U.S. patent application number 10/725701 was filed with the patent office on 2004-06-10 for ink-jet media having improved water fastness.
This patent application is currently assigned to Arkwright, Inc.. Invention is credited to Conforti, Robert M., Risen, William M. JR., Xu, Zhong.
Application Number | 20040109959 10/725701 |
Document ID | / |
Family ID | 32474558 |
Filed Date | 2004-06-10 |
United States Patent
Application |
20040109959 |
Kind Code |
A1 |
Xu, Zhong ; et al. |
June 10, 2004 |
Ink-jet media having improved water fastness
Abstract
Ink-jet recording media capable of producing high quality color
images that have good water-fastness are provided. The ink-jet
recording media comprise a base substrate material coated with an
ink-receptive layer comprising a polymer film-forming binder and
certain dye fixative particles. These particles having novel dye
fixative properties include silica particles with pendant
polyvinylamine, silica particles with pendant polyethyleneimine,
and silica particles with pendant trimethylammonium. Also, organic
metallic complexes can be added to the ink-receptive layer. The
resulting ink-jet recording media can produce images having high
color vibrancy and water-fastness.
Inventors: |
Xu, Zhong; (Worcester,
MA) ; Conforti, Robert M.; (Wakefield, RI) ;
Risen, William M. JR.; (Rumford, RI) |
Correspondence
Address: |
BARLOW, JOSEPHS & HOLMES, LTD.
101 DYER STREET
5TH FLOOR
PROVIDENCE
RI
02903
US
|
Assignee: |
Arkwright, Inc.
|
Family ID: |
32474558 |
Appl. No.: |
10/725701 |
Filed: |
December 2, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60430218 |
Dec 2, 2002 |
|
|
|
Current U.S.
Class: |
428/32.1 |
Current CPC
Class: |
Y10T 428/24802 20150115;
B41M 5/502 20130101; Y10S 428/914 20130101; B44C 1/1716 20130101;
Y10T 428/2486 20150115; Y10T 428/1486 20150115; D06P 5/003
20130101; B41M 5/0256 20130101; Y10T 428/2822 20150115 |
Class at
Publication: |
428/032.1 |
International
Class: |
B32B 003/00 |
Claims
What is claimed is:
1. An ink-jet recording medium, comprising a base substrate having
a surface coated with an ink-receptive layer comprising at least 5%
by weight of a polymer film-forming binder and at least 5% by
weight of dye fixative particles based on total dry weight of the
ink-receptive layer, the dye fixative particles being selected from
the group consisting of silica particles with pendant
polyvinylamine, silica particles with pendant polyethyleneimine,
silica particles with pendant trimethylammonium chloride, silica
particles with pendant pyridine groups, and polystyrene particles
with pendant piperidinomethyl groups.
2. The ink-jet recording medium of claim 1, wherein the
ink-receptive layer further comprises a non-polymeric organic metal
complex.
3. The ink-jet recording medium of claim 2, wherein the organic
metal complex is a an amine complex containing zirconium.
4. The ink-jet recording medium of claim 1, wherein the
ink-receptive layer further comprises a plasticizer.
5. The ink-jet recording medium of claim 1, wherein the base
substrate is a paper.
6. The ink-jet recording medium of claim 5, wherein the paper has a
glossy surface finish.
7. The ink-jet recording medium of claim 1, wherein the base
substrate is a film.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 60/430,218 having a filing date of Dec. 2, 2002,
the entire contents of which are hereby incorporated by
reference.
BACKGROUND OF THE INVENTION
[0002] The present invention generally relates to imaging media
suitable for use with narrow and wide format ink-jet color
printers. Particularly, the invention relates to ink-jet recording
media comprising a substrate material coated with an ink-receptive
layer comprising a polymer film-forming binder and certain dye
fixative particles. The media can be used to produce images having
high color quality and good water-fastness.
[0003] In recent years, the market for ink-jet color prints having
good water-fastness properties has grown. The ink-jet industry is
constantly looking to develop new ink-jet media that will accept
and hold the ink when the printed media is exposed to water and
other liquids. These properties are important for ink-jet media
used in indoor applications such as media used to record digital
photographs, and media used to make greeting cards, calendars,
invitations, announcements, leaflets, and the like. Good
water-fastness properties are also important for media used in
outdoor applications such as outdoor signs, posters, advertising
banners, and other display graphics. Narrow and wide format color
ink-jet printers are used to produce such imaged media products
depending upon the size of the media and intended end-use
application.
[0004] Generally, in an ink-jet printing process, liquid ink is
squirted through very fine nozzles in a printer to form an image
(print) directly on a recording medium. Typically, the ink-jet
recording medium is a film or paper substrate coated with a
specially designed ink-receiving coating. The quality of the final
image is partly dependent upon the structure of the ink-jet
recording medium particularly the coating composition and substrate
material.
[0005] The inks used in most ink-jet printers are aqueous-based
inks containing molecular dyes and/or pigmented colorants. Water is
the major component in aqueous-based inks and small amounts of
water-miscible solvents such as glycols and glycol ethers also may
be present. Other ink-jet inks used in the industry are non-aqueous
based inks containing organic vehicles. During the printing step,
dyes or colorants from the ink can penetrate into the ink-receptive
coating on the medium. Water and other solvents can evaporate from
the printed medium as the medium is dried. By "ink-receptive
coating" or "ink-receptive layer" as used herein, it is meant a
coating or layer that is capable of receiving (absorbing) at least
aqueous-based inks. The ink-receptive coating or layer may also
receive non-aqueous based inks in some instances.
[0006] In the past, many approaches have been employed to develop
ink-jet media capable of recording images having high color
brilliance, fidelity, sharpness, and water-fastness as well as
other desirable properties. Although some conventional ink-jet
media may be effective in some instances in producing such color
images, there is a need for an improved ink-jet recording medium.
The present invention provides such a medium. These and other
objects, features, and advantages of this invention are evident
from the following description.
SUMMARY OF THE INVENTION
[0007] The present invention relates to an ink-jet recording
medium, comprising a base substrate having a surface coated with an
ink-receptive layer comprising at least 5% by weight of a polymer
film-forming binder and at least 5% by weight of dye fixative
particles based on total dry weight of the ink-receptive layer. The
base substrate can be any suitable material such as a paper or
film. Papers having a glossy surface finish can be used. The dye
fixative particles have novel dye fixative properties and are
selected from the group consisting of silica particles with pendant
polyvinylamine, silica particles with pendant polyethyleneimine,
silica particles with pendant trimethylammonium chloride, silica
particles with pendant pyridine groups, and polystyrene particles
with pendant piperidinomethyl groups.
[0008] The ink-receptive layer may further comprise a non-polymeric
organic metal complex such as an amine complex containing
zirconium. Other additives such as ultraviolet light stabilizers
may be included in the ink-receptive layer.
DETAILED DESCRIPTION OF THE INVENTION
[0009] The present invention relates to an ink-jet recording medium
comprising a substrate material coated with an ink-receptive
composition comprising a film-forming binder and certain particles
having novel dye fixative properties (hereinafter referred to as
novel dye fixative particles or "NDFP").
[0010] The ink-jet recording media of the present invention are
constructed using a suitable substrate material. For example, the
substrate may be a paper material. Paper substrates are known in
the ink-jet industry and any suitable paper may be used in the
present invention. For example, plain papers, clay-coated papers,
or polyolefin-coated papers may be used. The paper substrate may
have different surface finishes. For instance, glossy paper
substrates, wherein the substrate has a relatively high surface
gloss may be used. In other embodiments, satin-like or semi-glossy
substrates may be used. In still other embodiments, matte-like
substrates may be used.
[0011] Alternatively, the substrate may be a polymeric film
comprising a polymer, such as, polyethylene, polypropylene,
polyester, naphthalate, polycarbonates, polysulfone, polyether
sulfone, poly(arylene sulfone), cellulose triacetate, cellophane,
polyvinyl chloride, polyvinyl fluoride, polyimide, polyesters,
polystyrene, polyacrylics, polyacetals, ionomers, and mixtures
thereof. In other instances, a metal foil such as aluminum foil or
a metal-coated material can be used as the substrate.
[0012] The substrate material has two surfaces. The first surface,
which is coated with the ink-receptive layer or layers in
accordance with this invention, may be referred to as the "front"
or "imaging" surface. The second surface, which is opposite to the
first surface, may be referred to as the "back" or "non-imaging"
surface.
[0013] The substrate material is coated with an ink-receptive
composition in accordance with the present invention to produce an
ink-receptive layer. The ink-receptive layer comprises about 5% to
about 95% by weight polymer film-forming binder and about 95% to
about 5% by weight novel dye fixative particles based on total dry
weight of the ink-receptive layer. The resulting ink-receptive
layer has a porous film-like structure with good cohesiveness and
mechanical strength.
[0014] Suitable polymer film-forming binders include, for example,
those selected from the group consisting of polyvinyl alcohols;
modified polyvinyl alcohols (e.g., carboxyl-modified PVA,
silicone-modified PVA, maleic acid-modified PVA, and itaconic
acid-modified PVA); poly(vinyl pyrrolidone); vinyl pyrrolidone
copolymers; poly(2-ethyl-2-oxazoline); poly(ethylene oxide);
poly(ethylene glycol); poly(acrylic acids); starch; modified starch
(e.g., oxidized starch, cationic starch, hydroxypropyl starch, and
hydroxyethyl starch), cellulose; cellulose derivatives (e.g.,
oxidized cellulose, cellulose ethers, cellulose esters, methyl
cellulose, hydroxyethyl cellulose, carboxymethyl-cellulose, benzyl
cellulose, phenyl cellulose, hydroxypropyl cellulose, ethyl
hydroxyethyl cellulose, hydroxyethyl methyl cellulose,
hydroxypropyl methyl cellulose, hydroxy butylmethyl cellulose,
dihydroxypropyl cellulose, hydroxypropyl hydroxyethyl cellulose,
chlorodeoxycellulose, aminodeoxycellulose, diethylammonium chloride
hydroxyethyl cellulose, hydroxypropyl trimethyl ammonium chloride
hydroxyethyl cellulose; polyamides; alginates and water-soluble
gums; dextrans; carrageenan; xanthan; chitin; proteins; gelatins;
agar; and mixtures thereof.
[0015] In one embodiment, a water-insoluble binder such as a
polyamide resin is used as the film-forming binder. The
ink-receptive layer of this invention further includes novel dye
fixative particles (NDFP) as described in further detail below.
[0016] A. Inorganic NDFP
[0017] The following inorganic NDFP can be used in the
ink-receptive layer: i) silica particles with pendant
polyvinylamine, and ii) silica particles with pendant
polyethyleneimine. These particle materials currently are available
as CuWram products from Purity Systems, Inc. (Missoula, Mont.) and
are available in an initial particle size of about 165-200 mesh, so
that particles of about 75 microns are readily available. Grinding
of the particles may be necessary depending on the intended media
application and coating smoothness requirement. Alternatively, such
NDFP can be produced with smaller silica particles to obtain
particles in the 0.05 to 75 .mu.m range. These particles currently
are produced and sold for a variety of non media applications, such
as metal ion recovery, chemical catalysis, etc., but the inventors
have discovered that they can be used in combination with a polymer
binder to form an ink-receptive layer having desirable
properties.
[0018] Also, trimethylammonium chloride propylsilicate particles
designed and used for chemical separations in the chemical analysis
and pharmaceutical synthesis areas (available from Silicycle, Inc.,
Quebec City, Canada as "Si-TMA Chloride) can be used in the
ink-receptive layer.
[0019] Additional compositions that are appropriate for achieving
the water-fastness include particles based on alumina with attached
dye-mordanting functional groups, other than OH groups, such as
those based on amine, quaternized amine, pyrridinium, or
pyrrolidone types.
[0020] Additional compositions that are useful for achieving the
water-fastness include silica-, alumina-, and/or titania-based
particles that are attached to polymeric molecules that can
comprise the matrix of the ink jet-receptive film. Still other
compositions of this type are characterized further by having the
inorganic or polymeric molecules comprise amine or quaternary amine
mordanting groups. Examples of the compositions of these types
include silica-based particles that are reacted first with
aminoalkyltriethoxysilane molecules and then subsequently with a
less than stoichiometric (NCO to NH.sub.2) amount of
isocyanate-terminated oligomers or polymers to form a NDFP attached
to a polymer or polymeric composite that comprises the matrix
material when used in an ink jet-receiving film. Other examples
include silica-based particles with pendant mordant groups based on
pyridine, pyridinium, polyvinylpyridine or
polyvinylpyrrolidone.
[0021] A range of NDFP materials can be synthesized within this
invention which have inorganic particles with attached polymeric or
non-polymeric dye-mordanting functionalities.
[0022] B. Non-Polymeric Organic Metal Complexes
[0023] In addition to the above-described NDFP and polymer
film-forming binders, the ink-receptive layer may contain organic
metal complexes. Organic metal complexes have been widely used as
adhesion promoters for many industry coatings on plastic or metal
surfaces. It has been found that these organic metal complexes can
fix ink-jet dyes effectively. One example of such an organic metal
complex is Chartwell B-515.1, available from Chartwell
International, Inc. (North Attleboro, Mass.), which is a bimetallic
amine complex containing the metal zirconium.
[0024] C. Other Additives
[0025] Also, the ink-receptive layer of this invention may contain
additional dye-fixative additives such as an inorganic metal
complex. For example, an aluminum chlorohydrol solution available
from Grace Davison (Columbia, Md.) as Sylojet A200 can be used. The
chemical structure of Sylojet A200 is Al.sub.2(OH).sub.5Cl. Also,
an amine-functionalized silica aerogel with a functionality of at
least 0.7 mmol amine per gram of a silica aerogel with an initial
surface area of at least 250 m.sup.2/g can be used. This aerogel
material is available from Industrial Science and Technology
Network, Inc.
[0026] The ink-receptive layer may further contain additives such
as inorganic and organic pigments, plasticizers, surface active
agents that control the wetting or flow behavior of the coating
solutions, antistatic agents, suspending agents, antifoam agents,
acidic compounds to control pH, optical brighteners, ultraviolet
light (UV) blockers/stabilizers, and the like. In cases where UV
stability is required, it particularly is contemplated that
alumina-containing particles can be added to the ink-receptive
layer.
[0027] The ink-receptive coating is applied to the front surface of
the substrate using conventional methods to form an uniform
ink-receptive layer. Suitable methods for coating the base
substrate with the ink-receptive coating include, for example,
Meyer-rod, slot-die, roller, blade, wire bar, dip, solution
extrusion, reverse roll, air-knife, curtain slide, doctor-knife,
and gravure methods. The slot-die and Meyer-rod methods are
preferred because of their ease of use. Then, the coating is dried
using forced hot air ovens or other suitable drying methods. It is
also recognized that the base substrate may be coated with multiple
ink-receptive layers. For example, in some instances, it may be
desirable to include one or more under layers or primer coatings
between the substrate and above-described ink-receptive layer.
Also, it may be desirable to coat top ink-receptive or protective
layers over the above-described ink-receptive layer.
[0028] The ink-receptive coatings of this invention provide good
ink absorption layers when applied to the substrate. As discussed
above, the particles in the ink-receptive layer can have functional
groups attached to them to help absorb the ink dyes or pigments.
Furthermore, the particles and film-forming binder form a porous
coating structure that efficiently absorbs water or other ink
solvents. The particles have a high surface area and form
interstitial pores or voids that are effective in wicking and
retaining the ink. A conventional ink-jet printer can be used to
print an image onto the ink-receptive coating. When the ink is
impinged on the coating, it can enter the interstitial voids and
spaces in the coating structure. The film-forming binder holds the
particles in place and provides cohesion to the layer and does not
detrimentally affect the porosity of the layer.
[0029] The resulting ink-jet recording media can be imaged by
narrow and wide format ink-jet printers with aqueous or pigmented
color inks to provide printed images having dense and bright
colors, high color sharpness, and good water-fastness.
Particularly, the ink-jet recording media of this invention are
characterized by having a percentage loss of color optical density
of less than about 20% as demonstrated in the Examples below.
[0030] The present invention is further illustrated by the
following examples using the below-described test methods, but
these examples should not be construed as limiting the scope of the
invention.
[0031] Test Methods
[0032] Water-Fastness
[0033] Ink jet image colors fade under exposure to water. A
commonly used method for measuring color is the color optical
density. In order to quantitatively measure the water-fastness,
optical density values of red, green, blue, cyan, magenta, yellow
and composite black colors are measured before and after the
samples are washed with water. The sum of the optical densities of
these colors is used to characterize the overall color vibrancy.
Percentage loss of optical density is a measure of the color
difference between the washed and unwashed imaged samples. Samples
and colors having poor water-fastness have larger percentage loss
values. The values of optical density were measured with a X-Rite
408 Colorimeter (X-Rite, Inc.)
[0034] The samples were printed with multicolor test patterns using
an HP 970CSE desktop ink-jet printer in a "photo paper" mode. The
water-fastness of the imaged samples was determined by exposing the
samples to flowing water over a period of 10 minutes under the room
temperature. The optical density values of the samples were
measured before and after being washed with water. The percentage
loss of optical density of the samples was calculated as described
above.
EXAMPLES
Example 1
[0035] In this Example 1, the following coating formulation was
prepared. The weight percentages of the components in the coating
are approximate weights based on total weight of the coating
formulation.
1 Ink-Receptive Coating Water 28% Ethanol 47% Elvamide 8023.sup.1
5% Orgasol 3501.sup.2 17.5% VP-1.sup.3 2.5% .sup.1Polyamide binder
resin, available from DuPont (Wilmington, Delaware).
.sup.2Polymeric particles of a polyamide, available from Elf
Atochem North America. .sup.3Silica particles with pendant
polyvinylamine, Purity Systems, Inc. (Missoula, MT).
[0036] The above-described ink-receptive coating was applied to a
base substrate as further described below. The resulting
ink-receptive layer contained about 70 weight percent of polyamide
particles (Orgasol 3501) and 10 weight percent of silica particles
with pendant polyvinylamine (VP-1); and about 20 weight percent of
a water-insoluble polymeric binder (Elvamide 8023) based on total
dry weight of the ink-receptive layer.
Example 2
[0037] In this Example 2, the following coating formulation was
prepared.
2 Ink-Receptive Coating Water 28% Ethanol 47% Elvamide 8023 5%
Orgasol 3501 17.5% Derivatized Silica Gel, TMA Chloride.sup.4 2.5%
.sup.4Silica particles with pendant trimethylammonium chloride,
Silicycle, Inc. (Quebec, Canada).
[0038] The above-described ink-receptive coating was applied to a
base substrate as further described below. The resulting
ink-receptive layer contained about 70 weight percent of polyamide
particles (Orgasol 3501) and 10 weight percent of silica particles
with pendant trimethylammonium chloride (Derivatized Silica Gel,
TMA Chloride); and about 20 weight percent of a water-insoluble
polymeric binder (Elvamide 8023) based on total dry weight of the
ink-receptive layer.
Example 3
[0039] In this Example 3, the following coating formulation was
prepared.
3 Ink-Receptive Coating Water 28% Ethanol 47% Elvamide 8023 5%
Orgasol 3501 17.5% Derivatized Silica Gel, Pyridine-2.sup.5 2.5%
.sup.5Silica particles with pendant pyridine, Silicycle, Inc.
(Quebec, Canada).
[0040] The above-described ink-receptive coatings were applied to a
base substrate as further described below. The resulting
ink-receptive layer contained about 70 weight percent of polyamide
particles (Orgasol 3501) and 10 weight percent of silica particles
with pendant pyridine group (Derivatized Silica Gel,
Pyridine-2);
[0041] and about 20 weight percent of a water-insoluble polymeric
binder (Elvamide 8023) based on total dry weight of the
ink-receptive layer.
Example 4
[0042] In this Example 4, the following coating formulation was
prepared.
4 Ink-Receptive Coating Water 28% Ethanol 47% Elvamide 8023 5%
Orgasol 3501 17.5% Piperidinomethyl Resin.sup.6 2.5%
.sup.6Polystyrene particles with pendant piperidinomethyl group,
Glycopep Chemicals, Inc. (Chicago, IL).
[0043] The above-described ink-receptive coatings were applied to a
base substrate as further described below. The resulting
ink-receptive layer contained about 70 weight percent of polyamide
particles (Orgasol 3501) and 10 weight percent of polystyrene
particles with pendant piperidinomethyl group (Piperidinomethyl
Resin); and about 20 weight percent of a water-insoluble polymeric
binder (Elvamide 8023) based on total dry weight of the
ink-receptive layer.
Prophetic Example
[0044] In this Example, the following coating formulation could be
prepared.
5 Ink-Receptive Coating Water 28% Ethanol 47% Elvamide 8023.sup.1
5% VP-1.sup.2 20% .sup.1Polyamide binder resin, available from
DuPont (Wilmington, Delaware). .sup.2Silica particles with pendant
polyvinylamine, Purity Systems, Inc. (Missoula, MT).
[0045] The above-described ink-receptive coating could be applied
to a base substrate as described below. The resulting ink-receptive
layer would contain about 80 weight percent of silica particles
with pendant polyvinylamine (VP-1) and about 20 weight percent of a
water-insoluble polymeric binder (Elvamide 8023) based on total dry
weight of the ink-receptive layer.
Comparative Example A
[0046] In this Comparative Example A, the following coating
formulation was prepared.
6 Ink-Receptive Coating Water 28% Ethanol 47% Elvamide 8023 5%
Orgasol 3501 17.5% Gasil IJ-35.sup.7 2.5% .sup.7Silica gel
particles, Ineos Silicas Americas LLC (Joliet, IL).
[0047] The above-described ink-receptive coating was applied to a
base substrate as further described below. The resulting
ink-receptive layer contained about 70 weight percent of polyamide
particles (Orgasol 3501) and 10 weight percent of regular silica
gel particles (Gasil IJ-35); and about 20 weight percent of a
water-insoluble polymeric binder (Elvamide 8023) based on total dry
weight of the ink-receptive layer.
Comparative Example B
[0048] In this Comparative Example B, the following coating
formulation was prepared.
7 Ink-Receptive Coating Water 28% Ethanol 47% Elvamide 8023 5%
Orgasol 3501 17.5% Luvicross M.sup.8 2.5% .sup.8Crosslinked
polyvinylpyrrolidone particle, BASF (Mount Olive, NJ).
[0049] The above-described ink-receptive coating was applied to a
base substrate as further described below. The resulting
ink-receptive layer contained about 70 weight percent of polyamide
particles (Orgasol 3501) and 10 weight percent of crosslinked
polyvinylpyrrolidone particle (Luvicross M); and about 20 weight
percent of a water-insoluble polymeric binder (Elvamide 8023) based
on total dry weight of the ink-receptive layer.
[0050] In above examples, the ink-receptive coating was applied to
a polyethylene-coated paper substrate using a Meyer metering rod
and dried in an oven at 110.degree. C. for about 2 minutes. The dry
weight of the ink-receptive coating was about 20 gsm. Per the Test
Methods described above, images (prints) were produced on the
coated ink-jet recording media, and the images were evaluated for
water-fastness. The results are reported below in Table I.
8TABLE I Percentage Loss of ID Type of surface modified particles
Color Optical Density Example 1 silica particles with pendant 1%
polyvinylamine (VP-1) Example 2 silica particles with pendant 5%
trimethylammonium chloride (Derivatized Silica Gel, TMA Chloride)
Example 3 Silica particles with pendant 13% pyridine group
(Derivatized Silica Gel, Pyridine-2) Example 4 Polystyrene
particles with pendant 16% piperidinomethyl group (Piperidinomethyl
Resin) Comparative Silica gel particles (Gasil IJ-35) 24% Example A
Comparative Crosslinked polyvinylpyrrolidone 24% Example B
particles (Luvicross M)
[0051] It is appreciated by those skilled in the art that various
changes and modifications can be made to the description and
illustrated embodiments herein without departing from the spirit of
the present invention. All such changes and modifications are
intended to be covered by the appended claims.
* * * * *