Go to Advanced Search

Home | Search Patents | Data Services | Help

Title:
Solid disperse dye formulations containing
non-ionic dispersants for transfer printing
inks
Document Type and Number:
United States Patent 4523923
Link to this page:
http://www.freepatentsonline.com/4523923.html
Abstract:
The invention relates to solid disperse dye
formulations which do not contain anionic
dispersants and which comprise one or more
disperse dyes having a particle size of less than 5
.mu.m, and one or more nonionic dispersants
selected from the group of the fatty alcohol
ethoxylates having a molecular weight of 800 to
2000, of the fatty amine ethoxylates having a
molecular weight of 500 to 1000, and of the
polyvinylpyrrolidones having a molecular weight of
10,000 to 25,000. These formulations are
particularly suitable for preparing organic printing
pastes and printing inks which contain synthetic
thickeners and which are suitable for textile printing
and for transfer printing.
Inventors:
Buchel, Urs (Biel-Benken, CH)
Muther, Paul
Application Number:
580908
Filing Date:
02/16/1984
Publication Date:
06/18/1985
View Patent Images:
Images are available in PDF form when logged in.
To view PDFs, Login or Create Account (Free!)
Referenced by:
View patents that cite this patent
Export Citation:
Click for automatic bibliography generation
Assignee:
Ciba-Geigy Corporation (Ardsley, NY)
Primary Class:
8/524
Other Classes:
8/471, 8/552, 8/553, 8/602, 8/609, 8/907
International Classes:
C09B 067/38, D06P 001/16
Field of Search:
8/553, 552, 609, 602, 524
US Patent References:
3960486 Jun, 1976 Danbach et al. 8/524.
4233026 Nov, 1980 Hitschfel et al. 8/524.
4249902 Feb, 1981 Kruckenberg et al. 8/525.
4295849 Oct, 1981 Nonn et al. 8/524.
Foreign References:
1467746 Mar, 1977 GB.
1538978 Jan, 1979 GB.

Claims:
What is claimed is:

1. A solid disperse dye formulation which does not

contain anionic dispersants and which comprises
one or more disperse dyes having a particle size of
less than 5 .mu.m, and one or more nonionic
dispersants selected from the group of the fatty
alcohol ethoxylates having a molecular weight in
the range from 800 to 2000, of the fatty amine
ethoxylates having a molecular weight in the range
from 500 to 1000 and of the polyvinylpyrrolidones
having a molecular weight in the range from 10,000
to 25,000.

2. A formulation according to claim 1, which

contains a disperse dye of the azo or anthraquinone
series which sublimes in the temperature range from
160.degree. to 220.degree. C.

3. A formulation according to claim 1, which

contains the nonionic dispersant in a concentration
of 5 to 20% by weight based on dye.

4. A formulation according to claim 1, wherein the

nonionic dispersant is a cetyl-stearyl alcohol
ethoxylate with a molecular weight of 1000 to 1500,
a laurylamine ethoxylate with a molecular weight of
500 to 800 and/or a C.sub.2 -C.sub.6
alkylpolyvinylpyrrolidone with a molecular weight
 of 13,000 to 22,000.

5. A formulation according to claim 1, which

consists of 80 to 95% by weight of a disperse dye
which sublimes in the temperature range from
160.degree. to 220.degree. C., and 20 to 5% of a
nonionic dispersant.

6. A process for the preparation of a formulation

according to claim 1, which comprises
homogeneously dispersing one or more disperse
dyes in water by adding at least one nonionic
dispersant of the indicated kind, grinding the
dispersion to a particle size of less than 5 .mu.m and
then drying, the fine dispersion so obtained.

7. A formulation according to claim 1, which

contains the nonionic dispersant in a concentration
of 8 to 15% by weight based on dye.

8. A process of claim 6 wherein the fine dispersion

is dried by spray drying.

9. A method of preparing an organic printing paste

or printing ink which comprises the step of
dispersing a solid dye formulation of claim 1 in a
printing ink vehicle.
Description:
The present invention relates to solid disperse dye
formulations which do not contain anionic
dispersants, to a process for the preparation thereof,
and to the use of said formulations for pre-paring
organic printing pastes and printing inks.

Solid powdered formulations of disperse dyes often

contain anionic dispersants such as lignosulfonates
or condensates of formaldehyde and aromatic
sulfonic acids. The presence of these components is
usually not disadvantageous when such
formulations are used for preparing dyebaths, as
anionic dispersants favourably influence the
stability of the dye dispersion at elevated
temperature. However, such dye formulations are
not suitable for preparing organic printing inks or
pastes which contain synthetic thickeners, because,
depending on the amount of anionic dispersant
added to the formulation, the viscosity of the
synthetic thickener decreases rapidly until all that
remains is a low-viscosity formulation which is
totally unsuitable for printing.

Moreover, lignosulfonates and condensates of

formaldehyde and aromatic sulfonic acids are
poorly soluble in the organic solvents normally
employed for preparing purely organic printing
pastes and printing inks.

Accordingly, it is the object of the present invention

to provide disperse dye formulations which do not
contain anionic dispersants and which are
particularly suitable for preparing organic printing
pastes and printing inks which contain synthetic
thickeners. Nonionic dispersants, such as the large
number of widely available adducts of ethylene
oxide and block polymers of ethylene oxide and
propylene oxide, are readily compatible with
synthetic thickeners. Nevertheless, the total
replacement of anionic dispersants by nonionic
dispersants must necessarily appear problematical,
as it means not using anionic dispersants when
grinding the crude disperse dye. However, it is
known that, during the grinding procedure,
mechanical pressure initially causes the formation
of microcracks in the crystal particles of the crude
dye. In order that these microcracks lead ultimately
to a division of the dye particles and do not
disappear again when pressure is eased, it is
common practice to grind the dye in the presence of
ionic dispersants. The dispersants penetrate the
cracks and, owing to their equidirectional charge,
diminish the mechanical energy necessary for
dividing the particles [q.v. S. HEIMANN, Melliand
12, 885 (1982)]. Although nonionic dispersants also
have affinity for the dye particles and penetrate the
microcracks formed during the grinding procedure,
they cannot so efficiently assist the process of
division because they carry no charge.

However, the requirement made of the dispersants

is not only that they shall be suitable grinding
assistants, but also that they must be soluble in the
media employed for preparing printing inks,
especially in alkyd resins, in order to make possible
in particular the preparation of non-aqueous printing
pastes and printing inks.

Surprisingly, it has now been found that nonionic

dispersants selected from the group consisting of
the fatty alcohol ethoxylates having a molecular
weight in the range from 800 to 2000, of the fatty
amine ethoxylates having a molecular weight in the
range from 500 to 1000, and of the
polyvinylpyrrolidones having a molecular weight in
the range from 10,000 to 25,000, meet these
requirements and are suitable for use as grinding
assistants and for incorporation in purely organic
printing pastes and printing inks.

Accordingly, the invention provides solid disperse

dye formulations which do not contain anionic
dispersants and which comprise one or more
disperse dyes having a particle size of less than 5
.mu.m and one or more nonionic dispersants
selected from the group of the fatty alcohol
ethoxylates having a molecular weight in the range
from 800 to 2000, of the fatty amine ethoxylates
having a molecular weight in the range from 500 to
1000, and of the polyvinylpyrrolidones having a
molecular weight in the range from 10,000 to
25,000.

Suitable dyes for the preparation of the formulations

of this invention are disperse dyes belonging to the
widest range of dyestuff classes, in particular dyes
of the azo and anthraquinone series. Particularly
preferred dyes are those which sublime in the
temperature range from 160.degree. to 220.degree.
C. and are conventionally used for transfer printing.

Specifically, the ethylene oxide adducts comprise

the following types of compounds:

reaction products of saturated and/or unsaturated

fatty alcohols of 10 to 20 carbon atoms with 15 to
35 moles of ethylene oxide per mole of hydroxyl
group;

reaction products of saturated and/or unsaturated

fatty amines of 10 to 20 carbon atoms with 7 to 18
moles of ethylene oxide per mole of amino group.

Mixtures of ethylene oxide adducts are also

suitable. Such mixtures are obtained by mixing
individual ethoxylates, or direct by reacting a
mixture of fatty alcohols and/or fatty amines with
ethylene oxide. Suitable saturated or unsaturated
fatty alcohols are dodecanol, palmityl alcohol,
stearyl alcohol, oleyl alcohol or tallow fatty
alcohols.

Representative fatty amines are stearylamine,

laurylamine, palmitylamine and oleylamine.
Suitable polyvinylpyrrolidones are in particular
those in which the heterocyclic radicals are
substituted by branched or unbranched C.sub.2
-C.sub.6 alkyl groups.

The formulations of the invention preferably

contain the nonionic dispersants in a concentration
of 5 to 20% by weight, most preferably of 8 to 15%
by weight, based on dye.

The following dispersants have been found to be

particularly suitable: cetyl stearyl alcohol ethoxylate
with a molecular weight of 1000 to 1500,
laurylamine ethoxylate with a molecular weight of
500 to 800, and C.sub.2 -C.sub.6
alkylpolyvinylpyrrolidone with a molecular weight
of 13,000 to 22,000.

For preparing the alkyd resin-based printing inks

which are used in particular for e.g. transfer
printing, those formulations have proved suitable
which comprise 80 to 95% by weight of disperse
dye having a sublimation point in the range from
160.degree. to 220.degree. C., and 20 to 5% by
weight of a nonionic dispersant, and which
substantially contain no further ingredients.

The novel formulations are obtained by preparing a

homogeneous dispersion of the disperse dye or dyes
in water by adding at least one of the nonionic
dispersants referred to above, and subjecting the
suspension so obtained to a grinding operation until
the primary particle size is less than 5 .mu.m. The
resultant fine dispersion is then converted into a dry
powdered form in a manner known per se.

The dye is ground in a conventional wet grinding

unit, e.g. an agitator ball mill or a sand mill.
Suitable driers are spray driers, fluid bed driers thin-
layer contact driers, e.g. cylinder driers, and
continuous paddle driers. It is advantageous to use a
spray drier, as it affords rapidly dispersible
formulations.

In the course of the drying operation, the nonionic

dispersants counteract agglomeration of the dye
particles and, in addition, prevent dust formation
during transportation and storage of the dye
powders.

The formulations of the invention are most suitable

for preparing non-aqueous organic printing pastes
and printing inks for textile printing, in particular
for printing supports for transfer printing.
Compared with known formulations which contain
anionic dispersants, these formulations are
distinguished by the following features:

excellent compatibility with synthetic thickeners,

e.g. alkyd resins, polyacrylates, or copolymers
based on vinylpyrrolidone or maleic acid;

easy dispersibility; and

complete solubility of the dispersant in the organic

media employed for preparing printing pastes and
printing inks, e.g. alcohols.

The invention is illustrated in more detail by the

following Examples, in which parts and percentages
are by weight.

EXAMPLE 1

With efficient stirring, 450 parts of the dry dye of

the formula ##STR1## are slowly added to 45 parts
of cetyl stearyl alcohol, etherified with 25 moles of
ethylene oxide, and 400 parts of water and the
mixture is homogenised for 1 hour and deaerated.
The 50% dyestuff suspension so obtained is ground
for about 15 hours in an open mill with 2000 parts
of siliquartzite beads (1 mm diameter). When the
wet grinding operation is complete, the particle size
is less than 5 .mu.m. The dispersion is separated
from the grinding elements, which are subsequently
washed with 105 parts of water.

The fine dispersion is dried in a spray drier to give a

free-flowing, non-dusting dyestuff powder
consisting of: 90% of dye, 9% of dispersant and 1%
of residual moisture. This powder can be rapidly
dispersed in alkyd resin-based organic printing
media. The formulation does not lower the viscosity
of synthetic thickeners.

EXAMPLES 2 TO 4

The procedure described in Example 1 is repeated,

using equal parts of one of the dyes listed below.
The formulations so obtained are likewise very
suitable for preparing organic printing pastes and
printing inks which contain synthetic thickeners.
##STR2##

EXAMPLE 5

With efficient stirring, 450 parts of the dry dye of

the formula ##STR3## are slowly added to 45 parts
of laurylamine ethoxylate (molecular weight 500 to
800) and 400 parts of water and the mixture is
homogenised for 1 hour and deaerated. The 50%
dyestuff suspension so obtained is ground for about
15 hours in an open mill with 2000 parts of
siliquartzite beads (1 mm diameter). When the wet
grinding operation is complete, the particle size is
less than 5 .mu.m. The dispersion is separated from
the grinding elements, which are subsequently
washed with 105 parts of water.

The fine dispersion is dried in a spray drier to give a

free-flowing, non-dusting dyestuff powder
consisting of: 90% of dye, 9% of dispersant and 1%
of residual moisture. This powder can be rapidly
dispersed in alkyd resin-based organic printing
 media.

EXAMPLE 6

The procedure of Example 5 is repeated, except that

the nonionic dispersant employed therein is
replaced by the same amount of a C.sub.2 -C.sub.6
alkylpolyvinylpyrrolidone with a molecular weight
of 13,000 to 22,000. The dye formulation so
obtained is very suitable for preparing organic
printing pastes and printing inks which contain
synthetic thickeners.
Heat transfer printing on a filled polymethyl methacrylate article
Document Type and Number:
United States Patent 4406662
Link to this page:
http://www.freepatentsonline.com/4406662.html
Abstract:
A process of heat transfer printing the surface of a filled polymeric article, wherein the
filled polymeric article consists essentially of an inorganic filler, preferably alumina
trihydrate, and a polymer with an affinity for disperse dyes, preferably polymethyl
methacrylate. A desired design is printed onto a carrier using sublimable disperse dyes.
The filled polymeric article is preheated, the carrier supporting sublimable disperse dye is
placed in intimate contact with the preheated article, and sufficient heat is applied to
cause the dye to sublime, then diffuse into the surface of the article.
Inventors:
Beran, Joseph F. (Wilmington, DE, US)
Gorondy, Emery J. (Chadds Ford, PA, US)
Application Number:
355170
Filing Date:
03/05/1982
Publication Date:
09/27/1983
View Patent Images:
Images are available in PDF form when logged in. To view PDFs, Login or Create
Account (Free!)
Referenced by:
View patents that cite this patent
Export Citation:
Click for automatic bibliography generation
Assignee:
E. I. Du Pont de Nemours and Company (Wilmington, DE)
Primary Class:
8/471
Other Classes:
8/509, 8/522
Field of Search:
8/471, 509, 522
US Patent References:
3847865 Nov, 1974 Duggins 524/437.
3877964 Apr, 1975 Orman 8/467.
4201821 May, 1980 Fromson et al. 8/444.
4202663 May, 1980 Haigh 8/471.
4354851 Oct, 1982 Hix et al. 8/471.
Foreign References:
1111717 Nov, 1981 CA.
14901 Sep, 1980 EP.
2817566 Oct, 1978 DE.
2940370 Apr, 1981 DE.
1463072 Feb, 1977 GB.
1463596 Feb, 1977 GB.
1517832 Jul, 1978 GB.
2095619 Oct, 1982 GB.

Primary Examiner:
Clingman, A. Lionel
Attorney, Agent or Firm:
Thrower; William H.
Claims:
We claim:

1. A process for heat transfer printing a design onto the surface of a filled polymeric
article, said article consisting essentially of 55 to 80% by weight alumina trihydrate and
20 to 45% by weight polymethyl methacrylate, said process comprising preheating said
article to a temperature of at least about 96.degree. C., placing a carrier supporting
sublimable disperse dye adjacent to said surface of said preheated article, said disperse
dye forming a design, and applying sufficient heat to said carrier in intimate contact with
said surface to cause said disperse dye to sublime and to diffuse into said surface.
Description:
FIELD OF THE INVENTION

The invention involves a process of heat transfer printing the surface of a filled polymeric
article, wherein the filled polymeric article consists essentially of an inorganic filler,
preferably alumina trihydrate, held together with a translucent polymer cement,
preferably polymethyl methacrylate. By heat transfer printing, it is meant that a desired
pattern is printed onto a carrier using inks containing sublimable disperse dyes, the
printed carrier is placed in contact with the surface of the filled polymeric article, and
sufficient heat is applied to cause the dyes to sublime, then subsequently to diffuse into
the surface of the article.
DESCRIPTION OF THE PRIOR ART

It is common commercial practice to print textile materials by subliming and transferring

dyes from carriers printed or coated with disperse dyes in the form of an ink or paste. The
textile material is contacted with the printed carrier in the presence of heat to cause the
dyes to sublime and to diffuse into the interior of the fiber contained in the textile
material. Fabrics comprised of polymers with an affinity for disperse dyes, such as
polyesters, acrylics, and acetates, may be printed by this process. See, for example,
Copending Application Ser. No. 098,977 of Emery J. Gorondy, filed Nov. 30, 1979;
which discloses level dyeing of textile material in a solid shade by means of a heat
transfer process. The carrier may be any of several appropriate materials including paper,
metal, such as aluminum or steel, plastic, or fabrics optionally coated with various resins
such as vinyl, polyurethane, polytetrafluoroethylene, or the like. All paper printing
techniques, including gravure, lithography, rotary screen, and flexography, with their
respective advantages and limitations may be used to print the carrier with the ink
containing sublimable disperse dyes.

Filled polymeric materials and various methods for their manufacture are known in the
art. The preparation of a polymerizable acrylic composition consisting essentially of a
syrup containing methyl methacrylate polymer dissolved in monomeric methyl
methacrylate (polymer-in-monomer syrup), a polymerization initiator, and an inorganic
filler, preferably alumina trihydrate, is disclosed in U.S. Pat. No. 3,847,865 issued to Ray
B. Duggins. The composition can be cast or molded and cured to produce a structure with
an important combination of properties including translucency, weather resistance,
resistance to staining by common household materials, flame resistance, and resistance to
stress cracking. In addition, the cured article can be easily machined by conventional
techniques including sawing and sanding. This particular combination of properties
makes such a structure particularly useful as kitchen or bathroom countertops, back
splash panels, molded articles such as towel racks, and the like.

The polymer constituent comprises 15 to 80%, preferably 20 to 45% by weight of the

filled article and may comprise methyl methacrylate homopolymers and copolymers of
methyl methacrylate with other ethylenically unsaturated compounds (e.g., vinyl acetate,
styrene, alkyl acrylates, acrylonitrile, alkyl methacrylates, multifunctional acrylic
monomers such as alkylene dimethacrylates and alkylene diacrylates). In. addition, the
polymer constituent can contain small amounts of other polymers including minor
amounts of polyester.

The filled polymeric article also contains 20 to 85%, preferably about 55 to 80% of an
inorganic filler. Materials generally used as fillers are, for example, titanates, barium
sulfates, calcium carbonate, lithopone, china clays, magnesite, mica, iron oxides, silicone
dioxide, and various siennas. A particularly preferred filler is alumina trihydrate,
disclosed in the above-referenced patent to Duggins.

While sublimation heat transfer printing utilizing disperse dyes of polymer fabrics,
including polyesters, acrylics, polyamides, and acetates, and of other polymer forms
including films and sheets has been known in the art, until this invention there has been
no process for heat transfer printing a filled polymeric article which contains a substantial
amount of inorganic filler material together with the polymeric constituent of the article.

SUMMARY OF THE INVENTION

A desired design may be printed onto the surface of a filled polymeric article containing
20 to 85% inert inorganic filler utilizing a heat transfer printing process. The design is
printed onto a carrier using inks comprising sublimable disperse dyes. The filled
polymeric article is preheated. The carrier with the printed design is brought into intimate
contact with the surface of the preheated article and sufficient heat is applied to cause the
dye to sublime and to diffuse into the surface of the article.

DETAILED DESCRIPTION OF THE INVENTION

A filled polymeric article consisting essentially of an inorganic filler held together with a
translucent polymer cement may be successfully printed with a design utilizing the heat
transfer process of this invention. A particularly preferred material subject to the process
of this invention is a filled polymeric article consisting essentially of 20 to 85%,
preferably about 55 to about 80% by weight of alumina trihydrate and 15 to 80%,
preferably about 20 to about 45% by weight polymethyl methacrylate, such as that
described in the above-referenced patent to Duggins. Of course, the process is applicable
to articles which may contain other inorganic fillers known in the art in lieu of all or a
portion of the alumina trihydrate. The article may optionally contain pigments in an
amount sufficient to achieve a desired color. As discussed earlier, the polymeric
constituent preferably comprises methyl methacrylate homopolymers and copolymers of
methyl methacrylate with other small ethylenically unsaturated compounds, and may
contain small amounts of other polymers including minor amounts of polyesters. The
article printed according to the invention provides aesthetically appealing tiles and panels
particularly useful as decorative wall tiles and backsplash panels and the like.

To accomplish the invention a desired design is printed onto a carrier, for example, a
paper web or polyester film, in ways known in the art utilizing inks comprising known
sublimable disperse dyes. The surface of the article is prepared by preheating. The carrier
with the desired design is placed in intimate contact with the surface of the preheated
article, and sufficient heat is applied to cause the disperse dye to sublime from the carrier
into the surface of the article.

The amount of heat necessary to cause sublimation depends on the vapor pressure of the
disperse dye utilized. Preheating the article before the heat transfer printing step is an
essential step to assure adequate heat to promote diffusion of the sublimated dye into the
surface of the article, otherwise there is uneven transfer of the dye and acceptable
printing quality is not obtained.

It is also essential to the invention that the carrier with the printed design be in intimate
contact with the surface of the article while applying heat to cause sublimation of the dye,
otherwise an inadequate image transfer will result. Intimate contact can be assured, for
example, by utilizing a heated press platen to apply the required heat of sublimation,
applying sufficient pressure with the press platen to cause the carrier to come into
intimate contact with the surface of the article. Lack of intimate contact between the
carrier and the surface of the article may result due to the lack of flatness of the press
platen, the surface of the article, or a combination of both. In such circumstances the lack
of intimate contact can be overcome by preheating the article above its glass transition
temperature before the heat transfer printing step so that, so softened, it will conform
intimately to the surface of the heated platen.

In applying the process of this invention to an article of the preferred material consisting
essentially of alumina trihydrate and polymethyl methacrylate, acceptable image transfer
has been obtained by preheating the article to a temperature of at least about 96.degree.
C. To insure intimate contact between the article, the carrier with the desired design
printed thereon, and the heated press platen during the heat transfer printing step, it may
be desirable to heat the article to the glass transition temperature of the preferred
material, about 110.degree. C., which would soften the material and enable it to more
intimately conform to the surface of the press platen. The glass transition temperature is
not to be construed as the upper temperature to be utilized for preheating, however, since
the preferred material has been successfully and routinely hot-shaped at higher
temperatures, for example 145.degree. C., to produce excellent finished articles.

EXAMPLE

A sheet of filled polymethyl methacrylate comprising 80% alumina trihydrate measuring

6".times.6".times.1/2" thick, was heated to 218.degree. F. (98.degree. C.) and placed into
a heat transfer press. A sheet of garment transfer paper, printed with a sublimable
disperse dye, was placed adjacent the surface of the polymeric sheet. The press was
activated at 20 psi (1.4 kg/cm.sup.2), the press plate contacting the garment transfer paper
at 410.degree. F., (210.degree. C.), for a print contact time of 30 sec. There was excellent
definition in transfer of the design from the garment transfer paper to the surface of the
polymethyl methacrylate sheet.

EXAMPLE 7 (PRINTING INK)

A 100 ml glass beaker is charged with 30 g of alkyd

resin thickener (Grinding Base 100-S, available
from Lawter Chemicals Inc.). Then 15 g of a dye
formulation according to Example 1 and 3 g of
desiccant paste (SIGBA) are added and the mixture
is stirred for 15 minutes to bring the dye particles
into homogeneous dispersion. The mixture is then
dispersed in a 3-roll mill (BUEHLER 3-roll mill,
type SDY 200) at 30.degree. C. A ready for use
printing ink is obtained.

EXAMPLE 8 (TRANSFER PRINTING ON PES)

The printing ink obtained in Example 7 is applied to

Transferotto-I paper (smooth transfer paper; 65
g/cm.sup.2) from a rubber printing roller using a
test printing machine (23.degree. C., 0.5 m/s and
590N). The add-on is 0.5 to 2.5 g/m.sup.2. The
printed support is dried and then polyester fabric is
printed with it by transfer printing (contact time 30
seconds, temperature 210.degree. C.). A brilliant
red print with sharp contours is obtained.