DE3411486A1 - METHOD FOR PRODUCING PATTERNS ON TEXTILE MATERIALS - Google Patents

Description

description

Process for generating patterns on textile materials

The invention relates to a method for generating patterns with a strong visual contrast on textile substrates as well as the new products manufactured using this process. In particular, the invention relates According to one embodiment, a method in which individual fibers in a surface area of a textile substrate, which form a pattern sawn, thermally conditioned or treated be a relatively rapid extraction of a dye from these fibers by a solvent to allow, while neighboring fibers that have not been so thermally conditioned or treated, one are resistant to such rapid dye-extraction, whereby substances are obtained from which ^ after they have been in The heat-treated areas of the pattern have been exposed to a suitable solvent in a controlled manner contain visibly less dye than adjacent ones also exposed to the solvent (untreated) Complementary areas of the pattern.

Methods for generating patterns on the surface of textile substrates *) are known. Such procedures can or can not apply *) or textile maierials corresponding to the pattern

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of dye to form a pattern or even a pattern formed by the dye on the Surface of the substrate. These processes do not require the application of dye to match the pattern include processes in which heat z. B. with the help of a heated embossing roller or by impinging on currents of a heated medium is applied to the surface of the substrate prior to dyeing in the form of the intended pattern. The thermally treated areas of the surface absorb the dye to different degrees (generally more strongly) than the untreated areas, which usually results in pattern areas, with a higher visual level contrasting dye concentration. Other procedures rely on a variety of physical effects to define patterned areas on the surface of the substrate ^ or to evoke. For example, some methods are based on physical compression (pressing) and possibly the consolidation of individual fibers by applying heat to indent or indent the surface To generate press or embossing patterns. Other systems may rely on the intertwining of fibers to be visual to produce different areas on the substrate surface.

One in Applicant's U.S. Application 253 135 filed April 13, 1981 to which reference is made here, the method described is based on the fact that Streams of a heated medium that impinge on the surface of the substrate in the form of a pattern Yarns or parts of individual yarns that make up the substrate surface make up melt or otherwise thermally deform or destroy and thereby visually different Create areas on the surface in such areas that contain yarns called the hot

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Medium.

This procedure can result in patterns that are well detailed; H. where details are clearly visible and which under certain circumstances can lead to rather strong visual contrasts between pattern and pattern complementary * (i.e. background) areas, although a dem Pattern corresponding application of dyes is not required. This is especially true when the substrate

z. B. is a pile fabric and the pile yarn has been heated sufficiently to have a substantial amount of heat induced Cause longitudinal shrinkage of the individual pile yarns or fibers. The resulting relief pattern can create a strong contrast between the pattern and complementary areas lead, provided that the finish is appropriate is illuminated. The strength of the contrast, however, often depends heavily on the type and direction of the incident Light. When non-pile fabrics are patterned using this method, the individual fibers will be softens and can suffer a certain shrinkage or melt; however, the contrast is in such fabrics often limited, even with optimal incidence of light. The use of a dye that is selective only on Pattern areas applied can lead to significant narrowing if fine details or accurate reproducibility how speed of production and inventive flexibility are desired. The colors must exactly right, the dye approaches coordinated and planned and of course the dye must be applied with great precision and accuracy. These constraints or restrictions are extremely uncomfortable.

It is therefore desirable _for an economical economically feasible method to have available, in which

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the patterning can be achieved by applying heat or another conditioning agent corresponding to the pattern and not by applying the dye to individual yarns or threads on the surface of the substrate in accordance with the pattern and in which the visual contrast between pattern and complementary areas on the The surface of the substrate can be varied in a controllable manner from relatively low to relatively high values and at which the contrast achieved is not essentially dependent on the type of irradiation or the incidence of light. The method according to the invention comprises the treatment or conditioning of individual yarns or threads in the pattern areas of the substrate by physical or other means in order to subsequently enable a selective extraction of the dye from the treated yarns _# if the fabric is subjected to a controlled extraction stage with solvent, wherein the extraction step has no significant visible effect on adjacent untreated yarns which form the complementary areas of the pattern on the substrate. The dye can be applied to the yarns or the areas to be treated either before or after the treatment or conditioning. The role played by the treating or conditioning agent in the process of the invention can be viewed as comparable to that of a catalyst in the sense that the selected solvent extracts the dye from the treated yarns at a much greater rate than from the untreated yarns . Generally speaking, the selected solvents useful in the method of the present invention, when in contact with the fabric long enough, will extract the dye from untreated areas as well as from treated areas and perhaps to the same extent but not the same Speed.

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Figure 1 shows a pile fabric made of thermoplastic and non-thermoplastic yarns in which the heat conditioning results in a thermal deformation in the form of a Longitudinal shrinkage of individual thermoplastic pile yarns has led; the dye has then been selectively extracted from such thermally deformed fibers.

Figure 2 shows a pile fabric in which a heat conditioning for thermal deformation in the form of a longitudinal ο shrinkage of tufts or groups of thermoplastic Has led pile yarns; the dye is then selectively extracted from such thermally deformed groups of yarns been.

Figure 3 shows a flat knitted fabric, consisting of thermoplastic yarns, in which a heat conditioning a thermal deformation in the form of melting and / or melting together of the individual yarns has caused; the dye is then selectively off extracted from the deformed areas of the fabric.

FIG. 4 shows a textile substrate in which dye is selected from the heat-treated diamond-shaped areas, extracted in accordance with the teachings of the invention.

In a preferred embodiment of the method according to the invention, hot streams or jets of a flowable medium, e.g. B. Air _{f directed} in a configuration corresponding to the pattern with a device similar to that described in US application 253 135, referenced above. These

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Apparatus is discussed here only as an example of an apparatus which can be used to carry out the method according to the invention. Applicant's US Pat. No. 4,364,156, also referred to herein, also describes a manifold which can prove advantageous when used with the apparatus described in US Pat. No. 253,135. It is believed that any means by which ο a suitable amount of heat in the pattern of appropriate configuration may be applied to the yarns in an appropriate manner, the surface of the may be applied _f represent involving the same pattern to be provided text lien substrate. For example, a laser beam of suitable strength and intensity directed onto or over the surface of the substrate in a configuration corresponding to the pattern may be used instead of streams of heated air.

It is believed that where thermal energy is applied to condition the yarns, the heat will result in a reduction in the internal orientation of at least a portion of the individual untensioned yarns in those pattern areas where maximum solvent extraction of the dye is desired. The decrease in orientation presumably leads to an increase in the penetration of the solvent into the interior of the yarn _/ possibly through the formation of voids between neighboring molecules and thus to an acceleration of the color extraction process. Possibly, the thermal conditioning leads to a radial migration of the dye molecules from the inside of the yarn to the surface of the yarn, which leads to the observed accelerated dye extraction by the solvent in thermal

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mixed nimble] tone Carrion leads. Generally speaking, will
the thermal conditioning of thermoplastic yarns from thermal deformation or destruction of the yarns e.g. B. softening, longitudinal shrinkage, melting or fusing of individual yarns. These effects are shown schematically in relation to different substrates in FIGS. It is believed that maximum rates of selective dye extraction according to the invention can be expected from such thermoplastic yarns or yarn portions as such

show thermally induced deformations in comparison with thermoplastic yarns in which no thermal deformation is observed. Such a softening
Shrinking, melting or fusing or other

easily observable external effects are presumably not necessary when carrying out the method according to the invention. The extent occur in which such observable effects depends on many factors such as the nature and composition of the yarn used _# the dimensions of the individual yarns can shrink the type of heat used, etc.

It is also believed that conditioned polymeric yarns have larger spaces between adjacent polymer molecules within the fibers making up the yarns compared to unconditioned yarns of the same type, thereby reducing the rate of migration of solvent molecules into and out of the yarns
is increased out.

The following table has been drawn up to illustrate these effects of thermal conditioning using an example of one Polyester yarn using a preferred

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to quantify suitable solvent. A package of 20/2 T-811W Bright DACRON yarn (DACRON is a trademark of DuPont) manufactured by Milliken & Company from DuPont polyethylene terephthalate fibers was made in a laboratory yarn package dyer using Eastman Polyester Blue GLF (Color Index _f name Dispers Blue 27) colored. Portions of this yarn were displaced by 5 s immersion in a fluidized bed model SBS-2 from Fisher Scientific Company of Pittsburg, Pennsylvania over a range of ¹ ^ O ° C to 260 o _C ^ _n stages of 13.9 ° C heat-treated. Length measurements before and after the heat treatment allowed the calculation of the percentage shrinkage at each temperature. Standard coupons were then extracted by immersion in 5 ml of room temperature methylene chloride for 1 minute and then removing the yarn from the solvent. The UV spectrum of these extracts was then noted, giving the absorption of the blue dye at a wavelength between 592 and 595 nm, which is a measure of the amount of dye that has been extracted by the solvent.

The results are given in the table below.

Table 1 relative absorption temperature % Shrinkage 0, 048 150 ⁰ C 0 0, 092 163 ° C 0.2 0, 10 8 1 77 ° C 0.8 0.057 1 91 ⁰ C 3.5 0.043 204 ⁰ C 6.8 0, 070 21 8 ° C 9.6 0.349 232 ° C 20, 5 0.699 246 ° C 28.2 260 ⁰ C melted

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From this table it can be seen that for this particular yarn / solute] system, the rate of dye extraction generally increases after brief thermal conditioning at temperatures above 110 ° C. and increases dramatically after brief thermal conditioning at temperatures above about 218 ° C to between about 246-260 ⁰ C, ie a temperature just below the melting point of the unconstrained yarn. When the yarn is under tension, slightly higher temperatures, ie 26 0 ^° C. and above, can be used in order to achieve increased shrinkage and increased color extraction speeds.

After the fabric has been suitably heat treated in the desired pattern, the fabric is then exposed to a solvent for a controlled period of time during which the dye is selectively extracted only from the heat-treated areas and the solvent is only a relatively small or im has essentially no effect on those areas of the fabric surface that have not been treated according to the invention. It is not necessary that the heat-treated fabric be exposed directly to the solvent or stored under any special conditions after the pattern has been heat-treated on the fabric. Nor is it necessary that the fabric be dyed prior to applying heat to the pattern. Good results can be achieved if heat is first applied to a fabric according to the pattern, the piece is then dyed and then exposed to a solvent, in each case in individual independent stages according to the invention. Since under such conditions the heat-treated areas tend to _{(take up} more dye than the untreated areas, the extraction

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times can be increased as more dye has to be extracted.

Any suitable solvent can be used. Solvents used in connection with substances which contain polyester yarns and which have been dyed using disperse dyes, include hot perchlorethylene and 1,1,1-trichloroethane. Other solvents which can lead to satisfactory results can be found in Table 2 of the Article] s "Interactions of Nonaqueous Solvents with Textile Fibers - Part I: Effects of Solvents on the Mechanical Properties of a Polyester Yarn "by A.S. Ribnick, H.-D. Weigmann and L. Rebenbeld appeared in the Textile Research Journal, December 1972, pp. 720-726 (Table II P. 722) · as well as in Table I of the article "Interactions of Nonaqueous Solvents with Textile Fibers - Part II: Application of the Solubility Parameter Concept to Polyester Fiber-Solvent Interactions "by B. H. Knox, H.-D. Weigmann and M.G. Scott, published in the Textile Research Journal, March 1975 pp. 203-217 (Table I p. 206) to the is expressly referred to here.

A preferred solvent for polyester yarn / disperse dye combination is methylene chloride which can and is capable of being used at room temperature substantial amounts of disperse dye in proportion quickly from the one heat-treated according to the sample Extract polyester. In one embodiment, can polyester-based fabric, which is made with Has been treated with heat, immersed in a methylene chloride bath at room temperature and agitated in it for a short time to ensure even circulation of the solvent near the the patterned areas of the fabric

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to ensure educational games. The methylene chloride is capable of extracting essentially all visible dye from pattern areas of the fabric that have been severely heat treated in 30 to 60 seconds or less. Over the same period of time, the solvent visibly extracts less dye from pattern areas or parts of individual yarns that have been treated less severely, ie exposed to lower temperatures ₍ and essentially does not extract any ο dye from those areas or yarns or parts of yarns that have not The use of warm or hot *. methylene chloride as a solvent gives the same selective extraction effects but within a much shorter time · almost complete dye extraction can be achieved in heavily patterned (heavily heat-treated) areas in a few seconds is not carefully controlled, a full color extraction also enters easily treated or untreated _areas; that _(if the time is exposed to the substance in the solvent to be reminded.

Measures other than immersion can optionally be used _(to bring the fabric into contact with the solvent, e.g. the solvent can be sprayed onto the fabric. It is also possible that the yarns can be physically moved after the solvent has been applied to wash solvent saturated with dye from the surface to facilitate the extraction process. The means to stop the solvent action may vary, most easily the solvent may be washed naturally or otherwise from the surface of the substrate

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be removed after the desired "residence time" or after the time for the fabric to be exposed to the solvent has passed.

Preferably the solvent selected is one that is not readily flammable and should, of course be one that is neither highly toxic to humans nor harmful to the yarns used. It is believed, that suitable solvents should be selected from those solvents which have a Hildebrand solubility parameter (* T) that is appropriate for the yarn of interest. It has been shown, for example, that for yarns which consist essentially of polyethylene terephthalate (10.7), applicable solvents have a Hildebrand solubility parameter should range from about 8 to about 14. Solvents with values as close as possible to 10.7 do not necessarily result in maximum dye extraction rates and are not necessarily against other solvents with more distant values preferred. Factors such as the size and thus the accessibility of the solvent molecule in relation to the Voids between the polymer chains within the fibers that make up the yarn must be chosen accordingly. High solvent migration rates are beneficial. Solvents with values substantially above or substantially below 10.7 can interact quite well with different parts of the polyethylene terephthalate molecule occur and high dye extraction speeds to lead. It has been shown that suitable solvents with Solubility parameter values between about 9 and about 10 and between about 11.5 to about 13 often work quite well. Suitable solvents from the first group work well the aromatic part of polyethylene. "! en-terephthalate-Mol eküls in interaction, while solvent from the latter Group well with the aliphatic part dos molecule in Interaction.

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The invention is illustrated in more detail by the following examples. The device that was applied to the fabric Using streams of heated or hot air to create a pattern was similar to that in U.S. Application 253,135 and Ui '.- PS 4 3G4 156 described.

Example 1

A 100% polyester pile fabric having a fluffy (rough) pile and weighing 339 g / m ² , designated by Milliken & Company as Style 8301, was dyed in the conventional manner with disperse dyes to obtain a uniform medium brown color. The fabric was then treated with streams of hot air from a heater as described above to form a relief pattern in the pile with a series of punctiform, recessed, thermally shrunk yarns. The speed of the fabric in the device was 5.9 m / min and the air temperature from the distributor device was 354 ^° C. Before the fabric was exposed to the solvent, the color was slightly darker in the recessed areas than in the other areas ( Background), where the pile remained essentially upright. The patterned fabric was immersed in a methylene chloride bath at 23 ^° C. for 1 min, removed therefrom and dried in a stream of air at room temperature. When completely dry, the fabric shows a pattern of very light brown recessed points

on a background that is essentially not in color was changed. The contrast that appeared in the pattern areas of the treated sample was excellent and so was the pattern was very easy to see from every angle.

Example 2

A polyester pile fabric from Milliken & Company knitted on a 44 gauae double needle raschel machine as Style 6590 bezoirhi.f-1 weighing about 305 g / in ² was used

dyed a disperse dye under image of a uniform deep blue color. This fabric was treated with streams of hot air using the apparatus indicated above to obtain a series of points of thermally shrunk pile fibers. The material speed in the device was 22.9 m / min. The temperature of the air from the distributor device was 438 ^° C. The end product, after being treated with methylene chloride for 1 min as described above, removed therefrom and air-dried, had a uniform deep blue color with a series of essentially white dots which exactly corresponded to the areas of the shrunk pile fibers.

Example 3

A Raschel machine-knitted pile fabric made of 100% polyester, designated by Milliken & Company as Style 180, weighing about 170 g / m ² , was dyed evenly green with a disperse dye. The fabric was treated with streams of hot air in a pattern using the apparatus indicated above. The speed of the material in the device was 6.4 m / min and the temperature of the air emerging from the distributor device was 371 ^° C. A relief pattern was obtained which was difficult to see at all angles of incidence of the light. The fabric was then immersed in methylene chloride at 23 ° C. for 30 seconds, removed therefrom and dried with a stream of cool air. A high-contrast white pattern was obtained in relation to the green background, which was much more recognizable than in the case of an untreated patterned fabric.

Example 4

A knitted fabric made of 100 % polyester (interlock), designated by Milliken & Company as Style 2651, with a

Weight of 102 g / m ² was dyed in a deep blue tone with the aid of a dispersion dye and patterned with the aid of a computer-controlled flow of hot air by means of the above-mentioned device. The material speed in the device was 3.4 m / min and the air exiting the distribution device had a temperature of about 438 ^° C. Before the material was exposed to the solvent, the pattern (picture) in the heated areas was darker. After soaking in methylene chloride at 23 ° C. for 30 seconds and drying in air, the (treated) image area became lighter. A 2 piece of the same fabric similarly patterned and exposed to methylene chloride for 30 seconds showed even greater contrast, with the background color remaining constant.

Example 5

A woven fabric of an intimate 65:35 blend of polyester and cotton manufactured by Milliken & Company and designated Style 2602 weighing about 161 g / m ² was evenly dyed a navy blue shade. The fabric was patterned in the shape of a diamond with flowers in the center 5 by means of hot air currents using the device indicated above. The speed of the fabric in the device was 5.5 m and the air exiting the distributor device was at a temperature of about 371 "C, only a slight contrast between the treated and the untreated areas was noticeable on the dark navy blue fabric. After immersion in methylene chloride at 23 ° C for 1 minute, the dye was from the polyester yarns made with the aid of the thermally converted from hot air, while it was not attacked in the cotton fibers.The result was a light blue pattern on a darker navy blue background,

called by the extraction of the dye ^- from the "poly-

ester fibers.

Example 6
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A coarse (ripped) Gswäoe containing a dyeable with disperse dyes polyester yarn in the weft direction and a cationic-dyeable polyester yarn in the warp direction was woven in such a way that, after the above color (cross-dyeing) the structure or roughening a relief effect _r returned in the form of square, Nichtflor - Areas with a side length of about 2.5 mm that appeared black (cationic dye) _r in a gray area (pile dyed with disperse dyestuff or dyed knobs). The fabric was made by Milliken & Company and designated Style 8317 weighing approximately 339 g / m *. A pattern or image was formed on the fabric with the aid of a stream of hot air using the apparatus identified above. The material velocity in the device was 6.2 m / min and the air exiting the distributor device had a temperature of about 354 ^° C. The material was immersed in methylene chloride at 23 ^° C. for 1 minute and then dried. The resulting pattern shows strongly contrasting white pattern areas and black dots on a gray background. The effect achieved was multicolored and showed good contrast, the cationic dye _{having been extracted to a much lesser extent (} if at all by the solvent).

Example 7
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A woven polyester fabric from both cationic dyeable polyester and dyeable with disperse dye polyester yarn, the träcrt the designation Style 8327 having a weight of 322 A / m ² was cross-dyed and then with a 5 hot air stream of 4 04 ⁰ C under Verwendunq the above-mentioned

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Provide device with a pattern. The speed of material was 6.2 m / min. The patterned fabric was then immersed in methylene chloride at 23 "C for 1 minute. After 1 minute, the sample removed and dried. She showed a strong one Contrast in the places where the hot air hit was in the form of a very light blue, diagonal stripe pattern against a medium to dark blue background .

Example 8

The fabric of Example 1 was similarly treated with hot air. The treated fabric was then immersed in a 35 ° C methylene chloride bath for 5 seconds. The results after solvent removal and drying were essentially identical to those achieved in Example 1.

Example 9

The process of Example 1 was repeated with the exception that ^{acetone, heated to 53 °} C., was used instead of methylene chloride. The results were similar to those obtained in Example 1.

Example 10

The procedure of Example 1 was repeated with the exception that 1,1,1-trichloroethane of 70 "C instead of methylene chloride was used. The results were similar to those obtained in Example 1.

Example 11

The procedure of Example 1 was repeated with the exception, that perchlorethylene of 95 ° C instead of methylene-ZI β

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chloride was used and the time during which the Cloth was immersed, extended to 5 minutes. The results were similar to those obtained in Example 1.

Example 12 ;

The procedure of Example 1 was repeated with the exception that ethanol at 73 ^° C. was used instead of methylene chloride and the immersion time was extended to 5 min. Very little change in color (visible color concentration) was observed in the treated areas.

Example 13

The procedure of Example 1 was repeated except that the heat treatment with hot air was carried out before the usual dyeing. The fabric obtained contained dark brown dots on a medium brown background. After 1 min of treatment of the patterned fabric to methylene chloride 0 of 23 ⁰ C, a clearly visible lightening of the dot areas were obtained. A further treatment up to a total time of 5 minutes resulted in a fabric that showed light beige dots on a medium brown background.

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Claims (14)

Claims IJ Process for generating patterns on textile materials that contain thermoplastic yarns and with a dye are colored by the pattern corresponding treatment of the surface of the textile material, g e ■ characterized by the following levels: a) the selective treatment of pattern areas on the surface of the substrate in order to increase the extractability of the To reinforce dye with the aid of a solvent of at least some yarns within the pattern areas, while the surface in the complementary areas is not treated, b) contacting the surface with a solvent that is selectively a visually distinct amount of the dye contained in the thermoplastic fibers in the treated pattern areas located before the solvent a visually significant amount of dye from the untreated complementary areas extracted, c) stopping the solvent extraction after the desired amount of dye in the pattern areas and Complementary areas has been extracted. 2. The method according to claim 1, characterized in that the relative internal orientation / 2 '- "- ■ · 341H86 _ 2 - of the treated yarns within the pattern areas is reduced will. 3. The method according to claim 1 or 2, characterized in that - indicates that the solvent is methylene chloride, perchloroethane and / or 1,1,1-trichloroethane .ist. 4. The method according to claim 1 to 3, characterized g e k e η η indicates that the thermoplastic yarns are polyester yarns. 5. The method according to claim 1 to 4, characterized in that the treatment of the pattern areas consists in the application of heat to these areas. 6. The method according to claim 1 to 5, characterized in that the thermoplastic yarns from Polyethylene terephthalate and the dye is a disperse dye. 7. The method according to claim 5 or 6, characterized in that g e k e η η shows that the treated areas are supplied with so much heat that the yarns in these areas be deformed. 8. The method according to claim 5 to 7, characterized in that the heat is applied by Currents of a hot medium or a laser beam] are directed onto the areas of the substrate to be treated. 9. The method according to claim 1 to 8, characterized in that polyester yarns dyed with a disperse dye ^{are heated in selected areas to a temperature of 183 to 260 0} C, the so loading / 3 341U86 acted substrate omem solvent with a solubility parameter in the range of about 8 to about 14 Hildebrand units containing the disperse dye extracted from the treated yarn areas much faster than from the untreated areas. 10. Textile material with a surface, the pattern areas and comprising complementary areas, the pattern areas being comprised of polyester yarns which are thermally deformed and the complementary areas consist of polyester yarns that are not substantially deformed are and the significantly more disperse dye per Unit of yarn length included as the deformed yarns 11. Material according to claim 10, characterized in that the thermally deformed yarns include those yarns of which at least a portion or segment has shrunk or melted longitudinally. T2. Material according to claim 10 or 11, characterized in that the surface is made of pile fibers and the thermally deformed yarns comprise pile fibers, in which at least some of the yarns has shrunk essentially longitudinally near the tip, 5 with these deformed pile fibers in the shrunk Area contains less dye per unit length than other areas. 13. Material according to claim 10 to 12, characterized in that that the surface comprises polyester yarns with the same density, based on the Substrate surface over which the pattern and complementary areas are distributed and an essential part of the yarn is thermally deformed in the pattern areas, while / 4 · - ■■ - * ^: 341U86 in the complementary areas a substantial part is not thermally deformed and contains significantly more disperse dye per unit length than the deformed yarns in the pattern areas.
5 14. Material according to claim 10 to 13, characterized in that there are areas of polyester yarns includes that are visually thermally deformed and areas of polyester yarns that are essentially none Contain dye, the latter being substantially congruent with the former and pattern areas form on the substrate surface. 6238