U.S. patent application number 11/088147 was filed with the patent office on 2006-09-28 for compositions useful to provide improved rheology and mist control to ink formulations and ink formulations containing such compositions.
This patent application is currently assigned to Elementis Specialties, Inc.. Invention is credited to Sel Avci, Dan Merchant.
Application Number | 20060213393 11/088147 |
Document ID | / |
Family ID | 37033903 |
Filed Date | 2006-09-28 |
United States Patent
Application |
20060213393 |
Kind Code |
A1 |
Avci; Sel ; et al. |
September 28, 2006 |
Compositions useful to provide improved rheology and mist control
to ink formulations and ink formulations containing such
compositions
Abstract
The invention is ink formulations that show improved rheological
and antimisting properties. The invention is particularly useful in
lithographic inks including heatset, sheetfed and UV curable
lithographic inks. The invention also includes novel additive that
enable the preparation of inks with required viscosities that are
needed to perform on high-speed printing presses with improved
performance. The additive is based on reaction products of
polyamines and carboxylic acids with two or more carboxylic
moieties mixed or combined with tridecyl alcohol. In addition, the
inventive additive is in the form of liquid and it is pourable and
pumpable for ink manufacturing processes.
Inventors: |
Avci; Sel; (Kendall, NJ)
; Merchant; Dan; (East Brunswick, NJ) |
Correspondence
Address: |
RHEOX, INC.;WYCKOFFS MILL ROAD
P O BOX 700
HIGHTSTOWN
NJ
08520
US
|
Assignee: |
Elementis Specialties, Inc.
Hightstown
NJ
|
Family ID: |
37033903 |
Appl. No.: |
11/088147 |
Filed: |
March 23, 2005 |
Current U.S.
Class: |
106/31.43 ;
106/31.58; 106/31.75; 106/31.86 |
Current CPC
Class: |
C09D 11/101
20130101 |
Class at
Publication: |
106/031.43 ;
106/031.75; 106/031.58; 106/031.86 |
International
Class: |
C09D 11/00 20060101
C09D011/00 |
Claims
1. A composition comprising: a) the reaction product of (i) a
carboxylic acid with at least two carboxylic moieties and (ii) a
polyamine having an amine functionality of two or more; and b) a
low volatility liquid alcohol which has a water solubility of less
than 10 mg/L.
2. The composition of claim 1, wherein the carboxylic acid is a
dimer fatty acid.
3. The composition of claim 2, wherein the dimer fatty acid is
selected from the group consisting of hydrogenated, partially
hydrogenated and non-hydrogenated dimer acids with from about 20 to
about 48 carbon atoms.
4. The composition of claim 1, wherein the polyamine is a
polyethylene polyamine.
5. The composition of claim 4, wherein the polyamine is selected
from the group consisting of ethylenediamine, diethylenetriamine,
triethylenetetramine and tetraethylenepentamine.
6. The composition of claim 4, wherein the polyamine is
diethylenetriamine.
7. The composition of claim 1 wherein the low volatility liquid
alcohol is tridecyl alcohol.
8. The composition of claim 1, wherein the tridecyl alcohol has the
chemical formula C.sub.13H.sub.28O.
9. The composition of claim 7, wherein the tridecyl alcohol is
isotridecanol.
10. A printing ink comprising an organic ink vehicle having
dispersed therein an ink coloring material and an additive
comprising the composition of claim 1.
11. The printing ink of claim 10 wherein the additive comprises the
composition of claim 2.
12. The printing ink of claim 10 wherein the additive comprises the
composition of claim 4.
13. The printing ink of claim 10 wherein said additive comprises
from 0.1% to 10% by weight of said printing ink.
14. The printing ink of claim 10 wherein said additive comprises
from 1.0% to 3.0% by weight of said printing ink.
15. A composition comprising the reaction product of a) a
carboxylic acid with at least two carboxylic acid moieties, b) a
polyamine having an amine functionality of two or more diluted with
a tridecyl alcohol.
16. A lithographic ink comprising the composition of claim 15.
Description
FIELD OF THE INVENTION
[0001] This invention relates to compositions suitable for use as
additives for ink, and to ink formulations comprising said
compositions. The invention particularly relates to additives that
provide improved rheological properties to lithographic printing
inks, sheetfed, heatset and UV curable offset ink formulations. The
rheological additive is pourable and pumpable, thereby making it
easy to use it in mechanical or automated ink manufacturing
processes.
BACKGROUND OF THE INVENTION
[0002] It is well known that the printing inks utilized today are
modified with various types of rheological additives to provide
required Theological properties to ensure quality printing on high
speed printing presses. Generally, polymer (or resin), solvent and
pigment types determine the intrinsic rheology of the ink
formulation. Ideally, the formulators hope to achieve all the
rheological properties from the resin system they choose. However,
to fine tune the rheology and improve overall performance
properties of their inks, formulators most often seek "rheological
additives." The rheological modifiers are one of the most important
additives utilized in printing ink formulations. The additives are
utilized to modify the rheological properties of printing inks to
meet the requirements of various types of printing presses. It has
been long known that organoclays have been used to control rheology
and reduce ink misting on high speed presses. The assignee hereof
has long offered a line of products sold under the trademark
BENTONE.RTM. to ink manufacturers.
[0003] It has been long known, since at least the 1950s, that
organoclays (also called organophilic clays) can be used to thicken
ink systems. See the very early article by an employee of the
assignee hereof J. W. Jordan, "Proceedings of the 10th National
Conference on Clays and Clay Minerals" (1963), which discusses a
range of applications of organoclays from high polarity liquids to
low polarity liquids. See also U.S. Pat. No. 4,475,950.
[0004] U.S. Pat. Nos. 5,735,943; 5,718,841 and 5,429,999 describe
the use of organoclays in various applications.
[0005] Organoclays are manufactured as dry powders and require
significant processing on the part of the ink
formulator/manufacturer to fully disperse and activate them into
ink formulations. The dry powders are often very difficult to
disperse in inks because of the need for high shear mixing
equipment, increased temperatures and longer mixing conditions. In
addition, the powdered materials require additional man-power to
handle the bags to charge them into the ink mixing kettle which
creates unhealthy dust conditions.
[0006] Ink manufacturers have long sought an easy to add, pumpable
or pourable rheological additive which can be incorporated without
handling dusty powders and requiring lengthy processing
requirements. A liquid rheological additive would also be
beneficial as a post additive to fine tune the viscosity of
finished inks. There is clearly a need for a liquid rheological
additive which can be utilized in an offset ink making process. The
use of liquid Theological additive would allow the ink
manufacturers to streamline the manufacturing process. As the ink
manufacturing process changes toward faster throughput and full
automation, the ink manufacturers demand easy to disperse, pumpable
raw materials in their formulations so that lengthy processing and
milling are eliminated.
[0007] Patents of the prior art that show developments related to
the chemistry of additives useful in various fields, other than
organoclays, include the following:
[0008] U.S. Patent Application Publication No. 2001/0009890 shows
an invert emulsion suitable for drilling a subterranean well which
uses an ester of a C.sub.1 to C.sub.12 alcohol and a C.sub.8 to
C.sub.24 monocarboxylic acid; Ethomeen C/15 can be used as an agent
in the invention described in the application.
[0009] U.S. Pat. No. 5,536,871 also issued to the assignee hereof
describes a Theological additive which comprises the reaction
product of a polyalkoxylated nitrogen-containing compound such as
polyoxyethylene (5) cocoalkylamine, a polycarboxylic acid including
dimer acids and a liquid diamine.
[0010] U.S. patent application Ser. No. 10/303,037, filed by
assignee hereto, describes an additive that provides flat rheology
to oil well drilling fluids, particularly those used in deep water
drilling comprised of a reaction product of a carboxylic acid with
at least two carboxylic acid moieties and a polyamine having an
amine functionality of two or more.
[0011] U.S. Pat. No. 5,610,110 also issued to assignee hereof shows
an improved drilling fluid containing a reaction product of an
alkoxylated aliphatic amino compound and an organic polycarboxylic
acid and a clay based organoclay.
SUMMARY OF THE INVENTION
[0012] The invention herein is directed to a liquid rheological
additive for heatset, sheetfed and UV curable offset inks. The
liquid rheological additive according to the present invention is
pourable and pumpable at room or ambient temperature and can be
incorporated into inks without the need of high shear mixing
equipment and mills.
[0013] Stated another way, this invention provides a composition
comprising the reaction product of a di-, tri- or polyamine with an
acid containing at least two carboxyl functional groups to form a
polyamide and as the second ingredient a low volatility liquid
alcohol which has a water solubility of less than 10 mg/L at
25.degree. C., which can be added to the polyamide before, during
or after its synthesis or added to the ink as a separate
component.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0014] An important embodiment of this invention relates to a
composition which is a mixture or blend of (1) a reaction product
of a specific polyamine and a carboxylic acid with at least two
carboxylic moieties and (2) a low volatility liquid alcohol which
has a water solubility of less than 10 mg/L at 25.degree. C. In
addition, the invention includes an ink fluid containing the above
composition. The use of this unique mixture as an additive for an
ink surprisingly improves the ink's rheological properties.
[0015] The additive comprises the following. First discussed are
the components of the reaction product and its production.
Fatty Acids
[0016] Any carboxylic acid with at least two carboxylic moieties
can be used for producing the reaction product component of the
present invention. Dimer acids are preferred; dimer acids of
C.sub.16 and C.sub.18 fatty acid are particularly preferred. Such
dimer acids can be fully hydrogenated, partially hydrogenated, or
not hydrogenated at all. Useful dimer acids include products
resulting from the dimerization of C.sub.16 to C.sub.18 unsaturated
fatty acids.
[0017] Generally when used, the dimer acids preferably have an
average from about 18, preferably from about 28 to about 48 and
more preferably to about 40 carbon atoms. Most preferably dimer
acids have 32 to 36 carbon atoms.
[0018] Useful dimer acids are preferably prepared from C.sub.18
fatty acids, such as oleic acids. Useful dimer acids are described
in U.S. Pat. Nos. 2,482,760, 2,482,761, 2,731,481, 2,793,219,
2,964,545, 3,157,681, and 3,256,304, the entire disclosures of
which are incorporated herein by reference.
[0019] Examples of most preferred dimer acids include the
Empol.RTM. product line available from Cognis, Inc., Pripol.TM.
dimer acids available from Uniqema and HYSTRENE.RTM. dimer acids
formerly available from Humko Chemical.
[0020] It is recognized that commercially available dimer fatty
acids contain a mixture of monomer, dimer, and trimer acids.
Preferably, suitable dimer acid has a dimer content of at least
80%, more preferably above 90%.
[0021] Empol.RTM. 1061 with a dimer acid content of 92-96% is the
preferred dimer acid for the present invention.
Polyamines
[0022] Polyamines having an amine functionality of two or more are
used for the preparation of the reaction product of the present
invention. Most preferably, polyamines from the family of
polyethylene polyamines having an amine functionality of two or
more should be used.
[0023] Di-, tri-, and polyamines and their combinations are most
suitable for use in this invention. Representative such amines
include ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine and other members of this series. Branched
polyamines and polyamines made with different alkyl groups may also
be used.
[0024] Triamines are most preferable, particularly
diethylenetramine (DETA). DETA has been assigned a CAS No. of
111-40-0. It is commercially available from Huntsman International
and others.
Making the Reaction Product
[0025] Specifics on processing of polyamines and carboxylic acids
are well known and can be used in making the reaction product of
this invention. Preferably, the molar ratio between the amine
functional group and carboxyl functional group is between 4:1 and
1:1. The preferred range is from 1:5:1.0 to 3:1, most preferably
about 2:1. Mixtures of more than one dimer acid and/or more than
one polyamine can be used. A representative manufacturing process
is illustrated in the examples following hereafter. It should be
noted that these reactions may generate imidazolines and other side
products.
[0026] While the above is the preferred formulation, other
compositions of varying molar ratios of raw materials can be used.
Additionally, alternate commercial dimer fatty acids can be reacted
with various amines to generate the reaction polymer.
Ink Formulations
[0027] In general, the printing ink compositions of the present
invention comprise (a) at least one organic ink fluid vehicle
broadly defined, (b) at least one additive as described, and (c) at
least one color-imparting material, such as a pigment. The
additive(s) is/are combined with the organic ink vehicle and
pigment in sufficient concentration to provide a composition which
exhibits desirable thixotropic properties as well as physical,
chemical, and visual color characteristics suited to the intended
application.
[0028] The organic ink vehicles usable as ink formulations of the
present invention include various (a) ink oils generally and (b)
ink systems containing organic resins and/or combinations thereof
whatever kind used as commercial inks sold for all types of
printing uses.
[0029] Examples of ink oils which are preferably used in the
present invention include high boiling point petroleum derivative
solvents and ink oils such as Magiesol 52, 47, and ink oil Magiesol
470. The solvent may be aliphatic, paraffinic or naphthenic in
nature. The ink oils may include vegetable oils such as Soya,
rapeseed, linseed oils which are hydrophobic and insoluble in
water.
[0030] Example of ink resins and or combinations thereof include
but are not limited to alkyds, hydrocarbon based resins, phenolic
modified rosins and esters, polyesters, acrylated oligomers such as
polyesters, urethanes and epoxy acrylates.
[0031] The color-imparting additives employable in ink compositions
of the present invention include various pigments and/or
pigment-containing pastes. Pre-dispersed pigment pastes generally
comprise one or more colored pigments dispersed in a vehicle and/or
solvent. The vehicle(s) employed in such pre-dispersed pigment
paste may comprise one or more of the organic ink vehicles
described herein as basic components of ink compositions of the
present invention and/or other vehicles which differ from the above
described organic ink vehicles.
Compatible Diluents
[0032] Critically important to this invention is that a low
volatility liquid alcohol or glycol be mixed into or blended into
the above discussed reaction product produced by the reaction of
the carboxylic acid with the polyamine as described above or is
otherwise added directly to the ink. Suitable low volatility liquid
alcohols and glycols must have solubility in water of less than 10
mg/L. Suitable alcohols must be compatible with both the polyamide
additive and the ink. Suitable alcohols or glycols should have
viscosity reducing power when it is incorporated into polyamide so
that the resultant product is pumpable and pourable. Suitable
diluents should have low volatility and low odor. TABLE-US-00001
TABLE 1 Boiling Pt. Melting Pt. Vapor Pressure Water Solubility
Trade Name Chemical Name (.degree. C.) (.degree. C.) (mm Hg@
100.degree. C.) (mg/L) Hexyl Hexanol, branched 152-163 -25.5 124
10,340-11,950 alcohol and linear Isoheptyl Alcohols C6-C8, 167-176
-49.2 78 3,539-11,950 alcohol branched Isooctyl Alcohols C7-C9 iso,
185-193 -117.2 27 1,379-1,485 alcohol C8 rich Nonanol Nonanol
192-204 -5 22 156-572 Isononyl Alcohols C8-10 iso, 203-215 64.5 16
164-614 alcohol C9 rich Isodecyl Alcohols C9-11 iso, 217-224 34.3
8.2 75 alcohol C10 rich Tridecyl Alcohols C11-14 iso 256-266 29.2
2.7 5.8 alcohol C13 rich 2-Octyl Alcohols C20 234-238 -1 to +1 NA
<10 dodecanol
[0033] The preferred alcohol is tridecyl alcohol also known as
isotridecanol. This preferred alcohol is, for example, available
from ExxonMobil Chemical under the trade name of Exxal 13.
[0034] Isotridecanol has the empirical formula C.sub.13H.sub.28O.
Tridecyl alcohol is preferred due to its low water solubility.
Tridecyl alcohol is also preferred because of its high boiling
point and low volatility.
[0035] Tridecyalcohol is the preferred diluent due to its low
volatility, compatibility, viscosity reducing properties and
readily availability.
[0036] In a preferred embodiment, the reaction product and alcohol
are mixed or blended in a weight ratio range of 95:5 to 5:95. The
preferred ratio range of the two components is 80:20 to 30:70 and
the most preferred ratio is 65:35.
Optional Components
[0037] Optionally, additional ingredients such as fatty amides and
related alkoxylated derivatives can be blended into or reacted with
the polyamide reaction product.
[0038] Suitable fatty amides, such as the Armid.RTM. product line
by Akzo Nobel includes high melting temperature amides of fatty
acids that are sparingly soluble in drilling muds. Additionally,
alkoxylated fatty amides, such as the Ethomid.RTM. product line by
Akzo Nobel can be used.
[0039] Organophilic Clays. Organoclays made from bentonite,
hectorite and attapulgite clays can be added to the inventive ink
formulation. There are a large number of suppliers of such clays in
addition to Elementis Specialties' BENTONE.RTM. product line,
including Rockwood Specialties, Inc. and Sud Chemie GmbH. Although
organoclay can be a useful component, it is not a necessary
component of the ink. If used, however, the preferred organoclays
are BENTONE 760, BENTONE 500, and BARAGEL 3000, all available from
Elementis Specialties, Inc.
Blending Process
[0040] Ink formulation preparations preferably contain 0.25 to 5
weight percent of the inventive additive; the more preferred
concentration is 0.5 to 2 weight percent.
[0041] As shown above, a skilled artisan will readily recognize
that additional additives, such as: dispersing agents, wetting
agents, viscosifiers, waxes and other agents can be used with this
invention.
[0042] The compositions of this invention described above will be
used primarily as an additive to inks and most particularly for
lithographic inks.
EXAMPLES
Example 1
Preparation of the Polyamide Reaction Product
[0043] Empol.RTM. 1061 (792.9 grams) was placed in a 2 liter,
4-neck, preweighed reactor equipped with a Barrett distilling
receiver and a Friedrichs condenser. The Empol.RTM. 1061 was heated
to 100.degree. C. and then diethylenetriamine (190.6 grams) was
added. The contents were heated to 240.degree. C. under a nitrogen
blanket while mixing at 300 RPM. A reaction occurred with the
liberation of water, which was collected in a receiver. The
reaction was allowed to continue until the acid value was
.ltoreq.2.0 (mg KOH/gram of reaction mixture). The reaction was
halted and the reactor reweighed.
Example 2
[0044] Product of Example 1 was allowed to cool to 80.degree. C.
under agitation. Reaction product in Example 1 (65 parts) was mixed
with tridecyl alcohol (35 parts). The composition was mixed for 15
minutes. The resulting product was poured into an appropriate
storage container.
Example 2A
[0045] The reaction product of example 1 (65 parts) was mixed
slowly at 500 RPM with polypropylene glycol MW 425 (35 parts). The
composition was mixed for 15 minutes. The resulting product was
poured into an appropriate storage container.
Example 2B
[0046] The reaction product of Example 1 (65 parts) was mixed
slowly at 500 RPM with polypropylene glycol MW 725 (35 parts). The
composition was mixed for 15 minutes. The resulting product was
poured into an appropriate storage container.
Example 2C
[0047] The reaction product of Example 1 (65 parts) was mixed
slowly at 500 RPM with polypropylene glycol MW 2000 (35 parts). The
composition was mixed for 15 minutes. The resulting product was
poured into an appropriate storage container.
Example 2D
[0048] The reaction product of Example 1 (65 parts) was mixed
slowly at 500 RPM with 2-octyl dodecanol (Isofol 20) MW 242 (35
parts). The composition was mixed for 15 minutes. The resulting
product was poured into an appropriate storage container.
Example 2E
[0049] The reaction product of Example 1 (65 parts) was mixed
slowly at 500 RPM with 2-decyl tetradecanol (Isofol 24) MW 354 (35
parts). The composition was mixed for 15 minutes. The resulting
product was poured into an appropriate storage container.
Example 3
[0050] Empol.RTM. 1008 (635.2 grams) and Ethomeen.RTM. C/15 (692.1
gram) were placed in a 2 liter, 4-neck, pre-weighed reactor
equipped with a Barrett distilling receiver and Friedrichs
condenser. The contents were heated to 240.degree. C. under a
nitrogen blanket while mixing at 300 rpm. The reaction was allowed
to continue until the acid value was .ltoreq.5.0 (mg KOH/gram of
reaction mixture). Once the acid value was .ltoreq.5.0,
diethylenetriamine (112.6 grams) was charged to the reactor. The
reaction continued for another two hours at 240.degree. C. After
this time, Armid.RTM. HT (164.0 grams) was added to the reactor and
cooked for an additional 3 hours at 240.degree. C. The resulting
product was poured into storage containers.
[0051] Preparation of the Ink Formulation and Testing Procedures
TABLE-US-00002 TABLE 2 Heatset Offset Base Ink Formulation
Component Generic Name Supplier Weight (g) Phthalo Blue Flush
Pigment Flush Magruder 31.6 Local A7T Heatset varnish Lawter 53.7
Magiesol 470 Ink Oil Magie Brothers 10.5 Wax Compound Wax additive
Elementis 4.2
[0052] Printing ink compositions using the present invention may be
prepared by conventional techniques, e.g. by preparing pigment
dispersion in an ink varnish or using a pre-dispersed pigment such
as pigment flush and the additive. A base ink from the components
described on Table 2 is as follows: The ink components without the
additive were mixed using a high speed mixer equipped with a Cowles
type blade such as Dispermat CV model at 3000 RPM for 15 minutes.
The mixture was then allowed to cool to room temperature and
equilibrate for 24 hours.
[0053] The additives were incorporated to the base ink and mixed
for 15 minutes at 4,000 RPM. The blending ratio of the base ink to
the rheological additive is 98:2.
[0054] After the inks were prepared, they were allowed to
equilibrate to room temperature overnight, and the ink properties
were measured as described below:
[0055] Fineness of grind or ink dispersion was measured on a NPIRI
Grindometer G-1 (25 micron) in accordance to ASTM D1316-93.
[0056] Viscosity measurements were taken on a fallen rod type
viscometer called a "Duke Rheometer" according to ASTM D2052.
[0057] Tack of the inks was measured with a Thwing-Albert
Electronic Inkometer, Model 101 in accordance to ASTM D4361-89 at
1200 RPM at 90.degree. F. for one minute. Misting was determined by
visual observation of the ink collected on a clean 51/2''.times.7''
blank white paper placed under the inkometer rollers during the
measurement. The misting was interpreted as poor to excellent by
visual comparison to a standards chart.
[0058] Ink emulsification or water pick-up test was measured with a
Duke Emulsification tester Model D-10 in accordance to ASTM
D4942-89 using a 5 minute single point water pickup test.
Ink Testing
Example 4
Blank Ink; No Rheological Additive
[0059] The components of the base formulation as described in Table
2. Example 4 represents the blank ink without any rheological
additive. This ink is considered a "blank ink".
Example 5
Control Ink; Prior Art Organoclay Rheological Additive
[0060] A composition of 98 parts of the Example 4 is blended with 2
parts of an organoclay (BENTONE.RTM. 760 rheological additive) by
using a high speed mixer equipped with a Cowles type blade such as
Dispermat CV model at 4000 RPM for 20 minutes. The mixture was then
allowed to cool to room temperature and equilibrate for 24
hours.
Example 6
[0061] A composition of 98 parts of the Example 4 is blended with 2
parts of the inventive additive from Example 2 (containing 35%
tridecyl alcohol) by using a high speed mixer equipped with a
Cowles type blade such as Dispermat CV model at 2000 RPM for 10
minutes. The mixture was then allowed to cool to room temperature
and equilibrate for 24 hours.
Example 7
[0062] A composition of 98 parts of the Example 4 is blended with 2
parts of the additive from Example 3 by using a high speed mixer
equipped with a Cowles type blade such as Dispermat CV model at
2000 RPM for 10 minutes. The mixture was then allowed to cool to
room temperature and equilibrate for 24 hours.
Example 8
[0063] A composition of 98 parts of the Example 4 is blended with 2
parts of the inventive additive as in Example 1 (no tridecyl
alcohol) by using a high speed mixer equipped with a Cowles type
blade such as Dispermat CV model at 2000 RPM for 10 minutes.
[0064] Note that the additive without the tridecyl alcohol was not
in a pourable or pumpable form. The product had to be heated to
140.degree. F. to make it pourable before addition into the ink.
The mixture was then allowed to cool to room temperature and
equilibrate for 24 hours.
[0065] Results TABLE-US-00003 TABLE 3 Water Pick Viscosity Yield
Value Misting up Tack (Poise) Dynes/cm.sup.2 (Visual) (%) (Value)
Example 4 64 559 Poor 24 10.1 (Blank) Example 5 90 1021 Good 48
12.4 (Control) Example 6 107 1197 Excellent 20 12.3 Example 7 116
1406 Good 100% 12.7 Example 8 157 2595 Good 75% 16.4
Discussion of Results:
[0066] Table 3 shows that Example 6, the inventive additive
containing tridecyl alcohol, produced excellent rheological and
antimisting properties compared to a traditional rheological
additive such as an organoclay, BENTONE.RTM. 760, in the Example 5.
The water emulsification properties of the inventive additive
(Example 6) is acceptable (<50%) whereas that of Examples 7 and
8 are unacceptable and these additives would not be useful in
offset ink applications because of their high level water
emulsification properties.
Comparative Diluents:
[0067] Alternative diluents include but are not limited to high
boiling point alcohols such as n-butanol, isobutanol, n-propanol,
2-ethylhexanol, glycol ethers such as butyl glycol, n-hexyl glycol,
methyl diglycol, butyl diglycol, phenyl glycol,
1-methoxy-2-propanol, methoxypropxypropanol, 3-butoxy-propanol-2,
saturated alcohols such as 2-alkyl-1-alkanols from C.sub.12 to
C.sub.26 can also be utilized for this application. Polypropylene
glycols at various molecular weights from 425 to 4,000 are
available. Low molecular glycols such as propylene glycol and
polypropylene glycol molecular weight 425 are not suitable due
their high water solubility characteristics. The higher molecular
weight polypropylene glycols provide the low water solubility and
performance properties to ink applications.
[0068] The following examples show the performance of low and high
molecular weight diluents such as polypropylene glycols and 2-Octyl
Dodecanol, Isofol 20 (C.sub.20) in the inventive product.
Example 9
[0069] To 98 parts of the base formulation as described in Table 2
are blended with 2 parts of the inventive additive of Example 2
(containing 35% tridecyl alcohol) mixed by using a high speed mixer
equipped with a Cowles type blade such as Dispermat CV model at
2000 RPM for 10 minutes. The mixture was then allowed to cool to
room temperature and equilibrate for 24 hours.
Example 10
[0070] To 98 parts of the base formulation as described in Table 2
are blended with 2 parts of the inventive additive Example 2A
(containing 35% polypropylene glycol diluent; molecular weight 425)
mixed by using a high speed mixer equipped with a Cowles type blade
such as Dispermat CV model at 2000 RPM for 10 minutes. The mixture
was then allowed to cool to room temperature and equilibrate for 24
hours.
Example 11
[0071] To 98 parts of the base formulation as described in Table 2
are blended with 2 parts of the inventive additive Example 2B
(containing 35% polypropylene glycol solvent; molecular weight 725)
mixed by using a high speed mixer equipped with a Cowles type blade
such as Dispermat CV model at 2000 RPM for 10 minutes. The mixture
was then allowed to cool to room temperature and equilibrate for 24
hours.
Example 12
[0072] To 98 parts of the base formulation as described in Table 2
are blended with 2 parts of the inventive additive Example 2C
(containing 35% polypropylene glycol solvent; molecular weight
2000) mixed by using a high speed mixer equipped with a Cowles type
blade such as Dispermat CV model at 2000 RPM for 10 minutes. The
mixture was then allowed to cool to room temperature and
equilibrate for 24 hours.
Example 13
[0073] To 98 parts of the base formulation as described in Table 2
are blended with 2 parts of the inventive additive Example 2D
(containing 35% 2-octyl dodecanol, C.sub.20 diluent; molecular
weight 298) mixed by using a high speed mixer equipped with a
Cowles type blade such as Dispermat CV model at 2000 RPM for 10
minutes. The mixture was then allowed to cool to room temperature
and equilibrate for 24 hours.
Example 14
[0074] To 98 parts of the base formulation as described in Table 2
are blended with 2 parts of the inventive additive Example 2E
(containing 35% 2-decyl tetradecanol, C.sub.24 solvent; molecular
weight 354) mixed by using a high speed mixer equipped with a
Cowles type blade such as Dispermat CV model at 2000 RPM for 10
minutes. The mixture was then allowed to cool to room temperature
and equilibrate for 24 hours.
[0075] Results TABLE-US-00004 TABLE 4 Water Pick Viscosity Yield
Value Misting up Tack (Poise) Dynes/cm.sup.2 (Visual) (%) (Value)
Example 9 107 1197 Good 20% 12.3 Example 10 118 1198 Good 71% 12.4
Example 11 107 1097 Good 58% 12.3 Example 12 107 1290 Good 20% 12.4
Example 13 134 1470 Good 28% 12.8 Example 14 136 1568 Good 26%
12.9
Discussion of Results:
[0076] Table 4 shows the comparison of the inventive additive
containing tridecyl alcohol, Example 9, to other co-solvents such
as C20 and C24 alcohols, polypropylene glycols from low molecular
weight of 425 to higher molecular weight of 2000. The lower
molecular weight polypropylene glycols, as in Example 10 and
Example 11, showed similar rheological properties compared to
Example 9; however low molecular weight polypropylene glycols
produced excessive water emulsification properties and therefore
would find limited use in offset ink applications. Higher molecular
weight polyglycols may be utilized as co-solvents due to their low
water emulsification properties and their low volatility. The
sample prepared with high molecular weight polypropylene glycol
2000 as in Example 12 produced similar rheological and
emulsification versus Example 9. Therefore, the higher molecular
weight polypropylene glycols can also be utilized for this
application.
[0077] As seen from the results, the use of diluents is not limited
to C13 alcohols.
[0078] Additional Ink Testing: TABLE-US-00005 TABLE 5 Sheetfed
Offset Base Ink Formulation Component Generic Name Suplier Weight
(g) Phthalo Blue Flush Pigment Flush Magruder 31.6 AKO 2035 Ink
varnish Akzo 20.0 AKO 2495 Ink varnish Akzo 34.0 Magiesol 52 Ink
Solvent Magie Brothers 8.0 Dryer 1 Cobalt dryer Mooney 1.0 Dryer 2
Mangenese Nuodex 1.0
[0079] A base sheetfed ink from the components described on Table 5
is as follows: The ink components without the additive were mixed
using a high speed mixer equipped with a Cowles type blade such as
Dispermat CV model at 4000 RPM for 15 minutes. The mixture was then
allowed to cool to room temperature and equilibrate for 24
hours.
[0080] The additives were incorporated into the base ink and mixed
for 20 minutes at 4,000 RPM. The blending ratio of the base ink to
the rheological additive is 98:2.
[0081] After the inks were prepared, they were allowed to
equilibrate to room temperature overnight, and the ink properties
were measured as described in the previous page.
Example 15
[0082] The Example 15 represents a sheetfed ink formulation as
described on Table 5 without any rheological additive. This ink
will be called "Blank".
Example 16
[0083] A composition of 98 parts of the Example 15 is blended with
2 parts of an organoclay (BENTONE.RTM. 760) by using a high speed
mixer equipped with a Cowles type blade such as Dispermat CV model
at 4000 RPM for 20 minutes. The mixture was then allowed to cool to
room temperature and equilibrate for 24 hours.
Example 17
[0084] A composition of 98 parts of the Example 15 is blended with
2 parts of the inventive additive Example 2 (containing 35%
tridecyl alcohol) mixed by using a high speed mixer equipped with a
Cowles type blade such as Dispermat CV model at 4000 RPM for 10
minutes. The mixture was then allowed to cool to room temperature
and equilibrate for 24 hours. TABLE-US-00006 TABLE 6 Results
Viscosity Yield Value Misting Water Pick up (Poise) Dynes/cm.sup.2
(Visual) (%) Example 15 286 2,605 Fair 44 (Blank) Example 16 355
4,320 Good 44 Example 17 423 6,497 Excellent 44
Discussion of Results:
[0085] Table 6 shows the performance results of the inventive
additive containing Example 17 versus the ink containing an
organoclay additive in example 16 and the blank ink without any
additive in Example 15.
[0086] The above results showed that viscosity and yield value of
the inventive additive (Example 17) is markedly better than a blank
ink (Example 15) as well as an ink containing a conventional
organoclay additive (Example 16).
Additional Ink Testing:
[0087] The inventive additive was also evaluated as an ink varnish
gellant in a hydrocarbon modified rosin ester type ink resin. As
shown in the following examples, the inventive additive produced
excellent Theological properties compared to a commercially known
gellant such as commercially available Manalox 130 (aluminum
chelating agent) from OMG Group of Bethlehem, Pa.
[0088] The reactive gellants may include aluminum soaps and
compounds, organic titanates, oxides/hydroxide of Ca, Mg, Zn and
polyamino-acids. The reactive chemical gellants can not be directly
added to ink due to heat activation and process requirements. These
gellants are rather incorporated into the ink varnishes by heating
the varnish to minimum temperature of 150.degree. C. The chemical
gellants thicken the ink varnishes by crosslinking the resin.
[0089] The inventive product produced excellent rheological
properties compared to a commercially known gellant such as Manalox
130 (aluminum chelating agent). The additives were incorporated at
150.degree. C. for 1 hour. The results are listed on the attached
Table 7.
Example 18
[0090] The composition of the Example 18 represents a commercially
available heatset ink varnish supplied by Varchem Chemicals Clifton
N.J., Varchem 5110S, without any rheological additive. This will be
labeled as "Blank".
Example 19
[0091] The heatset ink varnish supplied by Varchem Chemicals
Clifton N.J., Varchem 5110S, without any rheological additive in
Example 18 ( 99 parts) is blended with 1 part of a comparative
additive, Manalox 130, from Rhodia Company at 150.degree. C.
cooking temperature for 60 minutes. The mixture was then allowed to
cool to room temperature and equilibrate for 24 hours.
Example 20
[0092] The heatset ink varnish supplied by Varchem Chemicals
Clifton N.J., Varchem 5110S, without any rheological additive in
Example 18 is blended with 2 parts of the inventive additive in
Example 2 at 150.degree. C. cooking temperature for 60 minutes. The
mixture was then allowed to cool to room temperature and
equilibrate for 24 hours. TABLE-US-00007 TABLE 7 Duke Viscosity
Duke Viscosity @2.5 sec.sup.-1 @2500 sec.sup.-1 (Poise)
(Dynes/cm.sup.2) Example 18 328 157 (Blank) Example 19 4402 290
Example 20 3108 317
[0093] The present invention overcomes some or all of the
shortcomings of the prior art by identifying and providing new
thixotropic agents for use in organic based (e.g. oil based and/or
resin based) printing ink compositions. The thixotropic agents of
the present invention offer the advantage of being usable at room
temperature and/or normal processing temperatures which may widely
vary and also have been found to bring about desirable improvement
in the viscosity and yield value of the printing inks.
[0094] The foregoing description and examples have been set forth
merely to illustrate the invention and are not intended to be
limiting. Since modifications of the disclosed embodiments
incorporating the spirit and substance of the invention may occur
to persons skilled in the art, the invention should be construed
broadly to include all variations falling within the scope of the
appended claims and equivalents thereof.
* * * * *