Carpet Embossing In Register With Print

Abstract

Pile fabrics prepared from nylon carpet fibers having a textured or embossed surface and a process of developing the textured effect which comprises selectively contacting the surface of said carpet with a chemical fiber shrinking agent therefore, allowing the shrinking action to occur and, thereafter, effectively removing the shrinking agent from the surface, said shrinking serving to reduce the height of the pile in the treated areas and creating said textured surface.

Description

BACKGROUND OF THE INVENTION

In the production of nylon piles fabrics, it is often sirable to emboss the surface thereof in order to provide added decorative appeal. In some instances, the embossed areas are printed with dyes to further embellish the surface design.

Embossing of pile fabrics is conventionally accomplished with a heating embossing roll or plate which has been engraved or otherwise treated to create the design desired in raised relief on the surface. A method which eliminates the use of embossing rolls has been disclosed in U.S. Pat. Nos. 2,790,255 and 2,875,504. In accordance with these patents, the pile fabric is formed from a combination of shrinkable and non-shrinkable yarns. Upon subjecting the fabric to the influence of heat, the pile formed from the shrinkable yarns contracts while the base and the nonshrinkable yarns remains intact thereby yielding a pile made up of high and low areas to give the appearance of an embossed or carved product.

A chemical embossing method is disclosed in U.S. Pat. No. 2,020,698. According to this patent, fabric having a pile of organic ester of cellulose yarn is locally treated with an alkali or alkaline salt saponifying agent in order to obtain ornamental differential effects in the treated areas. Furthermore, since the organic ester of cellulose pile yarns that have not been saponified are more difficult to change from their position, after they are once set than are the saponified organic ester of cellulose yarns, it is possible to obtain a differential lay between the saponified and unsaponified organic ester of cellulose pile yarn. Thus, the fabric, after the application of the saponifying agent, many be washed, finished and dried with the pile erect, after which the fabric may be run through water and brushed across the piece to lay the pile towards the selvage and it is then dried. This causes the saponified pile yarn to lie flat while the unsaponified yarn remains substantially erect. Upon subsequent steaming and brushing the fabric in the opposite direction, any unsaponified yarn which may have been slightly bent from the vertical by the previous brushing toward the selvage is caused to stand erect without disturbing the position of the laid or crushed saponified organic ester of cellulose pile yarn.

SUMMARY OF THE INVENTION

It is the primary object of this invention to provide a simple process for producing a nylon pile having a textured or embossed surface.

Another object is to provide such a process which is readily adaptable to standard printing equipment.

Another object is to provide a process which allows the production of pile fabric having embossed areas in register with a printed design.

A further object is to provide an embossing process which is readily adaptable to curved and irregular surfaces.

Various other objects and advantages of this invention will be apparent from the following detailed description thereof.

It has now been discovered that it is possible to produce superior nylon fabrics having embossed surfaces by contacting selected portions of the surfaces with a chemical embossing agent for the fibers of said pile fabric causing dimensional change by linear contraction of the treated fibers and, thereafter, effectively removing the embossing agent. The resulting product is thus depressed at the treated areas.

The embossing composition can be transparent so that the appearance of the product is not altered other than in being embossed. Alternatively, the embossing agent can be part of a dye or pigment composition used in printing the fabric so that the color appears in perfect register in the areas of embossing agent application.

The depth of the depressed areas can be controlled by varying the concentration and/or type of embossing agent. This variation in concentration can be effected by the amount of vehicle applied as well as by the strength of the embossing reagent.

Furthermore, the embossed depth can be controlled to some degree by the depth of penetration of the print paste carrying the embossing agent as well as the steamer time and steamer temperatures to which the pile fabric is subjected in order to activate the chemical embossing agent which provide the desired effect.

This discovery makes possible the production of a product having embossed surfaces which can be in complete register with a printed design. Additionally, the discovery makes possible the utilization of many types of printing apparatus for purposes of effecting embossing, thereby eliminating the need for expensive embossing equipment. Further, it allows the embossing of a surface without exerting sufficient pressure to permanently deform the pile fabric. A great number of products can be produced by the process. They can be used for floor, wall and ceiling coverings, drapery, upholstery and the like, and, in fact, wherever pile fabrics are utilized. They are readily adaptable to decorating any surface on which pile fabrics can be applied. Many additional applications will occur to those skilled in the art.

This invention will be better understood from the following detailed description thereof together with the acompanying self-explanatory drawings in which:

FIG. 1 is enlarged top view of a section of an embossed product of this invention; and,

FIG. 2 is an enlarged cross-sectional view of the same product taken through line 2--2.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the production of the pile fabrics of this invention, the pile yarn employed is nylon. Synthetic fibers prepared from polyamides such as nylon are well known to those skilled in the art.

Likewise, the embossing agents which are applied to the nylon fibers in order to produce the desired effect are also known chemical compounds. For purposes of this invention, the term "embossing agent" is defined as any active chemical composition which when applied to the pile fabric produces a measurable reduction of pile height, but without significant deterioration of the nylon fibers. In fact, it is our objective to induce embossment and shrinkage without deteriorating the fiber. The exact chemical and physical mechanism by which this result is achieved is not completely understood. However, it is believed that the embossing agent may owe its effectiveness largely to its capability to function as a hydrogen bond breaker. Initially, the fibers are in a stretched and crystalline state. When the hydrogen bond is broken between the polymer chains, the fibers relax and shrink. Regardless of the mechanism, the overall effect produced is one of dimensional change, the most desirable effect, involving linear contraction of the fiber.

In order to be applicable for the novel process of this invention, the embossing agent should provide a reduction of the pile height through a shrinkage reaction, should not adversely affect the printing means, e.g., print screens, and should be capable of being substantially removed or inactivated subsequent to the embossing action. other characteristics of the embossing agent which are desirable, though not essential, include compatibility with dye print pastes, capability of being regulated by factors of time, temperature, and concentration, i.e., susceptibility to activation by a conventional steaming operation and exhibiting no residual embossing activity. Needless to say, minor adjustments in the nature of the components and process conditions, and/or the embossing apparatus can be employed to overcome the absence of certain of these desired characteristics.

The embossing agent for the nylon fibers is applied to one surface of the pile fabric in any desired design, whether it be random or predetermined. One of the easiest methods of applying the agent is by utilizing conventional printing technique such as silk screen or block printing. The embossing agent can be applied as a concentrate, as part of a transparent vehicle, or as part of a dye composition utilized for pile fabric printing. The nature of the embossing agent dictates the nature of the vehicle to be utilized. Among such applicable vehicles are included: water, and alcohols such as methanol and isopropanol. Often thickeners, e.g., gums, and cellulose derivatives, are included in order to obtain viscosity characteristics demanded in print technology and to enable the embossing agent to adhere to and operate on the synthetic fiber and to hold the printed pattern.

In those instances where it is desired to achieve a single- or multi-colored printed decoration with a distinct color for the embossed areas, the embossing agent can be incorporated into a particular dye or pigment composition. The dye or pigment will generally be in the form of a print paste ink to which the appropriate amount of agent is added. It is to be noted that in preparing these modified dye composition, the pH levels, viscosities, and dye concentrations which are essential to an efficient dyeing operation must also be controlled. The resultant effect is an embossed design in register with the printed pattern. If different depths of embossing are sought, they are achieved by use of different concentrations of agent in the areas calling for such different depths.

Generally, it is desirable that the embossing agent be soluble or in solution in the solvent medium from which it is applied to the selected areas of the fabric. However, if the agent is not soluble it should be in the composition in a form at least suficiently finely divided to pass through the print screen, that is, it should be present in a micro pulverized form which indicates particle diameter of the order of 100 microns or smaller. That is, it must not only pass through a screen but it must pass through freely, dispersed through the dye paste throughout the printing operation. The purpose of this, of course, is to make sure that the agent becomes uniformly dispersed over the fiber in the print process so that the shrinking effect will be uniformly developed in the fiber.

As previously indicated, the preferred embossing agnet is one which is dormant during the successive printing operations but then is activated by the elevated temperature of a steam chamber usually utilized to fix the dye onto the fibers. Embossing agents which can function in this manner on nylon and produce shrinkage of the nylon fibers comprise a metal halide such as zinc chloride in combination with an acid such as acetic acid. When this combination of chemicals is added to the dye print paste in the proper concentrations and proportions, nylon carpet pile can be embossed deeply wihtout significant fiber deterioration exactly in register with a printed design by shrinking the nylon fibers. While the preferred metal halides include zinc chloride, calcium chloride, lithium chloride, and aluminum chloride, other metal halides may be used such as zinc bromide, zinc iodide, cupric chloride, stannous chloride, stannic chloride, ferric chloride, and chromic chloride. Likewise, while acetic acid is the preferred acid, other acids may be used such as phosphoric, formic, maleic, citric, hydrochloric, sulfuric, oxalic, malonic, propionic, hydroxyacetic, and monochloroacetic. At the individual concentrations employed in this process, the metal halides alone, or the acids alone, are not useful. The advantages of this type of chemical embossing agent are that there is no need for rigid time control in the process and there is minimal concern regarding excessive uncontrollable embossing because other factors can be changed. Thus, the degree of diminution of the pile height can be controlled by adjusting the amount of dye paste applied, the concentration of embossing agent in the dye paste and the temperature and time of exposure in the steam chamber. All these factors can be adjusted according to properties of the nylon fiber comprising the pile fabric. While the depth of embossing will be determined by the practitioner in accordance with the type of embossed product being prepared, reduction in pile height will generally not exceed more than 50%, this value being indicative of excellent embossing without exposing the backing materials.

Embossing can be achieved, if desired, by subjecting the treated fibers to heat Thus, the treated surfaces may be subjected to the radiation from a bank of infrared lamps, particularly where the embossing agent is not part of a dye print paste. Additionally, even where the steaming operation is not essential to activate the embossing agent, such steaming may have the effect of increasing the penetration of the embossing agent and increasing the speed of its action on the fibers.

A critical step of the novel process of this invention involves terminating the embossing action and/or effecting substantial removal of the embossing agent from the pile fabric. It may be necessary to achieve complete elimination of all residues of the embossing process which may contribute undesirable properties to the finished fabric, such as odor, toxicity and color and texture change. Needless to say, any termination or quenching technique resorted to will depend on the particular embossing composition employed. The most useful technique for removing residues of the embossing process is by thoroughly washing the fabric with water and detergents. In those instances where the embossing agent is part of a dye or pigment composition, the washing cycle which is utilized to remove excess dye or pigment serves also to remove traces of the agent. Where an acidic embossing agent is utilized, e.g., formic acid on nylon, it is possible to halt the embossing action more rapidly by rinsing with an aqueous ammonia or mildly alkaline solution. This neutralization of the acid serves to insure the total removal thereof.

Other techniques for terminating the embossing action and/or removing the embossing agent include evaporation and dry cleaning. Thus, if the agent is volatile, steaming of the treated pile fabric will serve to evaporate a large portion of the embossing pile content. Where rinsing techniques are not effective, it may be necessary to resort to a dry cleaning procedure to remove the embossing residues.

The invention has particular application to tufted carpets which are to have a printed decoration applied thereon. Unusual design effects can also be obtained when the pile fabric is printed with a multi-colored design wherein one or more of the dye compositions contain the appropriate embossing agent. The process of printing such carpets includes the steps of passing carpets, tufted of unpigmented or colored fibers, into a screen printing apparatus whereby a design is printed on the surface of the carpet. Each screen applies a separate color to make up the final design. The embossing agent can be added to one or more of these printing stations by addition to the dye composition, or it can be applied by a separate station in a transparent vehicle. The fabric is then passed into a steaming chamber to set the dyes and cause embossing and then to a washing cycle which serves to remove excess dye as well as to terminate the embossing action and/or remove the embossing components.

Accordingly, in the embossing of carpet or textured pile fabric, and for all practical purposes we are discussing the embossing of carpeting, it is important that any color design on the surface of the carpet which is related to the embossing be in accurate register with the embossing. Since we are concerned only with chemical embossing the problem is then one of inducing the differential fiber length between the embossed colored areas and unembossed areas and, while it is possible to induce shrinkage of synthetic nylon fibers, it is necessary for preparation of the carpet that the fiber shrinkage be induced with no significant deterioration of what is left. Thus, if the operation of embossing involves true shrinkage the shrunk fabric fiber should have a texture approximating that of the original.

Suitable combinations of metal halide and acid will generally fall within approximately the following broad range of concentrations for each component so as to obtain nylon carpet embossment to the desired depth. These ranges represent parts per hundred of the total print paste:

Metal halide 5-50 Acid 60-5

A procedure of trial and error will determine within what narrower range of concentrations the individual components of each specific combination of metal halide and acid will be most effective. For example, the concentrations of zinc chloride and acetic acid (glacial) will generally be selected from within approximately the following narrower ranges:

Zinc Chloride 15-30 Acetic acid, Glacial 45-25

within these concentration ranges, the individual components used alone are not useful as carpet embossing agents.

As indicated previously, a procedure of trial and error is required in order to arrive at the best proportions of zinc chloride and acetic acid needed to achieve a desired depth of embossment without deterioration of the nylon carpet pile. It is, of course, important that the nylon fibers remain physically fibers and that the shrunk carpet pile retain its original physical character as well as acceptable appearance and feel. Generally, however, it will be found that the sum of the concentration of zinc chloride and the concentration of acetic acid in the print paste will fall within the limits of 40- 65%. Whenever maximum carpet embossment is obtained (that depth just short of fiber deterioration, unacceptable hardness or the like) any reformulation which calls for increasing either component should be accompanied by a reduction in the concentration of the other component otherwise fiber deterioration will occur.

The concentration range within which zinc chloride and acetic acid may be selected do not necessarily hold true for other metal halides and acids. Suitable concentrations and proportions must be determined by trial and error.

Depth of embossment as well as the deteriorating effect of the embossing agent upon the nylon carpet fibers is not only related to the strength of the embossing agent, but is also related to the distribution and penetration of the embossing agent into the nylon carpet pile.

Therefore, print paste viscosity is important in influencing the depth of embossing as well as the embossed pile character since it regulates the penetration of the dye print paste containing the embossing agent into the carpet pile as well as the quantity of embossing agent deposited. Both penetration and amount of embossing agent applied can also be regulated by the number of squeegee roller strokes. Other factors effecting both shrinkage and attack of nylon fibers are steamer time and temperature. Too long a steamer time or too high a temperature generally aggravate nylon fiber deterioration. Generally it appears that the maximum reduction in nylon carpet pile height will not exceed much more than about 50% without fiber deterioration reflected in unacceptable pile hardness, harshness, weakness, fusion, and the like. Lesser embossed depths are of course obtained by altering the proportions and/or concentrations of the components of the embossing agent.

In order to practially evaluate the utility of a particular chemical or combination of chemicals as an embossing agent for nylon carpet, the chemical system is incorporated in the dye print paste and applied to a section of the nylon carpet by means of a screen printing technique so as to simulate plant production procedure as closely as possible. The treated carpet is steamed usually for 15 minutes at 215.degree. to 220.degree. F (102.degree. C to 104.degree. C) thoroughly rinsed with water and dried at about 180.degree. F. Then the embossed area is rubbed briskly with the finger tips or for example a wooden knife handle to loosen and separate tufts. In the plant this is accomplished by brushing. The depth of embossment is then measured and observations made regarding the character of the embossed nylon, e.g., harshness, softness, strength, firmness, brittleness, intactness, definition, color. Measurement of the pile height at the embossed and unembossed area is made by means of a thin, steel ruler marked off in 1/64 inch (0.4 millimeter) intervals. Any method of measurement is useful so long as it is standardized from operation to operation and is reproducible to about 1/64 inch.

However, for the preliminary determination of whether or not a chemical composition is capable of shrinking nylon fibers and for thus determining its potential suitability as a chemical embossing agent for nylon carpet, we have devised a simpler, less time consuming beaker test procedure. Using this test, the per cent shrinkage and the per cent weight loss experienced by a 50 centimeter loop of nylon carpet filament or carpet yarn is determined by immersing the yarn loop in an aqueous solution or dispersion of the test chemical for 15 minutes at 215.degree.F (102.degree.C). This test affords a simple way of determining if a selected chemical will cause a shrinkage of the nylon fibers and provides a means of predicting whether or not a chemical will function as an embossing agent for nylon carpet. Also, the test provides a method for determining such effects as chemical concentration, temperature, time, print paste additives, solvents other than water, nylon type and construction and the like. Details of the test procedure are outlined as follows in Table I.

TABLE I

BEAKER TEST PROCEDURE

1. prepare a solution or dispersion of the chemicals to be tested in water.* If heated, cool to room temperature. Weigh 30 grams into a 32 .times. 200 mm test tube.

2. Place test tube in preheated Silicone bath and heat contents of test tube to the desired temperature (usually 215.degree.F = 102.degree.C).

3. cut approximately 1 meter length of nylon yarn or filament which has been held at 73.degree.F and 50% relative humidity for 24 hours, and tie in a single loop.

4. Hang the loop under 50 gram load for 30 seconds and measure the length of the loop to 0.1 cm.

5. Weigh loop to nearest 1/10 mg.

6. Immerse nylon loop in hot chemical solution, agitate gently and observe any change in character of the nylon fibers. Generally hold for 15 minutes or less.

7. Remove the nylon loop and wash thoroughly in copious amounts of water. Blot and dry to constant weight at 73.degree.F and 50% relative humidity.

8. Measure length of nylon loop as in 4.**

9. Determine weight of nylon loop as in 5.

10. Calculate % shrinkage and % weight loss.

With the information thus obtained concerning the extent of shrinkage of the nylon fibers as well as any deterioration of the nylon fibers, it then becomes possible to determine whether or not the chemical composition has any potential as an embossing agent, and eventually proceed to the formulation of a printing paste which includes the shrinking material. Experience has shown, however, that while such test results prove that the chemical agent will shrink nylon fiber and thus has an embossing capability for nylon carpet, these results tell us only approximately what concentration of the chemical agent is required to emboss nylon carpet. Nor do we know the exact extent of fiber deterioration that will be experienced on the nylon carpet. Generally, the following relationship seems to exist between beaker test results and screen printing test results on nylon carpet. Beaker test shrinkage results must reach at least about 50% shrinkage in 15 minutes at 215.degree.F (102.degree.C) in order for an embossing agent to produce even trace to very weak carpet embossment But Beyond about 50% shrinkage via the beaker test, the nylon filament begins to deteriorate rapidly (test loop weakening and fragmentation). On the other hand, it appears that deeply embossed carpet can only be anticipated if the chemical shrinking agent causes fiber destruction in the beaker within about 60 seconds. The maximum depth of embossment obtainable without causing unacceptable nylon carpet fiber deterioration is usually about 50%.

Apparently, the difference between beaker test shrinkage results obtained on a loop of nylon filament of yarn, and screen printing test results obtained on nylon carpet, occurs because the chemical is utilized much less effectively on the carpet pile than in the beaker test. Screen printing does not supply sufficient print paste (containing embossing agent) to the nylon carpet pile to provide a completely uniform coating of the nylon fibers. Furthermore, the depth of concentration into the carpet pile is often of the order of only about 50%. Also, during steaming, the concentration of the embossing agent may be reduced and chemical which may be consumed is not replaced. However, in the beaker test, the nylon loop is surrounded constantly and uniformly by a surplus of hot chemical solution of practically the same concentration throughout the duration of the test thus allowing the chemical to function more effectively.

The following examples will further illustrate the embodiment of this invention. In these examples, all parts given are by weight unless otherwise noted.

EXAMPLE I

The shrinkage and weight loss experienced by a test loop of DuPont type 846 bulk continuous filament nylon 6/6 (1,300 denier, 68 filaments, o twist, semi-dull, regular acid dyeable) was determined by means of the beaker test procedure described in Table I using the following aqueous recipes containing zinc chloride in combination with acetic acid at the concentrations (% of total batch) indicated. The test temperature and maximum duration of test was 215.degree.F and 15 minutes respectively.

Test results tabulated in Table II show that the chemical composition comprising zinc chloride and acetic acid can produce effects on nylon fibers ranging from strong shrinkage with fiber deterioration (usually about 50%) to immediate fiber disintegration depending upon the proportions and concentrations of chemicals used. Thus, these data indicate that the zinc chloride/acetic acid system has a strong potential as an embossing agent for nylon carpet since it is capable of causing fiber disintegration via the beaker test procedure within about 60 seconds. Generally zinc chloride/acetic acid combination which induces 50% shrinkage of nylon fiber in the beaker test will be found to produce very little carpet embossment.

At the maximum individual concentrations employed, neither zinc chloride (30%) nor acetic acid (30%) used alone, yield significant fiber shrinkage. In fact, the nylon fiber shrinkage induced is not much greater than obtained with water alone.

TABLE II __________________________________________________________________________ Nylon Filament Shrink- Weight age Loss Loop Run No. Chemicals (%) (%) Character __________________________________________________________________________ * Water 10.5 1.27 Good 357 Acetic Acid, Glacial, 30% 13.5 1.06 Good 762 Zinc Chloride, 30% 18.1 +1.76 Good 380 Zinc Chloride, 25%/Acetic Acid, Disintegrated 20 seconds 25% -403 Zinc Chloride, 20%/Acetic Acid, Disintegrated 30 seconds 30% 404 Zinc Chloride, 30%/Acetic Acid, Disintegrated 20 seconds 20% 408 Zinc Chloride, 30%/Acetic Acid, Disintegrated 10 seconds 30% 689 Zinc Chloride, 20%/Acetic Acid, 31.3 2.77 Good 20% 690 Zinc Chloride, 25%/Acetic Acid, 71.4 6.31 Harsh, 20% v. weak __________________________________________________________________________ * Avg. 13 runs in water alone at 212.degree.F

EXAMPLE II

The shrinkage and weight loss experienced by a test loop of DuPont type 846 bulk continuous filament nylon 6/6 (1,300 denier, 68 filaments, o twist, semi-dull, regular acid dyeable) was determined by means of the beaker test procedure described in Table I using the aqueous recipes shown in Table III containing a combination of acetic acid and a metal halide other than zinc chloride. The test temperature and maximum duration of test was 215.degree.F (102.degree.C) and 15 minutes respectively.

Test results (Table III) show that metal halides in acetic acid solution serve very effectively as shrinking agents for nylon fibers. Depending upon the particular metal halide and the ratio and concentration of metal halide and acetic acid, effects are produced ranging from strong fiber shrinkage to fiber destruction within about 60 seconds. Combinations which produce this latter effect can be anticipated to produce deep carpet embossment.

It will be observed that at the individual concentrations employed, neither the metal halides alone, nor the acetic acid alone, cause sufficient shrinkage of the nylon filament to produce carpet embossment. Usually at least 50% shrinkage of the nylon filament is required before perceptible carpet embossment can be expected.

TABLE III __________________________________________________________________________ Nylon Filament __________________________________________________________________________ Acetic Shrink Wt. Run Metal Halide Acid age Loss Loop ** No. type % (%) (%) (%) Character __________________________________________________________________________ * Water (tap) -- -- 7.03 0.68 Good 859 Acetic Acid 0 25 12.3 1.32 Good 659 Acetic Acid 0 45 27.0 3.92 Good 834 Cesium Chloride 25 25 13.3 1.23 Good 717 Sodium Chloride 25 25 Insoluble *** 761 Lithium Chloride 30 0 7.2 +1.3 Good 711 Lithium Chloride 25 25 60.2 2.67 Excellent 728 Lithium Chloride 25 30 Solid mass 15 secs. 796 Lithium Chloride 15 45 Disintegrate 20 secs. 784 Potassium Iodide 50 0 6.9 +3.01 Good 712 Potassium Iodide 25 25 18.6 1.01 Yellow 749 Potassium Iodide 30 30 39.7 3.28 Yellow 762 Zinc Chloride 30 0 18.1 +1.76 Good 760 Zinc Chloride 20 20 33.1 3.41 Good 690 Zinc Chloride 25 20 71.4 6.31 V. Weak 797 Zinc Chloride 15 45 Disintegrate 5 secs. 836 Barium Chloride .2H.sub.2 O 25 25 19.1 1.34 Good 765 Zinc Bromide 30 0 17.2 0.13 Good 744 Zinc Bromide 20 22.5 40.6 4.28 Good 742 Zinc Bromide 25 25 Disintegrate 10 secs. 835 Manganese Chloride .4H.sub.2 O 25 25 22.3 1.97 Good 764 Ferric Chloride .6H.sub.2 O 30 0 15.9 +11.7 Orange 754 Ferric Chloride .6H.sub.2 O 20 20 45.8 1.49 Yellow 743 Ferric Chloride .6H.sub.2 O 25 25 Solid mass 30 secs. 799 Ferric Chloride .6H.sub.2 O 15 45 Solid mass 15 secs. 766 Zinc Iodide 30 0 34.1 +6.53 Brown 758 Zinc Iodide 20 20 42.2 0 Orange 757 Zinc Iodide 25 20 Solid mass 15 secs. 748 Zinc Fluoride 25 25 Insoluble *** 721 Lead Chloride 25 25 Insoluble *** 785 Nickel Chloride .6H.sub.2 O 50 0 8.2 +0.8 Good 720 Nickel Chloride .6H.sub.2 O 25 25 22.4 2.24 Good 753 Nickel Chloride .6H.sub. 2 O 30 30 34.5 2.95 Good 786 Magnesium Chloride .6H.sub.2 O 50 0 7.6 +1.46 Good 715 Magnesium Chloride .6H.sub.2 O 25 25 19.9 1.80 Good 750 Magnesium Chloride .6H.sub.2 O 30 30 35.2 2.96 Good 767 Cupric Chloride .2H.sub.2 O 0 8.0 +2.65 Green 716 Cupric Chloride .2H.sub.2 O 25 25 30.0 2.85 Yellow 756 Cupric Chloride .2H.sub.2 O 30 30 Fragmented 15 mins. 783 Calcium Chloride .2H.sub.2 O 30 0 11.4 +1.23 Good 416 Calcium Chloride .2H.sub.2 O 25 25 48.1 4.28 Good 729 Calcium Chloride .2H.sub.2 O 30 30 Solid mass 30 secs. 802 Calcium Chloride .2H.sub.2 O 15 45 Disintegrate 5 secs. 769 Stannous Chloride .2H.sub.2 O 30 0 11.3 +20.3 Good 709 Stannous Chloride .2H.sub.2 O 25 25 57.0 +34.8 V. Weak 727 Stannous Chloride .2H.sub.2 O 25 30 Solid mass 30 secs. 798 Stannous Chloride .2H.sub.2 O 15 45 Disintegrate 5 secs. 787 Cobaltous Chloride .6H.sub.2 O 50 0 9l.3 +2.63 Blue 718 Cobaltous Chloride .6H.sub.2 O 25 25 19.4 1.98 Good 751 Cobaltous Chloride .6H.sub.2 O 30 30 36.8 3.76 Good 770 Chromic Chloride .6H.sub.2 O 30 0 9.6 +1.53 Green 731 Chromic Chloride .6H.sub.2 O 25 20 45.8 7.2 V. Weak 791 Chromic Chloride .6H.sub.2 O 25 30 Disintegrate 10 secs. 803 Chromic Chloride .6H.sub.2 O 15 45 Disintegrate 5 secs. 771 Aluminum Chloride .6H.sub.2 O 30 0 8.5 +1.0 Good 406 Aluminum Chloride .6H.sub.2 O 25 25 55.5 8.9 Good 714 Aluminum Chloride .6H.sub. 2 O 25 30 Disintegrate 20 secs. 801 Aluminum Chloride .6H.sub.2 O 15 45 Disintegrate 5 secs. 763 Stannic Chloride .5H.sub.2 O 30 0 25.8 +34.0 Good 759 Stannic Chloride .5H.sub.2 O 20 20 46.8 +67.7 Weak 710 Stannic Chloride .5H.sub.2 O 25 25 Solid mass 20 secs. 800 Stannic Chloride .5H.sub.2 O 15 45 Disintegrate 5 sec. __________________________________________________________________________ * Avg. 3 runs - Nos. 778, 788, 804 ** Good --No appreciable deterioration of nylon filament. No discoloration. *** Insoluble at room temperature and 215.degree.F

EXAMPLE III

The shrinkage and weight loss experienced by a test loop of DuPont type 846 bulk continuous filament nylon 6/6 (1,300 denier, 68 filaments, o twist, semi-dull, regular acid dyeable) was determined by means of the beaker test procedure described in Table I using zinc chloride and acids other than acetic acid. The test temperature and the maximum duration of testing was 215.degree.F and 15 minutes respectively.

Recipes and test results are shown in Table IV. These data show that acids other than acetic acid can be used successfully with zinc chloride to provide a strong shrinking agent for nylon fibers. These acids include phosphoric, formic, maleic, citric, hydrochloric, sulfuric, oxalic, malonic, hydroxyacetic, propionic and monochloroacetic. Depending upon the acid employed, and the ratio and concentrations of acid and zinc chloride used, the extent of shrinkage can range from very weak after 15 minutes at 215.degree.F to total destruction of the nylon filament within about 60 seconds. Combinations which produce this latter effect can be anticipated to produce strong embossment of nylon carpet. However, it may occur that a shrinking agent which exhibits a disintegrating time of a few seconds in the beaker will prove to be too destructive for carpet embossment. In this case, the ratio and concentration of chemicals must be changed by trial and error so as to produce the desired embossment.

At the individual concentrations used, neither the zinc chloride alone, nor the acids alone, provide sufficient shrinkage of the nylon filament to produce carpet embossment.

It would be expected that other metal halides besides zinc chloride would also perform satisfactorily with other acids besides acetic acid. For example, 25 % calcium chloride dihydrate combined with 25 % monochloroacetic acid in 50 % water (Run no. 807) caused nylon filament to disintegrate in 20 seconds at 215.degree.F. A weaker concentration comprising 20/20, calcium chloride .2H.sub.2 O, monochloroacetic acid produced a filament shrinkage of 64% (Run No. 882).

TABLE IV __________________________________________________________________________ Nylon Filament __________________________________________________________________________ Zinc Shrink Wt. Run Acid Chloride age Loss Loop * No. Type (%) (%) (%) (%) Character __________________________________________________________________________ ** Water (tap) -- -- 7.03 0.68 Good 762 Zinc Chloride 0 30 18.1 +1.76 Good 859 Acetic Acid 25 0 12.3 1.32 Good 760 Acetic Acid 20 20 33.1 3.41 Good 708 Acetic Acid 25 25 Disintegrate 5 secs. 151 Phosphoric Acid 25 0 16.5 +2.36 Good 874 Phosphoric Acid 20 20 Solid mass 30 secs. 860 Phosphoric Acid 25 25 Solid mass 20 secs. 147 Formic Acid 25 0 22.1 2.06 Good 875 Formic Acid 20 20 53.0 4.67 Weak Spot 861 Formic Acid 25 25 Solid mass 15 secs. 688 Maleic Acid 25 0 13.8 0.71 Good 867 Maleic Acid 20 20 47.4 5.06 Good 862 Maleic Acid 25 25 Solid mass 10 secs. 92 Citric Acid 50 0 23.8 +4.03 Good 877 Citric Acid 20 20 20.4 1.33 Good 865 Citric Acid 25 25 Solid mass 2 mins. 382 Hydrochloric Acid 7.4 0 15.1 3.25 Good 878 Hydrochloric Acid 10 20 Disintegrate 6 secs. 686 Sulfuric Acid 10 0 8.2 0.19 Good 879 Sulfuric Acid 12 20 Disintegrate 10 secs. 683 Oxalic Acid .2H.sub.2 O 35 0 19.6 1.80 Good 881 Oxalic Acid .2H.sub.2 O 20 20 Disintegrate 10 secs.*** 244 Malonic Acid 35 0 18.0 1.61 Good 880 Malonic Acid 20 20 29.1 3.28 Good 870 Malonic Acid 25 25 Solid mass 10 secs. 684 Hydroxyacetic Acid 25 0 8.4 0.58 Good 871 Hydroxyacetic Acid 25 25 46.0 3.16 Weak Spot 687 Propionic Acid 25 0 19.2 2.28 Good 896 Propionic Acid 25 25 Disintegrate 10 secs. 897 Monochloroacetic Acid 25 0 22.7 1.72 Good 554 Monochloroacetic Acid 21 21 Solid mass 20 secs. 568 Monochloroacetci Acid 24 20 Solid mass 30 secs. 558 Monochloroacetic Acid 21 18 59.1 4.18 Good __________________________________________________________________________ * Good = No appreciable deterioration of nylon filament. No discoloration ** Avg. = 3 runs - Nos. 778, 778, 804 *** Insoluble material at 215.degree.F

EXAMPLE IV

This example illustrates the preparation of an embossed pile fabric typical of the products of this invention.

A 4 inch by 7 1/2 inch rectangular area of nylon carpet was treated by means of a screen printing technique with a dye print paste containing 25% zinc chloride and 25% glacial acetic acid by weight as the embossing agent.

Carpet construction was as follows:

Type - 100% Nylon 6/6, spun yarn, non heat set

Face Weight - 28 oz./yd. sq. (950 grams/sq. meter)

Machine Gauge - 5/32 inch (3.96 millimeters)

Machine Stitch Rate - 9.6 stitches/inch (3.8 stitches/centimeter)

Pile Height - 17/32 inch, singles (1.35 centimeters)

The dye print paste recipe was as follows:

SAMPLE NO. 419SP-1 ______________________________________ Material* Grams ______________________________________ 1. Water 29.2 2. Cibaphasol AS 1.0 3. Antifoam 73 0.8 4. Polygum No. 260 (5%) 19.0 5. Acetic Acid, Glacial 25.0 6. Zinc Chloride 25.0 7. Dye 0.05 ______________________________________ * 2 = Sulfuric acid ester, levelling agent and penetrating agent. 3 = Alcohol ether, antifoaming agent 4 = Locust bean gum thickener providing a Brookfield viscosity of 600 cps at 78.degree.F (No. 3 spindle 21/2 rpm).

There was no evidence of embossing while the nylon carpet was held at room temperature for several minutes. Upon subjecting the carpet to steaming for 15 minutes at about 218.degree.F, significant embossing due to fiber shrinkage was observed. Thereafter, the embossed carpet was thoroughly rinsed with water and dried. The rinsing removed residual chemicals.

The resulting carpet exhibited excellent embossing with a 41% reduction in pile height in the treated area in perfect register with the printed rectangle. Despite this degree of shrinkage, the nylon tufts after rubbing retained their individuality and were soft and strong. There was no evidence of deterioration of fiber physical properties.

EXAMPLE V

A series of adjacent parallel rectangular areas of nylon carpet measuring 6 inches wide by 2 inches, 1 inch, 1/2 inch, 1/4 inch, and 1/8 inch respectively were treated simultaneously by means of a screen printing technique with a dye print paste containing 25% zinc chloride and 25% glacial acetic acid by weight as the embossing agent.

Carpet construction was as follows and differed from the carpet construction utilized in Example IV with respect to heat setting, face weight, machine stitch rate, and twist.

Type - 100% Nylon 6/6, spun yarn, heat set

Face Weight - 40 oz./sq. yd. (1,356 grams/sq. meter)

Machine Gauge - 5/32 inch (3.96 millimeters)

Machine Stitch Rate - 7 stitches/inch (2.76 stitches/centimeter)

Pile Height - 17/32 inch, double twist (1.35 centimeters)

The dye print paste recipe was as follows. In this instance, the thickener employed was an Xanthan gum instead of the locust bean gum used in Example IV.

SAMPLE NO. 452SP-2 ______________________________________ Materials* Grams ______________________________________ 1. Water 32.7 2. Cibaphasol AS 0.5 3. Antifoam 73 0.8 4. Kelzan (1%) (0.2% Dowicide A) 16.0 5. Acetic Acid, Glacial 25.0 6. Zinc Chloride 25.0 7. Dye 0.05 ______________________________________ * 4 = Xanthan gum thickener plus preservative in water to provide a Brookfield viscosity of 1080 cps. at 78.degree.F (No. 3 spindle, 21/2 rpm).

Again, there was little evidence of embossing while the nylon carpet was held at room temperature. Upon subjecting the carpet to steaming at about 217.degree.F for a period of 15 minutes, significant embossing resulted due to shrinkage of the nylon carpet pile. Thereafter, the carpet was rinsed and dried.

The resulting carpet exhibited a 35% reduction in pile height at the 2 inch by 6 inch area exactly in register with the printed area. A similar reduction in pile height was noted for the 1 inch by 6 inch area. However, the narrower width prints produced only about a 26% reduction in pile height (1/4 inch wide) and a 18% reduction in pile height (1/8 inch wide). These latter two reductions in pile height are a reflection of the reduction in the print paste penetration at very narow printed areas when no changes are made in print paste viscosity to compensate for narrow embossments. The embossed nylon pile was rubbed briskly. The tufts retained their individuality and were soft and strong. There was no evidence of deterioration of fiber physical properties.

EXAMPLE VI

The nylon carpet construction described in Example IV was again treated by means of a screen printing technique. This time, the embossing agent comprised 15% lithium chloride and 45% acetic acid, glacial, by weight.

The dye print paste recipe containing the embossing agent was as follows:

SAMPLE NO. 903SP-1 ______________________________________ Materials* Grams ______________________________________ 1. Water 22.7 2. Cibaphasol AS 0.5 3. Antifoam 73 0.8 4. Kelzan (11/2%) + (0.2% Dowicide A) 16.0 5. Acetic Acid, glacial 45.0 6. Lithium Chloride 15.0 7. Dye 0.05 ______________________________________ * 2 and 3 same as described in Example IV. 4 = Xanthan gum thickener in water plus the preservative Dowicide A yielding a Brookfield viscosity of 1040 cps. at 78.degree.F (No. 3 spindle, 21/2 rpm).

Upon subjecting the printed carpet to steaming at 217.degree.F for 15 minutes, significant embossing developed due to shrinking of the nylon carpet pile by the embossing agent. While the carpet was held at room temperature for a few minutes prior to steaming, there was no evidence of embossing. After steaming, the carpet was washed and dried.

The resulting carpet showed a 41% reduction in pile height exactly in register with the printed area. Despite this deep embossment, the rubbed nylon tufts retained there original character except for increased firmness and some slight hardness.

EXAMPLE VII

This example offers additional illustrations of the preparation of embossed nylon pile carpets typical of the products of this invention.

A series of adjacent parallel rectangular areas of nylon carpet measuring 6 inches wide by 2 inches, 1 inch, 1/2 inch, 1/4 inch, and 1/8 inch respectively were treated simultaneously by means of a screen printing technique using in one case a dye print paste containing 24% monochloroacetic acid and 20% zinc chloride by weight as the embossing agent, and in another case, 24% monochloroacetic acid and 20% calcium chloride .2H.sub.2 O as the embossing agent. In both instances, the nylon carpet construction was the same as cited in Example IV.

The dye print paste recipes were as follows:

Materials* Sample No. 670SP-1 914SP-1 ______________________________________ 1. Water (tap) 35.2 39.7 2. Cibaphasol AS 0.5 0.5 3. Antifoam 73 0.8 0.8 4. Polygum 260 (5%) 19.5 -- 5. Kelzan (11/2%) + (0.2% Dowicide A) -- 15.0 6. Monochloroacetic Acid 24.0 24.0 7. Zinc Chloride 20.0 -- 8. Calcium Chloride .2H.sub.2 O -- 20.0 9. Dye 0.05 0.05 ______________________________________ * 2,3,4, and 5 same as described in Examples IV and V.

Print paste viscosity was 40 cps. at 78.degree.F for Sample No. 670SP-1 and 1,000 cps. at 78.degree.F for Sample No. 914SP-1. (Brookfield No. 3 spindle, 2 1/2 rpm).

There was no sign of embossment while the printed nylon carpets remained at room temperature for several minutes. But after steaming for 15 minutes at 217.degree.F, significant embossing due to fiber shrinking was observed. Thereafter, the embossed carpets were thoroughly rinsed with water and dried. The rinsing removed residual chemicals.

Both of the resulting carpets exhibited excellent embossing in perfect register with the printed design. Pile reduction amounted to 47% for sample 670SP-1, while the reduction in pile height for sample 914SP-1 was 35%. After rubbing the dried, embossed areas, the resulting pile was soft, firm, and strong for both carpets. There was no apparent deterioration of fiber physical properties in either case.

EXAMPLE VIII

Embossed nylon carpets were prepared using the embossing procedure and carpet construction cited in Example IV. Various combination of metal halide and acid were employed as follows:

45% Acetic Acid, 15% Calcium Chloride .2H.sub.2 O

25% acetic Acid, 30% Aluminum Chloride .6H.sub.2 O

22.5% formic Acid, 25% Zinc Chloride

20.0% Phosphoric Acid, 25% Zinc Chloride

The dye print paste recipes used were as follows (Table V):

TABLE V __________________________________________________________________________ Carpet Sample No. Material* 907SP-1 910SP-1 913SP-1 911SP-1 __________________________________________________________________________ 1. Water (tap) 23.7 29.2 33.2 34.2 2. Cibaphasol AS 0.5 0.5 0.5 0.5 3. Antifoam 73 0.8 0.8 0.8 0.8 4. Kelzan (11/2%) + (0.2% Dowicide A) 15.0 14.5 15.5 16.0 5. Acetic Acid 45.0 25.0 -- -- 6. Formic Acid (90%) -- -- 25.0 -- 7. Phosphoric Acid (85%) -- -- -- 23.5 8. Calcium Chloride .2H.sub.2 O 15.0 -- -- -- 9. Aluminum Chloride .6H.sub.2 O -- 30.0 -- -- 10. Zinc Chloride -- -- 25.0 25.0 11. Dye 0.05 0.05 0.05 0.05 12. Brookfield viscosity (cps.) 1920 960 1000 1080 __________________________________________________________________________ * 2 - Sulfuric acid ester, leveling and penetrating agent. 3 - Alcohol ether, antifoaming agent. 4 - Xanthan gum thickener plus preservative Dowicide A in water yielding the Brookfield viscosities indicated at 78.degree.F (No. 3 spindle, 21/2 rpm).

There was no evidence of embossing while the carpet samples were held at room temperature for a few minutes prior to steaming. But upon subjecting the printed carpets to steaming for 15 minutes at 217.degree.F, significant embossing due to fiber shrinkage was observed in every case. Thereafter, the embossed carpets were thoroughly rinsed with water and dried.

The resulting carpets exhibited excellent embossing showing the following reductions in pile height exactly in register with the treated areas.

__________________________________________________________________________ Sample Embossment No. Embossing System (%) __________________________________________________________________________ 907SP-1 Acetic Acid, Calcium Chloride .2H.sub.2 O, 45/15 29 910SP-1 Acetic Acid, Aluminum Chloride .6H.sub.2 O, 25/30 29 913SP-1 Formic Acid, Zinc Chloride, 22.5/25 41 911SP-1 Phosphoric Acid, Zinc Chloride, 20/25 38 __________________________________________________________________________

After rubbing, the shrunk tufts were defined, strong and soft for the first three of the foregoing embossed carpets; while the tufts were firmer and somewhat harsh for the carpet embossed with the phosphoric acid/zinc chloride, 20/25 system.

EXAMPLE IX

A series of adjacent parallel rectangular areas of nylon carpet measuring 6 inches wide by 4 inches, 1 inch, 1/2 inch, 1/4 inch, and 1/8 inch respectively were treated simultaneously by means of a screen printing technique using a dye print paste containing 22.7% maleic acid and 22.7% zinc chloride by weight as the embossing agent. Carpet construction was the same as described in Example IV.

The dye print paste recipe was as follows:

SAMPLE NO. 906SP-1 ______________________________________ Material* grams ______________________________________ 1. Water (tap) 42.7 2. Cibaphasol AS 0.5 3. Antifoam 73 0.8 4. Kelzan (11/2%) + (0.2% Dowicide A) 16.0 5. Maleic Acid 25.0 6. Zinc Chloride 25.0 7. Dye 0.05 ______________________________________ * - 2, 3, and 4 same as described in Example VIII except Brookfield viscosity was not obtained.

Once again there was no indication of embossing while the nylon carpet was held for several minutes at room temperature before steaming. Upon subjecting the carpet to steaming for 15 minutes at about 217.degree.F, deep embossing due to fiber shrinkage was noted. Thereafer, the embossed carpet was thoroughly rinsed with water and dried.

The resulting carpet exhibited deep embossment amounting to 41% in perfect register with the treated area. After rubbing, the nylon tufts retained their individuality and were soft and strong. There was no evidence of deterioration of fiber physical properties.

EXAMPLE X

Additional embossed nylon carpets were prepared by means of the embossing procedure and carpet constructions described in Examples IV and V utilizing various concentrations and proportions of zinc chloride and acetic acid contianed in the dye print paste as shown in Table VI. Print paste viscosities were varied from 680 cps. to 4,560 cps. Two thickeners were used, a locust bean gum and an Xanthan gum.

The resulting carpet samples exhibited embossed depths ranging from 25% to 41% depending upon the proportins and concentrations of zinc chloride and acetic acid, the carpet construction and the dye print paste viscosity. Pile character ranged from soft to hard and harsh. Certain print paste recipes containing the zinc chloride and acetic acid will be seen to have a destructive effect on the nylon fibers. This may be attributed generally to too strong an embossing system and/or too high a dye print paste viscosity. In the former case, the condition can be corrected by altering the concentrations and/or proportions of the acetic acid and zinc chloride. In that latter case, a reduction in viscosity will be beneficial. It appears that too high a print paste viscosity caused excessive bulidup of embossing agent to a shallow depth of the carpet pile resulting in a localized concentration of embossing agent that is too strong. Conversely, the print paste viscosity must not be too thin or excessive lateral ##SPC1##

bleed will occur resulting in loss of design fidelity and embossed effect.

In the production of the pile fabrics of this invention, the pile yarn employed is prepared from fiber-forming synthetic linear polyamides. Examples of these fiber-forming synthetic linear polyamides are those obtainable from polymerizable monoaminomonocarboxylic acids and their amide-forming derivatives including caprolactam and those obtainable from the reaction of suitable diamines with suitable dibasic carboxylic acids or their amide-forming derivatives. Such synthetic linear polyamides are referred to as nylon.

Nylon or polyamide polymers, filaments and fibers are well known to those skilled in the art and extensive discussion is, therefore, unnecessary. Thus the term "polyamide" or "nylon" is known to include any long chain synthetic polymeric amide which has recurring amide groups as an integral part of the main polymer chain and which is capable of being formed into a filament in which the structural elements are oriented in the direction of the axis of the chain.

Polyamide resins coming within this definition and contemplated in the practice of the present invention are formed generally by reaction of a dicarboxylic acid with a diamine or by the self-condensation of an aminocarboxylic acid. Illustrative of these polyamide resins are nylon-6,6, prepared by the condensation of hexamethylenediamine and adipic acid; nylon-6,10, prepared from hexamethylenediamine and sebacic acid, both of the foregoing having, as prepared, molecular weights exceeding 10,000; nylon-6 produced by thermal polymerization of epsilon-aminocaproic acid or caprolactam; nylon-11, the self-condensation produce of 11-aminoundecanoic acid; as well as a variety of polymers prepared from polymerized, unsaturated fatty acids and polyamino compounds.

The practice of the present invention has, however, particular application to solid melt-extrudable and orientable fiber-forming polyamides and more particularly to fibers and filaments prepared therefrom which have a denier and tenacity appropriate, and well known to those skilled in the art, for use in carpet, rugs, tapestry and the like. Illustrative of these polyamides are those having a filament denier of 2-30 or higher or nylon yarns in the denier range of 15-15,000 or higher. The tenacities of nylon yarn for use herein are within the range of 3-10 grams per denier. The elongation of commercial fibers can range between 16 to 65%. The undrawn filament is capable of being stretched as much as 5 times. It is understood additionally that encompassed within the polyamides that can be employed in the practice of this invention are high mulecular weight synthetic linear polyamides, in addition to those described hereinabove, that have been modified, for example, to enhance their usefulness for particular applications.

An extended discussion of polyamides of sufficiently high molecular weight to be capable of being melt spun into filaments and comiing within the contemplation of this invention appears in D.E. Floyd, Polyamide Resins, Reinhold Plastics Application Series, Reinhold Publishing Corporation, N.Y., N.Y. (2nd Printing 1961), and H.R. Mauersberger, Matthews' Textile Chemical Properties, John Wiley and Sons, Inc., New York N.Y., pp. 933-971, 1034., (6th ed. 1954), Mary E. Carter, Essential Fiber Chemistry, Marcel Dekker, Inc., New York 1971, pp. 91-109, and H.F. Mark, S.M. Atlas, E. Cernia (Edited by), Man-Made Fibers, Science and Technology Volume 2, Interscience Publishers 1968, pp. 181-295, and Tech.-Talk from Monsanto Textiles Division, Bulletin TT-35 August 1969.

Summarizing, it is thus seen that this invention provides a novel and effective method for embossing nylon pile fabrics.

Variations may be made in procedures, proportions, and materials without departing from the scope of the invention as defined in the following claims.

Claims

What is claimed is:

1. A process for producing an embossed effect on nylon pile fabric having a surface of nylon fibers which comprises,

applying to defined areas of the pile surface of said fabric a chamical embossing agent for said fibers,

said agent being blended into a liquid base vehicle and being a metal halide and an acid,

allowing said embossing agent in its vehicle to remain in contact with said fibers for a period of time and at a temperature sufficient to reduce the height of said pile, without deterioration of said fibers and, thereafter, effectively removing the embossed agent from the fabric,

said reduction in height of the fibers being in the area contacted by said embossing agent only and being a reduction sufficieint to display a significant embossed effect in the overall fabric.

2. The process of claim 1 wherein said embossing agent is a metal halide selected from the group zince, calcium, lithium, aluminum, copper (cupric), tin (stannous), tin (stannic), ferric, chromic,

and an acid selected from the group acetic, phosphoric, formic, maleic, citric, hydrochloric, sulfuric, oxalic, malonic, propionic, hydroxyacetic, monochloracetic

in concentrations of 5 per cent to 50 per cent metal halide and 60 per cent to 5 per cent acid, by weight, of total embossing composition.

3. The process of claim 2 wherein said embossiing agent is incorporated in a transparent vehicle therefor.

4. The process of claim 2 wherein said embossed effect is made in register with a printed color design on said fabric and

said vehicle is a dye printing paste carrying said embossing agent.

5. The process of claim 2 wherein said embossing action occurs within approximately 15 minutes at a temperature above 50.degree.C.

6. The process in accordance with claim 5 wherein said embossing action occurs in a steam environment.

7. The process of claim 6 wherein said embossing composition is present in a concentration of about 40 to 65 percent in the vehicle therefor.

8. The process of claim 1 wherein said embossing agent is zinc chloride and acetic acid

containing 15-30 percent zinc chloride and

45-25 percent acetic acid.

9. The process of claim 8 wherein said embossing agent is zinc chloride and acetic acid, in equal percentage at about 25-25 percent.

10. The process of claim 7 wherein said embossing agent is calcium chloride and acetic acid.

11. The process of claim 7 wherein said embossing agent is aluminum chloride and acetic acid.

12. The process of claim 7 wherein said embossing agent is zinc chloride acid.

13. The process of claim 7 wherein said embossing agent is zince chloride and monochloroacetic acid.

14. The process of claim 7 wherein said embossing agent is zinc chloride and hydrochloric acid.

15. The process of claim 7 wherein said embossing agent is zinc chloride and maleic acid.

16. The process of claim 7 wherein said embossing agent is lithium chloride and acetic acid.

17. The process of claim 7 wherein said embossing agent is cupric chloride and aceetic acid.

18. The process of claim 7 wherein said embossing agent is stannous chloride and acetic acid.

19. The process of claim 7 wherein said embossing agent is stannic chloride and acetic acid.

20. The process of claim 7 wherein said embossing agent is ferric chloride and acetic acid.

21. The process of claim 7 wherein said embossing agent is chromic chloride and acetic acid.

22. The process of claim 7 wherein said embossing agent is zinc bromide and acetic acid.

23. The process of claim 7 wherein said embossing agent is zinc iodide and acetic acid.

24. The process of claim 7 wherein said embossing agent is zinc chloride and formic acid.

25. The process of claim 7 wherein said embossing agent is zinc chloride and phosphoric acid.

26. The process of claim 7 wherein said embossing agent is zinc chloride and propionic acid.

27. The process of claim 7 wherein said embossing agent is zinc chloride and oxalic acid.

28. The process of claim 7 wherein said embossing agent is zinc chloride and malonic acid.

29. The process of claim 7 wherein said embossing agent is zinc chloride and sulfuric acid.

30. The process of claim 7 wherein said embossing agent is calcium chloride and monochloroacetic acid.