Patent Application
20080200358
The present invention relates to a lubricant for fibers and, more particularly, to a lubricant for treating fibers to be used in the spinning step in the manufacture of elastic polyurethane fibers for obtaining elastic polyurethane fibers showing little tendency toward fiber-to-fiber tackiness and showing good rewindability.
Among the methods of producing elastic polyurethane fibers that are known in the art, there are the melt spinning, dry spinning and wet spinning methods, among others. However, every method encounters a problem, namely poor rewindability in a subsequent processing step due to a marked tendency for fiber-to-fiber tackiness.
In recent years, the need has been increasing to improve the productivity in producing elastic fibers by increasing the rate of rewinding. In the field of warp knitting, in particular, a high rate of rewinding is required in the step of warping. If the rewindability is poor, yarn breaking, among others, is caused in the step of warping, leading to a marked reduction in productivity. Thus, in the field of lubricants for elastic polyurethane fibers, it is an urgent need to develop a lubricant for elastic fibers capable of solving these problems.
A lubricant for treating fibers in the spinning step in elastic fiber production that has been proposed comprises an anti-tackiness agent added to such a lubricant. Lubricants for treating fibers with a solid metal soap suspended therein as such anti-tackiness agent (Patent Document 1: Japanese Kokoku Publication Sho41-286; Patent Document 2: Japanese Kokoku Publication Sho40-5557), lubricants for treating fibers with a polyether-modified silicone mixed therein (Patent Document 3: Japanese Kokoku Publication Sho61-459; Patent Document 4: Japanese Kokai Publication Hei02-127569; Patent Document 5: Japanese Kokai Publication Hei06-41873) and lubricants for treating fibers with a silicone resin mixed therein (Patent Document 6: Japanese Kokoku Publication Sho63-12197; Patent Document 7: Japanese Kokai Publication Hei08-74179), for instance, have been proposed.
However, such a solid ingredient as mentioned above in the lubricants proposed in Patent Documents 1 and 2 is poor in dispersion stability, aggregating and precipitating in lubricants with the passage of time; therefore, when such lubricants are used, uniform application thereof to fibers becomes difficult and, accordingly, the anti-tacking property can hardly be produced to a sufficient extent and such a problem as yarn breaking may possibly be produced due to changes in tension in a subsequent processing step.
As for the lubricants proposed in, Patent Documents 3 to 7, the lubricants obtained are uniform and transparent and show good time-dependent stability but fail to produce their anti-tacking property to a satisfactory extent. For attaining a sufficient anti-tacking property, the amount of addition of the anti-tackiness agent must be raised; the result is that the viscosity of the lubricants increases and the uniform application to fibers becomes difficult to attain. It is also a problem that the silicone-modified anti-tackiness agents are expensive.
Accordingly, it is an object of the present invention to provide a lubricant for treating fibers which produces good anti-tacking property against fiber-to-fiber tackiness in the production of fibers. A further object is to increase the time-dependent stability of a lubricant for fibers and provide a lubricant for fibers which makes it possible to stably produce fibers while eliminating the problem of aggregation and precipitation of anti-tackiness agents or the problem of uneven application to fibers, among others, in or during use thereof.
The present inventors made intensive investigations in an attempt to obtain such a lubricant for treating fibers as mentioned above and, as a result, found that when a lubricant for treating fibers having a characteristic such that the angle of contact with water at 25° C. of the surface of a sheet made of a textile material treated with the lubricant for treating fibers amounts to 70 to 180° is prepared, the problems mentioned above can be solved. Based on such and other findings, they have now completed the present invention.
Thus, the present invention relates to
a lubricant for treating fibers to be used for fibers made of a polymer material (a)
wherein the angle of contact with water at 25° C. of the surface of a sheet made of the material (a) is not greater than 60° and the angle of contact with water at 25° C. of the surface of the sheet made of the material (a) applied with the lubricant for treating fibers is 70° to 180°,
to a method of treating elastic fibers
which comprises applying 0.1 to 12 mass % of the lubricant for treating fibers to elastic fibers in the spinning step, if necessary followed by scouring, and
to an elastic fiber treated by the treatment method defined above.
In the present invention, the polymer material (a) may be a polymer material containing highly polar groups (e.g. amide, ester, urea and/or urethane groups) within the molecule, for example a polyester, polyurethane, polyamide, polycarbonate or nylon.
The upper limit to the contact angle, at 25° C., of the surface of the sheet made of such a material (a) is not greater than 60°, while the lower limit thereto is not smaller than 10° from the viewpoint that the material is available on the market.
The fibers made of (a) are, for example, elastic polyurethane fibers, elastic polyester fibers, elastic polyamide fibers, elastic polycarbonate fibers, nylon fibers or polyester fibers. Preferred among these are elastic fibers such as elastic polyurethane fibers, elastic polyester fibers, elastic polyamide fibers and elastic polycarbonate fibers. More preferred are elastic polyurethane fibers and elastic polyamide fibers. Particularly preferred are elastic polyurethane fibers.
The fineness of the elastic fibers to which the lubricant for treating fibers of the present invention can be applied is not particularly restricted but generally is 10 to 2,500 decitex (dtx), preferably 11 to 1,870 dtx.
The lubricant for treating fibers to be used in the invention is preferably one such that the angle (°) of contact with water, at 25° C., of the surface of the sheet of the polymer material (a) mentioned above after application thereof to that surface is 70 to 180, preferably 75 to 120, particularly preferably 75 to 100, from the fiber-to-fiber tackiness prevention and rewindability viewpoint.
In the present invention, the contact angle is the value measured by the following method.
The periphery of a smooth-surfaced glass plate (20 cm×25 cm) is covered with an outer frame made of a cardboard having a width of 1 cm and a thickness of 0.1 cm using, for example, a double sided adhesive tape for sticking, and 100 parts of a 40% (by mass) solution (e.g. in dimethylformamide (DMF)) of the resin to be used in manufacturing the fibers in question is gently poured into the central cavity (18 cm×23 cm, 0.1 cm in depth, about 41 cm3 in volume) and spread so that the whole resin solution may become even. The whole is allowed to stand in a horizontal position, and natural drying is allowed to proceed at room temperature (about 20° C.) for 24 hours, followed by further 2 hours of drying in a reduced-pressure drier controlled at 60° C. (pressure: about 6 kPa). After drying and the subsequent 24 hours of standing at room temperature (about 20° C.), the resulting resin sheet is cut into rectangles, 6 cm×3 cm in size, using a cutter or the like, followed by gentle peeling from the glass plate, whereby test specimen sheets (a1) of the polymer material (a) can be obtained.
Then, 10 μl of the lubricant for treating fibers of the invention is dropped onto each test specimen sheet obtained in the above manner, another test specimen sheet is placed thereon and the lubricant is caused to spread all over. The assembly is sandwiched between two glass plates and pressed at a pressure of 20 g/cm2 and, in that condition, maintained in an air-circulating drier at 700 for 1 hour. Thereafter, the two joined sheets are peeled from each other for use as test specimen sheets (a2).
Each sheet (a1) (e.g. about 200 μm thick, 6 cm×3 cm) is conditioned under conditions of a temperature of 25° C. and a relative humidity of 65% for 3 hours and then, under the same conditions, subjected to contact angle measurement just after placing of water on the test specimen sheet surface using an automatic contact angle meter (product of Kyowa Interface Science Co., Ltd.; “model CA-Z”). The sheets (a2), too, are measured in the same manner.
From the anti-tackiness viewpoint, the lubricant for treating fibers of the invention preferably comprise a base oil (A) selected from the group consisting of silicone oils (A1) and hydrocarbon-based lubricating oils (A2), an anti-tackiness agent (B) and a surfactant (C).
Usable as the silicone oils (A1) are polydimethylsiloxane, and partially C2-C20 alkyl- and/or phenyl-substituted polydimethylsiloxane, among others.
Usable as the hydrocarbon-based lubricating oils (A2) are mineral oils, purified mineral oils, hydrogenated mineral oils and cracked mineral oils, among others.
Preferred among these are base oils having a viscosity at 25° C. of 1 to 1,000 mm2/s, more preferably 2 to 500 mm2/s, particularly preferably 3 to 200 mm2/s.
(A) may comprise either of (A1) and (A2) singly or a mixture thereof. Preferred are (A2) alone and mixtures of (A1) and (A2). More preferred are mixtures of (A1) and (A2). In the case of mixtures, the content (mass %) of (A1) is preferably 5 to 80, more preferably 10 to 70, particularly preferably 20 to 50, based on the total mass of (A1)+(A2).
As the anti-tackiness agent (B), there may be mentioned compounds containing at least one carboxyl group and/or carboxylate group within the molecule.
As such compounds, there may be mentioned higher fatty acids (salts) (B1) and carboxyl and/or carboxylate group-containing polymers (B2).
As the higher fatty acids (B1), there may be mentioned saturated or unsaturated higher fatty acids generally containing 5 to 40 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 8 to 24 carbon atoms, still more preferably 12 to 24 carbon atoms, particularly preferably 16 to 22 carbon atoms. As specific examples of the higher fatty acids, there may be mentioned, for example, n-valeric acid, isovaleric acid, octanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, elaidic acid, erucic acid, linolic acid, linolenic acid and ricinoleic acid. Preferred among these are lauric acid, palmitic acid, stearic acid and behenic acid. Stearic acid is particularly preferred among others. These fatty acids may be used singly or in the form of a mixture of two or more of them.
The carboxyl group in (B1) may be in the form of a metal salt. Preferred as the metal for metal salt formation are alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (barium, calcium, magnesium, etc.), group IIB metals (e.g. zinc etc.), transition metals (nickel, iron, copper, manganese, cobalt, silver, gold, platinum, palladium, titanium, zirconium, cadmium, etc.), group IIIB metals (e.g. aluminum salt etc.), group IVB metals (tin, lead, etc.) and lanthanoid metals (lanthanum, cerium, etc.), among others. More preferred are alkali metals, alkaline earth metals and group IIIB metals. Alkaline earth metals are particularly preferred, and magnesium is preferred among others.
As specific examples of the higher fatty acid salts (B1), there may be mentioned, among others, 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, potassium behenate; magnesium dilaurate, calcium dilaurate, barium dilaurate; magnesium dimyristate, calcium dimyristate, barium dimyristate; magnesium dipalmitate, calcium dipalmitate, barium dipalmitate; magnesium distearate, calcium distearate, barium distearate; magnesium diisostearate, calcium diisostearate, barium diisostearate; magnesium dibehenate, calcium dibehenate, barium dibehenate; magnesium palmitate stearate, calcium palmitate stearate and barium palmitate stearate. Among these, stearic acid alkaline earth metal salts are particularly preferred, and magnesium distearate is most preferred. Although commercial grades of magnesium distearate, for instance, contain partly unreacted magnesium hydroxide stearate as an impurity, such grades can also be used without any problem.
The above-mentioned higher fatty acids or metal salts thereof, namely the higher fatty acids (salts) (B1), may be used singly or in the form of a mixture of two or more of them.
As the carboxyl and/or carboxylate group-containing polymers (B2), there may be mentioned, among others, polymers (B2-1) obtained by (co)polymerizing a monomer (X) containing at least one carboxyl group and/or carboxylate group within the molecule, if necessary together with another monomer (Y), and polymers (B2-2) obtained by carboxyl group and/or carboxylate group introduction into polymer molecules.
As the above monomer (X), there may be mentioned, for example, unsaturated monocarboxylic acids [e.g. (meth) acrylic acid, vinylbenzoic acid, allylacetic acid, etc.], unsaturated dicarboxylic acids and anhydrides thereof [e.g. maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), citraconic acid (anhydride), etc.], and metal salts of these.
Preferred among these are (meth) acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride) and metal salts of these. More preferred are (meth) acrylic acid, maleic acid (anhydride) and metal salts of these.
As the other monomer (Y) copolymerizable with the monomer (X), there may be mentioned the following water-soluble unsaturated monomers (Y1) and water-insoluble unsaturated monomers (Y2).
The water-soluble unsaturated monomers (Y1) include nonionic monomers (Y1-1), cationic monomers (Y1-2), and anionic monomers (Y1-3) other than the monomers (X).
As (Y1-1), there may be mentioned:
(Y1-1a): (Meth)acrylate derivatives [hydroxyethyl (meth)acrylate, diethylene glycol mono(meth)acrylate, polyethylene glycol (polymerization degree: 3 to 50) mono (meth)acrylate, polyglycerol (polymerization degree: 1 to 10) mono(meth)acrylate, 2-cyanoethyl (meth)acrylate, etc.],
(Y1-1b): (Meth)acrylamide derivatives [(meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-methylol(meth)acrylamide, etc.],
(Y1-1c): Nitrogen atom-containing vinyl monomers other than those mentioned above [acrylonitrile, N-vinylformamide, N-vinyl-2-pyrrolidone, vinylimidazole, N-vinylsuccinimide, N-vinylcarbazole, etc.], and the like, and mixtures of these.
As (Y1-2), there may be mentioned:
(Y1-2a): Nitrogen atom-containing (meth)acrylate derivatives [N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N-morpholinoethyl (meth)acrylate, etc.],
(Y1-2b): Nitrogen atom-containing (meth) acrylamide derivatives [N,N-dimethylaminoethyl(meth)acrylamide etc.],
(Y1-2c): Amino group-containing vinyl compounds [vinylamine, vinylaniline, (meth)allylamine, p-aminostyrene, etc.],
(Y1-2d): Amine/imide group-containing compounds [1,1,1-trimethylamine (meth)acrylimide, 1,1-dimethyl-1-ethylamine (meth)acrylimide, 1,1-dimethyl-1-(2′-phenyl-2′-hydroxyethyl amine (meth)acrylimide, 1,1,1-trimethylamine (meth)acrylimide, etc.],
(Y1-2e): Nitrogen atom-containing vinyl monomers other than those mentioned above [2-vinylpyridine, 3-vinylpiperidine, vinylpyrazine, vinylmorpholine, etc.] and the like, and salts thereof (e.g. hydrochloride, sulfate, phosphate, nitrate, methyl chloride salt, dimethyl sulfate salt and benzyl chloride salt, etc.), and mixture of these.
As (Y1-3), there may be mentioned:
(Y1-3a): Unsaturated sulfonic acids [unsaturated aliphatic sulfonic acids containing 2 to 20 carbon atoms (vinylsulfonic acid etc.), unsaturated aromatic sulfonic acids containing 6 to 20 carbon atoms (styrenesulfonic acid etc.), sulfonic acid group-containing (meth)acrylates [sulfo(C2-20)alkyl (meth)acrylates [2-(meth)acryloyloxyethanesulfonic acid, 2-(meth)acryloyloxypropanesulfonic acid, 3-(meth)acryloyloxypropanesulfonic acid, 2-(meth)acryloyloxybutanesulfonic acid, 4-(meth)acryloyloxybutanesulfonic acid, 2-(meth)acryloyloxy-2,2-dimethylethanesulfonic acid, p-(meth)acryloyloxymethylbenzenesulfonic acid, etc.], sulfonic acid group-containing (meth)acrylamides [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.], (C1-20) alkyl (meth)allyl sulfosuccinic acid esters [methyl (meth)allyl sulfosuccinate etc.], etc.],
(Y1-3b): (Meth) acryloylpolyoxy(C1-6) alkylene sulfate esters [(meth)acryloylpolyoxyethylene(polymerization degree: 2 to 50) sulfate ester etc.] and the like, and salts of these [alkali metal (lithium, sodium, potassium, etc.) salts, alkaline earth metal (magnesium, calcium, etc.) salts and (C1-20) amine salts, etc.], and mixtures of those mentioned above.
As the water-insoluble unsaturated monomers (Y2), there may be mentioned:
(Y2-1): Methacrylates containing 4 to 23 carbon atoms [(meth)acrylates of aliphatic and alicyclic alcohols containing 1 to 20 carbon atoms, for example methyl (meth)acrylate, ethyl (meth)acrylates, butyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, epoxy group-containing (meth)acrylates containing 4 to 20 carbon atoms {e.g. glycidyl (meth)acrylate etc.}, etc.],
(Y2-2): Polypropylene glycols (polymerization degree: 2 to 50) [mono (C1-20)alkyl, mono (C3-12) cycloalkyl or monophenyl ether] unsaturated carboxylic acid monoesters [monool or diol-propyleneoxide (hereinafter, “PO” for short) adducts, for example (C1-20) monool PO adduct (meth)acrylic acid esters [ω-methoxypoly-propylene glycol mono(meth)acrylate, ω-ethoxypolypropylene glycol mono(meth)acrylate, ω-propoxypolypropylene glycol mono(meth)acrylate, ω-butoxypolypropylene glycol mono(methacrylate, ω-cyclohexylpolypropylene glycol mono(meth)acrylate, ω-phenoxypolypropylene glycol mono (meth) acrylate, etc.], (C1-20) diol-PO adducts (meth)acrylates [ω-hydroxyethyl(poly)oxypropylene mono(meth)acrylate etc.], etc.],
(Y2-3): Unsaturated hydrocarbon monomers containing 2 to 30 carbon atoms [C2-30 olefin {e.g. ethylene, propylene, α-olefins containing 4 to 30 (preferably 4 to 12, more preferably 4 to 10) carbon atoms} (e.g. 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, etc.), etc.], dienes containing 4 to 30 (preferably 4 to 18, more preferably 4 to 8) carbon atoms {e.g. butadiene, isoprene, cyclopentadiene, 11-dodecadiene, etc.}, aryl group-containing olefins containing 8 to 30 carbon atoms {e.g. styrene, 1-methylstyrene, etc.}, etc.],
(Y2-4): Unsaturated alcohols [vinyl alcohol, (meth)allyl alcohol] C2-20 carboxylic acid esters (e.g. vinyl acetate) etc.,
(Y2-5): Halogen-containing monomers (e.g. vinyl chloride) and the like, and mixtures of those mentioned above.
Preferred among the above other monomers (Y) in view of the ready copolymerizability with the above-mentioned (X) and the affinity for the base oil (A) are (Y1-1), (Y2-1), (Y2-2) and (Y2-3); more preferred are (Y2-1) and (Y2-3); particularly preferred is (Y2-3). Most preferred are olefins containing 2 to 30 carbon atoms among (Y2-3).
These monomers (Y) may be copolymerized with (X) in arbitrary mixing ratios.
The content (mole percent) of the monomer (X) in the above-mentioned (B2-1) is generally 10 to 100, preferably 20 to 80, more preferably 30 to 70, relative to the total number of moles of the monomers (X) and (Y).
As for the method of producing (B2-1), such known techniques as radical polymerization, anionic polymerization and cationic polymerization may be employed. For example, (B2-1) can be produced by polymerizing the above-mentioned monomer (X), if necessary together with another monomer (Y), using a polymerization catalyst, if necessary together with a polymerization solvent (e.g. an organic solvent or water) and a chain transfer agent, among others.
Usable as the polymerization catalyst are those known in the art, including such radical polymerization catalysts as di-tert-butyl peroxide, benzoyl peroxide, decanoyl peroxide, dodecanoyl peroxide, hydrogen peroxide-Fe2+ salt and azo compounds.
As cationic polymerization catalysts, there may be mentioned protic acids (e.g. sulfuric acid, phosphoric acid, perchloric acid, etc.) and Lewis acids (e.g. boron trifluoride, aluminum chloride, titanium tetrachloride, tin tetrachloride, etc.), among others. As anionic polymerization catalysts, there may be mentioned sodium hydroxide, potassium hydroxide, sodium methoxide, butyllithium, pyridine, Ziegler catalysts and Ziegler-Natta catalysts (e.g. (C2H5)3Al—TiCl4 etc.), among others.
As (B2-2), there may be mentioned those resulting from modification of polyolefins (a0) by carboxyl and/or carboxylate group introduction thereinto, in which the carboxyl and/or carboxylate groups may be bound to (a0) either directly or via an organic group; those polymers include primarily modified polyolefins (aI) and modified polyolefins (aII) resulting from higher order modification (secondary modified, tertiary modification, etc.).
Usable as (a0) are polyolefins obtained by (co)polymerizing one or a mixture of two or more of olefins containing 2 to 30 (preferably 2 to 12, more preferably 2 to 10) carbon atoms or of dienes (by polymerization method), and low-molecular-weight polyolefins obtained by thermal degradation of high-molecular-weight polyolefins (by thermal degradation method).
Usable as the C2-30 olefins or dienes are those species enumerated hereinabove. Among them, ethylene, propylene, C4-12 α-olefins, butadiene and isoprene are preferred, ethylene, propylene, C4-8 α-olefins and butadiene are more preferred, and ethylene, propylene and butadiene are particularly preferred.
Usable as the high-molecular-weight polyolefins are (co)polymers of one or a mixture of two or more of olefins containing 2 to 30 (preferably 2 to 12, more preferably 2 to 10) carbon atoms. Usable as the C2-30 olefins are the same ones as those enumerated hereinabove and, among them, ethylene, propylene and C4-12 α-olefins are preferred, and propylene and ethylene are particularly preferred.
The low-molecular-weight polyolefins to be obtained by the thermal degradation can be readily obtained, for example, by the method described in Japanese Kokai Publication Hei03-62804. The polyolefins to be obtained by the polymerization method can be produced by the methods known in the art. For example, they can be readily obtained, for example, by the method comprising carrying out the (co)polymerization reaction in the presence of a radical polymerization catalyst, a metal oxide catalyst, a Ziegler catalyst or a Ziegler-Natta catalyst. The radical polymerization catalyst may be any of those known in the art, including those enumerated hereinabove, among others. As the metal oxide catalyst, there may be mentioned, for example, chromium oxide catalysts deposited on a silica-alumina support. The Ziegler catalyst and Ziegler-Natta catalyst are the same as those mentioned hereinabove, for example.
The polyolefins (a0) preferably have a number average molecular weight (Mn) of 800 to 20,000, more preferably 1,000 to 10,000, particularly preferably 1,200 to 6,000. That the Mn is within such range is more preferable from the anti-tackiness and lubricant viscosity viewpoint. The Mn values of (a0), (aI) and (aII) are determined by gel permeation chromatography using the following measuring apparatus and measurement conditions.
Measuring apparatus (Waters model 150C-V, column: PLgel MIXED-B, detection: RI)
Measurement conditions: Solvent: o-dichlorobenzene (hereinafter, “DCB” for short),
Injection size: 100 μl,
Flow rate: 1 ml/min,
Calibration curve: polystyrene.
As the primarily modified polyolefins (aI), there may be mentioned the ones obtained by the following methods.
(1) Those obtained by direct oxidation of (a0).
(2) Those obtained by hydroformylation of (a0), followed by oxidation.
(3) Those obtained by modification of (a0) with an α,β-unsaturated carboxylic acid (anhydride) [α,β-unsaturated carboxylic acid and/or anhydride thereof; hereinafter described in the same manner of expression]
(4) Those obtained by hydroboration of (a0), followed by oxidation, further followed by modification with an α,β-unsaturated carboxylic acid (anhydride).
As the modified polyolefins (aII) resulting from higher order modification (secondary modification, tertiary modification, etc.), there may be mentioned, for example, the ones obtained by further modification of the primarily modified polyolefins mentioned above under (1) to (4) with a lactam or aminocarboxylic acid and/or a lactone or hydroxycarboxylic acid, and mixtures of two or more of them.
The direct oxidation mentioned above under (1) can be carried out by oxidation with oxygen and/or ozone, for example by the method described in J. Org. Chem., vol. 42, page 3749 (1977) or U.S. Pat. No. 3,692,877, whereby modified polyolefins with a carboxyl group(s) directly bound to (a0) are obtained.
The reactions mentioned above under (2) can be carried out by the method comprising hydroformylation in the manner of oxo synthesis (reaction with carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst), followed by oxidation, for example by the method described in Tetrahedron Lett., 1979, page 399, whereby modified polyolefins with a carboxyl group(s) directly bound to (a0) are obtained.
The modification with an α,β-unsaturated carboxylic acid (anhydride) as described above under (3) can be carried out by thermally adding an α,β-unsaturated carboxylic acid and/or the anhydride thereof to the terminal double bond of (a0) (ene reaction) by the solution method or melting method. The temperature for reacting the α,β-unsaturated carboxylic acid (anhydride) with (a0) is generally 170 to 230° C. The number of molecules of the α,β-unsaturated carboxylic acid (anhydride) added terminally to (a0) may be one or two or more added in the manner of graft polymerization.
The reactions in the above method (4) involving hydroboration of (a0), followed by oxidation, further followed by modification with an α,β-unsaturated carboxylic acid (anhydride) can be carried out, for example, by the method described in Macromolecules, vol. 32, page 2525 (1999). The number of the α,β-unsaturated carboxylic acid (anhydride) terminally added to (a0) via an ether oxygen atom may be one or two or more added in the manner of graft polymerization.
Usable as the α,β-unsaturated carboxylic acid (anhydride) for the above-mentioned modifications (3) and (4) are the same ones as the monomers (X) mentioned above; preferred among them are fumaric acid and, in particular, maleic acid (anhydride).
The amount (mass %) of the α,β-unsaturated carboxylic acid (anhydride) to be used for modification is generally 0.5 to 40, preferably 1 to 30, based on the mass of (a0) The number of molecules of the α,β-carboxylic acid (anhydride) to be added is generally 1 to 10, preferably 1 to 8, per terminal double bond in (a0).
The lactam to be used for the higher order modification mentioned above includes C6-12 lactams, for example caprolactam, enantholactam, laurolactam and undecanolactam; the aminocarboxylic acid includes C2-12 aminocarboxylic acids, for example amino acids such as glycine, alanine, valine, leucine, isoleucine and phenylalanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; the lactone includes those lactones which correspond to the lactams mentioned above (e.g. caprolactone etc.); and the hydroxycarboxylic acid includes C2-12 aliphatic hydroxycarboxylic acids, for example glycolic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypelargonic acid, ω-hydroxycapric acid, 11-hydroxyundecanoic acid and 12-hydroxydodecanoic acid.
Preferred among them are C6-8 lactams and C8-12 aminocarboxylic acids, in particular caprolactam and 12-aminododecanoic acid. The amount (in mole equivalents) of the lactam or aminocarboxylic acid and/or the lactone or hydroxycarboxylic acid to be used for higher order modification is preferably 1 to 10 or more, more preferably 1 (equivalent) relative to the number of moles of the carboxyl group in the primarily modified polyolefin.
The acid number (mg KOH/g) of (B2-2) is generally 1 to 500, preferably 50 to 400, particularly preferably 100 to 350. Acid values within such range are preferred from the viewpoint of uniform application to fibers.
From the lubricant viscosity viewpoint, (B2) other than (a0) preferably has a number average molecular weight of 800 to 30,000, more preferably 1,000 to 15,000, particularly preferably 1,500 to 7,000.
The carboxyl and/or carboxylate group-containing polymers (B2) mentioned above may be used singly or in the form of a mixture of two or more of them.
A combination of (B1) and (B2) may also be used as (B). Preferred as the (B) are stearic acid alkaline earth metal salts; magnesium stearate is more preferred.
The volume average particle diameter (nm) of (B) is not particularly restricted but, in view of the stability of fiber production by the nozzle oiling system and of the time-dependent stability of the lubricant for treating fibers, it is preferably 1 to 2,000, more preferably 5 to 300, particularly preferably 10 to 100.
The volume average particle diameter is measured by the dynamic light scattering method {Surfactant Evaluation and Test Methods (Japan Oil Chemists' Society), page 212 (2002)} or the X-ray small angle scattering method, for instance. In the present invention, the volume average particle diameter is the value determined by the dynamic light scattering method.
In the present invention, the surfactant (C) is a surfactant other than the anti-tackiness agent (B1) and the solubility parameter (hereinafter, “SP value” for short) thereof is preferably 7 to 10.5, more preferably 7.5 to 10, particularly preferably 8 to 9.5. When the SP value is within such range, the compatibility thereof with the base oil (A) and anti-tackiness agent (B) becomes good, and the time-dependent stability of the lubricant for treating fibers becomes improved.
The “SP value” as the term is used herein is expressed in the square root of the ratio of cohesive energy density to molecular volume, as follows.
[SP value]=(ΔE/V)1/2
In the formula, ΔE stands for coherent energy density and V stands for molecular volume, the value of which is as calculated by the method of Robert F. Fedors et al. as described in, for example, Polymer Engineering and Science, 14, 147-154 (1974).
(C) comprises at least one species selected from the group consisting of anionic surfactants (C1), excluding the anti-tackiness agents (B1), and cationic surfactants (C2).
The anionic surfactants (C1) include, among others, sulfonic acids (salts) (C1-1), carboxylic acids (salts) (C1-2), sulfate esters (salts) (C1-3) and phosphate esters (salts) (C1-4).
As the sulfonic acids (salts) (C1-1), there may be mentioned C1-24 alcohol sulfosuccinic acid (mono-, di-) esters (salts) (C1-1A), C8-24 α-olefin sulfonation products (salts) (C1-1B), C8-14 alkyl group-containing alkylbenzenesulfonic acids (salts) (C1-1C) and petroleum sulfonates (salts) (C1-1D). The hydrophobic group constituting (C1-1A) or (C1-1B) may be a natural product-derived one or a synthetic one. Preferred among those mentioned above are (C1-1A) species represented by the following general formula (1).
In the above formula, R1 and R2 each independently represents an alkyl group containing 1 to 24 carbon atoms or an alkenyl group containing 2 to 24 carbon atoms. A represents an alkylene group containing 2 to 4 carbon atoms. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or an alkanolamine. m, n, and m+n each respectively represents an integer of 0 or 1 to 10.
The alkyl group containing 1 to 24 carbon atoms, which is represented by R1 and/or R2, may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, a methyl, ethyl, n- and i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, and 2-ethyldecyl groups.
The alkenyl group containing 2 to 24 carbon atoms, which is represented by R1 and/or R2, may be whichever of a straight-chain group or a branched-chain group, and there may be mentioned, for example, an n- and i-propenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, and 2-ethyldecenyl groups.
The preferred examples of R1 and R2 are alkyl groups of 3 to 24 carbon atoms, more preferably alkyl groups of 5 to 18 carbon atoms, and particularly preferably alkyl groups of 8 to 12 carbon atoms. R1 and R2 may be the same or different.
As A, there may be mentioned an ethylene, propylene, and butylene groups. Preferred among these are ethylene and propylene groups. When there are a plurality of A species, they may be the same or different and may be polymerized in a random manner or a block manner.
m, n, and m+n each respectively represents an integer of 0 or 1 to 6, preferably an integer of 0 or 1 to 3.
So long as m and n are within such range, the compatibility with the base oil (A) is good.
As regards M, the alkali metal atom includes potassium and sodium, among others, the alkanolamine includes monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine, among others. Preferred as the above-mentioned M are alkali metal atoms. In the above-mentioned (C1-1A), M may occur as a mixture of two or more species.
As specific examples of the sulfosuccinic ester anionic surfactants (C1-1A) represented by the general formula (1), there may be mentioned, for example, di-2-ethylhexyl sulfosuccinate sodium, palmityl stearyl sulfosuccinate potassium, and 6 mol ethylene oxide (hereinafter, abbreviated as EO) adduct of polyoxyethylene-di-2-ethylhexyl sulfosuccinate sodium (m=n=3).
As the carboxylic acids (salts) (C1-2), there may be mentioned ether-carboxylic acid anionic surfactants represented by the general formula (2) given below. The fatty acid and alcohol moieties constituting these may be natural product-derived ones or synthetic ones and, further, the site of bonding of the carboxyl group or hydroxyl group may be at the end or on a side chain of the hydrocarbon group.
R3—O-(AO)p—CH2COOM (2)
In the above formula, R3 represents an alkyl group containing 1 to 24 carbon atoms, an allyl group or an alkenyl group containing 2 to 24 carbon atoms; A represents an alkylene group containing 2 to 4 carbon atoms; M represents a hydrogen atom, an alkali metal atom, an ammonium group or an alkanolamine; p represents an integer of 0 or 1 to 10. Referring to the above formula, specific examples and preferred species of the C1-24 alkyl groups and C2-24 alkenyl groups represented by R3 are the same as those given hereinabove referring to R1 and R2. A and M are respectively the same as in the general formula (1), and p is an integer of 0 or 1 to 10, preferably 1 to 6.
So long as p is within such range, the compatibility with the base oil is good.
As specific examples of the ethercarboxylic acid anionic surfactants (C1-2) represented by the general formula (2), there may be mentioned, for example, octyl alcohol carboxymethyl ether sodium salt, decyl alcohol carboxymethyl ether sodium salt, lauryl alcohol carboxymethyl ether sodium salt, carboxymethyl ether sodium salt of isodidecyl alcohol and isotridecyl alcohol, tridecanol carboxymethyl ether sodium salt, octyl alcohol-EO(3 mol) adduct carboxymethyl ether sodium salt, lauryl alcohol-EO(4 mol) adduct carboxymethyl ether sodium salt, isotridecyl alcohol-EO(3 mol) adduct carboxymethyl ether sodium salt, EO (3 mol) adduct carboxymethyl ether sodium salt of isodidecyl alcohol and isotridecyl alcohol, tridecanol-EO (5 mol) adduct carboxymethyl ether sodium salt, lauryl alcohol carboxymethylate, and lauryl alcohol-EO(2.5 mol) adduct carboxymethylate.
As preferred specific examples of these, there can be mentioned sodium octyl-etherified acetate, sodium decyl-etherified acetate, sodium lauryl-etherified acetate, sodium tridecyl-etherified acetate, sodium polyoxyethylene (EO 3 mol) octyl ether acetate, sodium polyoxyethylene (EO 3 mol) lauryl ether acetate, sodium polyoxyethylene (EO 3 mol) tridecyl ether acetate, and polyoxyethylene (EO 2.5 mol) lauryl ether acetate, among others.
As the sulfate esters (salts) (C1-3), there may be mentioned higher alcohol sulfate esters (salts) [C8-18 aliphatic alcohol sulfate esters (salts)] (C1-3a), higher alkyl ether sulfate esters (salts) [C8-18 aliphatic alcohol-EO (1 to 10 moles) adduct sulfate esters (salts)] (C1-3b), sulfated oils (obtained by sulfating natural unsaturated oils or fats or unsaturated waxes as such, followed by neutralization) (C1-3c), sulfated fatty acid esters (obtained by sulfating unsaturated fatty acid lower alcohol esters, followed by neutralization) (C1-3d) and sulfated olefins (obtained by sulfating C12-18 olefins, followed by neutralization) (C1-3e), among others.
As preferred specific examples of (C1-3), there may be mentioned Turkey red oil, sulfated beef tallow, sulfated peanut oil, sulfated butyl oleate salts and sulfated butyl ricinoleate salts, among others.
As the phosphate esters (salts) (C1-4), there may be mentioned C8-24 higher alcohol phosphoric acid (mono-, di-)esters (salts) (C1-4a) and C8-24 higher alcohol-AO adduct phosphoric acid (mono-, di-)esters (salts) (C1-4-b), among others. The higher alcohols constituting these may be natural product-derived ones or synthetic ones. Preferred among these are C8-18 higher alcohol-AO adduct phosphoric acid (mono-, di-)esters (salts).
AO to be used in preparing (C1-4b) includes EO, propylene oxide (hereinafter, “PO” for short) and butylene oxide. Preferred among them are EO and PO. The number of moles of the AO added per mole of the higher alcohol is generally 1 to 50 moles, preferably 1 to 20 moles.
As preferred specific examples of (C1-4), there may be mentioned octyl alcohol phosphoric acid monoester potassium salt, octyl alcohol phosphoric acid diester dipotassium salt, lauryl alcohol phosphoric acid monoester monopotassium salt, lauryl alcohol phosphoric acid diester dipotassium salt, isostearyl alcohol-EO (5 moles) adduct phosphoric acid monoester potassium salt and isostearyl alcohol-EO (5 moles) adduct phosphoric acid diester dipotassium salt, among others.
In cases where the anionic surfactants (C1) take the form of salts, the salts are generally the sodium salt, potassium salt, ammonium salt and alkanolamine (e.g. monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine) salts. Among these, the sodium salt, potassium salt and alkanolamine salts are preferred.
Preferred as the cationic surfactants (C2) are, for example, quaternary ammonium salt type cationic surfactants (C2-1) represented by the general formula (3) and amine salt type cationic surfactants (C2-2) represented by the general formula (4).
[In the above formulae, R4, R5 and R6 each independently represents a group selected from among C1-24 alkyl or hydroxyalkyl groups, aryl groups, C2-24 alkenyl groups, polyoxyalkylene groups (number of carbon atoms in each alkylene moiety: 2 to 4) and groups represented by R8—T-R9— (in which R8 represents a residue derived from a C1-24 fatty acid by removal of a COOH group, R9 represents a C1-4 alkylene group or hydroxylaklylene group, and T represents —COO— or —CONH—), R7 represents a C1-24 alkyl or hydroxyalkyl group, a C2-24 alkenyl group or a polyoxyalkylene group (number of carbon atoms in each alkylene moiety: 2 to 4); any two of R4, R5 and R6 may be bound to each other to form, together with N, a heterocyclic or alicyclic compound; Q− represents an inorganic anion or organic anion, and QH represents an inorganic acid or an organic acid.]
The alkyl group containing 1 to 24 carbon atoms, which is represented by R4, R5 and/or R6, may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, a methyl, ethyl, n- and i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, and 2-ethyldecyl groups.
The alkenyl group containing 2 to 24 carbon atoms, which is represented by R4, R5 and/or R6, may be whichever of a straight-chain group or a branched-chain group, and there may be mentioned, for example, an n- and i-propenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, and 2-ethyldecenyl groups.
The C1-24 hydroxyalkyl group represented by R4, R5 and/or R6 may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, hydroxymethyl, hydroxyethyl, n- or iso-hydroxypropyl, hydroxybutyl, hydroxyhexyl, hydroxyoctyl, hydroxydecyl, hydroxydodecyl, hydroxytetradecyl and hydroxyhexadecyl and hydroxyoctadecyl groups.
As the polyoxyalkylene group represented by R4, R5 and/or R6, there may be mentioned the diethylene oxide group, dipropylene oxide group, dibutylene oxide group, triethylene oxide group and tetrapropylene oxide group, among others.
Among those, C8-24 alkyl or hydroxyalkyl groups and C8-24 alkenyl groups are more preferred.
As the heterocycle or alicyclic compound formed by two of R4, R5 and R6 bound to each other, together with N, there may be mentioned, for example, the imidazoline, imidazole, pyridine, pyrimidine, piperidine and morpholine rings, among others.
As the C1-24 alkyl, alkenyl or hydroxyalkyl group or the polyoxyalkylene group represented by R7, there may be mentioned the same ones as mentioned referring to R4, R5 and/or R6. Preferred among them are C1-4 alkyl or hydroxyalkyl groups.
The C1-24 fatty acid constituting the residue R8 may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, stearic acid, isostearic acid, behenic acid and 2-ethylhexanoic acid. Among them, C6-24 fatty acids are preferred, and C6-12 fatty acids are more preferred.
The C1-4 alkylene group represented by R9 may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, methylene, ethylene, n- or isopropylene and butylenes; and the C1-4 hydroxyalkylene group represented thereby may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, hydroxymethylene, hydroxyethylene, n- or isohydroxypropylene and hydroxybutylene.
Among these, C1-4 alkylene groups are preferred, and C2-3 alkylene groups are more preferred.
As the acid QH forming the anion Q− in general formula (3) and as the QH in general formula (4), there may be mentioned the following.
(q1) Inorganic Acids
Hydrohalic acids (hydrochloric acid, bromic acid, iodic acid, etc.), nitric acid, carbonic acid, phosphoric acid, etc.;
(q2) Organic Acids
(q2-a) Alkyl Sulfate Esters
C1-4 alkyl sulfate esters such as methylsulfuric acid and ethylsulfuric acid;
(q2-b) Alkyl Phosphate Esters C1-8 mono- and/or dialkyl phosphate esters such as dimethyl phosphate and diethyl phosphate;
(q2-c) C1-30 Aliphatic Monocarboxylic Acids
Saturated monocarboxylic acids (those mentioned above as fatty acids whose residue constitutes R8), unsaturated monocarboxylic acids (acrylic acid, methacrylic acid, oleic acid, etc.) and aliphatic hydroxycarboxylic acids (glycolic acid, lactic acid, hydroxybutyric acid, hydroxycaproic acid, ricinolic acid, hydroxystearic acid, gluconic acid, etc.);
(q2-d) C7-30 Aromatic or Heterocyclic Monocarboxylic Acids
Aromatic monocarboxylic acids (benzoic acid, naphthoic acid, cinnamic acid, etc.), aromatic hydroxycarboxylic acids (salicylic acid, p-hydroxybenzoic acid, mandelic acid, etc.) and heterocyclic monocarboxylic acids (pyrrolidonecarboxylic acid etc.);
(q2-e) Dibasic to Tetrabasic Polycarboxylic Acids
C2-30 straight or branched aliphatic polycarboxylic acids [saturated polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.), C4-30 unsaturated polycarboxylic acids (maleic acid, fumaric acid, itaconic acid, etc.)]; C4-20 aliphatic hydroxypolycarboxylic acids (malic acid, tartaric acid, citric acid, etc.); C8-30 aromatic polycarboxylic acids [dicarboxylic acids [phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid (2,2′-, 3,3′- and/or 2,7-isomers), etc.], tri- or tetracarboxylic acids (trimellitic acid, pyromellitic acid, etc.)]; sulfur-containing C4-30 polycarboxylic acids (thiodipropionic acid etc.);
(q2-f) C2-36 Amino Acids
Aspartic acid, glutamic acid, cysteic acid and like amino acids;
(q2-g) Organic Acid-Modified Silicones
Organic acids derived from diorganopolysiloxanes by substitution of —RCOOH and/or —RSO3H groups for part of the methyl groups thereof. R is a C2-5 alkylene group. The remaining methyl groups may be substituted by phenyl, C2-20 alkyl or —(CH2)1-Ph (Ph representing a phenyl group and 1 representing an integer of 1 to 4) groups.
(q2-h) Carboxymethylated Aliphatic Alcohols (C8-24)
Carboxymethylated octyl alcohol, carboxymethylated decyl alcohol, carboxymethylated lauryl alcohol and the product of carboxymethylation of tridecanol (e.g. product of KYOWA HAKKO CHEMICAL CO., LTD.), etc.;
(q2-i) Carboxymethylated Aliphatic Alcohol (C8-24)-EO and/or PO (1 to 20 moles) Adducts
Carboxymethylated octyl alcohol-EO (3 moles) adduct, carboxymethylated lauryl alcohol-EO (2.5 moles) adduct, carboxymethylated isostearyl alcohol-EO (3 moles) adduct, carboxymethylated tridecanol-EO (2 moles) adduct, etc.
More preferred among them are methylsulfuric acid, ethylsulfuric acid, adipic acid, gluconic acid, isostearic acid, carboxy-modified silicones having a viscosity at 25° C. of 10 to 8,000 (more preferably 20 to 5,000, particular preferably 30 to 1,000) mm2/s and a carboxy equivalent of 300 to 8,000 (more preferably 400 to 4,000, particularly preferably 500 to 1,500), and carboxymethylated lauryl alcohol-EO (1 to 5 moles) adducts. Isostearic acid is particularly preferred, however.
Preferred as the quaternary ammonium salt type cationic surfactants (C2-1) are alkyl (C1-30) trimethylammonium salts (e.g. inorganic acid salts such as lauryltrimethylammonium chloride; organic acid salts such as lauryltrimethylammonium isostearate and lauryltrimethylammonium carboxy-modified silicone salts, etc.), dialkyl (C1-30)dimethylammonium salts (e.g. didecyldimethylammonium chloride, dioctyldimethylammonium bromide and like inorganic acid salts; didecyldimethylammonium isostearate, di(didecyldimethylammonium) adipate, didecyldimethylammonium carboxy-modified silicone salt, didecyldimethylammonium carboxymethylated lauryl alcohol-EO (1 to 5 moles) adduct salts and like organic acid salts, etc.], nitrogen-containing heterocycle quaternary ammonium salts (e.g. cetylpyridinium chloride etc.), poly(number of moles added: 2 to 15)oxyalkylene(C2-4) chain-containing quaternary ammonium salts [e.g. poly(number of moles added: 3) oxyethylenetrimethylammonium chloride etc.], alkyl (C1-30) amidoalkyl (C1-10) dialkyl (C1-4) methylammonium salts (e.g. stearamidoethyldiethylmethylammonium methosulfate etc.), etc.
Among these, alkyltrimethylammonium organic acid salts are preferred and dialkyldimethylammonium organic acid salts are particularly preferred.
Preferably usable as the amine salt type cationic surfactants (C2-2) are those derived from tertiary amines by neutralization with an inorganic acid (e.g. hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid) or an organic acid (e.g. acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, alkylsulturic acid). More specifically, there may be mentioned inorganic salts or organic salts of C3-90 aliphatic tertiary amines (e.g. triethylamine, ethyldimethylamine, didecylmethylamine, N,N,N′,N′-tetramethylethylenediamine, lauramidopropyldimethylamine, etc.), C3-90 alicyclic (inclusive of nitrogen-containing heterocycles) tertiary amines (e.g. N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, 4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.), C3-90 hydroxyalkyl group-containing tertiary amines (e.g. triethanolamine monostearate ester, N-stearamidoethyldiethanolamine, etc.), etc.
More preferred among these are aliphatic amine inorganic or organic acid salts.
Among such surfactants (C), (C1-1a), (C1-2), (C2-1) and (C2-2) are preferred, and (C1-2) species are particularly preferred.
These (C) species may be used singly or in the form of mixtures of two or more of them.
From the anti-tacking property and smoothening effect viewpoint, the content (mass %) of (A) in the lubricant for treating fibers of the invention is preferably 70 to 99.6, more preferably 75 to 98, particularly preferably 80 to 97.5, based on the total mass of (A)+(B)+(C). Within such ranges, the smoothness is good and there is no possibility of such problems arising as fiber breakage even on the occasion of spinning such fine fibers as 11 to 22 decitex (dtx) fibers.
The content (mass %) of (B) is preferably 0.3 to 10, more preferably 0.5 to 5.0, particularly preferably 1.0 to 4.0, based on the total mass of (A)+(B)+(C). Within such ranges, a good anti-tacking property is produced, the viscosity of the lubricant for treating fibers itself rises little with time, and there is no possibility of such problems arising as fiber breakage even on the occasion of spinning such fine fibers as 11 to 22 dtx fibers.
The content (mass %) of (C) is preferably 0.1 to 20, more preferably 1 to 18, particularly preferably 2 to 15, based on the total mass of (A)+(B)+(C). Within such ranges, (B) will not clog nozzles on the occasion of production using the nozzle oiling system, hence spinning can be carried out stably, and such problems as fiber breakage can be alleviated more preferably.
The mixing ratio ((B)/(C)) by mass between (B) and (C) is preferably 90/10 to 1/99, more preferably 85/15 to 5/95, particularly preferably 67/33 to 10/90, from the viewpoint of the time-dependent stability and the anti-tacking property of the lubricant for treating fibers with time. Within such ranges, the smoothness becomes better and the production using the nozzle oiling system can be carried out stably.
The lubricant for treating fibers of the invention generally has a viscosity at 25° C. of 1 to 500 mm2/s, preferably 2 to 100 mm2/s, more preferably 3 to 50 mm2/s. Within such ranges, good smoothness can be obtained, and the lubricant for treating fibers will hardly scatter in the spinning step and there is no possibility of the work environment being contaminated by the lubricant.
The turbidity at 25° C. of the lubricant for treating fibers of the invention is not particularly restricted but, from the viewpoint of the stability in production using the nozzle oiling system and of the time-dependent stability of the lubricant for treating fibers, it is preferably not higher than 20 mg/L, more preferably not higher than 15 mg/L, particularly preferably not higher than 10 mg/L. From the measurement limit viewpoint, the lower turbidity limit is preferably 0.01 mg/L.
The turbidity can be measured by the integrating sphere photoelectric photometric method (JIS K 0101-1998.9.4., integrating sphere turbidity).
The lubricant for treating fibers of the invention may further contain a further component (D), if necessary, in addition to (A), (B) and (C). As (D), there may be mentioned, for example, an anti-tackiness agent (D1) other than (B), an antistatic agent (D2), a softening agent (D3), and an additive (D4) other than these. The lubricant may contain such an auxiliary solvent (E) as mentioned later herein.
(D1) may be supplementally added at levels at which the performance characteristics of the lubricant for treating fibers of the invention will never be impaired; the supplemental addition can increase the anti-tacking property.
As (D1), there may be mentioned, for example, silicones (D11), polyether-modified silicones (D12), other anti-tackiness agents (D13), all of which occur as solids at ordinary temperature, and combinations of two or more of these. The expression “solids at ordinary temperature” means “solids at 25° C.”.
As the silicones (D11) which occur as solids at ordinary temperature (25° C.), there may be mentioned, for example, polyorganosiloxanes (silicone resins) containing, within the molecule, trifunctional siloxane units or tetrafunctional siloxane units; thus, for example, mention may be made of solid polymers having highly branched three-dimensional structure [e.g. DT resins comprising difunctional siloxane units (D units) and trifunctional siloxane units (T units) as main constituents, MQ resins comprising monofunctional siloxane units (M units) and tetrafunctional siloxane units (Q units) as main constituents, polyorganosilsesquioxanes composed of T units alone, etc.].
Preferred are methylsilicone resins having a weight average molecular weight (as determined by gel permeation chromatography; referred to as “Mw” for short) of 1,000 to 100,000 and amino-modified organopolysiloxane resins having a Mw of 1,000 to 100,000. More preferred are methylsilicone resins having a Mw of 1,500 to 30,000.
As the polyether-modified silicones (D12), there may be mentioned, for example, polyether-modified silicones represented by the following formula (5):
In the above formula, at least one of R10, R11, R12 and R13 is a polyoxyalkylene chain-containing group. The remaining symbol or symbols each may be a methyl group, a C2-20 alkyl group, a phenyl group or a C1-5 alkoxy group.
The polyoxyalkylene group is a group represented by the general formula -A1-O— (A2-O)—R14 wherein R14 is a hydrogen atom or a C1-30 alkyl group; A1 is a C1-5 alkylene group; A2 is a C1-4 alkylene group; A1 and A2 may be the same or different and the repeating units may occur blockwise or randomwise; s represents an integer of 1 to 100. The symbols a and b each represents an integer of 1 to 10,000.
The amount of addition (mass %) of (D1) is preferably not higher than 4, more preferably not higher than 2, based on the weight of the lubricant for treating fibers. Further, the amount of (D1) is preferably not larger than 200 parts by mass, more preferably not larger than 100 parts by mass, per 100 parts by mass of (B).
As the antistatic agent (D2), there may be mentioned, for example, amphoteric surfactants (D21) and nonionic surfactants (D22).
Usable as (D21) are betaine type amphoteric surfactants, amino acid type amphoteric surfactants and sulfonic acid salt type amphoteric surfactants, among others.
Preferred among (D21) are, for example, those represented by the general formula (6), (7) or (8) given below, and mixtures of two or more of them.
In the above formula, R15, R16 and R17 each independently represents a group selected from among a C1-30, alkyl or hydroxyalkyl group, a C2-24 alkenyl group, a polyoxyalkylene group (number of carbon atoms in each alkylene group: 2 to 4) and a group represented by the formula R19-T-R20— (in which R19 represents the residue of a C1-30 fatty acid after removal of the COOH group, R20 represents a C1-4 alkylene or hydroxyalkylene group and T represents —COO— or —CONH—); R18 represents a C1-4 alkylene or hydroxyalkylene group; and X− represents COO— or SO3—.
In the above formulae, R21 represents a C1-30 alkyl or hydroxyalkyl group or a C2-24 alkenyl group; R22 represents a C1-4 alkylene or hydroxyalkylene group; R23 represents a hydrogen atom or a divalent group represented by the formula —R′—COOL1/r; R′ represents a hydrogen atom, a C1-30 alkyl group or a C2-24 alkenyl group; L represents a hydrogen atom, an alkali metal, an alkaline earth metal or an amine cation and, when there are a plurality of L species, they may be the same or different; r represents the valence of L and is 1 or 2.
Specific examples of the C1-30 alkyl groups and of the C2-30 alkenyl groups represented by R15, R16, R17, R21, and/or R23 are the same as those given hereinabove referring R1 and R2 and preferred species are also the same as mentioned hereinabove. The C1-30 hydroxyalkyl group represented by R15, R16, R17 and/or R21 may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, hydroxymethyl, hydroxyethyl, n- or iso-hydroxypropyl, hydroxybutyl, hydroxyhexyl, hydroxyoctyl, hydroxydecyl, hydroxydodecyl, hydroxytetradecyl and hydroxyhexadecyl and hydroxyoctadecyl groups.
As the polyoxyalkylene group represented by R15, R16 and/or R17, there may be mentioned groups represented by the formula R24—(OA3)t— (R24 being a hydrogen atom or a C1-4 alkyl group, A3 being a C2-4 alkylene group and t being an integer of 2 to 15). As the C2-4 alkylene group A3, there may be mentioned 1,2-ethylene, 1,2- and 1,3-propylene, and 1,2-, 2,3-, 1,3- and 1,4-butylene, among others. The C1-4 alkyl group R may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, a methyl, ethyl, n- or isopropyl and butyl groups.
The C1-30 fatty acid constituting the residue R19 in the group represented by R19-T-R20— may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, stearic acid, isostearic acid, behenic acid and 2-ethylhexanoic acid. Among these, C6-24 fatty acids are preferred, and C8-12 fatty acids are more preferred.
The C1-4 alkylene group represented by R20 may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, methylene, ethylene, n- or isopropylene, butylenes; and the C1-4 hydroxyalkylene group may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, hydroxymethylene, hydroxyethylene, n- or isohydroxypropylene, hydroxybutylene. Preferred among them are C1-4 alkylene groups.
Among those mentioned above, C6-24 alkyl or hydroxyalkyl groups, C2-24 alkenyl groups and R9CONHR20 groups are preferred as R15 and R21, C1-24 alkyl or hydroxyalkyl groups and C2-24 alkenyl groups are preferred as 16 and R17, and a hydrogen atom, C1-30 alkyl groups and C2-24 alkenyl groups are preferred as R′.
The C1-4 alkylene group and the hydroxyalkylene group, each represented by R18 and R22 include those respective species mentioned hereinabove referring to R20, and preferred species are also the same as mentioned above.
Among the X— species in the formula (6), COO— is preferred.
R23 is a hydrogen atom or the group —R′—COOL1/r. Preferred as the surfactants of the formula (7) or (8) are mixtures of one in which R23 is a hydrogen atom and one in which R23 is a —R′—COOL1/r group.
As for L, the alkali metal L includes lithium, potassium, sodium, etc.; the alkaline earth metal includes calcium, magnesium, etc.; and the amine cation includes mono-, di- and triethanolamine cation, 2-ethylhexylamine cation, etc. Among such species of L, a hydrogen atom and alkali metals are preferred.
As the betaine type amphoteric surfactant represented by the general formula (6), there may be mentioned, for example, alkyl(C1-30)dimethylbetaine, alkyl(C1-30)amidoalkyl(C1-4)dimethylbetaine, alkyl(C1-30)dihydroxyalkyl(C1-30)betaine, and sulfobetaine amphoteric surfactants. The preferred, among these, are alkyldimethylbetaines and alkylamidoalkyldimethylbetaines.
As the amino acid type amphoteric surfactant represented by the general formula (7), there may be mentioned, for example, alanine type [alkyl(C1-30)aminopropionic acid type and alkyl(C1-30)iminodipropionic acid type, etc.] amphoteric surfactants and glycine type [e.g. alkyl(C1-30)aminoacetic acid type] amphoteric surfactants. Preferred among these are alkylaminopropionic acid type amphoteric surfactants and alkyliminodipropionic acid type amphoteric surfactants.
As the sulfonate type amphoteric surfactant (aminosulfonic acid type amphoteric surfactant) represented by the general formula (8), there may be mentioned, for example, alkyl(C1-30) taurine type amphoteric surfactants.
As the nonionic surfactants (D22), there may be mentioned, for example, those represented by the following general formula (9):
In the above formula, R25 is a C1-24 alkyl group, and specific examples and preferred ones thereof are the same as those alkyl groups mentioned hereinabove referring to R1 and R2. As R26, there may be mentioned C1-5 alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc.). Among such R26 species, C1-3 alkyl groups are preferred. R25 and R26 may be the same or different. As R27, there may be mentioned a hydrogen atom and C1-3 alkyl groups (methyl, ethyl, propyl, isopropyl). The nonionic surfactants (D22) represented by the general formula (9) may be mixtures each including two or more different R27 species. AO is the same as in the general formula (1) (AO)q in the general formula (9) preferably results from single addition of EO or block addition of EO and PO, particularly preferably from single addition of EO. The symbol q represents an integer of 0 or 1 to 10, preferably 1 to 6.
When q is within such ranges, the compatibility with the base oil is good.
As specific examples of (D22) represented by general formula (9), there may be mentioned C3-33 secondary alcohol-EO and/or PO adducts, and preferably secondary alcohol (C13)-EO (3 mol) adduct, secondary alcohol(C13)-EO(5 mol) adduct, secondary alcohol(C13)-EO(7 mol) adduct, secondary alcohol(C13)-EO(9 mol) adduct, secondary alcohol(C15)-EO(3 mol) adduct, secondary alcohol(C15)-EO(5 mol) adduct, secondary alcohol(C11)-EO(5 mol) adduct, secondary alcohol(C18)-EO(5 mol) adduct, secondary alcohol(C24)-EO(5 mol) adduct, secondary alcohol (C18)-EO(3 mol)/PO(2 mol) block adduct, secondary alcohol(C24)-EO(5 mol)/PO(3 mol) block adduct.
(D22) may be used independently or as a mixture of 2 or more different species.
In cases where such an antistatic agent (D2) is used, the content (mass %) of (D2) is preferably 0 to 12, more preferably 0.1 to 10, based on the mass of the lubricant for treating fibers.
As the softening agent (D3), there may be mentioned, for example, epoxy-modified silicones (131), amino-modified silicones (D32) and carboxyl-modified silicones (D33).
(D31) may be represented by the general formula (5) given hereinabove in which at least one of R10, R11, R12 and R13 is an epoxy group-containing group. The remaining group or groups each may be a methyl group, a C2-20 alkyl group, a phenyl group or a C1-5 alkoxy group, and a and b each is an integer of 1 to 1,000.
The epoxy group-containing group may be represented by the general formula (10) given below (in which R28 is C1-4 alkylene group) and, for example, a glycidyl group.
(D32) may be represented by the general formula (5) given hereinabove in which at least one of R10, R11, R12 and R13 is an —R29—NH(R30NH)nH group-containing group (in which R29 is a C1-5 alkylene group, R30 is a C1-4 alkylene group and n is an integer of 0 or 1 to 3). The remaining group or groups each may be a methyl group, a C2-20 alkyl group, a phenyl group or a C1-5 alkoxy group, and a and b each is an integer of 1 to 10,000.
(D33) may be represented by the general formula (5) given hereinabove in which at least one of R10, R11, R12 and R13 is an —R3—COOL1/r group-containing group [in which R31 is a C1-5 alkylene group and L and r are as defined above referring to the general formula (7)]. The remaining group or groups each may be a methyl group, a C2-20 alkyl group, a phenyl group or a C1-5 alkoxy group, and a and b each is an integer of 1 to 10,000.
The C2-20 alkyl group in (D31) to (D33) may be whichever of a straight-chain group and a branched chain group, and there may be mentioned, for example, an ethyl, n- and i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and 2-ethyldecyl groups.
As the C1-5 alkoxy group, there may be mentioned, for example, a methoxy, ethoxy, n- or isopropoxy, and butoxy groups.
As the C1-4 alkylene group, there may be mentioned those given hereinabove referring to R18 and, as the C5 alkylene group, there may be mentioned 1,2-, 1,3-, 1,4-, 2,3-and-2,4-pentylene.
In cases where such a softening ingredient (D3) is used, the content (mass %) of (D3) is preferably 0 to 12, more preferably 0.1 to 10, based on the mass of the lubricant for treating fibers.
Usable as the additive (D4) other than those mentioned hereinabove are those ingredients generally used in lubricants for treating fibers, including antioxidants (hindered phenols, hindered amines, etc.) and ultraviolet absorbers, among others.
In cases where such additives are used, the amount of addition (mass %) of (D4) is preferably 0 to 5, more preferably 0 to 2, based on the mass of the lubricant for treating fibers.
The lubricant for treating fibers of the invention can also be prepared by mixing the anti-tackiness agent (B) dissolved in auxiliary solvent (E) with the base oil (A), surfactant (C) and so forth.
As the auxiliary solvent (E), there may be mentioned, for example, monohydric alcohols such as methanol, ethanol, propanol, butanol, pentyl alcohol, neopentyl alcohol, 2-ethylhexyl alcohol, etc.; dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, etc.; aliphatic hydrocarbons such as hexane, pentane, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; high-polar solvents such as dimethylformamide, dimethyl sulfoxide, etc.; and halogenated hydrocarbons such as chloroform, carbon tetrachloride and so forth, and they may be used independently or as a mixture of 2 or more different species.
It is to be understood that when a hydrocarbon-based lubricating oil (A2) is used as the base oil (A), (E) may be used as at least a partial constituent of (A). (E) may be formulated as it is in the lubricant of the invention or may be removed by stripping, for instance.
The technology for producing the lubricant for treating fibers of the invention there may be mentioned the following method as an example.
(1) The method comprising charging a reaction vessel capable of temperature control and stirring with (B), together with (A2) and (C), heating the mixture (50 to 100° C.), stirring the same until it becomes transparent (turbidity not higher than 20 mg/L), and then adding (A1), if necessary, with stirring, followed by cooling to room temperature (20 to 40° C.).
(2) The method comprising charging a reaction vessel capable of temperature control and stirring with (A2) and (C), heating the mixture (40 to 100° C.), adding (B) separately melted (100 to 250° C.) or dissolved in the auxiliary solvent (E) dropwise with stirring, and, if necessary, adding (A1) with stirring, followed by cooling to room temperature (20 to 40° C.).
Among these methods, the method (1) is more preferred from the viewpoint of the time-dependent stability of the lubricant for treating fibers of the invention obtained and from the anti-tackiness viewpoint.
When such a metal salt as mentioned above is used as (B), the metal salt may be one prepared in advance or may be formed during or after lubricant preparation by such a method as mentioned above by reacting with another metal salt (e.g. such a metal oxide or chloride as mentioned above).
While the lubricant for treating fibers obtained in the above manner, as such, may be used as the lubricant for treating fibers of the invention, the lubricant for treating fibers of the invention may also be prepared by supplementarily adding (D) and/or (E) according to need on the occasion of charging of (A1).
For uniform application and preventing roller wrap-up, the viscosity of the lubricant for treating fibers of the invention is preferably set to 1 to 500 mm2/s at 25° C.
The viscosity is measured by the following method.
A sample of the lubricant for treating fibers is placed in a 20 g Ubbelohde viscometer and the sample temperature is adjusted to 25±0.5° C. in a constant-temperature water bath. After 30 minutes, the viscosity is measured by the method of Ubbelohde.
As to the application mode of the lubricant for treating fibers, the lubricant may generally be used in an anhydrous form but, where necessary, be used in the form of an aqueous emulsion.
The use of the anhydrous form means the use of the lubricant as it is (straight lubrication), the use thereof as diluted with a diluent (e.g. an organic solvent or a low-viscosity mineral oil), or the like. The dilution ratio is not particularly restricted but the mass of the lubricant for treating fibers of the invention (total mass of monovolatile matter] is generally 1 to 80 mass %, preferably 5 to 70 mass %, based on the total mass of the diluted lubricant.
As the organic solvent, there may be mentioned, for example, the same ones as the auxiliary solvent mentioned above. As the low-viscosity mineral oil mentioned above, there may be mentioned, for example, liquid paraffin and purified spindle oil whose viscosities at 25° C. are less than 1 mm2/s.
The aqueous emulsion mentioned above can be prepared by known emulsification techniques; for example, the lubricant of the invention is optionally mixed with an emulsifier in advance and then emulsified in water.
Depending on the types of (A) and (C), the emulsifier need not necessarily be added but said anionic surfactant, cationic surfactant, and amphoteric surfactant, for instance, can be used.
The amount of use (mass %) of the emulsifier other than the emulsifiers corresponding to the above respective components is preferably 0 to 50% based on the total mass of the lubricant for treating fibers (nonvolatile matter) after formulation with the emulsifier.
As the emulsifying machine which is to be used in emulsification, there may be mentioned, for example, an emulsification tank equipped with a stirrer, a ball mill, a Gaulin homogenizer, a Homo-disper, and a bead mill.
The concentration of the emulsion is not particularly restricted but the mass (mass %) of the lubricant for treating fibers is preferably 0.01 to 30, more preferably 0.2 to 20, based on the total mass of the emulsion obtained by the above emulsification.
The method of elastic fiber treatment according to the invention consists in applying, in the spinning step, 0.1 to 20 mass % of the lubricant for treating fibers mentioned above relative to the elastic fiber.
The lubricant for treating fibers of the invention can be applied to fiber by the nozzle or roller oiling system in the elastic fiber spinning step (e.g. 200 to 1,200 m/min) in an arbitrary position downstream of the spinneret and upstream of the wind-up gear. The temperature of the lubricant for treating fibers to be fed is generally 10 to 80° C., preferably 15 to 60° C.
The amount of deposition of the lubricant for treating fibers according to the invention is preferably 0.1 to 12 mass % (more preferably 0.5 to 10 mass %, particularly preferably 1 to 8 mass %) as the nonvolatile matter relative to the elastic fiber.
The elastic fiber treated with the lubricant for treating fibers of the invention is processed into end-products through various post-processing (e.g. core-spun yarn step, covering step, air-covering step, knitting step, warping step, scouring step, dyeing step, and finishing step).
The elastic fiber can be blended with other synthetic fibers such as nylon fibers and polyester fibers. Therefore, after application of the lubricant for treating fibers according to the invention, the lubricant deposited is often washed and removed together with the spinning lubricant used for the other synthetic fiber. In the scouring step, aqueous scouring or solvent scouring is carried out.
Referring to end-products, the invention can be applied broadly to clothing [e.g. pantyhoses, socks, inner foundation (brassieres, girdles, bodysuits, etc.), outerware (jackets, slacks, etc.), sportsware (swimsuits, leotards, ski pants, etc.), etc.] and industrial materials (e.g. paper diapers, belts, and so forth).
The lubricant for treating fibers of the invention is excellent in anti-tackiness property against fiber-to-fiber tackiness on the occasion of fiber production and, further, in time-dependent stability and can be uniformly applied to the fiber surface, so that it produces such effect that stable rewindability can be maintained under high-speed conditions. Therefore, it is very effective as a lubricant for treating fibers for polyurethane elastic fibers showing a particularly marked tendency toward tacking.
The following examples are further illustrative but these examples are by no means definitive of the present invention. All parts in the text and table are parts by mass (active substance).
A powder (71.2 parts) of low-molecular-weight polypropylene with a Mn of 2,500 and a density of 0.89 as obtained by the thermal degradation method was dispersed in 500 ml of tetrahydrofuran (THF), 6.5 parts of 9-borabicyclononane was added, and the mixture was heated at 55° C. for 5 hours with stirring. The temperature was lowered to 45° C., 30 ml of oxygen was passed through the liquid, 22.3 parts of maleic anhydride was added, and the reaction was allowed to proceed for 16 hours. Thereafter, the reaction mixture was poured into 5 liters of 2-propanol, the solid was filtered off to give acid-modified polypropylene [acid value: 335.1, Mn: 3,000, number of carboxyl groups per molecule: 16.0].
According to the recipes shown in Table 1, various components were formulated and processed to prepare lubricants for treating fibers of the invention and Comparative Examples.
A mixture of 1 part of magnesium distearate, 2 parts of polyoxyethylene isotridecyl ether-acetic acid sodium salt (adduct with 3 moles of EO), 4 parts of polyoxyethylene lauryl ether-acetic acid (adduct with 2.5 moles of EO), 2 parts of didecyldimethylammonium polyoxyethylene lauryl ether-acetate (adduct with 2.5 moles of EO) and 60 parts of liquid paraffin was stirred at 70 to 80° C. for 1 hour. Then, 31 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Example 1 was prepared.
A mixture of 2 parts of magnesium distearate, 3 parts of polyoxyethylene isotridecyl ether-acetic acid sodium salt (adduct with 3 moles of EO), 6 parts of polyoxyethylene lauryl ether-acetic acid (adduct with 2.5 moles of EO), 3 parts of didecyldimethylammonium polyoxyethylene lauryl ether-acetate (adduct with 2.5 moles of EO) and 68 parts of liquid paraffin was stirred at 70 to 80° C. for 1 hour. Then, 18 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Example 2 was prepared.
A mixture of 4 parts of magnesium distearate, 3 parts of polyoxyethylene isotridecyl ether-acetic acid sodium salt (adduct with 3 moles of EO), 8 parts of polyoxyethylene lauryl ether-acetic acid (adduct with 2.5 moles of EO), 4 parts of didecyldimethylammonium polyoxyethylene lauryl ether-acetate (adduct with 2.5 moles of EO) and 64 parts of liquid paraffin was stirred at 80 to 90° C. for 1 hour. Then, 17 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Example 3 was prepared.
A mixture of 1.0 part of an α-olefin/maleic anhydride copolymer (product of Mitsubishi Chemical Corporation, “Diacarna 30L”, Mn; about 3,000, acid value (mg KOH/g); 120 to 140), 2 parts of polyoxyethylene isotridecyl ether-acetic acid sodium salt (adduct with 3 moles of EO), 4 parts of polyoxyethylene lauryl ether-acetic acid (adduct with 2.5 moles of EO), 2 parts of didecyldimethylammonium polyoxyethylene lauryl ether-acetate (adduct with 2.5 moles of EO) and 60 parts of liquid paraffin was stirred at 60 to 70° C. for 1 hour. Then, 31 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Example 4 was prepared.
A mixture of 1.0 part of the acid-modified polypropylene produced in Production Example 1, 2 parts of polyoxyethylene isotridecyl ether-acetic acid sodium salt (adduct with 3 moles of EO), 4 parts of polyoxyethylene lauryl ether-acetic acid (adduct with 2.5 moles of EO), 2 parts of didecyldimethylammonium polyoxyethylene lauryl ether-acetate (adduct with 2.5 moles of EO) and 60 parts of liquid paraffin was stirred at 60 to 70° C. for 1 hour. Then, 31 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Example 5 was prepared.
A mixture of 4 parts of polyether-modified silicone (product of Shin-Etsu Chemical Co., Ltd., “KF-351”) and 65 parts of liquid paraffin was stirred at 60 to 70° C. for 1 hour. Then, 31 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Comparative Example 1 was prepared.
A mixture of 1 part of magnesium distearate, 0.2 parts of polyoxyethylene isotridecyl ether-acetic acid sodium salt (adduct with 3 moles of EO), 0.4 parts of polyoxyethylene lauryl ether-acetic acid (adduct with 2.5 moles of EO), 0.2 parts of didecyldimethylammonium polyoxyethylene lauryl ether-acetate (adduct with 2.5 moles of EO) and 80.2 parts of liquid paraffin was stirred at 70 to 80° C. for 1 hour. Then, 18 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Comparative Example 2 was prepared.
A mixture of 2 part of magnesium distearate and 93 parts of liquid paraffin was stirred at 115 to 120° C. for 1 hour. Then, 5 parts of polydimethylsiloxane was added, and the resulting mixture was cooled to 30° C., whereby the lubricant for treating fibers of Comparative Example 3 was prepared.
In the dry spinning process for the production of polyurethane fiber, each lubricant for treating fibers of Examples 1 to 5 and Comparative Examples 1 to 3 was applied by the roller oiling system in a deposition amount of 6 mass % based on the mass of filament and the lubricant for treating fibers was taken up into a cheese form at a rate of 600 m/min to give a 40D (44.4 dtx) polyurethane fiber.
Further, the polyurethane fibers obtained as described above were subjected to testing for tackiness, and the lubricants for treating fibers to testing for time-dependent stability. The performance evaluation results are shown collectively in Table 1. In the table, the angle of contact with water was measured as follows: the fibers were dissolved in DMF to a concentration of 40 mass % and then molded into a sheet by the method mentioned hereinabove and, using this and following the method described hereinabove, the lubricant for treating fibers was applied thereto and the measurement was made (the angle of contact with water of the sheet surface without application of any lubricant for treating fibers was 50°). Further, the viscosity, at 25° C., of each lubricant for treating fibers as measured by an Ubbelohde viscometer and the turbidity, at 2.5° C., of each lubricant for treating fibers as measured using Water Analyzer-2000, which is a product of NIPPON DENSHOKU INDUSTRIES CO., LTD., are shown in Table 1. The methods used were as described later herein.
The viscosity measurement method, turbidity measurement method, time-dependent stability testing method for the lubricants for treating fibers obtained, and the tackiness testing method for the fibers applied with the lubricants for treating fibers obtained, in Examples 1 to 5 and Comparative Example 1 to 3, are as follows.
A sample of the lubricant for treating fibers is placed in a 20 g Ubbelohde viscometer and the temperature of the sample of the lubricant for treating fibers is adjusted to 25° C. in a constant-temperature water bath. After 30 minutes, the viscosity is measured by the method of Ubbelohde.
Each lubricant for treating fibers adjusted to a temperature of 25° C. was placed in a 10-mm-long cell and the turbidity was measured by integrating sphere photoelectric photometry using Water Analyzer-2000, which is a product of NIPPON DENSHOKU INDUSTRIES CO., LTD.
100 g of the prepared lubricant for treating fibers was put in a glass bottle of 145 ml capacity and allowed to stand in an incubator at −5° C., 25° C. or 50° C. for 30 days. The appearance of the lubricant for treating fibers was then visually examined, compared with the appearance of the lubricant for treating fibers immediately after preparation, and evaluated according to the following criteria.
Excellent: no change
Fair: no separation of layers nor sedimentation, but high degree of blur immediately after the preparation of the lubricant for treating fibers
Poor: separation of layers and/or sedimentation
The cheese obtained in the spinning step was subjected to 2-week-long aging at 50° C. and the aged fiber was supplied to a rewind/wind-up device with a variable speed ratio function (the ratio of wind-up speed/rewind speed is variable). The fiber was paid out at a rate of 50 m/min and the minimum speed in which the fiber could be taken up without wrap-up by tackiness was determined. The anti-tacking property was evaluated according to the following criteria.
Excellent: speed=50 to 65
Poor: speed≧66
The particulars of the components shown in Table 1 are as follows.
Polydimethylsiloxane: KF96-10CS (viscosity: 10 mm2/s (25° C.)) (product of Shin-Etsu Chemical Co., Ltd.)
Liquid paraffin: Liquid Paraffin 60S (viscosity: 15 mm2/s (25° C.) (product of Sanko Chemical Industry Co., Ltd.)
Surfactant-1: polyoxyethylene isotridecyl ether-acetic acid sodium salt (adduct with 3 moles of EO)
Surfactant-2: polyoxyethylene lauryl ether-acetic acid (adduct with 2.5 moles of EO)
Surfactant-3: didecyldimethylammonium polyoxyethylene lauryl ether-acetate (adduct with 2.5 moles of EO)
As is evident from Table 1, it was found that the lubricants for treating fibers (Examples 1 to 5) showing a contact angle within the range specified according to the invention are particularly excellent in anti-tackiness property. On the contrary, none among Comparative Examples 1 to 3 satisfied the anti-tackiness requirement. It is seen that the lubricants for treating fibers of Examples are also excellent in time-dependent stability.
The lubricant for treating fibers of the invention is excellent in anti-tackiness property against fiber-to-fiber tackiness and, further, excellent in time-dependent stability, so that the operation in the spinning step using the nozzle oiling system in the production of elastic fibers can be stably carried out while avoiding nozzle clogging. Further, the lubricant has a marked characteristic feature in that it can alleviate such troubles as fiber breakage in both the roller oiling and nozzle oiling spinning steps; thus, it is suited for use in the step of high-speed spinning of small-decitex fibers, in particular.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2004-148699 | May 2004 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2005/009069 | 5/18/2005 | WO | 00 | 12/12/2007 |
