U.S. patent number 3,853,607 [Application Number 05/407,573] was granted by the patent office on 1974-12-10 for synthetic filaments coated with a lubricating finish.
This patent grant is currently assigned to E. I. du Pont de Nemours and Company. Invention is credited to Yathiraja Iyengar, James Dean Lemley.
United States Patent |
3,853,607 |
Iyengar , et al. |
December 10, 1974 |
SYNTHETIC FILAMENTS COATED WITH A LUBRICATING FINISH
Abstract
A lubricating finish composition for filaments, yarns and cords
used as reinforcement in rubber articles is composed of a
polyorganosiloxane oil and a microcrystalline or polyalkylene wax
dispersed in a dialkyl phthalate oil having 8 to 14 carbon atoms in
each of the alkyl groups. A desirable combination of good adhesion
and fatigue resistance is provided in reinforced rubber tires.
Inventors: |
Iyengar; Yathiraja (Newark,
DE), Lemley; James Dean (Kinston, NC) |
Assignee: |
E. I. du Pont de Nemours and
Company (Wilmington, DE)
|
Family
ID: |
23612648 |
Appl.
No.: |
05/407,573 |
Filed: |
October 18, 1973 |
Current U.S.
Class: |
428/378; 428/395;
428/447; 428/484.1; 252/8.82; 428/391; 428/480 |
Current CPC
Class: |
D06M
15/643 (20130101); Y10T 428/2938 (20150115); Y10T
428/31801 (20150401); Y10T 428/31663 (20150401); Y10T
428/2969 (20150115); Y10T 428/2962 (20150115); Y10T
428/31786 (20150401) |
Current International
Class: |
D06M
15/37 (20060101); D06M 15/643 (20060101); D06m
013/16 (); D06m 015/66 () |
Field of
Search: |
;117/138.8F,138.8N,139.5CQ,139.5A ;252/8,6 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Guynn; Herbert B.
Claims
We claim:
1. A synthetic filament coated with a lubricating finish
composition consisting essentially of a linear polydimethylsiloxane
oil and microcrystalline or polyalkylene wax dispersed in dialkyl
phthalate oil carrier having from 8 to 14 carbon atoms in each of
said alkyl groups, the proportions of the specified ingredients
being from 0.1 to 25 weight percent of the polydimethylsiloxane
oil, from 0.1 to 10 weight percent of the wax and at least 65
weight percent of the dialkyl phthalate oil carrier.
2. The coated filament defined in claim 1 wherein the finish
composition contains from 0.1 to 3 weight percent of an organic
antioxidant.
3. The coated filament defined in claim 1 wherein the dialkyl
phthalate oil carrier consists essentially of diundecyl
phthalate.
4. The coated filament defined in claim 1 wherein the wax is a
polyethylene wax having a melting point between 80.degree.C. and
200.degree.C., a penetration number between 1 and 10, and a
saponification number between 9 and 100.
5. The coated filament defined in claim 1 wherein the wax is a
microcrystalline wax having a melting point between 80.degree.C.
and 150.degree.C., a penetration number between 1 and 10, an acid
number between 10 and 50, and a saponification number between 30
and 100.
6. The coated filament defined in claim 1 wherein the
polydimethylsiloxane oil is a polydimethylsiloxane having at
25.degree.C. a viscosity of 100 centistokes, a specific gravity of
0.968, a refractive index of 1.4030, and a surface tension of 20.9
dynes per centimeter.
7. The coated filament defined in claim 1 wherein there is from 0.1
to 5 weight percent of the finish composition, based on the weight
of the filament.
8. The coated filament defined in claim 1 wherein the synthetic
filament consists essentially of polyethylene terephthalate.
9. An industrial yarn composed of the coated filaments defined in
claim 1.
10. A high-tenacity tire-cord composed of the coated filaments
defined in claim 1.
Description
BACKGROUND OF THE INVENTION
This invention relates to yarns and cords composed of synthetic
filaments having a lubricating finish composition on their
surfaces. More particularly, it concerns filaments coated with a
finish which are particularly useful for industrial yarns and cords
used as reinforcement in rubber tires.
Vehicle tires are subjected to stresses and flexes which cause
gradual physical breakdown in filaments of reinforcing cords, a
phenomenum called "fatigue." As pointed out in Patterson U.S. Pat.
No. 3,475,204, resistance to fatigue can be improved by applying a
lubricating finish to the filaments, but it is quite difficult to
find a satisfactory finish which does not cause a serious lowering
of cord-to-elastomer adhesion. Finish compositions containing a
wide variety of oils and added materials have been tried in
attempts to obtain adequate adhesion with improved resistance to
fatigue.
Several processing characteristics are desirable for a satisfactory
lubricating finish composition. It should be one which is readily
prepared and is stable on standing, without phase-separation in
layers. It should be easily applied to form a uniform coating on
filaments, so a reasonably low viscosity without use of volatile
components is desirable to avoid having to dry the applied coating.
It should not form appreciable deposits on hot rolls used in
after-treatments, since a rapid rate of deposit formation would
cause unacceptable process interruptions. It should not fume
objectionably on hot rolls used in after-treatments. It should not
have a deleterious effect on the normal physical properties of
cords prepared for use in tires and other reinforced articles.
SUMMARY OF THE INVENTION
The present invention includes synthetic filaments, yarns and cords
having the surfaces of the filaments coated with a lubricating
finish composition which has satisfactory processing
characteristics and provides a desirable combination of
rubber-adhesion and fatigue resistance properties when the cords
are used as reinforcement in tires.
In accordance with the invention, the synthetic filaments are
coated with a lubricating finish composition containing linear
polyorganosiloxane oil and microcrystalline wax or polyalkylene wax
dispersed in dialkyl phthalate oil carrier having from 8 to 14
carbon atoms in each of the alkyl groups of the phthalate ester or
esters. The proportions of the specified ingredients are from 0.1
to 25 weight percent of the polyorganosiloxane oil, from 0.1 to 10
weight percent of the wax, and at least 65 weight percent of the
dialkyl phthalate oil carrier.
The finish composition may optionally contain an organic
antioxidant at a concentration of about 0.1 to 3 percent by weight.
Suitable antioxidants are those of the sterically hindered phenolic
type, such as 2,2'-thiobis(4-methyl-6-t-butylphenol);
2,2'-methylene-bis(4-methyl-6-tertiary-butylphenol);
4,4'-thiobis(2-t-butyl-5-methylphenol); and
4,4'-butylidene-bis(6-t-butyl-m-cresol).
Suitable oil carriers are the synthetic, non-volatile, di- esters
of orthophthalic acid and fatty alcohols containing from about 8
through 14 carbon atoms in their alkyl chain. A particularly
preferred oil because of its ease of use as a medium for forming
the dispersion of the wax consists essentially of diundecyl
phthalate.
Suitable polyorganosiloxane oils are of the linear type polymer
wherein the organo-substituents are selected from the group
consisting of lower alkyl and aryl substituents, particularly
wherein they are methyl or phenyl.
Suitable polyalkylene waxes and microcrystalline waxes for this
invention are those described in Columns 1 and 2 of U.S. Pat. No.
3,155,537. Among the polyalkylene waxes, the polyethylene waxes are
preferred. These polyethylene waxes may be either oxidized or
non-oxidized and preferably have a melting point (ASTM E-28-51T)
between 80.degree.C. and 200.degree.C., a penetration number (100
gms./5 sec./77.degree.F.) between 1 and 10 an acid number between 9
and 50, and a saponification number between 9 and 100.
The microcrystalline waxes may be either oxidized or non-oxidized
and preferably have a melting point (ASTM D-127-49) between
80.degree.C. and 150.degree.C., a penetration number (100 gms./5
sec./77.degree.F.) between 1 and 10, an acid number between 10 and
50, and a saponification number between 30 and 100.
DESCRIPTION OF THE INVENTION
The finish composition may be applied to filaments, yarns or cords
at any convenient stage of processing by known techniques, such as
by wiping contact with a rotating roll dipping into the finish. It
is preferably applied to yarns as an overlay finish following a
drawing operation which increases molecular orientation and
tenacity. The finish normally may be applied at a concentration of
from about 0.1 to 5 percent, preferably 0.5 to 1.5 percent, based
on the weight of the filaments.
Any of the known synthetic filaments may be used in this invention.
The invention is of particular value when used on filaments in
yarns and cords of high tenacity for use in reinforcement of
elastomeric structures, i.e. tires. Preferred filaments include
those of polyamides and of polyesters. Particularly suitable
polyamides include the nylons such as 6-nylon and 66-nylon, and
also the aromatic polyamides such as poly(meta-phenylene
isophthalamide) and poly(p-phenylene-terephthalamide). The
invention is particularly useful for polyester filaments of
poly(ethylene terephthalate) which are to be subjected to very high
temperatures during the usual cord hot-stretching employed in the
manufacture of tires. In such preparations, temperatures as high as
470.degree.F. (243 .degree.C.) are employed.
The finish composition is conveniently prepared by dissolving the
solid wax in the heated ester, stirring in the remaining
ingredients and allowing the mixture to cool with stirring.
Optionally, the polysiloxane may be stirred in after cooling. The
solid wax precipitates as a fine dispersion from the solution as it
cools. The particle size, and hence the stability and viscosity of
the resulting dispersion, depend on the relative
solubility-temperature relationship between the wax, the ester and
the rate of cooling. Diundecyl phthalate is particularly preferred
in this respect because of the ready manner in which the wax
dissolves in the hot ester and forms a stable dispersion upon
cooling. Where a phenolic antioxidant is employed, it is preferred
that the heating not be continued after the addition of the
antioxidant.
For a finish of the composition of Item F-O of Example I, the
effect of cooling time on finish viscosity is demonstrated by the
composition having a Brookfield viscosity in centipoise at
28.degree.C. of 181 when cooled from 110.degree. to 30.degree.C. in
15 minutes; the viscosity is 50 for cooling in 133 minutes and 45
upon cooling 151 minutes. The preferred heating temperature is in
the range of 105.degree.-110.degree.C. The composition is actually
a three-phase dispersion system in that the polysiloxane oil is
insoluble in both the wax and the ester.
The most preferred ester is diundecyl phthalate, the di-ester of
orthophthalic acid and undecanol, wherein the alcohol is about 65
percent linear and 35 percent branched chain alcohols which are
99.5 percent undecanol.
A preferred wax is an emulsifiable polyethylene wax of the
"oxidized type" containing both ester linkages as represented by
saponification value and free carboxyl groups represented by an
acid value. Such polymers may be obtained either by oxidation
processes or by copolymerization with the appropriate small amounts
of modifiers. Such materials are solids which generally soften in
the region of 100.degree.-110.degree.C. Preferred ranges are an
acid number of 12-18, a viscosity in centipoise at 125.degree.C. of
900-1500 and a molecular weight in the region of 3,000.
A typically preferred polysiloxane is polydimethyl-siloxane having
a viscosity at 77.degree.F. ( 25 .degree.C.) of 100 centistokes, a
specific gravity of 0.968 and a refractive index of 1.4030 with a
surface tension of 20.9 dynes per centimeter, all at 77.degree.F. (
25 .degree.C.).
EXAMPLE I
This example demonstrates improved flex fatigue performance in
combination with high levels of adhesion which results from the
combination of the wax and polysiloxane lubricants of the
invention.
The test finishes are applied to finish-free poly(ethylene
terephthalate) high tenacity, industrial yarn (Type 68 Dacron, E.
I. du Pont Company, Inc.) of 1,000 denier and 192 filaments on a
coning machine using a conventional rotating finish applicator roll
which is partially immersed in a reversoir of the finish
composition. The finish content on yarn (FOY) is controlled by
manipulating the rpm of the applicator roll. Three ends of the
treated yarn for each item are twisted and plied into a 1,000/1/3
ply cord construction using 8 turns/inch Z twist (3.15/cm.) in the
singles and 8 turns/inch (3.15/cm.) S twist in the plying.
Cords are prepared in this way from the finish compositions as
shown in Table I.
TABLE I ______________________________________ % Ingredients.sup.a
Item % FOY DUP Wax Si AO ______________________________________ F-O
1.1 97 2 0.5 0.5 F-1 1.1 97.5 2 0 0.5 F-2 0.9 99 0 0.5 0.5 F-3 0.6
99.5 0 0 0.5 ______________________________________ .sup.a DUP =
diundecyl phthalate wax = emulsifiable polyethylene wax as
described above Si = polydimethylsiloxane, 100 cs AO =
2,2'-thiobis(4-methyl-6-t-butylphenol) % by weight of the total
composition
The cords are dipped and hot-stretched using a two-step adhesive
system with an epoxide/isocyanate subcoat and an RFL overlay of the
type generally described in U.S. Pat. No. 3,307,966. For the
subcoat the cord is treated at 470.degree.F. (243 .degree.C.) under
an elongation of 8 percent and relaxed 4 percent at a temperature
of 425.degree.F. (218 .degree.C.) for the RFL application. Physical
properties of the dipped and stretched cords are shown in Table
II.
TABLE II ______________________________________ Break % Adhes.
Break Strength, Elong., Tenacity, Item Pickup lbs. (kg.) % gpd F-0
3.4 50.5 ( 23.0) 15.3 7.1 F-1 3.4 50.6 ( 23.0) 16.2 7.1 F-2 3.3
49.0 ( 22.3) 15.5 7.1 F-3 4.1 49.1 ( 22.3) 15.3 7.0
______________________________________
Relative flex fatigues of the cords in a typical test rubber stock
of 50 percent natural and 50 percent styrene/butadiene rubber are
tested using the disc fatigue method as described in U.S. Pat. No.
3,475,204, Col. 4, lines 17-35. Adhesion properties are compared at
140.degree.C. using a two-ply strip adhesion test of the type
described in U.S. Pat. No. 3,307,966, Col. 3, lines 43-58. Results
are shown in Table III.
TABLE III ______________________________________ Two-Ply Adhesion,
Fatigue, % Strength Item lbs./in. (kg./cm.) Loss
______________________________________ F-0 59 (10.6 ) 32 F-1 63
(11.3 ) 59 F-2 60 (10.7 ) 75 F-3 58 (10.4 ) 77
______________________________________
It is seen that Item F-0 containing both the wax and the
poly(dimethylsiloxane) provides equivalent adhesion with a
synergistic improvement in flex fatigue properties as shown by the
lowest strength loss in the disc fatigue test.
EXAMPLE II
This example compares the processability and dispersion stability
of a finish of the invention with similar finishes employing a
different ester not of the invention.
A finish composition the same as for Item F-0 in Example I is
compared with ones of similar composition except instead of the
diundecyl phthalate it is replaced by the same amount of isocetyl
stearate (also called hexadecyl stearate) as Item A and by
polyoxyethylene of 300 average molecular weight fully esterified
with lauric acid as Item B.
Upon standing 54 hours upon cooling Item A shows a solid phase
phase layer separated at the bottom of the container; Item B shows
a layer of solid phase separation at the top of the liquid. Item
F-0 remains as a uniformly, turbid oil with no appearance of phase
separation in layers.
When applied to filaments of poly(ethylene terephthlate) following
drawing and prior to contact with hot rolls, only Item F-0
processes acceptably, with Items A and B resulting in an
unacceptably rapid rate of deposit formation on the rolls.
* * * * *