U.S. patent application number 17/416412 was filed with the patent office on 2022-03-10 for textile printing.
This patent application is currently assigned to Hewlett-Packard Development Company, L.P.. The applicant listed for this patent is Hewlett-Packard Development Company, L.P.. Invention is credited to Jeffrey Matthew Stubbs, Qianhan Yang, Zhang-Lin Zhou.
Application Number | 20220074134 17/416412 |
Document ID | / |
Family ID | |
Filed Date | 2022-03-10 |
United States Patent
Application |
20220074134 |
Kind Code |
A1 |
Zhou; Zhang-Lin ; et
al. |
March 10, 2022 |
TEXTILE PRINTING
Abstract
A textile printing material set includes a fabric substrate and
an aqueous ink composition. The aqueous ink composition includes an
aqueous ink vehicle, pigment, and from 2 wt % to 15 wt % of acrylic
core-shell latex particles having an acrylic core copolymer with a
glass transition temperature from -50.degree. C. to 30.degree. C.
and an acrylic shell copolymer having a glass transition
temperature from 50.degree. C. to 130.degree. C. The acrylic core
copolymer and the acrylic shell copolymer of the acrylic core-shell
latex particles in this example are present at an average weight
ratio from 1:1 to 9:1.
Inventors: |
Zhou; Zhang-Lin; (San Diego,
CA) ; Stubbs; Jeffrey Matthew; (San Diego, CA)
; Yang; Qianhan; (San Diego, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hewlett-Packard Development Company, L.P. |
Spring |
TX |
US |
|
|
Assignee: |
Hewlett-Packard Development
Company, L.P.
Spring
TX
|
Appl. No.: |
17/416412 |
Filed: |
February 4, 2019 |
PCT Filed: |
February 4, 2019 |
PCT NO: |
PCT/US2019/016487 |
371 Date: |
June 18, 2021 |
International
Class: |
D06P 5/30 20060101
D06P005/30; D06P 1/52 20060101 D06P001/52 |
Claims
1. A textile printing material set, comprising: a fabric substrate;
and an aqueous ink composition including: an aqueous ink vehicle,
pigment, and from 2 wt % to 15 wt % of acrylic core-shell latex
particles having an acrylic core copolymer with a glass transition
temperature from -50.degree. C. to 30.degree. C. and an acrylic
shell copolymer having a glass transition temperature from
50.degree. C. to 130.degree. C., wherein the acrylic core copolymer
and the acrylic shell copolymer of the acrylic core-shell latex
particles have an average weight ratio from 1:1 to 9:1.
2. The textile printing material set of claim 1, wherein the glass
transition temperature of the acrylic core copolymer is from
-25.degree. C. to 15.degree. C. and the glass transition
temperature of the acrylic shell copolymer is from 75.degree. C. to
105.degree. C.
3. The textile printing material set of claim 1, wherein the
acrylic shell copolymer includes from 30 wt % to 80 wt %
copolymerized methyl methacrylate, ethyl methacrylate, or a
combination thereof.
4. The textile printing material set of claim 1, wherein the
acrylic shell copolymer includes from 1 wt % to 14 wt %
copolymerized acrylic acid, methacrylic acid, or a combination
thereof.
5. The textile printing material set of claim 1, wherein the
acrylic core copolymer and the acrylic shell copolymer
independently both include copolymerized propyl acrylate, butyl
acrylate, or a combination thereof.
6. The textile printing material set of claim 5, wherein the
acrylic core copolymer and the acrylic shell copolymer both include
copolymerized n-butyl acrylate.
7. The textile printing material set of claim 1, wherein the fabric
substrate is selected from cotton, polyester, nylon, silk, or a
blend thereof.
8. A textile printing system, comprising: a fabric substrate; an
inkjet printhead in fluid communication with a reservoir containing
an aqueous ink composition, comprising: an aqueous ink vehicle,
pigment, and from 2 wt % to 15 wt % of acrylic core-shell latex
particles having an acrylic core copolymer with a glass transition
temperature from -50.degree. C. to 30.degree. C. and an acrylic
shell copolymer having a glass transition temperature from
50.degree. C. to 130.degree. C., wherein the acrylic core copolymer
and the acrylic shell copolymer of the acrylic core-shell latex
particles have an average weight ratio from 1:1 to 9:1; and a
heating source positioned to heat the aqueous ink composition after
application onto the fabric substrate.
9. The textile printing system of claim 8, wherein the acrylic
shell copolymer includes from 30 wt % to 80 wt % copolymerized
methyl methacrylate, ethyl methacrylate, or a combination thereof,
and wherein the acrylic shell copolymer also includes from 1 wt %
to 14 wt % copolymerized acrylic acid, methacrylic acid, or a
combination thereof.
10. The textile printing system of claim 8, wherein the acrylic
core copolymer and the acrylic shell copolymer both include
copolymerized n-butyl acrylate.
11. The textile printing system of claim 8, wherein the heating
source is positioned and powerable to generate heat at the fabric
substrate at a temperature ranging from above the glass transition
temperature of the acrylic shell copolymer to 200.degree. C.
12. The textile printing system of claim 8, wherein the fabric
substrate is selected from cotton, polyester, nylon, silk, or a
blend thereof.
13. A method of textile printing, comprising: jetting an aqueous
ink composition onto fabric substrate, wherein the aqueous ink
composition comprises: an aqueous ink vehicle, pigment, and from 2
wt % to 15 wt % of acrylic core-shell latex particles having an
acrylic core copolymer with a glass transition temperature from
-50.degree. C. to 30.degree. C. and an acrylic shell copolymer
having a glass transition temperature from 50.degree. C. to
130.degree. C., wherein the acrylic core copolymer and the acrylic
shell copolymer of the acrylic core-shell latex particles have an
average weight ratio from 1:1 to 9:1.
14. The method of textile printing of claim 13, further comprising
heating the fabric substrate with the aqueous ink composition
thereon to a temperature a temperature ranging from above the glass
transition temperature of the acrylic shell copolymer to
200.degree. C.
15. The method of textile printing of claim 13, wherein the fabric
substrate is selected from cotton, polyester, nylon, silk, or a
blend thereof.
Description
BACKGROUND
[0001] Inkjet printing has become a popular way of recording images
on various media. Some of the reasons include low printer noise,
variable content recording, capability of high speed recording, and
multi-color recording. These advantages can be obtained at a
relatively low price to consumers. As the popularity of inkjet
printing increases, the types of use also increase providing demand
for new ink compositions. In one example, textile printing can have
various applications including the creation of signs, banners,
artwork, apparel, wall coverings, window coverings, upholstery,
pillows, blankets, flags, tote bags, clothing, etc. However, the
permanence of printed ink on textiles can be an issue.
BRIEF DESCRIPTION OF DRAWINGS
[0002] FIG. 1A schematically depicts an example textile printing
system including an ink composition and a fabric substrate in
accordance with the present disclosure;
[0003] FIG. 1B schematically depicts an example textile printing
system including an ink composition, a fabric substrate, an inkjet
printhead, and a heat curing device in accordance with the present
disclosure;
[0004] FIG. 2 provides a flow diagram for an example method of
textile printing in accordance with the present disclosure; and
[0005] FIG. 3 is a TOE curve graph showing Turn On Energy
comparisons of six (6) different example ink compositions with 6
different example acrylic latex particles in accordance with the
present disclosure.
DETAILED DESCRIPTION
[0006] The present disclosure is drawn to textile printing material
sets, textile printing systems, and textile printing methods. In
one example, a textile printing material set includes a fabric
substrate, and an aqueous ink composition. The aqueous ink
composition includes an aqueous ink vehicle, pigment, and from 2 wt
% to 15 wt % of acrylic core-shell latex particles having an
acrylic core copolymer with a glass transition temperature from
-50.degree. C. to 30.degree. C. and an acrylic shell copolymer
having a glass transition temperature from 50.degree. C. to
130.degree. C., wherein the acrylic core copolymer and the acrylic
shell copolymer of the acrylic core-shell latex particles have an
average weight ratio from 1:1 to 9:1. In one example, the glass
transition temperature of the acrylic core copolymer can be from
-25.degree. C. to 15.degree. C. and the glass transition
temperature of the acrylic shell copolymer can be from 75.degree.
C. to 105.degree. C. In another example, the acrylic shell
copolymer can include from 30 wt % to 80 wt % copolymerized methyl
methacrylate, ethyl methacrylate, or a combination thereof. The
acrylic shell copolymer can include from 1 wt % to 14 wt %
copolymerized acrylic acid, methacrylic acid, or a combination
thereof. The acrylic core copolymer and the acrylic shell copolymer
can independently both include copolymerized a propyl acrylate, a
butyl acrylate, or a combination thereof. In a more specific
example, the acrylic core copolymer and the acrylic shell copolymer
can both include copolymerized n-butyl acrylate. The fabric
substrate can be selected from cotton, polyester, nylon, silk, or a
blend thereof, for example.
[0007] In another example, a textile printing system includes a
fabric substrate, an inkjet printhead in fluid communication with a
reservoir containing an aqueous ink composition, and a heating
source positioned to heat the aqueous ink composition after
application onto the fabric substrate. The aqueous ink composition
includes an aqueous ink vehicle, pigment, and from 2 wt % to 15 wt
% of acrylic core-shell latex particles having an acrylic core
copolymer with a glass transition temperature from -50.degree. C.
to 30.degree. C. and an acrylic shell copolymer having a glass
transition temperature from 50.degree. C. to 130.degree. C. The
acrylic core copolymer and the acrylic shell copolymer of the
acrylic core-shell latex particles in this example have an average
weight ratio from 1:1 to 9:1. In one example, the acrylic shell
copolymer includes from 30 wt % to 80 wt % copolymerized methyl
methacrylate, ethyl methacrylate, or a combination thereof, and/or
the acrylic shell copolymer also includes from 1 wt % to 14 wt %
copolymerized acrylic acid, methacrylic acid, or a combination
thereof. In another example, the acrylic core copolymer and the
acrylic shell copolymer both include copolymerized n-butyl
acrylate. The heating source can be positioned and powerable to
generate heat at the fabric substrate at a temperature ranging from
above the glass transition temperature of the acrylic shell
copolymer to 200.degree. C. Furthermore, the fabric substrate can
be selected from cotton, polyester, nylon, silk, or a blend
thereof.
[0008] In another example, a method of textile printing includes
jetting an aqueous ink composition onto a fabric substrate. The
aqueous ink composition includes an aqueous ink vehicle, pigment,
and from 2 wt % to 15 wt % of acrylic core-shell latex particles
having an acrylic core copolymer with a glass transition
temperature from -50.degree. C. to 30.degree. C. and an acrylic
shell copolymer having a glass transition temperature from
50.degree. C. to 130.degree. C. The acrylic core copolymer and the
acrylic shell copolymer of the acrylic core-shell latex particles
in this example have an average weight ratio from 1:1 to 9:1. The
method can further include heating the fabric substrate with the
aqueous ink composition thereon to a temperature ranging from above
the glass transition temperature of the acrylic shell copolymer to
200.degree. C. The fabric substrate can be selected from cotton,
polyester, nylon, silk, or a blend thereof.
[0009] It is noted that when discussing the textile printing
material sets, textile printing systems, and/or the methods of
textile printing herein, these discussions can be considered
applicable to one another whether or not they are explicitly
discussed in the context of that example. Thus, for example, when
discussing an organic co-solvent related to the textile printing
systems, such disclosure is also relevant to and directly supported
in the context of the textile printing material sets and/or methods
of textile printing, and vice versa. It is also understood that
terms used herein will take on their ordinary meaning in the
relevant technical field unless specified otherwise. In some
instances, there are terms defined more specifically throughout the
specification or included at the end of the present specification,
and thus, these terms have a meaning as described herein.
[0010] Turning now to more specific detail regarding the textile
printing systems, in FIG. 1A, an example textile printing system
100 is shown which includes a fabric substrate 110 and an ink
composition 130. The ink composition can be printed from an inkjet
pen 120 which includes an ejector 122 or printhead, such as a
thermal inkjet ejector, for example. The ink composition includes
water and organic co-solvent (sometimes referred to collectively as
an ink vehicle), and a pigment (dispersed with a dispersant
associated with a surface of the pigment). The ink composition also
includes acrylic core-shell latex particles. The dispersant can be
associated with the pigment by adsorption, ionic attraction, or by
covalent attachment thereto. The acrylic core-shell latex particles
can have an acrylic core copolymer with a glass transition
temperature from -50.degree. C. to 30.degree. C. and an acrylic
shell copolymer having a glass transition temperature from
50.degree. C. to 130.degree. C. The acrylic core copolymer and the
acrylic shell copolymer of the acrylic core-shell latex particles
have an average weight ratio from 1:1 to 9:1.
[0011] In another example, as shown in FIG. 1B, an example textile
printing system 105 is shown that includes a fabric substrate 110,
an ink composition 130, an inkjet pen 120 which includes an ejector
122, e.g., inkjet printhead, and a heat curing device 140 which
emits heat 150 therefrom. The ink composition includes the acrylic
core-shell latex particles described herein. Thus, upon printing
the ink composition onto the fabric substrate, the ink composition
can be heated to heat cure the ink composition on the fabric
substrate, thus providing enhanced image durability on the fabric
substrate.
[0012] The acrylic core-shell latex particles can be formed by
emulsion polymerization of selected components. The emulsion
polymerization can thus be conducted in accordance with
conventional polymerization techniques, for example in a batch,
feed, or semi-batch process. Particularly, a combination of first
phase of monomers and second phase of monomers can be employed in
combination with a charge stabilizing agent, an emulsifier, and/or
an initiator, for example. The first phase of monomers can be a
batch or feed of softer monomers, e.g., monomers having a lower
glass transition temperature (Tg), though higher Tg monomers can be
used in smaller amounts, provided the resultant core copolymer
results in a core latex polymer that has a Tg from -50.degree. C.
to 30.degree. C. In one example, the acrylic core copolymer can
have a Tg from -25.degree. C. to 15.degree. C.
[0013] The second phase of monomers can be selected from harder
monomers, e.g., monomers having a relatively higher glass
transition temperature (Tg), though lower Tg monomers can likewise
be used in smaller amounts, provided the resultant shell copolymer
results in a shell latex polymer that has a Tg from 50.degree. C.
to 130.degree. C. In another example, the glass transition
temperature of the acrylic shell copolymer is from 75.degree. C. to
105.degree. C.
[0014] Reference within the present disclosure to the glass
transition temperature (Tg) of an acrylic polymer can refer to the
calculated glass transition temperature based on known Tg values
for homopolymers prepared from the monomers used to form the
copolymer core or the copolymer shell. Thus, "glass transition
temperature" or "Tg," can be calculated by the Fox equation:
copolymer Tg=1/(Wa/(Tg A)+Wb(Tg B)+ . . . ) where Wa=weight
fraction of monomer A in the copolymer and TgA is the homopolymer
Tg value of monomer A, Wb=weight fraction of monomer B and TgB is
the homopolymer Tg value of monomer B, etc. Example homopolymer Tg
values can be found in Table 2 in Example 1 hereinafter.
[0015] Monomers used to prepare the acrylic core/shell latex
particles can include, for either the core or the shell (at
appropriate concentrations to arrive at the glass transition
temperatures described herein), various monomers, but both the core
and the shell include a polymerized (meth)acrylic monomer. Thus the
term "acrylic core-shell latex" refers to latexes where both the
core and the shell include a polymerized (meth)acrylic monomer,
which is typically a copolymerized core and a copolymerized shell.
The term "(meth)acrylic" refers to monomers, copolymerized
monomers, etc., that can either be acrylate or methacrylate (or a
combination of both), or acrylic acid or methacrylic acid (or a
combination of both), as the acid or salt/ester form can be a
function of pH. Furthermore, even if the monomer used to form the
polymer was in the form of a (meth)acrylic acid during preparation,
pH modifications during preparation or subsequently when added to
an ink composition can impact the nature of the moiety as well
(acid form vs. salt or ester form). Thus, a monomer or a moiety of
a polymer described as (meth)acrylic should not be read so rigidly
as to not consider relative pH levels, ester chemistry, and other
general organic chemistry concepts.
[0016] Examples of monomers that can be used include monoacrylates,
diacrylates, or polyfunctional alkoxylated or polyalkoxylated
acrylic monomers comprising one or more di- or tri-acrylates.
Suitable monoacrylates include, for example, methyl acrylate,
methyl methacrylate, solketal acrylate, methacrylic acid, acrylic
acid, 6-(acrylamido)hexanoic acid, acrylamide, N-isopropyl
acrylamide, dimethyl acrylamide, methacrylamide, styrene, 4-vinyl
pyridine, 4-vinyl benzylchloride, N-acrylomorpholine, tert-butyl
methacrylate, 6-azidohexyl methacrylate, cyclohexyl acrylate,
2-ethoxy ethyl acrylate, 2-methoxy ethyl acrylate,
2(2-ethoxyethoxy)ethyl acrylate, stearyl acrylate,
tetrahydrofurfuryl acrylate, octyl acrylate, lauryl acrylate,
behenyl acrylate, 2-phenoxy ethyl acrylate, butyl acrylate (n-butyl
acrylate), tertiary butyl acrylate, propyl acrylate, glycidyl
acrylate, isodecyl acrylate, benzyl acrylate, hexyl acrylate,
isooctyl acrylate, isobornyl acrylate, butanediol monoacrylate,
ethoxylated phenol monoacrylate, oxyethylated phenol acrylate,
monomethoxy hexanediol acrylate, beta-carboxy ethyl acrylate,
dicyclopentyl acrylate, carbonyl acrylate, octyl decyl acrylate,
ethoxylated nonylphenol acrylate, hydroxyethyl acrylate,
hydroxyethyl methacrylate, and the like. Suitable polyfunctional
alkoxylated or polyalkoxylated acrylates are, for example,
alkoxylated, ethoxylated, or propoxylated, variants of the
following: neopentyl glycol diacrylates, butanediol diacrylates,
butanediol dimethacrylates, e.g., 1,3-butanediol dimethacrylate
(BDDMA), trimethylolpropane triacrylates, glyceryl triacrylates,
1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate,
diethylene glycol diacrylate, 1,6-hexanediol diacrylate,
tetraethylene glycol diacrylate, triethylene glycol diacrylate,
tripropylene glycol diacrylate, polybutanediol diacrylate,
polyethylene glycol diacrylate, propoxylated neopentyl glycol
diacrylate, ethoxylated neopentyl glycol diacrylate, polybutadiene
diacrylate, and the like. The monomer can be, for example,
propoxylated neopentyl glycol diacrylate, such as, for example,
SR-9003 (Sartomer Co., Inc., Exton, Pa.). Suitable reactive
monomers are likewise commercially available from, for example,
Sartomer Co., Inc., Henkel Corp., Radcure Specialties, and the
like.
[0017] The chemical structure and common abbreviations for a few
monomers listed above that can be used are shown as follows:
##STR00001##
[0018] The reaction medium used for preparing the acrylic
core-shell latex particles can use both a charge stabilizing agent
and an emulsifier in order to obtain a target particle size.
Particularly, the acrylic core-shell latex particles can have a D50
particle size from about 100 nm to about 350 nm, from about 150 nm
to about 350 nm, from about 200 nm to about 300 nm, or from about
240 nm to about 280 nm, for example. "D50" particle size is defined
here as the particle size at which about half of the particles are
larger than the D50 particle size and about half of the other
particles are smaller than the D50 particle size (by weight based
on the metal particle content of the particulate build material).
As used herein, particle size with respect to the acrylic
core-shell latex particles can be based on volume of the particle
size normalized to a spherical shape for a theoretical diameter
measurement, for example. Particle size can be collected using a
Malvern Zetasizer, for example. Likewise, the "D95" is defined as
the particle size at which about 5 wt % of the particles are larger
than the D95 particle size and about 95 wt % of the remaining
particles are smaller than the D95 particle size. Particle size
information can also be determined and/or verified using a scanning
electron microscope (SEM).
[0019] The charge stabilizing agent can be a monomer that includes
acid groups suitable for stabilizing the particles in the liquid
medium of the ink compositions. Various charge stabilizing agents
that can be used include methacrylic acid, acrylic acid, and/or a
salt thereof. Thus, methacrylic acid and acrylic acid are both also
listed as monomers herein, but can have the dual function of
copolymerization and charge stabilization. Sodium salts of
methacrylic acid and/or acrylic acid can be used in some specific
examples. The charge stabilizing agent may be employed in
relatively small concentrations, e.g., about 0.1 wt % to about 5 wt
% (based on the weight of the emulsion polymerization
components).
[0020] The emulsifier, as mentioned, can contribute to achieving a
target particle size, but can also contribute to a desired surface
tension of the acrylic core-shell latex particles, e.g., from about
35 dynes/cm to about 65 dynes/cm, from about 40 dynes/cm to about
60 dynes/cm, or about 45 dynes/cm to about 55 dynes/cm. The
emulsifier can include a fatty acid ether sulfate, such as lauryl
ether sulfate. Suitably, the emulsifier may be included at
relatively small concentrations, e.g., about 0.1 wt % to about 5 wt
% (based on the weight of the emulsion polymerization components).
The emulsion polymerization is conducted in accordance with
polymerization processes, such as, for example, a semi-batch
process.
[0021] The acrylic core-shell latex particles can be synthesized by
free radical initiated polymerization using a free radical
initiator, for example. The initiator can include a "per" compound
such as a diazo compound, persulfate, per-oxygen, or the like.
Thermal initiators that can be used include azo compounds:
1,1'-azobis(cyclohexanecarbonitrile) 98%, azobisisobutyronitrile 12
wt. % in acetone, 2,2'-azobis(2-methylpropionitrile) 98%,
2,2'-azobis(2-methylpropionitrile) recrystallized, 99%; inorganic
peroxides: ammonium persulfate reagent grade, 98%;
hydroxymethanesulfinic acid monosodium salt dihydrate; potassium
persulfate ACS reagent, 99.0%; sodium persulfate reagent grade,
.gtoreq.98%; dicumyl peroxide 98%; and organic peroxides:
tert-butyl hydroperoxide solution packed in FEP bottles, .about.5.5
M in decane (over molecular sieve 4 .ANG.); tert-butyl
hydroperoxide solution 5.0-6.0 M in nonane; tert-butyl peracetate
solution 50 wt. % in odorless mineral spirits; cumene hydroperoxide
technical grade, 80%;
2,5-di(tert-butylperoxy)-2,5-dimethyl-3-hexyne, blend; Luperox 101,
2,5-bis(tert-butylperoxy)-2,5-dimethylhexane technical grade, 90%;
Luperoe.RTM. 101XL45, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane,
blend with calcium carbonate and silica; Luperoe.RTM. 224,
2,4-pentanedione peroxide solution .about.34 wt. % in
4-hydroxy-4-methyl-2-pentanone and N-methyl-2-pyrrolidone;
Luperoe.RTM. 231,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane 92%;
Luperoe.RTM. 331M80, 1,1-bis(tert-butylperoxy)cyclohexane solution
.about.80 wt. % in odorless mineral spirits; Luperoe.RTM. 531M80,
1,1-bis(tert-amylperoxy)cyclohexane solution 80 wt. % in odorless
mineral spirits; Luperox A70S, benzoyl peroxide 70%, remainder
water; Luperoe.RTM. A75, benzoyl peroxide 75%, remainder water;
Luperoe.RTM. A75FP, benzoyl peroxide, 75% remainder water contains
25 wt. % water as stabilizer, 75%; Luperoe.RTM. A75FP, benzoyl
peroxide, 75% remainder water contains 25 wt. % water as
stabilizer, 75%; Luperoe.RTM. A98, benzoyl peroxide reagent grade,
.gtoreq.98%; Luperoe.RTM. AFR40, benzoyl peroxide solution 40 wt. %
in dibutyl phthalate; Luperoe.RTM. ATC50, benzoyl peroxide
.about.50 wt. % in tricresyl phosphate; Luperoe.RTM. DDM-9,
2-butanone peroxide solution .about.35 wt. % in
2,2,4-trimethyl-1,3-pentanediol diisobutyrate; Luperoe.RTM. DHD-9,
2-butanone peroxide solution .about.32 wt. % in phthalate-free
plasticizer mixture; Luperoe.RTM. DI, tert-butyl peroxide 98%;
Luperoe.RTM. P, tert-butyl peroxybenzoate 98%; Luperoe.RTM. TBEC,
tert-butylperoxy 2-ethylhexyl carbonate 95%; Luperoe.RTM. TBH70X,
tert-butyl hydroperoxide solution 70 wt. % in H.sub.2O.
[0022] The weight ratio of the acrylic latex core polymer to the
acrylic latex shell polymer can be from 1:1 to 9:1 (50:50 to 90:10;
or 50 wt % core and 50 wt % shell to 90 wt % core to 10 wt %
shell). Other weight ratios that can be used include from 60:40 to
90:10, from 60:40 to 85:15, from 65:35 to 90:10, or from 65:35 to
85:15, for example.
[0023] The acrylic core-shell latex particles can have any acid
number at the surface that is suitable for printing on fabric.
However, in some examples, the acid number (or acid value) can be
relatively low, e.g., from 0 mg KOH/g to 45 mg KOH/g, from 0 mg
KOH/g to 30 mg KOH/g, from 2 mg KOH/g to 20 mg KOH/g, or from 4 mg
KOH/g to 15 mg KOH/g, for example. The term "acid value" or "acid
number" refers to the mass of potassium hydroxide (KOH) in
milligrams that can be used to neutralize one gram of substance (mg
KOH/g), such as the latex polymers disclosed herein. This value can
be determined, in one example, by dissolving or dispersing a known
quantity of a material in organic solvent and then titrating with a
solution of potassium hydroxide (KOH) of known concentration for
measurement.
[0024] In certain more specific examples, the acrylic core-shell
latex particles can have a latex core weight average molecular
weight from 30,000 Mw to 1,500,000 Mw, from 50,000 Mw to 1,000,000
Mw, or from 75,000 Mw to 500,000 Mw. Furthermore, the acrylic
core-shell latex particles can have a latex shell weight average
molecular weight from 10,000 Mw to 1,000,000 Mw, from 20,000 Mw to
500,000 Mw, or from 30,000 Mw to 300,000 Mw.
[0025] In further detail, the acrylic shell copolymer can include
from 1 wt % to 14 wt % copolymerized acrylic acid, methacrylic
acid, or a combination thereof. In other examples, the
copolymerized acrylic acid and/or methacrylic acid can be present
at from 2 wt % to 12 wt %, or from 4 wt % to 10 wt %. In one
example, there is not acrylic acid, and the charge stabilizing
monomer is provided by methacrylic acid, e.g., from 1 wt % to 1 wt
%, from 2 wt % to 12 wt %, or from 4 wt % to 10 wt %.
[0026] In further detail, the acrylic shell copolymer can include
from 30 wt % to 80 wt % copolymerized methyl methacrylate, ethyl
methacrylate, or a combination thereof. In another example, the
copolymerized methyl methacrylate and/or ethyl methacrylate can be
present at from 35 wt % to 75 wt %, from 40 wt % to 70 wt %, or
from 40 wt % to 60 wt %, for example. In another example, the
methyl methacrylate can be present at from 30 wt % to 80 wt %, at
from 35 wt % to 75 wt %, from 40 wt % to 70 wt %, or from 40 wt %
to 60 wt %, and the acrylic shell copolymer can be devoid of ethyl
methacrylate.
[0027] Turning to further detail regarding other components of the
ink compositions that can be used for the systems and methods
described herein, the pigment can be any of a number of pigments of
any of a number of primary or secondary colors, or can be black or
white, for example. More specifically, colors can include cyan,
magenta, yellow, red, blue, violet, red, orange, green, etc. In one
example, the ink composition can be a black ink with a carbon black
pigment. In another example, the ink composition can be a cyan or
green ink with a copper phthalocyanine pigment, e.g., Pigment Blue
15:0, Pigment Blue 15:1; Pigment Blue 15:3, Pigment Blue 15:4,
Pigment Green 7, Pigment Green 36, etc. In another example, the ink
composition can be a magenta ink with a quinacridone pigment or a
co-crystal of quinacridone pigments. Example quinacridone pigments
that can be utilized can include PR122, PR192, PR202, PR206, PR207,
PR209, PO48, PO49, PV19, PV42, or the like. These pigments tend to
be magenta, red, orange, violet, or other similar colors. In one
example, the quinacridone pigment can be PR122, PR202, PV19, or a
combination thereof. In another example, the ink composition can be
a yellow ink with an azo pigment, e.g., PY74 and PY155. Other
examples of pigments include the following, which are available
from BASF Corp.: PALIOGEN.RTM. Orange, HELIOGEN.RTM. Blue L 6901F,
HELIOGEN.RTM. Blue NBD 7010, HELIOGEN.RTM. Blue K 7090,
HELIOGEN.RTM. Blue L 7101F, PALIOGEN.RTM. Blue L 6470,
HELIOGEN.RTM. Green K 8683, HELIOGEN.RTM. Green L 9140,
CHROMOPHTAL.RTM. Yellow 3G, CHROMOPHTAL.RTM. Yellow GR,
CHROMOPHTAL.RTM. Yellow 8G, IGRAZIN.RTM. Yellow SGT, and
IGRALITE.RTM. Rubine 4BL. The following pigments are available from
Degussa Corp.: Color Black FWI, Color Black FW2, Color Black FW2V,
Color Black 18, Color Black, FW200, Color Black 5150, Color Black
S160, and Color Black 5170. The following black pigments are
available from Cabot Corp.: REGAL.RTM. 400R, REGAL.RTM. 330R,
REGAL.RTM. 660R, MOGUL.RTM. L, BLACK PEARLS.RTM. L, MONARCH.RTM.
1400, MONARCH.RTM. 1300, MONARCH.RTM. 1100, MONARCH.RTM. 1000,
MONARCH.RTM. 900, MONARCH.RTM. 880, MONARCH.RTM. 800, and
MONARCH.RTM. 700.
[0028] The following pigments are available from Orion Engineered
Carbons GMBH: PRINTEX.RTM. U, PRINTEX.RTM. V, PRINTEX.RTM. 140U,
PRINTEX.RTM. 140V, PRINTEX.RTM. 35, Color Black FW 200, Color Black
FW 2, Color Black FW 2V, Color Black FW 1, Color Black FW 18, Color
Black S 160, Color Black S 170, Special Black 6, Special Black 5,
Special Black 4A, and Special Black 4. The following pigment is
available from DuPont: TI-PURE.RTM. R-101. The following pigments
are available from Heubach: MONASTRAL.RTM. Magenta, MONASTRAL.RTM.
Scarlet, MONASTRAL.RTM. Violet R, MONASTRAL.RTM. Red B, and
MONASTRAL.RTM. Violet Maroon B. The following pigments are
available from Clariant: DALAMAR.RTM. Yellow YT-858-D, Permanent
Yellow GR, Permanent Yellow G, Permanent Yellow DHG, Permanent
Yellow NCG-71, Permanent Yellow GG, Hansa Yellow RA, Hansa
Brilliant Yellow 5GX-02, Hansa Yellow-X, NOVOPERM.RTM. Yellow HR,
NOVOPERM.RTM. Yellow FGL, Hansa Brilliant Yellow 10GX, Permanent
Yellow G3R-01, HOSTAPERM.RTM. Yellow H4G, HOSTAPERM.RTM. Yellow
H3G, HOSTAPERM.RTM. Orange GR, HOSTAPERM.RTM. Scarlet GO, and
Permanent Rubine F6B. The following pigments are available from Sun
Chemical: QUINDO.RTM. Magenta, INDOFAST.RTM. Brilliant Scarlet,
QUINDO.RTM. Red R6700, QUINDO.RTM. Red R6713, INDOFAST.RTM. Violet,
L74-1357 Yellow, L75-1331 Yellow, L75-2577 Yellow, and LHD9303
Black. The following pigments are available from Birla Carbon:
RAVEN.RTM. 7000, RAVEN.RTM. 5750, RAVEN.RTM. 5250, RAVEN.RTM. 5000
Ultra.RTM. II, RAVEN.RTM. 2000, RAVEN.RTM. 1500, RAVEN.RTM. 1250,
RAVEN.RTM. 1200, RAVEN.RTM. 1190 Ultra.RTM.. RAVEN.RTM. 1170,
RAVEN.RTM. 1255, RAVEN.RTM. 1080, and RAVEN.RTM. 1060. The
following pigments are available from Mitsubishi Chemical Corp.:
No. 25, No. 33, No. 40, No. 47, No. 52, No. 900, No. 2300, MCF-88,
MA600, MA7, MA8, and MA100. The colorant may be a white pigment,
such as titanium dioxide, or other inorganic pigments such as zinc
oxide and iron oxide.
[0029] Specific other examples of a cyan color pigment may include
C.I. Pigment Blue -1, -2, -3, -15, -15:1, -15:2, -15:3, -15:4, -16,
-22, and -60; magenta color pigment may include C.I. Pigment Red
-5, -7, -12, -48, -48:1, -57, -112, -122, -123, -146, -168, -177,
-184, -202, and C.I. Pigment Violet-19; yellow pigment may include
C.I. Pigment Yellow -1, -2, -3, -12, -13, -14, -16, -17, -73, -74,
-75, -83, -93, -95, -97, -98, -114, -128, -129, -138, -151, -154,
and -180. Black pigment may include carbon black pigment or organic
black pigment such as aniline black, e.g., C.I. Pigment Black 1.
While several examples have been given herein, it is to be
understood that any other pigment can be used that is useful in
color modification, or dye may even be used in addition to the
pigment.
[0030] Furthermore, pigments and dispersants are described
separately herein, but there are pigments that are commercially
available which include both the pigment and a dispersant suitable
for ink composition formulation. Specific examples of pigment
dispersions that can be used, which include both pigment solids and
dispersant are provided by example, as follows: HPC-K048 carbon
black dispersion from DIC Corporation (Japan), HSKBPG-11-CF carbon
black dispersion from Dom Pedro (USA), HPC-0070 cyan pigment
dispersion from DIC, CABOJET.RTM. 250C cyan pigment dispersion from
Cabot Corporation (USA), 17-SE-126 cyan pigment dispersion from Dom
Pedro, HPF-M046 magenta pigment dispersion from DIC, CABOJET.RTM.
265M magenta pigment dispersion from Cabot, HPJ-Y001 yellow pigment
dispersion from DIC, 16-SE-96 yellow pigment dispersion from Dom
Pedro, or Emacol SF Yellow AE12F yellow pigment dispersion from
Sanyo (Japan).
[0031] Thus, the pigment(s) can be dispersed by a dispersant that
is adsorbed or ionically attracted to a surface of the pigment, or
can be covalently attached to a surface of the pigment as a
self-dispersed pigment. In one example, the dispersant can be an
acrylic dispersant, such as a styrene (meth)acrylate dispersant, or
other dispersant suitable for keeping the pigment suspended in the
liquid vehicle. In one example, the styrene (meth)acrylate
dispersant can be used, as it can promote .pi.-stacking between the
aromatic ring of the dispersant and various types of pigments. In
one example, the styrene (meth)acrylate dispersant can have a
weight average molecular weight from 4,000 Mw to 30,000 Mw. In
another example, the styrene-acrylic dispersant can have a weight
average molecular weight of 8,000 Mw to 28,000 Mw, from 12,000 Mw
to 25,000 Mw, from 15,000 Mw to 25,000 Mw, from 15,000 Mw to 20,000
Mw, or about 17,000 Mw. Regarding the acid number, the styrene
(meth)acrylate dispersant can have an acid number from 100 to 350,
from 120 to 350, from 150 to 300, from 180 to 250, or about 214,
for example. Example commercially available styrene-acrylic
dispersants can include Joncryl.RTM. 671, Joncryl.RTM. 71,
Joncryl.RTM. 96, Joncryl.RTM. 680, Joncryl.RTM. 683, Joncryl.RTM.
678, Joncryl.RTM. 690, Joncryl.RTM. 296, Joncryl.RTM. 671,
Joncryl.RTM. 696 or Joncryl.RTM. ECO 675 (all available from BASF
Corp., Germany).
[0032] The ink compositions of the present disclosure can be
formulated to include a liquid vehicle, which can include the water
content, e.g., 60 wt % to 90 wt % or from 75 wt % to 85 wt %, as
well as organic co-solvent, e.g., from 4 wt % to 30 wt %, from 6 wt
% to 20 wt %, or from 8 wt % to 15 wt %. Other liquid vehicle
components can also be included, such as surfactant, antibacterial
agent, other colorant, etc. However, as part of the ink composition
used in the systems and methods described herein, the pigment,
dispersant, and the acrylic core-shell latex particles can be
included or carried by the liquid vehicle components. Suitable pH
ranges for the ink composition can be from pH 6 to pH 10, from pH 7
to pH 10, from pH 7.5 to pH 10, from pH 8 to pH 10, 6 to pH 9, from
pH 7 to pH 9, from pH 7.5 to pH 9, etc.
[0033] In further detail regarding the liquid vehicle, the
co-solvent(s) can be present and can include any co-solvent or
combination of co-solvents that are compatible with the pigment,
dispersant, and acrylic core-shell latex particles. Examples of
suitable classes of co-solvents include polar solvents, such as
alcohols, amides, esters, ketones, lactones, and ethers. In
additional detail, solvents that can be used can include aliphatic
alcohols, aromatic alcohols, diols, glycol ethers, polyglycol
ethers, caprolactams, formamides, acetamides, and long chain
alcohols. Examples of such compounds include primary aliphatic
alcohols, secondary aliphatic alcohols, 1,2-alcohols, 1,3-alcohols,
1,5-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl
ethers, higher homologs (C.sub.6-C.sub.12) of polyethylene glycol
alkyl ethers, N-alkyl caprolactams, unsubstituted caprolactams,
both substituted and unsubstituted formamides, both substituted and
unsubstituted acetamides, and the like. More specific examples of
organic solvents can include 2-pyrrolidone,
2-ethyl-2-(hydroxymethyl)-1, 3-propane diol (EPHD), glycerol,
dimethyl sulfoxide, sulfolane, glycol ethers, alkyldiols such as
1,2-hexanediol, and/or ethoxylated glycerols such as LEG-1,
etc.
[0034] The liquid vehicle can also include surfactant and/or
emulsifier. In general, the surfactant can be water soluble and may
include alkyl polyethylene oxides, alkyl phenyl polyethylene
oxides, polyethylene oxide (PEO) block copolymers, acetylenic PEO,
PEO esters, PEO amines, PEO amides, dimethicone copolyols,
ethoxylated surfactants, alcohol ethoxylated surfactants,
fluorosurfactants, and mixtures thereof. In some examples, the
surfactant can include a nonionic surfactant, such as a
Surfynol.RTM. surfactant, e.g., Surfynol.RTM. 440 (from Evonik,
Germany), or a Tergitol.TM. surfactant, e.g., Tergitol.TM. TMN-6
(from Dow Chemical, USA). In another example, the surfactant can
include an anionic surfactant, such as a phosphate ester of a C10
to C20 alcohol or a polyethylene glycol (3) oleyl mono/di
phosphate, e.g., Crodafos.RTM. N3A (from Croda International PLC,
United Kingdom). The surfactant or combinations of surfactants, if
present, can be included in the ink composition at from about 0.01
wt % to about 5 wt % and, in some examples, can be present at from
about 0.05 wt % to about 3 wt % of the ink compositions.
[0035] Consistent with the formulations of the present disclosure,
various other additives may be included to provide desired
properties of the ink composition for specific applications.
Examples of these additives are those added to inhibit the growth
of harmful microorganisms. These additives may be biocides,
fungicides, and other microbial agents, which are routinely used in
ink formulations. Examples of suitable microbial agents include,
but are not limited to, Acticide.RTM., e.g., Acticide.RTM. B20
(Thor Specialties Inc.), Nuosept.TM. (Nudex, Inc.), Ucarcide.TM.
(Union carbide Corp.), Vancide.RTM. (R. T. Vanderbilt Co.),
Proxel.TM. (ICI America), and combinations thereof. Sequestering
agents, such as EDTA (ethylene diamine tetra acetic acid) or
trisodium salt of methylglycinediacetic acid, may be included to
eliminate the deleterious effects of heavy metal impurities, and
buffer solutions may be used to control the pH of the ink.
Viscosity modifiers and buffers may also be present, as well as
other additives known to those skilled in the art to modify
properties of the ink as desired.
[0036] These ink compositions can be suitable for printing on many
types of textiles, but can be particularly acceptable on treated or
untreated natural fabric textile substrates, e.g., wool, cotton,
silk, linen, jute, flax, hemp, rayon fibers, thermoplastic
aliphatic polymeric fibers derived from renewable resources (e.g.
cornstarch, tapioca products, sugarcanes), etc. Treated fabrics can
include a coating, for example, such as a coating including a
cationic component such as calcium salt, magnesium salt, cationic
polymer, etc. These types of substrates can provide acceptable
optical density (OD) and/or washfastness properties. The term
"washfastness" can be defined as the OD or delta E (.DELTA.E) that
is retained after five (5) standard washing machine cycles using
warm water and a standard clothing detergent (e.g., Tide.RTM.
available from Proctor and Gamble, Cincinnati, Ohio, USA).
Essentially, by measuring OD and/or L*a*b* both before and after
washing, .DELTA.OD and .DELTA.E value can be determined, which is
essentially a quantitative way of expressing the difference between
the OD and/or L*a*b*prior to and after undergoing the washing
cycles. Thus, the lower the .DELTA.OD and .DELTA.E values, the
better. In further detail, .DELTA.E is a single number that
represents the "distance" between two colors, which in accordance
with the present disclosure, is the color (or black) prior to
washing and the modified color (or modified black) after
washing.
[0037] Colors, for example, can be expressed as CIELAB values. It
is noted that color differences may not be symmetrical going in
both directions (pre-washing to post washing vs. post-washing to
pre-washing). Using the CIE 1976 definition, the color difference
can be measured and the .DELTA.E value calculated based on
subtracting the pre-washing color values of L*, a*, and b* from the
post-washing color values of L*, a*, and b*. Those values can then
be squared, and then a square root of the sum can be determined to
arrive at the .DELTA.E value. The 1976 standard can be referred to
herein as ".DELTA.E.sub.CIE." The CIE definition was modified in
1994 to address some perceptual non-uniformities, retaining the
L*a*b* color space, but modifying to define the L*a*b* color space
with differences in lightness (L*), chroma (C*), and hue (h*)
calculated from L*a*b* coordinates. Then in 2000, the CIEDE
standard was established to further resolve the perceptual
non-uniformities by adding five corrections, namely i) hue rotation
(R.sub.T) to deal with the problematic blue region at hue angles of
about 275.degree.), ii) compensation for neutral colors or the
primed values in the L*C*h differences, iii) compensation for
lightness (S.sub.L), iv) compensation for chroma (S.sub.C), and v)
compensation for hue (S.sub.H). The 2000 modification can be
referred to herein as ".DELTA.E2000." In accordance with examples
of the present disclosure, .DELTA.E value can be determined using
the CIE definition established in 1976, 1994, and 2000 to
demonstrate washfastness. However, in the examples of the present
disclosure, .DELTA.E.sub.CIE and .DELTA.E.sub.2000 are used.
[0038] In addition to good durability or washfastness, ink
compositions with these acrylic core-shell latex particles can also
exhibit good stability over time as well as good thermal inkjet
printhead performance such as high drop weight, high drop velocity,
good kogation, and acceptable "Turn On Energy" or "TOE" curve
values. Turn On Energy (TOE) can be defined as the measurement of
energy used to generate a given ink drop weight (DW) upon firing.
The goal is to achieve a consistent ink composition firing at a
drop weight at a lower energy. At some point, the DW that increases
with energy input starts to flatten out. Examples of TOE curves can
be found and described in the Examples hereinafter.
[0039] In further detail regarding the fabric substrates, the
fabric can include a substrate, and in some examples can be
treated, such as with a coating that includes a calcium salt, a
magnesium salt, a cationic polymer, or a combination of a calcium
or magnesium salt and cationic polymer. Fabric substrates can
include substrates that have fibers that may be natural and/or
synthetic, but in some examples, the fabric is particularly useful
with natural fabric substrates. The fabric substrate can include,
for example, a textile, a cloth, a fabric material, fabric
clothing, or other fabric product suitable for applying ink, and
the fabric substrate can have any of a number of fabric structures.
The term "fabric structure" is intended to include structures that
can have warp and weft, and/or can be woven, non-woven, knitted,
tufted, crocheted, knotted, and pressured, for example. The terms
"warp" and "weft" have their ordinary meaning in the textile arts,
as used herein, e.g., warp refers to lengthwise or longitudinal
yarns on a loom, while weft refers to crosswise or transverse yarns
on a loom.
[0040] It is notable that the term "fabric substrate" does not
include materials commonly known as any kind of paper (even though
paper can include multiple types of natural and synthetic fibers or
mixtures of both types of fibers). Fabric substrates can include
textiles in filament form, textiles in the form of fabric material,
or textiles in the form of fabric that has been crafted into a
finished article (e.g. clothing, blankets, tablecloths, napkins,
towels, bedding material, curtains, carpet, handbags, shoes,
banners, signs, flags, etc.). In some examples, the fabric
substrate can have a woven, knitted, non-woven, or tufted fabric
structure. In one example, the fabric substrate can be a woven
fabric where warp yarns and weft yarns can be mutually positioned
at an angle of about 90.degree.. This woven fabric can include but
is not limited to, fabric with a plain weave structure, fabric with
a twill weave structure where the twill weave produces diagonal
lines on a face of the fabric, or a satin weave. In another
example, the fabric substrate can be a knitted fabric with a loop
structure. The loop structure can be a warp-knit fabric, a
weft-knit fabric, or a combination thereof. A warp-knit fabric
refers to every loop in a fabric structure that can be formed from
a separate yarn mainly introduced in a longitudinal fabric
direction. A weft-knit fabric refers to loops of one row of fabric
that can be formed from the same yarn. In a further example, the
fabric substrate can be a non-woven fabric. For example, the
non-woven fabric can be a flexible fabric that can include a
plurality of fibers or filaments that are one or both bonded
together and interlocked together by a chemical treatment process
(e.g., a solvent treatment), a mechanical treatment process (e.g.,
embossing), a thermal treatment process, or a combination of two or
more of these processes.
[0041] Regardless of the structure, in one example, the fabric
substrate can include natural fibers, synthetic fibers, or a
combination thereof. Exemplary natural fibers can include, but are
not limited to, wool, cotton, silk, linen, jute, flax, hemp, rayon
fibers, thermoplastic aliphatic polymeric fibers derived from
renewable resources (e.g. cornstarch, tapioca products,
sugarcanes), or a combination thereof. In another example, the
fabric substrate can include synthetic fibers. Exemplary synthetic
fibers can include polymeric fibers such as, polyvinyl chloride
(PVC) fibers, PVC-free fibers made of polyester, polyamide,
polyimide, polyacrylic, polypropylene, polyethylene, polyurethane,
polystyrene, polyaramid (e.g., Kevlar.RTM.) polytetrafluoroethylene
(Teflon).degree. (both trademarks of E. I. du Pont de Nemours
Company, Delaware), fiberglass, polytrimethylene, polycarbonate,
polyethylene terephthalate, polyester terephthalate, polybutylene
terephthalate, or a combination thereof. In some examples, the
synthetic fiber can be a modified fiber from the above-listed
polymers. The term "modified fiber" refers to one or both of the
polymeric fiber and the fabric as a whole having undergone a
chemical or physical process such as, but not limited to, one or
more of a copolymerization with monomers of other polymers, a
chemical grafting reaction to contact a chemical functional group
with one or both the polymeric fiber and a surface of the fabric, a
plasma treatment, a solvent treatment, acid etching, or a
biological treatment, an enzyme treatment, or antimicrobial
treatment to prevent biological degradation. The term "PVC-free
fibers" as used herein means that no polyvinyl chloride (PVC)
polymer or vinyl chloride monomer units are in the fibers.
[0042] As previously mentioned, the fabric substrate can be a
combination of fiber types, e.g. a combination of any natural fiber
with another natural fiber, any natural fiber with a synthetic
fiber, a synthetic fiber with another synthetic fiber, or mixtures
of multiple types of natural fibers and/or synthetic fibers in any
of the above combinations. In some examples, the fabric substrate
can include natural fiber and synthetic fiber. The amount of each
fiber type can vary. For example, the amount of the natural fiber
can vary from about 5 wt % to about 95 wt % and the amount of
synthetic fiber can range from about 5 wt % to 95 wt %. In yet
another example, the amount of the natural fiber can vary from
about 10 wt % to 80 wt % and the synthetic fiber can be present
from about 20 wt % to about 90 wt %. In other examples, the amount
of the natural fiber can be about 10 wt % to 90 wt % and the amount
of synthetic fiber can also be about 10 wt % to about 90 wt %.
Likewise the ratio of natural fiber to synthetic fiber in the
fabric substrate can vary. For example, the ratio of natural fiber
to synthetic fiber can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8,
1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19,
1:20, or vice versa.
[0043] In one example, the fabric substrate can have a basis weight
ranging from about 10 gsm to about 500 gsm. In another example, the
fabric substrate can have a basis weight ranging from about 50 gsm
to about 400 gsm. In other examples, the fabric substrate can have
a basis weight ranging from about 100 gsm to about 300 gsm, from
about 75 gsm to about 250 gsm, from about 125 gsm to about 300 gsm,
or from about 150 gsm to about 350 gsm.
[0044] In addition, the fabric substrate can contain additives
including, but not limited to, one or more of colorant (e.g.,
pigments, dyes, and tints), antistatic agents, brightening agents,
nucleating agents, antioxidants, UV stabilizers, fillers and
lubricants, for example. Alternatively, the fabric substrate may be
pre-treated in a solution containing the substances listed above
before applying other treatments or coating layers.
[0045] In another example, and as set forth in FIG. 2, a method 200
of textile printing includes jetting 210 an aqueous ink composition
onto a fabric substrate. The aqueous ink composition in this
example includes an aqueous ink vehicle, pigment, and from 2 wt %
to 15 wt % of acrylic core-shell latex particles having an acrylic
core copolymer with a glass transition temperature from -50.degree.
C. to 30.degree. C. and an acrylic shell copolymer having a glass
transition temperature from 50.degree. C. to 130.degree. C. The
acrylic core copolymer and the acrylic shell copolymer of the
acrylic core-shell latex particles have an average weight ratio
from 1:1 to 9:1 in this example. In further detail, the method can
include heating the fabric substrate with the aqueous ink
composition thereon to a temperature ranging from above the glass
transition temperature of the acrylic shell copolymer to
200.degree. C. The fabric substrate can include, for example,
cotton, polyester, nylon, silk, or a blend thereof.
[0046] It is noted that, as used in this specification and the
appended claims, the singular forms "a," "an," and "the" include
plural referents unless the content clearly dictates otherwise.
[0047] As used herein, the term "about" is used to provide
flexibility to a numerical range endpoint by providing that a given
value may be "a little above" or "a little below" the endpoint. The
degree of flexibility of this term can be dictated by the
particular variable and would be within the knowledge of those
skilled in the art to determine based on experience and the
associated description herein.
[0048] As used herein, a plurality of items, structural elements,
compositional elements, and/or materials may be presented in a
common list for convenience. However, these lists should be
construed as though each member of the list is individually
identified as a separate and unique member. Thus, no individual
member of such list should be construed as a de facto equivalent of
any other member of the same list solely based on their
presentation in a common group without indications to the
contrary.
[0049] Concentrations, dimensions, amounts, and other numerical
data may be presented herein in a range format. It is to be
understood that such range format is used merely for convenience
and brevity and should be interpreted flexibly to include not only
the numerical values explicitly recited as the limits of the range,
but also to include all the individual numerical values or
sub-ranges encompassed within that range as if each numerical value
and sub-range is explicitly recited. For example, a weight ratio
range of about 1 wt % to about 20 wt % should be interpreted to
include not only the explicitly recited limits of about 1 wt % and
about 20 wt %, but also to include individual weights such as 2 wt
%, 11 wt %, 14 wt %, and sub-ranges such as 10 wt % to 20 wt %, 5
wt % to 15 wt %, etc.
Examples
[0050] The following examples illustrate the technology of the
present disclosure. However, it is to be understood that the
following are only exemplary or illustrative of the application of
the principles of the presented fabric print media and associated
methods. Numerous modifications and alternatives may be devised
without departing from the present disclosure. The appended claims
are intended to cover such modifications and arrangements. Thus,
while the disclosure has been provided with particularity, the
following describes further detail in connection with what are
presently deemed to be the acceptable examples.
Example 1--Seed Latex and Acrylic Latexes Prepared Therefrom
[0051] A seed latex (Seed Latex 1) was obtained to use as a common
seed latex for the preparation of several acrylic core-shell
latexes of several examples hereinafter. The seed latex was
selected to control particle size of the core-shell latex prepared
in accordance with the examples hereinafter, e.g., Examples 2-19
(Latexes 2-19). The seed latex was an all acrylic latex copolymer
with a D50 particle size of approximately 65 nm (diameter) and a
solids content of approximately 48 wt %. Tables 1A-1C below
summarize the acrylic latexes prepared in Examples 2-19, including
the amount of first stage (core) and second stage (shell) monomers
used as a percentage of the total monomer of the formulations.
Examples 13 and 14 are single-phase acrylic latexes, so they are
considered to be 100 wt % core, as notated in the summary tables
below. The details on the Seed Latex are not included in the
Tables. The examples were either dual-phase preparations to
generate acrylic core-shell latex particles (first stage core
varied wt % from 65 wt % to 85 wt; second stage shell varied wt %
from 15 wt % to 35 wt %); or single-phase (100 wt % first stage
monomer). The calculated glass transition temperature (Tg) for the
core and the shell (separately) were included, which can be
calculated based on the Fox equation using homopolymer Tg values
shown in Table 2. Theoretical acid values and measured solid
percentages were also provided for the completed acrylic latex
polymer particles.
TABLE-US-00001 TABLE 1A Summary of Examples 2-8 Acrylic Latex
Polymer Particles (Latexes 2-8) Latex 2 Latex 3 Latex 4 Latex 5
Latex 6 Latex 7 Latex 8 CORE Monomers BA BA BA BA BA BA BA Styrene
Styrene Styrene Styrene Styrene Styrene Styrene BBDA DAAM WAMII Wt
% Core 75 65 85 75 75 75 75 Tg (.degree. C.) 5 5 5 5 10 7 -14 SHELL
Monomers BA MMA BA MMA BA MMA BA MMA BA MMA BA MMA BA MMA Styrene
Styrene Styrene Styrene Styrene Styrene Styrene MAA MAA MAA MAA MAA
MAA MAA DAAM WAMII Wt % Shell 25 35 15 25 25 25 25 Tg (.degree. C.)
106 106 106 106 105 105 103 LATEX PARTICLES Acid Value 9.8 13.7 5.9
9.8 9.8 6.5 6.5 (mgKOH/g) D50 Particle 220 222 236 236 216 259 226
Size (nm) pH 7.4 8 7.2 9.1 7.5 7.5 8.2 Wt % Solids 38.5 38.5 38.7
39.3 39.2 36.9 38.85 Morphology Core/Shell Core/Shell Core/Shell
Core/Shell Core/Shell Core/Shell Core/Shell
TABLE-US-00002 TABLE 1B Summary of Examples 9-14 Acrylic Latex
Polymer Particles (Latexes 9-14) Latex 13 Latex 14 Latex 9 Latex 10
Latex 11 Latex 12 (Comp) (Comp) CORE Monomers BA BA BA BA BA BA
Styrene Styrene Styrene Styrene Styrene Styrene WAMII WAMII MAA MAA
Wt % Core 65 85 75 85 100 100 Tg (.degree. C.) 5 -14 -12 7 5 -14
SHELL Monomers BA BA BA BA -- -- Styrene Styrene Styrene Styrene
MMA MMA MMA MMA WAMII Wt % Shell 35 15 25 15 -- -- Tg (.degree. C.)
103 103 105 105 -- -- LATEX PARTICLES Acid Value 9.1 3.9 6.5 3.9
6.5 6.5 (mgKOH/g) D50 Particle 221 224 229 237 239 226 Size (nm) pH
8.2 7.4 7.7 8.1 7.8 9.2 Wt % Solids 38.3 38.96 37.68 37.27 41.8
38.83 Morphology Core/Shell Core/Shell Core/Shell Core/Shell
Single-phase Single-phase
TABLE-US-00003 TABLE 1C Summary of Examples 15-19 Acrylic Latex
Polymer Particles (Latexes 15-19) Latex 15 Latex 16 Latex 17 Latex
18 Latex 19 CORE Monomers Styrene Styrene BDDMA MAAM MAAM BA EHA
MAAM BA BDDMA AA AA BA MMA BA BA MAA MMA MMA Wt % Core 75 75 75 75
75 Tg (.degree. C.) -16.8 28.3 116.2 19.6 27.1 SHELL Monomers
Styrene Styrene Styrene Styrene Styrene EHA EHA EHA EHA EHA MAA MAA
MAA MAA MAA BA BA BA BA BA MMA MMA MMA MMA MMA Wt % Shell 25 25 25
25 25 Tg (.degree. C.) 105.7 105.7 105.7 105.7 105.7 LATEX
PARTICLES Acid Value 23.9 30.8 12.3 12.3 12.3 (mgKOH/g) D50
Particle 178.9 175.2 185.2 178.2 197.5 Size (nm) pH 12 12 11 11 11
Wt % Solids 29.43 29.19 23.58 26.77 27.2 Morphology Core/Shell
Core/Shell Core/Shell Core/Shell Core/Shell
TABLE-US-00004 TABLE 2 Monomer IDs and Homopolymer Glass Transition
Temperatures (Tg) Homopolymer Monomer Abbreviation Tg (.degree. C.)
methyl methacrylate MMA 119 n-butyl acrylate BA -45 styrene Styrene
104 methacrylic acid MAA 182 diacetone acrylamide DAAM 77 Sipomer
.RTM. WAMII WAMII 87 2-ethylhexyl acrylate EHA -50 acrylic acid AA
103
Example 2--Preparation of Acrylic Core-Shell Latex 2
[0052] 13.7 grams of Seed Latex 1 of Example 1 and 335.9 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 45.6 grams water) was started and fed continuously over 270
minutes. Concurrently with the start of the KPS feed, the first
monomer feed was fed over 150 minutes [149.8 grams n-butyl acrylate
(BA), 123.2 grams styrene, 13.7 grams Hitenol AR-1025
(polyoxyethylene styrenated phenyl ether ammonium sulfate anionic
surfactant) and 58.2 grams water]. When the first monomer feed
finished, the reactor was held at 77.degree. C. for 30 minutes, and
then the second monomer feed was fed over 90 minutes [66.8 grams
methyl methacrylate (MMA), 13.7 grams styrene, 4.6 grams n-butyl
acrylate (BA), 5.5 grams methacrylic acid (MAA), 0.5 gram iso-octyl
thioglycolate (i-OTG), 4.71 grams Hitenol AR-1025 and 18.4 grams
water]. Ten minutes after the end of the second monomer feed, 75
grams of a 5 wt % solution of KOH in water was fed to the reactor
over 10 minutes and then the reactor was held at 77.degree. C. for
another 30 minutes. Next, a mixture of 0.73 grams of 70 wt %
tert-butyl hydroperoxide in water plus 9.7 grams water was added to
the reactor, and then a solution of 0.73 grams of iso-ascorbic acid
in 9.7 grams water was fed over 60 minutes. The reactor was then
cooled and the latex filtered using a 200 mesh sieve. The D50
particle size measured by a Malvern Zetasizer was 220 nm
(diameter), the pH was 7.4, and the solids content was 38.5 wt
%.
Example 3--Preparation of Acrylic Core-Shell Latex 3
[0053] 13.7 grams of Seed Latex 1 of Example 1 and 336 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.6 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.38 grams
in 48.1 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [136.8 n-butyl acrylate (BA), 112.6 grams
styrene, 12.5 grams Hitenol AR-1025 (polyoxyethylene styrenated
phenyl ether ammonium sulfate anionic surfactant) and 53.2 grams
water]. When the first monomer feed finished, the reactor was held
at 77.degree. C. for 30 minutes, and then the second monomer feed
was fed over 90 minutes [98.6 grams methyl methacrylate (MMA), 20.2
grams styrene, 6.7 grams n-butyl acrylate (BA), 8.1 grams
methacrylic acid (MAA), 0.7 grams iso-octyl thioglycolate (i-OTG),
6.9 grams Hitenol AR-1025 and 27.1 grams water]. Ten minutes after
the end of the second monomer feed, 75.3 grams of a 5 wt % solution
of KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by a Malvern
Zetasizer was 222 nm (diameter), the pH was 8, and the solids
content was 38.5 wt %.
Example 4--Preparation of Acrylic Core-Shell Latex 4
[0054] 14 grams of Seed Latex 1 of Example 1 and 343 grams of water
were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.3 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 46.6 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [173.3 n-butyl acrylate (BA), 142.6 grams
styrene, 15.8 grams Hitenol AR-1025 (polyoxyethylene styrenated
phenyl ether ammonium sulfate anionic surfactant) and 67.3 grams
water]. When the first monomer feed finished, the reactor was held
at 77.degree. C. for 30 minutes, and then the second monomer feed
was fed over 90 minutes [40.9 grams methyl methacrylate (MMA), 8.4
grams styrene, 2.8 grams n-butyl acrylate (BA), 3.4 grams
methacrylic acid (MAA), 0.3 grams iso-octyl thioglycolate (i-OTG),
2.9 grams Hitenol AR-1025 and 11.3 grams water]. Ten minutes after
the end of the second monomer feed, 41 grams of a 5 wt % solution
of KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by a Malvern
Zetasizer was 236 nm (diameter), the pH was 7.2, and the solids
content was 38.7 wt %.
Example 5--Preparation of Acrylic Core-Shell Latex 5
[0055] 14 grams of Seed Latex 1 of Example 1 and 335 grams of water
were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.3 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.36 grams
in 45.5 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [149.3 n-butyl acrylate (BA), 122.9 grams
styrene, 2.7 grams of butanediol diacrylate (BDDA), 13.6 grams
Hitenol AR-1025 (polyoxyethylene styrenated phenyl ether ammonium
sulfate anionic surfactant) and 58 grams water]. When the first
monomer feed finished, the reactor was held at 77.degree. C. for 30
minutes, and then the second monomer feed was fed over 90 minutes
[66.1 grams methyl methacrylate (MMA), 13.7 grams styrene, 4.6
grams n-butyl acrylate (BA), 5.5 grams methacrylic acid (MAA), 0.5
gram iso-octyl thioglycolate (i-OTG), 4.7 grams Hitenol AR-1025 and
18.3 grams water]. Ten minutes after the end of the second monomer
feed, 60.8 grams of a 5 wt % solution of KOH in water was fed to
the reactor over 10 minutes and then the reactor was held at
77.degree. C. for another 30 minutes. Next, a mixture of 0.72 grams
of 70 wt % tert-butyl hydroperoxide in water plus 9.7 grams water
was added to the reactor, and then a solution of 0.72 grams of
iso-ascorbic acid in 8.3 grams water was fed over 60 minutes. The
reactor was then cooled and the latex filtered using a 200 mesh
sieve. The D50 particle size measured by a Malvern Zetasizer was
236 nm (diameter), the pH was 9.1, and the solids content was 39.3
wt %.
Example 6--Preparation of Acrylic Core-Shell Latex 6
[0056] 13.6 grams of Seed Latex 1 of Example 1 and 296.8 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 68.8 grams water) was started and fed continuously over 270
minutes. Concurrently with the start of the KPS feed, the first
monomer feed was fed over 150 minutes [137.6 grams n-butyl acrylate
(BA), 122.2 grams styrene, 10.9 grams diacetone acrylamide (DAAM),
13.6 grams Hitenol AR-1025 (polyoxyethylene styrenated phenyl ether
ammonium sulfate anionic surfactant) and 57.7 grams water]. When
the first monomer feed finished, the reactor was held at 77.degree.
C. for 30 minutes, and then the second monomer feed was fed over 90
minutes [64.4 grams methyl methacrylate (MMA), 13.6 grams styrene,
4.5 grams n-butyl acrylate (BA), 5.4 grams methacrylic acid (MAA),
0.5 gram iso-octyl thioglycolate (i-OTG), 1.8 grams DAAM, 4.6 grams
Hitenol AR-1025 and 18.2 grams water]. Ten minutes after the end of
the second monomer feed, 60.8 grams of a 5 wt % solution of KOH in
water was fed to the reactor over 10 minutes and then the reactor
was held at 77.degree. C. for another 30 minutes. Next, a mixture
of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water plus 9.7
grams water was added to the reactor, and then a solution of 0.72
grams of iso-ascorbic acid in 8.3 grams water was fed over 60
minutes. The reactor was then cooled and then 4.6 grams of adipic
dihydrazide was added and allowed to dissolve. Finally, the latex
filtered using a 200 mesh sieve. The D50 particle size measured by
a Malvern Zetasizer was 216 nm (diameter), the pH was 7.5, and the
solids content was 39.2 wt %.
Example 7--Preparation of Acrylic Core-Shell Latex 7
[0057] 13.7 grams of Seed Latex 1 of Example 1 and 336.4 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 45.6 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [144.3 grams n-butyl acrylate (BA), 123.2
grams styrene, 5.5 grams of Sipomer.RTM. WAMII (allyl ether of a
substituted urea co-monomer from Solvay, Belgium), 13.6 grams
Hitenol AR-1025 (polyoxyethylene styrenated phenyl ether ammonium
sulfate anionic surfactant) and 58.8 grams water]. When the first
monomer feed finished, the reactor was held at 77.degree. C. for 30
minutes, and then the second monomer feed was fed over 90 minutes
[65 grams methyl methacrylate (MMA), 13.7 grams styrene, 4.6 grams
n-butyl acrylate (BA), 3.7 grams methacrylic acid (MAA), 0.5 gram
iso-octyl thioglycolate (i-OTG), 3.7 grams Sipomer.RTM. WAMII, 4.7
grams Hitenol AR-1025 and 18.4 grams water]. Ten minutes after the
end of the second monomer feed, 62.9 grams of a 5 wt % solution of
KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by a Malvern
Zetasizer was 259 nm (diameter), the pH was 7.5, and the solids
content was 36.9 wt %.
Example 8--Preparation of Acrylic Core-Shell Latex 8
[0058] 13.7 grams of Seed Latex 1 of Example 1 and 336 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 45.6 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [190.9 n-butyl acrylate (BA), 82.2 grams
styrene, 13.7 grams Hitenol AR-1025 (polyoxyethylene styrenated
phenyl ether ammonium sulfate anionic surfactant) and 58.2 grams
water]. When the first monomer feed finished, the reactor was held
at 77.degree. C. for 30 minutes, and then the second monomer feed
was fed over 90 minutes [68.6 grams methyl methacrylate (MMA), 13.7
grams styrene, 4.6 grams n-butyl acrylate (BA), 3.7 grams
methacrylic acid (MAA), 0.5 gram iso-octyl thioglycolate (i-OTG),
4.7 grams Hitenol AR-1025 and 18.4 grams water]. Ten minutes after
the end of the second monomer feed, 60.8 grams of a 5 wt % solution
of KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by a Malvern
Zetasizer was 226 nm (diameter), the pH was 8.2, and the solids
content was 38.9 wt %.
Example 9--Preparation of Acrylic Core-Shell Latex 9
[0059] 13.7 grams of Seed Latex 1 of Example 1 and 336 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 45.6 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [164.9 n-butyl acrylate (BA), 71 grams
styrene, 11.8 grams Hitenol AR-1025 (polyoxyethylene styrenated
phenyl ether ammonium sulfate anionic surfactant) and 50.3 grams
water]. When the first monomer feed finished, the reactor was held
at 77.degree. C. for 30 minutes, and then the second monomer feed
was fed over 90 minutes [95.8 grams methyl methacrylate (MMA), 19.1
grams styrene, 6.4 grams n-butyl acrylate (BA), 5.1 grams
methacrylic acid (MAA), 0.6 grams iso-octyl thioglycolate (i-OTG),
6.6 grams Hitenol AR-1025 and 25.6 grams water]. Ten minutes after
the end of the second monomer feed, 64.5 grams of a 5 wt % solution
of KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by a Malvern
Zetasizer was 221 nm (diameter), the pH was 8.2, and the solids
content was 38.3 wt %.
Example 10--Preparation of Acrylic Core-Shell Latex 10
[0060] 13.7 grams of Seed Latex 1 of Example 1 and 335.8 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 45.6 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [216.2 n-butyl acrylate (BA), 93.1 grams
styrene, 15.5 grams Hitenol AR-1025 (polyoxyethylene styrenated
phenyl ether ammonium sulfate anionic surfactant) and 65.9 grams
water]. When the first monomer feed finished, the reactor was held
at 77.degree. C. for 30 minutes, and then the second monomer feed
was fed over 90 minutes [41.2 grams methyl methacrylate (MMA), 8.2
grams styrene, 2.7 grams n-butyl acrylate (BA), 2.2 grams
methacrylic acid (MAA), 0.3 grams iso-octyl thioglycolate (i-OTG),
2.8 grams Hitenol AR-1025 and 11 grams water]. Ten minutes after
the end of the second monomer feed, 60.2 grams of a 5 wt % solution
of KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by a Malvern
Zetasizer was 224 nm (diameter), the pH was 7.4, and the solids
content was 39 wt %.
Example 11--Preparation of Acrylic Core-Shell Latex 11
[0061] 13.8 grams of Seed Latex 1 of Example 1 and 335.8 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 45.8 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [185.4 grams n-butyl acrylate (BA), 82.2
grams styrene, 5.5 grams of Sipomer.RTM. WAMII (allyl ether of a
substituted urea co-monomer from Solvay, Belgium), 13.7 grams
Hitenol AR-1025 (polyoxyethylene styrenated phenyl ether ammonium
sulfate anionic surfactant) and 58.2 grams water]. When the first
monomer feed finished, the reactor was held at 77.degree. C. for 30
minutes, and then the second monomer feed was fed over 90 minutes
[65 grams methyl methacrylate (MMA), 13.7 grams styrene, 4.6 grams
n-butyl acrylate (BA), 3.7 grams methacrylic acid (MAA), 0.5 gram
iso-octyl thioglycolate (i-OTG), 3.7 grams Sipomer.RTM. WAMII, 4.7
grams Hitenol AR-1025 and 18.4 grams water]. Ten minutes after the
end of the second monomer feed, 51.5 grams of a 5 wt % solution of
KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by a Malvern
Zetasizer was 229 nm (diameter), the pH was 7.7, and the solids
content was 37.7 wt %.
Example 12--Preparation of Acrylic Core-Shell Latex 12
[0062] 13.8 grams of Seed Latex 1 of Example 1 and 335.8 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.37 gram of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feeds. After 5 minutes, a feed of KPS solution (0.37 gram
in 45.8 water) was started and fed continuously over 270 minutes.
Concurrently with the start of the KPS feed, the first monomer feed
was fed over 150 minutes [163.5 grams n-butyl acrylate (BA), 139.6
grams styrene, 6.2 grams of Sipomer.RTM. WAMII (allyl ether of a
substituted urea co-monomer from Solvay, Belgium), 15.5 grams
Hitenol AR-1025 (polyoxyethylene styrenated phenyl ether ammonium
sulfate anionic surfactant) and 65.9 grams water]. When the first
monomer feed finished, the reactor was held at 77.degree. C. for 30
minutes, and then the second monomer feed was fed over 90 minutes
[39 grams methyl methacrylate (MMA), 8.2 grams styrene, 2.7 grams
n-butyl acrylate (BA), 2.2 grams methacrylic acid (MAA), 0.3 grams
iso-octyl thioglycolate (i-OTG), 2.2 grams Sipomer.RTM. WAMII, 2.8
grams Hitenol AR-1025 and 11 grams water]. Ten minutes after the
end of the second monomer feed, 50.8 grams of a 5 wt % solution of
KOH in water was fed to the reactor over 10 minutes and then the
reactor was held at 77.degree. C. for another 30 minutes. Next, a
mixture of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water
plus 9.7 grams water was added to the reactor, and then a solution
of 0.72 grams of iso-ascorbic acid in 8.3 grams water was fed over
60 minutes. The reactor was then cooled and the latex filtered
using a 200 mesh sieve. The D50 particle size measured by Malvern
Zetasizer was 237 nm (diameter), the pH was 8.1, and the solids
content was 37.3 wt %.
Example 13--Preparation of Acrylic Single-Phase Latex 13
(Comparative)
[0063] 13.7 grams of Seed Latex 1 of Example 1 and 335.6 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77C and then a mixture of 0.36 grams of potassium
persulfate (KPS) and 9.1 grams of deionized water was added to the
reactor and held for 5 minutes before starting the monomer feed.
After 5 minutes, a feed of KPS solution (0.37 gram in 45.6 water)
was started and fed continuously over 180 minutes. Concurrently
with the start of the KPS feed, the monomer feed was fed over 150
minutes [195.9 grams n-butyl acrylate (BA), 164.2 grams styrene,
3.65 grams methacrylic acid (MAA), 18.2 grams Hitenol AR-1025
(polyoxyethylene styrenated phenyl ether ammonium sulfate anionic
surfactant) and 77.5 grams water] and afterwards the reactor was
held at 77.degree. C. for 30 minutes. Next, a mixture of 0.72 grams
of 70 wt % tert-butyl hydroperoxide in water plus 9.7 grams water
was added to the reactor, and then a solution of 0.72 grams of
iso-ascorbic acid in 8.3 grams water was fed over 60 minutes,
followed by cooling the reactor to room temperature. At room
temperature, the pH was adjusted by adding 12.8 grams of a 5 wt %
solution of KOH in water and was fed to the reactor over
approximately 10 minutes. The latex was then filtered using a 200
mesh sieve. The D50 particle size measured by a Malvern Zetasizer
was 239 nm (diameter), the pH was 7.8, and the solids content was
41.8 wt %.
Example 14--Preparation of Acrylic Single-Phase Latex 14
(Comparative)
[0064] 13.7 grams of Seed Latex 1 of Example 1 and 335.6 grams of
water were added to a 1 liter round bottom flask. Thermostatic
temperature control was employed throughout the process and the
reactor was continuously flushed with nitrogen gas. The reactor was
heated to 77.degree. C. and then a mixture of 0.36 grams of
potassium persulfate (KPS) and 9.1 grams of deionized water was
added to the reactor and held for 5 minutes before starting the
monomer feed. After 5 minutes, a feed of KPS solution (0.37 gram in
45.6 water) was started and fed continuously over 180 minutes.
Concurrently with the start of the KPS feed, the monomer feed was
fed over 150 minutes [250.6 grams n-butyl acrylate (BA), 109.4
grams styrene, 3.7 grams methacrylic acid (MAA), 18.2 grams Hitenol
AR-1025 (polyoxyethylene styrenated phenyl ether ammonium sulfate
anionic surfactant) and 77.5 grams water] and afterwards the
reactor was held at 77.degree. C. for 30 minutes. Next, a mixture
of 0.72 grams of 70 wt % tert-butyl hydroperoxide in water plus 9.7
grams water was added to the reactor, and then a solution of 0.72
grams of iso-ascorbic acid in 8.3 grams water was fed over 60
minutes, followed by cooling the reactor to room temperature. At
room temperature, the pH was adjusted by adding 60.2 of a 5 wt %
solution of KOH in water and was fed to the reactor over
approximately 10 minutes. The latex was then filtered using a 200
mesh sieve. The D50 particle size measured by a Malvern Zetasizer
was 226 nm (diameter), the pH was 9.2, and the solids content was
38.8 wt %.
Example 15--Preparation of Acrylic Core-Shell Latex 15
[0065] 3.1 grams of Seed Latex 1 of Example 1 was added into a
4-neck round bottom flask (500 mL) equipped with a mechanical
stirrer, a reflux condenser and a nitrogen inlet tube under
nitrogen atmosphere. The flask was then heated to 80.degree. C. A
mixture of 17.263 grams of styrene, 0.375 grams of sodium
persulfate, 1.5 grams of sodium dodecyl sulfate, 53.112 grams of
n-butyl acrylate (BA) and 1.493 grams of acrylic acid (AA) in 111
grams of DI water were mixed thoroughly and then pumped into the
flask for a duration of 1.5 hours. The reaction mixture was kept at
80.degree. C. for an additional 1 hour to allow it for continuing
polymerization. After that, 15.174 grams of styrene, 0.317 grams of
sodium persulfate, 0.5 gram of sodium dodecyl sulfate, 0.168 of
2-ethylhexyl acrylate (EHA), 1.575 grams of methacrylic acid (MAA),
0.468 grams of n-butyl acrylate (BA), and 7.299 grams of methyl
methacrylate (MMA) in 38 grams DI water were mixed and added to the
reactor within 1 hr. The reaction mixture was continuously stirred
at 80.degree. C. for 3 hours. Then 3.576 grams of NaOH (50 wt % in
water) and 63.106 grams of DI water were added to the flask. All
polymerization was carried out under a nitrogen atmosphere. The
latex was filtered through 400 mesh stainless sieve. The D50
particle size measured by Malvern Zetasizer was 178.9 nm
(diameter), the pH was 12, and the solid contents was 29.43 wt
%.
Example 16--Preparation of Acrylic Core-Shell Latex 16
[0066] 3.1 grams of Seed Latex 1 of Example 1 was added into a
4-neck round bottom flask (500 mL) equipped with a mechanical
stirrer, a reflux condenser and a nitrogen inlet tube under
nitrogen atmosphere. The flask was then heated to 80.degree. C. A
mixture of 14.919 grams of styrene, 0.375 grams of sodium
persulfate, 1.5 grams of sodium dodecyl sulfate, 15.839 grams of
2-ethylhexyl acrylate (EHA), 2.374 grams of acrylic acid (AA),
14.688 grams of n-butyl acrylate (BA) and 24.401 grams of methyl
methacrylate (MMA) in 111 grams of DI water were mixed thoroughly
and then pumped into the flask for a duration of 1.5 hours. The
reaction mixture was kept at 80.degree. C. for an additional 1 hour
to allow it for continuing polymerization. After that, 15.174 grams
of styrene, 0.317 grams of sodium persulfate, 0.5 gram of sodium
dodecyl sulfate, 0.168 of 2-ethylhexyl acrylate (EHA), 1.575 grams
of methacrylic acid (MAA), 0.468 grams of n-butyl acrylate (BA),
7.299 grams of methyl methacrylate (MMA) and 38 grams DI water were
mixed and added to the reactor within 1 hr. The reaction mixture
was continuously stirred at 80.degree. C. for 3 hours. Then 4.604
grams of NaOH (50 wt % in water) and 63.490 grams of DI water were
added to the flask. All polymerization was carried out under a
nitrogen atmosphere. The latex was filtered through 400 mesh
stainless sieve. The D50 particle size measured by Malvern
Zetasizer was 175.2 nm (diameter), the pH was 12, and the solids
content was 29.19 wt %.
Example 17--Preparation of Acrylic Core-Shell Latex 17
[0067] 3.1 grams of Seed Latex 1 of Example 1 was added into a
4-neck round bottom flask (500 mL) equipped with a mechanical
stirrer, a reflux condenser and a nitrogen inlet tube under
nitrogen atmosphere. The flask was then heated to 80.degree. C. A
mixture of 1.756 grams of 1,3-butanediol dimethacrylate
(1,3-BDDMA), 0.569 grams of sodium persulfate, 1.5 grams of sodium
dodecyl sulfate, 1.156 grams of methacrylamide (MAAM), 12.435 grams
of n-butyl acrylate (BA) and 50.553 grams of methyl methacrylate
(MMA) in 99 grams of DI water were mixed thoroughly and then pumped
into the flask for a duration of 1.5 hours. The reaction mixture
was kept at 80.degree. C. for an additional 1 hour to allow it for
continuing polymerization. After that, 15.174 grams of styrene,
0.317 grams of sodium persulfate, 0.5 gram of sodium dodecyl
sulfate, 0.168 of 2-ethylhexyl acrylate (EHA), 1.575 grams of
methacrylic acid (MAA), 0.468 grams of n-butyl acrylate (BA), 7.299
grams of methyl methacrylate (MMA) and 38 grams DI water were mixed
and added to the reactor within 1 hr. The reaction mixture was
continuously stirred at 80.degree. C. for 3 hours. Then 1.836 grams
of NaOH (50 wt % in water) and 83.197 grams of DI water were added
to the flask. All polymerization was carried out under a nitrogen
atmosphere. The latex was filtered through 400 mesh stainless
sieve. The D50 particle size measured by Malvern Zetasizer was
185.2 nm (diameter), the pH was 11, and the solids content was
23.58 wt %.
Example 18--Preparation of Acrylic Core-Shell Latex 18
[0068] 3.1 grams of Seed Latex 1 of Example 1 was added into a
4-neck round bottom flask (500 mL) equipped with a mechanical
stirrer, a reflux condenser and a nitrogen inlet tube under
nitrogen atmosphere. The flask was then heated to 80.degree. C. A
mixture of 0.569 grams of sodium persulfate, 1.5 grams of sodium
dodecyl sulfate, 1.043 grams of methacrylamide (MAAM), 34.730 grams
of n-butyl acrylate (BA) and 36.201 grams of methyl methacrylate
(MMA) in 111 grams of DI water were mixed thoroughly and then
pumped into the flask for a duration of 1.5 hours. The reaction
mixture was kept at 80.degree. C. for an additional 1 hour to allow
it for continuing polymerization. After that, 15.174 grams of
styrene, 0.317 grams of sodium persulfate, 0.5 gram of sodium
dodecyl sulfate, 0.168 of 2-ethylhexyl acrylate (EHA), 1.575 grams
of methacrylic acid (MAA), 0.468 grams of n-butyl acrylate (BA),
7.299 grams of methyl methacrylate (MMA) and 38 grams DI water were
mixed and added to the reactor within 1 hr. The reaction mixture
was continuously stirred at 80.degree. C. for 3 hours. Then 1.836
grams of NaOH (50 wt % in water) and 63.621 grams of DI water were
added to the flask. All polymerization was carried out under a
nitrogen atmosphere. The latex was filtered through 400 mesh
stainless sieve. The D50 particle size measured by Malvern
Zetasizer was 178.2 nm (diameter), the pH was 11, and the solids
content was 26.77 wt %.
Example 19--Preparation of Acrylic Core-Shell Latex 19
[0069] 3.1 grams of Seed Latex 1 of Example 1 was added into a
4-neck round bottom flask (500 mL) equipped with a mechanical
stirrer, a reflux condenser and a nitrogen inlet tube under
nitrogen atmosphere. The flask was then heated to 80.degree. C. A
mixture of 0.569 grams of sodium persulfate, 1.5 grams of sodium
dodecyl sulfate, 1.017 grams of methacrylamide (MAAM), 1.879 grams
of 1,3-Butanediol dimethacrylate (1,3-BDDMA), 33.860 grams of
n-butyl acrylate (BA) and 35.295 grams of methyl methacrylate (MMA)
in 108 grams of DI water were mixed thoroughly and then pumped into
the flask for a duration of 1.5 hours. The reaction mixture was
kept at 80.degree. C. for an additional 1 hour to allow it for
continuing polymerization. After that, 15.174 grams of styrene,
0.317 grams of sodium persulfate, 0.5 gram of sodium dodecyl
sulfate, 0.168 of 2-ethylhexyl acrylate (EHA), 1.575 grams of
methacrylic acid (MAA), 0.468 grams of n-butyl acrylate (BA), 7.299
grams of methyl methacrylate (MMA) and 38 grams DI water were mixed
and added to the reactor within 1 hr. The reaction mixture was
continuously stirred at 80.degree. C. for 3 hours. Then 1.836 grams
of NaOH (50 wt % in water) and 68.128 grams of DI water were added
to the flask. All polymerization was carried out under a nitrogen
atmosphere. The latex was filtered through 400 mesh stainless
sieve. The D50 particle size measured by Malvern Zetasizer was
197.5 nm (diameter), the pH was 11.0, and the solids content was
27.20 wt %.
Example 20--Preparation of Ink Compositions
[0070] Magenta (M) ink compositions were prepared in accordance
with the general formulations shown in Tables 3, with the Latex
Polymer (2-19) being the only component modified. The Ink ID
numbering hereinafter refers to the Ink formulation of Table 3
combined with the specific Latex Polymer ID number used to prepare
the ink composition. For example, Latex 2 corresponds to Ink 2,
Latex 5 corresponds to Ink 5, and so forth.
TABLE-US-00005 TABLE 3 Ink Compositions Magenta (M) Ink Ingredient
Type (Wt %) HPF-M046 Pigment Pigment Solids 3 Dispersion Latex
Polymer (2-19) Core/Shell or Single- 6 phase Acrylic Latex Glycerol
Organic Co-solvent 6 LEG-1 Organic Co-solvent 1 Crodafos .TM. N3
Acid Surfactant 0.5 Surfynol .RTM. 440 Surfactant 0.3 Acticide
.RTM. B20 Biocide 0.22 Deionized water Solvent Balance HPF-M046 is
a Magenta Pigment dispersed with styrene-acrylic polymer dispersant
from DIC Corporation (Japan). Crodafos .TM. N3A is available from
Croda International Plc. (Great Britain). Surfynol .RTM. 440 is
available from Evonik, (Germany). Acticide .RTM. B20 is available
from Thor Specialties, Inc. (USA).
Example 21--Ink Composition Stability
[0071] Ten of the Ink Compositions (listed in Table 4 below)
prepared in accordance with Example 20 were evaluated for particle
stability. The stability data was collected and evaluated based on
accelerated shelf-life (ASL) testing, where the ink compositions
were evaluated at the time of formulation, and then subjected to 1
week of elevated temperature (60.degree. C.), and then the same
data was collected to see what had changed.
TABLE-US-00006 TABLE 4 ASL Stability of Latex Particles in Ink
Compositions % .DELTA. Ink ID/Latex ID Viscosity .DELTA. pH %
.DELTA. Mv % .DELTA. D95 2 -5.3 -0.15 -2.1 1.0 3 0 0.08 -5.3 -5.9 4
0 -0.10 2.5 20.6 8 -5.3 0.06 4.9 0 9 0 0.01 -0.7 2.3 10 0 -0.07
-6.3 -1.6 11 0 -0.08 5.8 8.4 12 0 0.05 -4.3 3.5 13* -5.3 0.01 -3.7
6.8 14* -5.3 -0.12 -3.5 -3.1 *Single-phase latex
Example 22--Ink Composition Printability Performance
[0072] Several of the Ink Compositions prepared in accordance with
Example 20 were evaluated for print performance. Additionally, for
comparison, a Control Ink Composition was prepared using a
commercially available acrylic latex binder (Jantex.RTM.
924--styrene butyl acrylic polymer binder; 320,000 Mw; Acid Number
17.4; Tg -15.degree. C.; available from Jantex Inks, USA). Print
performance evaluations were based on jetting from a thermal inkjet
pen (A3410, available from HP, Inc.), and the data collected based
on several parameters, including: [0073] Decap is determined using
the indicated time (1 second or 7 seconds) where nozzles remain
open (uncapped), and then the number of lines missing during a
print event are recorded. Thus, the lower the number the better for
decap performance [0074] Percent Missing Nozzles (% MNZ), which is
calculated based on the number of nozzles incapable of firing at
the beginning of a jetting sequence as a percentage of the total
number of nozzles on an inkjet printhead attempting to fire. Thus,
the lower the percentage number, the better the Percent Missing
Nozzles value. [0075] Drop Weight (DW), which is an average drop
weight in nanograms (ng) across the number of nozzles fired
measured using a burst mode or firing at 30 kHz. [0076] Drop Weight
2,000 (DW 2K), which is measured using a 2-drop mode of firing,
firing 2,000 drops and then measuring/calculating the average ink
composition drop weight in nanograms (ng) at 30 kHz. [0077] Drop
Velocity (DV), which measures an average velocity of the drop as
initially fired from the thermal inkjet nozzles measured in meters
per second (m/s). [0078] Decel, which measures the loss in drop
velocity (m/s) after 5 seconds of ink composition firing. 0
indicates no drop velocity loss. A positive number indicates how
much drop velocity was lost. "Miss" indicates missing, where data
was not collectable. [0079] Turn On Energy (TOE) Curve, which
measures the energy used to generate consistent ink composition
firing at a drop weight (DW) threshold. Lower energy to achieve
higher drop weights tend to be desirable, with DW increasing with
increased energy and then flattening out as still more energy is
applied. The TOE Curve Scale can be graded as Good, Soft, or Bad.
On a scale of 0-3, with 3 being the best, Good=3, Soft=2, Bad=1.
Furthermore, low drop volume is also notated for informational
purposes, as low drop volumes can be acceptable in some
circumstances.
[0080] The data collected is provided in Table 4, as follows:
TABLE-US-00007 TABLE 4 Printability Performance Ink ID/ Decap Decap
DW DW 2K DV Decel TOE Latex ID (1 s) (7 s) % MNZ (ng) (ng) (m/s)
(-.DELTA.m/s) Curve Control Ink 21 43 0.5 11.7 12.8 10.2 0.2 Soft 2
24 25 1 12.5 12.9 12 0 Good 3 15 32 0 12.6 12.8 12.1 0 Good 4 22 32
0 12.4 12.6 12 0 Good 5 15 31 11 12.4 13.6 9 0.2 Good 6 31 39 8.5
12 13 7.4 0 Good 7 18 45 6 13 13.5 10.9 0 Good 8 24 39 45.8 11.2
12.1 7.7 0 Good, Low DV 9 32 46 2.1 11.4 12 7.9 0 Good, Low DV 10
14 24 0 12.7 12.5 12.5 0 Good 11 25 50 1 11.7 10.9 7.5 0 Good, Low
DV 12 19 42 0 12.4 11.6 11.9 0 Good 13* 14 25 0 12.1 13.4 11.7 0
Good 14* 18 28 0 12.3 11.8 11.7 0 Good 15 50 50 41 2.7 5.6 0 Miss
Bad 16 29 50 7.5 11 11.8 10.6 0 Soft 17 35 50 29 11.4 13.3 2.8 0.5
Bad 18 28 50 23 10.8 13.5 4.5 0.2 Bad 19 29 50 10 11.5 12.6 7.2 0.2
Soft *Single-phase latex
[0081] As can be seen in Table 4 above, many of the ink
compositions with the various corresponding acrylic latex
core-shell particles showed reasonable or good print performance
from a thermal inkjet printhead using varied testing protocols,
with Latexes 2-4 and 12-14 providing particularly good results when
combining both Decap and TOE Curve performance. Some of the ink
compositions had acceptable or reasonable TOE Curve data, but the
drop weight (DW) was slightly lower. TOE Curve data is considered
Acceptable or Good when lower levels of energy are used to achieve
higher drop weights (DW) as measured in nanograms (ng). For
example, achieving a drop weight (DW) of 10 ng or above at an
energy level 0.75 Joule may be considered "Good" TOE (with DW
getting larger with more energy input until the curve flattens out)
for this particular ink composition. Achieving a drop weight (DW)
of 8 ng or above at an energy level 0.75 Joule may be considered
"Acceptable" TOE (with DW getting larger with more energy input
until the curve flattens out). In further detail, however, lower
drop weights (DW) below 8 ng or even below 7 ng at 0.75 Joules may
provide for a "Good" TOE as long as the drop weights continue to
get larger as the energy increases and then flatten out at an
acceptable drop weight. Achieving a drop weight below 7 ng at an
energy level of 0.75 Joule may be considered "Good" TOE (with DW
getting larger with more energy input until the curve flattens out,
as long as the drop weight is acceptable for inkjet printing
applications).
Example 23--Washfastness Durability
[0082] Several of the Ink Compositions (Inks 2-19) prepared in
accordance with Example 20 were evaluated for washfastness
durability when printed on fabric. Additionally, for comparison, a
Control Ink Composition (Control Ink) was prepared using a
commercially available acrylic latex binder (Jantex.RTM.
924--styrene butyl acrylic polymer binder; 320,000 Mw; Acid Number
17.4; Tg 15.degree. C.; available from Jantex Inks, USA). The Ink
Compositions were jetted (3 dots per pixel or "dpp") onto gray
cotton fabric print media at 20 grams per meter (gsm) using a
thermal inkjet pen (A3410, available from HP, Inc.). Individual
samples were cured at either 80.degree. C. or at 150.degree. C. for
3 minutes. Printed samples were washed 5 times with a conventional
washer at 40.degree. C. with detergent and air drying between each
wash. Each sample was measured for OD and Lab before and after the
5 washes at 40.degree. C. using Tide.RTM. laundry detergent
available from Proctor and Gamble, Cincinnati, Ohio, USA. After the
five cycles, optical density (OD) and L*a*b* values were measured
for comparison, and delta E (.DELTA.E) values were calculated using
the 1976 standard denoted as .DELTA.E.sub.CIE. Results are depicted
in Tables 5A-5B, as follows:
TABLE-US-00008 TABLE 5A Gray Cotton Print Media; Cured at
80.degree. C. for 3 Minutes OD OD Ink ID/Latex ID (Pre-wash) (5
washes) % .DELTA.OD .DELTA.E.sub.CIE Control Ink 1.014 0.862 -15
7.6 2 1.022 0.762 -25.5 14.5 3 1.025 0.758 -26.1 14 4 1.028 0.778
-24.3 13.5 5 1.029 0.574 -44.2 25.8 6 1.033 0.791 -23.5 12.6 7
1.013 0.828 -18.3 9.6 8 1.012 0.814 -19.6 11.8 9 1.025 0.785 -23.5
12.6 10 1.034 0.823 -20.4 10.6 11 1.033 0.865 -16.2 9 12 1.021
0.817 -20 11.6 13* 1.037 0.800 -22.8 12.1 14* 1.038 0.869 -16.3 9.2
15 0.994 0.810 -18.5 10.1 16 1.006 0.748 -25.6 12.3 17 1.005 0.501
-50.1 29 18 1.012 0.680 -32.9 17.4 19 1.003 0.599 -40.2 22.8
*Single-phase latex
TABLE-US-00009 TABLE 5B Gray Cotton Print Media; Cured at
150.degree. C. for 3 Minutes OD OD Ink ID/Latex ID (Pre-wash) (5
washes) % .DELTA.OD .DELTA.E.sub.CIE Control Ink 1.013 0.996 -1.7
1.8 2 1.034 0.853 -17.5 8.8 3 1.038 0.866 -16.6 7.6 4 1.028 0.845
-17.8 9.0 5 1.040 0.827 -20.4 9.1 6 1.034 0.889 -14.0 7.6 7 1.034
0.933 -9.8 4.6 8 1.016 0.874 -14.0 7.3 9 1.032 0.885 -14.2 6.3 10
1.033 0.895 -13.3 7.2 11 1.035 0.925 -10.6 6.2 12 1.022 0.888 -13.1
7.3 13* 1.039 0.910 -12.4 6.3 14* 1.030 0.917 -10.9 5.7 15 0.985
0.904 -8.2 4.4 16 1.015 -0.906 -10.7 5.9 17 1.005 0.942 -6.3 3.8 18
1.013 0.918 -9.4 4.6 19 1.003 0.922 -8.1 3.7 *Single-phase
latex
[0083] As can be seen in the data presented in Tables 5A-5B,
acceptable washfastness for individual ink compositions with a
.DELTA.E around 5, e.g., ranging from 3.7 to 9, was verified by
comparing pre-wash optical density (OD) with post-wash OD and
.DELTA.E.sub.CIE or .DELTA.E2000 calculated from pre- and post-wash
L*a*b* values. Thus, most core-shell latex polymers have reasonable
washfastness with a .DELTA.E around 5, without external
cross-linkers. Some of them have better washfastness such as
Latexes 17-19.
[0084] As can be seen from the data collected above, most of the
latex-based ink compositions printed on gray cotton fabric
substrate showed good durability even without external
crosslinkers, with a few showing excellent durability which is
similar to commercially available Jantex.TM. polymers, available
from JANTEX INKS, (USA), which includes melamine crosslinkers that
can be toxic.
Example 24--Acrylic Core/Shell Latex Particles Vs. Acrylic
Single-Phase Latex Particles Compared Using TOE Curve Analysis
[0085] Printability with respect to Turn On Energy (TOE) can be
evaluated using a TOE curve, where the amount of energy (Joules)
was evaluated to determine where a more consistent ink composition
firing at a drop weight (DW) can be achieved. With this evaluation,
higher drop weights achieved at lower energy levels is considered
good. At some point the drop weight levels off so that more energy
does not generate a greater drop weight. At the location on the TOE
curve where an acceptable drop weight is achieved, and where it is
starting to flatten out, can indicate an ink composition that has a
desirable TOE curve. Stated another way, higher TOE curve is
better, meaning higher drop weight at a given firing energy input
level. With this analysis, it was found that adding even a thin
acrylic latex polymer shell to a latex polymer core tended to
increase drop weight and reduce energy input.
[0086] The data collected for six (6) different ink compositions is
shown in FIG. 3. Two of the ink compositions (Ink 13 and Ink 14)
included acrylic single-phase latex particles, and the remaining
four ink compositions (Ink 2, Ink 3, Ink 4, and Ink 10) included
acrylic core/shell latex particles. As can be seen in the data, in
all four cases, the higher curves were with the ink compositions
with the core/shell latex particles.
[0087] To compare one set of curves, the TOE curve of Ink 10 can be
compared to the TOE curve of Ink 14. These two ink compositions
include a latex with the same acrylic latex core (Latex 14 is 100
wt % "core"; Latex 10 includes the same core with a 15 wt % shell
thereon), and the TOE curve for Ink 10 is better at every point
along the curve where the curve starts to flatten out (shown in
FIG. 3 at (B) with an expanded Y-axis to more fully show the
separation between the respective TOE curves).
[0088] Another comparison to consider is to compare Ink 13 with 100
wt % acrylic single-phase latex particles to Inks 2-4, which
include different weight percentages of acrylic shell, but are
otherwise similar (except that the methacrylic acid is included in
the "core" of Ink 13 to provide dispensability). More specifically,
Ink 2 included 25 wt % shell polymer, Ink 3 included 35 wt % shell
polymer, and Ink 4 included 15 wt % shell polymer. The Ink that
performed the best in the TOE curve analysis was Ink 3, which had
the thickest acrylic shell, but even at 15 wt % shell as in Ink 4,
the TOE curve was better than with Ink 13.
[0089] These comparisons tend to show that jettability can be
improved with core-shell latexes as opposed to similar single-phase
latexes. In further detail, the core-shell latexes had a higher
surface Tg than the single-phase latexes, which may have also
contributed to the improved jettabilty as illustrated by the TOE
curve data.
[0090] While the present technology has been described with
reference to certain examples, various modifications, changes,
omissions, and substitutions can be made without departing from the
spirit of the disclosure. It is intended, therefore, that the
disclosure be limited only by the scope of the following
claims.
* * * * *