U.S. patent application number 11/569138 was filed with the patent office on 2008-08-21 for oiling agent for fiber treatment.
This patent application is currently assigned to SANYO CHEMICAL INDUSTRIES, LTD.. Invention is credited to Ikunori Azuse, Kazumitsu Suzuki, Yoshiyuki Wakahara.
Application Number | 20080200358 11/569138 |
Document ID | / |
Family ID | 35394189 |
Filed Date | 2008-08-21 |
United States Patent
Application |
20080200358 |
Kind Code |
A1 |
Azuse; Ikunori ; et
al. |
August 21, 2008 |
Oiling Agent for Fiber Treatment
Abstract
The present invention has its object to provide a lubricant for
fibers which shows, in particular, good anti-tackiness property
against fiber-to-fiber tackiness in the manufacture of elastic
fibers, and good time-dependent stability for a long period of time
as a lubricant for treating fibers. The present invention provides
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.degree. C. of the surface of a sheet made of the material (a) is
not greater than 60.degree. and the angle of contact with water at
25.degree. C. of the surface of the sheet made of the material (a)
applied with the lubricant for treating fibers is 70.degree. to
180.degree..
Inventors: |
Azuse; Ikunori; (Kyoto-shi,
JP) ; Wakahara; Yoshiyuki; (Kyoto-shi, JP) ;
Suzuki; Kazumitsu; (Kyoto-shi, JP) |
Correspondence
Address: |
WESTERMAN, HATTORI, DANIELS & ADRIAN, LLP
1250 CONNECTICUT AVENUE, NW, SUITE 700
WASHINGTON
DC
20036
US
|
Assignee: |
SANYO CHEMICAL INDUSTRIES,
LTD.
Kyoto-shi
JP
|
Family ID: |
35394189 |
Appl. No.: |
11/569138 |
Filed: |
May 18, 2005 |
PCT Filed: |
May 18, 2005 |
PCT NO: |
PCT/JP2005/009069 |
371 Date: |
December 12, 2007 |
Current U.S.
Class: |
508/207 ;
508/110 |
Current CPC
Class: |
D21C 9/002 20130101 |
Class at
Publication: |
508/207 ;
508/110 |
International
Class: |
C10M 105/76 20060101
C10M105/76; C10M 107/02 20060101 C10M107/02 |
Foreign Application Data
Date |
Code |
Application Number |
May 19, 2004 |
JP |
2004-148699 |
Claims
1. 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.degree. C. of the surface of a sheet made of the material (a) is
not greater than 60.degree. and the angle of contact with water at
25.degree. C. of the surface of the sheet made of the material (a)
applied with said lubricant for treating fibers is 70.degree. to
180.degree..
2. The lubricant for treating fibers according to claim 1 which
comprise at least one 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).
3. The lubricant for treating fibers according to claim 2 wherein
(B) comprises a compound containing at least one carboxyl group
and/or carboxylate group within the molecule.
4. The lubricant for treating fibers according to claim 1 wherein
the turbidity at 25.degree. C. of said lubricant for treating
fibers is not higher than 20 mg/L.
5. The lubricant for treating fibers according to claim 2 wherein
(B) is a stearic acid alkaline earth metal salt.
6. The lubricant for treating fibers according to claim 2 wherein
(C) is an ether-carboxylic acid anionic surfactant represented by
the following general formula (2):
R.sup.3--O--(AO).sub.p--CH.sub.2COOM (2) in the above formula,
R.sup.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.
7. The lubricant for treating fibers according to claim 2 wherein
(A) comprises (A1) and (A2), and the content of (A1) is 5 to 80
mass % based on the total mass of (A1)+(A2), and the content of (A)
is 70 to 99.6 mass %, the content of (B) is 0.3 to 10 mass %, and
the content of (C) is 0.1 to 20 mass %, based on the total mass of
(A)+(B)+(C).
8. The lubricant for treating fibers according to claim 1 wherein
the fiber is an elastic fiber.
9. A method of treating elastic fibers which comprises applying 0.1
to 12 mass % of the lubricant for treating fibers according to
claim 8 to elastic fibers in the spinning step, if necessary
followed by scouring.
10. An elastic fiber treated by the method according to claim 8.
Description
TECHNICAL FIELD
[0001] 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.
BACKGROUND ART
[0002] 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.
[0003] 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.
[0004] 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.
[0005] 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.
[0006] 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.
SUMMARY OF THE INVENTION
[0007] 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.
[0008] 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.degree. C. of the surface of a sheet made of a textile
material treated with the lubricant for treating fibers amounts to
70 to 180.degree. is prepared, the problems mentioned above can be
solved. Based on such and other findings, they have now completed
the present invention.
[0009] Thus, the present invention relates to
[0010] a lubricant for treating fibers to be used for fibers made
of a polymer material (a)
[0011] wherein the angle of contact with water at 25.degree. C. of
the surface of a sheet made of the material (a) is not greater than
60.degree. and the angle of contact with water at 25.degree. C. of
the surface of the sheet made of the material (a) applied with the
lubricant for treating fibers is 70.degree. to 180.degree.,
[0012] to a method of treating elastic fibers
[0013] 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
[0014] to an elastic fiber treated by the treatment method defined
above.
DETAILED DESCRIPTION OF THE INVENTION
[0015] 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.
[0016] The upper limit to the contact angle, at 25.degree. C., of
the surface of the sheet made of such a material (a) is not greater
than 60.degree., while the lower limit thereto is not smaller than
10.degree. from the viewpoint that the material is available on the
market.
[0017] 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.
[0018] 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.
[0019] The lubricant for treating fibers to be used in the
invention is preferably one such that the angle (.degree.) of
contact with water, at 25.degree. 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.
[0020] In the present invention, the contact angle is the value
measured by the following method.
[Method of Measuring Contact Angle]
(1) Preparation of Sheets for Measurements
[0021] The periphery of a smooth-surfaced glass plate (20
cm.times.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.times.23 cm, 0.1 cm in
depth, about 41 cm.sup.3 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.degree. C.) for 24 hours, followed by
further 2 hours of drying in a reduced-pressure drier controlled at
60.degree. C. (pressure: about 6 kPa). After drying and the
subsequent 24 hours of standing at room temperature (about
20.degree. C.), the resulting resin sheet is cut into rectangles, 6
cm.times.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.
[0022] Then, 10 .mu.l 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/cm.sup.2
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).
(2) Contact Angle Measurement
[0023] Each sheet (a1) (e.g. about 200 .mu.m thick, 6 cm.times.3
cm) is conditioned under conditions of a temperature of 25.degree.
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.
[0024] 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).
[0025] Usable as the silicone oils (A1) are polydimethylsiloxane,
and partially C.sub.2-C.sub.20 alkyl- and/or phenyl-substituted
polydimethylsiloxane, among others.
[0026] Usable as the hydrocarbon-based lubricating oils (A2) are
mineral oils, purified mineral oils, hydrogenated mineral oils and
cracked mineral oils, among others.
[0027] Preferred among these are base oils having a viscosity at
25.degree. C. of 1 to 1,000 mm.sup.2/s, more preferably 2 to 500
mm.sup.2/s, particularly preferably 3 to 200 mm.sup.2/s.
[0028] (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).
[0029] As the anti-tackiness agent (B), there may be mentioned
compounds containing at least one carboxyl group and/or carboxylate
group within the molecule.
[0030] As such compounds, there may be mentioned higher fatty acids
(salts) (B1) and carboxyl and/or carboxylate group-containing
polymers (B2).
[0031] 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.
[0032] 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.
[0033] 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.
[0034] 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.
[0035] 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.
[0036] 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.
[0037] 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.
[0038] 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).
[0039] 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).
[0040] 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.
[0041] 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.
[0042] 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(C.sub.2-20)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.],
(C.sub.1-20) alkyl (meth)allyl sulfosuccinic acid esters [methyl
(meth)allyl sulfosuccinate etc.], etc.], (Y1-3b): (Meth)
acryloylpolyoxy(C.sub.1-6) 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 (C.sub.1-20) amine salts,
etc.], and mixtures of those mentioned above.
[0043] 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 (C.sub.1-20)alkyl,
mono (C.sub.3-12) cycloalkyl or monophenyl ether] unsaturated
carboxylic acid monoesters [monool or diol-propyleneoxide
(hereinafter, "PO" for short) adducts, for example (C.sub.1-20)
monool PO adduct (meth)acrylic acid esters
[.omega.-methoxypoly-propylene glycol mono(meth)acrylate,
.omega.-ethoxypolypropylene glycol mono(meth)acrylate,
.omega.-propoxypolypropylene glycol mono(meth)acrylate,
.omega.-butoxypolypropylene glycol mono(methacrylate,
.omega.-cyclohexylpolypropylene glycol mono(meth)acrylate,
.omega.-phenoxypolypropylene glycol mono (meth) acrylate, etc.],
(C.sub.1-20) diol-PO adducts (meth)acrylates
[.omega.-hydroxyethyl(poly)oxypropylene mono(meth)acrylate etc.],
etc.], (Y2-3): Unsaturated hydrocarbon monomers containing 2 to 30
carbon atoms [C.sub.2-30 olefin {e.g. ethylene, propylene,
.alpha.-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] C.sub.2-20 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.
[0044] 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).
[0045] These monomers (Y) may be copolymerized with (X) in
arbitrary mixing ratios.
[0046] 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).
[0047] 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.
[0048] 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.sup.2+ salt and azo
compounds.
[0049] 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.
(C.sub.2H.sub.5).sub.3Al--TiCl.sub.4 etc.), among others.
[0050] 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.).
[0051] 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).
[0052] Usable as the C.sub.2-30 olefins or dienes are those species
enumerated hereinabove. Among them, ethylene, propylene, C.sub.4-12
.alpha.-olefins, butadiene and isoprene are preferred, ethylene,
propylene, C.sub.4-8 .alpha.-olefins and butadiene are more
preferred, and ethylene, propylene and butadiene are particularly
preferred.
[0053] 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 C.sub.2-30 olefins are the same ones as
those enumerated hereinabove and, among them, ethylene, propylene
and C.sub.4-12 .alpha.-olefins are preferred, and propylene and
ethylene are particularly preferred.
[0054] 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.
[0055] 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 .mu.l,
Temperature: 135.degree. C.,
[0056] Flow rate: 1 ml/min, Calibration curve: polystyrene.
[0057] 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 .alpha.,.beta.-unsaturated
carboxylic acid (anhydride) [.alpha.,.beta.-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
.alpha.,.beta.-unsaturated carboxylic acid (anhydride).
[0058] 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.
[0059] 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.
[0060] 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.
[0061] The modification with an .alpha.,.beta.-unsaturated
carboxylic acid (anhydride) as described above under (3) can be
carried out by thermally adding an .alpha.,.beta.-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 .alpha.,.beta.-unsaturated
carboxylic acid (anhydride) with (a0) is generally 170 to
230.degree. C. The number of molecules of the
.alpha.,.beta.-unsaturated carboxylic acid (anhydride) added
terminally to (a0) may be one or two or more added in the manner of
graft polymerization.
[0062] The reactions in the above method (4) involving
hydroboration of (a0), followed by oxidation, further followed by
modification with an .alpha.,.beta.-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 .alpha.,.beta.-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.
[0063] Usable as the .alpha.,.beta.-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).
[0064] The amount (mass %) of the .alpha.,.beta.-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 .alpha.,.beta.-carboxylic acid
(anhydride) to be added is generally 1 to 10, preferably 1 to 8,
per terminal double bond in (a0).
[0065] The lactam to be used for the higher order modification
mentioned above includes C.sub.6-12 lactams, for example
caprolactam, enantholactam, laurolactam and undecanolactam; the
aminocarboxylic acid includes C.sub.2-12 aminocarboxylic acids, for
example amino acids such as glycine, alanine, valine, leucine,
isoleucine and phenylalanine, .omega.-aminocaproic acid,
.omega.-aminoenanthic acid, .omega.-aminocaprylic acid,
.omega.-aminopelargonic acid, .omega.-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 C.sub.2-12 aliphatic hydroxycarboxylic acids, for example
glycolic acid, lactic acid, .omega.-hydroxycaproic acid,
.omega.-hydroxyenanthic acid, .omega.-hydroxycaprylic acid,
.omega.-hydroxypelargonic acid, .omega.-hydroxycapric acid,
11-hydroxyundecanoic acid and 12-hydroxydodecanoic acid.
[0066] Preferred among them are C.sub.6-8 lactams and C.sub.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.
[0067] 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.
[0068] 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.
[0069] 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.
[0070] 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.
[0071] 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.
[0072] 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.
[0073] 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.
[0074] 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]=(.DELTA.E/V).sup.1/2
In the formula, .DELTA.E 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).
[0075] (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).
[0076] 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).
[0077] As the sulfonic acids (salts) (C1-1), there may be mentioned
C1-24 alcohol sulfosuccinic acid (mono-, di-) esters (salts)
(C1-1A), C.sub.8-24 .alpha.-olefin sulfonation products (salts)
(C1-1B), C.sub.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).
##STR00001##
[0078] In the above formula, R.sup.1 and R.sup.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.
[0079] The alkyl group containing 1 to 24 carbon atoms, which is
represented by R.sup.1 and/or R.sup.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.
[0080] The alkenyl group containing 2 to 24 carbon atoms, which is
represented by R.sup.1 and/or R.sup.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.
[0081] The preferred examples of R.sup.1 and R.sup.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.sup.1 and R.sup.2 may be the same or
different.
[0082] 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.
[0083] 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.
[0084] So long as m and n are within such range, the compatibility
with the base oil (A) is good.
[0085] 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.
[0086] 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).
[0087] As the carboxylic acids (salts) (C.sub.1-2), 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.
R.sup.3--O-(AO).sub.p--CH.sub.2COOM (2)
In the above formula, R.sup.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. Referring to the above formula, specific examples
and preferred species of the C.sub.1-24 alkyl groups and C.sub.2-24
alkenyl groups represented by R.sup.3 are the same as those given
hereinabove referring to R.sup.1 and R.sup.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.
[0088] So long as p is within such range, the compatibility with
the base oil is good.
[0089] 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.
[0090] 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.
[0091] As the sulfate esters (salts) (C1-3), there may be mentioned
higher alcohol sulfate esters (salts) [C.sub.8-18 aliphatic alcohol
sulfate esters (salts)] (C1-3a), higher alkyl ether sulfate esters
(salts) [C.sub.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.sub.12-18 olefins, followed by
neutralization) (C1-3e), among others.
[0092] 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.
[0093] As the phosphate esters (salts) (C1-4), there may be
mentioned C.sub.8-24 higher alcohol phosphoric acid (mono-,
di-)esters (salts) (C1-4a) and C.sub.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.sub.8-18 higher alcohol-AO adduct phosphoric acid (mono-,
di-)esters (salts).
[0094] 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.
[0095] 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.
[0096] 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.
[0097] 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).
##STR00002##
[In the above formulae, R.sup.4, R.sup.5 and R.sup.6 each
independently represents a group selected from among C.sub.1-24
alkyl or hydroxyalkyl groups, aryl groups, C.sub.2-24 alkenyl
groups, polyoxyalkylene groups (number of carbon atoms in each
alkylene moiety: 2 to 4) and groups represented by
R.sup.8--T-R.sup.9-- (in which R.sup.8 represents a residue derived
from a C.sub.1-24 fatty acid by removal of a COOH group, R.sup.9
represents a C.sub.1-4 alkylene group or hydroxylaklylene group,
and T represents --COO-- or --CONH--), R.sup.7 represents a
C.sub.1-24 alkyl or hydroxyalkyl group, a C.sub.2-24 alkenyl group
or a polyoxyalkylene group (number of carbon atoms in each alkylene
moiety: 2 to 4); any two of R.sup.4, R.sup.5 and R.sup.6 may be
bound to each other to form, together with N, a heterocyclic or
alicyclic compound; Q.sup.- represents an inorganic anion or
organic anion, and QH represents an inorganic acid or an organic
acid.]
[0098] The alkyl group containing 1 to 24 carbon atoms, which is
represented by R.sup.4, R.sup.5 and/or R.sup.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.
[0099] The alkenyl group containing 2 to 24 carbon atoms, which is
represented by R.sup.4, R.sup.5 and/or R.sup.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.
[0100] The C.sub.1-24 hydroxyalkyl group represented by R.sup.4,
R.sup.5 and/or R.sup.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.
[0101] As the polyoxyalkylene group represented by R.sup.4, R.sup.5
and/or R.sup.6, there may be mentioned the diethylene oxide group,
dipropylene oxide group, dibutylene oxide group, triethylene oxide
group and tetrapropylene oxide group, among others.
[0102] Among those, C.sub.8-24 alkyl or hydroxyalkyl groups and
C.sub.8-24 alkenyl groups are more preferred.
[0103] As the heterocycle or alicyclic compound formed by two of
R.sup.4, R.sup.5 and R.sup.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.
[0104] As the C.sub.1-24 alkyl, alkenyl or hydroxyalkyl group or
the polyoxyalkylene group represented by R.sup.7, there may be
mentioned the same ones as mentioned referring to R.sup.4, R.sup.5
and/or R.sup.6. Preferred among them are C.sub.1-4 alkyl or
hydroxyalkyl groups.
[0105] The C.sub.1-24 fatty acid constituting the residue R.sup.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. Among them, C.sub.6-24 fatty acids are
preferred, and C.sub.6-12 fatty acids are more preferred.
[0106] The C.sub.1-4 alkylene group represented by R.sup.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.sub.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.
[0107] Among these, C.sub.1-4 alkylene groups are preferred, and
C.sub.2-3 alkylene groups are more preferred.
[0108] As the acid QH forming the anion Q.sup.- in general formula
(3) and as the QH in general formula (4), there may be mentioned
the following.
(q1) Inorganic Acids
[0109] Hydrohalic acids (hydrochloric acid, bromic acid, iodic
acid, etc.), nitric acid, carbonic acid, phosphoric acid, etc.;
(q2) Organic Acids (q2-a) Alkyl Sulfate Esters
[0110] C.sub.1-4 alkyl sulfate esters such as methylsulfuric acid
and ethylsulfuric acid;
(q2-b) Alkyl Phosphate Esters C.sub.1-8 mono- and/or dialkyl
phosphate esters such as dimethyl phosphate and diethyl phosphate;
(q2-c) C.sub.1-30 Aliphatic Monocarboxylic Acids
[0111] Saturated monocarboxylic acids (those mentioned above as
fatty acids whose residue constitutes R.sup.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.);
(q2-d) C.sub.7-30 Aromatic or Heterocyclic Monocarboxylic Acids
[0112] 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
[0113] C.sub.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.sub.4-30 unsaturated
polycarboxylic acids (maleic acid, fumaric acid, itaconic acid,
etc.)]; C.sub.4-20 aliphatic hydroxypolycarboxylic acids (malic
acid, tartaric acid, citric acid, etc.); C.sub.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, etc.)]; sulfur-containing C.sub.4-30
polycarboxylic acids (thiodipropionic acid etc.);
(q2-f) C.sub.2-36 Amino Acids
[0114] Aspartic acid, glutamic acid, cysteic acid and like amino
acids;
(q2-g) Organic Acid-Modified Silicones
[0115] Organic acids derived from diorganopolysiloxanes by
substitution of --RCOOH and/or --RSO.sub.3H groups for part of the
methyl groups thereof. R is a C.sub.2-5 alkylene group. The
remaining methyl groups may be substituted by phenyl, C.sub.2-20
alkyl or --(CH.sub.2).sub.1-Ph (Ph representing a phenyl group and
1 representing an integer of 1 to 4) groups.
(q2-h) Carboxymethylated Aliphatic Alcohols (C.sub.8-24)
[0116] 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 (C.sub.8-24)-EO and/or
PO (1 to 20 moles) Adducts
[0117] 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.
[0118] More preferred among them are methylsulfuric acid,
ethylsulfuric acid, adipic acid, gluconic acid, isostearic acid,
carboxy-modified silicones having a viscosity at 25.degree. C. of
10 to 8,000 (more preferably 20 to 5,000, particular preferably 30
to 1,000) mm.sup.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.
[0119] Preferred as the quaternary ammonium salt type cationic
surfactants (C2-1) are alkyl (C.sub.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.sub.1-30)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(C.sub.2-4)
chain-containing quaternary ammonium salts [e.g. poly(number of
moles added: 3) oxyethylenetrimethylammonium chloride etc.], alkyl
(C.sub.1-30) amidoalkyl (C.sub.1-10) dialkyl (C.sub.1-4)
methylammonium salts (e.g. stearamidoethyldiethylmethylammonium
methosulfate etc.), etc.
[0120] Among these, alkyltrimethylammonium organic acid salts are
preferred and dialkyldimethylammonium organic acid salts are
particularly preferred.
[0121] 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 C.sub.3-90
aliphatic tertiary amines (e.g. triethylamine, ethyldimethylamine,
didecylmethylamine, N,N,N',N'-tetramethylethylenediamine,
lauramidopropyldimethylamine, etc.), C.sub.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.sub.3-90 hydroxyalkyl group-containing tertiary amines (e.g.
triethanolamine monostearate ester,
N-stearamidoethyldiethanolamine, etc.), etc.
[0122] More preferred among these are aliphatic amine inorganic or
organic acid salts.
[0123] Among such surfactants (C), (C1-1a), (C1-2), (C2-1) and
(C2-2) are preferred, and (C1-2) species are particularly
preferred.
[0124] These (C) species may be used singly or in the form of
mixtures of two or more of them.
[0125] 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.
[0126] 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.
[0127] 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.
[0128] 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.
[0129] The lubricant for treating fibers of the invention generally
has a viscosity at 25.degree. C. of 1 to 500 mm.sup.2/s, preferably
2 to 100 mm.sup.2/s, more preferably 3 to 50 mm.sup.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.
[0130] The turbidity at 25.degree. 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.
[0131] The turbidity can be measured by the integrating sphere
photoelectric photometric method (JIS K 0101-1998.9.4., integrating
sphere turbidity).
[0132] 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.
[0133] (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.
[0134] 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.degree. C.".
[0135] As the silicones (D11) which occur as solids at ordinary
temperature (25.degree. 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.].
[0136] 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.
[0137] As the polyether-modified silicones (D12), there may be
mentioned, for example, polyether-modified silicones represented by
the following formula (5):
##STR00003##
[0138] In the above formula, at least one of R.sup.10, R.sup.11,
R.sup.12 and R.sup.13 is a polyoxyalkylene chain-containing group.
The remaining symbol or symbols each may be a methyl group, a
C.sub.2-20 alkyl group, a phenyl group or a C.sub.1-5 alkoxy
group.
[0139] The polyoxyalkylene group is a group represented by the
general formula -A.sup.1-O-- (A.sup.2-O)--R.sup.14 wherein R.sup.14
is a hydrogen atom or a C.sub.1-30 alkyl group; A.sup.1 is a
C.sub.1-5 alkylene group; A.sup.2 is a C.sub.1-4 alkylene group;
A.sup.1 and A.sup.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.
[0140] 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).
[0141] As the antistatic agent (D2), there may be mentioned, for
example, amphoteric surfactants (D21) and nonionic surfactants
(D22).
[0142] Usable as (D21) are betaine type amphoteric surfactants,
amino acid type amphoteric surfactants and sulfonic acid salt type
amphoteric surfactants, among others.
[0143] 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.
##STR00004##
In the above formula, R.sup.15, R.sup.16 and R.sup.17 each
independently represents a group selected from among a C.sub.1-30,
alkyl or hydroxyalkyl group, a C.sub.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.sup.19-T-R.sup.20-- (in which R.sup.19 represents the residue of
a C.sub.1-30 fatty acid after removal of the COOH group, R.sup.20
represents a C.sub.1-4 alkylene or hydroxyalkylene group and T
represents --COO-- or --CONH--); R.sup.18 represents a C.sub.1-4
alkylene or hydroxyalkylene group; and X.sup.- represents COO-- or
SO.sub.3--.
##STR00005##
[0144] In the above formulae, R.sup.21 represents a C.sub.1-30
alkyl or hydroxyalkyl group or a C.sub.2-24 alkenyl group; R.sup.22
represents a C.sub.1-4 alkylene or hydroxyalkylene group; R.sup.23
represents a hydrogen atom or a divalent group represented by the
formula --R'--COOL.sub.1/r; R' represents a hydrogen atom, a
C.sub.1-30 alkyl group or a C.sub.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.
[0145] Specific examples of the C.sub.1-30 alkyl groups and of the
C.sub.2-30 alkenyl groups represented by R.sup.15, R.sup.16,
R.sup.17, R.sup.21, and/or R.sup.23 are the same as those given
hereinabove referring R.sup.1 and R.sup.2 and preferred species are
also the same as mentioned hereinabove. The C.sub.1-30 hydroxyalkyl
group represented by R.sup.15, R.sup.16, R.sup.17 and/or R.sup.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.
[0146] As the polyoxyalkylene group represented by R.sup.15,
R.sup.16 and/or R.sup.17, there may be mentioned groups represented
by the formula R.sup.24--(OA.sup.3).sub.t-- (R.sup.24 being a
hydrogen atom or a C.sub.1-4 alkyl group, A.sup.3 being a C.sub.2-4
alkylene group and t being an integer of 2 to 15). As the C.sub.2-4
alkylene group A.sup.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.sub.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.
[0147] The C.sub.1-30 fatty acid constituting the residue R.sup.19
in the group represented by R.sup.19-T-R.sup.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. Among these, C.sub.6-24 fatty acids are
preferred, and C.sub.8-12 fatty acids are more preferred.
[0148] The C.sub.1-4 alkylene group represented by R.sup.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.sub.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.sub.1-4 alkylene groups.
[0149] Among those mentioned above, C.sub.6-24 alkyl or
hydroxyalkyl groups, C.sub.2-24 alkenyl groups and
R.sup.9CONHR.sup.20 groups are preferred as R.sup.15 and R.sup.21,
C.sub.1-24 alkyl or hydroxyalkyl groups and C.sub.2-24 alkenyl
groups are preferred as 16 and R.sup.17, and a hydrogen atom,
C.sub.1-30 alkyl groups and C.sub.2-24 alkenyl groups are preferred
as R'.
[0150] The C.sub.1-4 alkylene group and the hydroxyalkylene group,
each represented by R.sup.18 and R.sup.22 include those respective
species mentioned hereinabove referring to R.sup.20, and preferred
species are also the same as mentioned above.
[0151] Among the X-- species in the formula (6), COO-- is
preferred.
[0152] R.sup.23 is a hydrogen atom or the group --R'--COOL.sub.1/r.
Preferred as the surfactants of the formula (7) or (8) are mixtures
of one in which R.sup.23 is a hydrogen atom and one in which
R.sup.23 is a --R'--COOL.sub.1/r group.
[0153] 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.
[0154] As the betaine type amphoteric surfactant represented by the
general formula (6), there may be mentioned, for example,
alkyl(C.sub.1-30)dimethylbetaine,
alkyl(C.sub.1-30)amidoalkyl(C.sub.1-4)dimethylbetaine,
alkyl(C.sub.1-30)dihydroxyalkyl(C.sub.1-30)betaine, and
sulfobetaine amphoteric surfactants. The preferred, among these,
are alkyldimethylbetaines and alkylamidoalkyldimethylbetaines.
[0155] As the amino acid type amphoteric surfactant represented by
the general formula (7), there may be mentioned, for example,
alanine type [alkyl(C.sub.1-30)aminopropionic acid type and
alkyl(C.sub.1-30)iminodipropionic acid type, etc.] amphoteric
surfactants and glycine type [e.g. alkyl(C.sub.1-30)aminoacetic
acid type] amphoteric surfactants. Preferred among these are
alkylaminopropionic acid type amphoteric surfactants and
alkyliminodipropionic acid type amphoteric surfactants.
[0156] As the sulfonate type amphoteric surfactant (aminosulfonic
acid type amphoteric surfactant) represented by the general formula
(8), there may be mentioned, for example, alkyl(C.sub.1-30) taurine
type amphoteric surfactants.
[0157] As the nonionic surfactants (D22), there may be mentioned,
for example, those represented by the following general formula
(9):
##STR00006##
In the above formula, R.sup.25 is a C.sub.1-24 alkyl group, and
specific examples and preferred ones thereof are the same as those
alkyl groups mentioned hereinabove referring to R.sup.1 and
R.sup.2. As R.sup.26, there may be mentioned C.sub.1-5 alkyl groups
(methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc.). Among such
R.sup.26 species, C.sub.1-3 alkyl groups are preferred. R.sup.25
and R.sup.26 may be the same or different. As R.sup.27, there may
be mentioned a hydrogen atom and C.sub.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.sup.27 species. AO is the same as
in the general formula (1) (AO).sub.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.
[0158] When q is within such ranges, the compatibility with the
base oil is good.
[0159] As specific examples of (D22) represented by general formula
(9), there may be mentioned C.sub.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.
[0160] (D22) may be used independently or as a mixture of 2 or more
different species.
[0161] 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.
[0162] As the softening agent (D3), there may be mentioned, for
example, epoxy-modified silicones (131), amino-modified silicones
(D32) and carboxyl-modified silicones (D33).
[0163] (D31) may be represented by the general formula (5) given
hereinabove in which at least one of R.sup.10, R.sup.11, R.sup.12
and R.sup.13 is an epoxy group-containing group. The remaining
group or groups each may be a methyl group, a C.sub.2-20 alkyl
group, a phenyl group or a C.sub.1-5 alkoxy group, and a and b each
is an integer of 1 to 1,000.
[0164] The epoxy group-containing group may be represented by the
general formula (10) given below (in which R.sup.28 is C.sub.1-4
alkylene group) and, for example, a glycidyl group.
##STR00007##
[0165] (D32) may be represented by the general formula (5) given
hereinabove in which at least one of R.sup.10, R.sup.11, R.sup.12
and R.sup.13 is an --R.sup.29--NH(R.sup.30NH).sub.nH
group-containing group (in which R.sup.29 is a C.sub.1-5 alkylene
group, R.sup.30 is a C.sub.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.sub.2-20 alkyl group, a phenyl group or a C.sub.1-5
alkoxy group, and a and b each is an integer of 1 to 10,000.
[0166] (D33) may be represented by the general formula (5) given
hereinabove in which at least one of R.sup.10, R.sup.11, R.sup.12
and R.sup.13 is an --R.sup.3--COOL.sub.1/r group-containing group
[in which R.sup.31 is a C.sub.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.sub.2-20 alkyl
group, a phenyl group or a C.sub.1-5 alkoxy group, and a and b each
is an integer of 1 to 10,000.
[0167] The C.sub.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.
[0168] As the C.sub.1-5 alkoxy group, there may be mentioned, for
example, a methoxy, ethoxy, n- or isopropoxy, and butoxy
groups.
[0169] As the C.sub.1-4 alkylene group, there may be mentioned
those given hereinabove referring to R.sup.18 and, as the C5
alkylene group, there may be mentioned 1,2-, 1,3-, 1,4-,
2,3-and-2,4-pentylene.
[0170] 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.
[0171] 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.
[0172] 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.
[0173] 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.
[0174] 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.
[0175] 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.
[0176] 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.degree. 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.degree. 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.degree. C.), adding (B) separately melted (100 to 250.degree.
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.degree. C.).
[0177] 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.
[0178] 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).
[0179] 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).
[0180] 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 mm.sup.2/s at 25.degree. C.
[0181] The viscosity is measured by the following method.
<Viscosity Measurement Method>
[0182] 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.degree. C. in a constant-temperature water bath. After 30
minutes, the viscosity is measured by the method of Ubbelohde.
[0183] 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.
[0184] 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.
[0185] 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.degree. C. are less than 1 mm.sup.2/s.
[0186] 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.
[0187] 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.
[0188] 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.
[0189] 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.
[0190] 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.
[0191] 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.
[0192] 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.degree. C., preferably 15 to
60.degree. C.
[0193] 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.
[0194] 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).
[0195] 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.
[0196] 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).
(Effect of the Invention)
[0197] 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.
BEST MODE FOR CARRYING OUT THE INVENTION
[0198] 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).
PRODUCTION EXAMPLE 1
[0199] 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.degree. C. for 5 hours with stirring. The
temperature was lowered to 45.degree. 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].
EXAMPLES 1 TO 4 AND COMPARATIVE EXAMPLES 1 TO 3
[0200] 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.
EXAMPLE 1
[0201] 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.degree. C. for 1 hour. Then, 31 parts of
polydimethylsiloxane was added, and the resulting mixture was
cooled to 30.degree. C., whereby the lubricant for treating fibers
of Example 1 was prepared.
EXAMPLE 2
[0202] 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.degree. C. for 1 hour. Then, 18 parts of
polydimethylsiloxane was added, and the resulting mixture was
cooled to 30.degree. C., whereby the lubricant for treating fibers
of Example 2 was prepared.
EXAMPLE 3
[0203] 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.degree. C. for 1 hour. Then, 17 parts of
polydimethylsiloxane was added, and the resulting mixture was
cooled to 30.degree. C., whereby the lubricant for treating fibers
of Example 3 was prepared.
EXAMPLE 4
[0204] A mixture of 1.0 part of an .alpha.-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.degree. C. for 1 hour. Then, 31 parts of
polydimethylsiloxane was added, and the resulting mixture was
cooled to 30.degree. C., whereby the lubricant for treating fibers
of Example 4 was prepared.
EXAMPLE 5
[0205] 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.degree. C.
for 1 hour. Then, 31 parts of polydimethylsiloxane was added, and
the resulting mixture was cooled to 30.degree. C., whereby the
lubricant for treating fibers of Example 5 was prepared.
COMPARATIVE EXAMPLE 1
[0206] 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.degree. C. for 1 hour. Then, 31
parts of polydimethylsiloxane was added, and the resulting mixture
was cooled to 30.degree. C., whereby the lubricant for treating
fibers of Comparative Example 1 was prepared.
COMPARATIVE EXAMPLE 2
[0207] 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.degree. C. for 1 hour. Then, 18 parts of
polydimethylsiloxane was added, and the resulting mixture was
cooled to 30.degree. C., whereby the lubricant for treating fibers
of Comparative Example 2 was prepared.
COMPARATIVE EXAMPLE 3
[0208] A mixture of 2 part of magnesium distearate and 93 parts of
liquid paraffin was stirred at 115 to 120.degree. C. for 1 hour.
Then, 5 parts of polydimethylsiloxane was added, and the resulting
mixture was cooled to 30.degree. C., whereby the lubricant for
treating fibers of Comparative Example 3 was prepared.
[0209] 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.
[0210] 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.degree.). Further, the viscosity, at 25.degree. C.,
of each lubricant for treating fibers as measured by an Ubbelohde
viscometer and the turbidity, at 2.5.degree. 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.
TABLE-US-00001 TABLE 1 Example Comparative Example 1 2 3 4 5 1 2 3
<Composition> Polydimethylsiloxane (parts) 31 18 17 31 31 31
18 5 Liquid paraffin (parts) 60 68 64 60 60 65 80.2 93 Magnesium
distearate (parts) 1 2 4 -- -- -- 1 2 .alpha.-olefin/maleic
anhydride copolymer (parts) -- -- -- 1 -- -- -- -- Acid-modified
polypropylene (parts) -- -- -- -- 1 -- -- -- Polyether-modified
silicone (parts) -- -- -- -- -- 4 -- -- Surfactant-1 (SP = 8.1)
(parts) 2 3 3 2 2 -- 0.2 -- Surfactant-2 (SP = 9.4) (parts) 4 6 8 4
4 -- 0.4 -- Surfactant-3 (SP = 8.2) (parts) 2 3 4 2 2 -- 0.2 --
<Performance evaluation> Angle of contact with water
(.degree.) 80 90 95 75 75 65 65 60 Anti-tackiness Excellent
Excellent Excellent Excellent Excellent Poor Poor Poor Viscosity
(mm.sup.2/s) 15.2 16.1 18.4 20.3 19.4 17.7 12.7 14.9 Turbidity
(mg/L) 1.8 4.5 5.0 4.5 6.4 3.0 27.2 489 Time-dependent stability
-5.degree. C. Excellent Excellent Excellent Excellent Excellent
Excellent Poor Poor of the lubricant for 25.degree. C. Excellent
Excellent Excellent Excellent Excellent Excellent Fair Poor
treating fibers 50.degree. C. Excellent Excellent Excellent
Excellent Excellent Excellent Excellent Poor
[0211] 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.
<Viscosity Measurement Method>
[0212] 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.degree. C. in a
constant-temperature water bath. After 30 minutes, the viscosity is
measured by the method of Ubbelohde.
<Turbidity Measurement Method>
[0213] Each lubricant for treating fibers adjusted to a temperature
of 25.degree. 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.
<Time-Dependent Stability Test of Lubricant for Treating
Fibers>
[0214] 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.degree. C., 25.degree. C. or 50.degree. 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.
--Evaluation Criteria--
[0215] 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
<Anti-Tackiness Test>
[0216] The cheese obtained in the spinning step was subjected to
2-week-long aging at 50.degree. 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.
--Evaluation Criteria--
[0217] Excellent: speed=50 to 65 Poor: speed.gtoreq.66
[0218] The particulars of the components shown in Table 1 are as
follows.
[0219] Polydimethylsiloxane: KF96-10CS (viscosity: 10 mm.sup.2/s
(25.degree. C.)) (product of Shin-Etsu Chemical Co., Ltd.)
[0220] Liquid paraffin: Liquid Paraffin 60S (viscosity: 15
mm.sup.2/s (25.degree. C.) (product of Sanko Chemical Industry Co.,
Ltd.)
[0221] Surfactant-1: polyoxyethylene isotridecyl ether-acetic acid
sodium salt (adduct with 3 moles of EO)
[0222] Surfactant-2: polyoxyethylene lauryl ether-acetic acid
(adduct with 2.5 moles of EO)
[0223] Surfactant-3: didecyldimethylammonium polyoxyethylene lauryl
ether-acetate (adduct with 2.5 moles of EO)
[0224] 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.
INDUSTRIAL APPLICABILITY
[0225] 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.
* * * * *