JP2006037303A - Oil formulation for treating fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil formulation for elastic fibers stably produced for a long term without time dependent precipitation or aggregation of a conglutination preventive ingredient during storage or using the oil formulation by enhancing dispersion stability of the conglutination preventive ingredient in the oil formulation for treating the fibers. <P>SOLUTION: The oil formulation for treating the fibers comprises a silicone oil and/or a hydrocarbon-based lubricating oil (A), the conglutination preventive ingredient (B) and an oil-soluble high polymer (C) having 10,000-500,000 number average molecular weight. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an elastic fiber processing oil, and more particularly to a fiber processing oil used in a spinning process when producing polyurethane elastic fibers.

  Conventionally, an oil agent in which an anti-sticking agent is added to the oil agent has been proposed as a fiber treatment oil agent used in the spinning process in the production of elastic fibers having high adhesiveness such as polyurethane elastic fibers. As this anti-sticking agent, an oil for fiber processing (Patent Documents 1 and 2) in which a solid metal soap is suspended has been proposed. Recently, an oil for fiber treatment (Patent Document 3) in which a higher fatty acid metal salt having 12 to 24 carbon atoms is used as an anti-sticking agent and dispersed using a specific surfactant has been proposed.

Japanese Patent Publication No.41-286 Japanese Patent Publication No. 40-5557 JP 2003-328273 A

  However, the oil agents proposed in Patent Documents 1 and 2 have poor dispersion stability such that the anti-sticking agent aggregates and settles over time during storage or use. Adhesion becomes difficult and sufficient anti-sticking property cannot be exhibited, and there is a problem that thread breakage or the like occurs due to tension fluctuations in the post-processing step. For this reason, it has been necessary to go through complicated steps before or during use, such as the need to redisperse with great energy and cost. In addition, the oil agent proposed in Patent Document 3 has a small particle size, so the oil agent stability over time is somewhat improved, but has not yet reached a sufficient level. Furthermore, even when the anti-sticking agent is solubilized in the oil using the specific surfactant described in Patent Document 3, the stability at room temperature is somewhat excellent, but it is exposed to low temperatures such as in winter. Then, there exists a problem that an anti-sticking agent precipitates with time. For this reason, in the polyurethane-based elastic fiber processing oil agent, there is an urgent need to develop a fiber processing oil agent that can solve these problems.

  Accordingly, an object of the present invention is to provide an elastic fiber treatment oil agent that is excellent in dispersion stability and in which the anti-sticking agent does not aggregate and precipitate from the oil agent during storage or use. .

  As a result of intensive studies to obtain the above-mentioned fiber treatment oil, the present inventors have found that the above problems can be solved by adding a specific oil-soluble polymer to the fiber treatment oil, and the present invention has been achieved. .

  That is, the present invention provides at least one base oil (A) selected from the group consisting of a silicone oil (A1) and a hydrocarbon-based lubricating oil (A2), an anti-sticking agent (B), and a number average molecular weight of 10,000 to 500. An oil-soluble polymer (C) having a viscosity of 1,000,000; an oil agent for fiber treatment characterized by comprising 0.1 to 12% by mass of the fiber treatment oil agent with respect to the fiber in a spinning step; A processing method for fibers to be refined; and an elastic fiber processed by the above processing method.

  The fiber treatment oil according to the present invention is excellent in dispersion stability, so that there is no need for redispersion, which has been a conventional problem, and it is possible to realize extremely stable productivity over a long period in the spinning process. Moreover, since it is excellent in dispersion stability, when used in the spinning process, it can adhere uniformly to the fiber surface, and exhibits the effect of exhibiting excellent anti-sticking properties. For this reason, it is extremely effective as an oil agent for treating polyurethane elastic fibers having a particularly high adhesiveness.

As the silicone oil (A1) in the present invention, polydimethylsiloxane, those in which a part of polydimethylsiloxane is substituted with an alkyl group having 2 to 20 carbon atoms and / or a phenyl group can be used.
As the hydrocarbon-based lubricating oil (A2), mineral oil and its refined oil, hydrogenated oil, cracked oil and the like can be used.
Among these, a base oil having a viscosity at 25 ° C. of 1 to 1000 mm ² / s is preferable. More preferably, the base oil is ² to 500 mm ² / s, and particularly preferably 3 to 200 mm ² / s.

  (A) may be (A1) or (A2) each alone or a mixture. Preferred are (A2) alone and a mixture of (A1) and (A2), and more preferred is a mixture of (A1) and (A2). In the case of a mixture, based on the total mass of (A1) + (A2), the content (% by mass) of (A1) is preferably 5 to 80, more preferably 10 to 70, and particularly preferably 20 to 50. .

Examples of the anti-sticking agent (B) include compounds having at least one carboxyl group and / or carboxylate group in the molecule.
These compounds include higher fatty acids and salts thereof (B1), carboxyl group and / or carboxylate group-containing polymers (B2). Further, as (B2), a polymer (B2-1) obtained by (co) polymerizing an unsaturated carboxylic acid (Y0) to be described later and other monomers (Y1) to (Y11) to be described later if necessary, JP-A-2002 Examples thereof include a polymer (B2-2) obtained by introducing a carboxyl group and / or a carboxylate group into a molecule by a polymer reaction described in Japanese Patent No. -284880. Of these, (B1) and (B2-1) are preferable from the viewpoint of anti-sticking property, and (B1) is particularly preferable.
The number average molecular weight (hereinafter abbreviated as Mn) of (B2) is preferably 800 to 10,000, and preferably 1,500 to 7,500 from the viewpoints of anti-sticking property and oil viscosity.
Mn can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.

  Specific examples of (B1) include the following. The higher fatty acid in (B1) usually has 5 to 40 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 8 to 24 carbon atoms, more preferably 12 to 24 carbon atoms, and particularly preferably 16 to 22 carbon atoms. Saturated or unsaturated higher fatty acids are mentioned. Specific examples of higher fatty acids include, for example, n-valeric acid, iso-valeric acid, octanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, Examples include oleic acid, elaidic acid, erucic acid, linoleic acid, linolenic acid, and ricinoleic acid. Of these, preferred are lauric acid, palmitic acid, stearic acid, and behenic acid, and stearic acid is particularly preferred. These fatty acids may be used alone or in combination of two or more.

  In (B1), the carboxyl group may be a metal salt, and preferred metals forming the metal salt are alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (barium, calcium, magnesium, etc.) ), IIB group metals (eg, zinc), transition metals (nickel, iron, copper, manganese, cobalt, silver, gold, platinum, palladium, titanium, zirconium, cadmium, etc.), Group IIIB metals (eg, aluminum salts, etc.) ), Group IVB metals (tin, lead, etc.), and lanthanoid metals (lanthanum, cerium, etc.), more preferred are alkali metals, alkaline earth metals, and group IIIB metals, particularly preferred are alkaline earths It is a metal.

  Specific examples of the higher fatty acid salt (B1) include, for example, lithium laurate, sodium laurate, potassium laurate; lithium myristate, sodium myristate, potassium myristate; lithium palmitate, Sodium palmitate, potassium palmitate, lithium stearate, sodium stearate, potassium stearate; lithium isostearate, sodium isostearate, potassium isostearate; lithium behenate, sodium behenate, Behenic acid potassium salt; dilauric acid magnesium salt, dilauric acid calcium salt, dilauric acid barium salt; dimyristic acid magnesium salt, dimyristic acid calcium salt, dimyristic acid barium salt; dipalmitic acid Nesium salt, calcium dipalmitate, barium dipalmitate; magnesium distearate, calcium distearate, barium distearate; magnesium diisostearate, calcium diisostearate, barium diisostearate; magnesium dibehenate; Examples include dibehenic acid calcium salt, dibehenic acid barium salt; palmitic acid magnesium stearate, palmitic acid calcium stearate, and palmitic acid barium stearate. Of these, an alkaline earth metal salt of stearic acid is particularly preferable, and magnesium distearate is most preferable. In addition, commercially available magnesium distearate and the like partially contain unreacted agnesium hydroxide stearate as an impurity, but there is no problem.

Examples of (B2-1) include a polymer containing an unsaturated carboxylic acid (Y0) and a salt with a metal exemplified in (B1) as an essential component among monomers used in (C) described later. , (Y0) homopolymers, or (Y0) and other monomers include copolymers composed of any combination of (Y1) to (Y11).
Among the other monomers (Y1) to (Y11), (Y1), (Y2), (Y3), and (Y5) are preferable from the viewpoint of easy copolymerization with (Y0), and more preferably (Y1). Y1), (Y2), (Y5), particularly preferably (Y5).
The ratio (mol%) of the monomer (Y0) in the above (B2-1) is usually 10 to 100, preferably 20 to 80, further based on the total number of moles of the monomer (Y0) and the other monomers. Preferably it is 30-70.
As the production method of (B2-1), known radical polymerization, anionic polymerization, cationic polymerization and the like similar to (C) described later can be used.

  Examples of (B2-2) include those obtained by modifying the polyolefin (a0) and introducing a carboxyl group and / or carboxylate group, wherein the carboxyl group and / or carboxylate group is directly bonded to (a0). May be bonded via an organic group, and includes primary modified polyolefin (aI) and higher order modified (secondary modified, tertiary modified, etc.) polyolefin (aII).

(A0) is a polyolefin (polymerization method) obtained by a (co) polymer of one or a mixture of two or more olefins or dienes having 2 to 36 carbon atoms (preferably 2 to 12, more preferably 2 to 10). ) And low molecular weight polyolefins (thermal degradation methods) obtained by thermal degradation methods of high molecular weight polyolefins.
The olefin or diene having 2 to 36 carbon atoms is preferably ethylene, propylene, α-olefin having 4 to 12 carbon atoms, butadiene or isoprene, more preferably ethylene, propylene, α-olefin having 4 to 8 carbon atoms or butadiene. Particularly preferred are ethylene, propylene and butadiene.

  As the high molecular weight polyolefin, there can be used a (co) polymer of an olefin having 2 to 36 carbon atoms (preferably 2 to 12, more preferably 2 to 10), or a mixture of two or more. The same thing as the above can be used for a C2-C36 olefin, Among these, ethylene, propylene, and a C4-C12 alpha olefin are preferable, Especially preferably, they are propylene and ethylene.

  The low molecular weight polyolefin obtained by the thermal degradation method can be easily obtained, for example, by the method described in JP-A-3-62804. The polyolefin obtained by the polymerization method can be produced by a known method, and can be easily obtained, for example, by a (co) polymerization reaction in the presence of a radical polymerization catalyst, a metal oxide catalyst, a Ziegler catalyst and a Ziegler-Natta catalyst. . As the radical polymerization catalyst, a known catalyst can be used, and examples thereof include those exemplified by the oil-soluble polymer (C) described later. Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support. Examples of the Ziegler catalyst and the Ziegler-Natta catalyst include those exemplified in (C) below.

  The number average molecular weight (Mn) of (a0) is preferably 800 to 10,000, more preferably 1,000 to 8,000, and particularly preferably 1,200 to 6,000. Mn is preferably within this range from the viewpoint of anti-sticking properties and the viscosity of the oil. In addition, Mn of (a0), (aI), and (aII) can be measured by gel permeation chromatography (GPC) using polystyrene as a standard.

Examples of the primary modified polyolefin (aI) include those obtained by the following method.
(1) Obtained by direct oxidation of (a0).
(2) A product obtained by hydroformylating (a0) and then oxidizing it.
(3) (a0) is changed to α, β-unsaturated carboxylic acid (anhydride) [α, β-unsaturated carboxylic acid and / or anhydride thereof. Hereinafter, the same expression is used. ] Modified.
(4) A compound obtained by hydroborating (a0), then oxidizing, and further modifying with α, β-unsaturated carboxylic acid (anhydride). In addition, as the high-order modified (secondary modified, tertiary modified, etc.) polyolefin (aII), for example, the primary modified polyolefin obtained in the above (1) to (4) is converted to lactam or aminocarboxylic acid, and / or lactone or Further modified with a hydroxycarboxylic acid, and mixtures of two or more of these.

The direct oxidation of (1) is an oxidation with oxygen and / or ozone, for example J. Org. Org. Chem. 42, 3749 (1977), US Pat. No. 3,692,877, and a modified polyolefin having a carboxyl group directly bonded to (a0) can be obtained.
The reaction of (2) is a method of hydroformylating and then oxidizing by oxo synthesis (reacting carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst), for example, Tetrahedron Lett. In 1979, a modified polyolefin having a carboxyl group directly bonded to (a0) can be obtained by the method described on page 399.
The modification of (3) with an α, β-unsaturated carboxylic acid (anhydride) is performed on the terminal double bond of (a0) by either the solution method or the melt method, and the α, β-unsaturated carboxylic acid. And / or an anhydride thereof (ene reaction). The temperature at which (a0) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C. One or more α, β-unsaturated carboxylic acids (anhydrides) added to the end of (a0) may be grafted.
The reaction in which (a0) in (4) is hydroborated and oxidized and further modified with an α, β-unsaturated carboxylic acid (anhydride) is carried out, for example, by the method described in Macromolecules, Vol. 32, page 2525 (1999). be able to. The addition temperature of α, β-unsaturated carboxylic acid (anhydride) is the same as in (3). One or two or more α, β-unsaturated carboxylic acids (anhydrides) bonded to the terminal of (a0) via one ether oxygen atom may be graft-polymerized.

As the α, β-unsaturated carboxylic acid (anhydride) used for the modification of the above (3) and (4), the same as the unsaturated dicarboxylic acid and their anhydride (Y0-2) described later are used. Of these, fumaric acid and in particular (maleic anhydride) are preferred.
The amount (mass%) of the acid (anhydride) used for modification is usually 0.5 to 40, preferably 1 to 30, based on the weight of (a0). The number of added molecules of α, β-carboxylic acid (anhydride) is usually 1 to 10, preferably 1 to 8, per terminal double bond.

Examples of the lactam used for the higher-order modification include lactams having 6 to 12 carbon atoms such as caprolactam, enantolactam, laurolactam, undecanolactam; and aminocarboxylic acids such as aminocarboxylic acids having 2 to 12 carbon atoms such as glycine. Amino acids such as alanine, valine, leucine, isoleucine, phenylalanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid; Lactone corresponding to the above lactam as lactone (caprolactone, etc.); As hydroxycarboxylic acid, aliphatic hydroxycarboxylic acid having 2 to 12 carbon atoms such as glycolic acid, lactic acid, ω-oxycaproic acid, ω -Oxyenanthate, ω- Examples include oxycaprylic acid, ω-oxypelargonic acid, ω-oxycapric acid, 11-oxyundecanoic acid, and 12-oxide decanoic acid.
Of these, lactams having 6 to 8 carbon atoms and aminocarboxylic acids having 8 to 12 carbon atoms, particularly caprolactam and 12-aminododecanoic acid are preferable. The amount (molar equivalent) of the lactam or aminocarboxylic acid and / or lactone or hydroxycarboxylic acid used for the high-order modification is preferably 1 to 10 or more relative to the number of moles of the carboxyl group of the primary modified polyolefin. More preferably, it is 1 (equimolar).

  The acid value (mgKOH / g) of (B2-2) is usually 1 to 500, preferably 50 to 400, and particularly preferably 100 to 350. An acid value within this range is preferable from the viewpoint of adhesion to fibers.

  The higher fatty acid (salt) (B1) may be used alone or in combination of two or more. Further, (B1) and (B2) may be used in combination.

In the present invention, the oil-soluble polymer (C) has an Mn of 10,000 to 500,000, and preferably 30,000 to 400 from the viewpoint of dispersion stability of the oil and compatibility with other components of the oil. 50,000, particularly preferably 50,000 to 200,000, most preferably 80,000 to 150,000.
When Mn is less than 10,000, the dispersion stability of the oil agent, which is the effect of the present invention, tends to become unstable, and when Mn exceeds 500,000, it tends to be difficult to dissolve in the oil for fiber treatment. is there.

  The molecular weight distribution {weight average molecular weight (hereinafter abbreviated as Mw) / Mn} of (C) is usually 1 to 10, preferably 1 to 8, and particularly preferably 1 to 5. In addition, Mw is the value measured by gel permeation chromatography (GPC) like Mn mentioned above.

  (C) is obtained by polymerizing the following monomers (Y0) to (Y10) alone or in any combination.

(Y0); unsaturated carboxylic acid and the above metal salt (Y0-1) unsaturated monocarboxylic acid [for example, (meth) acrylic acid, vinylbenzoic acid, allyl acetic acid, (iso) crotonic acid, cinnamic acid, etc.],
(Y0-2) unsaturated dicarboxylic acids and their anhydrides [for example, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc.],
(Y0-3) Monoalkyl (C1-24) ester of unsaturated dicarboxylic acid [monoalkyl malate, monoalkyl fumarate, monoalkyl itaconate, etc.] and the like.

(Y1); C1-C36 linear or branched alkyl (meth) acrylate (Y1-1); C1-C4 alkyl (meth) acrylate [methyl, ethyl, n- and iso-propyl, and n -, Iso-, sec- and tert-butyl (meth) acrylates],
(Y1-2); C5-C7 alkyl (meth) acrylate [n-, neo- and iso-pentyl, and n- and iso-hexyl (meth) acrylate, etc.],
(Y1-3); linear alkyl (meth) acrylate having 8 to 17 carbon atoms [for example, n-dodecyl, n-tetradecyl and n-hexadecyl, and n-octyl, n-nonyl, n-decyl, n-tridecyl And n-pentadecyl (meth) acrylate, and (meth) acrylate of Ziegler alcohol],
(Y1-4); C8-C17 branched alkyl (meth) acrylate [for example, i-octyl, 2-ethylhexyl, i-nonyl, i-decyl, i-dodecyl, 2-methylundecyl, i-tridecyl 2-methyldodecyl, i-tetradecyl, 2-methyltridecyl, i-pentadecyl and 2-methyltetradecyl (meth) acrylate, etc.]
(Y1-5); (meth) acrylate of a mixture of a linear alkyl alcohol having 8 to 17 carbon atoms and a branched alkyl alcohol having 8 to 17 carbon atoms [for example, oxo alcohol {for example, “Neodol 23” and “Neodol 45” (Made by Shell Chemical Co., Ltd.), “Dovanol 23” and “Dovanol 45” (Mitsubishi Chemical Co., Ltd.), and “Oxocol 1213” and “Oxocol 1415” (Nissan Chemical Co., Ltd.)} ],
(Y1-6); C18-24 linear alkyl (meth) acrylate [for example, n-octadecyl (meth) acrylate, n-nonadecyl (meth) acrylate, n-eicosyl methacrylate, n-eicosyl acrylate, n-docosyl (meth) acrylate and n-tetracosyl (meth) acrylate, etc.]
(Y1-7) A branched alkyl (meth) acrylate having 18 to 36 carbon atoms having a polymethylene group having 17 or more carbon atoms [for example, 2-methyl-nonadecyl methacrylate (hereinafter abbreviated as M-NM) and the like].

(Y2); hydroxyl group-containing monomer (Y2-1); hydroxyl group-containing (meth) acrylic acid ester (Y2-1-1); (meth) acrylate represented by the general formula (1);
^{_{CH 2 = C (R 1)}} -COO- (AO) x -H (1)
In the formula, R ¹ is a hydrogen atom or a methyl group, A is an alkylene group having 2 to 4 carbon atoms, and x is an integer of 1 to 20 (preferably 1). Examples of (Y2-1-1) include 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth). Hydroxyalkyl (2 to 4 carbon atoms) (meth) acrylate such as acrylate and 2-hydroxyethoxyethyl (meth) acrylate,
(Y2-1-2) (meth) acrylate of a polyhydric alcohol containing 3 to 8 hydroxyl groups;
(Meta) of polyhydric alcohols {for example, alkane polyols having 3 to 12 carbon atoms, intramolecular or intermolecular dehydrates, and sugars (for example, glycerin, pentaerythritol, sorbitol, sorbitan, diglycerin, sucrose, methylglucoside, etc.)} ) Acrylates such as glycerin mono- and di- (meth) acrylates, trimethylolpropane mono- and di- (meth) acrylates and sucrose (meth) acrylates,
(Y2-2) C2-C12 alkenol [for example, vinyl alcohol (formed by hydrolysis of vinyl acetate units), and C3-C12 alkenol {(meth) allyl alcohol, (iso) propenyl alcohol Crotyl alcohol, 1-buten-3-ol, 1-buten-4-ol, 1-octenol, 1-undecenol, 1-dodecenol, etc.]
(Y2-3) C4-12 alkenediol [e.g., 2-butene-1,4-diol, etc.],
(Y2-4) a hydroxyl group-containing alkenyl ether having an alkenyl group having 3 to 12 carbon atoms [for example, hydroxyalkyl (1 to 6 carbon atoms) alkenyl (3 to 12 carbon atoms) ether {for example, 2-hydroxyethylpropenyl ether}, And alkenyl (3 to 12 carbon atoms) ethers of polyhydric alcohols listed in (Y212) {for example, trimethylolpropane mono- and di- (meth) allyl ethers and sucrose (meth) allyl ethers, etc.}],
(Y2-5) hydroxyl group-containing aromatic monomer [e.g., o-, m-, or p-hydroxystyrene],
(Y2-6) (Poly) oxyalkylene ethers of monomers (Y2-1) to (Y2-5) [for example, at least one of the hydroxyl groups of (Y2-1) to (Y2-5) is —O— (AO) _y- A-OH substituted monomer {provided that A is the same as in general formula (1). y is 0 or an integer of 1-20. }Such].

(Y3); Amide group-containing monomer (Y3-1); (meth) acrylamides represented by the following general formula (2) CH ₂ ═C (R ¹ ) —CO—N (R ′) — R ″ (2 )
In the formula, R ¹ is the same as in the general formula (1), R ′ and R ″ are each independently a group selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms. (Y31) includes, for example, unsubstituted and alkyl-substituted acrylamides [for example, acrylamide, methacrylamide, N-mono-alkyl (1 to 4 carbon atoms) and N, N-di-alkyl (1 to 4 carbon atoms). -Substituted (meth) acrylamides {eg (di) methyl, (di) ethyl, (di) i-propyl, (di) n-butyl and (di) i-butyl (meth) acrylamide)}, etc.], hydroxyalkyl Substituted acrylamides [e.g., N-mono-hydroxyalkyl (1 to 4 carbon atoms) and N, N-di-hydroxyalkyl (1 to 4 carbon atoms) substituted (meth) acrylic De {e.g., N- hydroxymethyl, N, N- dihydroxymethyl, N, N- di-2-hydroxyethyl, N, N- di-4-hydroxybutyl (meth) acrylamide}, etc.], etc.,
(Y3-2); N-vinyl carboxylic acid amide [for example, acyl-based N-vinyl carboxylic acid amide {for example, N-vinylformamide, N-vinylacetamide, N-vinyl n- and i-propionamide and N-vinyl Hydroxyacetamide and the like} and N-vinyl lactam {for example, N-vinylpyrrolidone and the like}.

(Y4); nitrogen atom-containing unsaturated monomer other than (Y3) (Y4-1); an amino group-containing monomer containing at least one primary, secondary and tertiary amino group,
(Y4-1-1) an amino group-containing aliphatic monomer,
(Y4-1-1-1) Mono- and di-alkenylamines represented by the general formula D-NHD ¹ (wherein D ¹ is a hydrogen atom or D, D is a carbon number of 2 to 10, preferably a carbon number) 3-6 alkenyl groups) [e.g. (di) (meth) allylamine and (iso) crotylamine etc.],
(Y4-1-1-2) Amino group-containing acrylic monomer [e.g., amino group-containing (meth) acrylate [e.g., {mono-alkyl (1 to 4 carbon atoms)} aminoalkyl (2 to 6 carbon atoms) ( Meth) acrylate {for example, aminoethyl, aminopropyl, methylaminoethyl, ethylaminoethyl, butylaminoethyl and methylaminopropyl (meth) acrylate}, di-alkyl (1 to 4 carbon atoms) aminoalkyl (2 carbon atoms) -6) (meth) acrylate {for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, etc.}, etc.] and amino group corresponding to these (meth) acrylates (Meth) acrylamide etc.],
(Y4-1-2) Amino group-containing heterocyclic monomer [for example, amino group-containing heterocyclic acrylic monomer [for example, morpholino-alkyl (2 to 4 carbon atoms) (meth) acrylate {for example, morpholinoethyl (meta ) Acrylates etc.], vinyl substituted heterocyclic amines [eg vinyl pyridine {4- and 2-vinyl pyridine etc.} etc.], N-vinyl pyrrole and N-vinyl pyrrolidine etc.],
(Y4-1-3) Amino group-containing aromatic monomer [for example, aminostyrenes {aminostyrene and (di) methylaminostyrene, etc.}, etc.]
(Y4-1-4) (Y4-1-1) to (Y4-1-3) salts [hydrochloride, sulfate, phosphate nitrate and carboxylate having 1 to 8 carbon atoms],
(Y4-2) Quaternary ammonium base-containing monomer [for example, quaternary ammonium salt obtained by quaternization of (Y4-1-1) to (Y4-1-3), etc.]
Examples of the quaternizing agent include alkyl (C1-C8) halides (for example, methyl chloride), benzyl halides (for example, benzyl chloride), dialkyl (C1-C2) sulfate (for example, dimethyl). Sulfates and diethyl sulfates) and dialkyl (C1-C2) carbonates (for example, dimethyl carbonate, etc.) can be used.
(Y4-2) is obtained by quaternizing (Y4-1-4) with one or more alkylene (2 to 4 carbon atoms) oxide (ethylene oxide and propylene oxide). Quaternary ammonium salts are also included.
(Y4-3) Nitrile or nitro group-containing monomer [for example, (meth) acrylonitrile, nitrostyrene, etc.].

(Y5); an unsaturated hydrocarbon having 2 to 36 carbon atoms,
(Y5-1); C2-C36 unsaturated aliphatic hydrocarbon [e.g. C2-C36 alkene {e.g. ethylene, propylene, isobutene, butene, pentene, heptene, diisobutylene, octene, dodecene and Octadecene and the like}, alkadienes having 4 to 12 carbon atoms (for example, butadiene, isoprene, 1,4-pentadiene, 1,6-heptadiene and 1,7-octadiene, etc.)]
(Y5-2); unsaturated alicyclic hydrocarbon having 5 to 24 carbon atoms [eg, cycloalkene (eg, cyclohexene, etc.), dicycloalkadiene (eg, cyclopentadiene, dicyclopentadiene, etc.), cyclic terpene (Such as pinene and limonene), vinyl (di) cycloalkene (such as vinylcyclohexene), ethylidene (di) cycloalkene (such as ethylidenebicycloheptene and ethylidene norbornene) and aromatic ring-containing cycloalkene (such as Inden etc.),
(Y5-3); unsaturated aromatic hydrocarbon [e.g., styrene and derivatives thereof {e.g., hydrocarbyl-substituted (carbon number 1 to 20) styrene (e.g., [alpha] -methylstyrene, vinyltoluene, 2,4-dimethylstyrene) 4-ethyl styrene, 4-isopropyl styrene, 4-butyl styrene, 4-phenyl styrene, 4-cyclohexyl styrene, 4-benzyl styrene, 4-crotyl benzene, etc.) and alkenyl (2 to 10 carbon atoms) naphthalene (For example, 2-vinyl naphthalene etc.) etc.].

(Y6); epoxy group-containing unsaturated monomer [for example, epoxy group-containing acrylic monomer {for example, glycidyl (meth) acrylate, etc.) and epoxy group-containing alkenyl (2 to 10 carbon atoms, preferably 3 to 6 carbon atoms) ether {For example, glycidyl (meth) allyl ether} and the like].

(Y7); halogen atom-containing unsaturated monomer [for example, vinyl or vinylidene halide (for example, vinyl chloride, vinyl bromide, vinylidene chloride, etc.), alkenyl (carbon number 3 to 6) halide {for example, chloride (meth) Allyl etc.} and halogen-substituted styrene {eg (di) chlorostyrene etc.} etc.].

(Y8); alkyl alkenyl ethers [for example, alkyl (C1-C10) alkenyl (C2-C10) ethers {e.g., alkyl vinyl ethers (e.g., methyl vinyl ether, n-propyl vinyl ether, and ethyl vinyl ether) and alkyl ( Meta) allyl ethers and (iso) propenyl ethers such as methyl allyl ether and ethyl allyl ether} etc.].

(Y9); Alkenyl carboxylates [for example, vinyl acid vinyl, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl heptanoate, vinyl 2-ethylhexanoate and vinyl n-octanoate].

(Y10); unsaturated dicarboxylic acid dialkyl ester [e.g., unsaturated dicarboxylic acid (e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, etc.) C1-C40 (preferably 1-20) dihydrocarb Bill (alkyl, cycloalkyl and aralkyl) esters {such as dimethyl, diethyl and dioctyl malate, and the corresponding fumarate and itaconate}, etc.].

(Y11); sulfonic acid group-containing monomer [for example, aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms (for example, vinyl sulfonic acid), aromatic unsaturated sulfonic acid having 6 to 20 carbon atoms (for example, styrene sulfone) Acid), sulfonic acid group-containing (meth) acrylate [for example, sulfoalkyl (2 to 20 carbon atoms) (meth) acrylate {for example, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropane Sulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethane Sulfonic acid, p- (meth) acryloyloxymethylbenzenesulfur Acid etc.], sulfonic acid group-containing (meth) acrylamide [eg, sulfoalkyl (2-20 carbon atoms) (meth) acrylamide {eg, 2- (meth) acryloylaminoethanesulfonic acid, 2- (meth) Acryloylaminopropanesulfonic acid, 3- (meth) acryloylaminopropanesulfonic acid, 2- (meth) acryloylaminobutanesulfonic acid, 4- (meth) acryloylaminobutanesulfonic acid, 2- (meth) acryloylamino-2,2 -Dimethylethanesulfonic acid, p- (meth) acryloylaminomethylbenzenesulfonic acid, etc.]], alkyl (1-20 carbon atoms) (meth) allylsulfosuccinic acid ester {eg, methyl (meth) allylsulfosuccinic acid ester} Etc.), and salts thereof [alkaline gold Salts (lithium, sodium, potassium, etc.), alkaline earth metal salts (magnesium, calcium etc.), ammonium salts and amine (C20) salt, etc.].

  Of these monomers, (Y), (Y1), (Y2), (Y3), (Y4), (Y5) are preferred as the essential constituents of (C) from the viewpoint of easy adjustment of the molecular weight. More preferably, (Y0-1), (Y1), (Y3), (Y4-1) of (Y4-1), (Y4-1) of (Y0). -2), (Y5-3) out of (Y5), and more preferably (Y1).

As the production method of (C), known radical polymerization, anionic polymerization, cationic polymerization and the like can be used. For example, it can be produced by using the above-exemplified monomers and polymerizing using a polymerization catalyst, if necessary, a polymerization solvent and a chain transfer agent.
Examples of the polymerization solvent include aromatic solvents such as alkylbenzene (for example, toluene, xylene and the like), aliphatic hydrocarbons having 6 to 18 carbon atoms such as hexane, heptane, cyclohexane and octane, 2-propanol, 1-butanol or A C3-C8 alcohol solvent such as 2-butanol, a ketone solvent such as methyl ethyl ketone, and mineral oil can be used. Preferred is mineral oil.
Known polymerization catalysts can be used. Examples of radical polymerization catalysts include azo catalysts [for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile). ), 2,2′-azobis (2,4-dimethylvaleronitrile) (hereinafter abbreviated as ADVN), dimethyl 2,2-azobisisobutyrate and the like], peroxide catalysts [for example, t-butyl per Oxypivalate, t-hexylperoxypivalate, t-butylperoxyneoheptanoate, t-butylperoxyneodecanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyiso Butyrate, t-amylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di- Chill peroxy trimethyl adipate, benzoyl peroxide, cumyl peroxide, lauryl peroxide, di-tert-butyl peroxide, decanoyl peroxide, dodecanoyl peroxide, hydrogen peroxide, the peroxide / reducing agent (Fe ²⁺ salt Etc.) can be used.
Examples of the cationic polymerization catalyst include protonic acids (for example, sulfuric acid, phosphoric acid, perchloric acid, etc.), Lewis acids (for example, boron trifluoride, aluminum chloride, titanium tetrachloride, tin tetrachloride, etc.), and anions. As a polymerization catalyst, sodium hydroxide, potassium hydroxide, sodium methoxide, butyl lithium, pyridine, Ziegler catalyst, Ziegler-Natta catalyst {for example, (C ₂ H ₅ ) ₃ Al—TiCl _4, etc.} can be used.
Furthermore, a chain transfer agent [for example, in the case of radical polymerization, a C2-C20 alkyl mercaptan etc.] can also be used if necessary. The reaction temperature is 50 to 140 ° C, preferably 60 to 120 ° C. In addition to the above solution polymerization, it can also be obtained by bulk polymerization, emulsion polymerization or suspension polymerization. Furthermore, the polymerization mode of the copolymer may be either random addition polymerization or alternating copolymerization, and may be either graft copolymerization or block copolymerization.
(C) may be used as a mixture of two or more.

Moreover, the oil agent for fiber treatment of this invention may contain surfactant (D), and it is more preferable that (D) is included from a viewpoint of dispersion stability.
(D) is a surfactant excluding the anti-sticking agent (B1), and has a solubility parameter (hereinafter abbreviated as SP value), preferably 7 to 10.5, more preferably 7.5 to 10, Particularly preferred is 8 to 9.5. Within these ranges, the compatibility with the base oil (A) and the anti-sticking agent (B) is improved, and the dispersion stability of the fiber treatment oil is improved.

The solubility parameter here (hereinafter abbreviated as SP value) is represented by the square root of the ratio between the cohesive energy density and the molecular volume as shown below.
[SP value] = (△ E / V) ^1/2
Here, ΔE represents the cohesive energy density. V represents the molecular volume, and its value is Robert F. Based on calculations by Robert F. Fedors et al., For example, described in Polymer Engineering and Science Vol. 14, pages 147-154 (1974).

  (D) is a group consisting of an anionic surfactant (D1) not containing an anti-sticking agent (B1), a cationic surfactant (D2), an amphoteric surfactant (D3), and a nonionic surfactant (D4). Although it is at least one or more selected from the above, (D1) and / or (D2) are preferred.

  Examples of the anionic surfactant (D1) include sulfonic acid (salt) (D1-1), carboxylic acid (salt) (D1-2), sulfate ester (salt) (D1-3), phosphate ester (salt) (D1 -4).

式中、Ｒ²、Ｒ³としては、それぞれ独立に炭素数１〜２４のアルキル基、炭素数２〜２４のアルケニル基が挙げられる。
炭素数１〜２４のアルキル基としては、直鎖状、分岐状のいずれでもよく、メチル基、エチル基、ｎ−およびｉ−のプロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基、ヘキコシル基およびドコシル基ならびに２−エチルデシル基などが挙げられる。
炭素数２〜２４のアルケニル基としては、直鎖状、分岐状のいずれでもよく、ｎ−およびｉ−のプロペニル基、ヘキセニル基、ヘプテニル基、オクテニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基およびノナデセニル基ならびに２−エチルデセニル基などが挙げられる。
Ｒ²、Ｒ³のうち好ましいものは炭素数３〜２４のアルキル基である。これらは２種以上の混合物であってもよい。 Examples of the sulfonic acid (salt) (D1-1) include sulfosuccinic acid (mono, di) ester (salt) (D1-1a) of an alcohol having 1 to 24 carbon atoms and sulfonation of an α-olefin having 8 to 24 carbon atoms. (Salt) (D1-1b), alkylbenzenesulfonic acid (salt) (D1-1c) having an alkyl group having 8 to 14 carbon atoms, and petroleum sulfonate (salt) (D1-1d). The hydrophobic group constituting (D1-2a) and (D1-1b) may be either a natural product-derived one or a synthesized one. Among these, (D1-1a) represented by the general formula (3) is preferable.

In the formula, R ² and R ³ each independently include an alkyl group having 1 to 24 carbon atoms and an alkenyl group having 2 to 24 carbon atoms.
The alkyl group having 1 to 24 carbon atoms may be linear or branched, and may be a methyl group, an ethyl group, an n- and i-propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group. Group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, hexosyl group, docosyl group and 2-ethyldecyl group Can be mentioned.
The alkenyl group having 2 to 24 carbon atoms may be linear or branched, and includes n- and i-propenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl, dodecenyl, tetradecenyl Group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group and 2-ethyldecenyl group.
Preferred among R ² and R ³ is an alkyl group having 3 to 24 carbon atoms. These may be a mixture of two or more.

AO in the formula represents an alkylene oxide (hereinafter abbreviated as AO), and A is the same as in the general formula (3) described above, and examples thereof include an ethylene group, a propylene group, and a butylene group. Of these, preferred are ethylene group and propylene group. These may be a mixture of two or more. In the case of a mixture, it may be random or block. m and n are each independently 0 or an integer of 1 to 10, preferably 0 or an integer of 1 to 6, more preferably an integer of 0 or 1 to 3.
Within these ranges, the compatibility with the base oil (A) is good.

  Examples of M include a hydrogen atom, an alkali metal atom (such as lithium, potassium, and sodium) or an amine (such as monoethanolamine, diethanolamine, triethanolamine, and 2-ethylhexylamine). Of these, preferred are alkali metal atoms. These may be a mixture of two or more.

  Specific examples of the sulfosuccinate anionic surfactant (D1-1a) represented by the general formula (3) include di-2-ethylhexyl sulfosuccinate, palmityl stearyl potassium sulfosuccinate, polyoxyethylene di-2- Examples include sodium ethylhexyl sulfosuccinate {ethylene oxide (hereinafter abbreviated as EO) 6-mol adduct (m = n = 3)} and the like.

式中、Ｒ⁴の具体例および好ましいものは、前記Ｒ²、Ｒ³と同様である。ＡおよびＭは、一般式（３）と同様である。ｐは０または１〜１０の整数であり、好ましくは１〜６である。これらの範囲であると、ベースオイルとの相溶性がよい。 Examples of the carboxylic acid (salt) (D1-2) include an ether carboxylate anionic surfactant represented by the following general formula (4). The fatty acids and alcohols constituting these may be derived from natural products or synthesized, and the bonding position of the carboxyl group or hydroxyl group may be either the end of the hydrocarbon group or the side chain.

In the formula, specific examples and preferred examples of R ⁴ are the same as those for R ² and R ³ . A and M are the same as those in the general formula (3). p is 0 or an integer of 1 to 10, preferably 1 to 6. Within these ranges, the compatibility with the base oil is good.

  Specific examples of the ether carboxylate anionic surfactant (D1-2) represented by the general formula (4) include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, and lauryl alcohol carboxymethylated sodium salt. , Dovanol 23 carboxymethylated sodium salt and tridecanol carboxymethylated sodium salt, octyl alcohol EO 3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO 4 mol adduct carboxymethylated sodium salt, isotridecyl alcohol EO 3 mol adduct Carboxymethylated sodium salt, dovanol 23 EO 3 mol adduct carboxymethylated sodium salt, tridecanol EO 5 mol adduct carboxymethylated sodium salt, and Uril alcohol carboxymethylated, such as lauryl alcohol EO2.5 mole adduct carboxymethylated and the like.

  Specific examples of these preferable ones include sodium octyl ether acetate, sodium decyl ether acetate, sodium lauryl ether acetate, sodium tridecyl ether acetate, sodium polyoxyethylene octyl ether acetate (EO 3 mol adduct), polyoxyethylene lauryl ether acetic acid. Examples include sodium (EO 3 mol adduct), sodium polyoxyethylene tridecyl ether acetate (EO 3 mol adduct), and polyoxyethylene lauryl ether acetic acid (EO 2.5 mol adduct).

  Examples of sulfate ester (salt) (D1-3) include higher alcohol sulfate ester (salt) [sulfate ester of aliphatic alcohol having 8 to 24 carbon atoms (salt)] (D1-3a), higher alkyl ether sulfate ester (salt). ) [Sulfate ester (salt) of 1 to 10 mol EO adduct of aliphatic alcohol having 8 to 24 carbon atoms] (D1-3b), sulfated oil (natural unsaturated oil or unsaturated wax is sulfated as it is. Neutralized) (D1-3c), sulfated fatty acid ester (sulfurized and neutralized lower alcohol ester of unsaturated fatty acid) (D1-3d) and sulfated olefin (olefin having 12 to 24 carbon atoms) And those obtained by neutralization by sulfation) (D1-3e).

  Specific examples of preferable (D1-3) include funnel oil, sulfated beef tallow, sulfated peanut oil, sulfated oleic acid butyl salt, and sulfated ricinoleic acid butyl salt.

Examples of the phosphoric acid ester (salt) (D1-4) include a phosphoric acid (mono, di) ester (salt) (D1-4a) of a higher alcohol having 8 to 24 carbon atoms and an AO adduct of a higher alcohol having 8 to 24 carbon atoms. Of phosphoric acid (mono, di) ester (salt) (D1-4b). The higher alcohols constituting these may be derived from natural products or synthesized.
Of these, preferred are phosphoric acid (mono, di) esters (salts) of AO adducts of higher alcohols having 8 to 18 carbon atoms.
Examples of AO used for (D1-4b) include EO, propylene oxide (hereinafter abbreviated as PO), and butylene oxide. Of these, EO and PO are preferred. Moreover, as addition mole number of AO with respect to 1 mol of higher alcohols, it is 1-50 mol normally, Preferably it is 1-20 mol.

  Specific examples of preferred (D1-4) include octyl alcohol phosphate monoester potassium salt, octyl alcohol phosphate diester dipotassium salt, lauryl alcohol phosphate monoester monopotassium salt, lauryl alcohol phosphate diester dipotassium salt, isostearyl Examples thereof include phosphoric acid monoester potassium salt of E05 mol adduct of alcohol and phosphoric acid diester dipotassium salt of E05 mol adduct of isostearyl alcohol.

  When (D1) takes the form of a salt, it is usually a sodium salt, potassium salt, ammonium salt or alkanolamine (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, etc.) salt . Of these, sodium salts, potassium salts, and alkanol salts are preferable.

What is preferable as the cationic surfactant (D2) is a quaternary ammonium salt type cationic surfactant (D2-1) represented by the general formula (5) and an amine salt type cation represented by the general formula (6). Surfactant (D2-2) etc. are mentioned.

[Wherein R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 24 carbon atoms, an allyl group, an alkenyl group having 2 to 24 carbon atoms, a hydroxyalkyl group, a polyoxyalkylene group (carbon of an alkylene group) Number: 2 to 4), and a group represented by the formula R ⁹ —T—R ¹⁰ − (R ⁹ is a residue obtained by removing a COOH group from a fatty acid having 1 to 24 carbon atoms, R ¹⁰ is a group having 1 to 4 carbon atoms) An alkylene group or a hydroxyalkylene group, T represents —COO— or —CONH—, and R ⁷ represents an alkyl group, alkenyl group, hydroxyalkyl group or polyoxyalkylene group having 1 to 24 carbon atoms; R Any two of ⁵ and R ⁶ and R ⁷ may combine to form a heterocyclic ring with N; Q ⁻ represents an inorganic acid anion or an organic acid anion, and QH represents an inorganic acid or an organic acid. ]

The alkyl group having 1 to 24 carbon atoms of R ⁵ , R ⁶ and R ⁷ may be linear or branched, and may be a methyl group, an ethyl group, an n- and i-propyl group, a butyl group, or pentyl. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, hexosyl group The alkenyl group having 2 to 24 carbon atoms may be linear or branched, and includes n- and i-propenyl, hexenyl, heptenyl, octenyl, Decenyl, undecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptade Group, such as octadecenyl and nonadecenyl and 2 Echirudeseniru group.
The hydroxyalkyl group having 1 to 24 carbon atoms of R ⁵ , R ⁶ and R ⁷ may be linear or branched, and may be a hydroxymethyl group, a hydroxyethyl group, n- and i-hydroxypropyl groups, Examples thereof include a hydroxybutyl group, a hydroxyhexyl group, a hydroxyoctyl group, a hydroxydecyl group, a hydroxydodecyl group, a hydroxytetradecyl group, a hydroxyhexadecyl group, and a hydroxyoctadecyl group.
Of these, more preferred are an alkyl group having 8 to 24 carbon atoms, an alkenyl group, and a hydroxyalkyl group.
Examples of the alkyl group, alkenyl group, hydroxyalkyl group or polyoxyalkylene group having 1 to 24 carbon atoms for R ⁸ are the same as those described for R ⁵ , R ⁶ and R ⁷ . Among these, a C1-C4 alkyl group and a hydroxyalkyl group are preferable.
Examples of those in which any two of R ⁵ , R ⁶ and R ⁷ are combined with N to form a heterocyclic or alicyclic compound include imidazoline ring, imidazole ring, pyridine ring, pyrimidine ring, piperidine ring And morpholine ring.

The fatty acid having 1 to 24 carbon atoms constituting the residue R ⁹ may be linear or branched, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, capryl Examples include acid, verargonic acid, lauric acid, myristic acid, stearic acid, isostearic acid, behenic acid, 2-ethylhexanoic acid and the like. Of these, more preferred are fatty acids having 6 to 24 carbon atoms.

The alkylene group having 1 to 4 carbon atoms of R ¹⁰ may be linear or branched, and includes a methylene group, an ethylene group, an n- and i-propylene group, a butylene group, etc .; The hydroxyalkylene group may be linear or branched, and examples thereof include a hydroxymethylene group, a hydroxyethylene group, n- and i-hydroxypropylene groups, and a hydroxybutylene group.
Of these, more preferred is an alkylene group having 1 to 4 carbon atoms.

In the general formula (5), examples of the acid QH that forms the anion Q ⁻ include the following.
(Q1) Inorganic acid Hydrohalic acid (hydrochloric acid, bromic acid, iodic acid, etc.), nitric acid, carbonic acid, phosphoric acid, etc .;
(Q2) Organic acid (q2-a) alkyl sulfate ester C1-C4 alkyl sulfate ester such as methyl sulfate or ethyl sulfate;
(Q2-b) alkyl phosphate ester mono- and / or dialkyl phosphate ester having 1 to 8 carbon atoms such as dimethyl phosphate and diethyl phosphate;

(Q2-c) C1-C24 aliphatic monocarboxylic acid Saturated monocarboxylic acid (such as those whose residues are listed as fatty acids constituting R ⁹ ), unsaturated monocarboxylic acid (acrylic acid, methacrylic acid, olein) Acids), and aliphatic oxycarboxylic acids (such as glycolic acid, lactic acid, oxybutyric acid, oxycaproic acid, ricinoleic acid, oxystearic acid, gluconic acid);
(Q2-d) Aromatic or heterocyclic monocarboxylic acid having 7 to 30 carbon atoms Aromatic monocarboxylic acid (benzoic acid, naphthoic acid, cinnamic acid, etc.), aromatic oxycarboxylic acid (salicylic acid, p-oxybenzoic acid) , And mandelic acid), and heterocyclic monocarboxylic acids (such as pyrrolidone carboxylic acid);

(Q2-e) 2- to 4-valent polycarboxylic acid Linear or branched aliphatic polycarboxylic acid having 2 to 30 carbon atoms [saturated polycarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, adipine Acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.), C4-C30 unsaturated polycarboxylic acid (maleic acid, fumaric acid, itaconic acid, etc.)]; C4-C20 aliphatic oxypoly Carboxylic acid (malic acid, tartaric acid, citric acid, etc.); aromatic polycarboxylic acid having 8 to 30 carbon atoms [dicarboxylic acid [phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and biphenyldicarboxylic acid (2 , 2'-, 3,3'- and / or 2,7-forms)], tri- or tetracarboxylic acids (trimellitic acid, pyromellitic acid, etc.)]; containing sulfur Polycarboxylic acids having 4 to 30 carbon atoms (such as thiodipropionic acid);
(Q2-f) an amino acid having 2 to 30 carbon atoms such as aspartic acid, glutamic acid, cysteic acid;
(Q2-g) an organic acid-modified part of the methyl groups of the silicone diorganopolysiloxane, organic acids substituted with -R ¹¹ COOH group and / or -R ¹¹ SO ₃ H group. R ¹¹ is an alkylene group having 2 to 5 carbon atoms, and the rest are a methyl group, a phenyl group, an alkyl group having 2 to 20 carbon atoms or — (CH ₂ ) _q —Ph (Ph is a phenyl group, p is 1 to 4). Or an integer).

(Q2-h) Carboxymethylated product of aliphatic alcohol (carbon number 8-24) Carboxymethylated product of octyl alcohol, Carboxymethylated product of decyl alcohol, Carboxymethylated product of lauryl alcohol, Tridecanol (manufactured by Kyowa Hakko) ), And the like;
(Q2-i) Carboxymethylated product of aliphatic alcohol (carbon number 8-24) EO and / or PO 1-20 mol adduct, octyl alcohol EO3 mol adduct, lauryl alcohol EO 2.5 mol adduct Carboxymethylated products, isostearyl alcohol EO3 molar adduct, carboxymethylated tridecanol EO2 molar adduct, and the like;

Of these, more preferred are methylsulfuric acid, ethylsulfuric acid, adipic acid, gluconic acid, especially isostearic acid, and a viscosity at 25 ° C. of 10 to 8,000 (further 20 to 5,000, especially 30 to 1000) mm ^2. Carboxy modified silicone having a carboxy equivalent weight of 300 to 8,000 (further 400 to 4,000, particularly 500 to 1,500), and a carboxymethylated product of 1 to 5 mol of lauryl alcohol EO.

Preferred as the quaternary ammonium salt type cationic surfactant (D2-1) are alkyl (C1-24) trimethylammonium salts (for example, lauryltrimethylammonium chloride, lauryltrimethylammonium isostearate, lauryltrimethylammonium carboxy). Modified silicone salts, etc.), dialkyl (1-24 carbon atoms) dimethylammonium salts [for example, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, didecyldimethylammonium isostearate, di (didecyldimethylammonium) adipate, didecyl Carboxymethylation of dimethylammonium carboxy-modified silicone salt, didecyldimethylammonium lauryl alcohol EO 1-5 mol adduct A quaternary ammonium salt containing a nitrogen ring (for example, cetylpyridinium chloride), a quaternary ammonium salt containing a poly (addition mole number 2 to 15) oxyalkylene (2 to 4 carbon atoms) chain [for example, Poly (addition mole number 3) oxyethylenetrimethylammonium chloride, etc.], alkyl (1 to 24 carbon atoms) amidoalkyl (1 to 10 carbon atoms) dialkyl (1 to 4 carbon atoms) methylammonium salt (for example, stearamide ethyl diethyl Methyl ammonium methosulfate, etc.).
Of these, an organic acid salt of alkyltrimethylammonium is more preferable, and an organic acid salt of dialkyldimethylammonium is particularly preferable.

As the amine salt type cationic surfactant (D2-2), a tertiary amine is preferably an inorganic acid (for example, hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid) or an organic acid (for example, acetic acid, formic acid, oxalic acid, Those obtained by neutralization with lactic acid, gluconic acid, adipic acid, alkyl sulfuric acid, etc.) can be used. C3-C90 aliphatic tertiary amine (for example, triethylamine, ethyldimethylamine, didecylmethylamine, N, N, N ′, N′-tetramethylethylenediamine, lauramidopropyldimethylamine, etc.), C3 ~ 90 alicyclic (including nitrogen-containing heterocycle) tertiary amines (e.g., N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, 4-dimethylaminopyridine, N-methylimidazole, 4,4 ' -Dipyridyl, etc.), inorganic acid salts or organic acid salts such as C3-90 hydroxyalkyl group-containing tertiary amines (for example, triethanolamine monostearate, N-stearamidethyl diethanolamine, etc.). .
Of these, more preferred are inorganic amine salts and organic acid salts of aliphatic amines.

Of these surfactants (D), (D1-1a), (D1-2), (D2-1), and (D2-2) are preferable.
These (D) may be used independently or may be used in mixture of 2 or more types.

The content (% by mass) of (A) is preferably 70 to 99. based on the total mass of (A) + (B) + (C) + (D) from the viewpoint of anti-sticking properties and smoothness. 6, More preferably, it is 75-98, Most preferably, it is 80-97.5.
Within these ranges, smoothness is good, and there is no possibility of problems such as yarn breakage even when spinning fine yarns such as 11-22 dtex (dtx).

  The content (% by mass) of (B) is preferably 0.3 to 10, more preferably 0.5 to 5, based on the total mass of (A) + (B) + (C) + (D). 0.0, particularly preferably 1.0 to 4.0. Within these ranges, the anti-sticking property is good, the increase in viscosity of the entire fiber processing oil agent over time is small, and problems such as yarn breakage may occur even when spinning fine yarns such as 11 to 22 dtx. Absent.

  The content (% by mass) of (C) is preferably 0.01 to 3, more preferably 0.05 to 2, based on the total mass of (A) + (B) + (C) + (D). Especially preferably, it is 0.1-1. Within these ranges, the dispersion stability is further improved, and (B) can be stably spun without being settled or aggregated during storage or use, which is more preferable.

  The content (% by mass) of (D) is preferably 0 to 20, more preferably 1.0 to 18, especially based on the total mass of (A) + (B) + (C) + (D). Preferably it is 2.0-15. Within these ranges, the dispersion stability can be further improved, and the same effect as described above can be obtained, which is more preferable.

The blending mass ratio of (B) and (C) is preferably 99.9 / 0.1 to 30/70, more preferably 99/1 to 50/50, particularly preferably 99 /, from the viewpoint of dispersion stability. 1-60 / 40.
The blending mass ratio of (B) and (D) is preferably 90/10 to 1/99, more preferably 85/15 to 5/95, from the viewpoint of dispersion stability and anti-sticking property of the fiber processing oil agent. Particularly preferred is 67/33 to 10/90.
Within these ranges, the dispersion stability is further improved by reducing the particle size of (B), and stable production can be achieved in any of the roller oil supply method and the nozzle oil supply method.

The viscosity at 25 ° C. of the fiber treatment oil of the present invention is usually 1 to 500 mm ² / s. Preferably it is 2-100 mm < ² > / s, More preferably, it is 3-50 mm < ² > / s.
Within these ranges, smoothness is good and there is little scattering of the fiber processing oil during the spinning process, so that the working environment is not deteriorated.

The turbidity at 25 ° C. of the fiber treatment oil of the present invention is not particularly limited, but is preferably 20 mg / L or less from the viewpoint of realizing stable productivity regardless of the oiling method such as the nozzle oiling method and the roller oiling method, More preferably, it is 15 mg / L or less, Most preferably, it is 10 mg / L or less.
Turbidity can be measured by the integrating sphere photoelectric photometry (JIS K0101-1998, 9.4. Integrating sphere turbidity).

The volume average particle size (nm) of (B) is not particularly limited, but is preferably 1 to 2,000, more preferably 5 to 300, from the viewpoint of nozzle feed stability and dispersion stability of the fiber processing oil agent. Especially preferably, it is 10-100.
The volume average particle diameter is measured by a dynamic light scattering method {surfactant evaluation / test method (Japan Oil Chemists' Society), page 212 (2002)}, or a small-angle X-ray scattering method. The particle diameter is a value measured by a dynamic light scattering method.

  The fiber treatment oil of the present invention may contain other components (E) as necessary in addition to (A), (B), (C), and (D). Examples of (E) include an anti-sticking component (E1) other than (B), an antistatic component (E2), a soft component (E3), and other additives (E4). Moreover, you may contain the solubilizing agent (F) mentioned later.

(E1) may be additionally blended to such an extent that the performance of the fiber treatment oil of the present invention is not impaired, and by adding it, the anti-sticking effect can be increased.
(E1) is an anti-sticking component having a composition not included in (B) and (C). For example, silicone (E11), polyether-modified silicone (E12), and these two types that are solid at room temperature The above combination is mentioned. Here, solid at room temperature means solid at 25 ° C.

Examples of the silicone (E11) that is solid at room temperature (25 ° C.) include polyorganosiloxane (silicone resin) containing a trifunctional siloxane unit or a tetrafunctional siloxane unit in the molecule. Solid polymer having a high three-dimensional structure [for example, a DT resin containing a bifunctional siloxane unit (E unit) and a trifunctional siloxane unit (T unit) as main components, a monofunctional siloxane unit (M unit) and a tetrafunctional MQ resin containing a functional siloxane unit (Q unit) as a main constituent, polyorganosilsesquion sun consisting only of T units, and the like.
Preferable is a methyl silicone resin having an Mw of 1,000 to 100,000 and an amino-modified organopolysiloxane having an Mw of 1,000 to 100,000, and more preferably an Mw of 1,500 to 1,000. 30,000 methyl silicone resin. In addition, Mw can be measured with the above-mentioned gel permeation chromatography (GPC).

式中、Ｒ¹²、Ｒ¹³、Ｒ¹⁴およびＲ¹⁵の少なくとも一つがポリオキシアルキレン鎖含有基である。残りはメチル基、炭素数２〜２０のアルキル基、フェニル基または炭素数１〜５のアルコキシ基でもよい。
ポリオキシアルキレン基としては、一般式−Ａ¹Ｏ−（Ａ²Ｏ）_s−Ｒ¹⁶で示される基であり、ここで、Ｒ¹⁶は水素原子または炭素数１〜２４のアルキル基；Ａ¹は炭素数１〜５のアルキレン基；Ａ²は炭素数１〜４のアルキレン基であり、同一でも異なっていてもよく、ブロック状でもランダム状でもよい。ｓは１〜１００の整数を表す。ａ，ｂはそれぞれ１〜１０，０００の整数である。 Examples of the polyether-modified silicone (E12) include polyether-modified silicone represented by the following general formula (7).

In the formula, at least one of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a polyoxyalkylene chain-containing group. The remainder may be a methyl group, an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkoxy group having 1 to 5 carbon atoms.
The polyoxyalkylene group is a group represented by the general formula —A ¹ O— (A ² O) _s —R ¹⁶ , where R ¹⁶ is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms; A ¹ Is an alkylene group having 1 to 5 carbon atoms; A ² is an alkylene group having 1 to 4 carbon atoms, which may be the same or different, and may be block or random. s represents an integer of 1 to 100. a and b are each an integer of 1 to 10,000.

  The blending amount (% by mass) of (E1) is preferably 4 or less, more preferably 2 or less, based on the weight of the fiber treatment oil agent. Moreover, (B) 200 mass parts or less are preferable with respect to 100 mass parts, and 100 mass parts or less are more preferable.

  Examples of the antistatic component (E2) include an amphoteric surfactant (E21) and a nonionic surfactant (E22).

As (E21), betaine-type amphoteric surfactants, amino acid-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and the like can be used.
Preferred examples of (E21) include those represented by the following general formula (8), (9) or (10), and mixtures of two or more thereof.

式中、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹はそれぞれ独立に炭素数１〜２４のアルキル基、アルケニル基、ヒドロキシアルキル基、ポリオキシアルキレン基（アルキレン基の炭素数：２〜４）、および式Ｒ²¹−Ｔ−Ｒ²²−で示される基（Ｒ²¹は炭素数１〜２４の脂肪酸からＣＯＯＨ基を除いた残基、Ｒ²²は炭素数１〜４のアルキレン基またはヒドロキシアルキレン基、Ｔは−ＣＯＯ−または−ＣＯＮＨ−を表す。）から選ばれる基を表し；Ｒ²⁰は炭素数１〜４のアルキレン基またはヒドロキシアルキレン基を表し；Ｘ^-はＣＯＯ^-またはＳＯ₃ ^-を表す。

In the formula, R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently an alkyl group having 1 to 24 carbon atoms, an alkenyl group, a hydroxyalkyl group, a polyoxyalkylene group (carbon number of alkylene group: 2 to 4), and formula R ²¹ -T-R ²² - residue group (R ²¹ indicated that fatty acid after removal of the COOH group of 1 to 24 carbon atoms in, R ²² is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms, T is - . COO- or representing a -CONH-) represents a group selected from; R ²⁰ represents an alkylene group or hydroxyalkylene group having from 1 to 4 carbon atoms; X ^- is COO ^- or SO ₃ ^- represents a.

式中、Ｒ²³は炭素数１〜２４のアルキル基、アルケニル基またはヒドロキシアルキル基を表し；Ｒ²⁴は炭素数１〜４のアルキレン基またはヒドロキシアルキレン基を表し；Ｒ²⁵は水素原子、炭素数１〜２４のアルキル基またはアルケニル基、式−Ｒ²⁴ＣＯＯL_1/r または式−Ｒ²⁴ＳＯ₃L_1/rで示される２価の基を表す。Ｌは水素原子、アルカリ金属、アルカリ土類金属またはアミンカチオンであってＬが複数の場合は同一でも異なっていてもよい；ｒはＬの価数を表し、１または２である。

In the formula, R ²³ represents an alkyl group, alkenyl group or hydroxyalkyl group having 1 to ²⁴ carbon atoms; R ²⁴ represents an alkylene group or hydroxyalkylene group having 1 to 4 carbon atoms; R ²⁵ represents a hydrogen atom or a carbon number. 1 to 24 alkyl group or alkenyl group, a divalent group represented by the formula —R ²⁴ COOL _{1 / r} or the formula —R ²⁴ SO ₃ L _{1 / r} . L is a hydrogen atom, an alkali metal, an alkaline earth metal, or an amine cation, and when L is plural, they may be the same or different; r represents the valence of L and is 1 or 2.

The alkyl group having 1 to 24 carbon atoms and the alkenyl group having 2 to 24 carbon atoms of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²³ and R ²⁵ are the same as R ² and R ³ described above, and preferable ones are also included. It is the same. The hydroxyalkyl group having 1 to 24 carbon atoms of R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²³ may be linear or branched, and may be a hydroxymethyl group, a hydroxyethyl group, an n- and i-hydroxy group. Examples include propyl group, hydroxybutyl group, hydroxyhexyl group, hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group, hydroxytetradecyl group, hydroxyhexadecyl group, and hydroxyoctadecyl group.

The polyoxyalkylene group represented by R ¹⁷ , R ¹⁸ and R ¹⁹ includes a group represented by the formula R ²⁶ — (OA ³ ) _t — (R ²⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, A ³ is carbon 2-4 alkylene groups, t is an integer of 2-15). Examples of the alkylene group A ³ having 2 to 4 carbon atoms include 1,2-ethylene group, 1,2- and 1,3-propylene group, and 1,2-, 2,3-, 1,3- and 1, 4-butylene group etc. are mentioned. The alkyl group R ²⁶ having 1 to 4 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n- and i-propyl group, and a butyl group.

The fatty acid having 1 to 24 carbon atoms constituting the residue R ^{21 of the} group represented by R ²¹ —T—R ²² — may be linear or branched, formic acid, acetic acid, propionic acid, butyric acid. , Isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, verargonic acid, lauric acid, myristic acid, stearic acid, isostearic acid, behenic acid, 2-ethylhexanoic acid and the like. Of these, fatty acids having 6 to 24 carbon atoms are preferred.
The alkylene group having 1 to 4 carbon atoms of R ²² may be linear or branched, and includes a methylene group, an ethylene group, an n- and i-propylene group, a butylene group, etc .; The hydroxyalkylene group may be linear or branched, and examples thereof include a hydroxymethylene group, a hydroxyethylene group, n- and i-hydroxypropylene groups, and a hydroxybutylene group. Among these, an alkylene group having 1 to 4 carbon atoms is preferable.

Among these, R ¹⁷ and R ²³ are preferably an alkyl group having 6 to 24 carbon atoms, an alkenyl group, a hydroxyalkyl group, and an R ²¹ CONHR ²² — group, and R ¹⁸ and R ¹⁹ are each having 1 to 24 carbon atoms. An alkyl group, an alkenyl group and a hydroxyalkyl group.

Examples of the alkylene group having 1 to 4 carbon atoms and the hydroxyalkylene group of R ²⁰ and R ²⁴ include the same groups as those of R ^22, and the preferable ones are also the same.
Among X ⁻ , COO ⁻ is preferable.

R ²⁵ is a hydrogen atom, a —R ²⁴ —COOL _{1 / r} group or a —R ²⁴ —SO ₃ L _{1 / r} group.
Among these, preferred is a mixture of R ²⁵ having a hydrogen atom and R ²⁵ having a —R ²⁴ —COOL _{1 / r} group.
Examples of the alkali metal of L include lithium, potassium and sodium; examples of the alkaline earth metal include calcium and magnesium; examples of the amine cation include mono-, di- and tri-ethanolamine cations and 2-ethylhexylamine cation. . Of these, preferred are a hydrogen atom and an alkali metal.

  Examples of the betaine-type amphoteric surfactant represented by the general formula (8) include alkyl (C1-24) dimethylbetaine, alkyl (C1-24) amidoalkyl (C1-4) dimethylbetaine. And alkyl (C1-24) dihydroxyalkyl (C1-24) betaine and sulfobetaine type amphoteric surfactants. Of these, alkyldimethylbetaine and alkylamidoalkyldimethylbetaine are preferred.

  As the amino acid type amphoteric surfactant represented by the general formula (9), for example, alanine type [alkyl (carbon number 1 to 24) aminopropionic acid type, alkyl (carbon number 1 to 24) iminodipropionic acid type, etc. ] Amphoteric surfactants, glycine type [alkyl (carbon number 1 to 24) aminoacetic acid type, etc.] amphoteric surfactants. Of these, alkylaminopropionic acid type amphoteric surfactants and alkyliminodipropionic acid type amphoteric surfactants are preferred.

  Examples of the sulfonate type amphoteric surfactant (aminosulfonic acid type amphoteric surfactant) represented by the general formula (10) include alkyl (carbon number 1 to 24) taurine type amphoteric surfactants. .

式中、Ｒ²⁷は炭素数１〜２４のアルキル基であり、具体例および好ましいものは、前記Ｒ³、Ｒ⁴のアルキル基と同様である。Ｒ²⁸としては炭素数１〜５のアルキル基（メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基）が挙げられる。Ｒ²⁸のうち好ましいものは炭素数１〜３のアルキル基である。これらは２種以上の混合物であってもよい。Ｒ²⁹としては水素原子または炭素数１〜３のアルキル基（メチル基、エチル基、プロピル基、イソプロピル基）が挙げられる。これらは２種以上の混合物であってもよい。ＡＯは一般式（３）におけるものと同様である。一般式（１１）中の（ＡＯ）_uは、好ましくはＥＯ単独付加、ＥＯとＰＯとのブロック付加、特に好ましくはＥＯ単独付加である。ｕは０または１〜１０の整数であり、好ましくは１〜６である。
これらの範囲であると、ベースオイルとの相溶性がよい。 Examples of the nonionic surfactant (E22) include those represented by the following general formula (11).

In the formula, R ²⁷ is an alkyl group having 1 to 24 carbon atoms, and specific examples and preferred ones are the same as the alkyl groups of R ³ and R ⁴ . R ²⁸ includes an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group). Preferred among R ²⁸ is an alkyl group having 1 to 3 carbon atoms. These may be a mixture of two or more. R ²⁹ includes a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). These may be a mixture of two or more. AO is the same as that in the general formula (3). (AO) _u in the general formula (11) is preferably EO single addition, block addition of EO and PO, particularly preferably EO single addition. u is 0 or an integer of 1 to 10, preferably 1 to 6.
Within these ranges, the compatibility with the base oil is good.

  Specific examples of (E22) represented by the general formula (11) are EO and / or PO adducts of secondary alcohols having 3 to 33 carbon atoms. Preferred specific examples include secondary alcohols (13 carbon atoms). ) EO 3 mol adduct, secondary alcohol (carbon number 13) EO 5 mol adduct, candary alcohol (carbon number 13) EO 7 mol adduct, secondary alcohol (carbon number 13) EO 9 mol adduct, secondary alcohol (carbon number 15) EO3 mol adduct, secondary alcohol (carbon number 15) EO5 mol adduct, secondary alcohol (carbon number 11) EO5 mol adduct, secondary alcohol (carbon number 18) EO5 mol adduct, secondary alcohol (carbon number 24) EO5 mol Additives, secondary alcohol (carbon 18) EO3PO2 mole block adduct, such as secondary alcohol (number 24) EO5PO3 mole block adduct carbon and the like.

  When these antistatic components are used, the content (% by mass) of (E2) is preferably 0 to 12, more preferably 0.1 to 10, based on the mass of the fiber treatment oil agent. .

  Examples of the flexible component (E3) include epoxy-modified silicone (E31), amino-modified silicone (E32), and carboxyl-modified silicone (E33).

As (E31), in the general formula (7), at least one of R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is an epoxy group-containing group. The remainder may be a methyl group, an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkoxy group having 1 to 5 carbon atoms. a and b are integers of 1 to 1,000.

Examples of the epoxy group-containing group include those represented by the following general formula (12) (wherein R ³⁰ is an alkylene group having 1 to 4 carbon atoms), for example, a glycidyl group.

（Ｅ３２）としては、前記一般式（７）中、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵の少なくとも一つが−Ｒ³¹−ＮＨ（Ｒ³²ＮＨ）_vＨ基含有基（Ｒ³¹は炭素数１〜５のアルキレン基、Ｒ³²は炭素数１〜４のアルキレン基、ｖは０または１〜３の整数である）であるもの。残りはメチル基、炭素数２〜２０のアルキル基、フェニル基または炭素数１〜５のアルコキシ基でもよい。また、ａ、ｂは１〜１０，０００の整数である。

As (E32), in the general formula (7), at least one of R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ is a —R ³¹ —NH (R ³² NH) _v H group-containing group (R ³¹ is a carbon number) 1 to 5 alkylene groups, R ³² is an alkylene group having 1 to 4 carbon atoms, and v is 0 or an integer of 1 to 3). The remainder may be a methyl group, an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkoxy group having 1 to 5 carbon atoms. A and b are integers of 1 to 10,000.

As (E33), in the general formula (7), at least one of R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ is a —R ³³ —COOL _{1 / r} group-containing group [R ³³ has 1 to 5 carbon atoms. An alkylene group, L and r are the same as those in the general formula (9)]. The remainder may be a methyl group, an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkoxy group having 1 to 5 carbon atoms. a and b are integers of 1 to 10,000.

In (E31) to (E33), the alkyl group having 2 to 20 carbon atoms may be linear or branched, and may be an ethyl group, an n- and i-propyl group, a butyl group, a pentyl group, or a hexyl group. Group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group, and 2-ethyldecyl group.
Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, n- and i-propoxy groups, and a butoxy group.
Examples of the alkylene group having 1 to 4 carbon atoms include those exemplified for R ^22. Examples of the alkylene group having 5 carbon atoms include 1,2-, 1,3-, 1,4-, 2,3- and A 2,4-pentylene group may be mentioned.

  When using these flexible components, the content (% by mass) of (E3) is preferably 0 to 12, more preferably 0.1 to 10, based on the mass of the fiber treatment oil.

  As additives (E4) other than those described above, components usually used in fiber treatment oils can be used, and examples thereof include antioxidants (such as hindered phenols and hindered amines) and ultraviolet absorbers. When using these additives, (E4) compounding quantity (mass%) becomes like this. Preferably it is 0-5 based on the mass of the oil agent for fiber treatment, More preferably, it is 0-2.

  Examples of the dissolution aid (F) include monohydric alcohols such as methanol, ethanol, propanol, butanol, pentyl alcohol, neopentyl alcohol, and 2-ethylhexyl alcohol; dihydric alcohols such as ethylene glycol, propylene glycol, and butylene glycol; Aliphatic hydrocarbons such as hexane and pentane; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; High polar solvents such as dimethylformamide and dimethyl sulfoxide; Chloroform and carbon tetrachloride, etc. Halogenated hydrocarbons may be mentioned, and two or more of these may be used.

  In addition, when using a hydrocarbon-type lubricating oil (A2) for base oil (A), (F) can be made into at least one part of (A). (F) may be contained in the oil of the present invention as it is, or may be removed by stripping or the like.

Although it does not specifically limit as a manufacturing method of the oil agent for fiber treatments of this invention, For example, the following method is mentioned.
(1) Put (B) together with (A2) and (C), if necessary, together with (D) in a temperature-controllable reaction tank, heat (50-80 ° C.), and clear (turbidity of 20 mg) / L). Then, (A1) is added as necessary with stirring, and the method is cooled to room temperature (20 to 40 ° C.).
(2) Put (B) in (A2), if necessary, together with (D) in a temperature-controllable stirring tank, heat (50-80 ° C), and clear (turbidity is 20 mg / L or less) Stir until. Thereafter, (C) with stirring, (A1) is added if necessary, and cooled to room temperature (20 to 40 ° C.).
(3) (B), and (A2) and / or a dissolution aid (F) are added to a reaction vessel capable of temperature control and stirring, if necessary, and melted (temperature 100 to 250 ° C.). (A2) and (C), and (D), if necessary, were placed in a reaction vessel capable of another temperature control and stirring, the temperature was adjusted (0 to 20 ° C.), and the above-mentioned melted (B) was stirred. It is dropped into the reaction vessel while stirring. Then, if necessary, (A1) is added with stirring and cooled to room temperature (20 to 40 ° C.).
Among these, the method of (1) or (2) is more preferable from the viewpoint of dispersion stability of the obtained fiber oil agent of the present invention.
In addition, when the metal salt is used as (B), a metal salt previously formed may be used, or another metal salt (for example, the metal oxide, chloride, or the like) may be used during or after the production of the above method. To form a metal salt.

  Although the fiber treatment oil obtained by the above method can be used as it is as the fiber treatment oil of the present invention, if necessary, (E), (F), etc. are added at the time of charging (A1). It is good also as an oil agent for fiber processing.

The viscosity of the fiber treatment oil of the present invention is preferably 1 to 500 mm ² / s at 25 ° C. in order to prevent uniform adhesion and roller winding.
The viscosity is measured by the following method.
[Measurement method of viscosity]
20 g of the sample fiber treatment oil is put in an Ubbelohde viscometer, and the temperature of the sample oil is adjusted to 25 ± 0.5 ° C. in a constant temperature water bath. After 30 minutes, the viscosity is measured by the Ubbelohde method.

The application form of the fiber treatment oil can be used in a non-hydrated state, but may be used as a water emulsion if necessary.
The non-hydrated state can be used as it is (straight oil supply) or diluted with a diluent (organic solvent, low viscosity mineral oil, etc.). The dilution ratio is not particularly limited, but the weight of the oil [total weight of non-volatile components] is usually 1 to 80% by mass, preferably 5 to 70% by mass, based on the total weight of the diluted oil after dilution.
As an organic solvent, the same thing as the dissolution aid (F) mentioned above is mentioned, for example. Examples of the low-viscosity mineral oil include liquid paraffin having a viscosity of less than 1 mm ² / s at 25 ° C. and refined spindle oil.

In the case of a water emulsion, it can be emulsified by a known method, but for example, it can be obtained by mixing the present oil with an emulsifier if necessary and emulsifying in water.
As the emulsifier, there is no particular need to add depending on the type of (A), (D), etc. For example, the anionic surfactants, cationic surfactants, amphoteric surfactants and the like described above can be used.

  The amount (% by mass) of the emulsifier when using an emulsifier other than those corresponding to the above components is preferably 0 to 50 based on the total mass of the oil agent (nonvolatile content) after the emulsifier is blended.

As an emulsifier, an emulsification tank equipped with a stirrer, a ball mill, a Gaurin homogenizer, a homodisper, a bead mill, and the like can be used.
The concentration of the emulsion is not particularly limited, but the amount (mass%) of the fiber treatment oil agent is preferably 0.01 to 30, more preferably 0.2 to 20, based on the total mass of the emulsion after emulsification. .

The fiber treatment oil of the present invention is applied to the yarn by nozzle or roller oiling at an arbitrary position after spinning in the elastic fiber spinning process (for example, 200 to 1,200 m / min) until the yarn is wound up. be able to. The temperature of the fiber treatment oil to be fed is usually 10 to 80 ° C., preferably 15 to 60 ° C.
The oil agent for fiber treatment of the present invention is usually 0.1 to 12% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 to 8% by mass as a non-volatile component with respect to the elastic fiber. Grant.

Examples of elastic fibers to which the fiber treatment oil of the present invention can be applied include polyurethane elastic yarns, polyester elastic yarns, polyamide elastic yarns, and polycarbonate elastic yarns. Particularly, the elastic fibers can be suitably used for polyurethane elastic yarns.
The elasticity of the elastic fiber to which the fiber treatment oil of the present invention can be applied is not particularly limited, but is usually 10 to 2500 dtx, preferably 11 to 1870 dtx.

The elastic fiber processed with the fiber processing oil of the present invention is a post-processing step (for example, air span yarn process, covering process, air covering process, knitting process, warping process, refining process, dyeing process and finishing process). Etc.) to finish the final product.
The elastic fiber is used by blending with other synthetic fibers such as nylon fiber and polyester fiber. Therefore, the fiber treatment oil of the present invention is often applied and then washed and removed together with the spinning oil of other synthetic fibers. In the scouring step, aqueous scouring or solvent scouring is performed.
Final products include clothing [eg pantyhose, socks, inner foundation (bras, girdles, body suits, etc.), outerwear (jackets, slacks, etc.), sportswear (swimwear, leotards, ski trousers, etc.) and industrial materials It can be widely applied to applications such as paper diapers and belts.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In addition, the part in a sentence and a table | surface represents a mass part (active ingredient), Mn of an oil-soluble polymer (C), and Mw are the values measured on the following measurement conditions with the gel permeation chromatography (GPC). .
(Method for measuring weight average molecular weight by GPC)
Apparatus: HLC-802A manufactured by Toyo Soda
Column: TSK gel GMH6 2 Measurement temperature: 40 ° C
Sample solution: 0.5 wt% THF solution Solution injection amount: 200 μl
Detector: Refractive index detector Standard: Polystyrene

Production Examples 1 to 5 and Comparative Production Examples 1 and 2;
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a dropping funnel, and a nitrogen blowing tube, mineral oil {flow pan 60S, manufactured by Sanko Chemical Co., Ltd., viscosity 15 mm ² / s (25 ° C.)} 100 In a separate thermometer / stirrer-equipped container, the monomers listed in Table 1, dodecyl mercaptan (abbreviated as DM) as a chain transfer agent, and 2,2′-azobis (2,4- Dimethylvaleronitrile (abbreviated as ADVN) was charged in the amounts shown in Table 1 and stirred and mixed at 20 ° C. to prepare a monomer solution, which was charged into a dropping funnel. After carrying out nitrogen substitution of the gas phase part of the reaction vessel, the monomer solution was added dropwise at 85 ° C. for 4 hours under sealing, and after aging at 85 ° C. for 2 hours from the end of the addition, the obtained polymer was added at 130 ° C., 3 ° C. Volatile monomers are removed under reduced pressure for a period of time, and the above-described mineral oil is added so that the polymer concentration becomes 30%. After further uniform dissolution for 1 hour, polymer solutions (C-1) to (C-5), ( X-1) and (X-2) were obtained. Table 1 shows Mn, Mw and Mw / Mn of the obtained polymer.

MMA: methyl methacrylate nDM: n-dodecyl methacrylate nTM: n-tetradecyl methacrylate nHM: n-octadecyl methacrylate St: styrene MEM: morpholinoethyl methacrylate NVP: N-vinylpyrrolidone

Examples 1-6 and Comparative Examples 1-5, 7-8
Components other than (A1) described in Tables 2 and 3 were added to a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, and mixed at 60 to 70 ° C. for 1 hour. Thereafter, (A1) was added, and the mixture was stirred until it became sufficiently uniform, and then cooled to 30 ° C. to prepare the fiber treatment oil agents of Examples 1 to 6, Comparative Examples 1 to 5, and 7 to 8.

Examples 7 to 8 and Comparative Example 6
(B), (C) and 10 parts of (A2) are mixed in a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer to obtain a melt (I) at 110 to 120 ° C. At this time, the transmittance of the melt (I) was 75%. The remaining 40 parts of (A2) was placed in a reaction vessel equipped with another stirring device, heating / cooling device, and thermometer, and the temperature was adjusted to 5 ° C. and stirred. The melt (I) was gradually poured into this bowl and stirred for 30 minutes. At this time, the temperature in the basket was 5 to 28 ° C. Next, a predetermined amount of (A1) shown in Table 2 and Table 3 was slowly added to prepare the fiber treatment oils of Examples 7 to 8 and Comparative Example 6.

In the dry spinning method of polyurethane fibers, the oils for fiber treatment shown in Table 2 and Table 3 are applied by roller lubrication so that the amount of the oil for fiber treatment is 6% by mass with respect to the filament mass, and wound on cheese at 600 m / min. , 40D polyurethane fiber was obtained.
Further, a sticking property test and a dispersion stability test of a fiber treatment oil were conducted. The performance evaluation results are also shown in Table 2. Tables 2 and 3 show the viscosity, turbidity, and volume average particle diameter of the oil agent for fiber treatment at 25 ° C., measured for each oil agent sample immediately after adjustment by the method described below.

Viscosity measurement method, turbidity measurement method, volume average particle diameter measurement method, dispersion stability test, and yarn obtained with the obtained fiber treatment oil obtained in Examples and Comparative Examples The stickiness test method is as follows.
<Measurement method of viscosity>
Put 20 g of the sample fiber treatment oil into a 20 g Ubbelohde viscometer, and adjust the temperature of the sample fiber treatment oil to 25 ° C. in a constant temperature water bath. After 30 minutes, the viscosity is measured by the Ubbelohde method.

<Measurement method of turbidity>
The fiber processing oil temperature-controlled at 25 degreeC was put into the cell of length 10mm, and it measured by the integrating sphere type | formula photoelectric photometry method using Water Analyzer-2000 by Nippon Denshoku Industries Co., Ltd.

<Measurement method of volume average particle diameter>
The oily composition temperature-controlled at 25 degreeC was put into the 10-mm-long cell, and it measured by the dynamic light-scattering method using ELS-800 made from Otsuka Electronics.

<Dispersion stability test of oil for fiber treatment>
100 g of the adjusted fiber treatment oil is placed in a 145 ml glass bottle and left to stand in a thermostatic bath at −10 ° C., 25 ° C., and 50 ° C. for 30 days, and then the appearance of the fiber treatment oil is visually observed and adjusted. Compared with the appearance of the fiber treatment oil just after, it was judged according to the following criteria.
-Criteria-
○: No change.
Δ: Slightly no layer separation or sediment formation, or layer separation or sediment formation, but the degree of scumming is stronger immediately after the preparation of the oil for fiber treatment.
X: Layer separation or sediment occurs.

<Adhesion test>
Using a fiber that has been aged for 2 weeks at 50 ° C., the cheese that has been wound in the spinning process is applied to a draw-up take-up device with a variable magnification (the ratio of draw speed and take-up speed can be changed), and a speed of 50 m / min. When the yarn was fed out, the minimum speed magnification at which the yarn could be wound up without being caught due to sticking was determined and judged according to the following criteria.
-Criteria-
○: The speed multiple is 50 to 65
X: Speed multiple is 66 or more

In addition, each component in Table 2 and Table 3 is as follows.
Polydimethylsiloxane: KF96-10CS {manufactured by Shin-Etsu Chemical Co., Ltd .: viscosity 10 mm ² / s (25 ° C)}
Mineral oil: flow pan 60S {manufactured by Sanko Chemical Co., Ltd .: viscosity 15mm ² / s (25 ° C)}
Surfactant-1: Sodium polyoxyethylene isotridecyl ether acetate (EO 3 mol adduct)
Surfactant-2: polyoxyethylene lauryl ether acetic acid (EO 2.5 mol adduct)

As is apparent from Table 2, it was found that the fiber treatment oils of the present invention (Examples 1 to 8) were very excellent in dispersion stability at any temperature. On the other hand, as shown in Table 3, none of Comparative Examples 1 to 8 satisfies the dispersion stability at room temperature (25 ° C.) or low temperature (−10 ° C.). Furthermore, since the fiber treatment oil of the present invention does not precipitate or aggregate over time during storage or use, it is possible to uniformly adhere the anti-stick component to the fiber and prevent sticking. It was also found to be excellent. From this result, since there is no precipitation or aggregation which has been a problem in the past, excellent productivity can be realized in the fiber manufacturing process.
In particular, the fiber treatment oil of the present invention (Examples 1 to 6) has a small particle size and low turbidity (transparency), so it is suitably used in both the roller oil supply method and the nozzle oil supply method. It has the feature that it can do.

Since the oil for fiber treatment of the present invention has excellent dispersion stability, it is not necessary to disperse and redisperse the anti-sticking component at the time of use, and productivity can be improved and stable operation can be achieved. As a result, uniform adhesion to the fibers of the anti-sticking component can be achieved, and excellent sticking properties can be exhibited, so that occurrence of troubles such as yarn breakage during the unwinding process can be reduced. For this reason, it is particularly suitable for the high-speed spinning process of fine decitex fibers.

Claims (11)

  At least one base oil (A) selected from the group consisting of silicone oil (A1) and hydrocarbon-based lubricating oil (A2), an anti-sticking agent (B), and an oil having a number average molecular weight of 10,000 to 500,000 An oil for fiber treatment, comprising a soluble polymer (C).   2. The oil agent for fiber treatment according to claim 1, wherein (C) is an oil-soluble polymer comprising an alkyl (meth) acrylate monomer having an alkyl group having 1 to 36 carbon atoms as an essential component.   3. The fiber treatment oil according to claim 1, wherein (B) comprises a compound having at least one carboxyl group and / or carboxylate group in the molecule.   Furthermore, surfactant (D) is contained, The oil agent for fiber treatment in any one of Claims 1-3 characterized by the above-mentioned.   The (D) is at least one surfactant selected from the group consisting of an anionic surfactant (D1) and a cationic surfactant (D2) having a solubility parameter (SP value) of 7 to 10.5. The oil agent for fiber treatment according to claim 4.   The oil agent for fiber processing in any one of 1-5 whose turbidity in 25 degreeC is 20 mg / L or less.   Based on the total mass of (A1) + (A2), the content of (A1) is 5-80% by mass, and based on the total mass of (A) + (B) + (C) + (D) The content of (A) is 70 to 99.6% by mass, the content of (B) is 0.3 to 10% by mass, the content of (C) is 0.01 to 3% by mass, The content of D) is 0 to 20% by mass, The fiber treatment oil according to any one of claims 1 to 6.   The said fiber is an elastic fiber, The oil agent for elastic fiber treatment in any one of Claims 1-7.   A method for treating a fiber, wherein the elastic fiber treating oil according to claim 8 is added in an amount of 0.1 to 12% by mass to the fiber in a spinning step.   The processing method according to claim 8, wherein further scouring is performed after applying the processing agent to the fiber. The elastic fiber processed by the processing method of Claim 9 or 10.