CA1043500A - Graphic arts and graphic media - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Graphic arts media are provided which off raised, three-dimensional effects. A basic medium is formulated of a colorant, a film-forming binder, a vehicle and thermally expandable micro-spheres. The medium is selectively applied to a substrate, dried, and heated to expand the microspheres.

Description

10~3500 .. .. . . .
The present invention relates to three-dimensional graphic arts, fine ar~s, printing, decoraLing and the like. More particularly, it relates to a method of forming three-dimensional graphic designs and the like on a substrate, the three-dimensDnal representations and forms produced thereby, and compositions em~loyed in the method. Still more particularly, the present invention relates to compositions of matter for use in the for-mation of three-dimensional designs, printing,and the like, the method of forming such three-dimensional graphic designs, print-ing,and the like, and the three-dimensional designs formed by such method.
A wide variety of compositions are employed in the graphic arts in order to obtain diverse optical effects. Yet there is always wide-spread demand for new compositions and new tech-niques which can increase the store of effects available to those of skill in such arts. While many of the compositions and téchniques have been known for centuries and yet still find wide spread usage, the field of graphics i9 ~uite a dynamic art, whatever particular branch thereof is considered. As employed in the present application, the term "graphic arts" is used in - a broad sense to include fine arts, commercial art, decorative arts, related arts such as printing and the like. Also included are photography and related arts. In particular, the term "graphic arts" as employed herein can be generalized to include

-2-1043~0 1 all those arts which involve the formation of a graphic repre-sentation or decorative pattern or the like upon a substrat0.
Particular examples include such diverse, but interrelated, subdivisions as painting, drawing, lithography, silk-screening, photolithography, wood-cuts, stencilling, printing, wall-paper 1~ ~r~grc~fh~
manufacture, photography, zorography and various combinations of such arts with one another and with still other arts, e.g.
sculpture, wood-carving, molding, ceramics and the like.
It is an object of the present invention to provide com-positions for use in the graphic arts for the formation ofraised or three-dimensional graphic representations, a method of forming such representations, and the representations so formed.
Another object of the present invention is to provide such compositions in such form that the raised or three-dimensional character is attained after the graphic representation is applied to a substrate, enabling the practitioner of the art to utilize conventional and well-known techniques to apply the graphic medium to the substrate and thereafter attain the raised or three-dimensional character.
Still another object is to provide the compositions of the present invention in such form that its utilization can be integrated with conventional procedures, techniques, processing equipment and apparatus without modification thereof and subse-quently further treating the compositions to achieve the raised or three-dimensional effect. These and still other objects, as will hereinafter become apparent, are attained by the present invention.

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1 It ha9 been found that raised or three-dimensional graphic effects can be attained by incorporating into graphic media a minor amount of thermally expandable microspheres, selectively applying such media to a substrate by the applicable techniques therefor, and thereafter heating the selectively coated sub-strate to expand the microspheres. ~he expansion thus attained creates a raised or three-dimensional result which can be characterized as a continuous matrix of the medium employed, containing a disperse phase of expanded microspheres.
The graphic media to which the present invention is applicable can be generally defined as any of the diverse media which can be characterized by the formation of a substantially continuous film where selectively applied to a substrate, and in which the microspheres can be incorporated as a disperse phase.
Such graphic media include, by way of example, paints, inks, laquers, enamels, photographic emulsions and the like. In the more common cases, such media include a pigment, or the equiva-lent, and a binder therefor which is capable of forming a sub-stantially continuous solid film upon the chosen substrate and often include a wide variety of other materials, such as one or more of the following: solvents, diluents, opacifiers, fillers, extenders, leveling agents flow promoters, plasticizers, driers, cross-linking agents, viscosity control agents, wetting agents, dispersing aids, gloss control agents, and the like.
As employed herein, the term "pigment" is intended to be inclusive of that class of materials which may be employed to impartoolor properties to a graphic medium or media. As such, it is intended to include not only literal pigments, but also dyes, lakes, and like materials, and precursors thereof as well, 104~S00 1 as is the case in photographic procedures.
The solid film~forming binder will most often be a natural or synthetic polyer material dissolved in a solvent therefor which, upon evaporation of the solvent or reaction thereof, results in the formation of a substantially continuous adherent film. In other cases, the polymeric material may be a disperse phase of an emulsion or latex or the like. In still other cases, the vehicle may be a liquid or semi-solid polymer precursor, i.e. monomer of "pre-polymer" which reacts ln situ to provide the film-forming polymer. In such cases, polymeri-zation catalysts may also be included. A solvent or thinner may or may not be required or desired in such systems. The polymeric film-forming binder can be thermoplastic or thermo-setting. Mixtures of polymers may be used as well as single materials.
Such graphic arts media are well known to those of ordinary skill in the art and are not per se a part of the pre-sent invention. It is accordingly not intended that the inven-tion be construed as limited narrowly to specific media or to particular categories thereof. Nor should the invention be limited with regard to component ingredients of such media except as herein defined.
In accordance with the present invention, expandable microspheres are dispersed into the graphic medium. The micro-spheres employed in the present invention are hollow thermo-plastic particles and are of relatively small size, usually less than from about 200 to 300 microns in diameter and can be as small as about 0.5 microns in diameter. Preferably micron diameters of from about 3 to 50, and more preferably about 5 ~04;~$00 1 to 20, are employed. The microspheres have a generally ~pherical shape and define a generally concentric spherical cavity inside containing about 5 to 50 weight percent of a volatile blowing agent, insoluble or at most only slightly soluble in the thermo-plastic material of the microsphere. Microspheres of such character can be prepared with bulk densities ranging from about 50 to 90 pounds per cubic foot. The thermoplastic of the microspheres can be generally any thermoplastic polymer but if the formation of a solution coating composition is con-templated, the thermoplastic of the microspheres should bedifferent from the foamable coating polymer and not soluble in the solvent.
The microspheres can be conveniently prepared by the techniques referred to as a "limited coalescence" polymerization technique. A typical preparation of such particles is as follows:
A polymerization reactor equipped with an agitator is charged with 100 parts by weight of deionized water and 15 parts by water of a 30 weight percent colloidal ~lica dispersion in 0 water. The colloidal silica dispersion is 30 weight percent ~m e ~do~s~
A solids and is available under the tradcnamc o--~ludo~II6.ll To this mixture is added 2.5 parts by weight of a 10 weight percent aqueous solution of a copolymer prepared from diethanol amine and adipic acid in equimolar proportions by carrying out a condensation reaction to give a product having a viscosity of about 100 centipoises at 25C. One part by weight of a solution containing 2.5 weight percent potassium dichromate is added.
The pH of theaqueous solution is adjusted to 4 with hydro-chloric acid. Vinylidene chloride is utilized as the monomer.

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1 An oil phase mixture is prepared by utilizing 100 parts by weight of vinylidene chloride and 20 parts by weight neopentane (27.6 volume percent based on the total volume of the monomer-neopentane mixture) and 0.1 part by weight of benzoyl peroxide as a catalyst. The oil phase mixture is added to the water phase with violent agitation supplied by a blade rotating at a speed of about 10,000 rpm. The reactor is immediately sealed and a portion sampled to determine the particle size. The droplets appear to have diameters of from 2 to about 10 microns.
After the initial dispersion, the reaction mixtures are main-tained at a temperature of about 80C. for a period of 24 hours.
At the end of this period, the temperature is lowered and the reaction mixture is found to have the appearance of a white milky liquid similar to a chalk-white milk. A portion of the mixture is filtered to remove the particles and the particles or beads are subsequently dried for about one hour in the air oven at a temperature of about 30C. A portion of the dried spherical particles are heated in an air oven at a temperature of 150C. for about 3 minutes. Upon heating, the particles show a marked increase in volume. Microscopic examination of the particles prior to foaming indicates particles having dia-meters of from about 2 to about 10 microns and having disposed therein a distinct spherical zone whlch appears to contain liquid and a small vapor space~ The paticles which are heated are examined microscopically and are found to have diameters of from about 2 to 5 times the diameter of the original particles and to have a relatively thin, transparent wall and a gaseous center, i.e. a monocell.

1043~ao 1 Preferred polymers for preparation of the microspheres are for example, polyvinylidene chloride, a copolymer of vinyl-idene chloride and acrylonitrile in weight ratios of about 100:1 to about 70:30, copolymers or acrylonitrile and methyl acrylate in weight ratios of from about 90:10 to 80:20, and copolymers of methacrylonitrile and methyl acrylate in weight ratios of about 93:7 to 82:18. While these materials and proportions are preferred, it is not intended that the invention be limited thereto. The preference is grounded principally in convenience and not in any substantive considerations.
By utilizing the technique of limited coalescence, a wide variety of expandable thermoplastic microspheres can be pro-duced and, if desired, may be specifically designed for incor-poration into a specific graphic medium. Such materials are now generally familiar and are commercially available. The term "microspheres" is herein employed as generic to all such materials.
In the present invention, the microspheres are incor-porated into the graphic medium in unexpanded form as a disperse phase. In order ~ preserve the expandable character of the microspheres, it is important that no component of the medium have any substantial solvent effect upon the thermoplastic of the spheres, or if such is not possible or convenient, as an alternative, the microspheres may be treated to preclude or retard solvation. A number of techniques are available to prevent dissolution of the microspheres. ~mong the simplest of these is a technique useful when the graphic medium contains a component having a definite but not great solvent activity.
The microspheres are coated with a material which preferentially 1~43SOO
wets the surface of the microspheres but which is not a solvent. Butyl alcohols, partlcularly n-butyl alcohol, are often useful for such purpose when the thermoplastic of the microspheres is poly(vinylidene chlorlde).
More generally, conpounds which may be utilized to preferentially wet the surface of the mlcrospheres include C4 to C20 n-alkyl alcohols, C10 to C20 n-alkyl carboxylic acids, and mixtures thereof.
In more extreme circumstances as when the graphic medium contains a strong solvent for the microspheres or when extended shelf life or storage stability i8 required, more extensive treatments are required. In such contexts, it is useful to coat the microspheres with an adherent polymer coating insoluble in the solvent system of the graphic medium. Among the polymers which can be effectively employed for such purpose, for example, are acrylics, polyesters, alkyds, polyamides, epoxies, urea formaldehydes, phenol formaldehydes, polysiloxanes, poly (ethylene-vinyl acetate), poly (ethulene-acrylic acid), poly (vinyl acetate), vinylidene chloride copolymers with ethylene and propylene, copolymers of vinyl chloride with ethylene and propylene and the like. By the utilization of such expedients, there is substantially no restrictions upon the solvent systems with which the microspheres can be employed and, consequently, there are correspondingly no related restrictions upon the graphic media with which the present invention may be practiced. Of course, many of the common solvent systems do not require any modification of the microspheres, and among these there may be mentioned as examples, water, alkanes (particularly straight chain alkanes), aliphatic alcohols (particularly straight chain aliphatic alcohols). Such solvents can be used singly or in combinations in known -fashion.
The microspheres may be incorporated into the graphic m~dia at any convenient stage, that i8, during the formulation of such media or at a later time up to ~ust prior to use. A wide variety of processing techniques can be employed to effect dispersion of the microspheres, which are readily wetted out g _ sm/ l r, ~043500 1 in most media and, because of the extremely small dimensions of the particles, are readily mixed. In most contexts, a thorough, uniform dispersion is desired, which is attained without difficulty by a simple mixing procedure. Unusual special effects may be attained by incomplete dispersion of the microspheres, and when such effects are desired, less than thorough mixing may be employed.
Depending upon the particular technigue of application to be employed with the graphic medium, it may be desirable to use an inert or solvent diluent to adjust the viscosity of the medium to compensate for the addition of the microspheres.
When the microsphere-modified medium requires such adjustment, it may be cut or thinned in accord with conventional practice applicable to the particular graphic medium employed. When formulated in accordance with the foregoing, the graphic media will have a shelf life and a storage stability usual for the particular medium employed.
Graphic media formulated in accordance with the present invention may be applied to a substrate by any of the known and conventional techniques appropriate thereto. Such techniques commonly include, for example, brushing, trowelling, spraying, pouring, dip-coating, printing, silk-screening, stencilling, electrostatic techniques and the like. All these techniques share in common the selective application of a graphic medium to a substrate, and all such techniques are contemplated herein.
Also contemplated are analogous techniques which involve a uniform application to a substrate, followed by the selective removal of portions of the medium. Such procedures are characteristic of photographic techniques, for example. Because 1()43~00 1 of the finely divided nature of the microspheres, there is no impediment ~-o any of the foregoing techniques attributable to the disperse phase.
The three-dimensional effect which characterizes the graphic media of the present invention is attained by heating the medium to a temperature at which the microspheres expand, usually on the order to about 90-150C., more often about 100-120C. The degree to which the applied medium expands to ; attain the raised effect is dependent primarily upon the con-centration of the microspheres therein. While some expansion is attained with concentrations of less than one percent based on the total non-volatile content of the medium, the more usually desired effects will require greater concentrations, up to as much as about 45 weight percent microspheres. If -greater amounts of microspheres are employed, adherence of the medium to the substrate may be impaired. Then the film form-ing ability of some types of vehicle may be insufficient.
Most often, the desired raised effect will be attained at a concentration of from about 5 to 40 percent, and preferably about 10 to 30 weight percent, although it should be noted that such concentrations are not ordinarily narrowly signi-ficant or critical.
When the graphic medium is based upon a thermoplastic polymeric binder or vehicle, which can be characterized by the formation of a coherent film by the removal of volatiles, the applied medium may be expanded at any convenient time to develop the raised effect. It will generally be preferable to develop after removal of the volatiles, although it is also possible to combine development and volatile removal in a single heat iO43SOO
1 treatment. Indeed, such development can in some contextq faci-litate formulation of graphic media with solvents of diluents not readily applicable by virtue of their low volatility and long drying times.
Many graphic media are based on vehicles which cure or cross-link to form permanent, hard films, Still others "cure"
by polymerization reactions. Since many, if not most, of the reactions involved proceed at room temperatures, it is usually advisable to develop the raised character of the medium promptly, as expansion of the microspheres may in some cases disrupt the continuity of the film which may be relatively brittle in the case of certain types of binder. In addition, it should be noted that many of the curing reactions are accelerated by heat.
Since the indices of refraction of the binder and the microspheres will not ordinarily be the same, ~n~ess particular pains are taken to so formulate the medium, the raised media will not ordinarily be transparent but rather will usually be opaque or translucent. S~ce transparency is ordinarily unde-sirable in graphic media, such effect may in fact be quitebeneficial, as the expanded microspheres will also serve to enhance the covering or tinting capacity o~ the medium and may even, in some cases, replace or reinforce the effect of addi-tives employed for such purpose, e.g. opacifiers, such as ti-tanium dioxide, zinc oxide, talc or the like. In the absence of colorant, the medium will have a white appearance or a color attributable to the binder.
The substrate to which the graphic media may be applied in accordance with the present invention can be any with which 104;~0() 1 the particular medium is compatible and to which such medium i9 adherent. Such substrates commonly will include various types and textures of paper, canvas, wood, plastics, metals, stone, plaster, fabrics, draperies, clothing, wall coverings, upholstery (particularly fabrics of such materials as cotton, rayon, rayon-acetate, fiberglass, polyesters, polyacrylates, polyacrylonitrile, poly hydrocarbons, and the like, and in-cluding both woven and non-woven fabrics), cement, fiberglass, glass, ceramics, leather. Also contemplated is the application of the media over or in combination with other diverse or similar media.
When the graphic media of the present invention are ap-plied to a substrate and developed by heating to the temperature at which the microspheres expand, the applied medium will have a raised and textured surface. The medium becomes a thin film of a syntactic foam which projects outwardly from the surface of the substrate. The thickness of the developed medium will be dependent upon the thickness of application of the medium and upon the concentration of the microspheres therein. The surface will be textured or roughened by the irregularities caused by expansion of the microspheres present just adjacent to the surface of the medium, and the degree of texture will be largely dependent upon the concentration of the microspheres.
In circumstances where the rough texture is not desirable, it can be eliminated by an overcoat of a conventional medium with-out loss of the raised or three-dimensional effect. It is noteworthy that the properties of the developed graphic media of the present invention will be determined by the basic medium formulation employed and will be little altered by the presence 11)43SOO
1 of the microspheres except in their function as "foaming agents".
Thus, it is apparent that the properties of the developed medium can be tailored to the intended use on the basis of the chemical and physical properties of the components included in the base formulation with emphasis upon the microspheres and their physical and chemical characteristics. In the com-positions generally contemplated in the present invention, the deve.oped medium will comprise a continuous phase matrix of the base medium and a disperse phase of the expanded micro-spheres. Because the expanded microspheres are not contiguous,the medium has a great degree of integrity determined by the cohesiveness of the continuous phase, which in most such media, will be considerable.
While may variations of the present invention are con-templated, the considerable simplicity of the invention and its fundamental concepts enablè those of ordinary skill in the graphic arts to implement the practice of the invention with a minimum of specific guidance once the basic nature of the inven-tion is clearly understood. However, it may be informative to refer to the following specific examples which illustrate a few of the numerous facets of graphic technology which can advantageously employ the present invention. These examples are intended to be illustrative only and should not be con-strued as limiting the scope of the invention, which is defined only by the claims appended hereto.
~X~MPLE I
A gravure press printing ink formulation was prepared by combining and mixing the following components in the indicated proportions:

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1 comPonent Parts bv Weiqht Aliphatic petroleum solvent 34.30 Toluene 18.60 Diphenyl octyl phosphate o.go Silicone fluid 0.45 Butyl methacrylate resin 25.75 Microspheres 20.00 The formulation thus formed was divided and a variety of colorants were added as noted:

SamPle ColorAmount, Weight %

A None B Carbon black4.0 C Nigrosine black 4.0 D Zinc Oxide 4.0 E Zinc oxide/
Prussian blue 3.95/0.05 F H Yellow #1 4.0 G H Yellow #l/TiO2 2.0/2.0 H Prussian Blue 4.0 J Prussian Blue/
Zinc Oxide1.0/3.0 K Carbon black/
Zinc Oxide1.0/3.0 Each formation was applied to a plurality of substrates with three different patterned 3-band quadrangular cell cylinder gravure rolls: #l = 120 line, 0,0032 inch cell depth; #2 = 150 .
line, 0.0025 inch cell depth; #3 = 180 line, 0.0018 inch cell depth. The substrates employed were aluminum foil, paper-backed aluminum foil, kraft paper, board stock and polyvinyl chloride film. The gravure roll pattern of each roll included a line of type, comprising a ten point bold face Roman type alphabet, a series of straight lines of varying widths, and a plurality of geometric and abstract designs.

1 After each substrate was printed with each roll and each formulation, the thickness of the unexpanded dried print was e:~amined and measured, the microspheres were expanded at a temperature of about 215F., and the print again examined and measured.
It was found that, except for color, the results were substantially uniform for each formulation and each substrate.
The unexpanded and expanded film thicknesses were:

Roll Lines Unexpanded ExPanded #1 120 0.75 mil 1.50 mil #2 150 0.50 1.00 #3 180 0.25 0.75 The unexpanded and expanded print showed excellent clarity and line resolution, while the surface of the expanded print was visibly textured in a fine, irregular pattern. The color of each ink was examined with the following results:

Sample Color Comment A White milky; poor covering power on foil : B Black flat appearance : 2 e Black glossy D White somewhat flat; good covering E White glossy; white & bright : F Yellow bright; glossy G Yellow pastel; glossy ~: H Blue bright; glossy J Blue pastel; glossy K Grey flat appearance With the exception of sample A, all showed good hiding power and excellent tinctorial effect. With sample A, poor hiding power was particularly notable on the foil substrata, which contributed a dully, greyish metallic cast to the milky white print.

1 In the present fonmulation, the component ingredients were as follows:
The aliphatic petroleum solvent was Super Lactol Spirits from American Mineral Spirits Co., having an initial boiling point of 203F., a final boiling point of 219~F., a specific gravity at 60/60 F. of 0.740, and containing 9.5 weight per-cent aromatics, 46.5 weight percent naphthenes, and 44.0 weight percent paraffins.
The toluene was a petroleum grade with a distillation range of 110.3 to 110.9C. and a specific gravity of 60/60F.
of 0.870.
The diphenyl octyl phosphate was Monsanto Co. Santizer 141 with a specific gravity 2~/25~C. of 1.089 to 1.093 and a Brookfield viscosity of 18 cps at 25~C.
The silicone fluid was Dow Corning Anti-foam A ~with a specific gravity of 0.97 at 25/25C.
The butyl methacrylate resin was duPont Elvacite 2044, with a specific gravity at 25/25C. of 1.07 and an acid number of zero.
The microspheres were from Dow Corning and were poly-vinylidene chloride containing 20 weight percent neopentane.
They had a particle size range, unexpanded, o 8 to 20 microns.

~XAMPL~ II

A ~raphic medium similar to that of Example I was pre-pared in accordance with the following recipe:

~()43S00 1 Aromatic hydrocarbon A10.35 Aromatic hydrocarbon B9.30 Xylene 21.55 Silicone fluid 0.55 Diphenyl octyl phosphate0.85 Butyl methacrylate resin39.80 Microspheres 17.60 The medium was applied by silk-screening onto a glass substrate to provide a decorative pattern. The screen was 300 mesh. The medium was applied in a thickness of 27 mils and was heated to 210F. which resulted in an expansion to 55 mils.
The expanded design was a translucent white having a distinc-tive three-dimensional finely textured appearance and had a very soft, felt-like feel to the touch.
In the foregoing formulation, aromatic hydrocarbon A was A Bxxon Aromatic lOO~having a boiling range of 311 to 344~F. and a specific gravity at 60/60~F. of 0.875. Hydrocarbon B was Exxon ~romatic 150~ boiling at 362 to 400F., specific gravity 0.902 at 60/50F. The xylene was a petroleum grade with a distillation range of 138 to 143~C. and a specific gravity at 60/60~F. of 0.8702. All other matQrials were those described in Example I.
EXAMPL~ III
The following formulation was prepared:

Ethylene-vinyl acetate emulsion A 15.4 Ethylene-vinyl acetate emulsion B 13.4 Acetoxylated polyethylene emulsion 39.4 Alkyl phenoxy polyethoxy ethanol 0.1 Silicone free-foam control agent 0.6 Water 4.1 Microspheres 27.0 Emulsion A was Flexbond 150, obtained from Air Products and Chemicals, Inc. containing 55 to 57 weight percent solids of an average particle size of 1.5 microns, a pH of 4.0 to 6.5, and having a vinyl acetate content in the polymer of about 15 weight percent.

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`A Emulsion B was Airflex 400 from the same company, at 55 to 57 weight percent solids of a 40 percent by weight vinyl acetate copolymer having a particle size average of 0.2 to 1.0 microns and a pH of 5.0 to 6.5.
The acetoxylated polyethylene was the same company's Aircoflex 510~ at 55 weight percent minimum solids of 0.3 microns average particle size and pH of 5 to 6.
The alkyl phenoxy polyethoxy ethanol was Rohm and Haas Triton X-lOO~with a specific gravity at 25/25C. of 1.065.
The silicone fluid was Troykyd Defoamer 999, Troy Chemical Co., with a specific gravity of 0.86 to 0.89 at 25/25C.
To the foregoing fo~mulation, there was added four parts by weight of titanium dioxide, pigment grade, and the resulting medium was employed in the following procedures:
The medium was selectively brushed onto a paper substrate in a random pattern, allowed to dry at ambient conditions, and then heated at 205F. to expand the microspheres. The resulting pattern exhibited excellent adhesion, a finely tex-tured, soft surface of varying thickness, and a sharp definition.
The medium was reduced 1:1 with water and sprayed with Sprayon Products, Inc. "Jet-Pak Sprayer" through a paper sten-cil onto an aluminum panel. The applied pattern was simultan-eously dried and expanded with a hot air blower at an air temp-erature of 300F. The stencilled design was sharp, adherent, - and finely textured, having a thickness of about 15 mils. The covering power was excellent.
The medium was reduced with wate~ 3:1 and printed on a pressure sensitive adhesive backed white wall paper stock in a regular, repeating design. Application was by a 55 line, 1043~i;00 1 0.0065 inch cell depth gravure roll. The printed stoak was heated by infrared lamps to a temperature of 250F. to dry and expand the pattern. The resultant wall paper was a raised white-on-white design of attractive appearance, good adhesion and a crisp definition of the raised pattern. The expanded pattern ranged in thickness from 16 to 21 mils.
EXAMPLE IV
A thermally cross-linkable latex was formed by copoly-merizing, in an aqueous medium, 30 parts by weight hydroxyethyl methacrylate, 6 parts by weight 2-ethyl-hexyl acrylate, and 64 parts by weight methyl methacrylate. There was then added to the latex 8 parts by weight melamine. The resulting latex contained 60 percent by weight solids.
A dispersion was formed of 19.4 parts by weight water, 0.75 parts defoamer, 6.50 parts expandable microspheres, and the resulting mixture was well stirred, 20 parts titanium di-oxide were then added and the dispersion was ground in a Cowles mill to ~o. 5 Hegman.
The latex, 50.35 parts by weight, the dispersion, 46.65 parts by weight, and poly(acrylic acid) thickener, 3.00 parts by weight, were combined and thoroughly mixed. The resulting medium was printed on a fiberglass drapery fabric by a patterned roto-gravure roll, 140 lines per inch. The printed fabric was dried one minute at 180F. and heat treated three minutes at 300F. The dried pattern before heat treatment was about 1.5 mils and after the heat treatment was about 3-4 milsl affording a raised, embo~sed pattern on the fabric.

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The procedure of Example IV was repeated with the excep-tion that an ethylene-hydroxyethyl acrylate latex was employed, with the monomers included in a 64:36 weight ratio.
The medium was printed, in the manner described in Example IV, onto a variety of fabrics and weaves as noted below:
Cotton Cotton-Polyester A Polyester ( Dacron ,~ ~
Polyacrlonitrile ("Orlon") Polypropylene The raised, embossed pattern was developed as before, again having a thickness of 3-4 mils and an excellent defini-tion of the pattern was obtained.
Each of the coated fabrics was tested for durability to both drycleaning and laundering. Durability to dry cleaning was tested by the following procedure:
Samples of each fabric were run for five 30 minute cycles rO~7 in a 'lLaunderometerll at rrom temperature using a stainless steel container with 100 stainless steel balls using perchloro-~; 20 ethylene. To extract the solvent, the samples were placed in a centrifuge tube over a bottom layer of stainless steel balls whichacted as a reservoir for the solvent and a varrier for the sample. ~fter centifuging for 15 minutes at high speed, the nearly dry samples were oven dried for five minutes at 120F. ~o change was noted in the fabric or in the applied pattern after the procedure.
The laundering test consisted of 10 cycles in a commercial Westinghouse automatic washer and tumble drying between wash cycles. The washer utilized hot water at 160F. and one-half ~ ~V43~
A 1 cup of "Tide~ laundry detergent for each cycle. When appro-priate, the washer was ballasted with cotton terry-cloth towels~
The drying stage of each cycle was conducted by tumbling in a stream of hot air at 160F. After the ten wash-dry cycles, the samples were examined and no change in either fabric or pattern was noted.

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Claims (21)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In a graphic arts medium for selective application to a substrate comprising a polymeric film forming binder and a volatile solvent vehicle therefor, the improvement comprising dispersing in said medium about 1 to 45 weight percent, based on the non volatile content of said medium, of thermally expandable thermoplastic microspheres having a particle size of 0.5 to 300 microns; said microspheres being insolubilized in said volatile solvent vehicle by a coating of a member selected from the group consisting of compounds which preferentially wet the surface of said microspheres ant a film-forming insoluble polymer coating whereby said microspheres are insoluble in said medium, and whereby said medium is adapted to the formation of raised graphic patterns upon a substrate.

2. The graphic arts medium of Claim 1 wherein said coat-ing preferentially wets the surface and is selected from the group consisting of C4 to C20 n-alkyl alcohols, C10 to C20 n-alkyl carboxylic acids, and mixtures thereof.

3. The graphic arts medium of Claim 2 wherein said com-pound is butyl alcohol.

4. The graphic arts medium of Claim 1 wherein said microspheres are rendered insoluble in said medium by coating the surface of said microspheres with a film-forming polymer coating wherein said polymer is insoluble in said medium.

5. The graphic arts medium of Claim 4 wherein said coat-ing film-forming polymer is a member selected from the group con-sisting of acrylics, polyesters, alkyds, polyamides, epoxides, urea formaldehydes, phenol formaldehydes, poly-siloxanes, poly (ethylene-vinyl acetate), poly (ethylene-acrylic acid), poly (vinyl acetate), vinylidene chloride copolymers with ethylene and propylene and copolymers of vinyl chloride with ethylene and propylene.

6. The graphic arts medium of Claim 1 wherein the thermally expandable microspheres contain a volatile blowing agent.

7. The graphic arts medium of Claim 6 wherein the thermally expandable thermoplastic microsphere is poly (vinylidene chloride) and the volatile blowing agent is neopentane.

8. The graphic arts medium of Claim 7 wherein the microspheres have a particle size of about 3 to 50 microns in diameter.

9. The graphic arts medium of Claim 8 wherein the microspheres have a particle size of about 5 to 20 microns in diameter.

10. The method of forming a raised graphic pattern upon a substrate which comprises selectively applying in a pattern to said substrate a graphic arts medium comprising a poly-meric film-forming binder and a volatile solvent vehicle therefor, said medium having dispersed therein about l to 45 weight percent, based on the non volatile content of said medium, of thermally expandable thermoplastic microspheres having a particle size of 0.5 to 300 microns, said microspheres being insolubilized in said volatile solvent vehicle by a coating of a member selected from the group consisting of compounds which preferentially wet the surface of said microspheres and a film-forming insoluble polymer coating whereby said microspheres are insoluble in said medium, drying said medium and thermally expanding said microspheres, whereby said medium forms a raised graphic pattern.

11. The method of Claim 10 wherein said coating preferentially wets the surface and is a member selected from the group consisting of C4 to C20 n-alkyl alcohols, C10 to C20 n-alkyl carboxylic acids, and mixtures thereof.

12. The method of Claim 11 wherein said com-pound is butyl alcohol.

13. The method of Claim 10 wherein said microspheres are rendered insoluble in said medium by coating the surface of said microspheres with a film-forming polymer coating wherein said polymer is insoluble in said medium.

14. The method of Claim 13 wherein said coating film-forming polymer is a member selected from the group consisting of acrylics, polyesters, alkyds, polyamides, epoxides, urea form-aldehydes, pheno formaldehydes, polysiloxanes, poly(ethylene-vinyl acetate), poly(ethylene-acrylic acid), poly(vinyl acetate), vinyl-idene chloride copolymers with ethylene and propylene and copolymers of vinyl chloride with ethylene and propylene.

15. The method of Claim 10 wherein the thermally expandable microspheres contain a volatile blowing agent.

16. The method of Claim 15 wherein the thermally expandable thermoplastic microsphere is poly(vinylidene chloride) and the volatile bowing agent is neopentane.

17. The method of Claim 16 wherein the micro-spheres have a particle size of about 3 to 50 microns in diameter.

18. The method of Claim 17 wherein the micro-spheres have a particle size of about 5 to 20 microns in diameter.

19. The product having a raised graphic pattern upon a substrate produced by selectively applying in a pattern to the substrate a graphic arts medium comprising a polymeric film-forming binder and a volatile solvent vehicle therefor, said medium having dispersed therein about 1 to 45 weight percent, based on the nonvolatile content of said medium, of thermally expandable thermo-plastic microspheres having a particle size of about 0.5 to 300 microns in diameter and containing a volatile blowing agent, said microspheres having a surface coating of a compound which renders the microspheres insoluble in the medium, drying said medium and heating to expand said microspheres, whereby said medium forms a raised graphic pattern.

20. The method of Claim 10 comprising the further step of overcoating the dried medium containing dispersed micro-spheres with a graphic medium without loss of the raised pattern.

21. The product of Claim 19 wherein the process for producing the product includes the further step of overcoating the dried medium containing dispersed microspheres with a graphic medium without loss of the raised pattern.