JP2000054265A - Additive for spinning oil solution for being applied to textile yarn and spinning oil solution including the same additive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively prevent spinning oil from secattering out of fibers in being spun at high speed by adding a specific amphiphatic vinyl based copolymer to an aqueous emulsion-type spinning oil. SOLUTION: The method of this invention is to add, to an aqueous emulsion- type spinning oil, 0.001-10 wt.% additive comfrising amphiphilic vinyl based copclymer (having 3,000-30,000,000 nunber average molecular weight) having structural units A, B, C and D expressed by formula I-IV [R1-R3 and R5 are each H or methyl; R4 is a 1-24C hydrocarbon: R6 is a 1-6C aliphatic hydrocarbon; X1 and X2 are each H, a 1-3C hydroxyalkyl or a 1-8C aliphatic hydrocarbon; M1 is an alkali metal, NH4 or a quaternary ammonium ion; (n) is an integer of 5-40] respectively, compresing 10-50 wt.% (pref. 8-40 wt.%) structural unit A, 10-50 wt.% (pref. 8-40 wt.%) structural unit B, 30-80wt.% (pref. 24-64 wt.%) structural unit C and (pref. 1-23 wt.%) structural unit D where the total of the structural units A, B and C is >=80 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive for a spinning oil agent (hereinafter referred to simply as "spinning oil agent") to be adhered in the form of a fiber as an aqueous emulsion, and a spinning oil agent containing the same. 2. Description of the Related Art In recent years, speeding up has been remarkably accelerated in order to save labor or rationalize a fiber manufacturing process. For example, the spinning speed of synthetic fibers such as polyester and nylon is shifting from 5000 to 8000 m / min.
When the running speed of the fiber yarn is increased in this way, the spun oil adhering to the fiber yarn becomes more scattered from the fiber yarn, thereby deteriorating the working environment, reducing the use efficiency of the spun oil agent, and flying Causes various problems such as running obstacles. Under these circumstances, additives having excellent compatibility with the spinning oil agent, having excellent anti-scattering properties capable of coping with high-speed fiber yarns, and not forming a solid obstacle in the running yarn path are used. Appearance is strongly requested. The present invention relates to an additive for a spinning oil agent that meets such a demand and a spinning oil agent containing the same.

[0002]

2. Description of the Related Art Hitherto, various polymer compounds have been proposed as additives used for preventing scattering of a spinning oil agent adhered thereto from a fiber yarn during high-speed running. For example, 1) a high molecular weight polyethylene oxide having a molecular weight of 100,000 to 6,000,000 (JP-A-2-6837)
0), 2) High molecular weight polyacrylamide or acrylamide copolymer having a molecular weight of 50,000 to 20,000,000 (JP-A-3-59
172), 3) Molecular weight of 100,000-derived from polyoxyalkylene compound and organic polyisocyanate compound
500,000 water-soluble polymer compounds (JP-A-4-11912)
8), 4) A chain high molecular compound having a lipophilic group at both terminals, which is a reaction product of a diester or a diepoxide of a polyalkylene glycol and an aliphatic carboxylic acid with an oxyalkylene adduct of an alcohol (Japanese Patent Laid-Open No. -44115)
Etc. However, these conventional additives have poor compatibility with the spinning oil agent, so that the oil agent is not sufficiently scattered from the fiber yarn during high-speed running, and the scattered material is solid on the running yarn path. There is the disadvantage of forming obstacles. If a solid obstacle is formed on the running yarn path, fluff or breakage of the yarn occurs, which not only reduces the quality of the fiber yarn, but also reduces the operability.

[0003]

The problem to be solved by the present invention is that the conventional additives have poor compatibility with the spinning oil agent, so that the oil agent cannot be scattered from the fiber yarn during high-speed running. It is sufficient that the flying objects form a solid obstacle on the running yarn path.

[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 a specific amphiphilic vinyl copolymer is correctly and suitably used as an additive to be added to a spinning oil.

That is, the present invention relates to an additive for a spinning oil agent to be attached to a fiber yarn as an aqueous emulsion,
The structural unit A represented by the following formula 1, the structural unit B represented by the following formula 2 and the structural unit C represented by the following formula 3 are main constituent units, and the constituent units A and B are included in all constituent units.
And an amphiphilic vinyl copolymer having a number average molecular weight of 30,000 to 300,000 and a total of 80% by weight or more of the structural unit C.

[0006]

(Equation 1)

(Equation 2)

(Equation 3)

In the equations (1), (2) and (3), R ¹ , R ² , R
³ : H or CH ₃ R ⁴ : a hydrocarbon group having 1 to 24 carbon atoms X ¹ , X ² : H, a hydroxyalkyl group having 1 to 3 carbon atoms or an aliphatic hydrocarbon group having 1 to 8 carbon atoms M ¹ : Alkali metal, NH ₄ or quaternary ammonium cation

The amphiphilic vinyl copolymer which is an additive of the present invention comprises a structural unit A represented by the formula 1, a structural unit B represented by the formula 2, and a structural unit C represented by the formula 3 as main structural units. However, those having a structural unit D represented by the following formula 4 as other structural units are preferable.

[0009]

(Equation 4)

In the formula 4, R ⁵ : H or CH ₃ R ⁶ : hydrogen or an aliphatic hydrocarbon group having 1 to 6 carbons n: an integer of 5 to 40

Each of the structural units A to D is formed by copolymerizing a corresponding vinyl monomer.
The vinyl monomer forming the structural unit A is a vinyl monomer a represented by the following formula 5, and the vinyl monomer forming the structural unit B is represented by the following formula 6. The vinyl monomer b, which is a vinyl monomer that forms the structural unit C, is a vinyl monomer c represented by the following formula 7. The vinyl monomer which forms the structural unit D is a vinyl monomer d represented by the following formula 8.

[0012]

(Equation 5)

(Equation 6)

Equation 7

(Equation 8)

In the formulas 5, 6, 7 and 8, R ^{1 to} R ⁶ , X ¹ , X ² , M ¹ and n are the same as in the formulas 1 to 4.

The vinyl monomer a that forms the structural unit A represented by the formula 1 includes: 1) acrylamide,
Methacrylamide, 2) N-methylolacrylamide, N-2-hydroxyethylacrylamide, N-3
-Hydroxypropylacrylamide, N, N-bis (2-hydroxyethyl) acrylamide, N, N-bis (3-hydroxypropyl) acrylamide, N-methylol methacrylamide, N-2-hydroxyethyl methacrylamide, N-3- N-substitution substituted with a hydroxyalkyl group having 1 to 3 carbon atoms, such as hydroxypropyl methacrylamide, N, N-bis (2-hydroxyethyl) methacrylamide, N, N-bis (3-hydroxypropyl) methacrylamide Or N, N substitution (meta)
Acrylamide, 3) N-methylacrylamide, N-
Ethyl acrylamide, N-propyl acrylamide,
N, N-diethylacrylamide, N, N-dipropylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N, N-diethylmethacrylamide, N, N-dipropylmethacrylamide, etc. N-substituted or N, N-substituted (meth) acrylamide substituted with an aliphatic hydrocarbon group having 1 to 8 carbon atoms, among which acrylamide and methacrylamide are preferable.

The vinyl monomer b that forms the structural unit B represented by the formula 2 includes: 1) an alkali metal salt of acrylic acid, an NH ₄ salt and a quaternary ammonium salt, 2)
Alkali metal salts of methacrylic acid, NH ₄ salts and quaternary ammonium salts are mentioned, and among them, alkali metal salts of acrylic acid and alkali metal salts of methacrylic acid are preferred.

The vinyl monomer c that forms the structural unit C represented by the formula 3 includes: 1) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate ,
Alkyl acrylate having an alkyl group having 1 to 24 carbon atoms, such as lauryl acrylate, stearyl acrylate, behenyl acrylate, etc., 2) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, Octyl methacrylate,
Examples of the alkyl methacrylate having an alkyl group having 1 to 24 carbon atoms, such as lauryl methacrylate, stearyl methacrylate, and behenyl methacrylate, include alkyl (meth) acrylates having an alkyl group having 1 to 8 carbon atoms. Is preferred.

The vinyl monomer d for forming the structural unit D represented by the formula (4) has a repeating number of ethoxy units of 5 to 40, and has hydroxy at one end being a hydroxypolyethoxyethyl acrylate. One end is hydrogen, hydroxypolyethoxyethyl methacrylate, one end is blocked with an aliphatic hydrocarbon group having 1 to 6 carbon atoms, one end is blocked polyethoxyethyl acrylate, one end is blocked, polyethoxyethyl methacrylate It is.
This includes, for example, 1) hydroxypolyethoxyethyl acrylate, 2) hydroxypolyethoxyethyl methacrylate, 3) methoxy polyethoxyethyl acrylate, ethoxy polyethoxyethyl acrylate, propoxy polyethoxyethyl acrylate, butoxy polyethoxyethyl acrylate, pentoxy poly One-end-blocked polyethoxyethyl acrylate such as ethoxyethyl acrylate, hexoxypolyethoxyethyl acrylate, cyclohexitochitopolyethoxyethyl acrylate, 4) methoxy polyethoxyethyl methacrylate, ethoxy polyethoxyethyl methacrylate, propoxy polyethoxyethyl methacrylate, Butoxypolyethoxyethyl methacrylate, pentoxypolyethoxyethyl methacrylate Rate, hexoxycarbonyl polyethoxy methacrylate, although the one-end-type polyethoxy methacrylate such cyclohexoxy polyethoxy methacrylate. Among them methoxy polyethoxy ethyl acrylate repeating number of ethoxy units is 6 to 30 is preferred.

The amphiphilic vinyl copolymer which is an additive of the present invention comprises the above-mentioned constitutional units A, B and C as main constitutional units, and comprises these in total in all constitutional units. Although it has a content of 80% by weight or more, it is preferable that the composition be composed of the structural units A, B, C and D.

In the present invention, the ratio of each structural unit constituting the amphiphilic vinyl copolymer is not particularly limited.
When the structural units A to C are the main structural units, 10 to 50% by weight of the structural unit A, 10 to 50% by weight of the structural unit B, and 30 to 80% by weight of the structural unit C in all the structural units.
(A total of 80 to 100% by weight),
20 to 45% by weight of the structural unit A in all the structural units,
Those having 45% by weight of structural unit B and 35 to 60% by weight of structural unit C (80 to 100% by weight in total) are more preferred. In the case of having a structural unit D as a structural unit other than the structural units A to C, 8 to 40% by weight of the structural unit A, 8 to 40% by weight of the structural unit B, 24 to 64% by weight of the structural unit C and 1 To 20% by weight of the structural unit D (total 10 units)
0% by weight), 10 to 35% by weight of the structural unit A, 10 to 35% by weight of the structural unit B, 3
More preferably, it is composed of the structural unit C of 0 to 35% by weight and the structural unit D of 3 to 15% by weight (total 100% by weight).

The amphiphilic vinyl copolymer as an additive of the present invention has a number average molecular weight (GPC method, in terms of pullulan, the same applies hereinafter) of 30,000 to 300,000,000, and 100,000 to 150,000,000. Is preferred.

The amphiphilic vinyl copolymer as an additive of the present invention can be obtained by the following synthesis method. For example, a non-radical polymerizable organic solvent such as mineral oil, kerosene or the like has a molecular weight of less than 2,000 and a nonionic surfactant having an HLB of 8 to 10, an oil-soluble nonionic surfactant having a molecular weight of 2,000 or more, and a sorbitan fatty acid ester having an HLB of 3 to 5 To prepare an oil phase. Separately, a required amount of each vinyl monomer to form each structural unit is dissolved in water to prepare an aqueous phase. The oil phase is placed in a reaction vessel, and the water phase is slowly added thereto under high-speed stirring to prepare a water-in-oil emulsion. Then, reduce the number of agitation and raise the internal temperature to 30 ° C
After the inside of the reaction vessel was replaced with nitrogen, polymerization was started by adding an oil-soluble radical initiator dissolved in a non-radical polymerizable organic solvent such as toluene, and the vinyl monomer mixture was dissolved in a water-in-oil system for a predetermined time. Radical copolymerization gives the amphiphilic vinyl copolymer as a water-in-oil emulsion.

In the case of synthesizing an amphiphilic vinyl copolymer by the above-mentioned water-in-oil radical copolymerization, a total of water and a mixture of a vinyl monomer which forms each structural unit and the water (the aqueous phase) ) / Non-radical polymerizable organic solvent = 20/80
８０80/20 (% by weight).
It is preferable that the ratio be 0/70 to 70/30 (% by weight). When an amphiphilic vinyl copolymer having the constitutional units A to C as main constitutional units and 80% by weight or more in all constitutional units is synthesized by water-in-oil radical copolymerization, for example, Vinyl monomer a to form A / vinyl monomer b to form structural unit B / vinyl monomer c to form structural unit C = 10-50 / 10-50 / 30-80 (% by weight) and a total of 80% by weight or more of a vinyl monomer mixture, and the total of the vinyl monomer mixture and water / non-radical polymerizable Organic solvent = 2
In a reaction system having a ratio of 0/80 to 80/20 (% by weight), a water-in-oil radical copolymerization is carried out. In addition, structural units A to D
When the amphiphilic vinyl copolymer composed of is synthesized by water-in-oil radical copolymerization, for example, the vinyl monomer a / the structural unit B that forms the structural unit A will be formed. Vinyl monomer b / vinyl monomer c to form structural unit C / vinyl monomer d to form structural unit D = 8 to 40/8 to 40/24 to 64 /
A vinyl monomer mixture having a ratio of 1 to 20 (% by weight) is obtained by adding a total of the vinyl monomer mixture and water / a non-radical polymerizable organic solvent = 20/80 to 80/20 (% by weight). In this reaction system, water-in-oil radical copolymerization is carried out.

The structural unit A is obtained by water-in-oil radical copolymerization.
When synthesizing an amphiphilic vinyl copolymer composed of the following (A) to (D), the following amphiphilic vinyl copolymer is used.
Those obtained through the step, the second step and the third step are particularly preferable. First step: a vinyl monomer mixture consisting of vinyl monomer a / vinyl monomer b / vinyl monomer c = 10 to 50/10 to 50/30 to 80 (% by weight) Total of monomer mixture and water / Non-radical polymerizable organic solvent =
Step of obtaining a radical-terminated copolymer by performing a water-in-oil radical copolymerization in the presence of an oil-soluble radical initiator and then terminating the radical in a reaction system having a ratio of 20/80 to 80/20 (% by weight) Second step: a step of adding an oil-soluble radical initiator to the reaction system containing the radical-terminated copolymer to radically activate the copolymer Third step: adding vinyl to the reaction system containing the radical-activated copolymer The monomer d was obtained by summing the vinyl monomer a, the vinyl monomer b, and the vinyl monomer c used in the first step / the vinyl monomer d = 80/20 to 99/1 (% by weight). Of water-in-oil radical copolymerization to obtain an amphiphilic vinyl copolymer

In the water-in-oil radical copolymerization of the vinyl monomers a to c in the first step, for example, a non-ionic surfactant having a molecular weight of less than 2,000 and a HLB of 8 to 10 or a molecular weight of 2,000 or more is previously added to a non-radical polymerizable organic solvent. An oil phase is prepared by dissolving the oil-soluble nonionic surfactant and the sorbitan fatty acid ester of HLB 3 to 5, and an aqueous phase is prepared by separately dissolving vinyl monomers a to c in water. .
The oil phase is placed in a reaction vessel, and the water phase is slowly added under high-speed stirring to prepare a water-in-oil emulsion.
Thereafter, the number of stirring was suppressed, the internal temperature was adjusted to about 30 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dissolved in a non-radical polymerizable organic solvent. Radical copolymerization is performed.

In the first step, in the water-in-oil radical copolymerization of the vinyl monomers a to c, the radicals in the reaction system are appropriately terminated to obtain a radical-terminated copolymer.
As a method of stopping the radical, a method of continuing the reaction until the radical is completely eliminated from the reaction system and the radical copolymerization reaction is substantially stopped may be used, but a method of forcibly decomposing and eliminating the radical is known per se. A method of adding a radical terminator to the reaction system is preferred. This is because the process smoothly proceeds to the second step and the third step described below, and the molecular weight of the obtained radical-terminated copolymer is easily adjusted.

In the second step, a known oil-soluble radical initiator per se is added to the reaction system containing the radical-terminated copolymer obtained in the first step to radically activate the copolymer.

In the third step, a vinyl monomer d is added to the copolymer which has been radically activated in the second step, and further a water-in-oil radical copolymerization is carried out to obtain a copolymer having an alkoxypolyoxyethylene chain, namely The amphiphilic vinyl copolymer of the invention is obtained. The amount of the vinyl monomer d used in the third step is preferably the sum of the vinyl monomers a to c used in the first step / vinyl monomer d = 80/20 to 99/1 (% by weight), preferably 85/15 to 97/3 (% by weight).

The amphiphilic vinyl copolymer obtained in the first, second and third steps is in the form of a water-in-oil emulsion. Such a water-in-oil emulsion can be used as an additive as it is because the present invention originally adheres the spinning oil agent to the fiber yarn as an aqueous emulsion, but for convenience in preparing an aqueous emulsion of the spinning oil agent, the molecular weight is 2,000. It is preferable to add a non-ionic surfactant having an HLB of less than 8 to 10, a water-soluble polyoxyethylene polyoxypropylene derivative, and a surfactant for phase inversion comprising a water-soluble non-ionic surfactant of HLB 12 to 14. .

The present invention does not particularly limit the method of using the additives described above. For example, 1) a method of adding an additive to a spinning oil and then forming an aqueous emulsion, 2) a method of adding an additive to an aqueous emulsion of the spinning oil, and 3) an aqueous emulsion of the spinning oil and an aqueous solution of the additive A method of mixing with an emulsion and the like can be mentioned.

The spinning oil of the present invention contains the above-described additives in a proportion of 0.001 to 10% by weight, preferably 0.01 to 5% by weight.

The spinning oil to which the additives are added generally has a lubricant component and a surfactant component as main components. Although the present invention does not particularly limit the lubricant component and the surfactant component, the lubricant component has a viscosity of 5 × at 30 ° C.
Mineral oil of 10 ^{-6 to} 2 × 10 ^-4 m ² / s, total carbon number is 14
Ester compound having a total carbon number of 16 to 70 and a weight average molecular weight of 500 to 15
One or more selected from polyether compounds having a total carbon number of 24 to 47, such as butyl stearate, isooctyl palmitate, isooctyl stearate, lauryl oleate, and isotridecyl stearate. Linear fatty acid ester, viscosity at 30 ° C is 1
× 10 ^-5 ~8 × 10 ^-5 mineral oil m ² / s is more preferable. These lubricant components are preferably contained in the spinning oil in an amount of 20 to 90% by weight, more preferably 30 to 80% by weight.

As the surfactant component, 1) a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl phenyl ether, a polyoxyalkylene fatty acid ester, wherein each of the oxyalkylene groups comprises an oxyethylene group and / or an oxypropylene group, Non-ionic surfactants having a polyoxyalkylene group, such as polyoxyalkylene castor oil, polyoxyalkylene alkylamino ether, polyoxyalkylene fatty acid amide, 2) sorbitan monolaurate, sorbitan triolate, glycerin monolaurate, Nonionic surfactants of polyhydric alcohol partial ester type such as diglycerin dilaurate, 3) dialkyl monoalkanolamine, alkyl dialkanolamine, fatty acid monoalkanolamide Fatty dialkanolamides, aliphatic nitrogen Motohi ionic surfactants such as fatty acid amides of polyalkylene polyamines, 4) alkyl sulfonate salts,
Anionic surfactants such as alkyl phosphate salts,
5) Cationic surfactants such as alkyltrimethylammonium salts, alkyldimethylethylammonium salts and alkylimidazolinium salts; and 6) amphoteric surfactants such as alkyldimethylbetaines and betaine compounds of alkylimidazolines are preferred. Such a surfactant component is preferably used in an amount of 5 to 75% by weight in the spinning oil, and 15 to 6% by weight.
More preferably, the content is 5% by weight.

When the spinning oil agent of the present invention is adhered to a fiber yarn, other components such as an antioxidant, a preservative, a rust inhibitor and the like can be used for the purpose. It is preferred to use as little as possible.

The present invention does not particularly limit the method of adhering the spinning oil agent of the present invention to the fiber yarn except that the spinning oil agent is an aqueous emulsion. A known method can be applied. For example, an aqueous emulsion of a spinning oil agent is applied to an unoriented yarn, a partially oriented yarn, a stretched oriented yarn, and the like in a spinning process of a synthetic fiber by a roller lubrication method, a guide lubrication method using a metering pump, an immersion lubrication method, and a spraying method. By a lubrication method or the like, 0.1 to 3% by weight is applied as a spinning oil agent.

As the fiber yarn to which the spinning oil agent of the present invention is adhered, 1) polyester filament yarn having ethylene terephthalate as a main constituent unit, 2) polyamide filament yarn such as nylon 6, nylon 66, etc.
3) Polyacryl filament yarns such as polyacrylonitrile and modacrylic; and 4) Polyolefin filament yarns such as polyethylene and polypropylene. Among them, the effect is high when they are attached to polyester filament yarns and polyamide filament yarns. It is more effective when attached to a polyester partially drawn yarn, a polyamide partially drawn yarn and a polyester directly spun drawn yarn.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the additive according to the present invention include the following 1) to 3). 1) A vinyl monomer mixture having a ratio of acrylamide / sodium acrylate / ethyl methacrylate = 25/25/50 (% by weight) was prepared by adding the vinyl monomer mixture and water / non-radical polymerizable organic solvent = 60/40 (% by weight), a water-in-oil radical copolymerized amphiphilic vinyl copolymer, comprising 25% by weight of a structural unit formed from acrylamide, An additive comprising an amphiphilic vinyl copolymer having a number average molecular weight of 10000000 and having a proportion of 25% by weight of constituent units formed and 50% by weight of constituent units formed of ethyl methacrylate.

2) Acrylamide / sodium acrylate / ethyl methacrylate / methoxypolyethoxy (the number of repeating ethoxy units n = 22) ethyl acrylate =
A vinyl monomer mixture having a ratio of 30/20/40/10 (% by weight) was prepared by adding a total of the vinyl monomer mixture and water / a non-radical polymerizable organic solvent = 60/40 (% by weight). A water-in-oil radical copolymerized amphiphilic vinyl copolymer, comprising 30% by weight of structural units formed from acrylamide, 20% by weight of structural units formed from sodium acrylate, Amphiphilic vinyl copolymer having a number average molecular weight of 15,000,000 having 40% by weight of constituent units formed from ethyl methacrylate and 10% by weight of constituent units formed from methoxypolyethoxy (n = 22) ethyl acrylate. An additive consisting of

3) An additive comprising an amphiphilic vinyl copolymer obtained through the following first, second and third steps. First step: A vinyl monomer mixture having a ratio of acrylamide / sodium acrylate / ethyl methacrylate = 17.6 / 35.3 / 47.1 (% by weight) is mixed with the vinyl monomer mixture and water. In a reaction system in which the ratio of total / non-radical polymerizable organic solvent = 60/40 (% by weight), 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) as an oil-soluble radical initiator was used. In the presence, after water-in-oil radical copolymerization, 3
-Step of adding a mercapto-1,2-propanediol and terminating the radical to obtain a radical-terminated copolymer 2nd step: 2,2- as an oil-soluble radical initiator in a reaction system containing the radical-terminated copolymer Step of adding azobis (4-methoxy-2,4-dimethylvaleronitrile) to radically activate the copolymer Third step: Add methoxypolyethoxy (n = 22) ethyl acrylate to the radical-activated copolymer Is the total of acrylamide, sodium acrylate and ethyl methacrylate used in the first step / methoxypolyethoxy (n
= 22) Ethyl acrylate = 85/15 (% by weight) In addition to the above, a water-in-oil radical copolymerization was conducted, and 15% by weight of a structural unit formed from acrylamide and a structure formed from sodium acrylate were used. 3 units
0% by weight, 40% by weight of a structural unit formed from ethyl methacrylate, and 15% by weight of a structural unit formed from methoxypolyethoxy (n = 22) ethyl acrylate
Of obtaining an amphiphilic vinyl copolymer having a number average molecular weight of 8,000,000 having a ratio of

Embodiments of the spinning oil agent according to the present invention include the following 4) and 5). 4) The additive of the above 1) is 0.05% by weight, and the viscosity of lauryl octanoate / 30 ° C. is 1.3 × as a lubricant component.
60% by weight of a mixture of mineral oil of 10 ⁻⁵ m ² / s = 67/33 (weight ratio) and polyoxyethylene oleyl ether (HLB 9.0) / potassium decyl sulfonate / oleic acid as a surfactant component Potassium salt = 9
A spinning agent containing a mixture at a ratio of 8/1/1 (weight ratio) in a proportion of 39.84% by weight.

5) 0.5 to 0.5%
% By weight, polyether having a weight average molecular weight of 1,000 as a lubricant component / polyether having a weight average molecular weight of 10,000 / butoxypolyethoxyethyl laurate = 60/10
85% by weight of a mixture having a ratio of / 15 (weight ratio) and polyoxyethylene oleyl ether (HLB11.4) / octanoic acid diethanolamide /
Lauryl phosphate diethanolamine salt = 40/3
13.38% by weight of a mixture having a ratio of 5/25 (weight ratio)
The spinning oil agent contained in the ratio of

[0041]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples. In the following examples, etc.
Parts mean parts by weight and% means percent by weight.

Test Category 1 (Synthesis of Amphiphilic Vinyl Copolymer and Preparation of Water-in-Oil Emulsion) Synthesis of Amphiphilic Vinyl Copolymer P-1 (Example 1) and Water-in-oil Emulsion PE- Preparation of 1 400 g of ion-exchanged water and 125 g of acrylamide (1.
75 mol), 125 g of sodium acrylate (1.38
Mol) and 250 g (2.25 mol) of ethyl methacrylate were treated with a high-pressure homogenizer to prepare an aqueous phase. Separately, 600 g of liquid paraffin having a viscosity of 4 × 10 ⁻⁶ m ² / s at 30 ° C. and polyoxyethylene nonylphenyl ether (HLB 9.2) 30 as a surfactant were added to the flask.
g of poly (12-hydroxystearic acid) -polyoxyethylene-poly (12-hydroxystearic acid) copolymer (HLB5.5) and 5 g of sorbitan oleate (HLB13.2) were charged and uniformly dissolved. To prepare an oil phase. The aqueous phase was slowly added to the prepared oil phase under high-speed stirring, and stirring was continued for 10 minutes to prepare a water-in-oil emulsion. The atmosphere in the flask was replaced with nitrogen, and the temperature of the reaction system was adjusted to 30 ° C. in a warm water bath.
Next, a solution in which 1 g of 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) was dissolved as a radical initiator in 15 g of toluene was added to start radical polymerization, and the polymerization reaction was continued for 8 hours. Thus, the water-in-oil radical copolymerization reaction was completed to obtain a water-in-oil emulsion containing an amphiphilic vinyl copolymer. When the obtained amphiphilic vinyl copolymer was analyzed, the constitutional unit formed from acrylamide / the constitutional unit formed from sodium acrylate / the constitutional unit formed from methyl methacrylate = 25/25/50 (% by weight) ) Having an average molecular weight of 10,000,000 and an amphiphilic vinyl copolymer P-
It was one. Further, after adjusting the temperature of the water-in-oil emulsion containing the amphiphilic vinyl copolymer P-1 to 20 ° C., 30 g of polyoxyethylene nonylphenyl ether (HLB9.2) as a phase inversion surfactant was added. Polyoxyethylene nonyl phenyl ether (HLB 13.7)
To 30 g of the amphiphilic vinyl copolymer P-1.
A water-in-oil emulsion PE-1 containing 0.8% was obtained.

· Amphiphilic vinyl copolymers P-2 to P-7
(Examples 2 to 7), Synthesis of Vinyl Copolymers R-1 to R-4 (Comparative Examples 1 to 4) and Water-in-Oil Emulsion PE-2
-PE-7, RE-1 to RE-4 The amphiphilic vinyl copolymer P- was prepared in the same manner as in the synthesis of the amphiphilic vinyl copolymer P-1 and the preparation of the water-in-oil emulsion PE-1. 2-P-7, vinyl copolymer R-1 to R-
4 and corresponding water-in-oil emulsions PE-2 to PE-
7, RE-1 to RE4 were obtained. These contents are summarized in Table 1.

Synthesis of amphiphilic vinyl copolymer P-8 (Example 8) and preparation of water-in-oil emulsion PE-8 430 g of ion-exchanged water, 75 g of acrylamide (1.0 g
5 mol), 150 g (1.65 mol) of sodium acrylate and 200 g (1.8 mol) of ethyl methacrylate were treated with a high-pressure homogenizer to prepare an aqueous phase. Separately, 570 g of liquid paraffin having a viscosity of 2 × 10 ⁻⁶ m ² / s at 30 ° C., 30 g of polyoxyethylene nonylphenyl ether (HLB9.2) as a surfactant and poly (12-hydroxystearic acid) -poly 15 g of an oxyethylene-poly (12-hydroxystearic acid) copolymer (HLB 5.5) and 5 g of sorbitan oleate (HLB 13.2) were charged and uniformly dissolved to prepare an oil phase. The aqueous phase was slowly added to the prepared oil phase under high-speed stirring, and stirring was continued for 10 minutes to prepare a water-in-oil emulsion. The atmosphere in the flask was replaced with nitrogen, and the temperature of the reaction system was adjusted to 30 ° C. in a warm water bath. Then 1
In 5 g of toluene, 1 g of 2,2-
A solution in which azobis (4-methoxy-2,4-dimethylvaleronitrile) was dissolved was added to start radical polymerization, and the polymerization reaction was continued for 8 hours (first step). And 3
-2 g of a 20% aqueous solution of mercapto-1,2-propanediol was charged to stop radicals (second step). Finally, 1 g of 2,2-azobis (4-
After adding a solution in which methoxy-2,4-dimethylvaleronitrile was dissolved to radically activate the radical-terminated copolymer, 75 g (0.075 mol) of methoxypolyethoxy (n = 22) ethyl acrylate was added. Throw in,
The reaction was continued for 6 hours to complete the water-in-oil radical copolymerization reaction to obtain a water-in-oil emulsion containing an amphiphilic vinyl copolymer. Analysis of the obtained amphiphilic vinyl copolymer revealed that the structural units formed from acrylamide / the structural units formed from sodium acrylate / the structural units formed from methyl methacrylate / methoxypolyethoxy (n = 22) It was an amphiphilic vinyl copolymer P-8 having a number average molecular weight of 8,000,000 and a constitutional unit formed of ethyl methacrylate = 15/30/40/15 (% by weight). Furthermore, after adjusting the temperature of the water-in-oil emulsion containing the amphiphilic vinyl copolymer P-8 to 20 ° C., 30 g of polyoxyethylene nonylphenyl ether (HLB9.2) as a phase inversion surfactant was added. 30 g of polyoxyethylene nonylphenyl ether (HLB 13.7) was added to obtain a water-in-oil emulsion PE-8 containing 30.4% of the amphiphilic vinyl copolymer P-8.

· Amphiphilic vinyl copolymer P-9, P-1
0 (Examples 9 and 10) and Preparation of Water-in-Oil Emulsions PE-9 and PE-10 In the same manner as in the synthesis of the amphiphilic vinyl copolymer P-8 and the preparation of the water-in-oil emulsion PE-8 Thus, amphiphilic vinyl copolymers P-9 and P-10 and corresponding water-in-oil emulsions PE-9 and PE-10 were obtained. These contents are summarized in Table 1.

[0046]

[Table 1]

In Table 1, * 1: Non-radical polymerizable organic solvent used for water-in-oil radical copolymerization of each vinyl monomer * 2: Reaction when water-in-oil radical copolymerization of each vinyl monomer The sum of the vinyl monomer mixture and water in the system / non-radical polymerizable organic solvent (% by weight), except that in Examples 8 to 10 their proportions (% by weight) in the first step A-1: formed from acrylamide component unit A-2: configuration formed methacrylamide units B-1: configuration unit B-2 is formed from sodium acrylate salt: constitutional unit C-1 formed from methacrylic acid NH ₄ salt: methallyl S-2: Structural unit formed from 2-ethylhexyl acrylate D-1: Structural unit formed from methoxypolyethoxy (n = 22) ethyl acrylate The structural unit D-2: hydroxy polyethoxy (n = 12) structural units formed from methacrylate S-1: 30 viscosity ℃ is 4 × 10 ^-6 m ² / s liquid paraffin S-2: 30 Mineral oil whose viscosity at 2 ℃ is 2 × 10 ^-6 m ² / s

Test Category 2 (Preparation of aqueous emulsion of spinning oil) Preparation of aqueous emulsion of spinning oil (Examples 11 to 20, Comparative Examples 5 to 8) Amphiphilic vinyl copolymer P prepared in Test Category 1 0.16 parts of water-in-oil emulsion PE-1 containing 30.8% of -1 (0.1 as amphiphilic vinyl copolymer P-1).
05 parts), lubricant component L-1 @ lauryl octanoate / mineral oil having a viscosity of 1.3 × 10 ⁻⁵ m ² / s at 30 ° C. = 6
7/33 (weight ratio) = 60 parts and surfactant component DT-2 {polyoxyethylene oleyl ether (HLB 9.0) / potassium decyl sulfonate / potassium oleate = 98/1 / 39.84 parts of a mixture の at a ratio of 1 (weight ratio) and 3.1 parts of water were weighed in a beaker and stirred to prepare a 97% aqueous emulsion of a spinning oil (Example 11). In the same manner as in the case of the spinning oil (Example 11), the spinning oil (Examples 12 to 2) was used.
0), 97% aqueous emulsions of (Comparative Examples 5 to 8) were prepared. These contents are summarized in Table 2.

Preparation of aqueous emulsion of spinning oil (Comparative Examples 9 to 12) 60 parts of lubricant component L-1 and surfactant component D
39.5 parts of T-1 and 3.1 parts of water were weighed into a beaker and stirred to form an aqueous emulsion. Separately, high molecular weight polyethylene oxide (molecular weight 2,000,000) was diluted with water to obtain a 1% aqueous solution. Then, the aqueous emulsion, a 1% aqueous solution of high molecular weight polyethylene oxide and water are mixed to form a lubricant component L-1 and a surfactant component D.
A 10% aqueous emulsion of a spinning oil (Comparative Example 9) was prepared such that the sum of T-1 and the high molecular weight polyethylene oxide (molecular weight 2,000,000) = 99.5 / 0.5 (weight ratio). In the same manner as in the case of the spinning oil (Comparative Example 9), a 10% aqueous emulsion of the spinning oil (Comparative Examples 10 to 12) was prepared. These contents are summarized in Table 2.

Test Category 3 (Evaluation of additives and spinning oils containing them) Evaluation of compatibility of additives in aqueous emulsion of spinning oils Compatibility test (Compatibility evaluation 1) Examples prepared in Test Category 2 Was left standing at 30 ° C. for 30 days, and its appearance was visually observed and evaluated according to the following criteria. However, for Comparative Examples 9 to 12, the aqueous emulsions prepared in Test Category 2 were subjected to water evaporation until the water content became 3%. ：: No solid matter or gel-like matter was observed, and the compatibility was good. Δ: Generation of a solid or gel-like substance was slightly observed, and the compatibility was slightly poor. X: The generation of a solid or a gel is remarkably observed, and the compatibility is poor.

Compatibility Test (Compatibility Evaluation 2) The aqueous emulsion of the spinning oil of each example prepared in Test Category 2 was diluted with water to obtain a 10% aqueous emulsion. 1 g of this 10% aqueous emulsion was placed in a petri dish having a diameter of 100 mm, and subjected to hot-air drying at 110 ° C. for 2 hours, and evaluated according to the following criteria. However, Comparative Examples 9 to 12 were subjected to the test as they were. Table 2 summarizes the above results. ：: No solid matter or gel-like matter was observed, and the compatibility was good. Δ: Generation of a solid or gel-like substance was slightly observed, and the compatibility was slightly poor. X: The generation of a solid or a gel is remarkably observed, and the compatibility is poor.

Evaluation of anti-scattering property from running thread and appearance of scattered matter A polyethylene terephthalate chip having an intrinsic viscosity of 0.64 and a titanium oxide content of 0.2% was dried by a conventional method.
The fiber was spun at 295 ° C. using an extruder. A 10% aqueous emulsion in which the aqueous emulsion of the spinning oil of each example prepared in Test Category 2 was further diluted with water was added to the running yarn discharged from the die and cooled and solidified. The prepared 10% aqueous emulsion of the spinning oil agent was applied by a guide lubrication method using a metering pump so as to have an adhesion amount of 1.1%, and then was bunched by a guide to obtain a surface speed of 4000 m / m2. A first gotted roller having a surface temperature of 90 ° C. per minute and a surface speed of 50
After stretching with a second gotted roller having a surface temperature of 130 ° C. at 00 m / min, it was wound up at a speed of 4900 m / min to obtain a drawn yarn of 75 denier and 36 filaments. Here, when the drawn yarn 50,000 m was manufactured, the emulsion of the spinning oil agent scattered at the lower part of the oil supply guide, the interlacer part located between the oil supply guide and the first gotted roller, and the lower part of the first gotted roller was collected by filter paper. did. After heat treatment of the recovered filter paper at 60 ° C. for 24 hours to remove moisture,
The weight of the weighed and collected spinning oil was calculated, and the scattering prevention was evaluated according to the following criteria. In addition, the evaluation of the flying object appearance,
The accumulation of solid matter on the refueling guide and the first gotted roller was performed by visual observation according to the following criteria. The results are summarized in Table 2.

Anti-scattering property A: The weight of the recovered spinning oil is less than 10 mg, which is excellent. ：: The weight of the recovered spinning oil agent is 10 mg or more and less than 30 mg, which is good. Δ: The weight of the recovered spinning oil was 30 mg or more and less than 100 mg, and there was a slight problem. X: The weight of the recovered spinning oil is 100 mg or more, which is problematic.

Appearance of flying objects A: Almost no solid matter is deposited. ：: Slight accumulation of solid matter is observed. Δ: Deposition of solid matter is observed to some extent. ×: Deposition of solid matter is remarkably observed.

[0055]

[Table 2]

In Table 2, P-1 to P-10, R-1 to R-4: amphiphilic vinyl copolymers and the like described in Table 1 PE-1 to PE-10, RE-1 to RE- 4: Water-in-oil emulsion containing amphiphilic vinyl copolymer prepared in Test Category 1 R-5: High molecular weight polyethylene (molecular weight 2,000,000) R-6: Polyacrylamide (molecular weight 10,000,000) R-7: Poly Polyurethane consisting of oxyalkylene glycol (compound having an average molecular weight of 2,000 to which ethylene oxide and propylene oxide are added to ethylene glycol at random) and 4,4′-diphenylmethane diisocyanate (molecular weight: 400,000) R-8: PEG2000 dicaprate L-1: lauryl Octanoate / viscosity at 30 ° C.
Mineral oil of 3 × 10 ⁻⁵ m ² / s = 67/33 (weight ratio) mixture L-2: polyether having a weight average molecular weight of 1000 / polyether having a weight average molecular weight of 10,000 / butoxypolyethoxyethyl laurate = 60/10/15 (weight ratio)
DT-1: polyoxyethylene oleyl ether (HL
B11.4) / octanoic acid diethanolamide / lauryl phosphate diethanolamine salt = 40/35/2
5 (weight ratio) mixture DT-2: polyoxyethylene oleyl ether (HL
B9.0) / potassium decyl sulfonate / potassium oleate = 98/1/1 (weight ratio) E-1 to E-4: Raw materials used in water-in-oil radical polymerization, E-1: water (400 parts), non-radical polymerizable solvent S-1 excluding vinyl monomer, radical initiator and radical stopper
(600 parts), a water-in-oil radical polymerization surfactant {polyoxyethylene nonylphenyl ether (HLB9.
2) / Poly (12-hydroxystearic acid) -polyoxyethylene-poly (12-hydroxystearic acid)
Copolymer (HLB 5.5) / sorbitan oleate (HLB 13.2) = 60/30/10 (weight ratio)
From 50 parts, 15 parts of toluene and a surfactant for phase inversion from polyoxyethylene nonyl phenyl ether (HLB 9.2) / polyoxyethylene nonyl phenyl ether (HLB 13.7) = 50/50 (weight ratio) E-2: A mixture composed of 60 parts by weight of the non-radical polymerizable solvent S
E-3: a mixture in which the amount of toluene was 30 parts in the above-mentioned E-1 E-4: a non-radical polymerizable solvent S in the above-mentioned E-3
Mixture in which -1 is S-2

[0057]

As is clear from the above, the additive of the present invention described above has excellent compatibility with the spinning oil agent, and the spinning oil agent containing the additive causes the aqueous emulsion to adhere to the fiber yarn during high-speed running. Also in this case, there is an effect that the scattering of the oil agent from the fiber yarn can be effectively prevented, and the obstacle to the fiber yarn shape due to the scattered matter can be prevented.

Claims (9)

[Claims] 1. An additive for a spinning oil agent adhered to a fiber yarn as an aqueous emulsion, comprising: a structural unit A represented by the following formula 1, a structural unit B represented by the following formula 2, and a formula 3 represented by the following formula 3. Is a main structural unit, and a number average molecular weight of 30 having a total of 80% by weight or more of the structural units A, B and C in all the structural units.
An additive comprising an amphiphilic vinyl copolymer of 000 to 300,000,000. (Equation 1) (Equation 2) (Equation 3) (In the formulas 1, 2 and 3, R ¹ , R ² , R ³ : H or CH ₃ R ⁴ : a hydrocarbon group having 1 to 24 carbon atoms X ¹ , X ² : H, a hydrocarbon group having 1 to 3 carbon atoms A hydroxyalkyl group or an aliphatic hydrocarbon group having 1 to 8 carbon atoms M ¹ : alkali metal, NH ₄ or quaternary ammonium cation) 2. The additive according to claim 1, wherein the amphiphilic vinyl copolymer is constituted by a structural unit A, a structural unit B, a structural unit C and a structural unit D represented by the following formula 4. Agent. (Equation 4) (In the formula 4, R ^5: H or CH ₃ R ^6: aliphatic hydrocarbon group having 1 to 6 hydrogen or carbon atoms n: 5 to 40 integer) 3. An amphiphilic vinyl copolymer comprising 10 to 50% by weight of the structural unit A in all the structural units, and 10 to 50% by weight.
2. The additive according to claim 1, which has a structural unit B of the formula (1) and 30 to 80% by weight of the structural unit C. 4. An amphiphilic vinyl copolymer comprising 8 to 40% by weight of a structural unit A, 8 to 40% by weight of a structural unit B, 24
3. The additive according to claim 2, wherein the additive is composed of the constituent unit C of ６４64% by weight and the constituent unit D of 1-20% by weight. 5. An amphiphilic vinyl copolymer comprising a structural unit A
= Vinyl monomer a to form structural unit B / vinyl monomer b to form structural unit C / vinyl monomer c to form structural unit C = 10-50 / 10-50
/ 30-80 (% by weight) and a total of 80% by weight or more of a vinyl monomer mixture, and the total of the vinyl monomer mixture and water / non-radical polymerizable 4. The additive according to claim 3, wherein a water-in-oil radical copolymer is obtained in a reaction system having an organic solvent ratio of 20/80 to 80/20 (% by weight). 6. An amphiphilic vinyl copolymer comprising a structural unit A
Forming vinyl monomer a / structural unit D to form vinyl monomer a / structural unit C / vinyl monomer b / structural unit C to form Vinyl monomer d = 8 to 40/8 to 40/24 to
A vinyl monomer mixture having a ratio of 64/1 to 20 (% by weight) is obtained by adding a total of the vinyl monomer mixture and water / a non-radical polymerizable organic solvent = 20/80 to 80/20 (% by weight). 5. The additive according to claim 4, wherein the reaction system is a water-in-oil radical copolymer in a reaction system having a ratio of: 7. The additive according to claim 2, wherein the amphiphilic vinyl copolymer is obtained through the following first step, second step and third step. First step: a vinyl monomer mixture consisting of vinyl monomer a / vinyl monomer b / vinyl monomer c = 10 to 50/10 to 50/30 to 80 (% by weight) Total of monomer mixture and water / Non-radical polymerizable organic solvent =
Step of obtaining a radical-terminated copolymer by performing a water-in-oil radical copolymerization in the presence of an oil-soluble radical initiator and then terminating the radical in a reaction system having a ratio of 20/80 to 80/20 (% by weight) Second step: a step of adding an oil-soluble radical initiator to the reaction system containing the radical-terminated copolymer to radically activate the copolymer Third step: adding vinyl to the reaction system containing the radical-activated copolymer The monomer d was obtained by summing the vinyl monomer a, the vinyl monomer b, and the vinyl monomer c used in the first step / the vinyl monomer d = 80/20 to 99/1 (% by weight). Of water-in-oil radical copolymerization to obtain an amphiphilic vinyl copolymer 8. A spinning oil agent to be attached to a fiber yarn as an aqueous emulsion, wherein the spinning oil agent is an aqueous emulsion.
A spinning oil agent comprising the additive according to 6 or 7 at a ratio of 0.001 to 10% by weight. 9. The spinning oil composition according to claim 8, further comprising the following lubricant component and surfactant component. Lubricant component: The viscosity at 30 ° C. is 5 × 10 ⁻⁶ to 2 × 10 ⁻⁴ m
² / s mineral oil, an ester compound having a total carbon number of 14 to 70, an ether ester compound having a total carbon number of 16 to 70, and one or more selected from polyether compounds having a weight average molecular weight of 500 to 15,000.