Dispersion composition and method for making and using same

Aqueous dispersion compositions comprise a binder component comprising a film-forming, water-dispersible, carboxyl group-containing elastomeric polymer composition, a thickener component, a chlorinated polyolefin component, and a polyorganosiloxane component dispersed in an aqueous liquid. Such compositions additionally comprising a crosslinking agent and, optionally, colorant composition are used for coating and printing substrates.

FIELD OF THE INVENTION 
This invention relates to dispersion compositions comprising a 
water-dispersible binder component comprising a film-forming, 
water-dispersible, carboxyl group-containing, elastomeric polymer 
composition; a thickener component; a chlorinated polyolefin component; a 
polyorganosiloxane component; and water. The invention also relates to a 
method for preparing such compositions and to coating and printing of 
substrates therewith. 
BACKGROUND OF THE INVENTION AND THE PRIOR ART 
U.S. Pat. No. 4,598,120, issued Jul. 1, 1986, to Thoma et al., discloses 
aqueous dispersion compositions useful as spreadable coating or printing 
pastes. The compositions contain an aqueous dispersion of a polyurethane 
or mixture thereof with an aqueous dispersion of a poly(meth)acrylate; a 
carboxyl group-containing, aqueous thickener polymer solution; a 
self-crosslinking polyorganosiloxane mixture comprising a polysiloxane 
with SiH groups and a polysiloxane with Si-vinyl groups; and a 
crosslinking agent for the polyurethane or polyurethane-poly(meth)acrylate 
mixture and thickener. Inclusion of pigments, antioxidants, flameproofing 
agents, antistatic agents, levelling aids, foam inhibitors, fungicides, 
bactericides, grip-improving agents and similar additives in the 
compositions also is disclosed as is application thereof to a textile 
substrate and heating to dry and react the compositions. Disclosed textile 
substrates are woven polyamide, polyester/cotton blend and polyester/rayon 
fabrics. 
U.S. Pat. No. 3,360,494, issued Dec. 26, 1967, to Bolinger, is directed to 
textile sizing and adhesive compositions of improved adhesion to fibers 
such as wool, nylon, Dacron and cotton. The compositions comprise a water 
soluble, unsaturated monocarboxylic acid polymer and a water-soluble 
polyurethane carried in an aqueous medium, with about 1-5 parts 
polyurethane component being present per part of the carboxylic acid 
polymer. According to the patent, the presence of the carboxylic acid 
polymer improves adhesion. Use of such compositions with Dacron/cotton, 
Dacron/viscose and Dacron/wool blended yarns, wool-worsted, spun nylon, 
cotton and Dacron yarns and with waterproof paper strips is shown in the 
examples of Bolinger. 
U.S. Pat. No. 3,529,990, issued Sep. 22, 1970, to Becker et al., discloses 
a finishing treatment for improving tear strength, crease-resistance, 
abrasion resistance and shape retention of various fabrics. The fabrics 
are treated with an aqueous bath containing polymers or copolymers of 
vinyl or divinyl monomers, including acrylic or methacrylic acid; a 
reaction product containing free isocyanate groups prepared from a 
polyisocyanate and an organic compound having at least two active hydrogen 
atoms selected from compounds having molecular weights of 500-10,000, 
organopolysiloxanes and combinations thereof; and water-soluble, 
carboxylic acid salts of Group I, II or VIII metals. The treated fabrics 
are subsequently treated with water or steam. Fabrics to be treated may be 
based on cotton, cellulose, wool, silk, polyamides, polyurethane, 
polyesters, polycarbonate, polyacrylonitrile, polypropylene and the like 
according to the patent. Use of polyacrylonitrile/wool blend fabrics, wool 
yarns, wool silver, polyacrylonitrile fibers, polyester/polyamide blend 
fabric, cotton fabric, knitted wool, wool georgette, wool cloque and wool 
fabric is disclosed in the examples. 
Aqueous coating and printing compositions, however, are poorly suited for 
use with hydrophobic and inert substrates, such as polyolefins, due to 
poor adherence thereto, poor abrasion, weather and stain resistance and 
poor launderability. 
Various organic solvent-based printing and coating compositions also are 
known. U.S. Pat. No. 3,547,870, issued Dec. 15, 1970, to Listner et al., 
is directed to organic solvent-based inks for application to plastic 
articles, including those of polypropylene, without surface treatments. 
The patent discloses inks with about 3-25 wt. % of a so-called 
"randiopropylene," defined as a diethyl ether-soluble polypropylene 
prepared by steric rearrangement of so-called "isotactic" polypropylene 
using a free radical initiator and a bromine compound; about 20-80 wt. % 
organic solvent, such as xylene, toluene, diethyl ether, methyl ethyl 
ketone, methyl isobutyl ketone, diisopropyl ether, ortho-dichlorobenzene, 
Solvesso 150, mixed aromatic solvent, hexane, heptane, decane and blends 
thereof; about 15-60 wt. % pigment; and, if needed, tackifiers, 
detackifiers, thickeners and other additives. U.S. Pat. No. 3,707,347, 
issued Dec. 26, 1972, to Mueller, discloses printing compositions for 
various plastics, including polyolefins, containing an organic colorant 
dispersed or dissolved in a dye carrier, such as a conventional 
lithographic varnish or an epoxy resin in a suitable organic solvent. 
Adjuvants such as thickening agents, e.g., silica and bentonite; 
anti-foaming agents, e.g. dimethylpolysiloxanes; and wetting agents, e.g. 
xylene, also may be included. Published European Patent Application No. 
84108904.8, published Dec. 11, 1985, of Boston S.p.A., discloses writable 
adhesive tapes having a polyolefin substrate film coated on one side with 
an adhesive layer, such as acrylic, polyurethane or polyester copolymers 
or natural or synthetic rubbers or resins, and coated on the other side 
with a writable or printable anti-adhesive layer containing a chlorinated 
polyolefin and a polyaldehyde resin as film-forming adhesion promoters to 
the substrate and anti-adhesive and matting agents. The anti-adhesive 
layer also can contain a linear elastomeric polyurethane. Application of 
the anti-adhesive layer to the polyolefin substrate is conducted by 
coating the same with the anti-adhesive layer components dissolved or 
dispersed in a hydrocarbon solvent according to this publication. U.S. 
Pat. No. 4,608,415, issued Aug. 26, 1986, to Nakajima et al., discloses 
compositions useful as a vehicle in coating materials, printing inks or 
adhesives for plastics, especially polyolefin plastics, containing a 
chlorinated polyolefin, with less than 50 wt. % chlorine, reacted with a 
fatty acid-modified resin such as an alkyd, epoxy, phenol, polyamide resin 
or a resin based on a conjugated diene, triene or acid or a copolymerized 
oil. The chlorinated polyolefin is preferably dissolved in a solvent such 
as toluene or xylene prior to reaction. The compositions are said to be 
adherent to polyolefins and, as such, suitable vehicles for printing inks. 
A disadvantage of organic solvent-based systems is the need for handling 
and disposal of the solvents in manufacture and use thereof. 
Thus, there remains a need for improved coating and printing compositions 
and methods for preparing and using the same. It is an object of this 
invention to provide such compositions and methods for preparing and using 
the same. A further object of this invention is to provide improved 
dispersion compositions. A further object of the invention is to provide 
dispersion compositions suitable for use in printing and coating 
polyolefin substrates, including polypropylene fabrics. A further object 
of the invention is to provide improved printed or coated polyolefin 
substrates in which adhesion to the substrate, abrasion resistance, crock 
resistance and ability to withstand laundering are improved. Other objects 
of the invention will be apparent. 
I have now found that the objects of this invention can be attained by 
providing dispersion compositions comprising a water-dispersible binder 
component comprising a film-forming, water-dispersible, carboxyl 
group-containing, elastomeric polymer composition; a thickener component; 
a chlorinated polyolefin component; a polyorganosiloxane component; and 
water. In another embodiment these objects are attained by providing such 
compositions additionally comprising a crosslinking agent. The latter 
compositions, when applied to substrates and cured, show excellent 
adhesion to the substrates. Such compositions also are suitable vehicles 
for colorants and, with addition thereto of colorant compositions, can be 
used for printing. Polyolefin fabrics printed or coated using such 
compositions have good abrasion resistance, resistance to crock, and 
retention of coatings and color after laundering. Advantageously, the 
present invention does not require modification of the substrate surfaces 
to achieve coloration and adhesion thereto. Further, the components of the 
invented compositions are readily available commercially and the 
compositions can be applied to substrates using equipment conventionally 
used in coating and printing operations. 
DESCRIPTION OF THE INVENTION 
Briefly, the dispersion compositions according to this invention comprise a 
binder component comprising at least one film-forming, water-dispersible, 
carboxyl group-containing, elastomeric polymer composition; a thickener 
component; a chlorinated polyolefin component; a polyorganosiloxane 
component; and water. These compositions also can contain a colorant 
composition dispersible therein. For use in printing and coating of 
substrates such compositions, with or without colorant compositions, 
additionally comprise a crosslinking agent. 
Also provided according to this invention is a method for preparing such 
dispersion compositions comprising combining components comprising a 
water-dispersible binder component comprising a film-forming, 
water-dispersible, carboxyl group-containing, elastomeric polymer 
composition, a thickener component and water to form a thickened aqueous 
dispersion and adding to such dispersion components comprising a 
chlorinated polyolefin component, a polyorganosiloxane component, a 
crosslinking agent and, optionally, a colorant composition, under shear 
sufficient to form a substantially uniform aqueous dispersion composition. 
For use in printing and coating, such compositions, with and without a 
colorant composition dispersed therein, respectively, are applied to a 
substrate and cured. 
In greater detail, the binder component of the invented compositions 
comprises a film-forming, water-dispersible, carboxyl group-containing 
elastomeric polymer composition. The binder component is capable of 
forming a continuous coating or film of sufficient elasticity to resist 
cracking due to stretching or folding of substrates coated or printed 
using the invented compositions. Aqueous dispersions of the binder 
component are capable of dispersing the colorant compositions used 
according to the invention into discrete particles and, upon curing of the 
compositions, the colorant particles are bound in the continuous film or 
coating. 
A preferred composition for use as a binder component of the invented 
compositions, and particularly those for use in coating or printing woven 
polyolefin substrates prepared from medium or high denier, continuous 
filament or spun yarns comprising polyolefin, e.g., polypropylene, is a 
water-dispersible, film-forming, elastomeric urethane polymer composition. 
Such compositions can be prepared by reaction of components comprising a 
glycol or polyol of polyester or polyether with diisocyanate by known 
methods. Urethane polymer compositions suitable as binder components in 
the invented compositions are water-dispersible in the sense that they are 
capable of forming an emulsion or dispersion that can be diluted with 
water. Aromatic and aliphatic urethane polymer compositions are suitable; 
however, the aliphatic compositions are preferred because they are less 
prone than the aromatic compositions to discolor due to exposure to 
ultraviolet light. Presence of residual hydroxyl or isocyanate groups in 
the polymers can cause undesirable reactions with water in the invented 
compositions; accordingly, urethane polymer compositions free or 
substantially free of unreacted isocyanate are preferred. 
Examples of water-dispersible urethane polymer compositions are those known 
as Spensol.RTM. water-dispersible polyurethane elastomers sold by Spencer 
Kellog, specific examples of which include those designated L44, L50, L51, 
L52, L54 and L56. Such compositions are described by the manufacturer as a 
dispersion of fully reacted thermoplastic urethane in a solvent mixture of 
water and N-methylpyrrolidone. Weight ratio of water to N-methyl 
pyrrolidone generally ranges from about 3:1 to about 10:1. Solids contents 
of such dispersions typically ranges from about 30 to about 40 wt. %. The 
urethane polymer may be present in such compositions as a tertiary amine 
salt, e.g. triethylamine salt, and minor amounts of free tertiary amine, 
for example up to about 5 wt. % based on solvent weight, may be present. 
Such polymers and preparation thereof are disclosed in U.S. Pat. No. 
4,203,883 to Hangauer, Jr., and U.S. Pat. No. 4,431,763 to Reed, issued 
Feb. 14, 1984, which are incorporated herein by reference for the purpose 
of describing such polymers and methods for preparing them. The polymers 
can be made by reacting an aqueous dispersion of a tertiary 
amine-neutralized, isocyanate-terminated urethane prepolymer with 
triamine-containing polyamine. The isocyanate-terminated urethane 
prepolymer is formed by the reaction of isocyanate and polyol, at least a 
portion of the polyol having at least one carboxylic group which is 
relatively non-reactive with isocyanates. A portion of all of the 
carboxylic groups of the urea-urethane is neutralized with tertiary amine 
groups to provide a polymer which can have a relatively neutral pH in an 
aqueous dispersion, e.g., pH less than about 11. The urea-urethane 
polymers have an average particle size in the colloidal size range, e.g., 
less than about 0.1 micrometer, and sufficient tertiary amine-neutralized, 
carboxylic groups to provide stable, aqueous dispersions having infinite 
dilutability with water. Monomers used in preparation of Spensol L-51 and 
Spensol L-54 are reported to include 4,4'-methylene 
bis(cyclohexylisocyanate), adipic acid, hexanediol, dimethylolpropionic 
acid and a glycol component which is neopentyl glycol in the case of 
Spensol L-51 and diethylene glycol in the case of Spensol L-54. 
Compositions suitable as a binder component of the invented compositions 
also include film-forming, water-dispersible, elastomeric acrylic polymer 
compositions. For some applications these can offer advantages over the 
urethane polymer compositions discussed above due to greater elasticity of 
compositions based thereon after curing, softness and flexibility of 
substrate fabrics printed or coated using such compositions. 
Such acrylic polymer compositions typically are water-insoluble but capable 
of being emulsified with water to form water-dilutable dispersions. The 
compositions comprise polyacrylate or polymethacrylate compositions 
prepared from monomers comprising acrylic or methacrylic acid and alcohol 
by known methods. 
Preferred acrylic polymer compositions are those capable of forming 
air-cured films, that is films cured by circulating air, at about 
212.degree.-300.degree. F., having elongations of at least about 300% 
because the invented compositions based on such binder components have 
sufficient elasticity to resist cracking due to stretching of substrates 
coated or printed using the invented compositions. More preferably, such 
acrylic polymer compositions, in the form of air-cured film, have 
elongations of about 600% to about 1200% as such binders exhibit excellent 
elasticity. 
Examples of acrylic polymer compositions suitable as a binder component of 
the invented compositions include elastomeric acrylic polymer latexes 
designated Elastomeric Latex V-29 and Elastomeric Latex V-43 from the B. 
F. Goodrich Company, both described by the manufacturer as suitable for 
pigment loading with pre-dispersed pigments and available as latexes 
having about 50 wt. % solids content. The former product is described as a 
water-based, anionic, elastomeric terpolymer latex or emulsion having 
solids content of 52%, pH of 5.0, surface tension of 42 dynes/cm, 
Brookfield viscosity of 70 cP and glass transition temperature of 
-29.degree. C., air-cured, 10 mil films of which have elongations of about 
750 to about 1100% when cured at 212.degree.-300.degree. F. The latter 
composition also is described as an elastomeric terpolymer latex, with 
total solids content of 50.5%, pH of 8.4, surface tension of 40 dynes/cm, 
Brookfield viscosity of 200 cP and glass transition temperature of 
-43.degree. C. 
The binder component of the invented compositions can comprise a 
combination of film-forming, water-dispersible, carboxyl group-containing, 
elastomeric polymer compositions. For example, a combination of urethane 
polymer and acrylic polymer compositions as described above is well suited 
for use when the invented compositions are to be used for coating or 
printing substrates woven or knit from fine or medium denier, continuous 
filament or spun yarns, as for example, low denier, air-textured 
continuous filament yarns used for apparel fabrics. For such applications, 
the urethane and acrylic polymer compositions preferably are used in a 
weight ratio of at least about 1 part acrylic polymer composition per part 
urethane polymer composition to achieve a desirable balance of stretch, 
mar resistance and lightfastness. 
The invented compositions also include a thickener component which 
functions to increase viscosity thereof to facilitate application to 
substrates of the compositions in paste from or by spreading. Suitable 
thickeners for aqueous coating and printing compositions are well known 
and include various gums, ammonia, ammonium sulfate and various 
water-soluble or water-dispersible, carboxyl group-containing polymers. 
Examples include various gums such as that identified as Paragum 109 and 
polyacrylic acid and polyacrylate salts, such as that designated Printing 
Concentrate.TM. 957 Thickener from Morton Thiokol, Inc., which is a 
polyacrylic acid salt dispersed in Stoddard Solvent, an aliphatic 
petroleum distillate, and described as having typical solvent content of 
26-28%, Brookfield viscosity at 25.degree. C. of 2000-8000 cps, typical pH 
of 7.5-8.5 and as being dispersible in water, and that designated Cru Thix 
46 from Crucible Chemical Company, a 13% solids content, aqueous solution 
of sodium polyacrylate described as having pH of 9.0 and Brookfield 
viscosity of 20,000 cps maximum. The latter is a preferred thickener 
component for use in the invented compositions containing a urethane 
polymer composition as a binder component, while the polyacrylic acid salt 
composition is preferred for use when the binder comprises an acrylic 
polymer composition, due to reactivity of such components. 
The invented compositions also comprise a chlorinated polyolefin component. 
As is known, chlorinated polyolefins adhere to a wide range of substrates, 
including polypropylene, and are sold as stir-in additives for promoting 
adhesion of coatings and inks to substrates, including those of 
polypropylene. In the invented compositions, the chlorinated polyolefin 
component functions as an adhesion promoter. 
Suitable chlorinated polyolefins include known materials and generally 
comprise one or more chlorinated homo- or copolymer polyolefins having 
chlorine content of about 15 to about 65 wt. %. The materials typically 
are commercially available as solutions in aromatic hydrocarbon solvents, 
for example, 25 or 40 wt. % in xylene or mixed aromatic solvents, e.g. 
aromatic naphtha, and can be diluted to lower concentrations with such 
solvents or others such as toluene. Examples of such chlorinated 
polyolefin components are those designated Chlorinated Polyolefin CP-515-1 
and CP-515-2 from Eastman Chemical Products, Inc. which are available as 
40 wt. % solutions in xylene or aromatic solvent, identified as Aromatic 
100, and described by the manufacturer as having specific gravities at 
25.degree./25.degree. C. of 0.955 and 0.944 and Brookfield viscosities at 
25.degree. C. of 80 and 220 cP, respectively. 
The polyorganosiloxane component of the invented composition is an 
organosilicone fluid and functions to improve mar, abrasion and crock 
resistance of the invented compositions after curing. Preferred 
polyorganosiloxane components comprise polydialkylsiloxane homo- and 
copolymer compositions, an example of which is that designated Silicone 
Fluid Y-9229 from Union Carbide Corporation which is described by the 
manufacturer as a water-insoluble, organomodified polydimethylsiloxane 
copolymer boiling at greater than 150.degree. C. and freezing below 
0.degree. C. and having specific gravity at 25.degree./25.degree. C. of 
0.98 and vapor pressure at 20.degree. C. below 1 mm mercury. 
Water is present in the invented compositions as a dispersant for the 
binder and other components of the compositions. 
Prior to use of the invented compositions for printing and coating, the 
same also must comprise a crosslinking agent although the compositions 
preferably are stored and handled with the crosslinking agent absent 
because shelf life after addition of the same is limited. Suitable 
crosslinking agents are those capable of causing crosslinking by reaction 
with carboxyl groups of the binder component. Preferred crosslinking 
agents for the invented compositions include carbodiimide compounds, an 
example of which is that designated Crosslinker XL-25 SE from Union 
Carbide Corporation. This material is described as a 50 wt. % total solids 
content solution of carbodiimide compound in propylene glycol monomethyl 
ether acetate having a flash point of 112.degree. F. and suitable for 
addition directly to most waterborne coating formulations with minimal 
agitation and useful for improving solvent resistance and durability of 
waterborne polyurethanes. Polymeric aziridine resins also are known 
crosslinking agents for urethane polymers and may be included in the 
invented compositions although use thereof is not preferred. 
The invented compositions comprise a dispersion of components as described 
above in an aqueous medium. Solids content of the dispersion can vary 
widely and be adjusted depending on various practical considerations such 
as storage, shipping and end use requirements. Preferably, total solids 
content of the compositions ranges from about 2 to about 60 wt. %, with 
about 25 to about 50 wt. % being more preferred when the binder component 
comprises a urethane polymer composition as described above and about 3 to 
about 30 wt. % being more preferred when acrylic polymer composition as 
described above is the binder component. The aqueous, liquid dispersing 
medium comprises water and may also contain minor amounts, e.g., up to 
about 25 wt. % based on total liquid, of organic materials such as those 
that may be present in the various components of the invented composition 
as used in preparation thereof. Examples of such organic materials include 
xylenes or mixed aromatic solvents of the type present in the chlorinated 
polyolefin component, nitrogen-containing organics, such as 
N-methylpyrrolidone, which may be present in some of the binder components 
in commercially available form and aliphatic petroleum distillates and 
deodorized kerosene which may be present in some thickener components. 
Preferably, water content of the aqueous, liquid dispersing medium is at 
least about 85 wt. % based on total dispersing medium weight. 
Component proportions in the invented compositions can be varied depending 
on end use and processing requirements. Generally, the binder component is 
present in an amount effective to form a continuous film on the surface of 
a substrate to which the compositions are applied after curing of the 
compositions. When using such compositions as vehicles for colorant 
compositions, the binder also should be present in an amount effective to 
achieve suitable dispersion of colorant. The chlorinated polyolefin 
component is present in an amount effective to promote adhesion of the 
invented compositions, after curing, to substrates to which they are 
applied. The polyorganosiloxane component is present in an amount 
effective to improve mar resistance of the cured compositions without 
contributing excessive oilness thereto. Thickener component is used in an 
amount effective to increase viscosity of the compositions of a level 
suitable for application thereof to substrates. The amount of crosslinking 
agent is an amount effective to promote substantial crosslinking of the 
binder component on curing. 
Preferably, binder component solids content in the invented compositions is 
at about 75 to about 98 wt. % of total solids content to obtain good 
film-forming characteristics and dispersibility of colorants if used, with 
about 80 to about 95 wt. % being more preferred. Chlorinated polyolefin 
component solids content preferably is about 0.5 to about 10 parts by 
weight per hundred parts by weight binder solids to achieve good adhesion 
promotion without difficulty in dispersing the component in the invented 
compositions. Polyorganosiloxane component content preferably ranges from 
about 2 to about 20 parts by weight per hundred parts by weight binder 
solids to provide mar and abrasion resistance without oiliness. Thickener 
component solids content preferably ranges from about 0.5 to about 30 
parts by weight per hundred parts by weight of binder solids with precise 
amounts varying with desired product viscosity. Preferred crosslinking 
agent solids content ranges from about 1 to about 10 parts by weight per 
hundred parts by weight binder component solids. 
Colorant compositions that can be included in the invented compositions are 
materials dispersible therein and include a wide range of materials known 
to the art. Examples include titanium dioxide, a well known white pigment, 
as well as various organic colorant compositions such as organic colorant 
dispersions and micronized powders capable of being dispersed in the 
invented compositions. Specific examples of organic colorant compositions 
include resin-dispersed pigments such as Flexiverse pigments from Sun 
Chemical Co. comprising colorants dispersed in acrylic resin compositions 
and those known as Hi-Fast N pigments from BASF. 
Colorants are included in amounts effective to achieve the desired degree 
of coloration in finished products, with greater amounts producing deeper 
shades and lesser amounts producing lighter shades. Preferred colorant 
levels range from about 0.05 to about 5 wt. % based on weight of the 
dispersion compositions to achieve coloration without reducing resistance 
to crock in finished products. 
Particularly preferred compositions according to the invention are shown in 
the following table wherein component proportions, in parts by weight per 
hundred parts by weight of total binder component, are designated "pbw": 
______________________________________ 
Composition: 
1 2 3 
______________________________________ 
Binder Spensol Elastomeric Spensol L-56 
Component L-56.sup.(1) 
Latex V-29.sup.(5) 
and Elasto- 
meric 
Latex V-29 
(wt ratio = 
1:3 to 1:9) 
Thickener 1-10 0.5-5 1-10 
Component (pbw) 
Cru Thix Printing Concen- 
Printing 
46.sup.(2) 
trate 957 Concentrate 
Thickener.sup.(6) 
957 
Thickener 
Chlorinated Poly- 
1-7 1-5 1-7 
olefin Component 
CP-515-2.sup.(3) 
CP-515-2 CP-515-2 
(pbw) 
Polyorgano 1-5 0.1-5 1-5 
siloxane Silicone Silicone Fluid 
Silicone 
Component (pbw) 
Fluid Y-9229 Fluid 
Y-9229.sup.(4) Y-9229 
Water (pbw) 200-400 
______________________________________ 
(1) aqueous dispersion of fully reacted aliphatic urethane polymer, 35-37 
wt. % solids content, in solvent of about 79% water, 19% 
Nmethylpyrrolidone and 2% amine. 
(2) aqueous sodium polyacrylate solution, 13% solids content. 
(3) 40 wt.% solution of chlorinated polyolefin in Aromatic 100 solvent. 
(4) copolymer organosilicone fluid comprising copolymer 
polydimethylsiloxane. 
(5) aqueousbased acrylic polymer latex, 52% solids. 
(6) polyacrylic acid salt dispersed in aliphatic petroleum distillate, 
26-28% solvent content. 
In such compositions, a preferred crosslinking agent is that identified as 
XL-25 SE, which comprises carbodiimide crosslinking agent as a 50 wt. % 
solids content solution in propylene glycol monomethyl ether acetate. 
Preferred levels of crosslinking agent in such compositions are about 1-5 
parts per hundred parts by weight of total binder component. 
Additives of various types, such as fillers, flame retardants, U.V. 
stabilizers, levelling agents and anti-bacterial agents may be included in 
the invented composites if desired. 
The invented compositions are prepared by a method comprising combining 
components comprising the binder and thickener components and water with 
agitation to form a thickened aqueous dispersion and adding to the 
thickened dispersion components comprising chlorinated polyolefin and 
polyorganosiloxane components and, optionally, colorant composition under 
shear effective to form a substantially uniform aqueous dispersion 
composition. If desired, colorant composition or additional thickener 
component or both may be added subsequently to the aqueous dispersion 
composition. Such later addition can afford flexibility and convenience in 
printing or coating operations by allowing addition of particular 
colorants or levels of thickeners tailored to specific end uses to a stock 
dispersion of the binder, thickener, chlorinated polyolefin and 
polyorganosiloxane components. Prior to use in printing or coating 
substrates, crosslinking agent is added to the aqueous dispersion 
composition under shear. Addition of crosslinking agent is conducted 
shortly before such use because shelf life of the compositions is limited 
after addition of crosslinking agent. 
In preparing the invented compositions, the components preferably are 
combined at ambient temperature. Mixing of the binder and thickener 
components and water is conducted with agitation sufficient to achieve 
substantially uniform dispersion. Addition of the remaining components is 
conducted under conditions of high shear to achieve substantially uniform 
dispersion. Preferably, mixing under high shear is continued for a period 
of time after the addition is complete. Generally, the time and rate of 
mixing and shearing can be varied to achieve adequate dispersion at 
suitable production rates. Conveniently, conditions of high shear are 
achieved by mixing the components in a mixing device equipped with a high 
speed impeller and, preferably, with sweep blades or other suitable means 
for avoiding accumulation of solids on the mixing vessel walls. 
The invented compositions are suitable vehicles for colorant compositions 
as described above and, with and without addition of colorant 
compositions, suitable for printing and coating, respectively, of 
substrates after addition of crosslinking agent. Colorant-free coatings of 
the invented compositions serve as useful stabilizers for fabric 
substrates. Coating and printing of substrates is conducted by applying 
the compositions, including crosslinking agent and desired levels of 
colorant compositions to the substrate and curing the composition. 
The invented compositions can be applied to substrates by any suitable 
technique such as by spreading and other coating and printing techniques. 
Flat bed screen printing and rotaty printing equipment can be used as can 
cylinder presses and gravure and flexographic printing equipment. For use 
in flat bed screen printing and rotary printing, viscosity of the 
compositions preferably is about 14,000 to about 20,000 CP as higher 
viscosities can be difficult to apply uniformly while lower viscosities 
may result in pour coating integrity after curing. Application rates 
depend on substrate characteristics, number of colors, design and other 
factors and preferably range from about 0.1 to about 2 ounces per square 
yard in the case of fabric substrates. 
Curing is conducted by heating the substrates with the invented 
compositions applied thereto to a temperature and for a time effective to 
achieve reaction of the reactive components of the composition and drive 
off water and other volatile components and form a continuous film or 
coating adhering to the substrate in the areas to which the invented 
compositions have been applied. Generally, heating is conducted at about 
165 to about 350.degree. C. for about 15 to about 100 seconds, although 
curing should not be so severe as to damage the substrate. For printing 
and coating polypropylene substrates, preferred curing conditions include 
temperatures of about 165 to about 205.degree. F. for about 20 to about 90 
seconds. 
Substrates suitable for coating or printing with the invented compositions 
include natural and synthetic materials such as cotton fabrics, 
cotton/polyester blends, polyester fabrics and polyolefin fabrics such as 
polypropylene and polyethylene. The invented compositions are particularly 
suited for printing and coating polyolefin fabrics, and especially woven, 
knit and nonwoven polypropylene fabrics, for example, fabrics prepared 
from texturized or nontexturized continuous filament yarns or spun yarns 
such as are used in manufacture of sporting apparel, softsided luggage and 
wall coverings. Such fabrics can be woven or knitted from fine, medium or 
heavy denier yarns. For use in printing fabrics prepared from fine denier 
yarns, the invented compositions in which the binder component comprises 
an acrylic polymer composition are preferred. For fabrics prepared from 
heavier yarns, preferred compositions are those for which the binder is a 
urethane polymer composition.

The present invention is described further in the following examples, it 
being understood that the same are for purposes of illustration and not 
limitation. 
EXAMPLE 1 
To a Meyers, Dual Action L-550 High Speed Mixer equipped with mixing and 
sweep blades were added 25 parts by weight of a 52% solids content, 
acrylic polymer latex identified as Elastomeric Latex V-29 from B. F. 
Goodrich Company, 75 parts by weight water and 1 part by weight of a 
polyacrylic acid salt dispersed in aliphatic petroleum distillate having 
solvent content of 26-28% and identified as Printing Concentrate 957 
Thickener from Morton Chemical. These components were sheared at about 
2000-3000 rpm for about 5 minutes to form a thickened aqueous dispersion 
having a milky white appearance. The thickened dispersion was subjected to 
shear by mixing at 2000-3000 rpm and to the vortex of the sheared 
dispersion were added 0.075 parts by weight polyorganosiloxane component 
identified as Silicone Fluid Y-9229 from Union Carbide Corporation, 0.375 
parts by weight of a 40 wt. % solution of chlorinated polyolefin in 
Aromatic 100 solvent, identified as CP-515-2, 0.25 parts by weight of an 
acrylic resin-dispersed colorant identified as Flexiverse from Sun 
Chemical Co. and 0.75 parts by weight carbodiimide crosslinking agent as a 
50% solids content solution in propylene glycol monomethyl ether acetate 
identified as Ucarlink XL-25 SE from Union Carbide Corporation. Shearing 
was continued for about 15-30 minutes after component addition was 
completed. 
The resulting dispersion was applied to a knitted apparel fabric prepared 
from untextured, continuous filament polypropylene yarns using a flat bed 
hand press at an application rate of about 0.1 ounce per square foot, 
after which the fabric with the dispersion applied thereto was cured in 
infrared-heated air at about 200.degree. F. for about 45 to about 85 
seconds. 
Samples of the resulting printed fabric, after curing, were tested for 
crock according to AATCC No. 8. After 20 cycles with a one pound weight 
and cotton cloth used for rubbing, the fabric had dry and wet crock 
ratings of 5 on a scale of 1-5, indicating resistance of the printed 
fabric to crock and essentially no color ruboff. 
Samples of the fabric also were tested for washability by AATCC No. 61 
using a Kenmore washing machine with 140.degree. F. water and recommended 
levels of Tide detergent. After 20 cycles, the samples were rated 5 on a 
scale of 1-5, indicating essentially no loss of color due to washing. 
EXAMPLE 2 
Following generally the procedure of EXAMPLE 1, a thickened dispersion was 
prepared from 100 parts by weight of a 35-37 wt % solids content 
dispersion of fully reacted aliphatic, elastomeric urethane polymer 
composition in a solvent mixture of 79% water, 19% N-methylpyrrolidone and 
2% amine, identified as Spensol L-56 from Spencer Kellogg, and 3 parts by 
weight of a 13% solids content, aqueous solution of sodium polyacrylate 
identified as Cru Thix 46 from Crucible Chemical Company. To the vortex of 
the sheared, thickened dispersion were added 2 parts by weight of the 
polyorganosiloxane used in EXAMPLE 1, 3 parts by weight of the chlorinated 
polyolefin solution used in EXAMPLE 1, 1 part by weight of the colorant 
used in EXAMPLE 1, and 3 parts by weight of the carbodiimide solution used 
in EXAMPLE 1. The resulting dispersion was then used to print a wall cover 
fabric woven from bulked continuous filament polypropylene warp yarns and 
spun polypropylene fill yarns by rotary screen printing. Curing was 
conducted in a gas-fired oven at about 185.degree. F. for about 60 
seconds. 
The resulting printed fabric was tested for crock as in EXAMPLE 1 and was 
rated 5 for both wet and dry crock. 
Samples also were tested for abrasion according to ASTM D-4157 at two 
pounds pressure and two pounds tension using a Wyzenbeek device and cotton 
duck fabric as an abrader. The samples were rated Heavy, indicating no 
noticeable wear. 
Samples of the fabric also were tested using a 2500 watt Carbon Arc 
Weatherometer. Water was periodically sprayed on the fabric during 
exposure. At 50 hours, samples showed no noticeable change, at 75 hours 
they exhibited noticeable change and at 150 hours there was radical 
changes. 
Testing of the fabric using a Fadeometer with a 6500 watt Xenon bulb showed 
no noticeable change at 100 and 250 hours, and minimal change, 
corresponding to a color loss of no more than 5% on the AATCC color scale, 
after 545 hours. 
Fabric samples also were stained with each of ketchup, mustard, cherry 
Kool-Aid, lipstick, chocolate syrup and crayon and then washed with 
various cleaners including undiluted Clorox bleach, undiluted white 
vinegar, 409 cleaner and Parson's Sudys Ammonia. In all tests, the stains 
washed off leaving the printed areas unaffected. 
EXAMPLE 3 
Following generally the procedure of EXAMPLE 1, an aqueous dispersion 
composition was prepared from 20 and 80 parts by weight, respectively, of 
the urethane and acrylic polymer-based binder components used in EXAMPLES 
1 and 2, 2.6 parts by weight of the thickener component used in EXAMPLE 1, 
1.5 parts by weight of the polyorganosiloxane component used in EXAMPLE 1, 
2 parts by weight of the chlorinated polyolefin component used in EXAMPLE 
1, 1 part by weight of the colorant used in EXAMPLE 1 and 3 parts by 
weight of the crosslinking agent used in EXAMPLE 1. 
The composition was used to print a stretch apparel fabric knit from 90% 
fine denier polypropylene yarns and 10% Lycra yarns. Printing and curing 
were conducted essentially as in EXAMPLE 1. 
Washability testing according to AATCC No. 61 as in EXAMPLE 1 gave a rating 
of 4 indicating good color retention.