CA1039005A - Carpet embossing in register with print - Google Patents

Abstract

ABSTRACT OF THE INVENTION:
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. The preferred chemical fiber shrinking agents comprise an azole such as benzotriazole in combination with an acid such as acetic acid.

Description

BACKCROUND OF T~E INVENT ION:
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In the production of nylon plle fabricR, lt 1~ often de~lrsble to embos~ the surface thereof ln order to provlde added decoratlve appeal. In some lnstances, the embossed areas are printed with dyes to further embelllsh the surface design.
Embosslng the pile fabrics is conventionally accomplished with a heating embossing roll or plate which has been engraved or otherwise treated to create the de~ign desired in raised relief on the surface. A method which eliminates the use of ~-embossing rolls has been disclosed in U.S. Patent 2,790,255 and

2,875,504. In accordance with these patents, the pile fabric is for~ed from a combination of shrinkable and non-shrinkable yarns.
Upon sub~ecting the fabric to the influence of heat, the pile formed from the shrinkable yarns contracts while the base and the non-shrinkable yarns remain intact thereby yielding a pile made up of high ant low areas to give the appearance of an em-bossed or carved product.
A chemical embossing method is disclosed in U.S. Patent 2,020,698. Accordlng to this pa~ent, fabric having a pile of ---organic e~ter of cellulose yarn is locally treated with an alkali ~ ;
or alkaline salt ~aponifying agent in order to obtain ornamental - differential effects in the treated areas. Furthermore, since the organic ester of cellulose pile yarn`s that have not been - saponified are more difficult to change from their position, after they are once ~et than are the saponified organic ester of cellulose yarns, it is po~sible to obtain a differential lay bet~een the saponified and unsaponified organic ester of cellulose plle yarn. Thus, the fabric, after the application of the ~aponifying agent, may be wa~hed, flnished snd drled with ehe pile erect, after which the fabric may be run through water and brushed across the piece to lay the pile towards the ~elvage and . ..................................... :

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lt 1~ then drled. Thl~ causes the s~ponifled pile yarn to lle flat while the unsaponified yarn re~ains ~ub~tantl~lly erect.
Upon ~ub~equent steaming and brushln~ the fabrlc ln the oppos1te dlrection, any un~aponified yarn ~hlch may have been sllghtly bent from the ~ertlcal by the previous brushing toward the selvage ls caused to stand erect without di~turbing the position of the laid or crushed saponified organic e~ter of cellulo~e pile yarn. ~ -SUMMARY OF THE INVENTION. ~-It i~ the primary ob~ect of this invention to provide a simple process for producing a nylon pile having a textured or embossed surface.
Another obiect is to provide ~uch a process which is readily adaptable to standard printing equipment.
~nother ob~ect is to provide a proce3s which allows the production of pile fabric having embo~sed are~3 in register with a printed de~ign. ~ ~ -A further ob~ect is to provide an embossing process which ~8 readily adaptable to curved and irregular surfaces. -20- Various other ob~ects and advantages of this invention will be apparent from the following detailed de~cription thereof. -~
It has now been discovered that it is possible -:o pro- ,-duce superior nylon pile fabrics having embossed surfaces by con-tactlng selected portions of the surface~ with a chemical em-~ossing a8ent for the fiber~ of said pile fabric causing di- -~entional change by llnear contraction of the treated fibers and, thereafter, effectively removing the embossing agent. The resulting product is thus depressed at the treated areas.
- The embosslng composition can be transparent 80 that the appearance of the product 18 not altered other than in belng e~bos~ed. Alternatlvely, the embo~slng a~ent can be part of a db/~
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lQ39005 dye or plgm~nt compo~ltion used ln prlntlng the fab~lc 90 that the color appears ln perfect reglster ln the area3 of e~bO88lng agent appllcatlon.
The depth of the depressed areas can be controlled by varylng the concentratlon and/or type of embossing agent. Thi~
variation in concentration can be effected by ~he 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 carry-ing 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 embos~ing agents which provide the desired effect.
This discovery makes possible the production of a pro-duct having embossed surfaces which can be in complete register . . .
with a printed design. Additionally, the discovery makes pos-sible the utilization of ~any types of printing apparatus for purposes of effecting embossing, thereby eliminating the need :-for expen3ive embossing equipment. Further, it allows the em-bossing of a surface *ithout exerting suffi~ient pressure to permanently deform the pile fabric. A great number of products can be produced by the process. They can be used for floor, ~all and ceiling coverings, drapery, upholstery and ~he like, and, in fact wherever pile fabrics are utilized. They are readily adaptable to decorating any surface on which plle fabrics csn be applied. Many additional applications will occur to those s~illed in tbe art.
Thls invention will be better understood from the foliow-ing detailed description theroof together wlth the acco~panying self-explanatory trawings ln whlch:

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103900s Flgure 1 1~ an enlarged top vlew of a ~ectlon of an em-bo~et product of thls lnventlon; and, Figure 2 1~ an enlarged cro~s-sectionsl view o~ the ~ame product taken through llne 2-2 DESCRIPTION OF THE PREFERRED EMBODIMENTS:
In the production of the pile fabrics ~f this invention, the pile yarn employed is nylon. Synthetic fibers prepared from polya~ides such as nylon are well known to those skilled in the art. -;
Likewise, the embossing agents which are applied to the nylon fibers in orter 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 ~easurable reduction of pile height, but without significant deterioration of the nylon fibers. The exact chemical/physical ~echanism by which this rèsult is achieved i8 not completely understood. ~owever. it is believed that the embossing agent may owe its effectiveness largely to lts capability to function as a hydrogen bond breaker. Initially, the fibers are in a stretc~ed and crystalline state. When the hydrogen bond is broken between the polymer chains, the fiberæ relax and shrink.
Regardless of the mechanism, the overall effect produced is one of dimensional change, the most tesirable effect, involving linear contraction of the fiber.
In order to be applicable for the novel process of this invention, the e~bossing agent should provide a reduction of the pile height through a sbrinkage reaction, should not adversely ~ffect the printlng means, e.g. prlnt screens, and should be capable of being substantially removed or lnactivated subsequent to the embosslng actlon. Other characteristics of the embossing ,. - '1 ., ., db/ ~ ~

103!~005 sgent whlch sre de~ir~ble, though not e~entlal, lnclude com-patlbillty wlth dye prlnt pastes, c~pabllity of belng regulated by factors of time, temperature and concentration, l.e.
~u~ceptibillty to activation by a conventlonal ~tesmlng operation and exhibiting no residual embossing actlvlty. Needless to ~ay, minor ad~ustments 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, wh~ther it be random or predetermined. One of the easie~t methods of applying the agent is by utllizing conventional printing tech- -nique 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 i~opropanol. Often thickeners, e.g. gum~, and cellulose derivatives, are included in order to obtain viscosity charact~
erist~ c8 demanded in print technology and to enable ~he embos-sing a8ent to adhere to and operate on the synthetic fiber and to hold the printed pattern.
In those instances where it ~s de~ired to achieve a - slngle- or multi-colored printed decoration with a distinct color for the embossed areas, the embossing agent can be in-corporated into a particular dye or pigment composition. The tye or pigment will generally be in the form of a print paste in~ to which the appropriate amount of agent 18 added. It is to be noted that ln preparing these modified dye compo~itions, the p~ levels, viscosities, and dye concentratlons which are ~`

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, e~entlal to an ef~lclent dyein~ oper~tlon must al~o be con- !
trolled. The re~ultaat effect 18 an embos~ed de~lgn ln reglster wlth the prlnted pattern. If dlfferent depth8 of embos~lng are sought, they are achieved by use of tlfferent concentrstlons of a~ent in the areas calling for such different depths.
Generally, it i~ tesirable that the embossing agent be soluble or ln solution ln the solvent medium from which it i~
applied to the selected areas of the fabric. However, if the agent is not soluble it should be in the composition in a form 10 at least sufficiently finely divided to pass through the print screen" that i8, it should be present in a micro pulverized form which lndicates particle diameter of the order of 100 microns or smaller. That is, it must not only pa~s 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 uni-formly disperset 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 agent 20 18 one which is dormant durlng the successiYe printing operations but then i8 activated by the elevated temperature of a steam chamber usually utilized to fix the dye onto the fibers. The embossing agents of this invention which can function in this ~snner on nylon and produce shrin~cage of the nylon fibers without - physlcal deterioration comprise an azole ~uch a~ benzotriazole ln combination wlth an acid such a~ acetic acid. When this combinatlon of chemlcals is added to the dye print paste in the proper concentrations and proportlons, nylon carpet pile can be embossed teeply without slgnlficant fiber deterioration exactly 30 in reglster with a printed d-~lgn by ~hrinklng the nylon fibers.
- Whlle the preferred azole is benzotriasole, other azoles G

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~039005 containlng one to four nltrogen~ ln the sromatlc, heterocycllc, 5-membered rlng may be used. Examples are pyrrole, 5-chlorolndazole, 5-chloroben~ot~a~ole, S-amlno tetrszole ~ono-hydrate and benzothiazole. While acetic acid i9 preferred, other acids may be used such as formlc, phosphorls, cltric, hydroxyacetlc, oxallc, propionic, maleic, hydrochloric and sulfuric. At the individual concentrations employed in this process benzotrlazole or its substituted products and ana-logues alone, or the acid alone, are not generally useful because of such factors as insolubility at room temperature, ineffectiveness, volatility, toxicity, destructiveness, cost.
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 mini~al concern regarding excessive uncontrollable embossing because other factors can be changed. Thus, the degree of diminution of the pile height can be controlled by ad~usting the amount of dye paste applied, the concentration of embossing agent in the dye paste and the temperature and time of exposure in the stea~ chamber. All these factors can be ad~usted accord-ing to properties of the nylon fiber comprising the pile fabric.~hile the depth of embossing will be determined by the practition- ~-er in accordance wlth the type of embossed product bein8 pre~
pared, reduction ln pile height will generally not exceed more than about 50X, thiQ value being indicative of excellent embos-sing without exposing the backing materials.
~ mbossing can be achieved, lf tesiret, by subJecting the treated fibers to heat for short periods of time. Thus, the treated surfaces may be subJected to the ratiation from the ~ank of infrared lamps, particularly where the embossing agent is not part of a dye print pastQ. Additionally, even whare the steaming operation 1~ not e~entlal to actlvate the Qmbossing db/~
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, agent, ~uch steamlng mAy h~ve the effect of lncres~lng the penetration of the embossing a8ent and lncrea~ing the speet of lts actlon on the fibers.
A critlcal step of the novel proce~s of thi~ lnventlon involves termlnating the embossing actlon and/or effective sub-9tantial removal of the embossing agent from the pile fabric.
It may be necessary to achieve complete eliminat~on of all resi-tues of the embosslng process which may contribute undesirable properties to the finished fabric, such as odor, toxicity and color and texture change. Needless to say, any terminstion or quenching technique resortet to will depend on the par~icular embossing composition employed. The most useful technique for removing residues of the embo~sing proce~s i8 by thoroughly washing the fabric with water and detergents. In those in~
stances where the embossing agent i8 part of a dye or pigment composition, the washing cycle is utilized to remove excess dye of pigment serves also to remove traces of the agent. Where an acidic embossing agent i~ utilized, e.g. formic acid on nylon, it i8 possible to halt the embossing action more rapidly by rinsing with an aqueous ammonia or mildly al~aline 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 cleanlng. Thu~, if the agent is volatile, steaming of the - treated pile fabric will serve to evaporate a large portlon of the e~bossing agent content. Where rinsing techniques are not offective, it may be necessary to resort to a dry cleaning procedure to remove the embogsing resitues.

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,,~ -~.03gO05 The lnventlon has partlcular appllcatlon to tufted carpet whlch are to have a printed decoratlon applied thereon. Un-usual tesign effects can also be obtalned when the plle fabrlc is prlnted wlth a multl-colored de~iBn whereln one or more of the dye compositions contaln the approprlate embossing agent.
The process of prlntlng such carpets lnclutes the ~teps of passing carpets, tufted or unpigmented or colored fibers, into a ~creen printing appa~atus 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 `~ ;
thè smbossing 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 ls related to the embo6sing be "~ ;
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in accurate register with the embossing. Since we are concerned only with chemical embossing tne problem is then one of inducing the differential fiber length between the embosset colored areas and unembossed areas and, while it is possible to induce shrinkage of synthetic nylon fibers, it i8 neces~ary for pre-paration of the carpet that the film shrinkage be induced with no significant deterioration of what iA left. Thus, if the operation of embossing involves true ~hrinkage the shrunk fabric fiber ~hould have a texture approximating that of the origlnal.
Many azoles are largely ln~oluble ln water at room temperature. Some become ~olublllzed, however, at room temperature tb/P ~
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ln an aclt solutlon such a~ acetlc aclt. Thu~, for exa~ple, whlle the preferred benzotriazole ls only ~lightly soluble in water at room temperature (about 2~ at 77F), up to at least 50% benzotriazole goes lnto solution in a 40% solution of glaclsl acetic acid in water at room temperature ~77F) and remain~ ln solution. Because of this, we are able to meet an lmportant practical requlrement that the embosslng agent be preferably soluble or at least finely dispersable ln the tye prine paste at room temperature. Complete solubility or dispersability to an extremely finely divited condition i9 required so that the individual particles contained in the printing paste can pass -through the ~arpet printing screen and reach a maximum area of the nylon fiber to develop the desired effect. Preferably the solubilizing medium should be wate~ although other solvents may be employed. However, the partial or total replacement of water by another solvent may cause a reduction in the extent of carpet embossment by the benzotriazole/acid embossing agent.
A number of factors appear to influence the effective- ~
ness of azoles as embossing agents for nylon carpet. These in- ~ -clude the location and number of nitrogen atoms in the azole ~ `
ring, the presence of' the active hytrogen atom on the azole ring nitrogen, the type and location of substituent groups, the presence of heteroatoms such as o~y~en and ~ulfur in the azole ring, the type and concentration of acit employed, the ratio of azole to acid and the extent of solubility of the azole in acid ~olution at room temperature. ~-As noted before, benzotriazole is the preferret azole.
In addition to its reaty solubility in acid solution at room temperature, benzotriazole i~ preferred because of lts manageabi-llty (safe margln between flber ~hrinkage and flber destructlon), effectiveness as ae embo--ing agent, nonoffen~lve odor, lack of - 1~

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volntillty, ease of handllng ~nd relatl~e non~oxlclty.
Sultable combinations of benzotrlazole and acetlc acld sre ~elected from wlthin approxlmately the followlng brosd range of concentration~ for each component ~o 8~ eO obtain nylon carpet embo~sment to the desired depth. The~e range~ repre~ent part~ per hundred of the total print paste.
Benzotriazole 5-50 Glacial Acetic Acid 60-15 Preferably, however, the proportions of benzotriazole and acetic acid will be 6elected from within approximately the follo~ing narrower range~.
Benzotriazole 15-30 -Glàcial Acetic Acid 45-25 Within these concentration rangeq, the individual com-ponents used alone are unsuitable for nylon carpet embossment.
At the concentration needed for carpet embo~sment, benzotriazole ~ ~-is insoluble in water at room temperature and the destructive effect of benzotriazole on nylon fibers is difficult to control, while the concentration of acetic acid alone needed to emboss carpet will generally exceed 60%. The combination of benzo- -triazole and acetic acid provides an easily manageable and effective emb 08 sing agent.
A procedure of trial ant error is required in order to arrive at the best proportions of benzotriazole and ace~ic acid or other azoles and other acids 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 phyeically fibers and that the shrunk carpet plle retain its original phy~ical character as well as acceptable appearance ant feel. Generally, however, lt will be found that the sum of the concentratlon of benzotrlazole ant the concantration of dbl P~
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~o3gO05 acetlc acid ln the prlnt paste wlll fall wlthln the llmlto of 45-65X. Whenever maxlmum carpet embo~sment 1~ obtalned (that depth ~ust short of flber deterloration, unacceptable hartness or the like) any reformulatlon whlch calls for increaslng elther component should be accompanied by a reduction in the concentration of the other component, otherwlse flber deterior-atlon wlll occur.
The concentratlon range wlthln whlch benzotriazole and acetic acid may be selected does not necessarily hold true for other acids and other azoles. Suitable concentrations snd proportion~ 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 i~ also related to the distribution and penetration of the embossing I agent into the nylon carpet pile. Therefore, print paste vis-il co~lty is important in influencing the depth of embossing as ;. ~ell as the embossed pile character since it regulates the pene-tration of the dye print paste containing the embossing agent ~^ 20 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 squeegea roller ~tro~e6. Other facto~s effecting both shrinkage and attack of nylon fibers are steamer tlme and temperature. Too long a ~teamer time or too high a temperature generally aggravate nylon flber deterioration. Generally, it appears that the maximum reductlon in nylon carpet pile height will not exceed much more than about 50Z wlthout fiber deterloration reflected ln un-acceptabls pile hardne~, harchne~o, weakne~o, fu~ion, snd thé

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like. Ls~er e~boo~ed tepth~ are o~ cour~e obtalned by altering ~- the proportion~ and/or concentrations of the compon~nts of tha , .. .
~ embossing agent. 12 . ., .- a db/~ ~

~03900S

In order to practlcally evaluate the utlllty of a partl-cular chemlcal or c~mblnation of chemlcal~ as an embo~slng agent for nylon carpet, the chemlcal system 18 lncorporatet ln the dye prlntlng paste and applied to a section of the nylon carpet by means of a screen printing technique 90 a~ to slmulate plant production procedure as closely as possible. The treated carpet sample is steamed about 15 minuteg at 215-200F, thoroughly rinsed with water and dried at 180~F. Then the embo~sed area i9 .
rubbed briskly with the finger tips or for example by means of a wooden knife handle to loosen and separate tuft~. In the plant, this is accomplished by brushing. The depth of emboss-ment is then measured and observations made regarding the character of the embossed nylon, e.g. strength, brittleness, ~;
softness, definition, color. Measurement of the pile height ~ ~
at the embossed and unembo~sed areas is made by means of a thin, - -- ,.
half-inch wide cteel ruler marked off in 1/64 inch intervals.
But any method of measurement is useful so long as it is ~- -standardized from operation to operation and is reproducible to about 1/64 inch.
~owever, for the preliminary determination of whether or not a chemical compo~ition is capable of shrinking nylon fibers ant for thus determining its potential suitability as a chemical embossing agent for nylo~ carpet, we have devised a ~impler, less time con~uming beaker test proceture. Using this test, the per cent ~hrinkage and the per cent weight loss experienced by a 50 centimeter loop of nylon carpet filament or carpet yarn is determinet by immersing the yarn loop in an aqueous solution or dispersion of the test chemical for 15 minutes at 215F (102F). Thls test affortg a ~imple way of determinin8 what effect a selected chemical wlll have on the nylon fibers and provides a means of predicting whether or not a chemlcal will db ,~4 1(~39005 functlon a~ an embo~Hing ~gent for nylon carpet. Also, the test provides a method for determining such effect~ as chemical con-centratlon, temperature, time, prlnt paste additlve~, ~olvent~
other than water, nylon type and constructlon and the like.
Details of the test procedure are outlined as follown in Table 1.
TABLE I
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BEARER TEST PROCEDURE

l. Prepare a solution or disperslon of the chemlcals to be tested in water.* If heated, cool to room temperature.
Weigh 30 grams into a 32 x 200 mm test tube.

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

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

4. ~ang 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 l/lO mg.

6. Immsrse nylon loop in hot chemical ~olution, sgitate gently and observe any change in character of the nylon fibers.
G~nerally hold for l5 minutes or less.

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

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

. Determine weight of nylon loop as in 5.

lO. Calculate % shrinkage and % weight loss. `~

* Dye print paste may be used if desired. Other 001vents may be used, especially when other solvent based printing systems are employed.

** If loop breaks or is already fragmented or dis-inte~rated, or if insignificant shrinkage i9 ob-talned, repeat at lower or higher chemical con-centration.

- Wlth the lnformation thus obtained concernlng the extent o~ shrinkage, deterloration or destructlon of the nylon fibers, lt then beComes posslble to predlct whether or not the chemlcal tb/~
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~03900s compo~ltion has any potentlal as an embo~s$ng agent, and even-tually proceed to the formulatlon of a prlntlng paste which ln-cludes the ~hrlnklng materlal. Experlence hss shown, however, that whlle such test result~ prove that the chemlcal agent will shrlnk nylon fiber snd thus has an embossing capabllity for nylon carpet, these result~ tell us only roughly what con-centration of the chemical agent is required to emboss nylon carpet. Nor do we know the exact extent of fiber deteriora-tion 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 ~est shrinkage results must reach at least abou~ 50% shrinkage in 15 minutes at 215F ln order for an embossing agent to pro-duce even trace to very weak carpet embossment. But beyond sbout 50% shrinkage via the beaker test, the nylon filament begins to deteriorate rapidly (test loop weakening and frag~
mentation). On the other hand, it appears that deeply embossed carpet can only be anticipated if the chemical shrinkage agent causes fiber destruction in the beaker within about 60 seconds.
Generally, the maximum tepth of embossment obtainable without causing unacceptable nylon carpet fiber deterioration is usually about 50%.
Apparently, the dlfference between beaker test shrinkage results obtained on a loop of nylon filament on yarn, and screen printing test results obtained on nylon carpet, occurs because the chemical is utilized much l~ess effectively on the carpet plle than in the beaker tegt. Screen printing does not supply ~ufflcient print paste (containing embossing agent) to the nylon carpst pile to provldo a completely unlform coatlng of the nylon fibers. Furthermore, the depth of penotratlon into the csrpet pile ls often of the order of only about 50%. Also, durlng db/~ ~
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stea~ing, the concentratlon of the embo~slng agent may be re-ducet, and chemlcal whlch may be consumed 18 not replaced.
However, ln the beaker test, the nylon loop i9 surrounded con-~tantly and unifor~ly by a ~urplus of hot chemlcal solutlon of practically the same concentration throughout the duration of the test thus allowing the chemlcal to function more effectively.
The following examples will further illustrate the em-bodiment of this invention. In these examples, all part~ given are by weight unless otherwise noted.
E~ANPLE I
The shrinkage and weight los~ experienced by a test loop of DuPont type 846 bulk continuous filament nylon 6/6 (1300 denier, 68 fila~ents, o twist, semi-dull, regular acid dyeable) was determinsd by means of the beaker test procedure described in Table I using benzotriazole in con~unction with glacial acetic acid in water. Test re~ulta in Table II show that, for example~
an embo~sing system comprising benzotriazole 20% and acetic acid 15X and water 65% causes the nylon loop to shrink 52X accompanied by a weight loss of 2.3% in the shrunk fiber3 without deteriora-; 20 tion of the fiber propertie~ in 15 minutes at 215F (Run ~676).
~ However, the concentration of embossing agent which produces -~ - this degree of nylon shrinkage in the beaker test generally produces little or no shrinkage when screen printed on nylon carpet face pile. Therefore, the beaker te~t proceture was further utilized to determine the concentrations and propor-tions of benzotriazole and acetic acid that would cause the nylon test loop to disintegrate within 60 seconds. As indicated prevlously, thi~ degree of attack of the nylon filsment in the be~ker test 1~ indlcative of the ~ub~tantlal embossment that can be espected to develop when nylon carpet 18 treated with the e~bos~ing agent uAing a screen prlntlng technlque. The test db/~

, ' temper~ture w~s 215F. ~039005 Te~t results are shown on Table 11 for various benzo-trlazole/acetic acld systems as well a~ for those comb~nation~
havlng cmall portlons of acetlc acid replaced by other aclds such a~ sulfuric acid, form~c acid, phosphoric acld, ant toluene-~ulfuric acid. It i9 under~tood that percentages shown re-present the percent contained in an aqueous solution. Also shown are shrinkage ant weight loss values for individual com-ponents at intermediate and maximum concentrat~ons used. A
variety of concentrations and proportions of benzotriazole and acetic acid were found to disintegrate the nylon test loop fiber6 within less than 60 seconds, e.g. 35/25, 35/20, 30/25, 25/30, 27.3/27.3, 15/45, 15/47.3, 10/50, 12.5/47.5, as well as benzotriazole 15%/acetic acid 45Z/85% phosphoric acid 2.7%.
Thus, these data show that the combination of benzotria-zole and acetic acid has the capability to cause nylon fibers to shrink strongly and therefore is a potentially good embossing ~;
agent for nylon carpet. The replacement of small portions of acetic acid by other ac~ds offered no particular advantage.

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~03gOOS
SABLe Il N~lon ~lement ~-lght ~u~ 5hrlnka6e Lo~ Loop ~o Chemlcals~ tZ) Charaeter ~* W-ter L0 51 27 Goot 673 3enzotrlazole (3TA)***, 10Z 43 0 +6 83 Good 612 ~en~otriazole*** 20Z Gu~my mass 3 ~leutes 671 Benzotrlazole*** 30% Gummy mass 20 seconds 681 Benzotrlazole*** 35~ ***~Dlslntegrate 12 seconds 68Z Benzotrlazole*** 40Z *~*Dlglntegrate 10 secoods 680 BeDzoeriazole***, 502 *~*Dlslntegrate 10 seconds 351 Aeotic Acld, 30Z 13 5 1 06 Cood 6S9 Aeetic Acld, 45Z 27 0 3 92 Cood 668 Acetic Acid, 50Z 35 5 6 73 ~oot 669 Acetic Acld, 552 ~roken loop 15 minutes 670 Ac-tlc Acld, 60Z Fragmented 15 ml~utes 337 Acetlc Acld, 45%/85%
Pho~phorlc Aclt, 2 7~ 29 7 3 89 Good 342 Aeetic Acit, 59 3%/85Z
~ho-phorlc Acid, 3 72 St-rt dlslntegrate 10 mlnutes 25d ~TA, 35X/Cellosolve Solvent, 25% 38 2 4 45 Good ~05 BSA, 20Z/I~opropyl Alcohol, 40Z 18 2 0 19 Good 676 BTA, 20Z/Acetlc Aclt 15% 52 2 2 32 Good 61S BS~, 25Z/Acetlc Acld 15Z ~roken loop 15 mlnute~ -619 BTA, 40Z/Aeetic Acld, 15% ****Dlslntegrated 12 ~econdg 614 3TA, 50Z/Acetlc Acld, 15Z **~*Dlslntegratet 8 ~econds 254 BT~, 352/Acetlc Acld, 252 ****Dl~integrated 10 seconds 265 BTA, 35%1Acetic Acld, 20X ~*~*Dlsintegrated 10 seconds 267 BS~, 3521Acetlc Acld, 152 ~ragmentet 15 mlnuees 26~ BTA, 30Z/Acetic Acit, 25% Di~l~tegrated 15 seconds 251 ~T~, 3021Acetic Acid, 202 ~r~g3ented 15 mlnutes 266 ~Th. 25%/Acetlc Acld, 25X ~rag~entet 15 ~lnute~
274 BTA, 25ZlAeetlc Acit, 30% ~*~*D~glntegratet 30 seconds 318 BTA, 27 3ZlAcetlc Acid, 27 3Z ~*~*DiAintegrated 30 seconds 324 BSA. 202/Acetlc Acid, 35Z ~oetly dislntegrated 15 mlnutes 338 BTA, 15X/Acetic Acid 47 3Z ~*~Dlslntegrated 10 saeondg 391 ~TA. 15Z/Aeetic Acld 45% ~**~Dislneegrated 25 seconds 392 BSA, 10%/Acetle Aclt, 50Z *~*Di~lntegrated 25 seconds 393 BSA, 102/Acetic Acld, 45Z ~reg~-nted 15 mlnutes 394 bSA, 5%/Acetlc Aeld, 55% rr-g~-nted 15 ~lnutes 398 BS~, 2521Acetie Acid 27 52 Prag~entet 6 mlnute~ -~
~02 BSA. 12 551Aeetlc Acld, 47 52 ~*~Dieintegrated 60 seconts 263 BS~, 352/Aeetle Aeld 12 52/
C-llo-olve Sol 12 52 ~r-g~-n~ot 15 ~lnutee 292 ~S-. 252/Aeetle Aeld 22 52/
Sulfurie Aeid, 2 52 - ~ri~bl- 15 ~in~e~
2q3 ~S~. 252/Ae-tic Aeld 22 5%¦902 Por lc Aclt 2 8Z 72 4 21.6 ` ~rlabl~
295 ~SA, 2521Acetlc Ac~t 22 52/85S
~ho-phorle Aelt 3 3% ~ra~ en~-d 15 ~lDut-~
327 ~S~, 25S Ac-tlc Acld 202¦85Z
PSorphoric Acld 62 ?g 7 25 0 ~rl~blo 33S ~I~, 15Z/Ac-eic Acld 45Z185S
Yho-phorlc Aclt 2 1S ~ Dlalnt-gr~t-d 20 ~-cond-300 3S~, 25S¦Ac-tlc Acld 22 5Z¦95S
Toluon--ul~onlc Acld 2 6S ~r-~-Dt-d 15 ~lnut-e db I ~a ~ . .

BTA ~ Benzotriazole. Tlle ben~otrlazole ls adde~ to the ~cld solutlon to facllltate room temperature ~olubllity.
** Avg. of 13 runs water alone at 212F.
*** Approx. 200F requlred to solubllize BTA ln water.
**** Deeply embossed carpet can be anticipated ln those in-stances where the beaker test ~hows the test loop dis-lntegratlng withln about 60 second~. However, it may occur that s~ch beaker disintegrating ~imes are too destructive for carpet embossment. Then, the chemical concentration must be regulated to produce a longer time to test loop disintegration.

EXANPLE II
.
The shrinkage and weight loss experienced by a test loop of DuPont type 846 bulk continuous filament nylon 6/6 t1300~ -denier, 68 filament, o twist, semi-dull, regular acid dyeable) was determined by means of the beaker test procedure described -in Table I using the following aqueous recipeg shown in Table III
containing a combination of benzotriazole and an acid other than acetic acid. The test temperature and maximum duration of test was 215F and 15 minutes respectively.
While the preferred acid is acetic acid as described in ~-Example 1, other acids such as formic, phosphoric, citric, hydro-xyacetic, oxalic, propionic, maleic, acrylic, hydrochloric, mono-chloroacetic and sulfuric will also function in combination with ~;
benzocriazole to produce shrinkage of nylon fibers. Test results are recorded in Table III. It i9 understood that the percentages of components 3hown represent the percent of each contained in an aqueous solution; These tata shown that by properly selecting the concentraeions and proportions of benzotrlazole and any one os more of these acids, the resultins chemical system can be ex-pected to e~boss nylon carpet via shrlnkage of the fibers. As $nticated, prevlously, it i9 generally nece~sary to obtain nylon fiber disintegration within 60 seconds ln tho beaker test in order to provlde a benzotrlazole/acld combination that will sub-stantially emboss nylon carpet. Usually, little or no carpet - 1 9 ``

db ~ ~

~039005 e~bo~ement c~n bc exp~ct~d untll be~ker te~t ~hrlnk~gc v~lues ex-ceed 50Z. Whenever be~ker te~t result~ ~how a tlsintegr~tlon tlme of more than 60 seconds, the concentration of one or both components of the benzotrlazole/acld embo~slng system should be lncrea~et 1~ order to real~ze a sy~tem that wlll deeply emboss nylon carpet. Les~er tepths of embossment can be obtained, of cour~e, by employing benzotrlazole/acid combinations which ln-crease disintegration time~.

~A~LE III

- Nvlon Filament Sh~lnk- Ueight ~un . ~e Loss Loop ~o Che~lcals* . ~X) (%) Character ~* W~ter 10,S 1.27 Goot 6~2 Bcnzotriazole, 20~*** Cu~my mass 3 mlnuees 681 ~enzotrlazole, 35X*** Di~lntegrated 12 seconts lSO 90% Formic Acld, 33.3Z 16.6 0.67 Good 688 Malelc Acld, 25% 13.8 0.71 Good 687 Ptoplon~c Acit, 25X 19.2 2.28 Good 348 Acrylic Acid, 25~ 16.0 1.05 Good 686 Sulfuric Acit, 10~ 8.2 0.19 Goot 92 Citric Acid 50Z 23.8 +4.~3 Good 68S 372 ~ydrochioric Acid, 26.7X 43.5 16.3 V. ~ea~

684 702~ydroxyacetic Acid 35.7Z 8.43 0.5R Good ~a3~* Oxalic acit 2B;~0, 35X 19.6 1.80 Good - 70 ~o~ochloroscet c Acit, 25229.3 2.71 Good IS1 85% Pho~phoric Acit, 29.3%16.S - ~2.36 Goot 283 BSA, 352/~onochloroacetic Acid,25Z Blslneegraeed 10 seconds 296 BTA. 252/~onochloroacetic Acit,25% Disintegratet 20 seconds 286 3TA, 252/Monoch}oroacetic Acid,202 Mostl~ disi~eegratet 15 ~inutes 316 BTA. 25~/Acetic Acit, 13%/~ono-chloroacetic Acid, 122 P-rtisl disintegrated 7 minutes 2~4 BTA, 352/Proplonic Acid, ~5% Di~lneegratet 10 second~
303 BTA, 25Z/Nalelc Acid~ 25Z Pr3gmc~ted 15 m~nutes 304**** BSA, 25Z/852 Phosphoric Acid, 25% 61.8 1.80 Frlaole - 31S**~* BSA, 25Z/85% Phosphoric Acit, 29.32 62.0 3.16 Fr~a~l~
317 BTA, 25Z/Oxalic Ac~d-2~0, 35X Friable 15 ~inutes 32S BS~, 252/70Z ~ytroxyaceElc Acid.
3S.72 S7.1 2.10 Good S2~ BTA, 2S213?2 ~ytrochloric Acid.
13.32 38~,6 1.17 Cood 328 BTA. 2S21Citric Acld.~20, 252 65.6 +2.1 Brlttle 329 ~S~, 2S2/372 ~ydrochloric Acid, `
26.72 5S.8 16.4 Fr~gile 330 BSA. 252/Sulfuric Aclt. lOX 36.3 0.35 Good 349 ~IA. 252/Acrylic Acld, 2S~ Fr~8~ent~d 15 mlnuCe~
678 BSA. lS2/89X For~lc Acid, 17X 49.3 0.97 Good 677 BTA, 202188X For~lc Acld, 1~X 3~oken loop 15 ~lnute~

db/~ ~ , ** Avg. 13 runs water Alone at 212F.
* BTA - ~enzotrl~zole. The BTA is sdded to the acid solution to facilltate room temperature ~olublllty.
*** Soluble about 200F.
**** Soluble above 170F.
EXAMPLE III
The shrlnkage and weight loss experiencet by a test loop of DuPont type 846 bulk contlnuous fllament nylon 6/6 (1300 denier, 68 filaments, 0 twist, semi-dull, regular acit dyeable) was determined by means of the beaker test procedure described in Table I uslng the aqueous recipes shown in Table IV containing azoles other than benzotriazole and glacial acetic acid. The test temperature and maximum duration of testing was 215F and 15 minutes respectively; Test results are recorded in Table IV.
These data show that there are a number of ~ubstituted products and analogues of benzotriazole, representative of the mono, di, tri, and tetra azoles, which can function as shrinking agents for nylon fi~ers. Depending upon the azole employed and the ratio and concentrations of acld and azole used, the extent ~ -~
of shrinkage can range from very weak after 15 minutes at 215F `~
to total disintegration of the nylon filamen~ withln 60 seconds. ~ -Combinations which produce this latter effect can be anticipated - ~ -to produce strong carpet embossment.
~hile the preferred acid is acetic acid, other acids should be ~ust as effective with other azoles as with benzo-triaaole (See Example II).

- 2 1 ` ` : `
.

dbi~ ~ ~
,. .... . . . .

IABLe IV
N~lon Yllsment ~*
Ac~t1c sOl.~ Shrlnk- Wt.
~un ~zole Aclt @ ge Lo~ Loop No. TYDe ~Z)~Z) RT. ~%) ~%) Char.
788) 778) Tsp Water O O -- 7.03 0.68 Cood 804) 3S7 Ac-tlc Acld 0 30 Y 13.5 1.06 Good 659 Acetlc Acid 0 45 Y 27.0 3.92 Good AZOLE
826 Pyrrole 2S 30 Y Dlslntegrate 5 secs.
856 Pyrrole 20 25 Y 80.2 15.6 ~rlable 850 Pyrrole 15 45 ~ Disintegrate 8 secs.
846 P~rrole 35 -- N Disintegrats 3 secs.
827 Intole 25 30 N Disintegrate 5 secs.
829 2-~ethyllntole 25 30 N Disintegrate 10 sec~.
828 N-~ethylpyrrole'25 30 N 32.5 2.22 Good ~':

-- ~ -~ . .

dbl , ~

S-bl- lV ~eont~d) ~lon ~ nt Ac-tlc ~ol ~ Shrln~- ~t lun ~ol- _~clt ~ cg- Lo~ Loop _O. ID ~ T ~ 2) Chsr _ DIAZOLB
822 ~rr~ol- 2S30 S ~ 5 11 - Cood ~ P~r-~ol- 350 130 2~ 1 3 9 Ooot 815 3 S-Dlo~thylp~r~ol- 2530 T 2~ 2 ~ 1 Good 813 5-~lnol~de~ol- 2530 S lg 0 0 S MerooD
~1~ 5-Chlorolnt-~ole 2S30 210 Dl-lntegr-t~ 45 ~c-JSl S-Chlorolndc~olc lS~5 120 Dl-lDt-gr-tc 10 ec-276 I~lt-~ol- 2S30 S 9.S 0 6 Cood 207 ~lt-~ol~ 500 1 2~ 3 7 2 ~oo~
27S ~ensl~Sdcsol- 2530 ~ 18 6~0 6 Oood 812 l-HOehyli~ld-~ol- 2530 ~ ô.l 0.6 oOod .
, .. ..

' ' ' ~ .
T~lAZOL~
23S ~eDsotrlesole 2S 30 S Dl-lnt-~r-te 3S ec-.
852 ~eD-otrl-sole 20 25 S 61 3 8 l CooJ
391 ~eDsotrl~solo lS ~5 S Dl-lnt~er-t~ 2S rc-.
681 ~ensotrl-sol- 35 0 200 Di-lntcgr-te lZ -e-825 l-Hethrlbcnsotrl~rolo -a2O 25 30 ~ 32 9 6 1 Cood ~1 l-HJdro~yb-nsotrl~ol- 25 30 180 65 2 ~ 8 Yr-gllo - 2~6 5-Chloroben otrl--ol- 25 30 190 Dl~lnteg~-t- 40 -c-~32 l-~rtro~y~-Dsotrl~sol- ~-a2O 28 3 30 lôO ~r-g~ntet lS ~
23~ 1.2.~-Srl-role 25 30 S 20 5 2.9 Cood 23J 3-A~lno-l 2 4-Trl-~ol- 25 30 150 13.0 l.S Oood 30 ~tesol- 25 30 215 20 9 1.2 Oood .. .
, ':

db/ D~
... . . .
''~ , ' -' ' ' - .
,. . .

T-blz IV (cont'd~ N~lo~ Pll~ment ~ _ ~c~tlc Sol ~ Shrlnk- Wt Run Azole Acld Q z~q Lo~ Loop NO. T~D- ~ ~%) RT.(%) tZ) Char -TITR~ZOLE
820 5-A~lnoteer~zol- ~225 3020033 2 4 9 Good 831 5-A~lnotetrazole ~0 30 5 30 200 40 1 7 0 Coot 852 5-~01notetrazole ~2 1545 190 62 ô 28 8 Fragile 84i 5-~lnotetrazole ~235 215 7 ~ ~0 3 Goot 8~3 1,5-Pentamethylene-t-tr-zole 25 30 Y22 54 67 Good _ _ OXAZGBE
821 2-~ethylbenzoYazole25 30 Y 41 3 2 7 Brown _ ISOO~A20LE
409 5-~thyllso~azole 25 30 Y 30 8 6 7 Good 808 3,S-Dl~ethyllaoYazole 25 30 Y 26 2 5 9 Good _ T~IAZOLE
833 B-nzothiazole 25 30 N Fragmented 15 ~lns 853 B-nbothlazol- lS 45 ~a2 . 336 7 Fragile al8 ~lnothiazole 25 30 ~13.80.7 Bro~n 823 2-A~ino-6-~ethoxy-~-nzothlazole 25 30 ~ 24 6 ~0 5 Gool 816 2-~e~thylbenzoth~azole 25 30 ~ 34.8 ~19 2 U~ 9pOt 844 2-Chlorobenzothlazole 25 30 N 26.0 +3 1 Good ~ O~DIAZOLE
4SS 3,4 Di~ethylfurazan 2530 Y 34 4 7 ~ Cood T~IA~IAZOBE
82S 2,1,3-Benzothladia201e 25 30 N 23 0 2.3 Good ~ tS ^ soo~ te~psratùre Y-Ye~ N-ln301ubl~ or l~lclble even st 215F
Oth-s fi~ute- Indlcate te~peratur- F at ~hlch olublller OCCUr9.
~ 15 ~lnut-s t 215F u~les- oth-rwlse iudlc-t-d ' ' .~ ,- ' - 2~

: ` `

d~/ ~B

103~0S
EXAMPLE IV
Thl~ example lllustrates the preparatlon of an embossed plle fabrlc typlcal of the products of thls lnvention.
A 4 inch by 7 1/2 lnch rectangular area of nylon carpet wa~ treated by means of a gcreen printlng technique wlth a dye prlnt paste containing 27.5% benzotriazole and 25% glacial acetlc 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) ~'. . .

.. ... :
:~

~:

``:
~.

db/J ~' ~
, . .

Plle ~elght - 17/32 lnch, (1.35 centlmeter~) ~lngle~
The dye print paste was formulated as follows:

SAMPLE N0. 278SP
Material* Gra~s 1. Water 24.2 2. Cibaphasol AS Sulfuric Acit Ester, 0.5 a trademark of Ciba-Geigy Corporation 3. Antifoam 73 2-Ethyl Hexanol, a 0.8 a trademark of Chemical Processing of Georgia 4. Relzan (1 1/2%) Xanthan Gum, a 22.0 synthetic biopolymer from fermentation of carbohydrates, ~ -a trademark of Kelco Company ~ -and 0.2% Dowicide A Sodium 0-phenylphenate, ~ t.
a trademark of Dow Chemical Company 5. Acetic Acid, Glacial 25.0 6. Benzotriazole 27.5 7. Dye ~ 0 1 *2 ~ Sulfuric acid ester, Levelling and penetrating agent ~-3 - Alcohol ether, antifoaming agent 4 - ~anthan gum thickner plus preservative in water to provide a Brookfield viscosity of 760 cps. at 78F (~3 Spindle, 2 1~2 rpm.) ~ - -There was no evidence of embossing while the nylon carpet was held at room temperature for several minutes. Upon sub-~ecting the carpet to steaming for 15 minutes at about 218F, signiiicant embossing due to fiber shrinkage was observed. There-after, the embossed carpet wa3 thoroughly rin~ed with ~ater and dried. The rin~ing removed residual chemicals. The embossed nylon pile was rubbed briskly.
The resulting carpet exhibited excellent emboasing with a 44% reduction in pile height in the treated area in perfect reglster with the printed roctangle. De~plte thls do~ree of shrlnkage, the nylon tuft~ retained thelr lndlvldualley and, . . _ - 2~ :

db/~
" '' ' while lncrea9lng ln flrmnes0 remalned acceptably ~oft. There wa~
no ~vidence of deterloratlon of fiber phy~lcsl propertie~. -EXAMPLE V
The nylon carpet construction cited in Example IV wa~
- agaln treated by means of a ~creen prlntlng technique. However, in thls case the concentratlon and proportion of benzotriazole and acetic acid were changed substantially so that the dye print paste contained 15~ benzotriazole and 45~ glaclal acetic acid by weight as the embossing agent.
The dye prlnt paste used was as follows:
SAMPLE N0. 411SP
Naterial* rams 1. Water 17.2 - -2. Cibapha~ol AS Sulfuric Acid Ester, 1.0 a trademark of Ciba-Geigy Corporation 3. Antifoam 73 2-Ethyl Hexanol, a 0.8 `~
trademark o Chem$cal Processing ~ ~ -of Georgia 4. Polygum 260 (5~) Locust Bean Gum21.0 -~
(carob-seed gum) a polysaccharide ~ -- plant musilarge essentially carbohydrate, a trademark of -Polymer Industries, Inc. ;~
5. Acstic Ac~d; Glacial 45.0 6. Benzotriazole 15.0 -- 7. Dye 0 05 *4 - Locust bean gum thickner providing a Brookfield viscosity of 1,200 cps. at 78F (#3 spintle, 2 1/ 2 rpm) O~ce again there was little evitence of embosslng while t~e nylon carpet was held at room temperature. Upon sub~ecting the carpet to steamlng at about 215F for a period of 15 minutes, ~ignificant embossing due to ~hrinkage of the nylon carpet pile wag noted. Thoreafter, the embo~sed carpet was rinsed and drled.
The embo~sed nylon plle wa~ rubbed brlskly.

dbl~

10;~005 The r~ultlng car~et exh~blted Bn ~rcs with ~ 41X re-ductlon ln plle helght ln reg~ter wlth the prlnted aren. The rhrunk tuft~ were ~ell defln~d, ~trong and whlle some~hat flrmer, were acceptable ~oft.
Whlle lt i~ obvious thAt a number of concentratlons and proportion~ of benzotriazole a~d acetlc acid ~erve very effecti~ely a~ embo~slng agents for nylon carpet ~see Exa~ple VI, $able V), generally that combination of benzotriazole and acit wlll be selected so as to provide the desired embossment most economical-ly. Thus, since benzotriazolP is by far the more expensive com- ~ -ponent, the most economical combination wlll co~prise a low con-ceatration of benzotriazole and a high concentration of acetic acid such as s~own by the subject example.
EXAMPLE VI .
Additional embossed nylon carpets were prepared by means ~ -of the embossing procedure described ln Example IV, hereinabove, ~til~zing variou~ concentrations and proportions o benzotriazole and acetic acid contained in the dye print paste as shown in `-~ .
Table IV. Correspo~ding depths of e~b~s~ment and e~bossed pile ~ . -character are indicated in Table Y.

3~A~LE V :
C-r~et Embossment -- -Sa~ple BS~lAcetic Aclt* Pa~tr~* Depth ~o. ~2 1~ Paste) Vi~c. ~C~5.) ~%) Plle Charactcr .
- 262sr 35t25 . 360 S3 B~rt, ~arsh - 271SP 25/25 U 0 31 . : Soft, Cood 229SP 30¦25 260 S0 V. rir~, Harsh 299SP 35J20 720 - .50. . ~. FirQ, Barsh - 301SP 28/2S 520 44 Jir~, Good 320SP 25130 960 ~1 J~r~, Good 32~SP ... 27.3t27.3 - 260 44. Elr3, Cood 321SP 25130 1160 ~7 Flrm, Good 3~2SP 15145 14~0 47 ~lr~, Good 3925P 10150 1320 35 So~t, Cood 395SP 3J60 1200 35 Soft, Cood ~18SP 15/45 1000 41 ~lr~ Good * ~T~ - ~onzoerla~ol-~rookflold 73-F, ~3 plndl-, 2~ rpn. X~nth-n ~u~ thlckanor ~ a~plo~.

- 2~ .

, db/~ ~ v 10390()5 In recapltulation, lt 1~ to be undere~ood that the pro-ces~ of embo~sed carpet lnvolve~ manipulatlon corre~ponding to that of pr~nting a pattern on the carpet. Where merc embos~-ment is sought the printed composition 19 colorle~s. Where the de~ign combines color with the embossment a dye paste 18 the vehicle generally, whether the operation be a mere emboss-ment os an embossment combined with dyeing. It is preferred that there be no shrinkage of the nylon fibers at ambient tempera-tures, even up to 50C. In plant operations the delay from --.:
printing to steaming may be as such as 8-10 minutes. Hence, if there i5 no s~gnificant effect on the material at temperatures -below 50C for 15-20 minutes there is ample time for operations. ;~
That i8, activation of the shrinkage is reserved for the stage where the printed material enters the ~teaming operatlon. In standard carpet handling the ~teaming is a 10-20 minute operation to fix the dye and in this stage the embossing is completed in the first few minutes.
For effective embossment there should be at least per-ceptible shrinkage in the tufts. Generally penetration of the -. .
embossing print paste will be of the order of 50Z. Where it is desired to have full depth coloration of the printed area uni-formly to the back of the fabric, this can be accomplished by predyeing the carpet completely to the back by means of an operation such as pad dyeing. Where it iB de~ired to have full coloration of the area uniformly to the back of the fabric it -~ is desirable to predye the carpet completely to the back by means of an operation such as pad dyeing. It should be apparent that in operations where mere embossment is sought there is no sig-n~ficant problem in the placement of the doslgn on the fabric.
Where embos~ment i8 combined wlth a multi-colored prlnt there is the reglster problem and the color area wlll be ln perfect - 2~ ` ~

db/~ ~
'': - ' , .

~03900S
reglster wlth the ~mbo~scd de gn when the shrlnking a8ent ls comblned wleh the color paste as ~et forth ln detall ln the exsmples.
It i8 thus seen from thls tata, that a vsrlety of con-centration~ and proportlons of benzotria~ole ant ~cetlc acld are readlly applicable to the novel process of this lnventlon.
In the production of the pile fabrics of ~his invention, the pile yarn employed i8 prepared from fiber-formlng syn-thetic linear polyamides. Examples of these fiber-forming syn-thetic linear polyamides are those obtainable from polymerizablemonoaminomonocarboxyllc acids and their amide-forming derivatives including caprolactam and thoge obtainable from the reaction of suitable diamines with suitable dibasic carboxylic scids or j~
their amide-forming derivatives. Such synthetic linear poly-amides are referred to as nylon.
~ ylon or polyamide polymer~, filaments and fibers are well known to those skilled in the art and extensive discussion i8, therefore, unnecessary. Thus the term "polyamide" or "nylon"
is k~own to include any long chain synthetic polymeric amide which has recurring amide groups as an integral part of the main polymer chain and wh$ch is capable of being formed into a filament in whlch the structural elements are oriented in the direction of the axis of that 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 diam~ne or by a self-condensation of an aminocarboxylic acid. Illustrative of these polyamide resins are nylon -6,6, prepared by the con- -;
densation of hexamethylenediamine and adiplc acid; nylon -6,10, prepared from hexamethylenediamine and 8ebacic acid, both of the foregolng havlng, as prepared ! molecular welghts exceedlng - 30 `

db/~'~

~03gOOS
10,000: nylon-6 producet by thermsl polymerizatlon of eps~lon-amlnocaprolc acid or caprolactam; nylon-11, the ~elf-condensation ~ -prod-~ct~ of 11-amlnoundecanolc scid; as well a9 a varlety of polymers prepared from polymeri~ed, unsaturated fatty acids and polyamine compound~
The practice of the present lnvention has, however, particular application to solid melt-extrudable and o~ientable ;-fiber-forming polyamites and more partlcularly to fibers and flla-ments prepared therefrom which have a denier and tenacity appro- - -~
priate, and well known to those skilled in ~he art, for use in ~;
carp~t, rugs, tapestry and the like. Illustrative of these poly-amides are those having a filament denier of 2-30 or hlgher or nylon yarns in the denier range of 15-15,000 or higher. The tena-cities of nylon yarn for use herein are within the range of 3-I0 ~ ;
grams per denier. The elongation of commercial fibers can range between 15 and 65%. ~he undrawn filament is capable of being 8tretched 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 molecular weig~t synthetic ~20 }inear polyamides, in addition to tho3e described hereinabove, -that have been modified, for example, to enhance their useful~
; ne~s for particu1ar applications.
~n extendet dlscussion of polyamides of sufficiently high molecular weight to be capable of being melt spun into filaments `~
a~d coming within the contemplation of this invention appears in ~ -D. E. Floyd, Polyamide Resins, Reinhold Plastlcs Application Series, Reinhold Publishing Corporation, New York, New York (2d printing, 1961), and H. R. Nauersberger, Matthews~ Textile ~ `"`
Chemical Propertie~, John Wiley & Sons, Inc., N-w York, New York, pp. 933-971, 1034., ~6th ot. 1954), Nary E. Carter, Essential Flber Chemistrv, Marcel Dekkor, Inc., Now York, New York 1971 dblP~
~ .......... .
. ., j , .
, - ` ~

~03900S
pp. 91-109, Il. F. M~rk, S. M. Atlas, E. Cernls (Edlted by), Man-Made Flber~, Sclence and Technology, Volume 2, Intersclence Publlsher~ 1968, pp. 181-295, Tech.-Talk from Monsanto Textiles Divislon Bulletin TT-35 August 1969.
Summarlzlng, lt i8 thus seen that thls inventlon provides a novel and effective method for embossing nylon pile fabrics.
Variations msy be made ln procedures, proportions, and materials without departlng from the scope of the invention as defined in the following claims.

,' `; .: " .

` - 32 ~. .

db/ &~

Claims (27)

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

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 chemical embossing agent for said fibers, said agent being an azole having a five membered hetero-cyclic aromatic ring or fused aromatic ring containing two or more heteroatoms, in the five membered ring, at least one of which is always nitrogen, blended into a liquid base vehicle, said liquid base vehicle also including an acid, allowing said embossing agent in its vehicle to remain in contact with said fibers for a period of time and at a tempera-ture sufficient to reduce the height of said pile, without de-terioration of said fibers, and, thereafter, effectively removing the embossing 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 suf-ficient to display a significant embossed effect in the overall fabric.

2. A process of claim 1 wherein said embossing agent is benzotriazole with acetic acid in concentrations of 5 percent to 50 percent benzotriazole and 15 percent to 60 percent glacial acetic acid by weight, of total embossing composition.

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

4. A 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°C.

6. A process in accordance with claim l wherein said embossing action occurs in a steam environment.

7. A process of claim 6 wherein said embossing com-position is present in a concentration of about 45 to 65 percent in the vehicle therefor.

8. A process of claim 7 wherein said embossing agent is benzotriazole and hydroxyacetic acid.

9. A process of claim 7 wherein said embossing agent is benzotriazole and formic acid.

10. A process of claim 7 wherein said embossing agent is benzotriazole and phosphoric acid.

11. A process of claim 7 wherein said embossing agent is benzotriazole and oxalic acid.

12. A process of claim 7 wherein said embossing agent is benzotriazole and hydrochloric acid.

13. A process of claim 7 wherein said embossing agent is benzotriazole and propionic acid.

14. A process of claim 7 wherein said embossing agent is benzotriazole and citric acid.

15. A process of claim 7 wherein said embossing agent is benzotriazole and sulfuric acid.

16. A process of claim 7 wherein said embossing agent is benzotriazole and maleic acid.

17. A process of claim 7 wherein said embossing agent is benzotriazole and monochloroacetic acid.

18. A process of claim 7 wherein said embossing agent is benzotriazole and acrylic acid.

19. A process of claim 7 wherein said embossing agent 19 pyrrole and acetic acid.

20. A process of claim 7 wherein said embossing agent is indole and acetic acid.

21. A process of claim 7 wherein said embossing agent is 2-methylindole and acetic acid.

22. A process of claim 7 wherein said embossing agent is pyrazole and acetic acid.

23. A process of claim 7 wherein said embossing agent is 5-chloroindazole and acetic acid.

24. A process of claim 7 wherein said embossing agent is 5-chlorobenzotriazole and acetic acid.

25. A process of claim 7 wherein said embossing agent is 1-hydroxylbenzotriazole monohydrate and acetic acid.

26. A process of claim 7 wherein said embossing agent is 5-aminotetrazole monohydrate, and acetic acid.

27. A process of claim 7 wherein said embossing agent is benzothiazole and acetic acid.