[0001] The present invention relates to water-dispersible compositions having a detergent
and/or protective action on steel sheet, and a process for their preparation.
[0002] More specifically, the present invention relates to water-dispersible compositions
that, when used in a diluted (3-5%) state, have a (temporary) detergent and protective
action, and, when used at higher concentration (≧ 40%), have a longer-lasting protective
action, in a similar way as the so-called slushing oils used up to now, and a process
for their preparation.
[0003] As is well known to the persons skilled in the art, the die-forming steel-sheets
are sheets that are obtained from low-carbon steel (0.15%, extra-mild steel; 0.15
- 0.30%, mild steel); the steel grades that are employed can be of the rimmed type,
semi-killed type, or of the killed type.
[0004] Said steel sheets are obtained by cold rolling. After this process, the steel sheet
is subjected to annealing and then to "temper milling" (milling in a mill that usually
exhibits a reversible quarter arrangement). The purpose of this treatment is to rise
the steel sheet yield point by means of a slight thickness reduction, thus imparting
to the steel sheet good forming characteristics.
[0005] As is known to the persons skilled in art, the steel sheet strip from the annealing
furnace is to be cleaned of "metal fines" formed during the rolling step and/or of
the carbonaceous particles from cracking of the lubricating agents employed in the
cold rolling process. This cleaning operation is usually performed by spraying a water
solution, said solution containing surface active agents, rust preventive additives
(such as, for example, boric amide, boron, nitrites, benzoates, carbonates, sulphonamides,
and so on) and small amounts of anionic compounds, such as soaps, amine salts, and
so on.
[0006] The application site for these detergent compositions is at the separation line between
the back-up rolls and the working rolls and/or at the separation line between the
working roll and the strip. Said cleaning solution should not stain the steel sheet
(that is they should be inert towards it), while preventing the surface of the steel
sheet from being oxidized within the time span elapsing between their application
and the following application of the protective agent (this is the reason why these
detergent compositions also contain rust preventing additives as summarily stated
above).
[0007] Said detergent compositions should also provide a lubricating action to remove wear
of working rolls and preserving for a longer time the roughness of the rolls themselves.
[0008] The detergent composition must have dried, before the protective agent is applied,
for the protective composition, which is an oil-or wax-base composition, to be easily
applied, as well as to prevent the water contained in the detergent composition from
giving rise to a rust layer under the oil/wax layer of the protective agent.
[0009] The known previous protective compositions usually consist of water-dispersions of
waxes, or they are based on paraffinic and/or naphthenic petroleum hydrocarbons. In
said protective compositions, dispersant amides, anionic oleophylic additives (such
as e.g. petroleum sulphonates, said sulphonates corresponding to the formula R SO₃X,
wherein R is an alkyl-aryl group with 20 to 30 carbon atoms, and X is usually a sodium
atom, or an amine or alkanolamine group) are usually compounded with petroleum hydrocarbons.
[0010] The main function of said protective compositions is to prevent the steel strip from
being oxidized within the time period, that can even last several months, between
the manufacture of steel sheets and their final use, e.g. in the car industry or in
the electrical household appliance industry.
[0011] The known previous detergent and protective compositions exhibit nevertheless several
draw-backs.
[0012] As the detergent compositions, e.g. are aqueous, they are little, if at all, compatible
with the wax-base or oil-base protective compositions. Therefore, if the detergent
composition is not thoroughly dried before the protective composition is applied there
is a serious risk that the residual water causes the steel sheet to be rust - stained,
notwithstanding the presence of the protective agent.
[0013] Moreover, also the known protective compositions exhibit various draw-backs:
- they are not easily distributed, especially the oil-based compositions, onto the
steel strip surface, especially at room temperature, thus making it necessary to apply
heat;
- the conventional protective compositions tend to cause the formation of deposits
onto the distribution rolls and to clog the nozzles of the devices that are used for
the application of the same, with the consequence that further maintenance work is
needed;
- the protective film formed by the known protective compositions is sometimes non-homogeneous
or non-continuous;
- the protective agents that are commercially available can form stable aereosols
by spray application;
- the known protective agents are sometimes not completely inert towards the steel
surface, thus causing stains on it;
- if the steel surface is handled shortly after said oil- or wax-based protective
agents have been applied, the protective agent becomes partly removed;
- when several steel plates are stacked, protective oil accumulates along the borders
due to pressure or gravity; moreover when plate reams are stacked onto joists, central
pockets of a fatty nature are formed internally thus giving rise to more or less evident
surface halos;
- the unsaturation or aromatic nature of the oily vehicle of the known protective
compositions can give rise to stains on the surface of the steel sheets;
- the known protective compositions are inflammable, thus giving rise to fire hazard;
- the presence of an oily or waxy film of the conventional protective agents imparts
to the steel sheets greasiness and/or tackiness, thereby making it more difficult
to operate on them by mechanical means and, further, the adherence between plates
makes their manipulation with suction cups problematic;
- the galvanization or phosphate-coating treatments require that the oily or waxy
protective film be completely removed, such a removal being difficult, if not impossible
, to be carried out with a cold process; the same problem occurs if the steel sheet
is to be lithographed.
[0014] It is therefore an object of the present invention to provide a detergent composition
and a protective composition for forming steel sheets not having the draw-backs of
the known compositions.
[0015] It has now been discovered a water-dispersible composition that exhibits a long-term
protective action when employed at a concentration of at least 40% or higher, said
water-dispersible composition exhibiting a detergent and a short term protective action
when employed at a concentration of 3-5%.
[0016] The compositions of the present invention consist substantially of four components:
1) base A, 2) base B, 3) dispersant, 4) co-solvent.
[0017] Base A serves mainly to impart detergency to the composition of the present invention
when this is employed in the diluted state (concentration 3-5%); said base can consist
of a mixture of different bases A.
[0018] Base B, on the contrary, serves mainly to impart film-forming properties to the composition
of the present invention when this is used in a concentrated state (≧ 40%); also base
B can consist of a mixture of different bases B.
[0019] The dispersant is water.
[0020] The cosolvent consists of one or a plurality of glycols.
[0021] According to the present invention, base A is obtained by reacting a water-dispersible
acid reagent Aa with a water-soluble basic reagent Ab; the product of said reaction
can be a salt, a soap and/or a condensation product. The reaction conditions normally
promote the condensation, but the quality of the final product will not be very different
if, instead of a condensation, a salt forming reaction between Aa and Ab occurs.
[0022] According to the present invention, any polycarboxylic and / or monocarboxylic acid
having more than 8 carbon atoms can be used as the acid reagent Aa to be used for
the preparation of base A, provided it is water-dispersible. Preferred are the water-soluble
polycarboxylic acids ; otherwise, the acidic reagent Aa can also be a phosphoric
ester that is obtained by reacting phosphoric anhydride (P₂O₅) with a fatty alcohol
having at least 8 carbon atoms in the molecule, or with a monosubstituted and/or
disubstituted phenol compound, oxo-alcohol compound, said compounds being condensed
or non-condensed with ethylene oxide and / or ethylene oxide / propylene oxide mixtures.
The term "oxo-alcohol" stands for an alcohol prepared by means of the oxo-process
from a polyolefine having at least 7 carbon atoms. Said alcohols are obtained by adding
one mole of carbon oxide and two moles of hydrogen to polyolefins, such as tri-, tetra-,
penta-propylene, di-, tri-, tetra-isobutylene, propylene-isobutylene, tributene, and
so on, with a Fischer-Tropsch catalyst (e.g. cobalt carbonyls, Raney cobalt): see
for example The Merck Index 10th edition, ONR-65 and references therein.
[0023] Illustrative examples of phosphoric esters that can be used for the preparation of
base A according to the present invention are described in US patent 3,004,056, the
disclosure of which is incorporated herein by reference.
[0024] Among the various alcohols that are described in said US patent, those having the
following formula:
R₁-(OCH₂CHR₂)
x-OH, (I)
wherein R₁ is an alkylene or aralkyl group having 8 to 24 carbon atoms, and
R₂ is a hydrogen atom or a methyl group,
x is an integer of from 0 to 20, included,
are especially preferred for the preparation of the phosphoric esters useful for the
present invention.
[0025] The esters according to the above-mentioned US patent can contain in their molecule
non-esterified phosphoric groups that impart acid properties the reto; in this case
they will be available for further reaction with any water-soluble, organic and/or
inorganic base. Among the various types of the above-mentioned acid reagent Aa that
can be used for the preparation of base A accordingly to the present invention, the
arylalkyl-ethoxyphosphate - type esters , commercially available under the trade
mark GAFEN, (GAF Corporation, New York, N.Y. ) or the organic, water-soluble polycarboxylic
acid with an oleic acid equivalent of 0.83, manufactured by Ciba-Geigy and sold under
trade mark REOCOR 190, or mixtures thereof are presently preferred.
[0026] As the based reagent Ab useful for the preparation of base A of the present invention,
an organic basic compound can be used, such as an amine, a diamine and/or a polyamide,
having 1 to 24 carbon atoms in their molecule and corresponding to the following formula:
H₂N-(RNH)
n-H (II)
wherein R stands for an alkylene group having 1 to 4 carbon atoms and n is an integer
of ≦ 6;
[0027] Preferably, the basic reagent Ab will consist of a propylene diamine having a primary
amine group and a secondary amine group, and corresponding to formula II, with or
without oxyethylene groups.
[0028] According to the present invention, as the basic reagent Ab also compounds of the
formula
R-NH-CH₂-CH₂-CH₂-NH₂ (III)
wherein R is an alkyl residue of fatty acid having 10 to 22 carbon atoms, preferably
12 to 18 carbon atoms, of the formula

can be advantageously used.
[0029] A product according to the above-mentioned formula, wherein R stands for the alkyl
residues of the tallow fatty acids, in the following proportions:
C₁₂:1%; C₁₄:4%; C₁₆:31%; C₁₈:64%; C₂₀:trace amounts
is sold by AKZO CHEMIE Italia S.p.A., Via Vismara 80, 20020 Arese, under the trade
name ETHODUOMEEN T 13.
[0030] As the Ab reagent, the mixture of diethanolamine and a diamine of formula (IIIa),
that is ETHODUOMEEN T 13, is presently preferred.
[0031] Moreover, also the alkanolamines, preferably the dialkanolamines of the formula
HN(ROH)₂ (IV)
wherein R is an aliphatic residue containing 2 to 6 alkylene groups, are useful basic
reagents Ab according to present invention. Depending on the reaction conditions,
the number and nature of the functional groups, the alkylamines, the alkanolamines
and the low and / or high molecular weight organic acids can give rise to different
compounds. If the reaction is carried out at room temperature, merely a neutralization
and /or saponification will occur.
[0032] For example, if a monoalkanolamine of formula HOCHRCH₂NH₂ is reacted with oleic acid
at room temperature ( or any temperature much lower then 100°C), an addition compound
of formula
HOCHRCH₂NH₂.HOOCC₁₇H₃₅ (V)
will be obtained, said compound being usually called a soap. This compound has a waxy
appearance, is non-crystalline and usually is thixotropic.
[0033] On the contrary if fatty acids or carboxylic acids are reacted with the above-mentioned
mono- alkanolamines and dialkanolamines in a molar ratio of 1:1, at a much higher
temperature (140-160°C), non-water-soluble N-alkylol amides will mainly be obtained.
[0034] If a mono-alkanolamine is reacted at 160°C with a carboxylic acid, the corresponding
monoalkanolamide will be obtained. However, in the course of said reaction perceptible
amounts of aminoesters and amidoesters will be formed due to the reaction of the OH
group of the monoalkanolamine with the carboxylic acid. Moreover, also small amounts
of amino-diesters and amido-diesters will possibly be formed in the case the monoalkanolamine
contains also dialkanolamines.
[0035] If, on the contrary, the alkanolamine /carboxylic acid molar ratio is 2:1, the reaction
at 140-160°C, yields a dialkanolamide that, contrary to the product obtained with
a molar ratio of 1:1, is water soluble. This product is actually a complex mixture
comprising N-alkylolamide, amino-ester, amino-diester, amido-ester, amido-diester,
free dialkanolamine and a major amount of dialkanolamide.
[0036] It is believed that the water-solubility is mainly due to the free alkanolamine.
In case the alkanolamine/carboxylic acid molar ratio is 1.4:1, a product is obtained
that is dispersible instead of being soluble. However, if the water contains glycols
(co-solvents) or dialkanolamine the dispersion is solubilized.
[0037] According to the present invention, base B is mainly a product or a mixture of products
of condensation or salification possibly containing free components resulting from
the reaction at a temperature of from 150°C to 190°C of a mono-carboxylic acid with
8-18 carbon atoms (reagent Ba), in mixture with a dicarboxylic acid having a maximum
of 36 carbon atoms (reagent Bb), with an alkanolamine, preferably a dialkanolamine
(reagent Bc) in a molar ratio of Bc: (Ba+Bb) ≦ 1.5:1.
[0038] The reagent Ba according to the present invention preferably consists of a monocarboxylic
aliphatic acid containing 10 to 20 carbon atoms, or a mixture of preponderantly unsaturated
fatty acids and 2-3% of rosin acids, said rosid acids consisting of abietic and neo-abietic
acid, such as, e.g., the tall oil fatty acid.
[0039] The reagent Bb useful for preparing base B according to the present invention is
preferably a dimer acid, said dimer acid being obtained from the polymerization of
an unsaturated fatty acid with 18 carbon atoms, containing about 80-97% of dimer acid,
about 20-3% of trimer acid and a maximum of about 1% of monomer acid. The reagent
Bb tipically consists of a dimer acid containing about 95% of dioleic acid, about
4% of trimer acid and about 1% of monomer acid. Said acid has an acid number of about
191, an equivalent weight of about 293 and a molecolar weight of about 365. Dimer
acids exhibiting said features are commercially available e.g. under the trade name
PRIPOL, UNICHEMA International.
[0040] The reagent Bb according to the present invention can also be a hydrogenated dimer
acid having an acid number of about 193, an equivalent weight of about 290 and an
iodine number of about 30.
[0041] The reagent Bc is preferably a dialkanolamine , said dialkanolamine being obtained
from a mixture of diethanolamine and diisopropylamine in the molar ratio of 2:1.
[0042] The co-solvent that can be used for the preparation of the composition of the present
invention can be a monoalkyl ether of an alkyleneglycol of the formula
R₁O[CH₂C(R₂)OH]
y-OH (VI)
wherein
R₁ stands for 1 to 4 alkyl groups
R₂ stands for an H atom or a methyl group and
y is an integer of from 1 to 3.
[0043] Preferred glycol ethers are, e.g. 2-ethyl-1,3-hexanediol and ethylene glycol in
a molar ratio of 3:1.
[0044] It must be taken into account that the present invention is practiced using commercially
available materials that consist of a mixture of compounds, not a single compound.
Therefore, even though in the course of the present disclosure reference is made to
single compounds, they are actually, in most cases, mixtures of compounds, said mixtures
containing the main compound in a preponderant amount, together with other compounds.
Thus, e.g. the fatty acid actually consists of a mixture of acids, such as, e.g.,
the tall oil acids. The mono-alkanolamine can actually contain various monoalkanolamines
and dialkanolamines. Same can be said of alcohols.
[0045] Therefore, also the reaction products obtained from said reagent will obviously consist
of more or less complexe mixture, as illustrated herein above for the alkanolamines.
[0046] The following examples serve to better illustrate the present invention. They have
not to be construed restrictively, because, as it is evident for the man skilled in
the art, the way the present invention is implemented can be varied within rather
large limits, due to the fact that many are the useful starting materials which normally
consist of mixtures rather then a single pure compound. However, the man skilled in
the art, based on the above disclosure, will meet no difficulties in adapting the
reaction conditions to the actual circumstances, thereby always being able to obtain
the desidered product. Unless otherwise stated, parts and percentages are on a weight
basis.
Preparation of base A
[0047] As already stated above, base A has the main purpose of imparting to the composition
of the present invention detergency when used in a diluted state (concentration of
3-5%).
Example 1 (Base A1; condensation reaction)
[0048] Into a four-necked two- liter glass reactor provided with vertex thermometer, stirrer,
reflux condenser and connection to the vacuum pump and a trap for measuring the reaction
water, 5.5 GAFEN LM 400 and 49.4 g REOCOR 190 are charged. The mixture is heated under
stirring, to 65 °C. After stirring for 10 minutes, 41.17 g diethanolamine and 41.7
g ETHODUEMEEN T 13 are added under continuous stirring.
[0049] To the heterogeneous mixture, having a molar ratio of 1:2, 100 g xylene is added.
[0050] The reflux condenser with trap is connected, and the temperature is raised to 150°C
- 160°C. The azeotrope is refluxed while maintaining the temperature for 14 hours
or until 14 ml of water is collected. This means that also a small amount of ester
has been formed besides the diethanolamide and, therefore, the base will exhibit also
a film-forming property, that however will not affect its detergent property.
[0051] After cooling to 60 °C, 10 g of diethanolamine or diisopropanolamine is added for
the purpose of increasing the water solubility.
[0052] The reflux condenser with trap is removed and the vacuun pump is connected.
[0053] At a pressure of 1 mmHg at a maximum temperature of 60°C, the xylene is distilled
off. This operation is rather long and requires the temperature to be thoroughly controlled
to avoid the further formation of ester.
[0054] To avoid this draw-back, the diethanolamine can be substituted with the same amount
of diisopropylamine, but this involves a partial loss of the latter through distillation.
[0055] The end product has a weight of about 132 g and a clear appearance, viscous consistency
and amber colour; it is completely soluble at any ratio in water of 50°HF (french
hardeness degrees).
[0056] A 10% solution in distilled water (pH about 8.8) passes a load of 2800 pounds and
does not give rise to corrosion on a mild steel foil after 5 cycles in the climatic
chamber (8 hours in a saturated ambient at 40°C plus 16 hours in a saturated ambient
at 25°C = 1 cycle). Draves test, average: 23 seconds (1% solution in distilled water).
[0057] Base A1 has the following initial percent composition:
Aa: 37.2 g (GAFEN LM 400 + REOCOR 190)
Ab: 52.9 g (diethanolamine + ETHODUOMEEN T 13)

Example 2 (base A2; salification reaction)
[0058] Into a 1-liter glass vessel provided with an electromagnetic stirrer, 11 g GAFEN
LE 500, and 100 g REOCOR 190, are added in said order, followed by 10 g water, and
the mixture is sturred, with optional heating to 40/45°C, for 30 ÷ 45 minutes, at
the most.
[0059] The solution is not clear.
[0060] Under steady stirring and with the heater off, 82 g diethanolamine and 82 g ETHODUOMEEN
T 13 are slowly and very cautiously added.
[0061] Stirring is continued until the solution is completely clear, adding more REOCOR
190 in case the solution remains turbid. A clear appearance and complete solubility
in water indicate that the salification is sufficient.
[0062] About 280 g salified product is obtained. The thus formed soap is a free flowing,
pale straw-colored mass and is completely water-dispersible in any ratio; it is rather
sensitive to water hardeness.
[0063] The percent composition of the starting materials for base A2 is:
Aa: |
39.0 g |
(GAFEN LE 500 + REOCOR 190) |
Ab: |
57.5 g |
(diethanolamine + ETHODUOMEEN T 13) |
Water: |
3.5 g |
|
[0064] A 10% solution in distilled water (pH about 9) passes a Falex load of 1700 pounds.
[0065] The protective power passes 12 cycles in the climatic chamber. A 1% solution in distilled
water provides an average of 18 seconds at the Draves test.
Example 3 (base A3; condensation reaction)
[0066] A two-liter glass reactor provided with at least 3 necks and equipped with vertex
thermometer, reflux condenser, and magnetic bar stirrer is used, said reflux condenser
being connectable to a vacuum pump and provided with a trap for collecting the water
evolving from the reaction.
[0067] 187.5 g REOCOR 190 and 350 g xylene are chatged into the reactor. The mixture is
heated to 105 °C after connection of the vacuum pump to the reflux condenser. The
temperature is gradually raised to 120°C under continuous stirring; this condition
is maintained until water is collected in the trap. The vacuum is disconnected. Stirring
is continued for about half an hour and 168.75 g diethanolamine is added. Further
25-30 g xylene is added and the reflux condenser with trap is connected. The temperature
is raused to 160 ÷ 165°C under stirring . The temperature is controlled at 165°C.
Stirring is continued and the temperature is kept constant for 12 hours, while noting
the level of the reaction water reached in the trap.
[0068] When 32 ml of water has been collected, the reaction mass will have the desired dialkanolamide/ester
ratio.
[0069] After cooling to 150°C, the reflux condenser is removed and xylene is distilled off
at 1 mmHg. The operation can also be carried out in a rotary evaporator connected
to a vacuum pump.
[0070] After removing the xylene, the reaction product is cooled down to 60°C. 143 g of
diethanolamine is added under stirring to fluidize and clear the product. Yield: 370
g.
[0071] The appearance of the mass is clear, non thixotropic, viscous but sufficiently flowing
and its color is markedly lighter than that of the product of example 1.
[0072] It is completely water dispersible, even into medium hardness water (pH ≧ 9).
[0073] The initial percent composition of base A3 is as follows:
Aa: 37.57 g (REOCOR 190)

Molar ratio: Aa : Ab = 1 : 2
[0074] A 10% solution in distilled water passes a Falex load of 2500 pounds. It causes no
corrosion on a mild steel plate after 10 cycles in the climatic chamber.
[0075] The wetting power referred to a 1% water solution, according to the Draves test,
shows an average value of 20 seconds.
[0076] According to the present invention in order to obtain a water-dispersible composition
of good quality it is necessary that base A exhibits, in a proper amount, the following
characteristics (listed in decreasing order of importance):
As) Degreasing and moistening-soaking properties;
Af) Film forming, polar and protecting properties;
Al) Lubricating properties.
[0077] In table I the evaluation of each of the above characteristics relative to bases
A prepared in the examples are reported.
TABLE I
Base |
As |
Af |
Al |
Average evaluation |
A1 |
I |
I |
O |
I |
A2 |
O |
O |
I |
O |
A3 |
S |
B |
B |
B |
Legend: |
|
|
|
|
I = insufficient |
S = sufficient |
B = good |
O = very good |
[0078] Based on these evaluation, base A2 is the best. Base A3 is a good alternative, especially
if the water-dispersible composition needs to have a good lubricating power (in the
case of great elongations at the temper mill).
Preparation of base B
[0079] As stated above, base B is preponderantly used to confer film forming power to the
composition of the present invention, when it is used in a concentrated state (conc.
≧ 40%).
Example 4 (base B1, condensation reaction).
[0080] Into a similar glass reactor as used for the preparation of base A3, 350 g tall
oil fatty acids and 150 g PRIPOL 1022 are added. The mixture is homogenized at a temperature
of 60 ÷ 70°C, with 300 g xylene added thereto. The reflux condenser with water trap
is connected and vertex thermometer is adjusted at 160 ±5°C the magnetic stirrer,
is introduced.
[0081] Through the neck for the reflux condenser, 224 g diethanolamine and 112 g diisopropanolamine
are introduced. The reflux condenser is inserted, followed by heating for 12 hours
at 160 ± 5°C.
[0082] When 52 ml reaction water has been collected in the trap, base B1 can be considered
to have achieved the desired composition.
[0083] The reflux condenser is removed and vacuum is connected then cooling to 120°C, or
the reaction mixture is poured into a rotary evaporator connected to the vacuum pump
for removing the azeotrope.
[0084] The mixture is allowed to cool to 60 ÷ 50°C. A sample is then taken for the determination
of the acid number, that must be ≦ 2 mg KOH/g.
[0085] The viscous compound thus obtained is poured off at room temperature. The weight
of the compound that is poured off is 780 g.
[0086] The original composition for base B1 is:
Ba: 41.86 g (tall oil fatty acids with a low content of rosin acids),
Bb: 17.9 g (dimer and trimer fatty acids: "PRIPOL 1022"),
Bc: 40 g (diethanolamine/diisopropanolamine, ratio 2:1; molar ratio: Bc:(Ba+Bb) =
1.4:1.
[0087] The colour of base B1 is amber; base B1 can be dispersed into hard water (50 HF)
yielding a dispersion having a pH = 9.2
[0088] A 10% dispersion in distilled water provides the following results:
- maximum Falex load passed: 2950 pound;
- Draves test, average value (1% average solution): 28 seconds.
- protective power: 14 cycles in the climatic chamber.
Example 5 (base B2; condensation)
[0089] Into a similar reactor as that used in example 4, and following the same procedure,
the following reagents are charged:
350 g PRIPOL 1022,
150 g tall-oil fatty acids,
292.5 g diethanolamine,
146.5 g diisopropanolamine.
[0090] The condensation is continued at 160 ± 5°C until 68 ml of reaction water is collected.
[0091] The very viscous liquid thus obtained is poured off at 60°C.
[0092] The weight of poured off product is 868 g.
[0093] The product does not flow at room temperature because it sets to a non-clear, slightly
thixotropic mass.
[0094] To ease the cold-water dispersibility, a little amount of PRIPOL 1022 is to be added.
The product is much more readily dispersed in hot water, indipendently of whether
it is soft or hard water. The pH of the dispersion is about 9.
[0095] A 10 % dispersion in distilled water at 60°C has provided the following results:
- maximum Falex load passed: 3350 pounds;
- protective power: 22 cycles in the climatic chamber.
[0096] Draves Test (1% dispersion in distilled water): non determinable.
[0097] The starting percent composition of base B2 is the following :
Bb: |
15.95 (dimer and trimer fatty acids: "PRIPOL 1022"), |
Ba: |
37.23 (tall oil fatty acids with 2% content of rosin acids), |
Bc: |
46.80 (diethanolamine/diisopropanolamine, ratio 2:1; |
molar ratio: |
Bc:(Ba+Bb) = 1.4:1. |
Example 6 (base B3; condensation reaction)
[0098] As for the preceeding example following the same procedure, the following reagents
are charged into the reactor:
250 g PRIPOL 1022,
250 g talloil fatty acids,
253.3 g diethanolamine,
126.7 g diisopropanolamine.
[0099] The condensation is continued at 160 ± 5°C until 60 ml of reaction water is collected.
[0100] A viscous product is obtained, said product being flowable at room temperature and
having an acid number of ≦ 1 mg KOH/g. The weight of the obtained product is 877 g.
[0101] Base B3 is not readily dispersible into a water room temperature, irrespective of
its hardness.
[0102] A 10% water dispersion of base B3 in distilled water at 60°C has provided the following
results:
- maximum Falex load passed: 3050 pounds;
- protective power: 22 cycles in the climatic chamber.
[0103] The Draves test on a 1% dispersion in distilled water is not evaluable.
[0104] The original percent composition for base B3 is as follows:
Bb: 28.42 (PRIPOL 1022)
Ba: 28.42 (tall oil fatty acids)
Bc: 43.15 (diethanolamine/diisopropanolamine).
[0105] For good quality water-dispersible compositions according to the present invention
to be obtained, it is necessary that base B exhibits, to a proper degree, the following
characteristics (listed in decreasing order of importance:
- Bf) film-forming and protective power
- Bp) polarity
- Bs) degreasing power.
[0106] In table II the evaluation of each of the above characteristics relative to the bases
B prepared in the examples are reported.
TABLE II
Base |
Bf |
Bp |
Bs |
Average evaluation |
B1 |
B |
S |
I |
I |
B2 |
O |
O |
N.V. |
O |
B3 |
O |
B |
N.V. |
O |
legend: |
|
|
|
|
I = insufficient |
S = sufficient |
B = good |
O = very good |
N.V. = non evaluable. |
[0107] As already stated in the introductory clauses, the water-dispersible compositions
of the present invention consist of four components, that are: base A, base B, dispersant
and co-solvent. For the formulation of said water-dispersible composition, the man
skilled in the art must above all keep in mind which among the various characteristics,
should be enhanced in view of the specific end-use of the composition. Therefore,
the various components will be chosen as needs be, keeping well in mind the particular
intended use.
[0108] The evaluations that have been reported in table I for bases A and in table II for
bases B, only have a relative, non absolute value, that means that also a base such
as, for example, base A1, the total (average) evaluation of which has been considered
as insufficient, can nevertheless be usefully employed where it is important to impart
the water-dispersible composition especially good lubricating properties. For example,
if base A1 is mixed with base B2 a water dispersible composition will be obtained
that, besides having good lubricating properties, will also exhibit film-forming and
polar properties.
[0109] Not only but, as stated above, the water-dispersible compositions of the present
invention can be employed both in a diluted state (conc. 3-5%) and in a concentrated
state (conc. ≧ 40%).
[0110] In the first case (conc. 3-5%) the composition will predominantly exhibit degreasing
and detergent properties. The water-dispersible composition should however show sufficient
film-forming properties too, because a protection, even though for a short time, of
the steel sheet is necessary (in this case a continuous film of monomolecular thickness
will suffice). In the second case (conc. ≧ 40%) the water-dispersible composition
will predominantly exhibit protective properties (that is, in this case it is preferable
that the composition be able to form a continuous film having a multimolecular thickness).
In some cases, it is necessary that the protective film be able to last many months
(at least 4-5 months).
[0111] This double function requires a compromise solution since a high detergent power
is not compatible with a high film-forming power.
[0112] There are also, further, less important factors that must sometimes be taken into
account.
[0113] As a guideline we will show hereinbelow some of the most common cases and suggest
the corresponding formulations for water-dispersible compositions.
1) The treatment of steel sheet with a very soiled surface is required, for which
a short time protection is necessary , or
2) A steel sheet having not a very soiled surface is to be treated, for which a long-lasting
protection is necessary, or
3) a steel sheet, the surface of which has not been temper milled for which a long-lasting
protection is required, or, finally,
4) a steel sheet with a very soiled surface for which a good detergent power, and
a temporary protection (diluted composition) and subsequently a durable protection
(concentrated composition) are required; this is the most frequent situation.
[0114] Having in mind the characteristics shown in tables I and II above, the following
conclusions can be drawn:
for the first case a composition of formula A at a concentration of 3-5% is suited;
for the second case the suitable composition will be formula B at a concentration
of 40-50%;
for the third case on the other hand a composition of formula C at a concentration
higher then 60% is more appropriate;
[0115] Finally, for the fourth case it will be useful to employ a composition of formula
D, first at a concentration of 3-5% and, then, the same composition at a concentration
higher then 40%; as far as the formulation those four compositions is concerned, Table
III can be referred to.
TABLE III
|
FORM. A % |
FORM. B % |
FORM.C % |
FORM. D % |
Base A2 |
50 |
28 |
7 |
38 |
Base B2 |
8 |
30 |
38 |
25 |
Base B3 |
- |
5 |
18 |
18 |
Ethyleneglycol |
7 |
- |
10 |
- |
Glycol ether |
21 |
10 |
- |
5 |
Water |
14 |
27 |
27 |
14 |
[0116] It is to be recalled that no difficulty is involved in the preparation of the various
water-dispersible compositions of the present invention, in that the various above-mentioned
components simply have to be mixed, preferably, but not necessarily, in the given
order (viz. base A, base B, dispersant, co-solvent), at a temperature of 40-50°C
under stirring until the mixture is completely homogeneous or clear. As already stated
above, if it is not possible to obtain a clear dispersion by simply mixing the components,
it will suffice to yet add a small quantity (0.5-1%) of co-solvent.