United States Patent (19) 11) 4,361,843

Cooke et al. 45) Nov.30, 1982

(54) INKJET COMPOSITIONS AND METHOD 4,269,891 5/1981 Minagawa ........................... 428/335
75) Inventors: Theodore M. Cooke, Danbury; FOREIGN PATENT DOCUMENTS
Richard G. Whitfield, Brookfield; -
An-Chung R. Lin, New Town, all of 12: Ag: E.
Conn.
Primary Examiner-Lorenzo B. Hayes
73 Assignee: Exxon Research and Engineering Co., Assistant Examiner-Amelia B. Yarbrough
Florham Park, N.J. Attorney, Agent, or Firm-Robert S. Salzman

22 Filed: Mar. 27, 1981 An inkjet composition and method of applying same is
5) Int. Cl......................... G08C 9/00; C09D 11/02 featured providing exceptionally good print quality on
52 U.S.C. ....................................... 346/1.1; 106/22; a wide range of printing papers. The ink composition
106/27; 346/75 includes a mixture of oleic acid in an approximate
58 Field of Search ..................... 106/22, 27; 346/1.1, weight of from 20 to 80 percent of the total mixture and
346/75 a dye in a dye solvent. The mixture is jetted at a temper
56 References Cited ature of approximately 135 F. The average dot circu
larity for a dot jetted upon the paper is approximately
U.S. PATENT DOCUMENTS 0.7 or better.
4,014,029, 3/1977 Lane et al. ........................... 34.6/1.1
4,153,467 5/1979 Yano et al............................. 106/27 18 Claims, 6 Drawing Figures
U.S. Patent Nov. 30, 1982 4,361,843
 1
4,361,843
2
INKJET COMPOSITIONS AND METHOD DISCUSSION OF THE RELATED ART
It has been suggested that oleic acid may be used in
FIELD OF THE INVENTION inks for ink injection apparatuses, as shown ip a Japa
This invention relates to inks and an inkjet method nese Patent application to General Corp., U.S. Pat. No.
for use in inkjet systems, and more particularly, to ink 132,548, filed 11-28-73, entitled: Ink Compositions for
jet inks which will provide superior printing qualities Ink Injection Type Recording Apparatus.
upon a wide variety of printing paper surfaces. This application which was published in 1975, also
BACKGROUND OF THE INVENTION 10
teaches formulating oleic acid with a DOSB nonionic
surfactant, probably as a means to improve the print
Inks for inkjet systems have been traditionally water quality or jetability of the fluid. Also this application
based compositions. There have been many problems suggests the use of an aromatic hydrocarbon solvent of
associated with water-based inks. These problems in high boiling point to dissolve the dye in the oil base.
clude nozzle clogging, nozzle crusting, alterations in 15
Aromatic hydrocarbons, however, are not generally
surface tension due to repeated exposure to the atmo preferred for use in inkjet inks because of their toxic,
sphere during the jetting and recirculation of the ink evaporative and carcinogenic properties.
fluid, print quality (including optical density and dot The present inventive composition does not use aro
characteristics), and lack of adhesion of ink to the sub matic hydrocarbons perse, nor does the use of surfac
strate. Many of these problems may be inter-related, tants appear to be necessary or desirable. The aforemen
e.g., alterations in surface properties of an ink caused by 20 tioned ink is not used (jetted) at elevated temperatures
repeated exposure to the atmosphere during jetting and as is the inventive inkjet ink, and it is not demonstrated
recirculation may cause nozzle clogging. Evaporation that its composition provides superior print quality as
of a portion of the base liquid or absorbance of atmo does the invention.
spheric moisture by the ink fluid may, for example, Another inkjet ink which comprises oleic acid is
change the solubility of a particular dye in the ink fluid. 25 shown in the Japanese Patent application number
U.S. Pat. No. 3,994,736, discloses the use of polyhyd 017,758; filed: Feb. 22, 1977 to Toyo Ink Mfg. This ink
ric alcohols such as propylene glycol and ethylene gly formulation comprises as one ingredient thereof: 6
col in the base liquid because of their ability to prevent acetoxy-2,4-dimethyl-m-dioxin, which is a toxic sub
the drying of the ink in the nozzle with subsequent 30 stance. Glycerin and triethylene glycol are used as sol
clogging of the nozzle orifice. The polyhydric alcohols vents for colloidal magnetite (magnetic iron particles of
may be mixed with a lower monohydric alcohol to 100A).
ensure rapid drying of the ink after deposition on the There is no teaching in this application that this com
substrate to be printed. position provides improved print quality of the magni
Even with the addition of humectants to solve the 35 tude claimed for the present invention. In addition,
drying problems, water-based inks are still troublesome there is no teaching that this composition is jetted at
because of the hydrophobic nature of most printing elevated temperatures.
papers. The addition of surfactants to these inks, while BRIEF SUMMARY OF THE INVENTION
improving the absorption of the inks into the paper,
often severely affect the surface tension and the jetabil 40 The invention pertains to fluid compositions and a
ity of the ink fluid. Therefore, the printing quality of method for an inkjet system. The fluid compositions
these inks is never any bettter than marginal as com have a surface tension approximately greater than 35
pared with impact printing quality. dynes/cm. The fluid compositions provide good print
Therefore, attention was directed towards the use of quality on a wide range of printing papers such as sulfite
dye materials which are physically more compatible 45 paper, coated and uncoated paper, erasble bond, and
with printing paper. paper containing 25, 50, 75 and 100% rag.
A fluid medium was selected from the typewriter art, Print quality is defined by an average dot circularity.
e.g. oleic acid. Oleic acid is known to provide good For the inventive composition the average dot circular
print quality, because it is easily absorbed into most ity is 0.7 or better.
printing papers. There are problems with the use of 50 The circularity of a dot "T" is 1.0 for a perfectly
oleic acid as an inkjet substance, however. The oleic circular dot.
acid has too high a viscosity for good jetability. While The fluid compositions comprise a substantially non
additives can be used to improve the viscosity, the nec aqueous printing medium including a mixture oleic acid
essary surface tension of the ink fluid will usually fall in an approximate weight of from 20 to 80 percent of the
below acceptable levels. 55 total mixture composition. The mixture also includes a
The present invention teaches how to properly for dye or a dye in a dye solvent. The solvent of the me
mulate and use oleic acid as a fluid medium for inkjet dium has a multiple function: (a) to cut the viscosity of
printing. Part of the solution to the problem of jetability the medium; (b) to dissolve the dye in the oleic acid; and
is to utilize the oleic acid compositions at elevated tem (c) to maintain or increase the surface tension. The
peratures, generally in a range from 125 F. to 145 F. 60 solvent is generally selected e.g. from a group consist
While it may have been suggested to use water-based ing of at least one of the following: an aromatic alcohol,
inkjet inks at elevated printing temperatures, the use of an aromatic ether, dimethyl sulfoxide, an alkyl pyrrol
oil based inks, and particularly, the use of oleic acid idone, methoxy- and ethoxytriglycol. More particu
based inkjet inks at elevated temperatures has never larly, the solvent can be: n-methyl pyrrolidone, benzyl
been described or suggested in the art. Neither has it alcohol, and benzyl ether.
been taught that ink jet ink formulations containing The dye can be selected from a group consisting of:
oleic acid can provide superior print quality as de typophor black, calco chinoline yellow, and calco oil
scribed herein. yellow.
 4,361,843
3 4.
The mixture will generally have a viscosity of from 5 Circularity is determined by first examining the ink
to 20 centipoises at a temperature of 135 F. dot under a microscope. FIG. 4 shows an enlarged
A preferred composition for the inkjet medium is photograph of a dot 10 as seen through the microscope,
approximately given as: oleic acid 34%; m-pyrol 60%; which has previously been jetted upon a printing paper.
and Typophor Black 6% (by weight). An overlay is placed over the dot 10. This overlay
The method by which the above inkjet ink can be comprises a number of concentric circles (not shown) of
used for fluid printing is comprised of the following varying size. Two of these circles 11 and 12, respec
steps: tively, are chosen. Circle 11 is a circle which will com
(a) formulating an inkjet medium having an approxi pletely encircle dot 10. The diameter "D1' of circle 11
mate surface tension greater than 35 dynes/cm., com 10 is determined.
prising a substantially non-aqueous fluid mixture of a Circle 12 is the largest circle which encloses the area
dye and approximately 20 to 80 weight percent of oleic of highest optical density inside the circumference of
acid in the total mixture; the dot 10. The diameter 'D' is determined for circle
(b) jetting said inkjet medium at a temperature in an 12.
approximate range of from 125 F. to 145 F. towards a 15 The sharpness or circularity "T" of the dot 10 is
printing paper medium; and defined as the ratio of the diameters: Do/D1.
(c) forming a plurality of dots upon said printing The above procedure is repeated for several dots and
paper medium having an average circulatity of better an average dot circularity is determined. This average
than 0.7. dot circularity is a good indication of the edge definition
The preferred jetting temperature is 135 F. 20 or print quality of an inkjet character or letter.
It is an object of this invention to provide an im Diameters of the overlaying circles from 5 to 2.5
proved inkjet composition and method. inches are used with dot diameters of 0.01 inches when
It is another object of the invention to provide non a magnification of 100X is used. Experience has shown
aqueous inkjet formulations and a method which will that segregated dots are more easily found along
produce good print quality as defined by an average dot 25 straight lines or in lighter areas of a caricature for pur
circularity of approximately 0.7 or better. poses of making the aforementioned test.
It is still another object of this invention to provide a Using the above definition, we can determine in a
superior inkjet ink composition of good print quality factual way the print quality of an ink composition.
without impairing its ability to jet properly, and without FIGS. 5 and 6, respectively, illustrate typical aqueous
resort to toxic or carcinogenic ingredients. 30 and non-aqueous ink dots. The dot shown in FIG. 6 is
These and other objects of the invention will be bet an ink dot comprised of the ink composition of this
ter understood and will become more apparent with invention, and delivered by the method of this inven
reference to the following detailed description of the tion. Each respective dot was delivered on a similar
invention taken in conjunction with the accompanying kind of printing paper.
drawings. 35 It is easily observable without any calculation that the
BRIEF DESCRIPTION OF THE DRAWINGS inventive oleic acid-based ink dot of FIG. 6 has pro
duced a superior dot when compared to the aqueous
FIG. 1 is an enlarged plan view of a Letter "M' based dot of FIG. 5.
formed by a typewriter font which has impacted upon a On the average, water-based inks will produce dots
typical printing paper; ; 40 with an average circularity of approximately 0.4 to 0.5.
FIG. 2 is an enlarged plan view of a letter “M” By comparison, the average circularity of the dots
formed by an inkjet system using an aqueous ink; products by the invention is in a range from approxi
FIG. 3 is an enlarged plan view of a letter “M” mately 0.7 to 0.8.
formed by an inkjet system using the ink composition The fluid compositions of this invention have a sur
and method of this invention; 45 face tension of approximately greater than 35 dy
FIG. 4 is an enlarged schematic view illustrating a nes/cm. The fluid compositions provide good print
method of determining dot circularity; quality on a wide range of printing papers such as sulfite
FIG. 5 is an enlarged plan view of a typical aqueous paper, coated and uncoated paper, erasable bond, and
ink dot; paper containing 25, 50, 75 and 100% rag.
FIG. 6 is an enlarged plan view of a typical ink dot 50 The fluid compositions comprise a substantially non
comprised of the ink composition of this invention, and aqueous printing medium including a mixture of oleic
delivered by the method of this invention. acid in an approximate weight of from 20 to 80 percent
of the total mixture composition. The mixture also in
DETAILED INVENTION
DESCRIPTION OF THE cludes a dye or a dye in a dye solvent. The solvent of
55 the medium has a multiple function: (a) to cut the vis
Generally speaking, the invention features an inkjet cosity of the medium; (b) to dissolve the dye in the oleic
ink composition and method for providing good print acid; and (c) maintain or increase surface tension. The
quality approaching that provided by typewriters and solvent is generally selected from a group consisting of
impact printers. The edge definition of a letter or char at least one of the following: an aromatic alcohol, an
acter produced by an inkjet mechanism can be ascribed 60 aromatic ether, dimethyl sulfoxide, an alkyl pyrrol
to the ability to form circular dots of perfect or near idone, methoxy- and ethoxy- triglycol. More particu
perfect circularity. larly, the solvent can be: n-methyl pyrrolidone, benzyl
With the use of aqueous-based inks, this circularity is alcohol, and benzyl ether.
never any better than marginal and is due in part to the The dye can be selected from a group consisting of:
inability of the ink to penetrate and be absorbed by the 65 typophor black, calco chinoline yellow, and calco oil
hydrophobic papercoating. yellow.
With the use of the non-aqueous ink and method of The mixture will generally have a viscosity of from 5
this invention, this circularity is dramatically improved. to 20 centipoises at a temperature of 135 F.
 5
is 4,361,843
6
A preferred composition for the inkjet medium is drying, non-hygroscopic uniform drop which prints on
approximately given as: oleic acid 34%; m-pyrol 60%; a broad range of papers.
and Typophor Black 6% (by weight). Referring to FIGS. 1 through 3, enlarged plan views
The method by which the above inkjet ink can be of a letter 'M' are illustrated for various printing tech
used for fluid printing is comprised of the following niques on similar printing paper. FIG. 1 depicts an ideal
steps: . 3 character formed by impact via a typewriter font. It can
(a) formulating an inkjet medium having an approxi be observed that the edge definition is very good.
mate surface tension greater than 35 dynes/cm, com FIGS. 2 and 3 depict a letter “M” respectively
prising a substantially non-aqueous fluid mixture of a formed by an impulse inkjet system having an orifice of
dye and approximately 20 to 80 weight percent of oleic 10 from approximately 1.9 to 3.2 thousandths of an inch
acid in the total mixture; and delivering approximately 1500 dots/sec.
(b) jetting said inkjet medium at a temperature in an FIG. 3 illustrates, the "M" formed by the inventive
approximate range of from 125 F. to 145 F. towards a composition of oleic acid 19.2%; m-pyrol 60.0%;
printing paper medium; and Typophor Black 20%; and calco chinoline yellow 0.8%
(c) forming a plurality of dots upon said printing 15 (by weight), which was jetted at 135 F. Note that the
paper medium having an average circularity of better edge definition approached that of the ideal typewriter
than 0.7. . . . character of FIG. 1.
The preferred jetting temperature is 135 F. By contrast in an opposite sense, the same letter "M'
Specific compositions for the inkjet fluid of this in is shown in FIG. 2 using an aqueous ink composition of:
vention are tabulated in weight percentages in Table I 20 15% ethylene glycol; 54% water; 2% diethylene glycol;
below: 1% glycerol; 8% m-pyrol; and 20% pontamine Black
TABLE I SP (by weight). It is observed that the aqueous ink fluid
Formula: 2 3 4. 5 did not provide a good quality print.
Oleic Acid m 9.2 9.2 -- 0.2
It is obvious from the above comparisons that the
MeOTG 75 --- -- -
25 non-aqueous ink of this invention has produced a supe
Typophor Black 25 20 20 20 24 rior print quality of exceptionally good edge definition.
DMSO --- - - Having met the objectives set forth earlier in this
M-Pyrol
Calco Chinoline
m
m
60
0.8
70
0.8
79.2
0.8
65
0.8
specification, what is desired to be protected by Letters
Yellow Patent is presented in the following appended claims.
Calco Oil --- ma- - - -
30 What is claimed is:
Yellow 1. A fluid composition which has a surface tension
Benzyl Ether m - - -
greater than approximately 35 dynes/cm. and which
---

Formula: 6 7 8 9 10 can provide good print quality defined by an average

Oleic Acid 6.2 1.2 0.8 30 9.2 dot circularity of approximately better than 0.7 for a
MeOTG ------ --- - - 35 wide range of printing papers such that it is suitable for
-

"Typophor Black 26 28 24 20 20 use as an ink in inkjet systems, comprising a substan

DMSO

M-Pyrol
-

67 70 65
-

-
-

-
- 60
tially non-aqueous printing medium including a mixture
Calco Chinoline 0.8 0.8 0.2 ----- - of oleic acid in an approximate weight of from 20 to 80
Yellow percent of the total mixture composition and a dye in a
Caico Oil
Yellow
-- -- - -
dye solvent, said solvent selected from a group consist
0.8

Benzyl Ether - - - SO ing of at least one of an aromatic alcohol, an aromatic

---

Formula: 2 13 14 15
ether, dimethyl sulfoxide, an alkyl pyrrolidone, me
thoxy- and ethoxy-triglycol.
Oleic Acid 9.2 29.2 4.2 20 - 2. The fluid composition of claim 1, wherein said
MeOTG -- --- ---
45 solvent comprises n -methyl pyrrollidone.
-

"Typophor Black 20 20 20 24 26
DMSO --- --- - 60 3. The fluid composition of claim 1, wherein said
M-Pyrol 70 50 75 73.2 73.2 solvent comprises benzyl alcohol.
Caico Chinoline
Yellow
- - 0.8 0.8 0.8 4. The fluid composition of claim 1, wherein said
solvent comprises benzyl ether.
Calco Oil
Yellow
0.8 0.8 - - --
50 5. The fluid composition of claim 1, wherein said dye
Benzyl Ether - - - - -is selected from a group of at least one of typophor
black, calco chinoline yellow, and calco oil yellow.
The following table (Table II) gives typical viscosi mixture 6. The fluid composition of claim 1, wherein said
ties for various formulations of oleic acid, n-methyl 55 centipoises has a viscosity in the range of from 5 to 20
pyrrolidone (m-pyrol) and typophor black at approxi at a temperature of 135 F.
mately 70 F. and 135 F. 7. The fluid composition of claim 1, wherein said
mixture has a viscosity in the range of from 10 to 40
TABLE II centipoises at a temperature of 76 F.
Formula: l 2 3 4. 5 6 8. The composition of claim 1, comprising: oleic acid
Oleic acid 80 60 40 65.0 500 300 34%; m-pyrrolidone 60%; and Nigrosine Black 6% by
M-Pyrol 0 20 40 15.0 300 50.0 weight. V
"Typophor black 20 20 20 20 20 20 9. A fluid composition which has a surface tension
Viscosity G76 F. 48.5 3.6 17.8 43.41 27,21 11.6 greater than approximately 35 dynes/cm. and which
(centipoises) G135 F. 19.5 2.0 9.01 S.S. 12 7.0
can provide good print quality defined by an averge dot
65. circularity of approximately better than 0.7 for a wide
Even though the ink fluid formulations above give range of printing papers such that it is suitable for use as
typical high viscosities of 10 to 20 cps and typically low an ink in inkjet systems, comprising a substantially
surface tension of 35 dynes/cm., they provide a non non-aqueous printing medium including a mixture of
 7 4,361,843 8
oleic acid in an approximate weight of from 20 to 80 12. The method of claim 11, wherein the temperature
percent of the total mixture composition and a dye. of said medium in said jetting step (b) is approximately
10. The fluid composition of claim 9, wherein said 135 F.
dye is selected from a group of at least one of: typophor 13. The method of claim 11, wherein said fluid mix
black, calco chinoline yellow, and calco oil yellow. 5 ture is formulated according to step (a) with the follow
11. A method of fluid printing, comprising the steps ing composition: oleic acid 34%; m-pyrrolidone 60%;
of: and Nigrosine Black 6% by weight.
(a) formulating an inkjet medium having an approxi 14. The method of claim 11, wherein said medium is
mate surface tension greater than 35 dynes/cm jetted onto a sulfite paper. -
comprising a substantially non-aqueous fluid mix O 15. The method of claim 11, wherein said medium is
ture of: a dye and approximately 20 to 80 weight jetted onto a coated paper.
percent of oleic acid in the total mixture; 16. The method of claim 11, wherein said medium is
(b) jetting said inkjet medium at a temperature in an jetted onto an uncoated paper.
approximate range of from 125 F. to 145 F. 17. The method of claim 11, wherein said medium is
towards a printing paper medium; and 15 jetted onto a paper containing at least 25% rag.
(c) forming a plurality of dots upon said printing 18. The method of claim 11, wherein said medium is
paper medium having an average circularity of jetted onto an erasable bond paper..
better than 0.7. is . . . .

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