Note: Descriptions are shown in the official language in which they were submitted.
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TEXTILE PRINTING SUBSTRATE
Background
The present invention generally relates to the printing of textiles.
Due to the many various types of textile substrates that printing is performed
on, and the many various types of printing inks, is often difficult to obtain
consistency
in the quality of the print between printed textiles. These complications are
magnified by the difficulty of obtaining a quick drying, sharp focused print
on textile
materials in general. Additionally, pigment based inks require additional
binders, and
most dyes require an additional dye fixing process when printing on a textile.
Therefore, there is a need for materials that allow the printing on various
different types of textiles with various different types of printing inks
thereon,
enhance the fast pickup of the ink on the textile and help in obtaining sharp
well
defined patterns, and assist in the reduction of the need for special binders
or fixing
processes for printing on textiles.
Detailed Description
The present invention is directed to the treatment of a textile substrate for
the
subsequent reception of a printing ink, such as ink from an ink jet printer.
In one
embodiment, the-treatment of the present invention includes the placement of a
treatment of a dye fixing/receiving composition on the surface of the textile
substrate
which is to receive the printed ink, prior to placement of the printing ink on
the textile
substrate. The dye fixing/receiving composition generally includes a dye
fixing agent
and an ink receiving agent. In one embodiment, the dye fixing/receiving
compound
can include a compatible resin binder. Additional additives can be used with
the dye
fixing/receiving composition, such as whitening agents, antimicrobial agents,
light
stabilizers/UV absorbers, and lubricants. The textile with the dye
fixing/receiving
agent thereon can also be subjected to a mechanical treatment to improve the
flexibility and surface touch of the treated textile. In another embodiment,
the
treatment of the present invention includes the placement of a UV absorber on
the
surface of the textile substrate which is to receive the printed ink, prior to
placement
of the printing ink on the textile substrate.
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The textile substrate contributes to whiteness, texture, and physical porous
structure for holding the ink. The textile substrate can be a knit, woven,
nonwoven,
or similar type textile. In one embodiment, the textile substrate is a tight
woven
fabric. It has been found that textile substrates formed of dull white opaque
textured
or spun yarns provide a good substrate for the present invention. For example,
tightly woven fabrics from cotton staple yarns provide opacity and absorbency
that
assists in the functions of the treatment of the textile substrate. The
material of the
textile substrate can be synthetic, natural, or regenerated. In most cases, it
is the
treatment that receives a majority of the dyes in the ink. It has been found
that the
present invention with a bright white substrate provides better brightness and
contrast for the resulting image on the textile. The surface touch of the
textile
substrate, before and after treatment and printing, can be greatly improved by
surface sanding, especially by the use of fine grade sanding media prior to
treatment
of the substrate. Sanding with fine grid sanding media, such as fine diamond,
gives
the fabric surface fine short fibers, which is responsible for smooth and soft
touch.
In one embodiment, the hairiness of the textile substrate was measured with
average
fiber heights of about 0.15 millimeters or greater, and an average level of
about 0.3
- 0.8 millimeters was preferred. In these hairiness levels, the present
inventors
have discovered that the inkjet printing process or print quality are not
effected.
The dye fixing/receiving composition of the present invention includes a dye
fixing agent and an ink receiving agent. In one embodiment, the fixing agent
has a
molecular weight of at least about 1000. The fixing agent of the present
invention
comprises reactive amino compounds of a highly cationic nature. A preferred
reactive amino compound is a compounds having a high positive charge density
(i.e., at least two (2) milliequivalents per gram). Reactive amino compounds
that can
be used in the present invention include compounds containing at least one
primary,
secondary, tertiary, or quaternary amino radical. Additionally, the reactive
amino
compounds can contain a reactive group that is capable of reacting with the
textile
substrate or resin binder to form a bond thereto. Examples of a reactive group
include epoxide, isocyanate, vinylsulphone, and halo-triazine.
Ink receiving agents of the present invention are inorganic particles that
receive the ink through adsorbancy or absorbancy. In one embodiment, the
particle
size of the ink receiving agent is equal to, or less than, about 10 microns.
In another
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embodiment, the particle size of the ink receiving agent is equal to, or less
than,
about 3 microns. In yet another embodiment, the particle size of the ink
receiving
agent is equal to, or less than, about 1 micron. Examples of ink receiving
agents of
the present invention include silica, silicate, calcium carbonate, aluminum
oxide,
aluminum hydroxide, and titanium dioxide.
In particular, it has been found that Bohemite alumina and silica gel work
well
in the present invention, especially silica gel particle that have been
treated to carry
a cationic charge. In the case of silica gel particles, alumina surface
coating and
cationic silane surface modification are preferred. It is believed that the
microporous nature of the bohemite alumia and silica gel allow further
physical
entrapment of a dye/pigment, such as an anionic dye/pigment, to afford
improved
wash fastness. In one embodiment, the inorganic particles have a porousity
with a
pore diameter from about 1 Onm to about 200nm.
In most formulations, the cationic charge from cationic reactive amino
compounds is much greater than the cationic charge present on the inorganic
particles. Therefore the mere presence of relative minor cationic charge on
the
inorganic particle would not significantly improve the dye/substrate
interaction
through cationic-anionic charge interaction. It is combination of highly
charged
reactive amino compound and the microporous inorganic particles that further
improves the washfastness of a printed article.
In one embodiment, the fixing agent typically will comprise from about 0.2% to
about 20% by weight of the treated textile substrate. In one embodiment, the
ink
receiving agent typically will comprise from about 0.2% to about 20% by weight
of
the treated textile substrate. In one embodiment, the dye fixing/adsorbing
composition comprises from about 1 % to about 10%, by weight, of the treated
textile
substrate. In another embodiment" the dye fixing/adsorbing composition
comprises
from about 1 % to about 5%, by weight, of th treated textile substrate. Prior
to
placement on the textile substrate, the dye fixing/receiving composition is
preferably
in the form of a stable aqueous solution or dispersion.
In the embodiment using a resin binder, the resin binder must be a binder that
will have good a bond with the fiber of the textile substrate. The resin
binder can be
a thermoplastic or thermosetting polymeric binder. It is preferable that the
resin
binder has a glass transition temperature of below about 40°C. It is
also preferred
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that the binder be durable when subjected to washing. Examples of resin
binders
include non-anionic or cationic latices, such as ethylenevinylacetate,
acrylic,
urethane polymer, polyamide, polyester, and polyvinyl chloride. In one
embodiment,
the resin binder comprises up to about 10% of the weight of the treated
substrate.
Whitening agents can include white pigments and optical brighteners. White
pigments provide an improved white background for the inks and dyes placed on
the
textile substrate, thereby increasing the contrast of the image on the textile
substrate. Examples of white pigments would include zinc oxide and titanium
oxide,
and calcium carbonate. Optical brighteners having photo-luminescent properties
brighten the background of the textile substrate to provide a greater contrast
with the
inks and dyes placed on the textile substrate. Examples of optical brighteners
could
include stylbene based materials such as Leucophor from Clariant Corporation.
An antimicrobial agent inhibits the growth of microorganisms, such as
bacteria, fungi, or the like, which can cause discoloring of an image on the
textile
substrate and/or degradation of the textile substrate itself. The
antimicrobial agent
can be an additive which is compatible with the cationic fixing agents, and is
durable
to weathering. Examples of suitable antimicrobial would include polyguanidine,
silver zirconium phosphate, and quaternary aminosilane.
Light stabilizers are materials that contribute to stabilizing the colorants
in the
printed ink and textile substrate. Examples of light stabilizers could include
hindered
amines and hindered phenol, such as Cyasorb 3346 by Cytec Industries and
Irganox by Ciba Specialty Chemicals.
UV absorbers are materials that strongly absorb harmful UV radiation, thereby
reducing the exposure of the colorants in the printed ink from the harmful UV
radiation. In one embodiment, the UV absorber comprises from about 0.1 % to
about 10% of the weight of the treated textile substrate. Traditionally, it
was believed
that the UV absorbers needed to be applied with the ink or cover the ink as a
post
treatment to provide protection. However, a surprising discovery of the
present
invention is that placement of the UV absorber on the textile before printing
of the
ink, provides an unexpected result of improved light fastness. Examples of UV
absorbers can includes benzyltriazoles, hydroxylphonones, and
Dihydroxygybenzylphenone, such as Tinuvin 1130 by Ciba Specialty Chemicals.
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It has been discovered by the present inventors that by incorporation of small
amount of lubricating agent, the friction force of a needle going through the
treated
textile in a sewing process can be greatly reduced. Lubricating agents are
materials
that significantly reduce surface friction. Examples of suitable lubricating
agents
5 would include olefin waxes, polysiloxanes, fatty acids and the derivatives
thereof,
and the like. The reduction of needle friction with a lubricant can be
accomplished
with out any adverse effect on the printing quality, or print durability. In
fact, the
fabric handle or surface touch is not usually afFected by the lubricant, while
needling
resistance is greatly improved.
The treatment can be applied to the textile substrate by dipping, coating,
spraying, powder coating, hot melt coating, and other similar methods. The
treatment can be applied to the textile substrate in a single application, or
multiple
applications. Additionally, the various components of the treatment can be
applied
together, in particular groupings, or individually. In one embodiment, the
treatment is
applied to the substrate textile by impregnation or coating, which is then
followed by
a drying process.
In the embodiment of the treatment having reactive amino compounds, the
drying process is typically conducted under an elevated temperature to
activate the
reactive amino compounds of the dye fixing agent for bonding with the textile
substrate and/or the resin binder. An elevated temperature for the drying
process is
a temperature that accelerates the evaporation of solvents in the treatment
and the
reaction of the reactive amino compound with the substrate and/or the binder.
Typically, an elevated temperature for the drying process would be from about
100°C
to about 150°C.
The present inventors have discovered that a water fast and wash durable
print can be obtained with a high and durable cationic chagred density on the
fabric.
Cationic charge density is measured by the moles of cationic charges bound to
the
textile substrate per unit area. It is believed that higher charge densities
provide
more anchoring sites for fixing anionic colorants to the fabric. The present
inventors
have found that a charge density of at least about 2meq/m2 provides a
satisfactory
charge density for the present invention.
Fabrics treated with charged materials and inorganic particles can be stiff
and
harsh to touch, which is undesirable. The present inventors have found that
the
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flexibility of the treated textile can be greatly improved by a mechanical
treatment,
such as intense vibration, stretching, and localized distortion. Surprisingly,
no
significant adverse effect on printing quality and print durability is
observed on
textiles that have been treated and then subjected to such mechanical
treatment.
The designs or images are placed on the treated surface of the substrate. In
one embodiment, the design or image is placed on the treated substrate by an
ink jet
printer, such as the type for home, office, or commercial uses. The printing
ink can
contain anionic dye and/or anionic pigments. It has been found that the
present
invention works well when the printing ink contains an acid dye, a reactive
dye, a
direct dye, or similar anionic colorants. It has also been found that by
ironing the
print on the textile substrate with or without steam, or by drying the printed
article in a
home dryer, the color fastness of the printed article may be improved.
The present inventors have also discovered that certain anionic dyes used in
combination the treated substrate give excellent water and washfastness to a
printed
article. Such anionic dyes are those containing at least 2 net anionic charge
on the
chromophore moiety on each molecule when fully disassociated in a polar
solvent.
Preferably, at least one of the anionic charges are provided by a ratical from
the
carboxylic acid group.
It is believed that the dye fixing agent interacts with the ionic dyes from an
ink
jet printer ink in a charge type attraction, and that the dye fixing agent of
the present
invention typically will react with the fiber of the textile substrate to form
a chemical
bond with the textile substrate. In an embodiment where a resin binder is
used, it is
believed that the dye fixing agent will chemically bond with the resin binder,
which
bonds with the textile substrate. It is also believed that the ink receiving
agent
provides surface area for the ink from the ink jet printer to interact with
the dye fixing
agent, thereby facilitating the effects of the dye fixing agent. The
interaction of the
dye fixing agent and the ink receiving agent provide a surprising result in an
improved color yield and image wash durability. The use of the dye
fixing/receiving
composition as the treatment in the present invention, provides a wash durable
and
crocking resistant print with little, or no, subsequent fixing procedures or
chemical
treatment.
The present invention allows well defined pixels to form and facilitates the
drying process of the print. The present invention improves the quality of the
printed
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image while preserving the flexible hand of the underlying textile substrate.
The
present invention also allows the use of various different types in inks
various
different types of substrate textiles.
The print exhibits good crocking resistance and water fastness within a few
minutes after printing. The article with the image can also withstand repeated
laundry cycles with little color fade. It has been discovered that the present
invention works well when the pH of the laundry detergent is in the range of
from
about 4 to about 8.
The present inventors have also discovered that textile substrates treated
with
the present invention can provide a printed textile with excellent color
brightness and
print resolution when an aqueous pigment ink is placed on the treated textile
substrate by an ink jet printing process. Pigment inks are commonly used to
provide
an image on a textile due to the superior lightfastness and environmental
stability of
such inks. However, when the image is placed on the textile with an ink jet
printer,
the ink jet printer needs an ink with low viscosity and that does not dry up
to plug the
ink jet nozzles. To meet the needs of an ink jet printer, pigment ink without
resin
binders are becoming commonly used in ink jet printing processes. However,
inks
without resin binders typically have poorer rub fastness and washfastness. In
order
to overcome these characteristics, the prior art has used post-printing
lamination or
coating to provide a permanency to the print.
Surprisingly, an aqueous pigment ink containing virtually no resin binder can
be ink jet printed printed on a treated textile substrate of the present
invention to
produce a water fast and weatherable printed image on the treated textile
without the
use of post-printing lamination or coating. It is believed that the inventive
treatment
swells when it receives the aqueous ink. It is also believed that this
swelling will
increase the chances of the interaction between the pigment particles of the
ink and
highly cationic and porous features of the treatment. As a result, a long-
lasting print
can be placed on a textile substrate using either a thermal or piezo ink jet
printing
process without post-printing lamination.
The present invention can be better understood with reference to the following
examples:
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EXAMPLES 1-3
A treatment mixture containing a reactive dye fixing agent, Kymene 736
(manufactured by Hercules, Wilmington, DE), a inorganic silica particle
dispersion,
Ludox CL-P (manufactured by W.R. Grace & Co., Columbia, MD), and a ethylene
vinylacetate latex binder, Airflex TL -51 (manufactured by Air Products and
Chemicals, Inc., Allentown, PA) was made according to the following formula:
Ludox' CL-P 8 parts by weight
Kymene 736 12 parts by weight
Airflex TL-51 4 parts by weight
Water 76 parts by weight
A small amount of ammoina hydroxide solution was added to adjust the pH to 11.
A woven cotton Poplin substrate (Example 1 ), a plain woven polyester
substrate with textured yarns (Example 2), and a plain woven 50/50
polyester/cotton
substrate (Example 3) were separately impregnated with the above treatment
solution, passing through nip rolls to get a wet pickup of about 60%. The
impregnated substrates were dried in a convection oven at 300°F for 3
minutes.
The treated substrates were printed with solid circles and squares of 3
primary colors (red, blue, yellow) and black using Hewlett Packard DeskJet
932C ink
jet printer. The images on each of the treated substrates showed very good
sharpness at the edges, with excellent color holdout and no evidence of ink
feathering. The printed substrates were then washed in a regular home washer
using delicate cycle using Gentle Cycle Woolite neutral detergent following
AATCC
Standardization of Home Laundry Text Condition (Developed in 1984 by AATCC
Committee RA88, and as revised in 1986, 1992, and 1995.). The substrates were
then dried in a regular home dryer at low heat for 20 minutes. Very little
color loss
was observed after the washing. No color bleeding or migration was observed.
Color value (CIE L*, a* and b* values) of each of the colors on the printed
substrates
after one wash and five washes was measured using an X-Rite SP78
Spectrophotometer utilizing the QA Master software for Microsoft Windows
Version
1.71 (both manufactured by X-Rite Inc., Grandville, MI). E versus the color
printed
on a piece of white paper was used to measure the degree of color loss. Wet
crocking (AATCC test method 8-1996), and waterfastness (AATCC test method 107-
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1997) were also measured on each primary color on the substrates after one
wash.
The test results are summarized in Table 1 and Table 2.
Table 1
Test Values After One Wash
Black Yellow Red Blue
DE vs. paper 2.05 18.41 7.20 8.21
Cotton Wet Crocking* 1 4 4 3
Water Colorfastness 5 5 5 5
DE vs. paper 3.35 26.31 14.17 9.00
50/50 Wet Crocking* 1 2.5 3 3
/PET
C
t
on 5 5 5 5
ot
Water Colorfastness
DE vs. paper 2.74 39.27 23.00 12.80
PET Wet Crockin * 1.5 3 1.5 2.5
Water ColorFastness 5 5 5 5
* AATCC Grey Scale for Staining
Table 2
Test Values After Five Washes
Black Yellow Red Blue
Cotton DE vs. paper ~ 0.63 5.67 5.25 4.96
50/50 pE vs. paper 8.62 11.20 9.73 9.06
Cotton/PET
PET DE vs. paper 5.40 14.82 11.73 9.92
* AATCC Grey Scale for Staining
EXAMPLES 4-6
Control examples were formed using the same substrates as in Examples 1-3
without treatment, as the corresponding Examples 4-6. The untreated substrates
were printed using the same printer with the same prints as in Examples 1-3. A
significant ink feathering was noticed on the control example of the polyester
fabric,
and a small degree of ink feathering was noticed on the control example of the
50/50
polyester cotton blend substrate. Lower color yield was observed on all the
control
examples compared with corresponding treated substrates in Exmaples 1-3. After
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one home wash as described in Examples 1-3, there was very little color
remained
on the fabric.
EXAMPLE 7
Similar formula as in Examples 1-3 was used, except that Ludox CP-L was
5 not included. The same cotton woven cotton substrate as in Example 1 was
treated
in the same manner as Example 1. Print quality and color fastness were
measured.
The color yield of Example 7 was lower and the print was not as wash fast as
treated
cotton substrate in Example 1.
EXAMPLE 8
10 Similar formula as in Examples 1-3 was used, except that Kymene 736 was
not included. The same cotton woven cotton substrate as in Example 1 was
treated
in the same manner as Example 1. Print quality and color fastness were
measured.
The color yield of Example 8 was significantly lower and dramatic color loss
was
observed after one wash.
EXAMPLE 9
Similar formula as in Example 1 was used, except that 1 part of Reputex 20
(antimicrobial agent manufactured by Avecia Biocides, Wilmington, Delaware)
was
added to 100 parts by weight of the treatment mixture in Example 1. The
treated
cotton substrate of Example 1, the untreated cotton substrate of Example 4,
and the
treated antimicrobial substrate of Example 9 were tested for antimicrobial
performance. Antibacteria testing was performed using AATCC test method 100,
and the results are shown in Table 3. An antifungal test using ISO 846 Test
method
was also conducted on these substrates and the results are shown in Table 4.
The
cotton substrate of Example 9 treated with the antimicrobial showed excellent
antibacteria and antifungal performance. Aspergillus niger is one of the most
common fungus that causes mildew staining. Chaetomium globosum is one fungus
that can grow on cellulosic material and therefore can biologically degrade
and
destroy cotton fabric. A treatment containing Reputex 20 therefore can help
prevent
mildew staining and biological degradation of cotton fabric.
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Table 3
Antibacteria Test Against Staphylococcus
Test Sample Lo Reduction
Example 4
Without Treatment 1.37
Example 1
Treatment w/o Antimicrobial 0.57
Example 9
(Treatment with Antimicrobial) 4.40
Table 4
Antifungal Test*
Test Sample Asper illus Ni er Chaetomium Globosum
Example 4
Without Treatment 10/10 10/10
Example 1
(Treatement w/o Antimicrobial)10/10 1/10
Example 9
Treatment with Antimicrobial0/10 1/10
* Number of drops of standard fungus solution showing growth out of 10 drops
of
inoculum after one week.
EXAMPLE 10
Similar formula as in Examples 1-3 was used, except that 1 part by weight of
Sunlife LPS-911 (UV absorber manufactured by Nicca USA, Fountain Inn, South
Carolina) was added to 100 parts by weight of the treatment mixture in Example
1.
A cotton substrate as described in Example 1 was treated and printed as
described
for Example 1. Xenon lightfastness (AATCC test method 16-1998) at 20 hours
exposure were tested and compared with treated cotton in Example 1 and printed
paper subjected to the same exposure. The results of the testing are
summarized in
Table 5. Lightfastness was improved by using the treatment formula for Example
10
containing UV absorber. It is somewhat surprising as the colorants were
applied on
top UV absorber treatment. The present inventors believe that some of the UV
absorber must have migrated towards the surface and/or the dyes in the
printing ink
migrate beneath the treatment.
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Table 5
Light Fastness
Test Sample Black Yellow Red Blue Avera
a
Paper 5.0 4.5 2.5 1.5 3.4
Example 1 5.0 1.0 1.0 1.5 2.1
Example 10 5.0 4.0 3.5 2.0 3.6
EXAMPLE 11
The following formula, in parts by weight, was used as a treatment on a
woven Poplin cotton fabric:
Epi-rez 6006-w-70 4 parts
(waterborne epoxy resin, by Shell
Chemical Company, Houston Texas)
Ancamide 500 4 parts
Ludox CI-P 10 parts
Water 82 parts
Epi-rez acts both as resin binder and reactive agent that couples with
Ancamide (amino compound containing both primary and secondary amines) to
generate a durable amine containing finish. The cotton fabric was treated
using this
formula in the same manner as described in Example 1, and printed and test in
the
same manner.
EXAMPLE 12
A treatment mixture containing a reactive dye fixing agent, Kymene 736
(manufactured by Hercules, Wilmington, DE), a silane-surface-modified silica
gel
dispersion, Sylojet 703C (manufactured by W.R. Grace & Co., Columbia, MD), and
a
ethylene-vinyl acetate latex binder, Airflex TL -51 (manufactured by Air
Products and
Chemicals, Inc., Allentown, PA), a silicone softener, Dousoft OH (manufactured
by
Boehme Filatex, Reidsville, NC), and a fluorescent whitening agent, Ultraphor
SFN
(manufactured by BASF, Charlotte, NC) was made according to the following
formula in parts by weight:
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Water 53 parts
Kymene 736 30 parts
Airflex TL-51 10 parts
Sylojet 703C 5 parts
Dousoft OH 1.5 parts
Ultraphor SFN 0.5 parts
A woven cotton fabric (cotton Poplin) substrate was impregnated with the
above solution, passing through nip rolls to get a wet pickup of about eighty
percent
(80%). The impregnated substrate was dried in a convection oven at
300°F for five
(5) minutes. The treated substrate was printed and tested for washfastness as
described below, and the results are shown in Table 6.
The treated substrate was printed with solid squares of 4 primary colors (red,
blue, yellow and black) using a Hewlett Packard DeskJet 932C ink jet printer.
The
treated substrate showed very good sharpness at the edges with excellent color
holdout and no evidence of ink feathering. The washing procedure was the same
as
used in Examples 1-3, including the drying. This washing process was repeated
up
to values of five (5) and fifteen (15) times. Color value (CIE L*, a* and b*
values) of
each primary color on the printed fabrics after one wash was measured using X-
Rite
SP78 Spectrophotometer utilizing the QA Master software for Microsoft Windows
Version 1.71 (both manufactured by X-Rite Inc., Grandville, MI). Delta E (cmc)
versus the color printed on a piece of white paper (Hammermill Inkjet 24 Ib.
paper
manufactured by International Paper of Memphis, TN) was used to measure the
color loss reported in Table 6.
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Table 6
Washfastness
0E CMC
vs. Hammermill
Jet Print
24# Paper
Example Washes
Black
Yellow
Red Blue
5 1.54 6.14 3.78 4.23
Example 12
15 4.04 8.11 6.36 6.44
5 1.51 2.14 2.47 2.23
Example 13
15 1.67 5.00 5.68 5.07
Example 12 was used to test several ink jet dyes by making about a 5%
solution in mixture of water and propylene glycol and a solid color circle was
inkjet
printed using each dye on an unprinted fabric of Example #15 using a thermal
inkjet
printing head. Waterfastness of the print was tested by soaking the printed
circle in
small amount of water for 5 days and observe the color bleeding into water and
color
migration to outside the color circle, and the results are shown below in
Table 7.
Table 7
Ink Bleed And Migration
Dye Molecules Anionic GroupNet Bleed IntoColor
On The NegativeWater Migration
Chromophore Char
a
C.I. Acid red 2 SO31- 2 Minimal No Mi ration
1
C.I. Acid red One -O+ - 1 SignificantSevere
52 ,
2 5031
C.I. Acid red One -O+ - 1 SignificantModerate
289 ,
2 SO31-
C.I. Direct Red 6 S031- 6 Minimal No Mi ration
227
Pro-Jet fast None No Migration
Red
Noticeable
C.I. Acid yellow2 S031-, 3 None No Migration
23
One COO-1 Noticeable
C.I. Acid blue One =N+ , 2 Slight Slight
9
3 SO31-
C.I. Direct blue2 S031- 2 Minimal No Migration
86
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As can be seen in Table 7, dye molecules with more than 2 net negative
charges on the chromophor of the molecule give satisfactory water fastness on
this
inventive highly cationic treated fabric. Dye molecules with carboxylic acid
radical,
such as Pro-Jet Fast Red and C.I. Acid yellow 23, have superior water
fastness.
5 EXAMPLE 13
A treatment mixture was formed of the same components as in Example 12 in
the following formula in parts by weight:
Water 33 parts
Kymene 736 30 parts
10 Airflex TL-51 10 parts
Sylojet 703C 25 parts
Dousoft OH 1.5 parts
Ultraphor SFN 0.5 parts
15 The above treatment was aplaced on the same woven cotton Poplin fabric
substrate as Example 12, in the same manner as Example 12. The washfastness of
Example 13 was tested in the same manner as prescribed in Example 12, and the
results are reported in Table 6. Suprisingly, as shown in Table 6, increasing
the
amount of surface-modified inorganic particles of the treatment increases the
wastfastness of the treated substrate.
EXAMPLES 14-17
Varying levels of a lubricant (Duosoft OH) were added to the treatment
formula used in Example 13, and impregnated onto the same substrate as Example
13 in the same manner to form Examples 14-17. The amount of lubricant added to
the treatment formula for each example as specified in Table 3. A test was
then
performed to determine the amount of force needed to pass a sewing needle
through
the treated substrates. To determine the force necessary to pass the needle
through
the treated substrates, a quilting/between hand sewing needle size 10 was
mounted
facing upward to a AccuForce III force meter manufactured by AMETEK of Largo,
FL. Samples of the treated substrates of Examples 14-17 were folded over
itself (2-
ply) and mounted in an embroidery frame. The folded and treated substrates
were
then pressed down onto the mounted needle, and the maximum force of
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16
compression to pass the needle through both layers of substrate was recorded
as a
measure of the easeldifficulty of passing a needle through the fabric and
averaged
over several trials. The larger the force recorded, the more difficult it is
to pass a
needle through the fabric. The values for each Example were recorded and are
listed in Table 8.
Table 8
Lubricant Levels and Needle Force
Example Lubricant Level (%) Needle Force (kg)
Example 13 0 1.3
Example 14 1.0 0.8
Example 15 2.0 0.7
Example 16 3.0 0.6
Example 17 5.0 0.5
As shown in Table 8, addition of a compatible softener can reduce the needle
force
required to pass a needle through the treated substrate.
EXAMPLES 18-21
A woven Poplin cotton fabric was treated with a treatment mixture containing
various amounts of a reactive dye fixing agent, Kymene 736 (manufactured by
Hercules, Wilmington, DE), a silane-surface-modified silica gel dispersion,
Sylojet
703C (manufactured by W.R. Grace & Co., Columbia, MD), and a ethylene-vinyl
acetate latex binder, Airflex TL -51 (manufactured by Air Products and
Chemicals,
Inc., Allentown, PA), a silicone softener, Dousoft OH (manufactured by Boehme
Filatex, Reidsville, NC), a fluorescent whitening agent, Ultraphor SFN
(manufactured by BASF, Charlotte, NC), and sufficient 50% caustic (sodium
hydroxide) to adjust th3 pH of the mixture to about 7, as specified below in
Table 9.
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17
Table 9
Treatment Mixture (Parts by Weight)
Component Example Example 19 Example Example 21
18 20
Water 23.2 33.4 43.6 53.8
50% Caustic 0.8 0.6 0.4 0.2
Kymene 736 40 30 20 10
Airflex TL-51 7 7 7 7
S lojet 703C 25 25 25 25
Dousoft OH 3 3 3 3
Ultraphor SFN 1 1 1 1
The woven poplin cotton fabrics for Examples 18-21 were impregnated with
the corresponding treatment above, passing through nip rolls to get a wet
pickup of
about 80%. The impregnated fabrics were dried in a convection oven at
300°F for
about 5 minutes.
Samples of each of the Examples were printed with solid squares of 4 primary
colors (red, blue, yellow and black) 'using a Hewlett Packard DeskJet 932C ink
jet
printer. The printed substrates were then washed in a regular home washer
using
delicate cycle using Gentle Cycle Woolite neutral detergent following AATCC
Standardization of Home Laundry Text Condition (Developed in 1984 by AATCC
Committee RA88, and as revised in 1986, 1992, and 1995.). These fabrics were
then dried in a regular home dryer at low heat for 20 minutes. This washing
process
was performed on the treated and printed fabrics for a total of one (1 ), five
(5) and
ten (10) times. Color value (CIE L*, a* and b* values) of each primary color
on the
printed fabrics was measured using an X-Rite SP78 Spectrophotometer utilizing
QA
Master software for Microsoft Windows Version 1.71 (both manufactured by X-
Rite
Inc., Grandville, MI) before any washing, and after each washing. Delta E
(cmc)
versus the color printed on a piece of white paper (Hammermill Inkjet 24 Ib.
paper
manufactured by International Paper of Memphis, TN) was used to measure the
color loss, summarized below in Table 10.
Non-printed samples of each of the Examples 18-21 were tested for charge
density as explained below, at zero (0) washes, one (1 ) washing, five (5)
washings,
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18
and ten (10) washings, as described above. The data obtained from these
measurements is summarized below in Table 10.
To determine the charge density of a substrate, a sample of the substrate is
placed in a master solution containing dye molecules of a known charge, the
light
absorbency of the master solution is measured before and after immersion, the
difference in absorbency is used to calculate the amount of dye molecules left
on the
sample, and the amount of dye molecules left on the sample and the area of the
sample are used to calculate the charge density of the substrate before
immersion.
Two inch (2") by two inch (2") samples of the textile substrate were immersed
into a
twenty five (25) gram master solution for ten (10) minutes. The master
solution was
formed using 121.5 mg of cresol red (CAS# 1733-12-6) dye (404.2g/mol. by
Aldrich)
into 431.0g de-ionized water to make a 0.0282% solution by weight. Samples of
the
untreated substrate with no washings, and treated substrates with no (0)
washes,
one (1 ) washing, and five (5) washings, were each placed in its own master
solution.
The light absorbency of the master solution for each sample was measured at
434nm in the UV-Visible spectrum before and after immersion of the sample.
The change in light absorbency of the master solution for each sample can be
used to determine the amount of dye left on the sample. To determine the
amount of
dye left on the sample from the master solution, a plot of dye concentration
verses
light absorbency must be calculated from known dye concentration standards.
The
dye concentration standards can be created by diluting the master solution.
Ten dye
concentration standards were created by diluting the master solution, forming
ten
dye concentration standards with known dye concentrations (w/w) ranging
between
5 x 10-6 to 4 x 10-5. The light absorbency of each dye concentration standard
was
measured at 434nm in the UV-Visible spectrum, and the concentration and light
absorbency data were fitted into Beer's law to form the plot of dye
concentration
verses light absorbency.
For each of the samples, the difference in light absorbency of the master
solution before and after the immersion of the samples is used to determine
from the
dye concentration verses light absorbency plot the amount of dye left on the
sample.
Since cresol red dye has only one negative charge per molecule, the amount of
cationic charge on the substrate can be calculated based on the number of dye
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WO 03/020502 PCT/US02/27759
19
molecules absorbed over the unit area of the substrate. The charge density of
the
substrate is then reported in milli-mole/m2 or mill-equivalent/m2.
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WO 03/020502 PCT/US02/27759
EXAMPLES 21-22
A woven cotton Poplin fabric and a polyester Poplin woven fabric treated with
the following formula:
Kymene 736 20 parts
5 Sylojet 703 25 parts
Airflex TI-51 10 parts
water 45 parts
A photo-image and a set of black, red, blue and yellow color blocks were
printed on
each fabric using Epson Stylus Photo 2000P printer with aqueous pigment ink.
10 Printed fabrics were washed once in a home washing machine with added
liquid detergent. There was virtually no visible color loss after 1 wash. In
comparison, an untreated polyester fabric printed with the same pattern using
the
same printer, showed dramatic visible color loss after one home wash.
For outdoor weather durability, the printed fabrics were tested in an
15 accelerated weather-o-meter using SAE J1960 method where fabric samples
were
exposed to high intensity of UV radiation, and intermitted water spray for 21
days.
The amount of exposure in the weather-o-meter is equivalent to 3 month Florida
outdoor life. The color changes in terms of DEcMC before and after weather-o-
meter
exposure were measured and summarized below in Table 11. As can be seen from
20 the results in the table, there was little color change on both printed
fabrics. There
were no chalking or any other obvious degradation on those printed fabric at
the end
of 21 day exposure.
Table 11
Color Change, DEcMC After Weather-O-Meter Exposure
Color block Black Yellow Red Blue
Example 21 (Treated polyester 4.06 0.99 0.82 4.26
fabric)
Example 22 (Treated Cotton fabric)3.57 0.55 0.29 6.52
The same treated fabrics were also printed with Mimaki JV-4 wide format
printer using aqueous pigment ink without resin binder. The resulted prints
have the
same water fast, wash fast and weather durable properties.
