WO2015025668A1 - Synthetic-fiber-treating agent, method for treating synthetic fiber, and synthetic fiber - Google Patents

Abstract

The present invention provides: a synthetic-fiber-treating agent for suppressing the accumulation of tar over a long period by maintaining exceptional heat resistance from the manufacture through the processing of a synthetic fiber to which thermal treatment is applied, the synthetic-fiber-treating agent exhibiting exceptional process passability by maintaining exceptional extreme-pressure lubricity; a method for treating a synthetic fiber using such a synthetic-fiber-treating agent; and a synthetic fiber obtained by such a treatment method. A smoothing agent blended with two specific kinds of phosphate compound is used as the synthetic-fiber-treating agent.

Description

Synthetic fiber treatment agent, synthetic fiber treatment method and synthetic fiber

The present invention relates to a synthetic fiber treating agent, a synthetic fiber treatment method, and a synthetic fiber. In recent years, in synthetic fiber manufacturing or processing steps, speeding-up has been promoted, and accordingly, heat treatment at high temperature is performed on synthetic fibers. Among them, synthetic fiber for industrial materials used for applications covered with organic polymer resins such as polyvinyl chloride resin and polypropylene resin is important for the dimensional stability of the molded product, and is required to reduce the shrinkage of the fiber. The degree is high, and there is a tendency that heat treatment at a severer high temperature is performed on a heat stretching roller (hot roller). As a result, due to tar (dirt) accumulated on the hot roller, tension fluctuations frequently occur and operability (process passability) is lowered. For this reason, the treatment agent attached to the synthetic fiber has a high degree of ability to prevent the occurrence of dirt and tension fluctuation on the hot roller as described above, even when the synthetic fiber is produced at high temperature and high contact pressure. Extreme pressure lubricity and heat resistance are required. The present invention maintains excellent heat resistance even in the production or processing of synthetic fibers accompanied by heat treatment at severe high temperatures, suppresses fluctuations in tension due to insufficient extreme pressure lubricity, and thus exhibits excellent processability. It is related with the processing agent for fibers, the processing method of synthetic fiber, and synthetic fiber.

Conventionally, as a treatment agent for synthetic fibers as described above, a treatment agent for synthetic fibers containing an ester compound having a thioether group (for example, see Patent Document 1), a treatment agent for synthetic fibers containing a benzimidazole compound (for example, Patent Documents) 2) has been proposed, but in recent years, the spinning speed has been increased and the heating temperature has been increased, so that heat resistance is insufficient, so that tar accumulates over time, causing fuzz and yarn breakage. There is a problem of worsening the passability. A treatment agent for synthetic fibers with a reduced maximum water viscosity (for example, see Patent Document 3) has also been proposed in order to reduce fluff and yarn breakage, but due to insufficient extreme pressure lubricity, fluctuations in tension are likely to occur and pass through the process. There is a problem of insufficient sex.

Japanese Patent Laid-Open No. 09-188968 JP-A-10-292261 JP 2012-92482 A

The problem to be solved by the present invention is to suppress tar accumulation over a long period of time and maintain excellent extreme pressure lubricity by maintaining excellent heat resistance in the production or processing of synthetic fibers subjected to heat treatment. Therefore, the present invention provides a treatment agent for synthetic fibers that exhibits excellent process passability, a method for treating synthetic fibers using such a treatment agent for synthetic fibers, and a synthetic fiber obtained by such a treatment method.

As a result of studies conducted by the present inventors to solve the above-mentioned problems, it is correctly preferable to use a treatment agent for synthetic fibers formed by blending a specific phosphate compound A and a specific phosphate compound B with a smoothing agent. I found out.

That is, the present invention relates to a synthetic fiber treating agent characterized by comprising the following phosphoric acid compound A and the following phosphoric acid compound B in a smoothing agent. The present invention also relates to a synthetic fiber treatment method using such a synthetic fiber treating agent and a synthetic fiber obtained by such a synthetic fiber treatment method.

Phosphoric acid compound A: One or two or more selected from the phosphoric acid ester represented by the following chemical formula 1 and the organic amine salt of the phosphoric acid ester represented by the chemical formula 1 below.

In chemical formula 1,
R ¹ : a hydroxyl group from a residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 24 carbon atoms, or a total of 1 to 20 moles of ethylene oxide and / or propylene oxide added to an aliphatic alcohol having 8 to 24 carbon atoms Excluded residue R ² : a hydrogen atom, a residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 24 carbon atoms, or a total of 1 to 20 ethylene oxide and / or propylene oxide to an aliphatic alcohol having 8 to 24 carbon atoms Residue obtained by removing the hydroxyl group from the mole added n: an integer of 2 or 3

Phosphoric acid compound B: phosphoric acid ester represented by the following chemical formula 2, organic amine salt of the phosphoric acid ester represented by the chemical formula 2 below, phosphoric acid ester represented by the chemical formula 3 below and phosphorus represented by the chemical formula 3 below One or more selected from organic amine salts of acid esters.

In Chemical Formula 2 and Chemical Formula 3,
R ³ , R ⁴ , R ⁵ : Residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 24 carbon atoms or 1 to 20 mol of ethylene oxide and / or propylene oxide in total in an aliphatic alcohol having 8 to 24 carbon atoms Residues that have hydroxyl groups removed from the addition

First, the treatment agent for synthetic fibers according to the present invention (hereinafter referred to as the treatment agent of the present invention) will be described. The treatment agent of the present invention is obtained by blending the above-described phosphoric acid compound A and phosphoric acid compound B with a smoothing agent.

As the phosphoric acid compound A, 1) phosphate esters such as monododecyl pyrophosphate, didodecyl pyrophosphate, monooleyl pyrophosphate, dioleyl pyrophosphate, dodecyl oleyl pyrophosphate, dioleyl polyphosphate represented by the above-mentioned chemical formula 1 2) Organic amine salts of phosphate esters such as monododecyl pyrophosphate, didodecyl pyrophosphate, monooleyl pyrophosphate, dioleyl pyrophosphate, dodecyl oleyl pyrophosphate and dioleyl polyphosphate represented by the above-mentioned chemical formula 1 It is done. Alkali metal salts of phosphoric acid esters such as monododecyl pyrophosphate, didodecyl pyrophosphate, monooleyl pyrophosphate, dioleyl pyrophosphate, dioleyl polyphosphate and the like are not preferable because they deteriorate the heat resistance.

As R ^{1 in} Chemical Formula 1, 1) octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, dodecyl alcohol, 2-butyl-octyl alcohol, tridecyl Residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 24 carbon atoms such as alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, docosyl alcohol, tetracosyl alcohol, etc. ) Octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, dodecyl alcohol, 2-butyl-octyl alcohol Ethylene oxide and / or aliphatic alcohols having 8 to 24 carbon atoms such as alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, docosyl alcohol and tetracosyl alcohol Or the residue remove | excluding the hydroxyl group from what added 1-20 mol of propylene oxide in total is mentioned. Among them, R ¹ includes a) from an aliphatic alcohol having 12 to 18 carbon atoms such as dodecyl alcohol, 2-butyl-octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol and the like. A residue excluding a hydroxyl group; b) an aliphatic alcohol having 12 to 18 carbon atoms such as dodecyl alcohol, 2-butyl-octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, etc. A residue obtained by removing a hydroxyl group from a total of 1 to 20 moles of ethylene oxide and / or propylene oxide added is preferable.

As R ^{2 in} Chemical Formula 1, 1) hydrogen atom, 2) octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, dodecyl alcohol, 2-butyl- Exclude hydroxyl groups from C8-24 aliphatic alcohols such as octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, docosyl alcohol, tetracosyl alcohol 3) Octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, dodecyl alcohol, 2-buty Ethylene to aliphatic alcohols having 8 to 24 carbon atoms such as ru-octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, docosyl alcohol, tetracosyl alcohol Examples thereof include residues obtained by removing a hydroxyl group from a total of 1 to 20 moles of oxide and / or propylene oxide added. Among them, R ² includes a) hydrogen atom, b) 12 to 18 carbon atoms such as dodecyl alcohol, 2-butyl-octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol and the like. C) Residues obtained by removing hydroxyl groups from aliphatic alcohols, c) 12-18 carbon atoms such as dodecyl alcohol, 2-butyl-octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, etc. A residue obtained by removing a hydroxyl group from a total of 1 to 20 moles of ethylene oxide and / or propylene oxide added to the above aliphatic alcohol is preferable.

Examples of the phosphoric acid compound B include 1) didodecyl phosphate, di-2-butyl-octyl phosphate, ditridecyl phosphate, dimyristyl phosphate, dicetyl phosphate, distearyl phosphate, diisostearyl phosphate, dioleyl phosphate, dodecyl oleyl phosphate, etc. 2) Didodecyl phosphate, di-2-butyl-octyl phosphate, ditridecyl phosphate, dimyristyl phosphate, dicetyl phosphate, distearyl phosphate, diisostearyl phosphate, dioleyl phosphate , Organic amine salts of phosphate esters represented by the above formula 2 such as dodecyl oleyl phosphate, 3) monododecyl phosphate, mono 2-butyl-oct Ruphosphate, monotridecyl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, monoisostearyl phosphate, monooleyl phosphate, etc. 4) monododecyl phosphate, mono 2-decyl phosphate Examples thereof include organic amine salts of the phosphoric acid ester represented by Chemical Formula 3 such as butyl-octyl phosphate, monotridecyl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, monoisostearyl phosphate, monooleyl phosphate and the like. Alkali metal salts of phosphoric acid esters such as potassium salt of dioleyl phosphate, sodium salt of monododecyl phosphate, sodium salt of monooleyl phosphate are not preferred because they deteriorate the heat resistance.

R ³ , R ⁴ and R ^{5 in} Chemical Formula 2 or Chemical Formula ³ are the same as those described above for R ^{1 in} Chemical Formula ¹ .

As the treating agent of the present invention, the phosphoric acid compound B is represented by chemical formula 1 or two or more selected from the phosphoric acid ester represented by chemical formula 2 and the organic amine salt of the phosphoric acid ester represented by chemical formula 2. 1 or a mixture of two or more of the phosphoric acid ester organic amine salts represented by Chemical formula 3 and the P nuclear integral ratio of the phosphoric acid compound A determined from the following formula 1 is 10 A content adjusted to ˜99% is preferable, and a value set to 25% to 75% is more preferable.

In Equation 1,
## STR1 ## P nuclear NMR integral value attributed to the potassium salt of the phosphate ester represented by Chemical Formula 1 P2: P nuclear NMR integral value attributed to the potassium salt of the phosphate ester represented by Chemical Formula 2 3: P-nuclear NMR integrated value attributed to the potassium salt of phosphate represented by Chemical Formula 3

The P nuclear integral ratio of the phosphoric acid compound A can be calculated from the measured value of ³¹ P-NMR by neutralizing a phosphate ester and / or phosphate ester salt with an excess of potassium hydroxide. Generally, the peak attributed to chemical formula 1 appears below 0 ppm, the peak attributed to chemical formula 2 appears above 0 ppm and below 4 ppm, and the peak attributed to chemical formula 3 appears at 4 ppm or higher. Obtained and calculated by the above-mentioned formula 1.

The P nuclear integral ratio of the phosphoric acid compound A obtained from Equation 1 is preferably 10 to 99%, more preferably 25 to 75%.

The smoothing agent used in the treatment agent of the present invention includes 1) fats such as octyl palmitate, oleyl laurate, oleyl oleate, isotetracosyl oleate, polyoxyethylene octyl decanoate and polyoxyethylene lauryl erucate. Compounds of aliphatic monoalcohols and aliphatic monocarboxylic acids, and compounds obtained by adding alkylene oxides having 2 to 4 carbon atoms to such ester compounds, 2) 1,6-hexanediol didecanoate, glycerin trioleate, trimethylol Complete ester compounds of aliphatic polyhydric alcohols and aliphatic monocarboxylic acids, such as propane trilaurate, pentaerythritol tetraoctanoate and polyoxypropylene 1,6-hexanediol dioleate, and such complete ester compounds Compounds having an alkylene oxide having 2 to 4 carbon atoms added thereto, 3) aliphatic monoalcohols such as bispolyoxyethylene decyl adipate, dioleyl azelate, dioleyl thiodipropionate and bispolyoxyethylene lauryl adipate; A complete ester compound with an aliphatic polycarboxylic acid, or a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to the complete ester compound, 4) benzyl oleate, benzyl laurate and polyoxypropylene benzyl stearate, An ester compound of an aromatic monoalcohol and an aliphatic monocarboxylic acid, or a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to the ester compound, 5) bisphenol A dilaurate, polyoxyethylene bisphenol A dilaurate, etc. Complete ester compounds of aromatic polyhydric alcohols and aliphatic monocarboxylic acids, and compounds in which alkylene oxides having 2 to 4 carbon atoms are added to such complete ester compounds, 6) bis-2-ethylhexyl phthalate, diisostearyl isophthalate A complete ester compound of an aliphatic monoalcohol and an aromatic polycarboxylic acid, such as trioctyl trimellitate, or a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to such a complete ester compound, 7) coconut oil, Publicly known smoothing agents used in synthetic fiber treating agents such as rapeseed oil, sunflower oil, soybean oil, castor oil, sesame oil, fish oil, and beef tallow can be used. Among them, as a smoothing agent, an ester of a polyhydric alcohol such as trimethylolpropane trilaurate, dioleylthiodipropionate, or oleyl oleate and a monovalent carboxylic acid, a monohydric alcohol and a polyvalent carboxylic acid Esters and esters of monohydric alcohols with monovalent carboxylic acids are preferred.

The total ratio of phosphoric acid compound A and phosphoric acid compound B to the smoothing agent used in the treatment agent of the present invention is not particularly limited, but the smoothing agent is 95 to 99.9% by mass, phosphoric acid compound A and phosphoric acid compound It is preferable to contain B in a ratio of 0.1 to 5% by mass (total 100% by mass in total).

As the treating agent of the present invention, a nonionic surfactant and an antioxidant are further blended, the smoothing agent is 20 to 90% by mass, and the total of the phosphoric acid compound A and the phosphoric acid compound B is 0.1 to 5% by mass. It is preferable to contain 10 to 90% by weight of nonionic surfactant and 0.1 to 3% by weight of antioxidants (100% by weight in total).

Nonionic surfactants used in the treatment agent of the present invention include: 1) a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an organic acid, organic alcohol, organic amine and / or organic amide molecule, such as polyoxyethylene lauric acid Esters, polyoxyethylene oleate, polyoxyethylene laurate methyl ether, polyoxyethylene oleate diester, polyoxyethylene octyl ether, polyoxypropylene lauryl ether methyl ether, polyoxybutylene oleyl ether, polyoxyethylene polyoxy Ether type nonionic surfactants such as propylene nonylphenyl ether, polyoxyethylene lauryl amino ether, polyoxyethylene lauroamide ether, etc., 2) sorbitan triolea Polyoxyalkylenes such as polyoxyalkylene sorbitan trioleate, polyoxyalkylene sorbitan trioleate, polyoxyalkylene castor oil, polyoxyalkylene hydrogenated castor oil trioctanoate, etc. Polyhydric alcohol fatty acid ester type nonionic surfactants, 4) alkylamide type nonionic surfactants such as diethanolamine monolauramide, and 5) polyoxyalkylene fatty acid amide type nonionic surfactants such as polyoxyethylene diethanolamine monooleylamide Among them, ether type nonionic surfactants are preferable.

Examples of the antioxidant used in the treatment agent of the present invention include 1) 1,3,5-tris (3 ′, 5′-di-t-butyl-4-hydroxybenzyl) isocyanuric acid, 1,3,5-tris (4-Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene -3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] phenolic antioxidants such as methane, 2) octyldiphenyl phosphite, trisnonylphenylphosphine And phosphite antioxidants such as tetratridecyl-4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol) diphosphite, 3) 4,4′-thiobis- (6-t -Butyl-3-methylphenol) and thioether antioxidants such as dilauryl-3,3'-thiodipropionate. These can be used alone or in combination of two or more.

The treatment agent of the present invention is used for known synthetic fibers, and the type and use thereof are not particularly limited, but the treatment agent of the present invention may be used for industrial material synthetic fibers having particularly severe heat resistance requirements. It is preferable in that excellent heat resistance can be exhibited.

Next, the synthetic fiber processing method according to the present invention (hereinafter referred to as the processing method of the present invention) will be described. The treatment method of the present invention is 0.1 to 3% by mass, preferably 0.5 to 1.5% by mass, based on the synthetic fiber filament yarn subjected to the heat treatment step with the treatment agent of the present invention as described above. It is the method of making it adhere. Examples of the process for attaching the treatment agent of the present invention to the synthetic fiber include a spinning process, a stretching process, and a process in which spinning and stretching are performed simultaneously. Examples of the method for attaching the treatment agent of the present invention to synthetic fibers include a roller oiling method, a guide oiling method using a metering pump, an immersion oiling method, and a spray oiling method. Furthermore, examples of the form in which the treatment agent of the present invention is attached to the synthetic fiber include aqueous liquids, organic solvent solutions, and neat.

Finally, the synthetic fiber according to the present invention (hereinafter referred to as the synthetic fiber of the present invention) will be described. The synthetic fiber of the present invention is a synthetic fiber obtained by the treatment method of the present invention described above. Synthetic fibers include: 1) Polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, polylactic acid ester, 2) Polyamide fibers such as nylon 6 and nylon 66, 3) Polyacryl fibers such as polyacryl and modacrylic, 4) Polyolefin fibers such as polyethylene and polypropylene, 5) Polyurethane fibers, 6) Polyphenylene sulfide (PPS) fibers, etc. Among them, industries such as polyester fibers and polyamide fibers that have severe heat resistance requirements It is preferable that it is used for material synthetic fiber since the heat resistance which was excellent in the processing agent of this invention can be exhibited.

According to the present invention described above, in the production or processing of synthetic fibers subjected to heat treatment, tar accumulation is suppressed over a long period by maintaining excellent heat resistance, and excellent extreme pressure lubricity is maintained. There is an effect that excellent process passability can be exhibited.

Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test category 1 (Preparation of phosphate compounds)
Preparation of phosphoric acid compound (P-1) A reaction vessel was charged with 381 parts of oleyl alcohol, dehydrated at 120 ° C. under a pressure of 0.05 MPa or less for 2 hours, returned to normal pressure, and stirred for 60 ± 5 81 ° C. of diphosphorus pentoxide was added at 1 ° C. over 1 hour. After aging at 80 ° C. for 3 hours, 543 parts of dibutylethanolamine was added dropwise at 50 ° C. to neutralize to prepare a phosphoric acid compound (P-1).

Calculation of the P nucleus integral ratio of the phosphoric acid compound (P-1) Under the condition that the pH was increased to 12 or more by adding excess KOH to the phosphoric acid compound (P-1), the P nucleus was measured using ³¹ P-NMR. When the integral ratio was calculated, the phosphate ester represented by Chemical Formula 1 was 30%, the phosphate ester represented by Chemical Formula 2 was 35%, and the phosphate ester represented by Chemical Formula 3 was 35%.

The P nuclear integral ratio was calculated from the above formula 1 using the measured value of ³¹ P-NMR (trade name MERCURY plus NMR Spectrometer System, 300 MHz, the same applies hereinafter, manufactured by VALIAN). The solvent used was a mixed solvent of heavy water / tetrahydrofuran = 8/2 (volume ratio).

Preparation of phosphoric acid compounds (P-2 to P-10 and RP-1 to RP-3) In the same manner as the phosphoric acid compound (P-1), other phosphoric acid compounds (P-2 to P-10 and RP-1 to RP-3) were prepared.

-Preparation of phosphate compound (RP-4)
A reaction vessel was charged with 327 parts of oleyl alcohol and 3 g of ion-exchanged water, and 69 parts of diphosphorus pentoxide were added at 60 ± 5 ° C. over 1 hour with stirring. Aging was performed at 80 ° C. for 3 hours. After adding 4 g of ion-exchanged water and hydrolyzing at 100 ° C. for 2 hours, 604 parts of dibutylethanolamine was added dropwise at 50 ° C. for neutralization to prepare a phosphoric acid compound (RP-4). When the P nuclear integral ratio was calculated using ³¹ P-NMR under the condition that the pH was increased to 12 or more by adding excess KOH to the phosphoric acid compound (RP-4), the phosphate ester represented by Chemical Formula 1 was found to be 0%, 45% of the phosphate ester represented by Chemical Formula 2 was 55%, and 55% of the phosphate ester represented by Chemical Formula 3 The contents of the phosphoric acid compounds prepared above are summarized in Tables 1 to 3.

Test category 2 (Preparation of synthetic fiber treatment agent)
Example 1 (Preparation of synthetic fiber treatment agent (PT-1))
As a smoothing agent, 40 parts of trimethylolpropane trioleate (L-1), 17 parts of glycerin trilaurate (L-2), 5 parts of sorbitan monooleate (L-3), and phosphate compounds as Table 1 to Ether monool (S-1) obtained by adding 2 parts of phosphoric acid compound (P-1) shown in Table 3 and 5 moles of EO (ethylene oxide, the same applies hereinafter) to 1 mole of lauryl alcohol as a nonionic surfactant 5 parts of polyoxyalkylene aliphatic polyvalent ester compound (S-2) in which 8 parts of EO is added to 1 part of hardened castor oil and 20 parts of EO to 1 part of hardened castor oil 15 parts of an aromatic polyvalent ester compound (S-3), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) as an antioxidant Ruphenyl) butane (AO-1) was uniformly mixed at a ratio of 1 part to prepare a treating agent for synthetic fiber (PT-1) of Example 1.

Examples 2 to 12 and Comparative Examples 1 to 5 (Preparation of synthetic fiber treatment agents (PT-2) to (PT-12) and (RT-1) to (RT-5))
In the same manner as the synthetic fiber treatment agent (PT-1) of Example 1, the synthetic fiber treatment agents (PT-2) to (PT-12) and (RT) of Examples 2 to 12 and Comparative Examples 1 to 5 -1) to (RT-5) were prepared. The contents of the treating agent for synthetic fibers of each example prepared above are shown in Table 4 together with Example 1.

In Table 4,
L-1: Trimethylolpropane trioleate L-2: Glycerin trilaurate L-3: Sorbitan monooleate L-4: Dioleyl adipate L-5: Isostearyl stearate S-1: 1 mol of lauryl alcohol Ether monool with 5 moles of EO S-2: Polyoxyalkylene aliphatic polyvalent ester compound with 8 moles of EO added to 1 mole of hardened castor oil S-3: Poly with 20 moles of EO added to 1 mole of hardened castor oil Oxyalkylene aliphatic polyvalent ester compound AO-1: 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (trade name ADK STAB AO30 manufactured by ADEKA)
AO-2: Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (trade name ADK STAB AO60 manufactured by ADEKA)

Test category 3 (Adhesion and evaluation of synthetic fiber treatment agents on synthetic fibers)
Example 13
The synthetic fiber treating agent (PT-1) prepared in Example 1 of Test Category 2 was uniformly diluted with ion-exchanged water to obtain a 15% solution. The 15% solution was adhered to an oil-free polyethylene terephthalate filament yarn of 192 filaments and an intrinsic viscosity of 0.93 at 1100 dtex by an oiling roller lubrication method.

Examples 14 to 16, 18 to 23 and Comparative Examples 6 to 9
Synthetic fiber treatment agents (PT-2) to (PT-4) of Examples 2 to 4 and synthetic fiber treatment agents (PT-6) to (PT-) of Examples 6 to 11 in the same manner as in Example 13. 11) and treatment agents for synthetic fibers (RT-1) to (RT-4) of Comparative Examples 1 to 4 were adhered.

Example 17
The synthetic fiber treating agent (PT-5) prepared in Example 5 of Test Category 2 was uniformly diluted with mineral oil to obtain a 70% solution. The 70% solution was adhered to a non-oiled polyethylene terephthalate filament yarn of 192 filaments and an intrinsic viscosity of 0.93 at 1100 dtex by a guide oiling method using a metering pump.

Example 24 and Comparative Example 10
In the same manner as in Example 17, the synthetic fiber treatment agent (PT-12) of Example 12 and the synthetic fiber treatment agent (RT-5) of Comparative Example 5 were adhered.

・ Measurement of the amount of synthetic fiber treatment agent attached In accordance with JIS-L1073 (Synthetic Fiber Filament Yarn Test Method), synthetic fiber using a mixed solvent of normal hexane / ethanol = 50/50 (volume ratio) as an extraction solvent The amount (%) of the treatment agent adhered to the surface was measured. The results are summarized in Table 5.

・ Sashimi Chrome Pin Dirt Test (Pin Dirt Test in Table 5)
In each case, the test yarn collected from the cake with the synthetic fiber treatment agent attached was run in contact with a satin chrome pin having a surface temperature of 240 ° C. at an initial tension of 1 kg and a yarn speed of 100 m / min. The amount of later tar was observed with the naked eye and evaluated according to the following criteria. The results are summarized in Table 5.

◎: Dirt is not recognized or slightly recognized ○: Dirt is slightly recognized ×: Dirt is clearly recognized

-Wipe-off test The stain | pollution | contamination which generate | occur | produced on the satin chrome pin obtained by the said satin chrome pin stain test was wiped off with the gauze which soaked 5% sodium hydroxide glycerin solution, and the wiping property was evaluated on the following reference | standard. The results are summarized in Table 5.

A: The dirt can be wiped off by wiping less than 10 times.
○: Dirt can be wiped off by wiping 10 times or more and less than 50 times.
X: Dirt cannot be wiped off even by wiping 50 times or more.

・ Tension variation test In each case, the test yarn collected from the cake with the synthetic fiber treatment agent attached was run in contact with a satin chrome pin with a surface temperature of 240 ° C at an initial tension of 1 kg and a yarn speed of 100 m / min. The tension value of the thread after the chrome pin is measured by the tension value (F1) after 1 hour of running and the tension value (F12) after 12 hours of running, and the tension fluctuation rate obtained from Equation 2 using these values is the following standard: It was evaluated with. The results are summarized in Table 5.

A: The tension value is stable, and the tension fluctuation rate is less than 1%.
A: The tension value is slightly unstable, and the tension fluctuation rate is 1% or more and less than 3%.
X: The tension value is unstable, and the tension fluctuation rate is 3% or more.

In Equation 2,
F1: Tension value after 1 hour of travel F12: Tension value after 12 hours of travel

Claims (10)

A treating agent for synthetic fibers, characterized by comprising the following phosphoric acid compound A and the following phosphoric acid compound B in a smoothing agent.
Phosphoric acid compound A: one or two or more selected from the phosphoric acid ester represented by the following chemical formula 1 and the organic amine salt of the phosphoric acid ester represented by the following chemical formula 1

(In chemical formula 1,
R ¹ : a hydroxyl group from a residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 24 carbon atoms, or a total of 1 to 20 moles of ethylene oxide and / or propylene oxide added to an aliphatic alcohol having 8 to 24 carbon atoms Excluded residue R ² : a hydrogen atom, a residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 24 carbon atoms, or a total of 1 to 20 ethylene oxide and / or propylene oxide to an aliphatic alcohol having 8 to 24 carbon atoms Residue obtained by removing a hydroxyl group from a mole added n: an integer of 2 or 3)
Phosphoric acid compound B: phosphoric acid ester represented by the following chemical formula 2, organic amine salt of the phosphoric acid ester represented by the chemical formula 2 below, phosphoric acid ester represented by the chemical formula 3 below and phosphorus represented by the chemical formula 3 below One or more selected from organic amine salts of acid esters.

(In Chemical Formula 2 and Chemical Formula 3,
R ³ , R ⁴ , R ⁵ : Residue obtained by removing a hydroxyl group from an aliphatic alcohol having 8 to 24 carbon atoms or 1 to 20 mol of ethylene oxide and / or propylene oxide in total in an aliphatic alcohol having 8 to 24 carbon atoms Residues from which the hydroxyl group is removed from the added one) The phosphoric acid compound B is represented by one or two or more selected from the phosphoric acid ester represented by Chemical Formula 2 and the organic amine salt of the phosphoric acid ester represented by Chemical Formula 2, and the phosphoric ester represented by Chemical Formula 3 and Chemical Formula 3 One or a mixture of two or more selected from the organic amine salts of phosphoric acid esters, and the P nuclear integral ratio of phosphoric acid compound A calculated from the following formula 1 is 10 to 99%. Item 10. A synthetic fiber treatment agent according to Item 1.

(In Equation 1,
## STR1 ## P nuclear NMR integral value attributed to the potassium salt of the phosphate ester represented by Chemical Formula 1 P2: P nuclear NMR integral value attributed to the potassium salt of the phosphate ester represented by Chemical Formula 2 3: P-nuclear NMR integral value attributed to the potassium salt of phosphate ester represented by Chemical Formula 3) R ¹ in Chemical Formula ¹ , R ³ and R ^{4 in} Chemical Formula ^2, and R ^{5 in} Chemical Formula 3 are residues obtained by removing a hydroxyl group from an aliphatic alcohol having 12 to 18 carbon atoms, an aliphatic having 12 to 18 carbon atoms This is a residue obtained by removing 1 to 20 mol of ethylene oxide and / or propylene oxide in total from alcohol and removing the hydroxyl group, wherein R ^{2 in} Chemical Formula 1 is a hydrogen atom and an aliphatic alcohol having 12 to 18 carbon atoms. 3. A residue obtained by removing a hydroxyl group from a residue obtained by adding 1 to 20 mol of ethylene oxide and / or propylene oxide in total to an aliphatic alcohol having 12 to 18 carbon atoms, excluding a hydroxyl group. Treatment agent for synthetic fibers. The treating agent for synthetic fibers according to claim 3, wherein the P nucleus integral ratio of the phosphoric acid compound A obtained from the formula 1 is 25 to 75%. The smoothing agent is one or two selected from an ester of a polyhydric alcohol and a monovalent carboxylic acid, an ester of a monovalent alcohol and a polyvalent carboxylic acid, and an ester of a monovalent alcohol and a monovalent carboxylic acid. The treatment agent for synthetic fibers according to any one of claims 1 to 4, wherein the treatment agent is one or more. The smoothing agent is contained in 95 to 99.9% by mass and the phosphoric acid compound A and the phosphoric acid compound B are contained in a total amount of 0.1 to 5% by mass (total 100% by mass). The treating agent for synthetic fibers according to one item. Further, a nonionic surfactant and an antioxidant are blended, and a smoothing agent is 20 to 90% by mass, a total of 0.1 to 5% by mass of phosphoric acid compound A and phosphoric acid compound B, and a nonionic surfactant is 10 to 10%. The treatment agent for synthetic fibers according to any one of claims 1 to 5, comprising 90% by mass and an antioxidant in a proportion of 0.1 to 3% by mass (total 100% by mass). The treating agent for synthetic fibers according to any one of claims 1 to 7, which is for industrial materials synthetic fibers. A synthetic fiber treatment agent according to any one of claims 1 to 8, wherein the synthetic fiber treatment agent is adhered to the synthetic fiber filament yarn to be subjected to the heat treatment step so as to be 0.1 to 3% by mass. Fiber processing method. A synthetic fiber obtained by the synthetic fiber processing method according to claim 9.