U.S. patent application number 12/803263 was filed with the patent office on 2010-11-18 for coating for metal containers, metalworking lubricant compositions, compositions for electroplating and electrowinning, latex compositions and processes therefor.
This patent application is currently assigned to Cognis Corporation. Invention is credited to Kenneth Breindel, Ronald W. Broadbent, David W. Brown, Shailesh Shah, Michael S. Wiggins.
Application Number | 20100288644 12/803263 |
Document ID | / |
Family ID | 32719646 |
Filed Date | 2010-11-18 |
United States Patent
Application |
20100288644 |
Kind Code |
A1 |
Brown; David W. ; et
al. |
November 18, 2010 |
Coating for metal containers, metalworking lubricant compositions,
compositions for electroplating and electrowinning, latex
compositions and processes therefor
Abstract
Coatings for metal containers, metalworking lubricant
compositions, compositions for electroplating and electrowinning,
and latex compositions comprising a base-catalyzed reaction product
of (a) at least one compound of formula I R.sup.1(X).sub.3 (I)
wherein each X group is a halogen atom or one X group is a halogen
atom and two X groups represent an epoxy oxygen atom, which is
attached to two adjacent carbon atoms in the R.sup.1 group to form
an epoxy group, and R.sup.1 is an alkanetriyl group containing from
3 to 10 carbon atoms; and (b) at least one compound having the
formula II R.sup.2X(AO).sub.nY (II) wherein R.sup.2 is a
substituted or unsubstituted, saturated or unsaturated, organic
group having from 1 to 36 carbon atoms; X is --O--, --S--, or
--NR.sup.3-- where R.sup.3 is hydrogen or a C.sub.1-C.sub.18 alkyl
group; each AO group is independently an ethyleneoxy,
1,2-propyleneoxy, or 1,2-butyleneoxy group, n is a number from 0 to
200; and Y is hydrogen, or Y can be a mercapto group or an amino
group or a C.sub.1-C.sub.6 alkylamino group in place of a terminal
--OH group, provided that when Y is mercapto or an amino group, or
a C.sub.1-C.sub.6 alkylamino group, n is at least 1; wherein the
mole ratio of component a) to b) is from 0.1:1 to 5:1; are
described.
Inventors: |
Brown; David W.; (Ambler,
PA) ; Breindel; Kenneth; (Lansdale, PA) ;
Wiggins; Michael S.; (Lansdale, PA) ; Broadbent;
Ronald W.; (Horsham, PA) ; Shah; Shailesh;
(Dresher, PA) |
Correspondence
Address: |
FOX ROTHSCHILD LLP
997 Lenox Drive, Bldg. #3
Lawrenceville
NJ
08648
US
|
Assignee: |
Cognis Corporation
Ambler
PA
|
Family ID: |
32719646 |
Appl. No.: |
12/803263 |
Filed: |
November 12, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10700167 |
Nov 3, 2003 |
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12803263 |
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60423118 |
Nov 1, 2002 |
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60424249 |
Nov 6, 2002 |
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60430485 |
Dec 3, 2002 |
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60434477 |
Dec 18, 2002 |
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Current U.S.
Class: |
205/80 ;
72/42 |
Current CPC
Class: |
C10M 2209/105 20130101;
C10M 173/00 20130101; C10M 2207/042 20130101; C10N 2060/06
20130101; C25D 3/02 20130101; C10M 2209/103 20130101; C10M 2207/046
20130101; C10M 2209/104 20130101; C10M 159/12 20130101 |
Class at
Publication: |
205/80 ;
72/42 |
International
Class: |
C25D 3/02 20060101
C25D003/02; B21B 45/02 20060101 B21B045/02 |
Claims
1-12. (canceled)
13. A method of metalworking lubrication, comprising: i) providing
a metalworking lubricant composition, comprising A) at least one
lubricating oil; B) at least one base-catalyzed branched reaction
product of: a) at least one compound of formula I R.sup.1(X).sub.3
(I) wherein each X group is a halogen atom or one X group is a
halogen atom and two X groups represent an epoxy oxygen atom, which
is attached to two adjacent carbon atoms in the R.sup.1 group to
form an epoxy group, and R.sup.1 is an alkanetriyl group containing
from about 3 to about 10 carbon atoms; b) at least one compound
having the formula II R.sup.2X(AO).sub.nY (II) wherein R.sup.2 is a
substituted or unsubstituted, saturated or unsaturated, organic
group having from 1 to about 36 carbon atoms; X is --O--, --S--, or
--NR.sup.3-- where R.sup.3 is hydrocarbon or a C.sub.1-C.sub.18
alkyl group; each AO group is independently an ethyleneoxy,
1,2-propyleneoxy, or 1,2-butyleneoxy group, n is a number from 0 to
about 200; and Y is hydrogen, or Y can be a mercapto group or an
amino group or a C.sub.1-C.sub.6 alkyl amino group in place of a
terminal --OH group, provided that when Y is mercapto or an amino
group or a C.sub.1-C.sub.6 alkyl amino group, n is at least 1; and,
optionally c) a glycidyl ether and/or a glycidyl amine; wherein the
mole ratio of the linking compound a) to b) is from about 0.1:1 to
about 5:1, and wherein the metalworking lubricant composition has
reduced foaming properties in aqueous and non-aqueous metalworking
formulations and improved lubricating and extreme pressure
properties and, wherein, R.sup.2 is optionally substituted with a
member selected from the group consisting of mercaptan
functionality, thio functionality, amine functionality, amide
functionality, alcohol functionality, silicone functionality, ether
functionality, and combinations thereof; ii) applying the lubricant
composition to a metal object to be worked; and iii) subjecting the
metal object to a working step select from cutting, machining,
grinding, or other metal processing or metalworking, whereby the
composition modifies the harmful effects of friction and/or high
temperatures caused by the working.
14. The method of claim 13 wherein said lubricant composition
comprises from about 0.001% to about 10% by weight of the reaction
product B.
15. The method of claim 15 wherein said lubricant composition
comprises from about 0.1% to about 3% by weight of the reaction
product B.
16. The method of claim 15 wherein c) is present, and comprises
from about 1 to about 20 mole percent based on the moles of b).
17. The method of claim 13 wherein said lubricant composition
further comprises at least one additive selected from the group
consisting of viscosity improvers, pour-point depressants,
antioxidants, amine solvents, buffers, nonionic surfactants (other
than B), corrosion inhibitors, and coupling agents.
18. The method of claim 13 wherein said lubricant composition
comprises from about 30% to about 90% by weight of A.
19. A method of electroplating, comprising: i) providing an aqueous
electroplating composition, comprising A) at least one metal or
metalloid and ions thereof; and B) at least one base-catalyzed
reaction product of: a) at least one compound of formula I
R.sup.1(X).sub.3 (I) wherein each X group is a halogen atom or one
X group is a halogen atom and two X groups represent an epoxy
oxygen atom, which is attached to two adjacent carbon atoms in the
R.sup.1 group to form an epoxy group, and R.sup.1 is an alkanetriyl
group containing from about 3 to about 10 carbon atoms; b) at least
one compound having the formula II R.sup.2X(AO).sub.nY (II) wherein
R.sup.2 is a saturated or unsaturated, organic group having from 1
to about 36 carbon atoms; X is --O--, --S--, or --NR.sup.3--where
R.sup.3 is hydrogen or a C.sub.1-C.sub.18 alkyl group; each AO
group is independently an ethyleneoxy, 1,2-propyleneoxy, or
1,2-butyleneoxy group, n is a number from 0 to about 200; and Y is
hydrogen, or Y can be a mercapto group or an amino group or a
C.sub.1-C.sub.6 alkylamino group in place of a terminal-OH group,
provided that when Y is mercapto or an amino group, or a
C.sub.1-C.sub.6 alkylamino group, n is at least 1; and, optionally
c) a glycidyl ether and/or glycidyl amine; wherein the mole ratio
of component a) to b) is from about 0.1:1 to about 5:1, and wherein
the base catalyzed reaction product is not epoxy functional and
provides improved brightening and reduced foaming and, wherein,
R.sup.2 is optionally substituted with a member selected from the
group consisting of mercaptan functionality, thio functionality,
amine functionality, amide functionality, alcohol functionality,
silicone functionality, ether functionality, and combinations
thereof; and ii) using said composition as the aqueous electrolyte
solution in an electroplating operation.
20. The method of claim 14 wherein said electroplating composition
comprises from about 0.001% to about 5% by weight of the reaction
product B.
21. The method of claim 20 wherein said electroplating composition
comprises from about 0.1% to about 3% by weight of the reaction
product B.
22. The method of claim 19 wherein c) is present, and comprises
from about 1 to about 20 mole percent based on the moles of b).
23. The method of claim 19, wherein said metal, metalloid, and ions
of the composition are selected from the group consisting of zinc,
nickel, copper, chromium, manganese, iron, cobalt, gallium,
germanium, arsenic, selenium, ruthenium, rhodium palladium silver,
cadmium, indium, tin, lead, bismuth, mercury, antimony, gold,
indium, platinum, brass, bronze, gold alloys, lead-tin, nickel
iron, nickel cobalt, nickel-phosphorus, tin-nickel, tin-zinc,
zinc-nickel, zinc-cobalt, zinc-iron, lead-indium, nickel-manganese,
nickel-tungsten, palladum alloys, silver alloys and zinc-manganese.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority, under 35 U.S.C.
.sctn.119(e), of U.S. Provisional Patent Application Nos.
60/423,118, 60/424,249, 60/430,485, and 60/434,477, filed on Nov.
1, 2002, Nov. 6, 2002, Dec. 3, 2002 and Dec. 18, 2002,
respectively, the entire contents of each of which are hereby
incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] One of the last stages in the manufacture of aluminum cans
and other metal containers such as ferrous metal containers is the
application of one or more finishing coatings for decorative
purposes and/or identification.
[0003] Such finishing coatings include acrylic paints, phenolic
coatings which are used for baked can coatings, bitumen paints
which are used for aluminum paints, coumarone-indene paints which
are used to make aluminum paints, lacquers (which is a term also
applied to the baking finish applied to the interior of food and
beverage cans), and enamels.
[0004] Lubricating oils are fluids whose function is the reduction
of friction and wear between solid surfaces, usually metals, in
relative motion. Aside from the primary function of friction and
wear control, lubricating oils are often called upon to serve other
purposes, such as corrosion prevention, electrical insulation,
power transmission, and cooling. The latter is particularly
important in metal cutting and grinding.
[0005] There are two fundamental classes of lubricating agents,
natural and synthetic. These lubricating agents include
petroleum-derived oils, natural fatty acid esters, hydrocarbons
prepared by the polymerization of olefinic hydrocarbons,
polyalkylene glycol oils, synthetic esters which are primarily
esters of dibasic acids or organic esters of phosphoric or silicic
acid, silicone oils which are linear or cyclic siloxane polymers,
halogenated hydrocarbons, perfluorinated polyalkylene glycols,
polyphenyl esters, polyglycols, and neopentyl polyol esters.
[0006] In the production of metals by electrolysis of aqueous
solutions, the electrowinning of the metals is usually carried out
in tank cells. Developments in the electrowinning of metals from
aqueous solutions have been directed toward improved anodes,
improved additives, higher current densities, the use of
ion-exchange membranes, better electrolyte quality control, and
computer modeling of the processes.
[0007] Electroplating is the process of applying a metallic coating
to an article by passing an electric current through an electrolyte
in contact with the article. The ASTM adds some quality restriction
by defining electroplating as electrodeposition of an adherent
metallic coating on an electrode such that a surface having
properties or dimensions different from those of the basic metal is
formed.
[0008] Progress in electroplating is linked to improvements in
materials of construction, power supplies and other plating
equipment, purer industrial chemicals and anodes, improved
additives for the plating baths, and improved analytical test and
control methods. The quality of electroplating is dependent on the
basic metal surface. Cleaner, less porous castings and better
casing alloys, and improved steel and steel finishes have helped
significantly.
[0009] Electroforming involves the electrodeposition upon a mandrel
or mold in which the separated electrodeposit is the manufactured
article.
[0010] The use of natural rubber in latex form for the preparation
of rubber-containing articles is known.
[0011] However, the use of wetting and/or defoaming agents in
natural rubber latex compositions has not been uniformly
satisfactory, since a number of criteria must be met, e.g. the
wetting and/or defoaming agent must not destabilize the latex
composition, and the defoaming agent must be highly effective since
otherwise small holes may be present in the finished article, which
can be a serious problem for dipped articles such as gloves for
medical and surgical use.
BRIEF SUMMARY OF THE INVENTION
[0012] This invention relates to coatings for metal containers
wherein the coatings contain at least one branched reaction product
comprising the following reactants:
[0013] A) at least one compound of formula I
R.sup.1(X).sub.3 (I) [0014] wherein each X group is a halogen atom
or one X group is a halogen atom and two X groups represent an
epoxy oxygen atom, which is attached to two adjacent carbon atoms
in the R.sup.1 group to form an epoxy group, and R.sup.1 is an
alkanetriyl group containing from 3 to 10 carbon atoms; and
[0015] B) at least one compound having the formula II
R.sup.2X(AO).sub.nY (II) [0016] wherein R.sup.2 is a substituted or
unsubstituted, saturated or unsaturated, organic group having from
1 to 36 carbon atoms; X is --O--, --S--, or NR.sup.3-- where
R.sup.3 is hydrogen or a C.sub.1-C.sub.18 alkyl group; each AO
group is independently an ethyleneoxy, 1,2-propyleneoxy, or
1,2-butyleneoxy group, n is a number of from 0 to 200, preferably
from 1 to 100, more preferably from 2 to 20; and Y is hydrogen, or
Y can be a mercapto group or an amino group (amino or
C.sub.1-C.sub.6 alkylamino group) in place of a terminal --OH
group, provided that when Y is mercapto or an amino group, n is at
least 1; wherein the mole ratio of the linking compound A) to B) is
from 0.1:1 to 5:1, preferably from 0.6:1 to 2:1 and more preferably
from 0.8:1 to 1.5:1.
[0017] The presence of the above reaction product or products in
the metal container coatings improves wetting of the substrate to
be coated, improves the flow and leveling of the coating, improves
the gloss of the dried coating, and enables the manipulation of the
shear viscosity of spray applied coatings, i.e. the viscosity can
be either increased or decreased by selection of the molecular
weight and quantity of the reaction product or products.
[0018] This invention also relates to lubricant compositions used
for the working of metals. The term "metalworking lubricants" used
herein is to be understood to include cutting fluids, boundary
lubricants, and extreme pressure lubricants.
[0019] The metalworking lubricant compositions of the invention
comprise the following components: [0020] A) a lubricating oil; and
[0021] B) at least one branched reaction product comprising the
following reactants: [0022] a) at least one compound of formula
I
[0022] R.sup.1(X).sub.3 (I) [0023] wherein each X group is a
halogen atom or one X group is a halogen atom and two X groups
represent an epoxy oxygen atom, which is attached to two adjacent
carbon atoms in the R.sup.1 group to form an epoxy group, and
R.sup.1 is an alkanetriyl group containing from 3 to 10 carbon
atoms; and [0024] b) at least one compound having the formula
II
[0024] R.sup.2X(AO).sub.nY (II) [0025] wherein R.sup.2 is a
substituted or unsubstituted, saturated or unsaturated, organic
group having from 1 to 36 carbon atoms; X is --O--, --S--, or
--NR.sup.3-- where R.sup.3 is hydrogen or a C.sub.1-C.sub.18 alkyl
group; each AO group is independently an ethyleneoxy,
1,2-propyleneoxy, or 1,2-butyleneoxy group, n is a number of from 0
to 200, preferably from 1 to 100, more preferably from 2 to 20; and
Y is hydrogen, or Y can be a mercapto group or an amino group
(amino or C.sub.1-C.sub.6 alkylamino group) in place of a terminal
--OH group, provided that when Y is mercapto or an amino group, n
is at least 1; [0026] wherein the mole ratio of the linking
compound a) to b) is from 0.1:1 to 5:1, preferably from 0.6:1 to
2:1, more preferably from 0.8:1 to 2:1, and most preferably from
0.8:1 to 1.5:1.
[0027] The presence of component B) in the metalworking lubricant
compositions of the invention enhances the wettability of the
lubricant and helps disperse metal fines. In addition, the
lubricating and defoaming properties of the compositions are
improved as well as their extreme pressure properties. The
composition provides excellent wetting properties under dynamic and
high shear applications without creating foam. Also, very
consistent performance is obtained under a wide range of metal
processing conditions.
[0028] This invention also relates to aqueous compositions for
electroplating, electroforming, and/or electrowinning comprising:
[0029] A) at least one metal or metalloid; and [0030] B) at least
one branched reaction product comprising the following reactants:
[0031] a) at least one compound of formula I
[0031] R.sup.1(X).sub.3 (I) [0032] wherein each X group is a
halogen atom or one X group is a halogen atom and two X groups
represent an epoxy oxygen atom, which is attached to two adjacent
carbon atoms in the R.sup.1 group to form an epoxy group, and
R.sup.1 is an alkanetriyl group containing from 3 to 10 carbon
atoms; and [0033] b) at least one compound having the formula
II
[0033] R.sup.2X(AO).sub.nY (II) [0034] wherein R.sup.2 is a
substituted or unsubstituted, saturated or unsaturated, organic
group having from 1 to 36 carbon atoms; X is --O--, --S--, or
--NR.sup.3-- where R.sup.3 is hydrogen or a C.sub.1-C.sub.18 alkyl
group; each AO group is independently an ethyleneoxy,
1,2-propyleneoxy, or 1,2-butyleneoxy group, n is a number of from 0
to 200, preferably from 1 to 100, more preferably from 2 to 20; and
Y is hydrogen, or Y can be a mercapto group or an amino group
(amino or C.sub.1-C.sub.6 alkylamino group) in place of a terminal
--OH group, provided that when Y is mercapto or an amino group, n
is at least 1; [0035] wherein the mole ratio of the linking
compound a) to b) is from 0.1:1 to 5:1, preferably from 0.6:1 to
2:1, more preferably from 0.8:1 to 2:1 and most preferably from
0.8:1 to 1.5:1.
[0036] The presence of component B) in the aqueous compositions of
the invention acts as an effective brightener in electroplating,
electrowinning, and electroforming baths. Component B) is a low
foaming surfactant and is quite stable in both aqueous acidic and
alkaline solutions. In addition, very consistent performance is
achieved over a wide range of processing conditions due to the
presence of component B) in the above aqueous compositions.
[0037] The present invention also relates to aqueous latex
compositions which possess the above attributes, and which comprise
the following components:
[0038] I) a natural rubber; and
[0039] II) at least one reaction product comprised of the following
reactants: [0040] A) at least one compound of formula I
[0040] R.sup.1(X).sub.3 (I) [0041] wherein each X group is a
halogen atom or one X group is a halogen atom and two X groups
represent an epoxy oxygen atom, which is attached to two adjacent
carbon atoms in the R.sup.1 group to form an epoxy group, and
R.sup.1 is an alkanetriyl group containing from 3 to 10 carbon
atoms; and [0042] B) at least one compound having the formula
II
[0042] R.sup.2X(AO).sub.nY (II) [0043] wherein R.sup.2 is a
substituted or unsubstituted, saturated or unsaturated, organic
group having from 1 to 36 carbon atoms; X is --O--, --S--, or
--NR.sup.3-- where R.sup.3 is hydrogen or a C.sub.1-C.sub.18 alkyl
group; each AO group is independently an ethyleneoxy,
1,2-propyleneoxy, or 1,2-butyleneoxy group, n is a number of from 0
to 200, preferably from 1 to 100, more preferably from 2 to 20; and
Y is hydrogen, or Y can be a mercapto group or an amino group
(amino or C.sub.1-C.sub.6 alkylamino group) in place of a terminal
--OH group, provided that when Y is mercapto or an amino, or a
C.sub.1-C.sub.6 alkylamino group, n is at least 1.
[0044] In the reaction products of component II), the mole ratio of
the linking compound A) to B) is from 0.1:1 to 5:1, preferably from
0.6:1 to 2:1, more preferably from 0.8:1 to 2:1 and most preferably
from 1.0:1 to 1.5:1.
[0045] Component II) is present in the aqueous natural rubber latex
compositions of the invention in a wetting and/or defoaming
effective quantity, which is usually in the range of from 0.001 to
5% by weight, preferably from 0.1 to 3% by weight, based on the
weight of the aqueous latex composition.
[0046] This invention also relates to processes for preparing and
methods for using the above latex compositions to form
rubber-containing articles.
DETAILED DESCRIPTION OF THE INVENTION
[0047] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients or
reaction conditions used herein are to be understood as modified in
all instances by the term "about".
Coatings for Metal Containers:
[0048] The metal container coatings of the invention contain from
0.001 to 5% by weight of the above branched reaction product or
products, preferably from 0.1 to 3% by weight. These coatings
normally contain at least one and usually a mixture of the
following: binders, pigments, solvents, and additives.
[0049] Binders (or resins) are generally organic compounds, usually
polymeric or oligomeric in nature, which provide a continuous
matrix in the final film and have a major influence on the
toughness, flexibility, gloss, chemical resistance and cure/dry
properties of the coating.
[0050] Pigments are finely divided powders (particles between 0.1
and 50 micrometers in diameter) which are dispersed throughout the
binder. In addition to reinforcing the final film, much as they do
in composite plastics, they influence a coating's resistance to
abrasion and are designed to react with the resin and become part
of the binder system.
[0051] Major organic solvents include mineral spirits, ketones,
acetates, alcohols, and xylene.
[0052] Among the more important classes of additives used in the
coatings are: (a) surfactants, which are used to suspend pigment
and binder particles; (b) thickeners to obtain proper rheology
(especially in latex paints); (c) plasticizers, which lower the
glass transition temperature of the binder and increase the
flexibility of the coating; (d) antifoam agents to prevent bubbles
in aqueous coatings; (e) antiskin agents, which prevent the
formation of a dry layer on top of the coating while it is still in
the container; (f) preservatives, such as biocides and mildewcides
to protect the binder from microscopic organisms both before and
after application; (g) ultraviolet light absorbers to protect the
binder and/or substrate from degradation due to sunlight; and (h) a
variety of surface conditioners and lubricants, which help the film
adhere to the substrate or protect the film by giving it a
lubricated surface. Additives will often interact and coating
formulators must be careful to watch for synergistic and
antagonistic effects.
[0053] The branched reaction products used in the coatings of the
invention are low foaming surfactants, which can be used as the
only surfactant in the coating compositions, or as a defoaming
agent in conjunction with other surfactants.
[0054] The coating compositions of the invention can be used to
coat metal cans and containers, especially aluminum cans used in
the beverage and food industries, although other metal containers
such as iron, steel, iron alloy, and the like can also be coated
with the coating compositions of the invention. Typically, primers
or conversion coatings are applied first to the metal
containers.
[0055] Where aluminum cans and containers are to be coated,
conversion coatings such as amorphous phosphate coatings are
generally applied first.
[0056] They provide a continuous uniform green coating with
excellent paint-bonding properties and underfilm corrosion
protection. The coatings consist of varying ratios of chromic
phosphate and hydrated aluminum oxide. The bath contains
hydrofluoric acid, which removes the natural oxide to permit
contact of the coating-forming chemicals with the metal. The
complexity of the reactions involved makes it difficult to present
a simplified chemistry, but the results of many tests and analyses
give the following coating composition:
xCrPO.sub.4.yAl.sub.2O.sub.3.zH.sub.2O. The phosphate coatings vary
from 10 to 300 milligrams per square foot (108 to 3228 milligrams
per square meter), depending on the end use. The lower coating
weights are used for paint bonding; the higher range is used for
decorative purposes.
[0057] Gold-colored conversion coatings are formed in baths
containing hydrofluoric acid to remove the natural oxide, and
chromic acid. The coating composition is chromic chromate plus
varying amounts of hydrated aluminum oxide. Some baths also contain
ferricyanide iron, which greatly accelerates the coating action and
forms some chromic ferricyanide in the coating. This constitutes
one of the most widely used conversion coatings on aluminum because
of its high speed, excellent corrosion resistance, and high
affinity for organic finishes. The hexavalent chromium content
permits these coatings to withstand some what more severe corrosive
environments than do the amorphous phosphate coatings. The baths
have a pH of about 1.2 to 1.9 and can be applied by dip, brush,
spray, or reverse roll coater.
[0058] Proprietary chromate rinses are frequently used over
conversion coatings on aluminum for increased corrosion
resistance.
[0059] Conversion coatings can also be applied by
autodeposition.
[0060] Conversion coatings are of course undercoatings to which the
finishing coatings of the invention can be applied.
[0061] The metal container coatings of the invention are nonaqueous
compositions that include, but are not limited to, the following:
[0062] 1. Enamels, which are types of oil-base paints containing
binders that form a film by oxidation or polymerization on exposure
to air and which have an outstanding ability to level off brush
marks, etc., and form an especially smooth film. Enamels are
usually intended for use as top coats and contain relatively less
pigment than paint formulations for priming or surfacing. Enamels
consist of an intimate dispersion of pigments in a varnish or resin
vehicle. The vehicle may be an oil-resin mix or entirely synthetic
resin. Those containing drying oils are converted to films by
oxidation; those comprised wholly of synthetic resins may be
converted by either heat or oxidation, or both. [0063] 2. Lacquers,
which are protective or decorative coatings that dry primarily by
evaporation of solvent, rather than by oxidation or polymerization.
Lacquers were originally comprised of high-viscosity
nitrocellulose, a plasticizer (dibutyl phthalate or brown castor
oil), and a solvent. Later, low-viscosity nitrocellulose became
available; this was frequently modified with resins such as ester
gum or rosin. The solvents used are ethanol, toluene, xylene, and
butyl acetate. Together with nitrocellulose, alkyd resins are used
to improve durability. The nitrocellulose used for lacquers has a
nitrogen content of 11-13.5% and is available in a wide range of
viscosities, compatibilities, and solvencies. Chief uses of
nitrocellulose-alkyd lacquers are for coatings for metal as well as
other products. Various types of modified cellulose are also used
as lacquer bases, combined with resins, and plasticizers. Many
non-cellulosic materials, such as dibutyl phthalate, butylbenzyl
phthalate, vinyl and acrylic resins are also used, as are bitumens,
with or without drying oils, resins, etc. [0064] The term lacquer
is also applied to the baking finish applied to the interior of
food and beverage cans. [0065] 3. Baking finishes, which are paints
or varnishes that require baking at temperatures greater than
66.degree. C. for the development of desired properties. Such
finishes are based on oil-modified alkyd, melamine, epoxy, e.g.
epoxy esters, nitrocellulose, or urea resins, or combinations of
these. Baking is often done by infrared radiation producing high
molecular weight coatings that are dense and tough. [0066] 4. Other
solvent-borne coatings containing resins such as alkyds (polyester
resins made from polybasic acids and polyhydric alcohols),
epoxides, polyurethanes, polyesters other than alkyds, and amino
crosslinkers which are modified melamines. [0067] 5. Thermosetting
acrylic resin based coatings. The acrylic resins are monomer
copolymers of acrylic acid or methacrylic acid esters. Some of the
common monomers are methyl methacrylate, butyl methacrylate, methyl
acrylate, butyl acrylate, ethyl acrylate, and 2-ethylhexyl
acrylate. Thermosetting acrylic resins have at least one monomer
belonging to the acrylic family which will react with itself or
other resins at elevated temperatures to crosslink in order to
cure. In addition to acrylic monomers previously mentioned,
acrylonitrile, acrylamide, styrene, and vinyl toluene are often
used in these polymers. Polymers which react to crosslink primarily
because of hydroxyl groups are usually combined with an epoxy
resin; those which react mainly with carboxyl groups usually are
combined with an amine resin. Thermosetting acrylic paints are hard
and stain-resistant and have high gloss. [0068] 6. Phenolic
coatings, which contain phenolic resins as used in coatings are
primarily made from phenol and para-substituted phenols reacted
with formaldehyde to form methylol groups on the phenol ring.
Condensation polymers are then produced by reacting these groups
with phenol. Phenolic coatings are fast drying and have high build
and good resistance to moisture and chemicals. Phenolic coatings
are sometimes used for baked can coatings, and oil-modified
phenolaldehyde finishes are sometimes used for aluminum paints.
[0069] 7. Polyurethane coatings are based upon reactions of
isocyanates. Urethane coatings have excellent solvent and chemical
resistance, abrasion resistance, hardness, flexibility, gloss, and
electrical properties. The above coatings containing the above
branched reaction product or products, can then be applied to one
or more surfaces of metal containers. Application methods include
the use of air or airless spray equipment; electrostatic, hot or
steam spraying; and the use of dip, or flow coating. With
electrostatic spraying, the atomized coating is attracted to the
conductive object to be coated by an electrostatic potential
between the coating and the object. Very little coating is lost
with this process, and irregular objects can be coated uniformly.
Heat spray application consists of heating the coating so that it
is more fluid and higher-solids coatings can be applied. With steam
spraying, steam is used to atomize the coating. Two-component spray
equipment consists of two material lines to the spray gun so that
two materials, e.g., an epoxy and a catalyst, can be mixed in the
gun just before application.
[0070] In the branched reaction products used in the metal
container coating compositions of the invention, the linking
compound of formula I in component A is preferably epichlorohydrin
or another epihalohydrin. However, trihaloalkanes can be used, such
as 1,2,3-trichloropropane, 1,2,4-trichlorobutane,
1,3,6-trichlorohexane, and the like. Instead of chlorine in the
epihalohydrins and trihaloalkanes, the corresponding bromine and
iodine compounds can also be used, including compounds containing
two or even all three of the above halogens.
[0071] The component B) compounds of formula II are organic
(optionally alkoxylated) alcohols or the corresponding sulfhydryl
or amine compounds.
[0072] The R.sup.2 group can be a substituted or unsubstituted,
saturated or unsaturated hydrocarbon group having from 1 to 36
carbon atoms. Examples of such hydrocarbon groups include linear or
branched alkyl groups having from 1 to 36 carbon atoms, preferably
from 4 to 22 carbon atoms, linear or branched alkenyl or alkynyl
groups having from 2 to 36 carbon atoms, preferably from 4 to 22
carbon atoms, aryl groups having from 6 to 22 carbon atoms, and
arenyl groups having from 7 to 36 carbon atoms. Arenyl groups are
alkyl-substituted aromatic radicals having a free valence at an
alkyl carbon atom such as a benzylic group.
[0073] The R.sup.2 group can also be a saturated carbocyclic group,
an unsaturated carbocyclic group having one or more multiple bonds,
a saturated heterocyclic group, an unsaturated heterocyclic group
having one or more multiple bonds. Any of the above R.sup.2 groups
can be substituted groups, i.e. the groups can be single or
multiple substituents such as a sulfur functionality such as a
mercaptan or thio group; a nitrogen functionality such as an amine
or amide functionality; an alcohol functionality, a silicon
functionality, e.g., a siloxane; an ether functionality, e.g. a
C.sub.1-C.sub.6 alkoxy group, or any combination thereof.
[0074] The R.sup.2 group in formula II is preferably a branched
chain alkyl group containing from 4 to 36 carbon atoms, preferably
from 4 to 12 carbon atoms, and more preferably from 8 to 12 carbon
atoms.
[0075] When the X group of formula II is an --S-- group, the
R.sup.2 group will preferably have from about 4 to about 22 carbon
atoms, examples of which include but are not limited to, dodecyl
mercapto and 1-hexadecanethio.
[0076] When the R.sup.2X-group of formula II is a secondary or
tertiary amino group, the group preferably contains from 4 to 22
carbon atoms, and n is preferably a number of from 1 to 50.
Examples of primary and secondary amines useful for obtaining the
R.sup.2X-group include, but are not limited to, cyclohexyl amine,
isodecyl amine, and dioctylamine.
[0077] Optionally an additional component C) can be reacted with
the linking agent of formula I and the compound of formula II. A
glycidyl ether or amine can be added to the reaction of formula I
and formula II. The amount of the glycidyl ether or glycidyl amine
is from about 1 to about 20 mole percent based on the moles of the
compounds of formula II used in the reaction. When the glycidyl
ether or glycidyl amine is added, the ratio of component A) plus
the glycidyl ether or glycidyl amine to component B) is preferably
from about 1.2:1 to about 5:1. Examples of glycidyl ether include,
but are not limited to, PEG 600 diglycidyl ether, TETRONIC.TM. 701
tetraglycidyl ether, triglycidyl di or triethanolamine,
polyoxyethylene (POE) 200 tallow amine diglycidyl ether,
propoxylated (POP10) trimethylol propane triglycidyl ether,
propoxylated (POP7) pentaerythritol tetraglycidyl ether. Examples
of glycidyl amines include, but are not limited to, tetraglycidyl
1,6-hexane diamine, tetraglycidyl JEFFAMINE.TM. EDR-148, and
tetraglycidyl isophorone diamine.
[0078] When Y in formula II is an amine or sulfhydryl group, the
resulting compounds can be readily prepared from the corresponding
alcohols wherein the terminal hydroxy group is replaced by an --SH
group or by an amine nitrogen. For example, a compound of formula
II where Y is --OH can be subjected to a catalyzed ammoniation
(with ammonia, or a lower alkylamine) for replacement of the
hydroxyl, or to a capping of the hydroxyl with epichlorohydrin
followed by ammoniation (with ammonia, or a lower alkylamine) of
the resulting glycidyl group.
[0079] In the compounds of formula II, the AO groups when present
are preferably all ethyleneoxy groups. However, as stated above,
each OA group can be independently an ethyleneoxy (EO),
1,2-propyleneoxy (PO), 1,2-butyleneoxy (BO) group, i.e. any one or
more of such groups can be present, and they can be present in any
order, as well as be present in blocks, e.g. compounds of formula
III:
R.sup.2O(EO).sub.m(PO).sub.p(BO).sub.qH (III)
wherein R.sup.2 has the meaning given above, m is a number of from
0 to 100, preferably from 1 to 50, p is a number of from 0 to 50,
e.g. from 1 to 50, and q is a number of from 0 to 50, e.g. from 1
to 50. Compounds of formula III in which R.sup.2 is a branched
chain alkyl group having from 4 to 12 carbon atoms, m is a number
of from 2 to 20, and p and q are 0 are preferred.
[0080] The degree of hydrophilic and hydrophobic properties of the
reaction products of components A) and B) can be readily controlled
by controlling the type and number of alkyleneoxy groups in
component B). For example, the greater the number of ethyleneoxy
groups present, the greater the water solubility, while the
presence of 1,2-propyleneoxy groups and/or 1,2-butyleneoxy groups
for example, will decrease water solubility.
[0081] In general, the compounds of formula III wherein the sum of
n, m, and p is at least 1, and especially at least 2 are preferred
for use herein.
[0082] The branched reaction products used in the practice of the
invention can be prepared by reacting components A) and B) (and C
if present) together, preferably in the presence of an inert
organic solvent, preferably a solvent such as toluene that will
azeotrope water, and in the presence of an inorganic base such as
an alkali metal hydroxide, e.g. aqueous sodium hydroxide or
potassium hydroxide, at a temperature in the range of from 60 to
125.degree. C. In a preferred embodiment of the process, component
B) is first mixed with the base, and the organic solvent, if
present, and water is removed, e.g. by azeotropic distillation.
Then component A) (and C, if present) is slowly added and the
reaction continued until the reaction is completed. The reaction
mixture is filtered and the filtrate vacuum stripped to remove any
organic solvent.
[0083] Inert organic solvents that can be used in the above process
are nonmiscible with water and nonhydroxylic. Examples of such
solvents include toluene, CHCl.sub.3, CH.sub.2Cl.sub.2,
chlorobenzene, acetonitrile, and petroleum ethers, preferably
toluene.
[0084] This invention will be illustrated but not limited by the
following examples.
EXAMPLES
Example 1
Preparation of the Reaction Product of Decyl Alcohol.4EO and
Epichlorohydrin
[0085] About 150 grams of decyl alcohol ethoxylated with an average
of 4 moles of ethylene oxide (0.45 OH equivalents) were mixed with
385 grams of toluene and 54 grams of 50% aq. NaOH (0.675
equivalents). The water was removed by azeotropic distillation and
when a moisture level of less than 0.8% was reached, about 46 grams
(0.51 equivalents) of epichlorhydrin were slowly added. This
mixture was allowed to react at 100.degree. to 110.degree. C. for
24 hours. An aliquot of this mixture was removed and filtered to
remove the NaCl and vacuum stripped to remove the toluene to give
an amber, easily pourable liquid product that was dispersible in
water.
Example 2
[0086] To an Acryloid.TM. Coating Resin (acrylic ester polymers in
an organic solvent solution) is added 1.0% by weight of the
reaction product of Example 1.
[0087] Two piece clean aluminum cans are coated with the above
mixture by dipping the cans into a vat containing the mixture.
[0088] The cans are dried, leaving a clear resistant coating on the
metal surfaces of the cans. The coating has high gloss and is
highly uniform, without discernable bubbles or pits.
Example 3
Preparation of the Reaction Product of Octyl Alcohol 4EO and
Epichlorohydrin
[0089] About 200.0 gm (0.654 hydroxyl equivs.) of octyl alcohol
ethoxylated with an average of 4 moles of ethylene oxide was mixed
with 400 gm toluene and 78.4 gm (0.98 equivs.) of 50% NaOH. Water
was removed by azeotropic distillation until the level was below
0.8%. The mixture was cooled to 80.degree. C. and 67.2 gm (0.72
moles) of epichlorohydrin was added over 45 mins. The mixture was
stirred for 24 hrs at 110.degree. C. until the epoxy titration
showed no epoxide left. The material was cooled, filtered and the
toluene was removed by vacuum distillation leaving a dark brown low
viscosity liquid.
Example 4
[0090] To an Acryloid.TM. Coating Resin (acrylic ester polymers in
an organic solvent solution) is added 2.5% by weight of the
reaction product of Example 3.
[0091] Two piece clean aluminum cans are coated with the above
mixture by dipping the cans into a vat containing the mixture.
[0092] The cans are dried, leaving a clear resistant coating on the
metal surfaces of the cans. The coating has high gloss and is
highly uniform, without discernable bubbles or pits.
Metalworking Lubricant Compositions:
[0093] Component B) is present in the metalworking lubricant
compositions of the invention in a surfactant effective amount,
which is usually in the range of from 0.001 to 10% by weight of the
compositions, preferably from 0.1 to 3% by weight.
[0094] The branched reaction products (component B) used in the
compositions of the invention are low-foaming surfactants, which
can be used as the only surfactant in the compositions, or as a
defoaming agent and/or surfactant in conjunction with other
surfactants.
[0095] The metalworking lubricant compositions of the invention are
referred to as "cutting fluids" when used in machine-tool
operations to modify the harmful effects of friction and high
temperatures. Their major function is to lubricate and cool. When
cutting a screw thread, either on a lathe or with a tap, the
lubricating function is most important; in production-grinding
operations, the cooling function predominates. Lard oil has
excellent lubricating qualities, but it tends to become rancid.
Sulfurized mineral oil is one of the most popular cutting fluids.
The sulfur tends to prevent chips from the workpiece from welding
to the tip of the tool. For sawing and grinding operations, soluble
oil, which is an oily emulsion freely miscible in water, is
commonly used. Soluble oil, also called emulsifying oil, is a milky
emulsion containing e.g. sodium and potassium petroleum
sulfonates.
[0096] Cutting fluids can be used in the operation of drilling
machines, milling machines, turret lathes, grinding machines, power
saws, presses, multiple-station vertical lathes, gang drills,
production millers, gear-cutting machines, broaching machines,
lapping and honing machines, boring machines, and the like. Also
included is the cold forming of metal parts, such as cooking
utensils, automobile bodies, and the like, which are carried out on
punch presses.
[0097] Boundary lubricants are used where boundary conditions are
encountered in metal forming processes in which the pressures
required to deform the metal are too high to allow an oil film to
form. In such applications, fatty oils, such as palm oil, or
lubricants containing fatty materials are employed to reduce the
friction and wear; the fatty acids react with the metal surface to
form a tenacious soap film which provides lubrication up to
temperatures near the melting point of the soap, usually about
250.degree. F. (120.degree. C.). Where conditions are not severe,
long chain fatty alcohols can also act as boundary lubricants.
[0098] If the pressures and temperatures between contacting
surfaces are moderate, the provision of a boundary lubricating film
will suffice, whereas if conditions of both temperature and
pressure are severe, some form of extreme pressure (EP) lubrication
may be necessary.
[0099] Under the very severe conditions sometimes encountered in
machining operations, it is necessary to prevent the chip from
welding to the cutting tool, and only those compositions act as
extreme pressure (EP) lubricants which contain, in addition to
components A) and B), an additive as component C) which is a
compound containing chemically active chlorine, sulfur, or
phosphorus to form the corresponding iron chloride, sulfide, or
phosphide, by instantaneous attack on the surface hot spots
resulting from the collisions of surface asperities. The chemical
stability of these so-called E.P. agents is designed to permit
activity at the temperature near the rubbing surface, say
200.degree. C. and above, but not be corrosive under normal
conditions, i.e. at ambient temperatures and pressures.
[0100] It should be noted that mixed film lubrication is almost
invariably the true state of affairs when boundary and E.P.
lubrication are encountered, i.e., an appreciable fraction of the
load is carried by the fluid film in the "valleys" of the surface
while the asperities in contact are permitted to carry the balance
of the load without seizure through the beneficent intervention of
the boundary or EP lubricant.
[0101] The very important break-in process of rubbing surfaces
consists of the controlled reduction of the number and the size of
the surface asperities so that fluid lubrication will prevail for
most of the time.
[0102] The metalworking compositions of the invention can
optionally contain one or more of the following additives: [0103]
D) a viscosity improver, e.g. a polymeric substance such as
polybutene and copolymers of polymethacrylates. [0104] E) a
pour-point depressant, e.g. a metallic soap, a condensation product
of chlorinated wax and alkyl naphthalenes or phenols,
polymethacrylates, and the like. [0105] F) an antioxidant, e.g. a
hindered phenol such as dibutyl-p-cresol, amines such as
phenyl-.alpha.-naphthylamine metal phenates which are alkaline
earth salts of phenol disulfides, zinc salts of thiophosphates and
carbamates, and the like. [0106] G) an amine such as an
ethanolamine to provide alkalinity. [0107] H) a solvent, generally
water. [0108] I) a buffer, e.g. boric acid. [0109] J) other
nonionic surfactants. [0110] K) a corrosion inhibitor, e.g. tall
oil fatty acid, octyl alcohol, and the like. [0111] L) a coupling
agent, e.g. butoxyethanol, butyldiglycol, and the like.
[0112] The component A) lubricating agent is usually a mineral oil,
such as a naphthenic oil, or an ester lubricating oil, although
other lubricating agents described in the BACKGROUND OF THE
INVENTION can also be used herein.
[0113] Component A) is usually present in from 30 to 90% by weight
of the composition, preferably from 35 to 65% by weight.
[0114] In the component B) reaction products used in the
metalworking compositions of the invention, the linking compound of
formula I in component a) thereof is preferably epichlorohydrin or
another epihalohydrin. However, trihaloalkanes can be used, such as
1,2,3-trichloropropane, 1,2,4-trichlorobutane,
1,3,6-trichlorohexane, and the like. Instead of chlorine in the
epihalohydrins and trihaloalkanes, the corresponding bromine and
iodine compounds can also be used, including compounds containing
two or even all three of the above halogens.
[0115] The component b) compounds of formula II are organic
(optionally alkoxylated) alcohols or the corresponding sulfhydryl
or amine compounds. The R.sup.2 group can be a substituted or
unsubstituted, saturated or unsaturated hydrocarbon group having
from 1 to 36 carbon atoms. Examples of such hydrocarbon groups
include linear or branched alkyl groups having from 1 to 36 carbon
atoms, preferably from 4 to 22 carbon atoms, linear or branched
alkenyl or alkynyl groups having from 2 to 36 carbon atoms,
preferably from 4 to 22 carbon atoms, aryl groups having from 6 to
22 carbon atoms, and arenyl group having from 7 to 36 carbon atoms.
Arenyl groups are alkyl-substituted aromatic radicals having a free
valence at an alkyl carbon atom such as a benzylic group.
[0116] The R.sup.2 group can also be a saturated carbocyclic group,
an unsaturated carbocyclic group having one or more multiple bonds,
a saturated heterocyclic group, or an unsaturated heterocyclic
group having one or more multiple bonds. Any of the above R.sup.2
groups can be substituted groups, i.e. the substituents can be
single or multiple substituents such as a sulfur functionality such
as a mercaptan or thio group; a nitrogen functionality such as an
amine or amide functionality; an alcohol functionality, a silicon
functionality, e.g., a siloxane; an ether functionality, e.g. a
C.sub.1-C.sub.6 alkoxy group; or any combination thereof.
[0117] The R.sup.2 group in formula II is preferably a branched
chain alkyl group containing from 4 to 36 carbon atoms, preferably
from 4 to 12 carbon atoms, and more preferably from 8 to 12 carbon
atoms.
[0118] When the X group of formula II is an --S-- group, the
R.sup.2 group will preferably have from 4 to 22 carbon atoms,
examples of which include but are not limited to, dodecyl mercapto
and 1-hexadecanethio.
[0119] When the R.sup.2X-group of formula II is a secondary or
tertiary amino group, the group preferably contains from 4 to 22
carbon atoms, and n is preferably a number of from 1 to 50.
Examples of primary and secondary amines useful for obtaining the
R.sup.2X-group include, but are not limited to, dibutyl amine,
cyclohexyl amine, isodecyl amine, and dioctylamine.
[0120] Optionally an additional component c) can be reacted with
the linking agent of formula I and the compound of formula II. A
glycidyl ether or amine can be added to the reaction of formula I
and formula II. The amount of the glycidyl ether or glycidyl amine
is from about 1 to about 20 mole percent based on the moles of the
compounds of formula II used in the reaction. When the glycidyl
ether or glycidyl amine is added, the ratio of component a) plus
the glycidyl ether or glycidyl amine to component b) is preferably
from about 1.2:1 to about 5:1. Examples of glycidyl ether include,
but are not limited to, PEG 600 diglycidyl ether, TETRONIC.TM. 701
tetraglycidyl ether, triglycidyl di- or triethanolamine,
polyoxyethylene (POE) 200 tallow amine diglycidyl ether,
propoxylated (POP10) trimethylol propane triglycidyl ether,
propoxylated (POP7) pentaerythritol tertraglycidyl ether. Examples
of glycidyl amines include, but are not limited to, tetraglycidyl
1,6-hexane diamine, tetraglycidyl JEFFAMINE.TM. EDR-148, and
tetraglycidyl isophorone diamine.
[0121] When Y in formula II is an amine or sulfhydryl group, the
resulting compounds can be readily prepared from the corresponding
alcohols wherein the terminal hydroxy group is replaced by an --SH
group or by an amine nitrogen. For example, a compound of formula
II where Y is --OH can be subjected to a catalyzed ammoniation
(with ammonia, or a lower alkylamine) for replacement of the
hydroxyl.
[0122] In the compounds of formula II, the AO groups when present
are preferably all ethyleneoxy groups. However, as stated above,
each OA group can be independently an ethyleneoxy (EO),
1,2-propyleneoxy (PO), or 1,2-butyleneoxy
[0123] (BO) group, i.e. any one or more of such groups can be
present, and they can be present in any order, as well as be
present in blocks, e.g. compounds of formula III:
R.sup.20(EO).sub.m(PO).sub.p(BO).sub.qH (III)
wherein R.sup.2 has the meaning given above, m is a number of from
0 to 100, preferably from 1 to 50, p is a number of from 0 to 50,
e.g. from 1 to 50, and q is a number of from 0 to 50, e.g. from 1
to 50. Compounds of formula III in which R.sup.2 is a branched
chain alkyl group having from 4 to 12 carbon atoms, m is a number
of from 2 to 20, and p and q are 0 are preferred.
[0124] The degree of hydrophilic and hydrophobic properties of the
reaction products of components a) and b) can be readily controlled
by controlling the type and number of alkyleneoxy groups in
component b). For example, the greater the number of ethyleneoxy
groups present, the greater the water solubility, while the
presence of 1,2-propyleneoxy groups and/or 1,2-butyleneoxy groups
for example, will decrease water solubility.
[0125] In general, the compounds of formula III wherein the sum of
n, m, and p is at least 1, and especially at least 2 are preferred
for use herein.
[0126] The branched reaction products used in the practice of the
invention can be prepared by reacting components a) and b) (and c)
if present) together, preferably in the presence of an inert
organic solvent, preferably a solvent such as toluene that will
azeotrope water, and in the presence of an inorganic base such as
an alkali metal hydroxide, e.g. aqueous sodium hydroxide or
potassium hydroxide, at a temperature in the range of from 60 to
125.degree. C. In a preferred embodiment of the process, component
b) is first mixed with the base, and the organic solvent, if
present, and water is removed, e.g. by azeotropic distillation.
Then component a) (and c), if present) is slowly added and the
reaction continued until the reaction is completed. The reaction
mixture is filtered and the filtrate vacuum stripped to remove any
organic solvent.
[0127] Inert organic solvents that can be used in the above process
are nonmiscible with water and nonhydroxylic. Examples of such
solvents include toluene, CHCl.sub.3, CH.sub.2Cl.sub.2,
chlorobenzene, acetonitrile, and petroleum ethers, preferably
toluene.
[0128] The invention will be illustrated but not limited by the
following examples.
EXAMPLES
Example 1
Preparation of the Reaction Product of Decyl Alcohol.4EO and
Epichlorohydrin
[0129] About 150 grams of decyl alcohol ethoxylated with an average
of 4 moles of ethylene oxide (0.45 OH equivalents) were mixed with
385 grams of toluene and 54 grams of 50% aq. NaOH (0.675
equivalents). The water was removed by azeotropic distillation and
when a moisture level of less than 0.8% was reached, about 46 grams
(0.51 equivalents) of epichlorohydrin were slowly added.
[0130] This mixture was allowed to react at 100-110.degree. C. for
24 hours. An aliquot of this mixture was removed and filtered to
remove the NaCl and vacuum stripped to remove the toluene to give
an amber, easily pourable liquid product that was dispersible in
water.
Example 2
[0131] Two water-miscible metalworking fluid concentrates are
prepared by mixing together the following components shown in Table
1 below. The emulsifier pre-mixes are prepared first, and then
mixed with either a mineral oil or an ester oil shown in Table 1
below.
TABLE-US-00001 TABLE 1 Emulsifier Pre-mix Mineral Oil Ester Raw
Material Functions % % Monoethanolamine Alkalinity 15.6 15.0
Triethanolamine Alkalinity 3.1 1.3 Boric Acid Buffer System,
Biostability 7.8 3.1 Deionized Water Solvent 8.2 1.6 Tall Oil Fatty
Acid Corrosion Inhibitor, 28.6 15.0 25/30 Anionic Emulsifier LOROL
.RTM. C8-98.sup.1 Corrosion Inhibitor, -- 6.0 Anionic Emulsifier
EUMULGIN .RTM. 3499.sup.2 Corrosion Inhibitor, 7.1 11.0 Coupling
Agent EUMULGIN .RTM. 3370V.sup.3 Nonionic Surfactant 7.2 17.0
EUMULGIN .RTM. EP5LV.sup.4 Nonionic Surfactant 14.3 16.0
Butoxyethanol Coupling Agent 7.1 -- Butyldiglycol Coupling Agent --
11.0 Example 1 Reaction Wetting Agent, Defoaming 3.0 3.0 Product
Agent, Dispersing Agent, Lubricant Enhancer, Extreme Pressure Agent
Appearance Clear Clear Liquid Liquid Soluble Oil Emulsifier Pre-Mix
50.0 40.0 Naphthenic Oil Base Oil 50.0 -- EDENOR .RTM. EHO.sup.5
Base Oil, Lubricity -- 60.0 .sup.1Octyl alcohol .sup.2A proprietary
emulsifier blend .sup.3Ethoxylated cetyl/oleyl alcohol
.sup.4Ethoxylated cetyl/oleyl alcohol with 5EO groups .sup.5a
lubricating ester oil
[0132] For commercial purposes, it is desirable to add additional
components to the above metal working fluids, e.g. copper corrosion
inhibitors, biocides, and fungicides.
[0133] The above metalworking fluid concentrates can be mixed with
water to form a metalworking lubricant composition for use in the
working of metals, e.g. a 3% solution in water.
Example 3
Preparation of the Reaction Product of Octyl Alcohol.4EO and
Epichlorohydrin
[0134] About 200.0 gm (0.654 hydroxyl equivs.) of octyl alcohol
ethoxylated with an average of 4 moles of ethylene oxide was mixed
with 400 gm toluene and 78.4 gm (0.98 equivs.) of 50% NaOH. Water
was removed by azeotropic distillation until the level was below
0.8%. The mixture was cooled to 80.degree. C. and 67.2 gm (0.72
moles) of epichlorohydrin was added over 45 mins. The mixture was
stirred for 24 hrs at 110.degree. C. until the epoxy titration
showed no epoxide left. The material was cooled, filtered and the
toluene was removed by vacuum distillation leaving a dark brown low
viscosity liquid.
Example 4
[0135] Two water-miscible metalworking fluid concentrates are
prepared by mixing together the following components set forth in
Table 2 below.
TABLE-US-00002 TABLE 2 Metalworking Fluid Concentrate Mineral Oil -
Based Ester - Based % % Monoethanolamine 8.3 5.7 Triethanolamine
1.6 0.6 Boric Acid 3.9 1.4 Deionized Water 3.4 0.7 Tall Oil Fatty
Acid (25/30) 12.7 4.3 LOROL .RTM. C8 98 -- 2.5 EUMULGIN .RTM. 3499
4.0 5.7 EUMULGIN .RTM. 3412V.sup.6 6.6 6.5 EUMULGIN .RTM. ET
5V.sup.7 -- 6.4 EUMULGIN .RTM. EP 5 LV 5.0 -- 2-Butoxyethanol 2.5
-- Butyldiglycol -- 4.2 Naphthenic Oil 50.0 -- EDENOR .RTM. EHO --
60.0 Example 3 Reaction Product 2.0 2.0 Appearance Clear Liquid
Clear Liquid .sup.6an ethoxylated alcohol .sup.7Ethoxylated
cetyl/stearyl alcohol (5EO groups)
[0136] The above concentrate can be diluted to a 3% concentration
in water for use in metalworking. In addition to the above
components, it is desirable to also include copper corrosion
inhibitors, biocides, and fungicides.
Compositions for Electroplating and Electrowinning:
[0137] The branched reaction products (component B)) used in the
aqueous compositions of the invention are low foaming surfactants,
which can be used as the only surfactant in the aqueous
compositions, or as a defoaming agent and surfactant in conjunction
with other surfactants.
[0138] Component B) is present in the aqueous compositions of the
invention in a surfactant effective amount, which is usually in the
range of from 0.001 to 5% by weight of the compositions, preferably
from 0.1 to 3% by weight.
[0139] The component A) metals or metalloids can be one or more of
zinc, nickel, copper, chromium, manganese, iron, cobalt, gallium,
germanium, arsenic, selenium, ruthenium, rhodium, palladium,
silver, cadmium, indium, tin, lead, bismuth, mercury, antimony,
gold, iridium, and platinum. The above metals or metalloids can be
added to the aqueous compositions in metallic form and/or in the
form of anions.
[0140] In addition to the metals listed above, many alloys are
commercially electroplated, such as brass, bronze, many gold
alloys, lead-tin, nickel-iron, nickel-cobalt, nickel-phosphorous,
tin-nickel, tin-zinc, zinc-nickel, zinc-cobalt, and zinc-iron.
Electroplated alloys in lesser use include lead-indium,
nickel-manganese, nickel-tungsten, palladium alloys, silver alloys,
and zinc-manganese.
[0141] Another type of electrodeposit in commercial use is the
composite form, in which insoluble materials are codeposited along
with the electrodeposited metal or alloy to produce particular
desirable properties. Polytetrafluoroethylene
[0142] (PTFE) particles are codeposited with nickel to improve
lubricity. Silicon carbide and other hard particles including
diamond are co-deposited with nickel to improve wear properties or
to make cutting and grinding tools.
[0143] The term "metalloid" is to be understood to mean nonmetals
which are semiconductors, e.g. arsenic, germanium, and the like,
which can be electroplated in the same manner as metals.
[0144] The essential components of an electroplating process are an
electrode to be plated (the cathode); a second electrode to
complete the circuit (the anode); an electrolyte containing the
metal ions to be deposited; and a d-c power source. The electrodes
are immersed in the electrolyte such that the anode is connected to
the positive leg of the power supply and the cathode to the
negative. As the current is increased from zero, a minimum point is
reached where metal plating begins to take place on the
cathode.
[0145] There are a number of electroplating methods for which the
compositions of the invention can be used. Materials such as strip
steel can be plated in plating tanks where coils of steel are
unrolled on a continuous basis, fed through a series of preparation
steps, and then into the plating tank. To electroplate wire, the
wire is uncoiled from spools or reels, passed through processing
steps and then plated as individual strands. Wire is plated
commercially with metals such as copper, copper alloys, zinc, iron,
iron alloys, nickel, nickel alloys, gold, and silver. Stampings,
moldings and castings are typically mounted onto specially designed
plating racks. Bulk plating methods can be used for small parts,
e.g. dipping baskets and plating barrels made of inert plastic
materials. Where parts are large and only smaller areas of the
parts are to be plated, brush plating is used, i.e. using plating
tools which are shaped anode materials covered with an absorbent
material saturated with the plating solution.
[0146] Plating tanks are formed from materials which are either
totally inert to the plating solution or are lined with inert
materials to protect the tank. For alkaline plating solutions, mild
steel materials are used. For acid plating solutions other
materials are used, depending on the chemical composition of the
plating bath, such as titanium and various stainless steel alloys,
polytetrafluoroethylene, KARBATE.RTM., HASTALLOYS.RTM., zirconium
alloys, and the like.
[0147] The plating tanks are fitted for d-c power, usually with
round copper busbars. Filters are usually present to remove fine
particulate matter. Heating or cooling units may be present, such
as heating coils or cooling water coils. Two types of anodes can be
used, i.e. soluble or insoluble.
[0148] Soluble anodes are designed to dissolve effectively with
current flow and preferably, not to dissolve when the system is
idle. A plating solution having the anode efficiency close to the
cathode efficiency provides a balanced process that has fewer
control problems and is less costly. If the anode efficiency is
much greater than the cathode efficiency and there are only small
solution losses, the dissolved metal concentration rises until at
some time the bath has to be diluted back or the excess metal has
to be reduced by some other means. If the anode efficiency is less
than the cathode efficiency, the dissolved metal decreases, pH
decreases, and eventually metal salt additions and other solution
corrections are required. Based on the cost of metal, it is usually
considerably more economical to plate from the anode rather than
add metal salt. (See e.g. Kirk-Othmer, Encyclopedia of Chemical
Technology, 4.sup.th Edition under the heading Electroplating).
[0149] Insoluble anodes are used exclusively in some plating baths.
Chromium plating solutions utilize lead-tin, lead-antimony, or lead
anodes. Gold and other precious metal plating processes use
stainless steel anodes, keeping inventory costs down.
[0150] Whenever insoluble anodes are used, the pH of the plating
solution decreases along with the metal ion concentration. In some
plating baths, a portion of the anodes is replaced with insoluble
anodes in order to prevent metal ion buildup or to reduce metal ion
concentration.
[0151] The use of insoluble anodes can also result in side effects.
In alkaline cyanide solutions, the generation and buildup of
carbonates is accelerated remarkably, along with a significant
reduction in alkalinity. In acid solutions the pH decreases as
well, requiring frequent adjustments. In sulfamate nickel plating
solutions, insoluble anodes, and even slightly passive soluble
anodes, partially oxidize the sulfamate ion to form sulfur-bearing
compounds which change the character and performance of the deposit
(See Kirk-Othmer, supra).
[0152] The substrates being electroplated must usually be prepared
prior to electroplating. Because electroplating takes place at the
exact molecular surface of a work, it is important that the
substrate surface be absolutely clean and receptive to the plating.
In the effort to get the substrate into this condition, several
separate steps may be required, such as soak cleaning, followed by
electrocleaning, followed by rinsing.
[0153] Formulations of plating baths can be flexible in some
systems and very sensitive to variations in others. Many of the
more recent changes have resulted from waste treatment and safety
requirements. Besides the ability to deposit a coating having
acceptable appearance and physical properties, the desired
properties of a plating bath would include: high metal solubility,
good electrical conductivity, good current efficiencies for anode
and cathode, noncorrosivity to substrates, nonfuming, stable, low
hazard, low anode dissolution during down-time, good throwing
power, good covering power, wide current density plating range,
ease of waste treatment, and economical to use. Few formulas have
all these attributes. Only a few plating solutions are commercially
used without special additives, but chemical costs often constitute
a relatively low percentage of the total cost of electroplating.
Additives are used to brighten, reduce pitting, or otherwise modify
the character of the deposit or performance of the solution.
Preferred formulations are normally specified by the suppliers of
the proprietary additives.
[0154] Purification, often needed once a plating bath is made, is
used periodically to maintain the plating solutions. Alkaline zinc
plating solutions are sensitive to a few mg/L of heavy-metal
contamination, which can be precipitated using sodium sulfide and
filtered out. Nickel plating solutions may contain excess iron and
unknown organic contaminants. Iron is removed by peroxide
oxidation, precipitation at a pH of about 5, then filtered out. The
more complex, less water-soluble organic contaminants along with
some trace metals are removed with activated carbon treatments in
separate treatment tanks.
[0155] Another common purification treatment used both on new and
used plating solution is dummying. Heavy-metal impurities are
removed by electrolyzing, usually at low current densities, using
large disposable steel cathodes. Good agitation and lower pH speed
the process.
[0156] Analysis and testing are required whenever a new plating
solution is made up, and thereafter at periodic intervals. The
analyses are relatively simple and require little equipment. Trace
metal contaminants can be analyzed by using spot tests,
colorimetrically, and with atomic absorption spectrophotometry.
Additives, chemical balance, impurity effects, and many other
variables are tested with small plating cells, such as the Hull
cell.
[0157] The precise makeup of plating bath compositions depends on
the metal being plated. For example, alkaline cadmium plating baths
usually contain cyanide salts, such as sodium cyanide, while acidic
baths contain an acid, usually sulfuric acid. Various additives may
also be present.
[0158] Cyanide copper plating baths typically contain copper metal,
copper cyanide, potassium cyanide, potassium hydroxide, Rochelle
salts, and sodium carbonate. Acid copper plating baths typically
contain copper metal, copper sulfate, sulfuric acid, and
additives.
[0159] Watts nickel plating baths typically contain nickel metal,
nickel sulfate, nickel chloride, boric acid, and additives.
Sulfamate nickel plating baths contain nickel sulfamate instead of
nickel sulfate.
[0160] Silver plating baths typically contain silver cyanide,
potassium cyanide, potassium carbonate, and sometimes potassium
nitrate and potassium hydroxide, plus additives.
[0161] Zinc plating baths can range from simple zinc sulfate
solutions to zinc plus chloride/boric acid baths with brighteners
and wetting agents. Also, zincate baths and cyanide baths are also
used.
[0162] Electroforming is the production or reproduction of articles
by electrodeposition upon a mandrel or mold that is subsequently
separated from the deposit. The separated electrodeposit becomes
the manufactured article. Of all the metals, copper and nickel are
most widely used in electroforming. Mandrels are of two types:
permanent or expendable. Permanent mandrels are treated in a
variety of ways to passivate the surface so that the deposit has
very little or no adhesion to the mandrel, and separation is easily
accomplished without damaging the mandrel. Expendable mandrels are
used where the shape of the electroform would prohibit removal of
the mandrel without damage. Low melting alloys, metals that can be
chemically dissolved without attack on the electroform, plastics
that can be dissolved in solvents, are typical examples.
[0163] Electrowinning is used in the process of recovering metals
from ores. The aqueous processes for electrowinning of metals from
ores have the following common unit operations or steps: (1) the
metal in the ore is converted to an acid-soluble form and this may
be an oxidizing roast or a reduction; (2) ores from step 1 are
leached, usually in sulfuric acid; (3) metal solutions from step 2
are purified and in some cases concentrated; (4) purified metal
solutions are electrolyzed in cells where the metal is deposited on
the cathode; and (5) acid is produced at the anode and recycled to
the leaching step 2. Some acid values are lost, usually in the
purification step 3. Makeup acid is added in the leaching step 2.
In most cases the metal solution from leaching step 2 contains
impurities, other metals. Many of these metals have the
characteristics of low hydrogen over-voltage. Codeposition of the
impurity metals causes contamination of the desired product and
decreases current efficiencies. The removal of impurities before
electrolysis is very important. This is especially true in the case
of the more reactive metals such as zinc, and manganese. These
metals have deposition potentials close to the hydrogen evolution
potential. The current efficiency of manganese electrowinning is
about 60 to 68%. The principal inefficiency is hydrogen
evolution.
[0164] The electrowinning of metals from aqueous solutions is
generally carried out in tank cells. Developments in the
electrowinning of metals from aqueous solutions have been directed
toward improved anodes, improved additives, higher current
densities, the use of ion-exchange membranes, better electrolyte
quality control, and computer modeling of the processes.
[0165] Another electroplating process in which the component B)
branched reaction products used in the aqueous compositions of the
invention can be employed is the electrochemical treatment of waste
solutions containing dissolved metals.
[0166] It is to be understood that the term "electroplating
composition" used in the claims includes electroplating
compositions, electroforming compositions, electrowinning
compositions, and waste solutions containing dissolved metals.
[0167] It is also understood that the component A) metals and
metalloids can be present in ionic form and/or in elementary
form.
[0168] In the component B) branched reaction products used in the
aqueous compositions of the invention, the linking compound of
formula I in component B)a) is preferably epichlorohydrin or
another epihalohydrin. However, trihaloalkanes can be used, such as
1,2,3-trichloropropane, 1,2,4-trichlorobutane,
1,3,6-trichlorohexane, and the like. Instead of chlorine in the
epihalohydrins and trihaloalkanes, the corresponding bromine and
iodine compounds can also be used, including compounds containing
two or even all three of the above halogens.
[0169] The component B)b) compounds of formula II are organic
(optionally alkoxylated) alcohols or the corresponding sulfhydryl
or amine compounds.
[0170] The R.sup.2 group can also be a substituted or
unsubstituted, saturated or unsaturated hydrocarbon group having
from 1 to 36 carbon atoms. Examples of such hydrocarbon groups
include linear or branched alkyl groups having from 1 to 36 carbon
atoms, preferably from 4 to 22 carbon atoms, linear or branched
alkenyl or alkynyl groups having from 2 to 36 carbon atoms,
preferably from 4 to 22 carbon atoms, aryl groups having from 6 to
22 carbon atoms, and arenyl groups having from 7 to 36 carbon
atoms. Arenyl groups are alkyl-substituted aromatic radicals having
a free valance at an alkyl atom such as a benzylic group.
[0171] The R.sup.2 group can be a saturated carbocyclic group, an
unsaturated carbocyclic group having one or more multiple bonds, a
saturated heterocyclic group, or an unsaturated heterocyclic group
having one or more multiple bonds.
[0172] Any of the above R.sup.2 groups can be substituted groups,
i.e. the substituents can be single or multiple substituents such
as a sulfur functionality such as a mercaptan or thio group; a
nitrogen functionality such as an amine or amide functionality; an
alcohol functionality, a silicon functionality, e.g., a siloxane;
an ether functionality, e.g. a C.sub.1-C.sub.6 alkoxy group; or any
combination thereof.
[0173] The R.sup.2 group in formula II is preferably a branched
chain alkyl group containing from 4 to 36 carbon atoms, preferably
from 4 to 12 carbon atoms, and more preferably from 8 to 12 carbon
atoms.
[0174] When the X group of formula II is an --S-- group, the
R.sup.2 group will preferably have from about 4 to about 22 carbon
atoms, examples of which include but are not limited to, dodecyl
mercapto and 1-hex adecanethio.
[0175] When the R.sup.2X-group of formula II is a secondary or
tertiary amino group, the group preferably contains from 4 to 22
carbon atoms, and n is preferably a number of from 1 to 50.
Examples of primary and secondary amines useful for obtaining the
R.sup.2X-group include, but are not limited to, dibutyl amine,
cyclohexyl amine, isodecyl amine, and dioctylamine.
[0176] Optionally, an additional component B)c) can be reacted with
the linking agent of formula I and the compound of formula II. A
glycidyl ether or amine can be added to the reaction of formula I
and formula II. The amount of the glycidyl ether or glycidyl amine
is from about 1 to about 20 mole percent based on the moles of the
compounds of formula II used in the reaction. When the glycidyl
ether or glycidyl amine is added, the ratio of component B)a) plus
the glycidyl ether or glycidyl amine to component B)b) is
preferably from about 1.2:1 to about 5:1. Examples of glycidyl
ether include, but are not limited to, PEG 600 diglycidyl ether,
TETRONIC.TM. 701 tetraglycidyl ether, triglycidyl di or
triethanolamine, polyoxyethylene (POE) 200 tallow-amine diglycidyl
ether, propoxylated (POP10) trimethylol propane triglycidyl ether,
propoxylated (POP7) pentaerythritol tertraglycidyl ether. Examples
of glycidyl amines include, but are not limited to, tetraglycidyl
1,6-hexane diamine, tetraglycidyl JEFFAMINE.TM. EDR-148, and
tetraglycidyl isophorone diamine.
[0177] When Y in formula II is an amine or sulfhydryl group, the
resulting compounds can be readily prepared from the corresponding
alcohols wherein the terminal hydroxy group is replaced by an --SH
group or by an amine nitrogen. For example, a compound of formula
II where Y is --OH can be subjected to a catalyzed ammoniation
(with ammonia, or a lower alkylamine) for replacement of the
hydroxyl. In the compounds of formula II, the AO groups when
present are preferably all ethyleneoxy groups. However, as stated
above, each OA group can be independently an ethyleneoxy (EO),
1,2-propyleneoxy (PO), or 1,2-butyleneoxy (BO) group, i.e. any one
or more of such groups can be present, and they can be present in
any order, as well as be present in blocks, e.g. compounds of
formula III:
R.sup.20(EO).sub.m(PO).sub.p(BO).sub.qH (III)
wherein R.sup.2 has the meaning given above, m is a number of from
0 to 100, preferably from 1 to 50, p is a number of from 0 to 50,
e.g. from 1 to 50, and q is a number of from 0 to 50, e.g. from 1
to 50. Compounds of formula III in which R.sup.2 is a branched
chain alkyl group having from 4 to 12 carbon atoms, m is a number
of from 2 to 20, and p and q are 0 are preferred.
[0178] The degree of hydrophilic and hydrophobic properties of the
reaction products of components B)a) and B)b) can be readily
controlled by controlling the type and number of alkyleneoxy groups
in component B)b). For example, the greater the number of
ethyleneoxy groups present, the greater the water solubility, while
the presence of 1,2-propyleneoxy groups and/or 1,2-butyleneoxy
groups for example, will decrease water solubility.
[0179] In general, the compounds of formula III wherein the sum of
m, p, and q is at least 1, and especially at least 2 are preferred
for use herein.
[0180] The branched reaction products used in the practice of the
invention can be prepared by reacting components B)a) and B)b) (and
B)c), if present) together, preferably in the presence of an inert
organic solvent, preferably a solvent such as toluene that will
azeotrope water, and in the presence of an inorganic base such as
an alkali metal hydroxide, e.g. aqueous sodium hydroxide or
potassium hydroxide, at a temperature in the range of from 60 to
125.degree. C. In a preferred embodiment of the process, component
B)b) is first mixed with the base, and the organic solvent, if
present, and water is removed, e.g. by azeotropic distillation.
Then component B)a) (and B)c), if present) is slowly added and the
reaction continued until the reaction is completed. The reaction
mixture is filtered and the filtrate vacuum stripped to remove any
organic solvent.
[0181] Inert organic solvents that can be used in the above process
are nonmiscible with water and nonhydroxylic. Examples of such
solvents include toluene, CHCl.sub.3, CH.sub.2Cl.sub.2,
chlorobenzene, acetonitrile, and petroleum ethers, preferably
toluene.
[0182] This invention will be illustrated but not limited by the
following examples.
EXAMPLES
Example 1
Preparation of the Reaction Product of Decyl Alcohol.4EO and
Epichlorohydrin
[0183] About 150 grams of decyl alcohol ethoxylated with an average
of 4 moles of ethylene oxide (0.45 OH equivalents) were mixed with
385 grams of toluene and 54 grams of 50% aq. NaOH (0.675
equivalents). The water was removed by azeotropic distillation and
when a moisture level of less than 0.8% was reached, about 46 grams
(0.51 equivalents) of epichlorohydrin were slowly added. This
mixture was allowed to react at 100.degree.-110.degree. C. for 24
hours. An aliquot of this mixture was removed and filtered to
remove the NaCl and vacuum stripped to remove the toluene to give
an amber, easily pourable liquid product that was dispersible in
water.
Example 2
[0184] An aqueous copper plating bath is formulated with the
following components:
TABLE-US-00003 Component Concentration, g/l Cu metal 57
CuSO.sub.4.cndot.5H.sub.2O 225 H.sub.2SO.sub.4 60 Cl.sup.- 0.5
reaction product 0.2 of Ex. 1
[0185] The above plating bath has a pH of less than 0. Nonetheless,
the reaction product of Example 1 is stable in this bath at typical
plating temperatures, e.g. 25.degree. C. The above bath can be used
for electroplating, electrowinning, and electroforming.
Example 3
Preparation of the Reaction Product of Octyl Alcohol.4EO and
Epichlorohydrin About 200.0 gm (0.654 hydroxyl equivs.) of octyl
alcohol ethoxylated with an average of 4 moles of ethylene oxide
was mixed with 400 gm toluene and 78.4 gm (0.98 equivs.) of 50%
NaOH. Water was removed by azeotropic distillation until the level
was below 0.8%. The mixture was cooled to 80.degree. C. and 67.2 gm
(0.72 moles) of epichlorohydrin was added over 45 mins. The mixture
was stirred for 24 hrs at 110.degree. C. until the epoxy titration
showed no epoxide left. The material was cooled, filtered and the
toluene was removed by vacuum distillation leaving a dark brown low
viscosity liquid.
Example 4
[0186] An aqueous acidic nickel plating bath is formulated with the
following components:
TABLE-US-00004 Component Concentration, g/l Ni metal 82
NiSO.sub.4.cndot.6H.sub.2O 300 NiCl.sub.2.cndot.6H.sub.2O 60
H.sub.3BO.sub.3 40 reaction product 0.15 of Ex. 3
Latex Compositions:
[0187] In the above compounds of component A), the linking compound
of formula I is preferably epichlorohydrin or another
epihalohydrin. Also, trihaloalkanes can be used, such as
1,2,3-trichloropropane, 1,2,4-trichlorobutane,
1,3,6-trichlorohexane, and the like. Instead of chlorine in the
epihalohydrins and the trihaloalkanes, the corresponding bromine
and iodine compounds can also be used, including compounds
containing two or even all three of the above halogens.
[0188] The component B) compounds of formula II are organic
(optionally alkoxylated) alcohols or the corresponding sulfhydryl
or amine compounds.
[0189] The R.sup.2 group can be a substituted or unsubstituted,
saturated or unsaturated hydrocarbon group having from 1 to 36
carbon atoms. Examples of such hydrocarbon groups include linear or
branched alkyl groups having from 1 to 36 carbon atoms, preferably
from 4 to 22 carbon atoms, linear or branched alkenyl or alkynyl
groups having from 6 to 22 carbon atoms, and arenyl groups having
from 7 to 36 carbon atoms. Arenyl groups are alkyl-substituted
aromatic radicals having a free valance at an alkyl carbon atom
such as a benzylic group.
[0190] The R.sup.2 group can also be a saturated carbocyclic group,
an unsaturated carbocyclic group having one or more multiple bonds,
a saturated heterocyclic group, or an unsaturated heterocyclic
group having one or more multiple bonds. Any of the above R.sup.2
groups can be substituted groups, i.e. the groups can be single or
multiple substituents such as one or more halogen substituents, for
example, Cl, Fl, I, and Br; a sulfur functionality such as a
mercaptan or thio group, a nitrogen functionality such as an amine
or amide functionality; an alcohol functionality, a silicon
functionality, e.g., a siloxane; an ether functionality, e.g. a
C.sub.1-C.sub.6 alkoxy group; or any combination thereof.
[0191] The R.sup.2 group in formula II is preferably a branched
chain alkyl group containing from 4 to 36 carbon atoms, preferably
from 4 to 12 carbon atoms, and more preferably from 8 to 10 carbon
atoms.
[0192] When the X group of formula II is an --S-- group, the
R.sup.2 group will preferably have from about 4 to about 22 carbon
atoms, examples of which include but are not limited to, dodecyl
mercapto and 1-hexadecanethio.
[0193] When the R.sup.2X-group of formula II is a secondary or
tertiary amino group, the group preferably contains from 4 to 22
carbon atoms, and n is preferably a number of from 1 to 50.
Examples of primary and secondary amines useful for obtaining the
R.sup.2X-- group include, but are not limited to, dibutyl amine,
cyclohexyl amine, isodecyl amine, and dioctylamine.
[0194] Optionally an additional component C) can be reacted with
the linking agent of formula I and the compound of formula II. A
glycidyl ether or amine can be added to the reaction of formula I
and formula II. The amount of the glycidyl ether or glycidyl amine
is from about 1 to about 20 mole percent based on the moles of the
compounds of formula II used in the reaction. When the glycidyl
ether or glycidyl amine is added, the ratio of component A) plus
the glycidyl ether or glycidyl amine to component B) is preferably
from about 1.2:1 to about 5:1. Examples of glycidyl ether include,
but are not limited to, PEG 600 diglycidyl ether, TETRONIC.TM. 701
tetraglycidyl ether, triglycidyl di- or triethanolamine,
polyoxyethylene (POE) 200 tallow amine diglycidyl ether,
propoxylated (POP10) trimethylol propane triglycidyl ether,
propoxylated (POP7) pentaerythritol tetraglycidyl ether. Examples
of glycidyl amines include, but are not limited to, tetraglycidyl
1,6-hexane diamine, tetraglycidyl JEFFAMINE.TM. EDR-148, and
tetraglycidyl isophorone diamine.
[0195] When Y in formula II is an amine or sulfhydryl group, the
resulting compounds can be readily prepared from the corresponding
alcohols wherein the terminal hydroxy group is replaced by an --SH
group or by an amine nitrogen. For example, a compound of formula
II where Y is --OH can be subjected to a catalyzed ammoniation
(with ammonia, or a lower alkylamine) for replacement of the
hydroxyl.
[0196] In the compounds of formula II, the AO groups when present
are preferably all ethyleneoxy groups. However, as stated above,
each OA group can be independently an ethyleneoxy (EO),
1,2-propyleneoxy (PO), or 1,2-butyleneoxy (BO) group, i.e. any one
or more of such groups can be present, and they can be present in
any order, as well as be present in blocks, e.g. compounds of
formula III:
R.sup.20(EO).sub.m(PO).sub.p(BO).sub.qH (III)
wherein R.sup.2 has the meaning given above, m is a number of from
0 to 100, preferably from 1 to 50, p is a number of from 0 to 50,
e.g. from 1 to 50, and q is a number of from 0 to 50, e.g. from 1
to 50. Compounds of formula III in which R.sup.2 is a branched
chain alkyl group having from 4 to 12 carbon atoms, m is a number
of from 2 to 20, and p and q are 0 are preferred.
[0197] The degree of hydrophilic and hydrophobic properties of the
reaction products of components A) and B) can be readily controlled
by controlling the type and number of alkyleneoxy groups in
component B). For example, the greater the number of ethyleneoxy
groups present, the greater the water solubility, while the
presence of 1,2-propyleneoxy groups and/or 1,2-butyleneoxy groups
for example, will decrease water solubility.
[0198] In general, the compounds of formula III wherein the sum of
n, m, and p is at least 1, and especially at least 2 are preferred
for use herein.
[0199] The above reaction products can be prepared by the process
disclosed in U.S. Pat. No. 5,827,453, the disclosure of which is
expressly incorporated herein by reference.
[0200] In general, the component A) and B) (and C) if present)
reactants are reacted together, preferably in the presence of an
inert organic solvent such as toluene that will azeotrope water,
and in the presence of a base, such as aqueous sodium hydroxide, at
a temperature of from 60.degree. to 125.degree. C. Preferably
component B) is first mixed with the base and the organic solvent,
and water is removed by azeotropic distillation. Then component A)
(and C) if present) is slowly added and the reaction continued
until the reaction is completed. The reaction mixture is filtered
and vacuum stripped to remove the organic solvent.
[0201] The above Component II) reaction products are readily
soluble in the aqueous latex compositions; are both surfactants and
defoaming agents; are highly stable yet readily biodegradable; and
in addition possess all of the advantages discussed above, e.g.
they do not destabilize the latex compositions; they do not
interfere with dipping or coating or other procedures; they defoam
the latex compositions so effectively that no holes are present in
the resulting articles; they are highly effective wetting agents;
they are compatible with soap and other surfactants; and they are
stable under a wide range of processing conditions including
temperature stability.
[0202] In natural rubber latex technology, which includes natural
rubber latex from rubber trees, and aqueous finely divided
dispersions from solid natural rubbers, materials to be added to
the rubber are colloidally dispersed in water and mixed into the
latex, a process involving the use of lighter equipment and less
power than the mixing of solid rubber compounds. The latex compound
can then be used in a variety of processes such as coating or
impregnating of cords, fabrics, or paper; in adhesives; molding
(such as in toys); dipping (for thin articles like balloons, or
household and surgeon's gloves); rubber thread (for garments); and
production of foam. Latex technology is particularly important in
producing articles for medical and surgical uses, such as latex
gloves and other medical and surgical articles. Natural rubber
latex is a milky white liquid emulsion found in the cells of
flowering plants such as the Para rubber tree (Hevea brasiliensis).
It is also produced by the cells of plants of the family
Asclepiadaceae but also by those in the families Apocynaceae,
Sapotaceae, Euphorbiaceae, Papaveraceae, Moraceae, and Asteraceae
(Compositae). The latex circulates in branched tubes that penetrate
the tissues of the plant in a longitudinal direction, conducting
substances and acting as an excretory reservoir.
[0203] Latex represents rubber in its most tractable form.
Concentration of latex to a content of 60 to 70 percent dry rubber
is performed either at the source or in the user country by means
of centrifuging, evaporation, or a process known as creaming, in
which an agent is added to the latex that causes the rubber
particles to swell and rise to the surface of the liquid.
[0204] Latex is an excellent adhesive and is widely used in its
natural state, but for most industrial uses it needs additives and
vulcanization. Accelerating agents for vulcanizing and other
essential fillers are added. One of the oldest uses of latex is in
the production of such dipped goods as rubber gloves and
prophylactics. The process consists of dipping formers of the
correct size and shape into compounded latex, then drying,
repeating the operations, and vulcanizing.
[0205] Rubber (elastic) thread also is produced from latex.
Initially, strips were cut from a thin sheet to form a thread of
square cross section. Later, the much superior round thread was
obtained by extruding compounded latex into a bath of coagulant
through glass nozzles.
[0206] Foam rubber has been one of the most important latex
products since its discovery in the 1920s. The confinement of
thousands of gaseous bubbles in natural rubber cells provides ideal
resilience. In the simple manufacturing process, excess ammonia is
removed from the latex, and after a vigorous stirring with
dispersions of soap, sodium fluorosilicate is added to the frothy
mixture as a gelling agent, along with accelerating agents, zinc
oxide, and antioxidant. After the liquid has stood in a mold for
several minutes to permit gelling, it is vulcanized. In practice,
the process requires the most careful control and the judgment of
experienced personnel.
[0207] Foam products were made originally in individual molds which
progressed along a conveyor in series and into each of which a
predetermined quantity of foam was inserted, the mold closing
during its progress to the oven. Washing, drying, and finishing
completed the process. For large-scale production, a new method has
supplanted this early method, which is still in active service. The
process consists of filling a fixed mold with a metered quantity of
foam, sealing it with its lid, and evacuating the air; the foam
expands to partly fill the resulting vacuum, and then is frozen;
next, carbon dioxide gas is passed in to fill the remaining vacuum
in the foam, and the temperature is raised to 104.degree. C.
(219.degree. F.) for curing.
[0208] The carpet industry has made increasing use of latex not
only as a separate foam rubber underlay but as an undercoating on
the carpet itself and as an anchoring matrix for tufted
carpets.
[0209] Foams may also comprise a blend of natural and
styrene-butadiene rubbers, the latter reducing the cost with some
reduction in resilience.
[0210] Vulcanization is usually the last step in preparing a final
product. It gives strength, hardness, and elasticity to rubber by
treating it with heat and vulcanizing agents, such as sulfur.
During vulcanization, the heat causes the sulfur to combine with
the rubber and cure it. This makes the rubber stronger and more
durable. Generally, the more sulfur that is added, the firmer the
vulcanized compound will be. Vulcanization may take from a few
minutes to several hours.
[0211] Manufacturers vulcanize and shape molded products at the
same time by heating the molds under pressure. They vulcanize
extruded and sheet products on pans in hot-air or steam chambers.
Dipped products are vulcanized in hot water, hot air, or open steam
while still on the molds. Foam products in their molds are
vulcanized in steam chambers or in boiling water.
[0212] One or more additives that can be added to natural rubber
latex, in addition to component II) above, include inorganic sulfur
for vulcanization, clay fillers, molten resins, zinc oxide (used to
absorb evolved hydrochloric acid), silica, accelerators such as
aldehyde-amines, guanidines, thiuram sulfides, thiazoles,
thiazolines, dithiocarbamates, and mercaptoimidazolines, light
process oil free from polyacrylic aromatics, other mineral fillers
in addition to or instead of clay, plasticizers such as elastic
plasticizers, strong acid soaps, sodium or potassium salts of rosin
acids, and the like.
[0213] Other vulcanizing agents that can be used in place of
inorganic sulfur include oxidizing agents such as selenium,
tellurium, organic peroxides, and nitro compounds, and also
generators of free radicals, such as organic peroxide, and azo
compounds. In addition, sulfur-containing compounds such as
dimorpholinyl disulfide and tetraethylthiuram disulfide can be used
as vulcanizing agents and which also function as accelerators.
[0214] Antioxidants can also be added, including highly hindered
phenols, obtained by alkylation of phenols or cresols, and
derivatives of aromatic phosphite esters.
[0215] Also, antiozonates can be added, such as p-phenylenediamines
e.g. N,N.sup.1-dialkyl-p-phenylenediamines, and the condensation
products of amines and ketones.
[0216] Vulcanization retarders can be present, such as organic
acids and anhydrides, cyclohexylthio-phthalimide, and
sulfenamides.
[0217] Moreover, while natural rubber latex normally contains fatty
acids or their soaps, it is sometimes necessary to add more.
[0218] All of the above additives are known additives (except of
course component II of the present latex compositions) and one or
more thereof can be added to the present latex compositions in
quantities that are well known to the art.
[0219] Also, in order to better achieve a homogeneous and stable
latex composition, any insoluble additives that are added to the
latex should be reduced in particle size to an optimum of about 5
micrometers and preferably added in dispersed or emulsified form in
water.
[0220] Natural rubber latex is collected from the rubber-producing
plants and trees, and a small quantity of a preservative is added
to prevent premature coagulation before the latex is brought to a
factory or processing center. Rubber collected in this manner is
known as field latex.
[0221] The main distinguishing feature of rubber products made from
latex rather than dry rubber is the rubber thickness, which is
limited to a few millimeters. In producing latex products, the
chemicals required for vulcanization, stiffening, coloring,
antioxidant protection, or other purposes are added as solutions,
emulsions, or fine dispersions to the latex before forming the
product. Because no heat is generated during this mixing, it is
possible to use ultrafast accelerators that would cause scorch
problems in dry rubber compounds.
[0222] The most important group of latex products are the dipped
goods. As discussed above, these are produced by dipping a shaped
former into a suitably formulated latex compound, and then
withdrawing it. The latex deposit is dried and vulcanized in hot
air to give the product, which is then stripped from the former.
Aside from dipping, the other main products produced from natural
rubber latex are elastic thread and foam products.
[0223] Natural rubber latex also finds application in adhesives for
tape, packaging, envelopes; in the footwear industry; and in the
carpet industry.
[0224] The invention will be illustrated but not limited by the
following examples.
EXAMPLES
Example 1
Preparation of the Reaction Product of Decyl Alcohol.4EO and
Epichlorhydrin
[0225] About 150 grams of decyl alcohol ethoxylated with an average
of 4 moles of ethylene oxide (0.45 OH equivalents) were mixed with
385 grams of toluene and 54 grams of 50% aq. NaOH (0.675
equivalents). The water was removed by azeotropic distillation and
when a moisture level of less than 0.8% was reached, about 46 grams
(0.51 equivalents) of epichlorhydrin were slowly added. This
mixture was allowed to react at 100.degree. to 110.degree. C. for
24 hours. An aliquot of this mixture was removed and filtered to
remove the NaCl and vacuum stripped to remove the toluene to give
an amber, easily pourable liquid product that was dispersible in
water.
Example 2
[0226] A natural rubber latex composition is prepared by mixing
together the following components:
[0227] A) a natural rubber latex which is a milky white liquid
emulsion obtained from the cells of the Para rubber tree (Hevea
brasiliensis); and
[0228] B) 0.25% by weight of the reaction product of Example 1.
Example 3
Preparation of the Reaction Product of Octyl Alcohol.4EO and
Epichlorohydrin
[0229] About 200.0 gm (0.654 hydroxyl equivs.) of octyl alcohol
ethoxylated with an average of 4 moles of ethylene oxide was mixed
with 400 gm toluene and 78.4 gm (0.98 equivs.) of 50% NaOH. Water
was removed by azeotropic distillation until the level was below
0.8%. The mixture was cooled to 80.degree. C. and 67.2 gm (0.72
moles) of epichlorohydrin was added over 45 mins. The mixture was
stirred for 24 hrs at 110.degree. C. until the epoxy titration
showed no epoxide left. The material was cooled, filtered and the
toluene was removed by vacuum distillation leaving a dark brown low
viscosity liquid.
Example 4
[0230] A natural rubber latex composition is prepared from the
following components: [0231] A) a natural rubber latex which is a
milky white liquid emulsion obtained from the cells of the Para
rubber tree (Hevea brasiliensis); and [0232] B) 1% by weight of the
reaction product of Example 3.
Example 5
[0233] A ceramic mold for forming a latex glove is dipped into a
tank containing the natural rubber latex composition of Example 2,
to which is added a small quantity of sulfur and a dithiocarbamate.
Excess latex is drained from the mold and the mold is dried at room
temperature. The above process is repeated several times until the
latex glove has the desired thickness. The latex glove is treated
with hot air until the rubber is vulcanized, and is then removed
from the mold. The latex glove is free from holes. The latex
composition is stable and is substantially free from foam during
the above procedure.
[0234] It will be appreciated by those skilled in the art that
changes could be made to the embodiments described above without
departing from the broad inventive concept thereof. It is
understood, therefore, that this invention is not limited to the
particular embodiments disclosed, but it is intended to cover
modifications within the spirit and scope of the present invention
as defined by the appended claims.
* * * * *