Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/001—Modification of pulp properties
  • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
  • C10M101/02—Petroleum fractions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/50—Lubricating compositions characterised by the base-material being a macromolecular compound containing silicon
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/26—Carboxylic acids; Salts thereof
  • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms

Definitions

• 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.
• a lubricant for treating fibers in the spinning step in elastic fiber production 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.
• 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.
• 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.
• 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.
• the present invention relates to
• a lubricant for treating fibers to be used for fibers made of a polymer material (a)
• 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°,
• 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.
• highly polar groups e.g. amide, ester, urea and/or urethane groups
• 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.
• 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.
• 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 cm 3 in volume) and spread so that the whole resin solution may become even.
• a 40% (by mass) solution e.g. in dimethylformamide (DMF)
• test specimen sheets (a1) of the polymer material (a) can be obtained.
• Each sheet (a1) (e.g. about 200 ⁇ m 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) are measured in the same manner.
• 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).
• A base oil
• A1 silicone oils
• A2 hydrocarbon-based lubricating oils
• B anti-tackiness agent
• C surfactant
• silicone oils (A1) are polydimethylsiloxane, and partially C 2 -C 20 alkyl- and/or phenyl-substituted polydimethylsiloxane, among others.
• hydrocarbon-based lubricating oils are mineral oils, purified mineral oils, hydrogenated mineral oils and cracked mineral oils, among others.
• base oils having a viscosity at 25° C. of 1 to 1,000 mm 2 /s, more preferably 2 to 500 mm 2 /s, particularly preferably 3 to 200 mm 2 /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).
• anti-tackiness agent (B) there may be mentioned compounds containing at least one carboxyl group and/or carboxylate group within the molecule.
• 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.
• 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.
• magnesium distearate is most preferred.
• 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.
• higher fatty acids or metal salts thereof namely the higher fatty acids (salts) (B1)
• higher fatty acids (salts) (B1) may be used singly or in the form of a mixture of two or more of them.
• 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.
• 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.
• metal salts of these e.g. maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), citraconic acid (anhydride), etc.
• 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).
• water-insoluble unsaturated monomers (Y2) there may be mentioned:
• glycidyl (meth)acrylate etc. ⁇ , etc.] (Y2-2): Polypropylene glycols (polymerization degree: 2 to 50) [mono (C 1-20 )alkyl, mono (C 3-12 ) cycloalkyl or monophenyl ether] unsaturated carboxylic acid monoesters [monool or diol-propyleneoxide (hereinafter, “PO” for short) adducts, for example (C 1-20 ) monool PO adduct (meth)acrylic acid esters [ ⁇ -methoxypoly-propylene glycol mono(meth)acrylate, ⁇ -ethoxypolypropylene glycol mono(meth)acrylate, ⁇ -propoxypolypropylene glycol mono(meth)acrylate, ⁇ -butoxypolypropylene glycol mono(methacrylate, ⁇ -cyclohexylpolypropylene glycol mono(meth)acrylate, ⁇ -phenoxy
• ethylene, propylene, ⁇ -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.
• 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).
• (B2-1) such known techniques as radical polymerization, anionic polymerization and cationic polymerization may be employed.
• (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.
• a polymerization solvent e.g. an organic solvent or water
• polymerization catalyst 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-Fe 2+ salt and azo compounds.
• 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.
• protic acids e.g. sulfuric acid, phosphoric acid, perchloric acid, etc.
• Lewis acids e.g. boron trifluoride, aluminum chloride, titanium tetrachloride, tin tetrachloride, etc.
• anionic polymerization catalysts there may be mentioned sodium hydroxide, potassium hydroxide, sodium methoxide, butyllithium, pyridine, Ziegler catalysts and Ziegler-Natta catalysts (e.g. (C 2 H 5 ) 3 Al—TiCl 4 etc.), among others.
• polystyrene resin 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.).
• (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).
• C 2-30 olefins or dienes are those species enumerated hereinabove. Among them, ethylene, propylene, C 4-12 ⁇ -olefins, butadiene and isoprene are preferred, ethylene, propylene, C 4-8 ⁇ -olefins and butadiene are more preferred, and ethylene, propylene and butadiene are particularly preferred.
• 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.
• olefins containing 2 to 30 (preferably 2 to 12, more preferably 2 to 10) carbon atoms.
• C 2-30 olefins are the same ones as those enumerated hereinabove and, among them, ethylene, propylene and C 4-12 ⁇ -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.
• 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.
• Mn values of (a0), (aI) and (aII) are determined by gel permeation chromatography using the following measuring apparatus and measurement conditions.
• modified polyolefins (aII) resulting from higher order modification (secondary modification, tertiary modification, etc.)
• 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 ⁇ , ⁇ -unsaturated carboxylic acid (anhydride) as described above under (3) can be carried out by thermally adding an ⁇ , ⁇ -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 ⁇ , ⁇ -unsaturated carboxylic acid (anhydride) with (a0) is generally 170 to 230° C.
• the number of molecules of the ⁇ , ⁇ -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 ⁇ , ⁇ -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 ⁇ , ⁇ -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.
• ⁇ , ⁇ -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 ⁇ , ⁇ -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 ⁇ , ⁇ -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 C 6-12 lactams, for example caprolactam, enantholactam, laurolactam and undecanolactam;
• the aminocarboxylic acid includes C 2-12 aminocarboxylic acids, for example amino acids such as glycine, alanine, valine, leucine, isoleucine and phenylalanine, ⁇ -aminocaproic acid, ⁇ -aminoenanthic acid, ⁇ -aminocaprylic acid, ⁇ -aminopelargonic acid, ⁇ -aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid;
• the lactone includes those lactones which correspond to the lactams mentioned above (e.g.
• the hydroxycarboxylic acid includes C 2-12 aliphatic hydroxycarboxylic acids, for example glycolic acid, lactic acid, ⁇ -hydroxycaproic acid, ⁇ -hydroxyenanthic acid, ⁇ -hydroxycaprylic acid, ⁇ -hydroxypelargonic acid, ⁇ -hydroxycapric acid, 11-hydroxyundecanoic acid and 12-hydroxydodecanoic acid.
• C 6-8 lactams and C 8-12 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.
• (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.
• 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.
• the volume average particle diameter is the value determined by the dynamic light scattering method.
• 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.
• SP value solubility parameter
• 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.
• ⁇ E coherent energy density
• V molecular volume
• (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).
• C1-1 As the sulfonic acids (salts) (C1-1), there may be mentioned C1-24 alcohol sulfosuccinic acid (mono-, di-) esters (salts) (C1-1A), C 8-24 ⁇ -olefin sulfonation products (salts) (C1-1B), C 8-14 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).
• R 1 and R 2 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 R 1 and/or R 2 , 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 R 1 and/or R 2 , 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.
• R 1 and R 2 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.
• R 1 and R 2 may be the same or different.
• 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.
• n, and m+n each respectively represents an integer of 0 or 1 to 6, preferably an integer of 0 or 1 to 3.
• 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.
• EO 6 mol ethylene oxide
• carboxylic acids salts
• 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.
• R 3 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.
• specific examples and preferred species of the C 1-24 alkyl groups and C 2-24 alkenyl groups represented by R 3 are the same as those given hereinabove referring to R 1 and R 2 .
• 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.
• 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 carb
• 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.
• sulfate esters (salts) there may be mentioned higher alcohol sulfate esters (salts) [C 8-18 aliphatic alcohol sulfate esters (salts)] (C1-3a), higher alkyl ether sulfate esters (salts) [C 8-18 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 C 12-18 olefins, followed by neutralization) (C1-3e), among others.
• (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.
• C1-4 As the phosphate esters (salts) (C1-4), there may be mentioned C 8-24 higher alcohol phosphoric acid (mono-, di-)esters (salts) (C1-4a) and C 8-24 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 C 8-18 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.
• (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.
• the salts are generally the sodium salt, potassium salt, ammonium salt and alkanolamine (e.g. monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine) salts.
• alkanolamine e.g. monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine
• the sodium salt, potassium salt and alkanolamine salts are preferred.
• 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).
• R 4 , R 5 and R 6 each independently represents a group selected from among C 1-24 alkyl or hydroxyalkyl groups, aryl groups, C 2-24 alkenyl groups, polyoxyalkylene groups (number of carbon atoms in each alkylene moiety: 2 to 4) and groups represented by R 8 —T-R 9 — (in which R 8 represents a residue derived from a C 1-24 fatty acid by removal of a COOH group, R 9 represents a C 1-4 alkylene group or hydroxylaklylene group, and T represents —COO— or —CONH—), R 7 represents a C 1-24 alkyl or hydroxyalkyl group, a C 2-24 alkenyl group or a polyoxyalkylene group (number of carbon atoms in each alkylene moiety: 2 to 4); any two of R 4 , R 5 and R 6 may be bound to each other to form, together with N, a heterocyclic or alicyclic compound; Q
• the alkyl group containing 1 to 24 carbon atoms which is represented by R 4 , R 5 and/or R 6 , 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 R 4 , R 5 and/or R 6 , 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 C 1-24 hydroxyalkyl group represented by R 4 , R 5 and/or R 6 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.
• R 4 , R 5 and/or R 6 there may be mentioned the diethylene oxide group, dipropylene oxide group, dibutylene oxide group, triethylene oxide group and tetrapropylene oxide group, among others.
• C 8-24 alkyl or hydroxyalkyl groups and C 8-24 alkenyl groups are more preferred.
• heterocycle or alicyclic compound formed by two of R 4 , R 5 and R 6 bound to each other, together with N there may be mentioned, for example, the imidazoline, imidazole, pyridine, pyrimidine, piperidine and morpholine rings, among others.
• alkenyl or hydroxyalkyl group or the polyoxyalkylene group represented by R 7 there may be mentioned the same ones as mentioned referring to R 4 , R 5 and/or R 6 .
• Preferred among them are C 1-4 alkyl or hydroxyalkyl groups.
• the C 1-24 fatty acid constituting the residue R 8 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.
• C 6-24 fatty acids are preferred, and C 6-12 fatty acids are more preferred.
• the C 1-4 alkylene group represented by R 9 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 C 1-4 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.
• C 1-4 alkylene groups are preferred, and C 2-3 alkylene groups are more preferred.
• Hydrohalic acids hydrohalic acid, bromic acid, iodic acid, etc.), nitric acid, carbonic acid, phosphoric acid, etc.;
• C 1-4 alkyl sulfate esters such as methylsulfuric acid and ethylsulfuric acid
• Saturated monocarboxylic acids (those mentioned above as fatty acids whose residue constitutes R 8 ), 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.);
• 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.);
• C 2-30 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.), C 4-30 unsaturated polycarboxylic acids (maleic acid, fumaric acid, itaconic acid, etc.)]; C 4-20 aliphatic hydroxypolycarboxylic acids (malic acid, tartaric acid, citric acid, etc.); C 8-30 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, p
• Aspartic acid glutamic acid, cysteic acid and like amino acids
• R is a C 2-5 alkylene group.
• the remaining methyl groups may be substituted by phenyl, C 2-20 alkyl or —(CH 2 ) 1 -Ph (Ph representing a phenyl group and 1 representing an integer of 1 to 4) groups.
• 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.
• 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.
• methylsulfuric acid 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) mm 2 /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.
• quaternary ammonium salt type cationic surfactants are alkyl (C 1-30 ) 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 (C 1-30 )dimethylammonium salts (e.g.
• cetylpyridinium chloride etc. poly(number of moles added: 2 to 15)oxyalkylene(C 2-4 ) chain-containing quaternary ammonium salts [e.g. poly(number of moles added: 3) oxyethylenetrimethylammonium chloride etc.], alkyl (C 1-30 ) amidoalkyl (C 1-10 ) dialkyl (C 1-4 ) methylammonium salts (e.g. stearamidoethyldiethylmethylammonium methosulfate etc.), etc.
• quaternary ammonium salts e.g. poly(number of moles added: 3) oxyethylenetrimethylammonium chloride etc.
• alkyl (C 1-30 ) amidoalkyl (C 1-10 ) dialkyl (C 1-4 ) methylammonium salts e.g. stearamidoethyldiethylmethylammonium methosulfate etc.
• alkyltrimethylammonium organic acid salts are preferred and dialkyldimethylammonium organic acid salts are particularly preferred.
• 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 C 3-90 aliphatic tertiary amines (e.g.
• C 3-90 alicyclic (inclusive of nitrogen-containing heterocycles) tertiary amines e.g. N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, 4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.
• C 3-90 hydroxyalkyl group-containing tertiary amines e.g. triethanolamine monostearate ester, N-stearamidoethyldiethanolamine, etc.
• More preferred among these are aliphatic amine inorganic or organic acid salts.
• surfactants (C), (C1-1a), (C1-2), (C2-1) and (C2-2) are preferred, and (C1-2) species are particularly preferred.
• 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).
• 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 mm 2 /s, preferably 2 to 100 mm 2 /s, more preferably 3 to 50 mm 2 /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).
• a further component (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.
• solids at ordinary temperature means “solids at 25° C.”.
• silicones (D11) which occur as solids at ordinary temperature (25° C.)
• polyorganosiloxanes silicone resins
• T units trifunctional siloxane units
• MQ resins monofunctional siloxane units
• Q units tetrafunctional siloxane units
• 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.
• polyether-modified silicones (D12) there may be mentioned, for example, polyether-modified silicones represented by the following formula (5):
• R 10 , R 11 , R 12 and R 13 is a polyoxyalkylene chain-containing group.
• the remaining symbol or symbols each may be a methyl group, a C 2-20 alkyl group, a phenyl group or a C 1-5 alkoxy group.
• the polyoxyalkylene group is a group represented by the general formula -A 1 -O— (A 2 -O)—R 14 wherein R 14 is a hydrogen atom or a C 1-30 alkyl group; A 1 is a C 1-5 alkylene group; A 2 is a C 1-4 alkylene group; A 1 and A 2 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).
• antistatic agent (D2) there may be mentioned, for example, amphoteric surfactants (D21) and nonionic surfactants (D22).
• (D21) Usable as (D21) are betaine type amphoteric surfactants, amino acid type amphoteric surfactants and sulfonic acid salt type amphoteric surfactants, among others.
• (D21) 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.
• R 15 , R 16 and R 17 each independently represents a group selected from among a C 1-30 , alkyl or hydroxyalkyl group, a C 2-24 alkenyl group, a polyoxyalkylene group (number of carbon atoms in each alkylene group: 2 to 4) and a group represented by the formula R 19 -T-R 20 — (in which R 19 represents the residue of a C 1-30 fatty acid after removal of the COOH group, R 20 represents a C 1-4 alkylene or hydroxyalkylene group and T represents —COO— or —CONH—); R 18 represents a C 1-4 alkylene or hydroxyalkylene group; and X ⁇ represents COO— or SO 3 —.
• R 21 represents a C 1-30 alkyl or hydroxyalkyl group or a C 2-24 alkenyl group
• R 22 represents a C 1-4 alkylene or hydroxyalkylene group
• R 23 represents a hydrogen atom or a divalent group represented by the formula —R′—COOL 1/r
• R′ represents a hydrogen atom, a C 1-30 alkyl group or a C 2-24 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.
• C 1-30 alkyl groups and of the C 2-30 alkenyl groups represented by R 15 , R 16 , R 17 , R 21 , and/or R 23 are the same as those given hereinabove referring R 1 and R 2 and preferred species are also the same as mentioned hereinabove.
• the C 1-30 hydroxyalkyl group represented by R 15 , R 16 , R 17 and/or R 21 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.
• R 15 , R 16 and/or R 17 there may be mentioned groups represented by the formula R 24 —(OA 3 ) t — (R 24 being a hydrogen atom or a C 1-4 alkyl group, A 3 being a C 2-4 alkylene group and t being an integer of 2 to 15).
• R 24 being a hydrogen atom or a C 1-4 alkyl group
• a 3 being a C 2-4 alkylene group and t being an integer of 2 to 15.
• C 2-4 alkylene group A 3 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 C 1-4 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 C 1-30 fatty acid constituting the residue R 19 in the group represented by R 19 -T-R 20 — 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.
• C 6-24 fatty acids are preferred, and C 8-12 fatty acids are more preferred.
• the C 1-4 alkylene group represented by R 20 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 C 1-4 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 C 1-4 alkylene groups.
• C 6-24 alkyl or hydroxyalkyl groups, C 2-24 alkenyl groups and R 9 CONHR 20 groups are preferred as R 15 and R 21
• C 1-24 alkyl or hydroxyalkyl groups and C 2-24 alkenyl groups are preferred as 16 and R 17
• a hydrogen atom, C 1-30 alkyl groups and C 2-24 alkenyl groups are preferred as R′.
• the C 1-4 alkylene group and the hydroxyalkylene group, each represented by R 18 and R 22 include those respective species mentioned hereinabove referring to R 20 , and preferred species are also the same as mentioned above.
• R 23 is a hydrogen atom or the group —R′—COOL 1/r .
• Preferred as the surfactants of the formula (7) or (8) are mixtures of one in which R 23 is a hydrogen atom and one in which R 23 is a —R′—COOL 1/r group.
• 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.
• a hydrogen atom and alkali metals are preferred.
• betaine type amphoteric surfactant represented by the general formula (6) there may be mentioned, for example, alkyl(C 1-30 )dimethylbetaine, alkyl(C 1-30 )amidoalkyl(C 1-4 )dimethylbetaine, alkyl(C 1-30 )dihydroxyalkyl(C 1-30 )betaine, and sulfobetaine amphoteric surfactants.
• amino acid type amphoteric surfactant represented by the general formula (7) there may be mentioned, for example, alanine type [alkyl(C 1-30 )aminopropionic acid type and alkyl(C 1-30 )iminodipropionic acid type, etc.] amphoteric surfactants and glycine type [e.g. alkyl(C 1-30 )aminoacetic acid type] amphoteric surfactants. Preferred among these are alkylaminopropionic acid type amphoteric surfactants and alkyliminodipropionic acid type amphoteric surfactants.
• sulfonate type amphoteric surfactant represented by the general formula (8)
• alkyl(C 1-30 ) taurine type amphoteric surfactants there may be mentioned, for example, alkyl(C 1-30 ) taurine type amphoteric surfactants.
• nonionic surfactants (D22) there may be mentioned, for example, those represented by the following general formula (9):
• R 25 is a C 1-24 alkyl group, and specific examples and preferred ones thereof are the same as those alkyl groups mentioned hereinabove referring to R 1 and R 2 .
• R 26 there may be mentioned C 1-5 alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc.). Among such R 26 species, C 1-3 alkyl groups are preferred.
• R 25 and R 26 may be the same or different.
• R 27 there may be mentioned a hydrogen atom and C 1-3 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 R 27 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.
• C 3-33 secondary alcohol-EO and/or PO adducts there may be mentioned C 3-33 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.
• 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.
• 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 R 10 , R 11 , R 12 and R 13 is an epoxy group-containing group.
• the remaining group or groups each may be a methyl group, a C 2-20 alkyl group, a phenyl group or a C 1-5 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 R 28 is C 1-4 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 R 10 , R 11 , R 12 and R 13 is an —R 29 —NH(R 30 NH) n H group-containing group (in which R 29 is a C 1-5 alkylene group, R 30 is a C 1-4 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 C 2-20 alkyl group, a phenyl group or a C 1-5 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 R 10 , R 11 , R 12 and R 13 is an —R 3 —COOL 1/r group-containing group [in which R 31 is a C 1-5 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 C 2-20 alkyl group, a phenyl group or a C 1-5 alkoxy group, and a and b each is an integer of 1 to 10,000.
• the C 2-20 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.
• C 1-5 alkoxy group there may be mentioned, for example, a methoxy, ethoxy, n- or isopropoxy, and butoxy groups.
• C 1-4 alkylene group there may be mentioned those given hereinabove referring to R 18 and, as the C5 alkylene group, there may be mentioned 1,2-, 1,3-, 1,4-, 2,3-and-2,4-pentylene.
• 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.
• 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.
• 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.
• 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.
• monohydric alcohols such as methanol, ethanol, prop
• (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.
• 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.).
• 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.).
• 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.
• 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).
• another metal salt e.g. such a metal oxide or chloride as mentioned above.
• the lubricant for treating fibers obtained in the above manner 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).
• the viscosity of the lubricant for treating fibers of the invention is preferably set to 1 to 500 mm 2 /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.
• 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.
• a diluent e.g. an organic solvent or a low-viscosity mineral oil
• 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.
• organic solvent there may be mentioned, for example, the same ones as the auxiliary solvent mentioned above.
• auxiliary solvent there may be mentioned, for example, the same ones as the auxiliary solvent mentioned above.
• 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 mm 2 /s.
• 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.
• 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.
• emulsifying machine which is to be used in emulsification
• 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).
• 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.
• 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).
• clothing e.g. pantyhoses, socks, inner foundation (brassieres, girdles, bodysuits, etc.), outerware (jackets, slacks, etc.), sportsware (swimsuits, leotards, ski pants, etc.), etc.
• 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.
• 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.
• THF tetrahydrofuran
• a mixture of 1.0 part of an ⁇ -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.
• an ⁇ -olefin/maleic anhydride copolymer product of Mitsubishi Chemical Corporation, “
• 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.
• 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.
• 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°).
• 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.
• 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.
• Polydimethylsiloxane KF96-10CS (viscosity: 10 mm 2 /s (25° C.)) (product of Shin-Etsu Chemical Co., Ltd.)
• Liquid paraffin Liquid Paraffin 60S (viscosity: 15 mm 2 /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)
• 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.

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• 2005
  • 2005-05-18 WO PCT/JP2005/009069 patent/WO2005111298A1/ja active Application Filing
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