that is a component and does not have a polyoxyalkylene group in the molecule. One or more ester compounds (A2) can be used.

The aliphatic polyhydric alcohol constituting the ester compound (A2) is not particularly limited as long as it is trivalent or more, and one or more kinds can be used. The polyhydric alcohol is more preferably trivalent to tetravalent, and more preferably trivalent, from the viewpoint of oil film strength.
Examples of the trihydric or higher aliphatic polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, triglycerin, tetraglycerin, and sucrose. No. Among these, glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose are preferred, and glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, and sorbitan Is more preferable, and glycerin and trimethylolpropane are still more preferable.

  The fatty acid constituting the ester compound (A2) may be saturated or unsaturated. The number of unsaturated bonds is not particularly limited. However, when the number of unsaturated bonds is three or more, one or two is preferable because deterioration progresses due to oxidation, the treatment agent is thickened, and lubricity is impaired. The carbon number of the fatty acid is preferably from 8 to 24, more preferably from 10 to 20, and even more preferably from 12 to 18, in order to achieve both oil film strength and lubricity. One or more fatty acids may be used, and a saturated fatty acid and an unsaturated fatty acid may be used in combination.

Fatty 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, isosetilic acid, margarine Acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, isoeicosaic acid, gadolinic acid, eicosenic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid, isotetracosanoic acid, Nervonic acid and the like.
Among these, 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, gadolinic acid, eicosenoic acid, docosanoic acid, isodocosanoic acid, erucic acid, tetracosanoic acid, and isotetracosanoic acid are preferred, and capric acid, lauric acid, myristic acid, and myristoleic acid are preferred. , Pentadecanoic acid, palmitic acid, palmitoleic acid, isocetylic acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, isoeicosaic acid, Drain acid, eicosenoic acid is more preferable, lauric acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, isosetyl acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linole Acids and linolenic acid are more preferred.

The ester compound (A2) is a compound having three or more ester bonds in the molecule, but is a compound having three ester bonds in the molecule from the viewpoint of reducing smoke emission during yarn production and oil film strength. Is preferred.
There is no particular limitation on the iodine value of the ester compound (A2).

  The weight average molecular weight of the ester compound (A2) is preferably from 300 to 1200, more preferably from 300 to 1,000, and still more preferably from 500 to 1,000. If the weight average molecular weight is less than 300, the oil film strength may be insufficient, resulting in an increase in fluff or an increase in smoke during heat treatment. On the other hand, when the weight average molecular weight is more than 1200, smoothness is insufficient and fluff is frequently generated, and not only high quality fibers cannot be obtained, but also the quality in the weaving or knitting process may be poor. The weight average molecular weight in the present invention was measured using a high-speed gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation at a sample concentration of 3 mg / cc, and separation columns KF-402HQ and KF-403HQ manufactured by Showa Denko KK. And calculated from the peak measured with a differential refractive index detector.

  Examples of the ester compound (A2) include trimethylolpropane tricaprylate, trimethylolpropane tricaprinate, trimethylolpropane trilaurate, trimethylolpropane trioleate, trimethylolpropane (laurate, myristylate, palmitate), trimethylol Propane (laurate, myristylate, oleate), trimethylolpropane (tripalm kernel fatty acid ester), trimethylolpropane (tricoco fatty acid ester), trimethylolpropane dicaprylate, trimethylolpropane dicaprinate, trimethylolpropane dilaurate, trimethylolpropane Dioleate, trimethylolpropane (laurate, myristylate), trimethylolpropane (laureate) Oleate), trimethylolpropane (myristylate, oleate), trimethylolpropane (dipalmune fatty acid ester), trimethylolpropane (dicoco fatty acid ester), coconut oil, rapeseed oil, palm oil, glycerin trilaurate, glycerin trioleate, Glycerin triisostearate, glycerin dioleate, glycerin monolaurate, diglycerin dioleate, sorbitan trioleate, sorbitan (laurate, myristylate, oleate), sorbitan dilaurate, sorbitan monooleate, pentaerythritol tetracaprylate, penta Erythritol tetracaprinate, pentaerythritol tetralaurate, erythritol tetralaurate, pentaerythritol (teto Palm kernel fatty acid esters), pentaerythritol (Tetorayashi fatty acid ester), erythritol trioleate, and erythritol dipalmitate and the like.

  As the ester compound (A2), a compound synthesized by a known method using a commercially available fatty acid and an aliphatic polyhydric alcohol may be used. Moreover, you may use the ester obtained by transesterifying two or more types of natural esters (oils and fats).

3) Ester compound (A3)
The ester compound (A3) is a compound having a structure in which an aliphatic monohydric alcohol and an aliphatic polycarboxylic acid are ester-bonded, and has no polyoxyalkylene group in the molecule. One or more ester compounds (A3) can be used.

  The aliphatic monohydric alcohol constituting the ester compound (A3) is not particularly limited, and one kind or two or more kinds can be used. The aliphatic monohydric alcohol may be saturated or unsaturated. The number of unsaturated bonds is not particularly limited, but when two or more are used, one is preferable because deterioration proceeds due to oxidation, the treatment agent is thickened, and lubricity is impaired. The number of carbon atoms of the aliphatic monohydric alcohol is preferably from 8 to 24, more preferably from 12 to 24, and still more preferably from 16 to 22, from the viewpoint of smoothness and oil film strength. One or more aliphatic monohydric alcohols may be used, and a saturated aliphatic monohydric alcohol and an unsaturated aliphatic monohydric alcohol may be used in combination.

  As the aliphatic monohydric alcohol, octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristoleyl alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Baxenyl alcohol, gadoleyl alcohol, arachidyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetracosanyl alcohol, nerbonyl alcohol, Cerotinyl alcohol, montanyl alcohol, melisinyl alcohol and the like can be mentioned. Among them, octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristoleyl alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, vaccenyl alcohol Gadoleyl alcohol, arachidyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanil alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetradocosanyl alcohol, nerbonyl alcohol is preferred, and myristoleyl Alcohol, cetyl alcohol, isocetyl alcohol, oleyl alcohol, elaidyl alcohol Baxenyl alcohol, gadoleyl alcohol, eicosenoyl alcohol, ercanyl alcohol, nerbonyl alcohol are more preferred, oleyl alcohol, elaidyl alcohol, baxenyl alcohol, gadreyl alcohol, eicosenoyl alcohol, ercanyl alcohol More preferred.

The aliphatic polycarboxylic acid constituting the ester (A3) is not particularly limited as long as it is divalent or higher, and one or two or more types can be used. The aliphatic polycarboxylic acid used in the present invention does not include a sulfur-containing polycarboxylic acid such as thiodipropionic acid. The valence of the aliphatic polycarboxylic acid is preferably divalent. Similarly, it is preferable not to include a hydroxyl group in the molecule.
Aliphatic polycarboxylic acids include citric acid, isocitric acid, malic acid, aconitic acid, oxaloacetic acid, oxasuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid Acid, sebacic acid and the like. Among these, aconitic acid, oxaloacetic acid, oxalosuccinic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid are preferred, and fumaric acid, maleic acid, adipine are preferred. Acids, pimelic acid, suberic acid, azelaic acid and sebacic acid are more preferred.

  Examples of the ester compound (A3) include dioctyl adipate, dilauryl adipate, dioleyl adipate, hypoisocetyl adipate, dioctyl sebacate, dilauryl sebacate, dioleyl sebacate, diisocetyl sebacate, and the like.

  The ester compound (A3) is a compound having two or more ester bonds in a molecule. The iodine value of the ester compound (A3) is not particularly limited.

  The weight average molecular weight of the ester compound (A3) is preferably from 500 to 1,000, more preferably from 500 to 800, and still more preferably from 500 to 700. If the weight-average molecular weight is less than 500, the oil film strength may be insufficient, resulting in increased fluff or increased smoke during heat treatment. On the other hand, when the weight average molecular weight is more than 1000, the melting point becomes high, causing scum in the weaving or knitting process, and the quality may be poor.

  The ester compound (A3) can be synthesized and obtained by a known method using a commercially available aliphatic monohydric alcohol and aliphatic polycarboxylic acid.

4) Aromatic ester compound (A4)
The aromatic ester compound (A4) is an ester compound having at least one aromatic ring in a molecule. Specifically, an ester compound (A4-1) having a structure in which an aromatic carboxylic acid and an alcohol are ester-bonded and an ester compound (A4-2) having a structure in which an aromatic alcohol and a carboxylic acid are ester-bonded are exemplified. Can be. The aromatic ester compound (A4) is a compound having no polyoxyalkylene group in the molecule. One or more aromatic ester compounds (A4) can be used.

The aromatic carboxylic acid constituting the ester compound (A4-1) may be a monocarboxylic acid or a polycarboxylic acid. One or more kinds may be used.
Examples of the aromatic carboxylic acid include benzoic acid, toluic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, melitic acid, cinnamic acid, trimellitic acid, and pyromellitic acid. Among these, trimellitic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, and trimellitic acid is more preferred.

  The alcohol constituting the ester compound (A4-1) may be a monohydric alcohol or a polyhydric alcohol. Further, any of aliphatic alcohol, alicyclic alcohol and aromatic alcohol may be used. One or two or more monohydric alcohols can be used. Of these, monohydric alcohols are preferred, and aliphatic monohydric alcohols are more preferred.

Examples of the monohydric alcohol include alkylbenzene alcohol, dialkylbenzene alcohol, octyl alcohol, isooctyl alcohol, lauryl alcohol, myristyl alcohol, myristoleyl alcohol, cetyl alcohol, isocetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol. , Elaidil alcohol, bacenyl alcohol, gadoleyl alcohol, arachidyl alcohol, isoicosanyl alcohol, eicosenoyl alcohol, behenyl alcohol, isodocosanyl alcohol, ercanyl alcohol, lignocerinyl alcohol, isotetracosanyl alcohol , Nerbonyl alcohol, Cerotinyl alcohol, Montanyl alcohol, Merisini Alcohol and the like.
Examples of the polyhydric alcohol include the aliphatic polyhydric alcohol described for the ester compound (A2) and the aromatic polyhydric alcohol described for the ester compound (A4-2).

One or more aromatic alcohols constituting the ester compound (A4-2) can be used. As the aromatic alcohol, an aromatic polyhydric alcohol is preferable, and an aromatic trihydric alcohol is more preferable.
Examples of the aromatic alcohol include an aromatic monohydric alcohol such as an alkylbenzene alcohol, a dialkylbenzene alcohol, an aromatic polyhydric alcohol such as bisphenol A, bisphenol Z, and 1,3,5-trihydroxymethylbenzene. Among these, bisphenol A, bisphenol Z and 1,3,5-trihydroxymethylbenzene are preferred, and 1,3,5-trihydroxymethylbenzene is more preferred.

  The carboxylic acid constituting the ester compound (A4-2) may be any of an aliphatic carboxylic acid and an aromatic carboxylic acid. Further, either a monovalent carboxylic acid or a polyvalent carboxylic acid may be used. One type or two or more types may be used. Of these, monovalent carboxylic acids are preferred, and fatty acids are more preferred. Fatty acids are preferably saturated from the viewpoint of persistence. Fatty acids may be linear or branched.

Examples of the monovalent carboxylic acid include alkylbenzene carboxylic acid, dialkylbenzene carboxylic acid, butyric acid, crotonic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, myristoleic acid, Pentadecylic acid, palmitic acid, palmitoleic acid, isosetilic acid, margaric acid, stearic acid, isostearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, arachidic acid, isoicosanoic acid, gadolinic acid, eicosenoic acid, behenic acid , Isodocosanoic acid, erucic acid, lignoceric acid, isotetracosanoic acid, nervonic acid, cerotic acid, montanic acid, melicic acid and the like.
Examples of the polycarboxylic acid include the aliphatic polycarboxylic acid described for the ester compound (A3) and the aromatic polycarboxylic acid described for the ester compound (A4-1).

5) Sulfur-containing ester compound (A5)
The sulfur-containing ester compound is at least one selected from a diester compound of thiodipropionic acid and an aliphatic alcohol and a monoester compound of thiodipropionic acid and an aliphatic alcohol.
The sulfur-containing ester compound is a component having antioxidant ability. By using the sulfur-containing ester compound, the heat resistance of the treating agent can be increased. One or more sulfur-containing ester compounds can be used. The molecular weight of thiodipropionic acid constituting the sulfur-containing ester compound is preferably from 400 to 1,000, more preferably from 500 to 900, and still more preferably from 600 to 800. The aliphatic alcohol constituting the sulfur-containing ester compound may be saturated or unsaturated. The aliphatic alcohol may be linear or have a branched structure, but preferably has a branched structure. The aliphatic alcohol preferably has 8 to 24 carbon atoms, more preferably 12 to 24 carbon atoms, and even more preferably 16 to 24 carbon atoms. Examples of the aliphatic alcohol include octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, isocetyl alcohol, oleyl alcohol, and isostearyl alcohol. Among these, oleyl alcohol and isostearyl alcohol are exemplified. preferable.
The sulfur-containing ester compound is a diester compound of thiodipropionic acid and an aliphatic alcohol (simply referred to as diester in this paragraph) and a monoester compound of thiodipropionic acid and an aliphatic alcohol (simply referred to as monoester in this paragraph). )). In this case, the molar ratio of the diester to the monoester is preferably from 100/0 to 70/30, more preferably from 100/0 to 75/25, and even more preferably from 100/0 to 80/20.

6) Ester compound (A6)
An ester compound (A6) having a structure in which an aliphatic dihydric alcohol and a fatty acid are ester-bonded (hereinafter, sometimes simply referred to as an ester compound (A6)) has two ester bonds in a molecule and also has a structure in a molecule. It is a compound having no polyoxyalkylene group. It is excellent in oil film strength as compared with the above ester compound (A1).

Examples of the aliphatic dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol and the like.
As the fatty acid constituting the ester compound (A6), the same fatty acid as the fatty acid constituting the ester compound (A2) can be used.

  Among these smoothing components (A), it is preferable to include an ester compound (A2), an ester compound (A3) and a sulfur-containing ester compound (A5) as the smoothing component of the present treatment agent from the viewpoint of oil film strength and smoothness. More preferably, it contains the ester compound (A2) and the ester compound (A3), and even more preferably, it contains the ester compound (A2).

  As a catalyst for synthesizing the smoothing component (A), paratoluenesulfonic acid, sulfuric acid, and a metal catalyst are used. Among the catalysts, metal catalysts are preferably used for improving productivity such as improving the reaction rate, shortening the reaction time, and improving the yield. In particular, since the ester compound (A2) and the ester compound (A3) have a structure having a trivalent or higher ester group, it is difficult to obtain a high esterification rate due to steric hindrance, and a metal catalyst showing high reactivity is more suitable. Used. In addition, a metal catalyst is a concept including both an organic metal catalyst and an inorganic metal catalyst.

  As the metal catalyst used for the esterification, a catalyst containing Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr or Hf is used because of its high reactivity, safety, and availability. Among them, a catalyst containing Ti, Sn, Zr or Hf is particularly preferably used, and a catalyst containing Ti or Zr is more preferably used.

The metal catalyst used for the ester reaction is not particularly limited, and generally commercially available ones can be used.
Examples of the metal catalyst containing Zn include zinc acetate and zinc oxalate.
Examples of the metal catalyst containing Mn include manganese acetate and manganese nitrate.
Examples of the metal catalyst containing Co include cobalt acetate, cobalt nitrate, and the like.
Examples of the metal catalyst containing Sb include antimony trioxide, antimony acetate, antimony triacetate and the like.

  Examples of the metal catalyst containing Ti include, for example, dichlorotitanium oxide, dichlorodibutyltitanium, tetrachlorotitanium, tributoxydecanoate titanate, tetramethyltitanate, tetraethyltitanate, tetraisopropyltitanate, tetra-n-butyltitanate, and tetra-2-titanate. Ethylhexyl titanate, tetraoctyl titanate, tetra-isobutyl titanate, tetra-sec-butyl titanate, di-isopropoxy-bis (acetylacetonate) titanate, di-isopropoxy-bis (ethylacetylacetonate) titanate, di-n- Butyl-bis (acetylacetonate) titanate, di-n-butyl-bis (ethylacetoacetate) titanate, tri-isopropoxy-bis (acetylacetonate) Cyclopentadienyl titanium trichloride, titanium lactate, titanium lactate ammonium salt, titanium triethanol aminate, tetrastearyl titanate, diisopropoxybis (triethanol aminate) titanium and the like, among which isopropyl-n-butyl titanate , Tetra (isopropyl) orthotitanate or tetra (butyl) orthotitanate, and titanium lactate are preferred.

  Examples of the metal catalyst containing Sn include, for example, tin tetraethylate, butyltin maleate, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dibutyltin octate, methylphenyltin oxide, didodecyltin oxide, triethyltin hydroxide, and triethyltin oxide. Phenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide, monobutylhydroxytin oxide, monobutyltin triacetate , Monobutyltin monoacetate, monobutyltin triethylhexanate, monobutyltin sulfide and the like.

Examples of the metal catalyst containing Ni include nickel acetate, nickel nitrate and the like.
Examples of the metal catalyst containing Zr include, for example, dichlorozirconium oxide, dichlorodibutylzirconium, tetrachlorozirconium, trichlorozirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetraisopropoxyzirconium, Examples thereof include tetrabutoxyzirconium, tetra (tert-butoxy) zirconium, tetraphenoxyzirconium, zirconium octylate, zirconium stearate, zirconium acetate, zirconium naphthenate, and the like, or a mixture of two or more kinds thereof. From tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium And at least one tetraalkoxy zirconium selected from the group consisting of tetrabutoxyzirconium are preferred.

  Examples of the metal catalyst containing Hf include hafnium tetrachloride, hafnium butoxide and the like.

  As the smoothing component (A), from the viewpoint of improving heat resistance, it is preferable to use a material which is purified by removing a catalyst or the like. Specifically, the metal content (excluding the alkali metal) detected from the nonvolatile components of the smooth component (A) is preferably 50 ppm or less, more preferably 30 ppm or less, more preferably 20 ppm or less, and more preferably 10 ppm or less. More preferably, it is particularly preferably at most 5 ppm. A preferred lower limit is 0 ppm.

  It is desirable that the catalyst other than the metal catalyst be further removed. Examples of the catalyst other than the metal catalyst include p-toluenesulfonic acid.

  As a method of removing the catalyst, a known technique can be used, and is not particularly limited, but a method of filtering using diatomaceous earth, a method of performing adsorption removal using an inorganic synthetic adsorbent, and a method of using an ion exchange resin are described. And a method of removing a smooth component by washing with water.

[Nonionic surfactant component (B)]
The treating agent of the present invention has a nonionic property in addition to the above-mentioned smooth component (A), in order to impart an oil film strength and a bundle property to the raw yarn, to improve the yarn forming property, and to be able to dissolve in water so as to be applied. Contains surfactant component (B). The nonionic surfactant component (B) is a component excluding the smoothing component (A). As the nonionic surfactant component (B), one type or two or more types may be used.

Examples of the nonionic surfactant component (B) include a nonionic surfactant component (B1) having an ester bond in the molecule and a nonionic surfactant component (B2) having no ester bond in the molecule.
Examples of the nonionic surfactant component (B1) include polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester (hereinafter sometimes referred to as polyhydroxy ester), and esters in which at least one hydroxyl group of polyhydroxy ester is blocked with a fatty acid. , Polyoxyalkylene polyhydric alcohol fatty acid esters, polyalkylene glycol fatty acid esters, and the like.
Examples of the nonionic surfactant component (B2) include polyoxyalkylene polyhydric alcohol ethers and polyoxyalkylene aliphatic alcohol ethers.

  It is preferable that the nonionic surfactant component (B) contains the nonionic surfactant component (B1). When the nonionic surfactant component (B1) is not contained, it may not be possible to simultaneously satisfy the oil film strength, the bunching property, the spinning property and the solubility.

(Polyhydroxyester, ester in which at least one hydroxyl group of polyhydroxyester is blocked with fatty acid)
The polyhydroxy ester is structurally an ester of a polyoxyalkylene group-containing hydroxy fatty acid and a polyhydric alcohol, and it is preferable that two or more hydroxyl groups among the hydroxyl groups of the polyhydric alcohol are esterified. Therefore, the polyoxyalkylene group-containing hydroxy fatty acid polyhydric alcohol ester is an ester having a plurality of hydroxyl groups.

The polyoxyalkylene group-containing hydroxy fatty acid has a structure in which a polyoxyalkylene group is bonded to the hydrocarbon group of the fatty acid via an oxygen atom, and one end of the polyoxyalkylene group that is not bonded to the hydrocarbon group of the fatty acid is It is a hydroxyl group.
Examples of the polyhydroxyester include an alkylene oxide adduct of an esterified product of a hydroxy fatty acid having 6 to 22 (preferably 16 to 20) carbon atoms and a polyhydric alcohol.

  Examples of the hydroxy fatty acid having 6 to 22 carbon atoms include hydroxycaprylic acid, hydroxycapric acid, hydroxylauric acid, hydroxystearic acid, and ricinoleic acid, and hydroxyoctadecanoic acid and ricinoleic acid are preferred. Examples of the polyhydric alcohol include ethylene glycol, glycerin, sorbitol, sorbitan, trimethylolpropane, pentaerythritol and the like, and glycerin is preferable. Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide.

The addition mole number of the alkylene oxide is preferably from 3 to 60, and more preferably from 8 to 50. The proportion of ethylene oxide in the alkylene oxide is preferably at least 50 mol%, more preferably at least 80 mol%.
When two or more kinds of alkylene oxides are added, their addition order is not particularly limited, and the addition form may be any of a block form and a random form. The addition of the alkylene oxide can be performed by a known method, but is generally performed in the presence of a basic catalyst.

  The polyhydroxyester can be produced, for example, by esterifying a polyhydric alcohol and a hydroxy fatty acid (hydroxymonocarboxylic acid) under ordinary conditions to obtain an esterified product, and then subjecting the esterified product to an addition reaction with an alkylene oxide. The polyhydroxyester can also be suitably produced by using a naturally obtained oil or fat such as castor oil or hydrogenated hardened castor oil, and further subjecting the alkylene oxide to an addition reaction.

  The nonionic surfactant component (B1) also includes an ester obtained by blocking at least one hydroxyl group of the above-mentioned polyhydroxyester with a fatty acid. The number of carbon atoms of the fatty acid to be blocked is preferably 6 to 24, and more preferably 12 to 18. The carbon number of the hydrocarbon group in the fatty acid may have a distribution, the hydrocarbon group may have a straight-chain or may have a branch, may be saturated or unsaturated, It may have a polycyclic structure. Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, eicosanoic acid, behenic acid, and lignoceric acid. There is no particular limitation on the esterification method, reaction conditions, and the like, and known methods and ordinary conditions can be employed.

  Examples of polyhydroxyesters and esters in which at least one hydroxyl group of the polyhydroxyester is blocked with a fatty acid include, for example, hydrogenated castor oil ethylene oxide adduct, castor oil ethylene oxide adduct, hydrogenated castor oil ethylene oxide adduct monooleate, and hydrogenated castor oil ethylene oxide adduct Dioleate, hydrogenated castor oil ethylene oxide adduct trioleate, castor oil ethylene oxide adduct trioleate, hydrogenated castor oil ethylene oxide adduct tristearate, castor oil ethylene oxide adduct tristearate, among them, compatibility of processing agents, oil film strength, fluff In terms of reduction, hydrogenated castor oil ethylene oxide adduct, hydrogenated castor oil ethylene oxide adduct trioleate, hydrogenated castor oil ethylene oxide adduct tristeate Rate is preferable.

(Polyoxyalkylene polyhydric alcohol fatty acid ester)
The polyoxyalkylene polyhydric alcohol fatty acid ester is a compound having a structure in which an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide is added to a polyhydric alcohol and a fatty acid is ester-bonded.
Examples of the polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol, erythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose. Of these, glycerin, diglycerin, sorbitan and sorbitol are preferred.

  Fatty acids include lauric acid, myristic acid, myristoleic acid, palmitic acid, palmitoleic acid, isocetyl acid, stearic acid, isostearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidic acid, eicosenoic acid, behenic acid, Examples include isodocosanoic acid, erucic acid, lignoceric acid, and isotetracosanoic acid.

The number of moles of the alkylene oxide added is preferably 3 to 100, more preferably 5 to 70, and still more preferably 10 to 50. The proportion of ethylene oxide in the alkylene oxide is preferably at least 50 mol%, more preferably at least 80 mol%.
The weight average molecular weight of the polyoxyalkylene polyhydric alcohol fatty acid ester is preferably from 300 to 7000, more preferably from 500 to 5,000, and even more preferably from 700 to 3,000. If the molecular weight is less than 300, smoke is generated in the heat treatment step, which may deteriorate the environment. Further, the occurrence of thread breakage may not be reduced. On the other hand, when the molecular weight exceeds 7000, the friction of the treating agent becomes high, and not only the generation of fluff and yarn breakage cannot be reduced, but also it may worsen.

  Polyoxyalkylene polyhydric alcohol fatty acid esters include glycerin ethylene oxide adduct monolaurate, glycerin ethylene oxide adduct dilaurate, glycerin ethylene oxide adduct trilaurate, trimethylolpropane ethylene oxide adduct trilaurate, sorbitan ethylene oxide adduct monooleate, sorbitan ethylene oxide adduct dioleate Sorbitan ethylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide adduct monooleate, sorbitan ethylene oxide propylene oxide adduct dioleate, sorbitan ethylene oxide propylene oxide adduct trioleate, sorbitan ethylene oxide propylene oxide adduct trilaurate, Include sugar ethylene oxide adducts Toriraureto like, but is not limited thereto.

(Fatty acid ester of polyalkylene glycol)
The fatty acid ester of polyalkylene glycol is a compound having a structure in which polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and a fatty acid are ester-bonded. The weight average molecular weight of the polyalkylene glycol is preferably from 100 to 1,000, more preferably from 150 to 800, and still more preferably from 200 to 700.

  Polyalkylene glycol fatty acid esters include polyethylene glycol monolaurate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene polypropylene glycol monolaurate, polyethylene Examples include, but are not limited to, polypropylene glycol dilaurate, polyethylene polypropylene glycol monooleate, polyethylene polypropylene glycol dioleate, and the like.

(Polyoxyalkylene polyhydric alcohol ether)
The polyoxyalkylene polyhydric alcohol ether is a compound having a structure in which an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide is added to a polyhydric alcohol.
Examples of the polyhydric alcohol include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, sorbitan, sorbitol, ditrimethylolpropane, dipentaerythritol, and sucrose. Of these, glycerin, trimethylolpropane, and sucrose are preferred.

The number of moles of the alkylene oxide added is preferably 3 to 100, more preferably 4 to 70, and still more preferably 5 to 50. The proportion of ethylene oxide in the alkylene oxide is preferably at least 50 mol%, more preferably at least 80 mol%.
The weight average molecular weight of the polyoxyalkylene polyhydric alcohol ether is preferably from 300 to 10,000, more preferably from 400 to 8,000, even more preferably from 500 to 5,000. When the molecular weight is less than 300, generation of fluff and breakage may not be reduced. On the other hand, when the molecular weight exceeds 10,000, the friction of the treating agent becomes high, so that not only the generation of fluff and breakage cannot be reduced, but also it may worsen.

  Polyoxyalkylene polyhydric alcohol ethers include polyethylene glycol, glycerin ethylene oxide adduct, trimethylolpropane ethylene oxide adduct, pentaerythritol ethylene oxide adduct, diglycerin ethylene oxide adduct, sorbitan ethylene oxide adduct, sorbitan ethylene oxide propylene oxide adduct, sorbitol Examples include, but are not limited to, ethylene oxide adducts, sorbitol ethylene oxide propylene oxide adducts, ditrimethylolpropane ethylene oxide adducts, dipentaerythritol ethylene oxide adducts, and sucrose ethylene oxide adducts.

(Polyoxyalkylene aliphatic alcohol ether)
The polyoxyalkylene aliphatic alcohol ether is a compound having a structure in which an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide is added to an aliphatic monohydric alcohol.
Examples of polyoxyalkylene aliphatic alcohol ethers include, for example, alkylene oxides of aliphatic alcohols such as octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol. Adducts.
The number of moles of the alkylene oxide added is preferably from 1 to 100 mol, more preferably from 2 to 70 mol, even more preferably from 3 to 50 mol. Further, the ratio of ethylene oxide to the entire alkylene oxide is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more.

Since the nonionic surfactant component (B1) includes an ester reaction, paratoluenesulfonic acid, sulfuric acid, and a metal (excluding alkali metal) catalyst are used as a catalyst for ester synthesis.
As the metal catalyst, the same one as described in the catalyst for synthesizing the smooth component (A) can be used.

  Regarding the nonionic surfactant component (B2), examples of a catalyst used for adding ethylene oxide include an alkali catalyst (eg, potassium hydroxide and sodium hydroxide) and an acidic catalyst (sulfuric acid, phosphoric acid, nitric acid, and the like). Salts), and metal alcoholate catalysts (sodium methylate, potassium butyrate, etc.).

As the nonionic surfactant component (B1) and the nonionic surfactant component (B2), those purified by removing a catalyst or the like are preferably used from the viewpoint of improving heat resistance.
The metal content (excluding the alkali metal) detected from the nonvolatile components of the nonionic surfactant component (B1) is preferably 50 ppm or less, more preferably 30 ppm or less, more preferably 20 ppm or less, and more preferably 10 ppm or less. More preferred. A preferred lower limit is 0 ppm.
As a method of removing the catalyst, a known technique can be used, and is not particularly limited, but a method of filtering using diatomaceous earth, a method of performing adsorption removal using an inorganic synthetic adsorbent, and a method using an ion exchange resin are used. And a method for removing the same.

[Anionic surfactant (C)]
The treating agent of the present invention preferably further contains an anionic surfactant (C) in addition to the smoothing component (A) and the nonionic surfactant component (B) from the viewpoint of reducing fluff. .
Examples of the anionic surfactant (C) include an organic phosphate compound, an organic sulfonic acid compound, and a fatty acid alkali soap. Among them, an organic phosphate compound and an organic sulfonic acid compound are preferred from the viewpoint of reducing fluff.

The organic phosphate compound is not particularly limited, and examples thereof include POE (8) oleyl phosphate alkylamino ether salt, isocetyl phosphate POE alkylamino ether salt, and oleyl phosphate dibutylethanolamine salt.
In addition, POE (8) means addition of 8 mol of polyoxyethylene.

  Although it does not specifically limit as an organic sulfonic acid compound, Dioctyl sulfosuccinate Na salt, alkyl sulfonate Na salt, etc. are mentioned.

[Synthetic fiber treatment agent]
The treating agent of the present invention contains a smooth component (A) and a nonionic surfactant component (B), and the component (A) has a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded. It has an ester compound (A2). Further, the metal (excluding the alkali metal) detected from the nonvolatile components of the treating agent by ICP emission spectrometry is 50 ppm or less, preferably 30 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less, and more preferably 3 ppm or less. Particularly preferred. A preferred lower limit is more than 0 ppm, and a more preferred lower limit is 0 ppm.
If it exceeds 50 ppm, the metal catalyst causes a polymerization reaction of the treating agent attached on the roll to form a polymer compound, so that fluff, yarn breakage and roll stain cannot be reduced. As described above, it is a feature of the present invention that fluff, thread breakage, and roll dirt can be dramatically reduced by reducing the amount of metal detected from the nonvolatile components of the treatment agent to a predetermined weight ratio or less.
If the component (B) essentially contains the nonionic surfactant component (B1) having an ester bond in the molecule, the ester reaction is often performed in the presence of a catalyst because of the necessity of improving the reaction efficiency. It is preferable from the viewpoint that effects can be easily obtained.
Further, in order to reduce the amount of the catalyst remaining in the treating agent, the weight ratio of the total weight of the smoothing component (A) and the nonionic surfactant component (B) to the nonvolatile content of the treating agent is 60%. -100% by weight is preferred, 70-99% by weight is more preferred, and 80-95% by weight is even more preferred.
If it is less than 60% by weight, the smoothness, oil film strength, and emulsification failure may be poor.

The reason why the alkali metal is excluded is that the alkali metal is contained in the component (A) and the component (B) but has good compatibility with the oil agent and has a low ability as a catalyst. The reason is that the oil agent adhered to the upper portion is less likely to be polymerized, and thus is not involved in fluff, thread breakage, or roll contamination.
The method of analyzing the metal content by ICP emission spectrometry in the present invention is based on the method described in Examples. In addition, the non-volatile component in the present invention refers to an absolutely dry component when the treating agent is heat-treated at 105 ° C. to remove a solvent or the like and reaches a constant weight.

(Other components)
The synthetic fiber treating agent of the present invention is used for emulsifying the treating agent, assisting the adhesion to the fiber, washing the treating agent from the fiber with water, antistatic property to the fiber, lubricating property, imparting convergence, and the like. A surfactant other than the nonionic surfactant component (B) and the anionic surfactant (C) may be contained. Examples of such surfactants include cationic surfactants such as alkylamine salts, alkylimidazolinium salts, and quaternary ammonium salts; amphoteric surfactants such as lauryl dimethyl betaine and stearyl dimethyl betaine; dimethyl lauryl amine oxide; POE (10) stearyl amino ether, POE (3) lauryl amino ether, and the like. One or more of these surfactants can be used. When the surfactant is contained, the weight ratio of the surfactant to the nonvolatile content of the treating agent is not particularly limited, but is preferably 0.01 to 15% by weight, more preferably 0.1 to 10% by weight. preferable. The term “surfactant” used herein refers to a surfactant having a weight average molecular weight of less than 1,000.

  The synthetic fiber treating agent of the present invention may further contain an antioxidant in order to impart heat resistance. Known antioxidants include phenol-based, thio-based, and phosphite-based antioxidants. One or more antioxidants can be used. When the antioxidant is contained, the weight ratio of the antioxidant to the non-volatile content of the treating agent is not particularly limited, but is preferably 0.1 to 5% by weight, and more preferably 0.1 to 3% by weight.

  The synthetic fiber treating agent of the present invention may further contain a stock solution stabilizer (for example, water, ethylene glycol, propylene glycol). The weight ratio of the stock solution stabilizer to the treating agent is preferably from 0.1 to 30% by weight, more preferably from 1 to 20% by weight.

The treating agent for synthetic fibers of the present invention may be composed of the above-mentioned components consisting only of nonvolatile components, or may be composed of a nonvolatile component and a stock solution stabilizer, and the nonvolatile components are diluted with a low-viscosity mineral oil. Or an aqueous emulsion in which nonvolatile components are emulsified in water. When the treating agent for synthetic fibers of the present invention is an aqueous emulsion in which nonvolatile components are emulsified in water, the concentration of the nonvolatile components is preferably from 5 to 35% by weight, more preferably from 6 to 30% by weight. The viscosity (30 ° C.) of the treatment agent obtained by diluting the non-volatile components with the low-viscosity mineral oil is preferably from 3 to 120 mm ² / s, more preferably from 5 to 100 mm ² / s, from the viewpoint of uniformly imparting the treatment to the fiber material.
Another embodiment of the synthetic fiber treating agent of the present invention is a synthetic fiber treating agent containing a smooth component (A) and a nonionic surfactant component (B), wherein the component (A) Contains an ester compound (A2) having a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded, and the component (B) contains a nonionic surfactant component (B1) having an ester bond in the molecule. , Containing at least one metal selected from the group consisting of Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf, wherein the metal content detected from the non-volatile content of the treatment agent by ICP emission spectrometry is 10 ppm or less. It is.
Another embodiment of the treating agent for synthetic fibers of the present invention is a treating agent for synthetic fibers in the case of using an ester synthesized using a metal catalyst, wherein the treating agent for a smooth component (A) and the nonionic surfactant And a component (B), wherein the component (A) contains an ester compound (A2) having a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded, and the component (B) is contained in the molecule. It contains a nonionic surfactant component (B1) having an ester bond, has a metal content of 10 ppm or less detected from the non-volatile content of the treating agent by ICP emission spectrometry, and the metal is Zn, Mn, Co, Sb, It is at least one selected from Ti, Sn, Ni, Zr and Hf.

(Production method of treating agent for synthetic fiber)
The method for producing a synthetic fiber treating agent of the present invention is a method for producing a synthetic fiber treating agent having a metal content of 10 ppm or less as detected from the non-volatile components of the treating agent by ICP emission spectrometry,
The metal is at least one selected from Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf;
The treatment agent contains a smooth component (A) and a nonionic surfactant component (B),
The step (I) of producing the component (A) and / or the component (B) containing at least one selected from the following step (IA), the following step (IB) and the following step (IC), and removing the catalyst: Step (II) and a mixing step (III) of mixing the component (A) and the component (B),
The component (A) contains an ester compound (A2) having a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded, and the component (B) has a nonionic surfactant component having an ester bond in a molecule. This is a method for producing a synthetic fiber treating agent containing (B1). Examples of the smoothing component (A) and the nonionic surfactant component (B) include those described above for the treating agent.
Step (IA): Esterification reaction between polyhydric alcohol and aliphatic monovalent carboxylic acid in the presence of a catalyst containing at least one selected from Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf Step (IB) of making an aliphatic monohydric alcohol and an aliphatic polyhydric carboxylic acid in the presence of a catalyst containing at least one selected from Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf. (IC): an alkylene oxide is reacted with a polyhydric alcohol in the presence of a catalyst containing at least one selected from Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf. A step of subjecting the added compound to an esterification reaction with a fatty acid

The step (I) is a step of carrying out an esterification reaction in the presence of a catalyst containing at least one selected from Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf, wherein the alcohol, carboxylic acid Are classified into step (IA), step (IB) and step (IC) as described above. As the catalyst containing at least one selected from Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr, and Hf, the same catalyst as that described in each component of the synthetic fiber treating agent can be used.
The temperature of the esterification reaction is preferably from 150 to 280C, more preferably from 160 to 270C, even more preferably from 180 to 260C. If the temperature is lower than 150 ° C., it takes a long time for the reaction, which is not suitable. If the temperature is higher than 250 ° C., the component (A) or the component (B) may have disadvantages such as coloring.
The reaction time of the esterification reaction is preferably 4 to 20 hours, more preferably 5 to 12 hours, and even more preferably 6 to 10 hours. If it exceeds 20 hours, it may be disadvantageous in terms of cost.

The step (II) of removing the catalyst includes the step of removing by adsorption with an inorganic synthetic adsorbent, the step of removing with diatomaceous earth, the step of removing with a filter paper, and the step of adsorbing a metal catalyst on the inorganic synthetic adsorbent and then placing the metal on the filter paper. A catalyst containing at least one selected from the step of laminating and removing the inorganic synthetic adsorbent on which the catalyst has been adsorbed is selected from Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf. It is preferable from the viewpoint that can be removed.
After the metal catalyst is adsorbed on the inorganic synthetic adsorbent, the inorganic synthetic adsorbent obtained by adsorbing the metal catalyst on the filter paper is laminated and removed. After cooling to 110 ° C. after the esterification reaction, the smooth component ( A) or the nonionic surfactant component (B), 2% by weight of the inorganic synthetic adsorbent with respect to the smoothing component (A) or the nonionic surfactant component (B), and 1.5% by weight of ion-exchanged water And maintaining the temperature at 105 ° C. for 3.0 hours to allow the inorganic synthetic adsorbent to adsorb the metal catalyst. Thereafter, a method of laminating and removing an inorganic synthetic adsorbent having a metal catalyst adsorbed thereon on a filter paper may be mentioned.
In the method for producing a treating agent for synthetic fibers of the present invention, the weight ratio of the component (A) to the non-volatile content of the treating agent is 30 to 70% by weight, and the weight ratio of the component (B) is 20 to 70% by weight. When the total weight ratio of the component (A) and the component (B) to the nonvolatile content of the treating agent is 70 to 100% by weight, Zn, Mn, Co, Sb, Ti, Sn, Ni, Zr and Hf It is preferable from the viewpoint that a catalyst containing at least one selected from the group consisting of:

In the step (III) of mixing the synthetic fiber treating agent, the smoothing component (A), the nonionic surfactant component (B), the anionic surfactant (C) and other components are added and mixed in an arbitrary or specific order. It is a process.
These components may be the same as those described above for the synthetic fiber treating agent.

  Hereinafter, the present invention will be described by way of examples. The present invention is not limited to the examples described herein. It should be noted that “%” in the text and tables means “% by weight”.

(Synthesis of Raw Material A2-1)
After adding 134 g (1 mol) of trimethylolpropane and 600 g (3.00 mol) of lauric acid to a 1.5-liter four-neck separable flask at room temperature, the mixture was heated to 70 ° C. to dissolve the metal. Catalyst W1 (3.8 g, 0.51% by weight based on the total of alcohol and acid) was charged, and the temperature was raised to 210 ° C., and the reaction was performed for 1 hour. The reaction was performed while continuing. After the reaction, the mixture was cooled to room temperature to obtain (A2′-1) trimethylolpropane trilaurate before removal of the catalyst.
15 g of the inorganic synthetic adsorbent and 10 g of ion-exchanged water are added to (A2′-1) trimethylolpropane trilaurate before removing the catalyst, and the mixture is added to the inorganic synthetic adsorbent at 105 ° C. for 3 hours while continuously introducing nitrogen. After adsorbing the metal catalyst, filtration under reduced pressure was performed using a filter paper to obtain trimethylolpropane trilaurate according to (A2-1). The Zr content by ICP emission analysis was 3 ppm.

Similarly, (A1-1) to (A1-3), (A2-2), (A2-3), (A5-1), (A5-2) and (A6-1) shown in Table 1 below. ) Was prepared. The catalysts used in each synthesis are as follows, and the metal contents determined by ICP emission analysis are shown in Table 1. However, B2-1 is assumed to be B1-7.
W1: catalyst containing Zr normal propyl zirconate W2: catalyst containing Ti titanium lactate

[Examples 1 to 10, Comparative Examples 1 to 5]
The components shown in Table 2 were mixed and stirred until the mixture became uniform to prepare a treating agent. Using each of the prepared treating agents, the accumulation of stain on the pin, the wiping property of the stain on the pin, and the fluctuation in tension were evaluated by the following methods. Table 2 shows the results.
In addition, the number of the non-volatile component composition of the treating agent in Table 2 indicates the weight ratio of each component to the non-volatile component of the treating agent. In Table 2, C-1 to C-5, D-1 and D-2 used the following components.
C-1: Dioctyl sulfosuccinate Na salt C-2: Oleic acid K salt C-3: Alkyl sulfonate Na salt C-4: Isocetyl phosphate POE alkyl amino ether salt C-5: Oleyl phosphate dibutyl ethanolamine salt D- 1: POE (10) stearyl amino ether D-2: POE (3) lauryl amino ether

(Method of measuring metal detected from non-volatile components of treatment agent by ICP emission spectrometry)
(1) Pretreatment (Ti, Zr)
5 g of the nonvolatile content of the synthetic fiber treating agent is weighed in a platinum crucible, carbonized on an electric heater, ashed in an electric furnace, 4 ml of sulfuric acid is added, and water is distilled off on the electric heater until a small amount remains. Add ultrapure water to 50 ml and use it as a measurement sample.
(2) Calibration curve The known concentrations of 10 ppm and 5 ppm of Ti and Zr are adjusted in advance. The sample is supplied to an ICP (measurement device name: ICPS-8100, manufactured by Shimadzu Corporation, ICP emission spectrometer) to prepare a calibration curve.
(3) Measurement The above measurement sample was supplied to ICP (measurement instrument name: ICPS-8100, manufactured by Shimadzu Corporation, ICP emission spectrometer), and the non-volatile content of the synthetic fiber treating agent for each metal element was determined using the calibration curve created in (2) above. Was measured. The components (A) and (B) synthesized as described above and the non-volatile components of the treating agents of Examples 1 to 10 and Comparative Examples 1 to 5 were measured in the same manner.
The content of Zn, Mn, Co, Sb, Sn, Ni and Hf contained in the component (A), the component (B), and the nonvolatile components of the treatment agents of Examples 1 to 10 and Comparative Examples 1 to 5 is as follows. , In each case was 0 ppm.
The metal species in the treating agents of Examples 1 to 10 and Comparative Examples 1 to 5 correspond to the metal species detected in component (A) and / or component (B) in Table 1 above, respectively.

(Evaluation of accumulation of dirt on pins, wiping property of dirt on pins, fluctuation in tension)
The above-prepared treating agent was quantitatively applied to an oil-free polyester filament of 1000 denier and 96 filaments in an amount of 20% by weight, and passed through a roller heated to 150 ° C. by a friction measuring machine for yarn removal to remove volatile components. At a temperature of 250 ° C., and was run for 4 hours at an initial tension of 500 g and a yarn running speed of 2 m / min. The degree of accumulation of dirt on the pin, the dirt wiping property of the pin, and the variation in tension were evaluated. In order to perform a stricter evaluation, a treatment agent was added at 20% by weight.

The degree of accumulation of dirt on the pins was evaluated according to the following criteria.
◎: Almost no dirt observed ○: Dirt was slightly observed ×: Dirt was clearly accumulated

The tension fluctuation value was calculated by the following equation.
Tension fluctuation value (g) = tension after running the yarn for 4 hours (g)-initial tension (g)
Further, the tension fluctuation was evaluated from the tension fluctuation value according to the following criteria.
◎: 0 g to less than 30 g ：: 30 g or more and less than 50 g ×: 50 g or more

The dirt wiping property of the pin was evaluated by the following method.
The dirt generated on the chrome pin during pear was wiped off by soaking a solution of sodium hydroxide in water and glycerin into a gauze. The wiping property was evaluated by the number of times required for wiping.
◎: Wipes can be wiped off by wiping less than 5 times ５: Wipes can be wiped by wiping 5 times or more and less than 20 times ×: Cannot be wiped by wiping more than 20 times

As can be seen from Table 2, Examples 1 to 10 are treatment agents for synthetic fibers containing a smooth component (A) and a nonionic surfactant component (B), wherein the component (A) is a fatty acid. And an ester compound (A2) having a structure in which a trivalent or higher aliphatic alcohol is ester-bonded, and the content of metals (excluding alkali metals) detected from the non-volatile components of the treating agent by ICP emission spectrometry. It can be seen that the roll contamination can be reduced and the heat resistance is excellent because the content is 50 ppm or less. Particularly, in Examples 1 to 4 and 6 to 9, since the nonionic surfactant component (B1) having an ester bond in the molecule in which the metal catalyst is reduced is included, it is possible to particularly reduce roll dirt and have excellent heat resistance. I understand.
On the other hand, when the content of metals (excluding alkali metals) detected from the nonvolatile components of the treating agent by ICP emission spectrometry is more than 50 ppm (Comparative Examples 1, 2, and 5), the ester compound (A2) is not included. In the case (Comparative Example 3), when no nonionic surfactant component (B) was contained (Comparative Example 4), any of the problems of the present application could not be solved.

Industrial applicability

  Since the synthetic fiber treating agent of the present invention has excellent heat resistance, it is used for industrial materials such as tarpaulins, tire cords, seat belts, airbags, fish nets, ropes, slings, and the like, and used for clothing such as woven and knitted fabrics. Suitable for fiber filament yarn.

Claims (2)

A synthetic fiber treating agent comprising a smoothing component (A) and a nonionic surfactant component (B),
The component (A) includes an ester compound (A2) having a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded,
ICP emission wherein the component (B) includes a nonionic surfactant component (B1) having an ester bond in the molecule, and is at least one selected from Zn, Mn, Co , Ti, Sn, Ni, Zr and Hf. A synthetic fiber treating agent comprising a metal element detectable by an analytical method, wherein the content of the metal element detected from non-volatile components of the treating agent by ICP emission spectrometry is more than 0 ppm and 10 ppm or less. A synthetic fiber treating agent when using an ester synthesized using a metal catalyst,
It contains a smoothing component (A) and a nonionic surfactant component (B),
The component (A) includes an ester compound (A2) having a structure in which a fatty acid and a trihydric or higher aliphatic alcohol are ester-bonded,
When the component (B) contains a nonionic surfactant component (B1) having an ester bond in the molecule, and the content of the metal element detected from the nonvolatile components of the treatment agent by ICP emission spectrometry is more than 0 ppm and 10 ppm or less. A synthetic fiber treating agent, wherein the metal is at least one selected from Zn, Mn, Co , Ti, Sn, Ni, Zr and Hf.