JP2000154473A - Finishing oil for synthetic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a finishing oil capable of preventing the generation of fuzz and yarn break of a synthetic yarn even in a high speed finishing step when the lubricant is imparted to the yarn by blending an acylated polyether and a polyether-polyester with a lubricant component and a surfactant component. SOLUTION: This finishing oil for a synthetic fiber is prepared by blending 1-20 wt.% acylated polyether having 1,000-7,000 number average molecular weight and represented by the formula with 30-70 wt.% lubricant component and 10-50 wt.% surfactant component. Preferably, the lubricant is prepared by blending 2-40 wt.% total of the mixture of the acylated polyether with a specified polyether-polyester in the weight ratio of (30/70)-(70/30) therewith. The lubricant is imparted to a polyester fiber or a polyamide fiber to be subjected to the weaving in a water-jet type loom so that the proportion may be 0.1-3 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oil agent for synthetic fibers. 2. Description of the Related Art In recent years, speeding up has been remarkably accelerated in synthetic fiber production and processing steps. In the manufacturing process, the spinning speed is about to reach 5000 to 8000 m / min, and in the processing process, the weaving speed is 1000 to 1200 m / min.
rpm, the knitting speed is about to reach 1200 to 1500 times / min. When the running speed of the synthetic fiber filament is increased in this manner, in the manufacturing and processing steps, the friction between the synthetic fiber filament and the yarn-joining equipment and the friction between the single fibers constituting the synthetic fiber filament are increased. In addition, scum is generated on the yarn-attaching equipment due to insufficient bundle property of the synthetic fiber filaments, scum of the attached oil agent from the synthetic fiber filament yarns, and fuzzing and yarn breakage due to abrasion of the yarn-attaching equipment are significantly increased. Therefore, the synthetic fiber oil agent to be attached to the synthetic fiber filament yarn, even if it is manufactured and processed at high speed as described above, while imparting a high degree of convergence to the synthetic fiber filament yarn, It is required that the generation of scum on the yarn-attaching equipment and the wear of the yarn-attaching equipment due to the detachment of the attached oil agent from the filament form of the synthetic fiber filament and the like are suppressed, and the fluffing and yarn breakage are reduced. The present invention relates to an oil agent for synthetic fibers that meets such a demand.

[0002]

2. Description of the Related Art Conventionally, a synthetic lubricating oil has been used as an oil agent for synthetic fibers which imparts bundling properties to synthetic fiber filament yarns to prevent fluffing and yarn breakage even when it is manufactured and processed at high speed. In addition to the agent component and the surfactant component,
1) Those containing a polyetherester in which the main constituent unit of the polyether is polytetramethylene glycol (JP-A-59-59978); 2) Those containing an aromatic polyether polyester (JP-A-62-29898)
2) 3) Those containing a modified polyester copolymer having a sulfonic acid group (JP-A-3-64517), 4) Those containing a relatively low-molecular-weight polyetherester and a partially oxidized polyethylene wax (JP-A-Hei. 7-8470
7), 5) Those containing a maleated wax (JP-A-63-126918) have been proposed. However,
In all of these conventional synthetic fiber oil agents, when the running speed of the synthetic fiber filament yarn is increased as in recent years, the convergence imparting to the synthetic fiber filament yarn is imparted,
It is not possible to simultaneously and sufficiently suppress the generation of scum on the yarn-attaching equipment and the wear of the yarn-attaching equipment due to the detachment of the attached oil agent from the synthetic fiber filament yarn and the like. There is a problem that it is not possible to sufficiently prevent the filament yarn from fluffing or yarn breakage.

[0003]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is that, with the conventional synthetic fiber oil, when the running speed of the synthetic fiber filament yarn is increased as in recent years,
It is possible to simultaneously and sufficiently impart the sizing property to the synthetic fiber filament yarn, suppress the generation of scum on the yarn-attaching equipment due to the detachment of the attached oil agent from the synthetic fiber filament yarn, and suppress the wear of the yarn-attaching equipment. For this reason, it is not possible to sufficiently prevent the synthetic fiber filament yarn from fuzzing or breaking during the manufacturing and processing steps.

[0004]

Means for Solving the Problems Thus, the present inventors have
As a result of research to solve the above problems, it has been found that an oil agent for synthetic fibers containing a specific acylated polyether at a predetermined ratio is correct and suitable.

That is, the present invention is characterized in that an oil agent for synthetic fibers containing a lubricant component and a surfactant component contains 1 to 20% by weight of an acylated polyether represented by the following formula 1. According to the present invention.

[0006]

(Equation 1)

In the formula (1): X: a poly (oxytetramethylene oxyethylene) random copolymer obtained by random copolymerization of tetrahydrofuran and ethylene oxide in the presence of water and / or ethylene glycol, and an oxytetramethylene unit Poly (oxytetramethylene-oxyethylene) random copolymer having a number-average molecular weight of 500 to 10,000 having a ratio of / oxyethylene units = 20/80 to 80/20 (molar ratio), from which all hydroxyl groups have been removed. (Oxytetramethylene / oxyethylene) random copolymer block Y ¹ , Y ² : repeating number of oxyethylene units is 5 to 70
A polyoxyethylene block Z ¹ , Z ² : hydrogen or an aliphatic acyl group having 2 to 26 carbon atoms, at least one of which is an aliphatic acyl group having 2 to 26 carbon atoms

The acylated polyether used in the present invention includes: 1) an acylated polyether in which one of Z ¹ and Z ^{2 in} Formula 1 is an acyl group and the other is hydrogen;
2) An acylated polyether in which both Z ¹ and Z ^{2 in} Formula 1 are acyl groups is included.

The acylated polyether is prepared by first randomly copolymerizing tetrahydrofuran and ethylene oxide in the presence of water and / or ethylene glycol to synthesize a poly (oxytetramethylene oxyethylene) random copolymer. Is obtained by addition-polymerizing ethylene oxide to the hydroxyl groups at both ends, and then acylating one or both of the hydroxyl groups at both ends.

In the acylated polyether used in the present invention, the poly (oxytetramethylene / oxyethylene) random copolymer which forms X in the formula (1) is
It can be obtained by a known synthesis method, for example, a synthesis method described in JP-A-62-205120. In this synthesis method, while continuously circulating and supplying a mixture of tetrahydrofuran, ethylene oxide, and water onto a bleaching soil maintained at 47 to 49 ° C. as a catalyst bed, the ethylene oxide concentration in the mixture is maintained at a predetermined level. This is a method in which random copolymerization is performed by further supplementing ethylene oxide so as to maintain the same. The ratio of oxytetramethylene units to oxyethylene units in the poly (oxytetramethylene oxyethylene) random copolymer obtained by such a synthesis method is as follows: oxytetramethylene units / oxyethylene units = 20/8
0-80 / 20 (molar ratio), but 40/60
It is preferable to set the ratio to 60/40 (molar ratio). The poly (oxytetramethylene / oxyethylene) random copolymer has a number average molecular weight of 500 to 10.
000, but preferably 800 to 5000.

In the acylated polyether used in the present invention, the polyoxyethylene blocks represented by Y ¹ and Y ² in the formula (1) correspond to the poly (oxytetramethylene oxyethylene) random copolymer obtained above. It is formed by addition polymerization of ethylene oxide to both terminal hydroxyl groups by a known method. For example, ethylene oxide is addition-polymerized to a poly (oxytetramethylene-oxyethylene) random copolymer in the presence of a basic catalyst such as sodium hydroxide or potassium hydroxide. The number of repeating oxyethylene units in the polyoxyethylene block is 5 to 5.
70, but preferably 10 to 50.

The acylated polyether used in the present invention is:
One or both of the hydroxyl groups at both ends of a block copolymer comprising a polyoxyethylene block having a hydroxyl group at a terminal-poly (oxytetramethylene oxyethylene) random block-a polyoxyethylene block having a hydroxyl group at a terminal have 2 to 2 carbon atoms. It is obtained by acylation with 26 fatty acids and / or ester-forming derivatives thereof.
Examples of such fatty acids having 2 to 26 carbon atoms include acetic acid, octanoic acid, lauric acid, isolauric acid, stearic acid, behenic acid, isostearic acid, palmitoleic acid, oleic acid, and erucic acid. In addition, such carbon number 2
The ester-forming derivatives of the fatty acids Nos. 26 to 26 include methyl acetate, methyl octoate, methyl laurate, methyl isolaurate, methyl stearate, methyl isostearate, methyl behenate, methyl palmitoleate, methyl oleate, methyl erucate And the like. Among them, fatty acids having 8 to 18 carbon atoms and ester-forming derivatives thereof are preferable, and oleic acid and methyl oleate are particularly preferable.

The present invention does not particularly limit the number average molecular weight of the acylated polyether used in the present invention.
1000 to 15000, preferably 1000 to 7
It is particularly preferred to be 000.

The oil agent for synthetic fibers of the present invention comprises 1 to 20% by weight of the above-mentioned acylated polyether represented by the formula (1).
, Preferably 3 to 15% by weight.

The acylated polyether of the formula 1 is
When used in combination with a specific polyether polyester, the expression of the effect is further enhanced. Such a specific polyether polyester is one or more polyether polyesters selected from the following polyether polyester M and polyether polyester N. Polyether polyester M; 4 to 20% by weight of the following structural unit (1), 2 to 20% by weight of the following structural unit (2) and 6 of the following structural unit (3) in all the structural units.
Polyether polyester having a number average molecular weight of 5,000 to 100,000 having a ratio of 0 to 94% by weight (total 100% by weight) Polyether polyester N; 3 to 20% by weight of the following structural unit (1) in all the structural units; 1 to 15% by weight of the following structural unit (2) and 40 of the following structural unit (3)
Polyether polyester having a number average molecular weight of 5,000 to 100,000 and having a weight ratio of ８０80% by weight and the following structural unit (4) in a ratio of 15 to 40% by weight (total 100% by weight) Structural unit (1): formed from phthalic acid Structural unit and / or structural unit formed from ester-forming derivative of phthalic acid Structural unit (2): Structural unit formed from aliphatic dibasic acid having 4 to 22 carbon atoms and / or having 4 to 22 carbon atoms Structural unit formed from ester-forming derivative of aliphatic dibasic acid Structural unit (3): oxyalkylene unit having 2 to 2 carbon atoms
Structural unit formed from polyoxyalkylene diol having a number average molecular weight of 200 to 6000, which is 4, a structural unit formed from polytetramethylene glycol having a number average molecular weight of 200 to 2,000.

The polyether polyester M is composed of a compound that forms the structural unit (1) and a compound that forms the structural unit (2).
And a compound which forms the structural unit (3) by a condensation polymerization reaction. Further, the polyether polyester N includes a compound that forms the structural unit (1), a compound that forms the structural unit (2), and a compound that forms the structural unit (3).
And a compound which forms the structural unit (4) by a condensation polymerization reaction.

The compounds forming the structural unit (1) include phthalic acid, isophthalic acid and terephthalic acid, as well as their ester-forming derivatives such as dimethyl phthalate, diethyl phthalate, dimethyl isophthalate and isophthalic acid. And diethyl terephthalate and diethyl terephthalate. Among them, those containing 50% by mole or more of isophthalic acid and / or an ester-forming derivative thereof are preferable.

Compounds forming the structural unit (2) include succinic acid, adipic acid, azelaic acid, sebacic acid, α, ω-dodecanedicarboxylic acid, dodecenylsuccinic acid, octadecenyldicarboxylic acid, These ester-forming derivatives include dimethyl succinate, dimethyl adipate, dimethyl azelate, dimethyl sebacate and the like. Among them, aliphatic dibasic acids having 6 to 12 carbon atoms such as adipic acid, azelaic acid and sebacic acid,
These ester-forming derivatives are preferred.

The compound that forms the structural unit (3) is a polyoxyalkylene diol having a number average molecular weight of 200 to 6000 in which the oxyalkylene unit has 2 to 4 carbon atoms. Such polyoxyalkylene diols include polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol,
And polyoxyalkylene diols having at least one kind of oxyalkylene unit. Among them, those having a number average molecular weight of 1,000 to 5,000 are preferred, and in particular, the oxyalkylene unit comprises an oxypropylene unit or an oxyethylene unit and an oxypropylene unit, and oxypropylene unit / oxyethylene unit = 100/0 to 5
Those having a ratio of 0/50 (mol%) are preferred.

The compound forming the structural unit (4) is polytetramethylene glycol having a number average molecular weight of 200 to 4,000, and a number average molecular weight of 300 to 3,000.
Are preferred.

The polyether polyester M contains 4 to 20% by weight, preferably 5 to 15% by weight of the structural unit (1), and 2 to 20% by weight, preferably 4 to 20% by weight of the structural unit (2) in all the structural units. To 15% by weight, and the structural unit (3) is 60 to 94%.
%, Preferably 65 to 86% by weight. In the polyether polyester N, the structural unit (1) is 3 to 20% by weight, preferably 5 to 15% by weight, and the structural unit (2) is 1 to 15% by weight in all the structural units.
Preferably 3 to 10% by weight, structural unit (3) is 40 to 8
It has 0% by weight, preferably 45 to 70% by weight, and 15 to 40% by weight, preferably 20 to 35% by weight of the structural unit (4). Each of the polyether polyesters M and N has a number average molecular weight of 5,000 to 5,000.
100,000 to 50,000
Preferably,

The present invention does not particularly limit the method for synthesizing the polyether polyester to be used in the present invention, and any known synthesis method can be applied thereto. For example, phthalic acid that forms the structural unit (1), aliphatic dibasic acid that forms the structural unit (2), and polyoxyalkylene diol that forms the structural unit (3) And a polytetramethylene glycol to form the structural unit (4) are converted to a low molecular weight compound under high temperature and high vacuum in the presence of a known anion polymerization catalyst, cationic polymerization catalyst, coordination anion polymerization catalyst and the like. Examples include a method of performing a condensation polymerization reaction while distilling off. For example, dimethyl phthalate that forms the structural unit (1), dimethyl aliphatic dibasic acid that forms the structural unit (2), A polyoxyalkylene diol that forms the structural unit (3) and a polytetramethylene glycol that forms the structural unit (4) are combined with a known anion polymer. Catalyst, cationic polymerization catalyst, in the presence of such coordination anionic polymerization catalyst, after transesterification, and a method in which a condensation polymerization reaction while distilling off the low-molecular weight compounds to high temperature and high vacuum.

In the acylated polyether represented by the formula 1,
When the above-described polyether polyester is used in combination, the polyether polyester is preferably contained in the synthetic fiber oil at a ratio of 2 to 40% by weight as a total amount with the acylated polyether, preferably 10 to 10% by weight. ~
More preferably, it is contained in an amount of 20% by weight. In this case, the acylated polyether and the polyether polyester preferably have an acylated polyether / polyether polyester ratio of 30/70 to 70/30 (weight ratio), and 40/60 to 60/60.
/ 40 (weight ratio) is more preferable.

The oil agent for synthetic fibers of the present invention contains, in addition to the lubricant component and the surfactant component, the above-mentioned acylated polyether or furthermore a polyether polyester. Such lubricant components include 1) mineral oil,
2) Ester compound of aliphatic monocarboxylic acid and aliphatic monohydric alcohol, complete ester compound of aliphatic monocarboxylic acid and aliphatic polyhydric alcohol, complete ester of aliphatic polycarboxylic acid and aliphatic monohydric alcohol Aliphatic esters such as compounds, and 3) polyether compounds.

As the mineral oil, mineral oils having various viscosities can be used. Among them, the viscosity at 25 ° C. is 2 ×
It is preferably 10 ^{-6 to} 2 × 10 ^-4 m ² / s. Liquid paraffin oil can be advantageously used as such a preferred mineral oil.

Examples of the fatty acid ester include: 1) ester compounds of an aliphatic monocarboxylic acid and an aliphatic monohydric alcohol such as lauryl octanoate, lauryl oleate, isooctyl stearate, isobutyl stearate and isotridecyl stearate. 2) neopentyl glycol dilaurate, 1,6-hexanedioldiolate, trimethylolpropane triperargonate, etc.
Complete ester compounds of aliphatic monocarboxylic acids and aliphatic polyhydric alcohols, 3) Complete ester compounds of aliphatic polycarboxylic acids and aliphatic monohydric alcohols such as di-2-ethylhexyl azelate and dioleyl adipate. No.

As the polyether compound, known polyether compounds, for example, those described in JP-A-56-31077 and JP-B-63-57548 can be applied. Examples of such a polyether compound include polyether polyols such as polyether monool, polyether diol, and polyether triol in which the oxyalkylene unit is an oxyethylene unit and an oxypropylene unit. As these polyether compounds, an average molecular weight of 500 to
20,000 are advantageously available.

Examples of the surfactant component include anionic surfactants, nonionic surfactants, amphoteric surfactants and the like. Examples of the anionic surfactant include: 1) an alkali metal salt of an aliphatic sulfonate having 8 to 24 carbon atoms, an aliphatic sulfonate amine salt having 8 to 24 carbon atoms, and 2) an organic phosphorus having a hydrocarbon group having 8 to 24 carbon atoms. Acid ester alkali metal salt, organic phosphate ester amine salt having a hydrocarbon group having 8 to 24 carbon atoms, 8 to 2 carbon atoms
(4) an alkali metal salt of a terminal-blocked polyethoxyethyl organic phosphate ester whose terminal is blocked by a hydrocarbon group of 4) an alkali metal salt of a fatty acid having 8 to 24 carbon atoms, a fatty acid amine salt of a fatty acid having 8 to 24 carbon atoms, and the like. Can be The surfactant component preferably contains such an anionic surfactant. Among them, an alkali metal salt of an aliphatic phosphate having 8 to 18 carbon atoms, an alkoxy group having 8 to 18 carbon atoms and an ethoxy unit An alkali metal salt of an alkoxypolyethoxyethyl phosphate having a repetition number of 1 to 5,
Those containing an alkali metal salt of an alkenoxy polyethoxyethyl phosphate in which the alkenoxy group has 8 to 18 carbon atoms and the number of repeating ethoxy units is 1 to 5 are preferred.

Examples of the nonionic surfactant include: 1) polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl esters, each of which has an oxyalkylene group comprising an oxyethylene group and / or an oxypropylene group;
Non-ionic surfactants having a polyoxyalkylene group, such as polyoxyalkylene castor oil and polyoxyalkylene alkylamino ether; 2) sorbitan monolaurate, sorbitan triolate, glycerin monolaurate, diglycerin dilaurate, etc. Non-ionic surfactants of the polyhydric alcohol partial ester type and the like can be mentioned.

As the amphoteric surfactant, a carbon number of 8 to 22 is used.
And an aliphatic betaine-type surfactant having 8 to 22 carbon atoms.

In the present invention, the content ratio of the above-mentioned lubricant component and surfactant component in the synthetic fiber oil is not particularly limited.
Those containing at a ratio of 50% by weight are preferable, and those containing at a ratio of 50 to 65% by weight are more preferable. The surfactant is preferably contained at a ratio of 10 to 50% by weight, more preferably at a ratio of 20 to 40% by weight. Among them, those containing the aforementioned anionic surfactant in a ratio of 1 to 10% by weight are particularly preferable.

The oil agent for synthetic fibers of the present invention is usually applied in an amount of 0.1 to 3% by weight based on the synthetic fibers. An oil agent for synthetic fibers is an unoriented yarn in the spinning process of synthetic fibers,
It can be attached to a partially oriented yarn, a stretched oriented yarn, or the like. Examples of the form of the synthetic fiber oil when attached to synthetic fibers include a stock solution of the synthetic fiber oil (neat),
An aqueous emulsion and an organic solvent solution are mentioned, but an aqueous emulsion is preferred. Known methods can be applied to the method of attaching the treatment oil, and examples thereof include a roller lubrication method, a guide lubrication method using a metering pump, an immersion lubrication method, and a spray lubrication method.

The synthetic fibers to which the oil agent for synthetic fibers of the present invention is applied include polyamide fibers, polyester fibers, acrylic fibers, polyolefin fibers and the like. Among them, they are particularly effective for polyester fibers or polyamide fibers. It is effective for polyester fibers or polyamide fibers used for weaving in a water jet loom system.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the oil agent for synthetic fibers of the present invention include the following 1) to 3). 1) 8% by weight of the following acylated polyether (A-1), 8% by weight of the following polyether polyester (P-1), and lubricant component (L-1) @lauryl octanoate / 30 ° C. Mineral oil with a viscosity of 2.1 × 10 ⁻⁵ m ² / s = 7
62% by weight of a mixture consisting of 4/26 (weight ratio), surfactant component (D-1) {polyoxyethylene (the average addition mole number of oxyethylene units is 20, hereinafter n = 20) castor oil / Polyoxyethylene (n = 10) oleyl ether / octanoic acid diethanolamide / decylsulfonate sodium salt / lauryl phosphate potassium salt = 35/29/12/12/12/12 (weight ratio). An oil agent for synthetic fibers contained in proportions. Acylated polyether (A-1): X in the formula 1 is oxytetramethylene unit / oxyethylene unit = 42/58
A poly (oxytetramethylene-oxyethylene) random copolymer block obtained by removing all hydroxyl groups from a poly (oxytetramethylene-oxyethylene) random copolymer having a number-average molecular weight of 1200 (molar ratio),
Y ¹ and Y ² are polyoxyethylene blocks having a repetition number of 13 of oxyethylene units, Z ¹ and Z ² are oleoyl groups, and an acylated polyether polyether polyester (P-1) having a number average molecular weight of 2870 ): In all the structural units, 8% by weight of the structural unit (1) formed from dimethyl phthalate, 4% by weight of the structural unit (2) formed from dimethyl adipate, and oxyethylene units / Oxypropylene units = 10/90
(Molar ratio) Polystyrene having a structural unit (3) formed from polyoxyalkylene diol having a number average molecular weight of 1200 and having a number average molecular weight of 1,200 by weight and having a number average molecular weight of 21,500. Ether polyester

2) The following acylated polyether (A-
8% by weight of the following polyether polyester (P)
-4) in 8% by weight, a lubricant component (L-2) / lauryl oleate / a mineral oil having a viscosity of 2.1 × 10 ⁻⁵ m ² / s at 30 ° C. = 67/33 (weight ratio) ６２ in an amount of 62% by weight and the surfactant component (D-1) in an amount of 22% by weight. Acylated polyether (A-4): X in the formula 1 is oxytetramethylene unit / oxyethylene unit = 56/44
A poly (oxytetramethylene-oxyethylene) random copolymer block in which all hydroxyl groups have been removed from a poly (oxytetramethylene-oxyethylene) random copolymer having a number average molecular weight of 2340 (molar ratio),
An acylated polyether polyether polyester (P-4) wherein Y ¹ and Y ² are polyoxyethylene blocks having 16 repetitions of oxyethylene units, Z ¹ and Z ² are octanoyl groups and the number average molecular weight is 4000; : 6% by weight of the structural unit (1) formed from dimethyl phthalate, 8.5% by weight of the structural unit (2) formed from dimethyl adipate in all the structural units, and oxyethylene units as oxyalkylene units / Oxypropylene unit = 10/90
(Molar ratio) 60% by weight of a structural unit (3) formed from a polyoxyalkylenediol having a number average molecular weight of 1200, which was block-addition-polymerized, and a number average molecular weight of 5
Polyether polyester having a constitutional unit (4) formed of polytetramethylene glycol of 80 at a ratio of 25.5% by weight and a number average molecular weight of 17,800

3) The above-mentioned acylated polyether (A-
1) 6% by weight, lubricant component (L-1) 70% by weight,
Surfactant component (D-2) ｛polyoxyethylene (n =
20) Castor oil / polyoxyethylene (n = 7) lauryl ether / polyoxyethylene (n = 7) oleate / lauryl sulfonate sodium salt / polyoxyethylene (n = 2) oleyl phosphate potassium salt = 34/21 / An oil agent for synthetic fibers containing 24% by weight of a mixture の at a ratio of 21/12/12 (weight ratio).

Hereinafter, examples and the like will be described in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following examples, parts mean parts by weight, and% means% by weight.

[0038]

[Example] Test Category 1 (Synthesis of acylated polyether) ・ Synthesis of acylated polyether (A-1) A small stick-shaped dry bleaching soil having a diameter of 2-3 mm and an average length of 4 mm was used as a catalyst bed in a reactor. After charging, the catalyst bed was kept at 47 to 49 ° C, and 720 g of tetrahydrofuran (10 g
Mol) and 3.1 g (0.07 mol) of ethylene oxide
While continuously circulating and supplying a mixture of water and 32 g (2 mol) of water, ethylene oxide is further blown in at a rate of 30 g / hour, and the ethylene oxide concentration in the mixture is maintained at 0.5% by weight, and the mixture is taken for 6 hours. And ethylene oxide 180
g was subjected to the reaction. The reaction was continued for another 3 hours, and the reaction was completed by setting the ethylene oxide concentration to 0% by weight. The reaction mixture was transferred to a vacuum vessel, and unreacted raw materials were distilled off under reduced pressure to obtain 598 g of a product. This product was analyzed by NMR, GC
When analyzed by MASS, GPC (use of pullulan for conversion of the number average molecular weight, the same applies hereinafter) and the like, the number average molecular weight of 1200 having a ratio of oxytetramethylene units / oxyethylene units = 42/58 (molar ratio) was obtained. It was a poly (oxytetramethylene / oxyethylene) random copolymer. 240 g of the obtained random copolymer of poly (oxytetramethylene / oxyethylene) and 1.2 g of sodium hydroxide were charged into an autoclave, purged with nitrogen gas, and 229 g of ethylene oxide while maintaining the temperature at 100 to 120 ° C. (5.2 moles) and then 2
An aging reaction was performed for a time, cooled to room temperature, and the catalyst was removed to obtain 468 g of a product. When the obtained product was analyzed in the same manner, a poly (oxytetramethylene / oxyethylene) random copolymer was found to be a block copolymer in which a polyoxyethylene block having 13 repetitions of oxyethylene units was added to both terminals. Was. 234 g (0.1 mol) of this block copolymer, 56.4 g of oleic acid
(0.2 mol) and paratoluenesulfonic acid monohydrate 3
g was charged into a flask and heated to 120 to 130 ° C. while stirring under a nitrogen gas stream. The reaction was continued for 2 hours while removing water generated at the same temperature under reduced pressure to obtain a product.
When the obtained product was analyzed by IR, GPC, etc., it was found to be an acylated polyether (A-1) having a number average molecular weight of 2870 and an oleoyl group introduced into both ends of the block copolymer. Was.

Acylated polyethers (A-2) to (A)
-6) and the synthesis of (AR-1) to (AR-7) In the same manner as in the synthesis of the acylated polyether (A-1),
Polyether polyester block copolymer (A-2)
To (A-6) and (AR-1) to (AR-7).
Table 1 summarizes the contents of the synthesized acylated polyethers.

Synthesis of acylated polyether (AR-8) 720 g (1 mol) of polyoxytetramethylene glycol having an average molecular weight of 720 and 2 g of sodium hydroxide were charged into an autoclave, and after purging with nitrogen gas, 120 g or less. 1
880 g of ethylene oxide while maintaining the temperature at 30 ° C
(20 mol) was injected, and after an aging reaction for 2 hours, the mixture was cooled to room temperature and the catalyst was removed to obtain 1600 g of a product. When the obtained product was analyzed in the same manner, it was found to be a block copolymer in which a polyoxyethylene block having a repetition number of oxyethylene units of 10 was added to both ends of the polyoxytetramethylene block. This block copolymer 160
g (0.1 mol), 56.4 g (0.2 mol) of oleic acid and 3 g of paratoluenesulfonic acid monohydrate were charged into a flask, and the mixture was stirred at 120 to 1 under a nitrogen gas stream.
Warmed to 30 ° C. The reaction was continued for 2 hours while removing water generated at the same temperature under reduced pressure to obtain a product. The product obtained here was analyzed by IR, GPC and the like. As a result, an acylated polyether (AR-8) having a number average molecular weight of 2130 and having an oleoyl group introduced into both ends of the block copolymer was obtained.
Met.

[0041]

[Table 1]

In Table 1, * 1: oxytetramethylene unit / oxyethylene unit (molar ratio) * 2: number of repeating oxyethylene units

Test Category 2 (Synthesis of Polyether Polyester) Synthesis of Polyether Polyester (P-1) 55 g (0.28 mol) of dimethyl isophthalate, 25 g (0.17 mol) of dimethyl adipate, ethylene to propylene glycol Oxide / propylene oxide =
550 g (0.46 mol) of polyoxyalkylene diol block-added at a ratio of 10/90 (molar ratio), 0.35 g of zinc acetate dihydrate and 0.1 g of antimony trioxide were charged into a reaction vessel. Atmosphere, 140 ~
The reaction was carried out at 220 ° C. for 6 hours while distilling off methanol, and when almost the theoretical amount of methanol was distilled off, 0.25 g of phosphorous acid was added. Subsequently, 22 mm under reduced pressure of 20 mmHg
The condensation polymerization reaction was carried out at 0 to 250 ° C for 60 minutes and further at 250 to 280 ° C for 60 minutes under a reduced pressure of 0.8 to 0.6 mmHg to obtain a reaction product. The reaction product was analyzed by NMR, GC-MAS
When analyzed by S, GPC, etc., 8% of the isophthalic acid residue corresponding to the structural unit (1) and 4% of the adipic acid residue corresponding to the structural unit (2) were propylene glycol in all the structural units. It is a polyether polyester (P-1) having a number average molecular weight of 21,500 and having a polyoxyalkylene diol residue in a block-form addition-polymerized ethylene oxide / propylene oxide = 10/90 (molar ratio) ratio of 88%. Was.

Polyether polyester (P-2)
Synthesis of (P-5) Polyether polyester (P-2) to (P-5) in the same manner as in the synthesis of polyether polyester (P-1).
Was synthesized. Table 2 summarizes the content of each synthesized polyether polyester.

[0045]

[Table 2]

In Table 2, MP-1: isophthalic acid residue MP-2: terephthalic acid residue MA-1: adipic acid residue MA-2: sebacic acid residue MD-1: propylene glycol to ethylene oxide / propylene Oxide = polyoxyalkylene diol residue having a number average molecular weight of 1200 obtained by block addition polymerization at a ratio of 10/90 (molar ratio) MD-2: ethylene oxide / ethylene oxide /
Propylene oxide = polyoxyalkylene diol residue having a number average molecular weight of 500, which is randomly addition-polymerized at a ratio of 20/80 (molar ratio) MT-1: polytetramethylene glycol residue having a number average molecular weight of 580

Test Category 3 (Preparation of Oil for Synthetic Fiber) Examples 1 to 6 Acylated polyether synthesized in Test Category 1 (A-1)
8 parts, the polyether polyester (P-1) synthesized in Test Category 2 was 8 parts, and the viscosity of the lubricant component (L-1) @lauryl octanoate / 30 ° C. was 2.1 × 10 ⁻⁵ m ^2. /
s mineral oil = 74/26 (weight ratio)} and 62 parts of surfactant component (D-1) {polyoxyethylene (n = 20) castor oil / polyoxyethylene (n =
10) 22 parts of a mixture of oleyl ether / octanoic acid diethanolamide / sodium salt of decyl sulfonate / potassium lauryl phosphate = 35/29/12/12/12 (weight ratio) were weighed in a beaker,
These were stirred to prepare a uniform synthetic fiber oil agent (Example 1). In the same manner as the synthetic fiber oil agent (Example 1),
Oil agents for synthetic fibers (Examples 2 to 6) were prepared. These contents are summarized in Table 3.

Examples 7 to 12 and Comparative Examples 1 to 10 Acylated polyether (A-1) prepared in Test Category 1
6 parts, lubricant component (L-1) @lauryl octanoate / mineral oil having a viscosity at 30 ° C. of 2.1 × 10 ⁻⁵ m ² / s =
74/26 (by weight)} and 70 parts of a surfactant component (D-2) {polyoxyethylene (n = 2)
0) Castor oil / polyoxyethylene (n = 7) lauryl ether / polyoxyethylene (n = 7) oleate / lauryl sulfonate sodium salt / polyoxyethylene (n = 2) oleyl phosphate potassium salt = 34/21 / 24 parts of a mixture の at a ratio of 21/12/12 (weight ratio) was weighed in a beaker, and these were stirred to prepare a uniform synthetic fiber oil agent (Example 7). In the same manner as the synthetic fiber oil agent (Example 7), synthetic fiber oil agents (Examples 8 to 12) and (Comparative Examples 1 to 10) were prepared. The contents are summarized in Tables 3 and 4.

Test Category 4 (Adhesion of synthetic fiber oil to synthetic fibers, measurement and evaluation thereof) Adhesion of synthetic fiber oil to synthetic fibers Polyethylene having an intrinsic viscosity of 0.64 and a titanium oxide content of 0.2% After drying the terephthalate chip by the usual method,
Spinning at 295 ° C. using an extruder, and a 10% aqueous emulsion of a synthetic fiber oil agent obtained in Test Category 3 on a running yarn discharged from a die and cooled and solidified, and a guide lubrication method using a metering pump. Then, after adhering so as to have an adhesion amount of 1.1%, the bundle is successively converged by a guide, and a first gotted roller having a surface speed of 90 ° C. at a surface speed of 4000 m / min and a surface having a surface speed of 5000 m / min. 130 ° C
And then wound at a speed of 5000 m / min to obtain a drawn yarn of 75 denier and 36 filaments.

Evaluation of yarn breakage The number of yarn breaks per ton of the drawn yarn was measured, and the measured value was evaluated according to the following criteria. The results are summarized in Tables 3 and 4. Evaluation criteria ◎: Number of thread breaks is 0 ○: Number of thread breaks is 1 △: Number of thread breaks is 2 to 4 times ×: Number of thread breaks is 5 or more

Evaluation of Fuzz The number of surface fluff was measured for 100 kg of cheese wound with 10 kg of the above drawn yarn, and the measured value was converted into the average number of fluff per cheese and evaluated according to the following criteria. The results are summarized in Tables 3 and 4. Evaluation criteria ◎: The number of fluffs is less than 0.01 ○: The number of fluffs is 0.01 or more and less than 0.1 △: The number of fluffs is 0.1 or more and less than 1 ×: The number of fluffs is 1 or more

Evaluation of Scum A The appearance of the scum dropped on the refueling guide and the first gotted roller when the above-mentioned drawn yarn of 1200000 m was manufactured was evaluated according to the following criteria. The results are shown in Tables 3 and 4. Evaluation criteria ：: No scum is observed. ：: Liquid scum is slightly observed, but there is no practical problem. Δ: Liquid or paste-like scum is slightly recognized, and there is a practical problem. ×: Solid or paste-like. Noticeable scum

Evaluation of sizing property Using a TM-type conjugation tester, applying a load of 15 g per one drawn yarn at 20 ° C. and 65% RH, 5000 times at an angle of 140 ° After the rubbing test was performed, the external appearance was observed and judged according to the following criteria. Evaluation Criteria 単: No single yarn cracking was observed at all, and excellent bunching properties 極: Single yarn cracking was slightly observed, but there was no problem in bunching properties △: Single yarn cracking was slightly recognized, and bunching properties were good There is a problem ×: Single yarn crack is remarkably observed, and bunching property is poor.

Evaluation of Wear of Yarning Equipment The above drawn yarn was unwound at 20 ° C. in an atmosphere of 65% RH at an unwinding speed of 20 m / min. At 30 g, the knitting needle was bent at a 60-degree angle and hung continuously for 2 hours. After washing the knitting needle with an organic solvent, the portion of the knitting needle through which the drawn yarn passed was observed with an electron microscope and evaluated according to the following criteria. Judgment criteria ：: No wear observed ○: Slight wear observed, but no practical problem △: Clear wear observed, practically problematic X: Significant wear observed

Evaluation of scum B The above drawn yarn was unwound at an unwinding speed of 0.5 m / min at 20 ° C. in an atmosphere of 65% RH, and subsequently dipped in a water bath. Then, the reed was bent at an angle of 140 degrees and hung continuously for one hour. The portion of the reed passing through the drawn yarn was visually observed and evaluated according to the following criteria. Criteria ◎: No white powder is observed at all ○: Slight white powder is observed but there is no practical problem △: White powder is clearly observed and practically problematic ×: White powder is remarkably observed

[0056]

[Table 3]

In Table 3, ratio: acylated polyether / polyether polyester (weight ratio) A-1 to A-6: acylated polyether synthesized in test category P-1 to P-5: test category 2 Polyether polyester L-1: lauryl octanoate / viscosity at 30 ° C.
Mixture consisting of 1 × 10 ⁻⁵ m ² / s mineral oil = 74/26 (weight ratio) L-2: lauryl oleate / viscosity at 30 ° C. 2.1 × 1
Mixture of mineral oil of 0 ^-5 m ² / s = 67/33 (weight ratio) D-1: Polyoxyethylene (n = 20) castor oil / polyoxyethylene (n = 10) oleyl ether / diethanol octanoate Do / decyl sulfonate sodium salt / lauryl phosphate potassium salt = 35/29
Mixture in the ratio of / 12/12/12 (weight ratio) D-2: polyoxyethylene (n = 20) castor oil / polyoxyethylene (n = 7) lauryl ether / polyoxyethylene (n = 7) oleic acid Ester / lauryl sulfonate sodium salt / polyoxyethylene (n =
2) Oleyl phosphate potassium salt = 34/21/2
Mixture in proportion of 1/12/12 (weight ratio)

[0058]

[Table 4]

In Table 4, AR-1 to AR-8, A-6: acylated polyethers L-1, D-1, D-2 synthesized in Test Category 1: same as in Table 3.

[0060]

As is apparent from the above description, the present invention described above provides the sizing property to the filament shape of the synthetic fiber filament even in the process of manufacturing and processing the synthetic fiber yarn which has been accelerated in recent years. It is possible to simultaneously and sufficiently suppress the generation of scum on the yarn-attaching equipment due to the detachment of the adhering oil agent from the synthetic fiber filament thread and the wear of the yarn-attaching equipment, and have the effect of sufficiently preventing the generation of fluff and yarn breakage. .

Claims (6)

[Claims] 1. A synthetic fiber oil composition containing a lubricant component and a surfactant component, wherein the composition contains an acylated polyether represented by the following formula 1 in a ratio of 1 to 20% by weight. Oil agent for textiles. (Equation 1) (In the formula 1, X: a poly (oxytetramethylene oxyethylene) random copolymer obtained by random copolymerization of tetrahydrofuran and ethylene oxide in the presence of water and / or ethylene glycol, and oxytetramethylene units / oxy A poly (oxytetramethylene oxyethylene) random copolymer having a number average molecular weight of 500 to 10,000 having a ratio of ethylene units = 20/80 to 80/20 (molar ratio), in which all hydroxyl groups are removed from poly (oxytetramethylene). Methylene / oxyethylene) random copolymer block Y ¹ , Y ² : repeating number of oxyethylene units is 5 to 70
A polyoxyethylene block Z ¹ , Z ² : hydrogen or an aliphatic acyl group having 2 to 26 carbon atoms, at least one of which is an aliphatic acyl group having 2 to 26 carbon atoms) 2. The synthetic fiber oil agent according to claim 1, wherein the acylated polyether has a number average molecular weight of 1,000 to 7000. 3. The synthetic fiber oil agent according to claim 1, further comprising the following polyether polyester in a ratio of 2 to 40% by weight in total with the acylated polyether. Polyether polyester: one or more polyether polyesters selected from the following polyether polyester M and polyether polyester N Polyether polyester M; 4 to 20 of the following structural units (1) in all structural units % By weight, 2 to 20% by weight of the following structural unit (2) and 6% of the following structural unit (3)
Polyether polyester having a number average molecular weight of 5,000 to 100,000 having a ratio of 0 to 94% by weight (total 100% by weight) Polyether polyester N; 3 to 20% by weight of the following structural unit (1) in all the structural units; 1 to 15% by weight of the following structural unit (2) and 40 of the following structural unit (3)
Polyether polyester having a number average molecular weight of 5,000 to 100,000 and having a weight ratio of ８０80% by weight and the following structural unit (4) in a ratio of 15 to 40% by weight (total 100% by weight) Structural unit (1): formed from phthalic acid Structural unit and / or structural unit formed from ester-forming derivative of phthalic acid Structural unit (2): Structural unit formed from aliphatic dibasic acid having 4 to 22 carbon atoms and / or having 4 to 22 carbon atoms Structural unit formed from ester-forming derivative of aliphatic dibasic acid Structural unit (3): oxyalkylene unit having 2 to 2 carbon atoms
Structural unit formed from polyoxyalkylene diol having a number average molecular weight of 200 to 6000, which is 4. Structural unit (4): Structural unit formed from polytetramethylene glycol having a number average molecular weight of 200 to 2,000 4. The synthetic fiber oil agent according to claim 3, which contains acylated polyether / polyether polyester in a ratio of 30/70 to 70/30 (weight ratio). 5. The synthetic fiber oil composition according to claim 1, which contains a lubricant component in an amount of 30 to 70% by weight and a surfactant component in an amount of 10 to 50% by weight. 6. The surfactant component is an alkali metal salt of an aliphatic phosphate having 8 to 18 carbon atoms, the alkoxy group has 8 to 18 carbon atoms, and the number of repeating ethoxy units is 1
The alkali metal salt of an alkoxypolyethoxyethyl phosphate and an alkenoxy group having 8 to 18 carbon atoms
And one or more anionic surfactants selected from alkali metal salts of alkenoxy polyethoxyethyl phosphates having a repeating number of ethoxy units of 1 to 5. 5. The oil agent for synthetic fibers according to 5.