JPS5982482A - Fiber product fabric having opaque printing and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the printing of textile 011 articles, and in particular to the printing of textile 011 articles characterized in that the printed areas are substantially opaque and therefore unaffected by the color of the underlying threads. This relates to the manufacture of textile products.

Pigment printing of textile products is, by definition, the printing of specific areas of textile fabrics with insoluble coloring agents (pigments). Although the pigment has no affinity for the fibers of the fabric, it is bonded to the fabric using a resin binder. The term "resin-bound pigment" is often used for this textile printing method and product.

In conventional textile pigment printing operations, the pigment colorant and resin binder are contained in an aqueous emulsion in the form of a thick printing paste, and this printing paste is applied to the fabric by a patterned roller or by a screen. Ru. After the paste is printed onto the fabric, the fabric is heat treated to dry and harden the resin binder.

In conventional resin-bonded pigment prints of this type, the printed areas are relatively transparent. Pigments help color the yarn, but the color of the underlying yarn shows through. For this reason, pigment printing is usually carried out on colorless or f'J white fabrics. When pigment printing is performed on predyed fabrics, it is generally limited to dark prints over a light background color. Even then, in order to obtain the desired color, t? Landscape effects must be considered. For example, printing a blue pigment on a fabric with a yellow background will result in a greenish appearance due to the additive effect of yellow and blue. As a result, only limited colors can be obtained when printing on pre-dyed fabrics using conventional pigment printing methods.

Attempts to overcome the background color effect by applying a thick layer of water-based printing paste have generally been unsuccessful. For example, French Patent No. 2,402,733 relates to a method of applying printing paste in the form of a thick layer to create opaque printed areas and to form a skin on the surface of the fabric. When the printing paste is applied to the fabric in a thick enough layer to completely cover the underlying threads and the fabric is allowed to dry and harden, the surface area of the printed area dries first and the moisture is removed from the printing paste. forms a skin that prevents the evaporation of This results in a poorly cured product and/or a cracked mud appearance. Such products have an abrasion resistance and washfastness of just under 6.

There are many textile designs and patterns that require relatively small areas of light color against a dark background color.To create such patterns with traditional pigment printing techniques, it is necessary to separate light and dark areas. It was necessary for the double swords to be made by printing on an unpigmented fabric, so that the entire surface of the fabric was coated with resin-bonded pigment.

Such fabrics tend to have a relatively hard rough/grainy feel, and the color fastness is not as strong as in dyed fabrics. Although suitable for certain applications such as clothing, it has had limited applicability in other fields, such as clothing fabrics.

Printing highly opaque light or dark colors on undyed or pre-dyed fabrics, as traditional pigment printing techniques have limited ability to create the types of designs and patterns mentioned above. Special methods and g4
f7'f was developed. This method and apparatus d may include, for example:
It has been used commercially to print specialty fabrics having an opaque spotted pattern resembling the appearance of Swiss spotted fabrics coated with jacquard. This technique uses a 4:1 solvent-based pigmented lacquer.

This is roughly like a paint and is applied to the fabric in relatively thick layers in a special rotating stencil printing range using a perforated roll with the desired mottled pattern. Perforated rolls are expensive, which limits the number of vine patterns produced. Because printing pastes are solvent-based, this method and equipment requires an explosion-proof curing oven and relatively expensive solvent recovery equipment for recovering volatile dichloromethane and maintaining acceptable air quality. shall be.

In order to avoid oozing of the dye from the fabric into the printed areas and to ensure the safety of process f1, the fabric must be hardened at relatively low temperatures. As a result, the equipment has a relatively slow processing speed. On top of that,
Since the device (, + only one printing stage is installed in the second drawer, only one printing machine can be printed in the weight).It is very difficult to remove the device and it takes a long time. It also requires the use of volatile solvents.In fabrics produced by this method and apparatus, lacquer spots or printed areas may wear off or become oxidized.
When in contact with certain Japanese chemicals contained in HL products, they tend to smudge or smear. Furthermore, if such fabrics are ironed with an iron that is too hot, spots of lacquer will run or discolor on the iron.

In view of the above two points, it is an object of the present invention to provide a method for printing highly opaque colors on textile fabrics and overcoming the limitations and disadvantages of conventional pigment printing and lacquer printing techniques. This is the purpose of -.

It is a further object of the present invention to provide a method for producing printed fabrics having a variety of patterns and colors that could not be obtained by printing techniques used heretofore.

In accordance with the present invention, these and other objects and advantages are achieved by providing an aqueous opaque printing paste formulation and application method as described in more detail below. Unlike the water-based printing pastes used in traditional screen printing operations, this printing paste is opaque and can be applied onto fabrics on either dark or light backgrounds without being affected by the color of the underlying threads. is also available. Since this printing paste is aqueous-based, it eliminates the problems inherently associated with the lacquer printing technology (as described above) due to the presence of volatile solvents. The need for ovens and solvent regeneration equipment is eliminated. Cleaning of the equipment can be done with water without solvents, and the cleaning time is a fraction of the time required for lacquer printing methods. Furthermore, and quite surprisingly, the water-based opaque printing pastes of the present invention require significantly lower pigment pick-up levels than are required in lacquer printing systems. This provides another advantage in cost. The fabric also has significantly improved wash fastness compared to fabrics printed using the lacquer method.

In addition to the above-mentioned advantages, the water-based opaque printing paste of the present invention is extremely versatile in its application method and is of the type used in lacquer printing, which is relatively slow moving and limited to only one color printing station. Not only can it be applied to fabric using a conventional rotary stencil printing oven (,
The fabric can be applied using a rotating screen printing range that moves at higher speeds and has multiple printing stations. The invention therefore now makes it possible to produce multicolor prints with an infinite number of color possibilities, patterns and background colors not available with conventional rotary screen printing or lacquer printing techniques.

The printed textile fabric according to the present invention is formed of intertwined threads of a predetermined color, and certain areas of the fabric have areas of a printed pattern of a predetermined color that contrasts with the color of the threads, The pattern area is characterized in that it is substantially opaque and therefore unaffected by the color of the thread. The printed A-lambda-like area includes an opaque 172u covering the exposed surface of the yarn, which coating includes an opacifying pigment that imparts opacity to the coating and an opacifying pigment that is affixed to the yarn and binds the opacifying pigment to the yarn. a cured water-insoluble polymeric binder.

The opaque coating forming the printed pattern area individually coats each of the threads in the printed area so that the intertwined thread structure of the fabric remains visible rather than being erased. More particularly, the opaque coating wraps and covers the exposed fibers individually on the surface of the yarn such that the individual surface fibers of the yarn also remain unobliterated and visible.

In one embodiment of the invention, the printed pattern areas are contrasted with each other by the use of a rotating screen printing range or other suitable equipment to impart a plurality of opaque printing paste colors. New types of visually appealing fabrics are created that are composed of colors that contrast with a given color and that have fewer colors (one brighter than the color of the threads). Detailed description below. As will become clear from the examples, various other unique patterns and effects can be created.

The aqueous opaque printing paste of the present invention is constituted by a stable aqueous dispersion of an opacifying pigment and a polymeric binder which is curable to a water-insoluble state and adheres to the yarn, binding the opacifying pigment to the yarn.

Printing pastes optionally contain crosslinking agents, thickening agents, emulsifiers, as well as colorants such as dyes or colored pigments to provide the desired overall color. It may also contain relatively small amounts of other materials such as H modifiers and the like. The opacifying pigment, colorant, and curable polymeric binder are the major components and have a very high solids content, such as preferably about 2% total solids.
It is present in a concentration to provide a printing paste with a solids content of 5% or more, which is significantly higher than conventional aqueous printing pastes. The printing paste contains at least about 20% by weight (as solids) pigment and at least about 5% by weight (as solids)
It is desirable to include a polymeric binder of. This combination of pigment and polymeric binder is present in sufficient quantities to form a highly opaque coating in the dried, cured fabric that covers the exposed surfaces of the fabric threads and completely hides the color of the underlying threads. Ask about the fabric.

The aqueous printing paste formulation of the present invention penetrates into the fabric by coating each yarn individually and is generally found on both its front and back sides. This penetration and individual coating or encapsulation of the threads into the fabric provides the printed fabric with excellent durability and wash fastness. The porosity, flexibility and hand of the fabric are not adversely affected and are in fact much better than in the printed areas obtained by the conventional pigment printing mentioned above or by the prior art solvent-based lacquer printing methods. be. The areas produced and printed by these techniques, in contrast to the areas produced and printed according to the invention, are characterized in that they form a skin or coating that remains on the fabric surface and is therefore susceptible to abrasion.

Another aspect of the invention involves the use of dyes, alone or in combination with colored pigments, to reduce the color of aqueous opaque printing pastes of the type described above.

The use of dyes, by themselves or in combination with colored pigments, extends the possible range of colors obtainable and provides a means of achieving brighter colors and bathochromic properties. The use of water-soluble dyes also provides better printability by reducing the tendency for screen blockage. Dyes are selected by their compatibility with the polymeric materials used in the binder system, and are actually polymeric. The binder has the effect of coloring. The polymeric binder contains reactive dye sites that are available for binding with dyes, at which the dyes may react chemically. Preferred in the present invention Dyes that may be used include any dye commonly used for dyeing textile fabrics. Examples of preferred dye types for use in the present invention include acid dyes, cationic dyes, direct dyes,
It contains at least one dye selected from the group consisting of disperse dyes, fiber-reactive dyes, mordant dyes, and solvent dyes.

Having set forth some features and advantages of the invention, others will become apparent from the following detailed description and examples, and from the accompanying drawings. In the accompanying drawings, FIG. 1 is a photomicrograph showing a fabric with printed areas thereon;

Figures 2 and 3 are for comparison purposes, and show similar structures having opaque print areas thereon produced by commercially practiced water-based printing techniques and known solvent-based lacquer printing techniques, respectively. This is a microscopic photograph showing the fabric.

The opaque aqueous opaque printing paste of the present invention has a relatively high solids content, e.g. preferably at least 25% total solids, and is mixed therewith primarily with an opacifying pigment in the form of a stable aqueous dispersion. and a curable polymeric binder.

In order to serve as an opacifying pigment for the purposes of this invention, the material must be very indistinct and exhibit color properties that can be used alone or mixed with other colorants such as dyes and colored pigments. Must have. And it must be easily dispersible within the aqueous binder system at relatively high concentrations. There are many commercially available materials that have these properties. Preferred opacifying pigments for use in the print paste formulations of the present invention are white pigments, especially when it is desired to scale white or relatively brightly colored print areas against a dark background color. A particular white pigment that has been found to be particularly suitable is titanium dioxide because of its bright white appearance, cost and ease of nesting.Other suitable white pigments are silicates, aluminide compounds, carbonates, etc. Calcium, etc. When opaque white print areas are desired, a white opacifying pigment is used as the sole pigment. When opaque colored print areas are desired, suitable colorants such as colored pigments and/or dyes are used. into the water-based printing paste.

In order to achieve high roman (color saturation) at a given hue, less white or intermediate color opacifying pigments of 14-1 or higher may be used alone or in combination with white pigments.

In addition to the opacifying pigments mentioned above, examples of other compounds suitable for use as opacifying pigments in Mokujome include:
Zinc oxide, zinc sulfide, lithopone (ZnS/BaSO
4) Basic carbonate white lead, basic sulfate white lead, lead oxide (lead dioxide), calcium sulfate, barium sulfate, silica, clay (Al 203/25i02/2H20)
, lead sulfate, magnesium silicate, mica, wollastonite (C
aSiO3), aluminum hydrate, magnesium oxide, magnesium carbonate, aluminum oxide, ferric oxide,
carbonate) IJium, strontium sulfide, calcium sulfide, barium carbonate, e44[-antimony, zirconium white, barium tungstate, bismuth oxychloride, silver white, lead silicate, chalk, bentonite, barium sulfate, gloss white, gypsum, phosphorus Contains zinc acid, lead phosphate, and calcium silicate. For printing in relatively dark colors, carbon black may be used as an opacifying pigment instead of a brightly colored pigment.

The use of opacifying pigments, especially white opacifying pigments, and printing them against a dark background color are features that clearly distinguish the present invention from conventional pigment printing. In conventional pigment printing, white pigments are used only on white background fabrics to achieve a "white on white" effect. White pigment printing pastes are generally not provided with dark background colors, since such printing pastes do not provide sufficient contrast against dark background colors.

The amount of opacifying pigment used in the printing paste formulations of the present invention is significantly greater than the pigment content used in conventional aqueous-based printing pastes (and usually significantly greater than the total isomorphic content of the polymeric binder). In one preferred formulation, the printing paste contains a small amount of both 20% by weight opacifying pigment (based on solids) and at least 5% by weight polymeric binder (based on solids).

Polymeric binders for opacifying pigments can be applied from aqueous systems, forming stable dispersions with insoluble opacifying pigments and other additives in the binder system, and providing good film formation when applied to fabrics. It must be able to dry and harden to a water-insoluble state5 and give the print good washfastness and abrasion resistance. The polymeric binder can suitably be applied as a solution or as an aqueous dispersion or latex. Drying and curing of the printing paste can be accomplished by any suitable means, such as heating, in order to cure the binder, i.e. to change the polymeric binder from its original aqueous solution or dispersion to a water-insoluble state in the final product. Various mechanisms can be used. For example, curing includes decomposition or reaction of water-soluble groups such as carboxyl groups, condensation or addition polymerization, powder wire curing or crosslinking.

One example of a particularly suitable curable polymeric binder system for opacifying pigments is an aqueous film-forming crosslinkable latex. Latex compositions suitable for use in the present invention are stable dispersions in water of polymers and/or copolymers that effectively maintain the pigments as a homogeneous suspension so that they can be printed onto fabrics. This involves coating the threads of the fabric with a thin film of latex and pigment.

When heated, the latex film dries and hardens, resulting in a crosslinking reaction between the reactive side groups of the polymer chains.

In this way, a tough, flexible, water-insoluble, pigmented, opaque film is formed around the yarns in the areas of the fabric where the print paste has been applied. If the particular latex polymer used is not thermally reactive on its own, a suitable catalyst or curing agent is added to promote curing and crosslinking upon heating.

One preferred type of film-forming aqueous latex for use in the present invention is acrylic latex. These are aqueous anionic colloidal dispersions of acrylic polymers and copolymers. An example of a suitable commercially available acrylic latex is the Hycar series of acrylic latexes available from BF Gutdrich. Heat-responsive film-forming aqueous latexes suitable for use in the present invention include styrene-O-butadiene latex, polyvinyl chloride and polyvinylidene chloride latex, polyvinylpyrimidine latex, and polyacrylonitrile latex.

Optionally, a heat-reactive crosslinking agent capable of crosslinking with the latex may be included in the binder system to impart high abrasion and wash fastness properties. The crosslinking agent serves to strengthen the cured latex polymer, thereby imparting high wet abrasion resistance and i51: washfastness to the printed areas. A cross-wetting agent is a compound or resin (polymer) having a functional group that reacts with the reactive sites of the latex to create a cross-linked structure under curing conditions. Examples of reactive chemical compounds suitable as crosslinking agents include aldehydes and dialdehydes, such as formaldehyde and glyoxal. Examples of reactive thermoplastic or thermosetting resins suitable as crosslinkers include glyoxal, melamine, triazone,
There are turmeric, carbamates, acrylamide and silicone resins. The only commercially viable heavy class of heat-reactive crosslinking resins is melamine-formaldepide.
An example of this is AEROTEX RESIJJ MW manufactured by American Imasu Ianamide.

The polymeric binder system is also not crosslinked per se, and polymers may be used without additional crosslinking agents. Suitable non-reactive polymeric resins of this type may be based on polyvinyl chloride or polyvinylidene chloride, such as the Ge0n series resins available from BF-Gudrich. Other suitable non-reactive resins include polyester resins, polysiloxanes Jfi
There are polyvinyl alcohol and polyvinyl acetate. Instead of forming crosslinks, these resins, when cured, melt the individual polymer particles and form interlocking particles that form entangled polymer chains with good adhesion. The selected polymeric material may be present as a suspension, emulsion, or in solution.

Vine dyes are used appropriately to color the binder.
The dye may be at least one selected from the group consisting of acid dyes, cationic dyes, direct dyes, disperse dyes, fiber-reactive dyes, mordant dyes, and solvent dyes. azoic dye,
Vat dyes and sulfur dyes can also be used, but L7 azoitsk compounds, vat dyes and non-reducing sulfur dyes are
In their unreduced form, they behave effectively as pigments because they are insoluble.

Certain monomers or polymers having cationic or acidic dye moieties may also be included in the binder system to enhance the shine and fastness of the particular dye selected. Natural rubbers and polymers or synthetic polymers containing hydroxy groups, amide bonds, and amide 7 groups are also incorporated to provide improved fastness and shine of the fiber-reactive dyes.

When acid dyes are used, the binder system may suitably include certain monomers or polymers containing vine dyeing sites that are utilized to form ionic bonds with the acid dyes. Urethane polymers such as Nopcothnne-D610 or American Fist Cyanamide Size T
Acrylamide copolymers such as S-IQM may be included in the binder system along with acid dyes such as Acitol Yellow 3 OLE.

If cationic dyes are used, the binder system may include certain monomers or polymers that contain vine dyeing sites that are utilized to form ionic bonds with the cationic dye. For example, BF Gutdrich's) Itl-1,
A nitrile latex such as 572 may also be incorporated.

Disperse dyes may be used to color the opaque printing paste by adding certain polymers that allow the absorption of disperse dyes by diffusion during the curing process.

Such polymers can be, for example, water-dispersible polyester sizing compounds such as Eastman Fist Size WD. Holon Red 5EVS is a disperse dye that has been found to produce red opaque prints on black fabrics in such systems.

Direct dyes may also be added directly to the opaque printing mixture. They are due to hydrogen bonding and physical encapsulation within the polymer matrix. An example of such a dye that has been found to give good coloration to opaque print mixtures is Sol-Aqua Fast Scarlet TFL.

Fiber-reactive dyes may be added directly to the printing paste (and polymers containing hydroxyl or amino groups may be added to promote sites for covalent bonding with the fiber-reactive dyes.

Opaque printing pastes were made by incorporating synthetic polymers such as polyvinyl alcohol to provide hydroxyl groups or natural rubbers such as Kelgin XL. A fiber-reactive dye that has been found to give good results is Remazol Green G.
It is B.

The amount of dye to be included in the printing paste depends on the desired color. Combinations of dyes and dyes from different types, and combinations of dyes and colored pigments can also be used to achieve various desired colors. If additional polymer is added to the printing paste, it can be added at a concentration of typically about 10-20% based on the total R of the mixture.

Examples of aqueous opaque mixtures with dyes added as colorants include: Pioneer and White BS 57.
．． 5 propylene glycol
3.1 basol
31 Hiker 2679 or Hiker 1572
15.4 Blockout”
13. Luzin MW
4.6 ammonia
0.8 Quick Set PO, 9 Thickener φ Concentrate T1.5 Silicone fluids and elastomers may be incorporated into the print paste to help apply the pigment smoothly to the fabric. It has been found that the use of silicone polymers provides spots and designs without rough edges or cracks. Silicone resin polymers can also be used in place of or in addition to thermoplastic or thermosetting resins.

Conventional thickeners may be used to adjust the viscosity and flowability of the paste depending on the size and design of the print pattern and the speed of printing screen travel.

The glue may also contain other conventional additives such as emulsifiers, defoamers, pH regulators.

It is important that the printing paste has good wetting and film forming properties so that when it is applied to the fabric it does not remain on the fabric surface but penetrates and coats the individual threads of the fabric. If these properties are not adequately achieved by the polymeric binder itself, suitable wetting agents or emulsifying agents may be included.

The printing paste can be applied to undyed (e.g. white) or pre-dyed fabric, and the pre-dyed fabric is one that has been dyed all over to a predetermined color, e.g. , yarn dyeing, pigment padding, etc.

The particular proportion of printing paste applied to the fabric will vary depending on a variety of factors, including the basis weight and texture of the fabric, the color of the fabric, and the color of the print.

Drying and curing of printing pastes is carried out at temperatures and temperatures customary for specific printing methods.
It can be carried out under time conditions.

For example, for rotary screen printing, drying and curing are 121 to 2.
It can be performed in seconds to minutes at temperatures up to 04°C (250'F to 400"F). Selection of appropriate low temperature curing polymeric binders and curing at low temperatures provides energy savings and improvements. Fabric properties are achieved. It is desirable to include a cross-linking catalyst for low temperature curing. The particular catalyst selected is dependent on its interaction with the cross-linking resin, polymeric binder and other components in the glue. Polymer latex and resin emulsions are soluble in solution in the presence of acid catalysts and catalysts containing polyvalent ions such as those found in metal catalysts such as magnesium chloride and organometallic catalysts. One type of catalyst that has been found to be particularly useful for low-temperature facilitation is QuikSet P (Qu
ammonium-blocked sulfonic acid catalysts such as ickeet P).

This catalyst is weakly acidic and will not destroy the weakly alkaline H of the latex mixture in the state in which it is used. During curing, ammonia is released leaving behind sulfonic acid groups, thus making the H acidic and providing an acidic catalyst for the reaction system.

The catalyst is then a conventional methane-sulfonic acid or p-)
Works as a luene sulfonic acid catalyst (.

When the fabric is cured and dried, the areas printed with the printing paste have a thin flexible opaque coating covering the exposed surface of the yarn;
Therefore, the color of the base of the thread is hidden from view. The coating consists primarily of an opacifying pigment tightly bound to the threads by a hardened water-insoluble polymeric binder.

The micrograph in FIG. 1 clearly shows the structure of the opaque coating produced by the printing paste of the invention. The opaque coating is characterized by penetrating each thread and individually wrapping and covering the exposed fibers at the surface of the thread. However, the fabric structure defined by the interwoven threads is not obliterated by the coating, but remains clearly visible. Additionally, the individual surface fibers of the yarn also remain visible, indicating that the coating has penetrated into the yarn rather than remaining on the fabric surface or the outer surface of the individual yarn. The integrity and opacity of the coating is evident from the visual contrast between printed areas and adjacent unprinted areas. A flat or dull appearance is exhibited by the opaque coating in the printed areas, in contrast to the luster of the uncoated fibers in the non-printed areas.

FIG. 2 shows a printed area produced in an industrial practice where a water-based printing paste is applied as a very thick layer to the fabric in an attempt to achieve the desired opacity. As is clear from the photomicrograph, the printing paste dries and hardens to form a "skin" that remains on the surface of the fabric rather than penetrating into the fabric. The texture of the fabric has been erased and hidden from view by a hideous deposit. Microscopes clearly show that a crust forms during the drying and hardening process, giving it the appearance of cracks in the mud.

These printed areas exhibit poor abrasion resistance and washfastness.

FIG. 3 shows a printed area produced with a solvent-based lacquer printing formulation. The printed areas exhibit a glossy appearance indicative of the lacquer composition. Although the formulation penetrated the fabric to such an extent that the fabric structure did not completely disappear, most of the composition remained on the surface of the fabric and the outermost parts of the individual fibers, so that in many areas The individual threads on the outer surface of the thread are hidden from view by the coating.

Because of the excellent opacity of the water-based opaque colored printing pastes of the present invention, printing on pre-dyed fabrics of any color provides vivid contrasting colors, and the printing paste formulations of the present invention can be used in conventional rotary screen printing. It is said that this can be done easily with a device! Because of its uniqueness, the present invention allows for various colors and film thicknesses that were previously impossible! make it possible to create Accordingly, one further aspect of the invention resides in the manufacture of printed textile fabrics formed from pre-colored yarns, particularly dyed yarns of predetermined colors, wherein selected areas of the fabric are formed from dyed yarns of a predetermined color. having a printed pattern area of a predetermined color that contrasts with the color, the printed pattern area being substantially opaque and thus unaffected by the color of the thread, and the membrane material areas being transparent to each other and the thread. formed from a plurality of colors contrasting with the above-mentioned pre-dyed colors, at least one of the colors being lighter than the thread dyed with the pre-determined colors, and the patterned area covers the exposed surface of the thread. The present invention includes an overlying film-like coating, the coating containing an opacifying pigment that imparts opacity to the coating, and a thermosetting crosslinked latex polymer binder bonding the opacifying pigment to the yarn.

The following examples are included to illustrate the invention and to show how it may be practiced. These examples should not be construed as limiting the scope of the invention. Parts, percentages and ratios are relative unless otherwise specified.

white opaque printing Example 1 A white printing paste having the following formulation was prepared.

Percent water in total composition 1
A commercially available rotary stencil printing range commonly used for 0.8 lacquer spot printing was used to print spots of the above aqueous printing paste formulation onto a polyester/cotton blend printing fabric. After that, the fabric was heated at 127℃ (26oy) for 10
Cured for minutes.

The printed fabric had points of good opacity with sharp borders. When a washing test was conducted, the durability was very good.

Example 2 The following white printing paste formulation was prepared.

Bioneer White BS Pigment (Bioneer Chemical) 75°0 Hiker 2679 Latex (B, F, Gudrich) 17°0 Aerotinx Wa 111 Effect λ (W (American Cyanamid) 3'4 Emulsion Fire 1535 0.5 Ammonia 0425 water
1.4
25 This printing paste had a total solids content of about 43%, of which about 31% was pigment and about 8% latex.

The above formulation was printed in speckled patterns on a white polyester/cotton blend printing fabric and on similar fabrics yarn-dyed in the following colors (pimento, green, cream and pink) using a rotating screen printing range. The fabric was heated to 177℃ (350'
F) was cured for 90 seconds. The spots had clear boundaries and appeared pure white on a dark background.

Example 3 The following white printing paste formulation was prepared.

Hiker 2679 Radex 15
．． 4 Propylene glycol 3
．． 1 parsol
3 Luzin Mw
4. ．． 6 ammonia
0.8 quick set p
0.9 thickener concentrate T
15 This printing paste was printed on a fabric in a rotating screen printing range as in Example 2, and the drying rate was 31%, l.
Hardened.

Opaque Colored Printing The above examples illustrate aqueous printing paste formulations useful for printing opaque white patterns on unpigmented or yarn-dyed fabrics. In these applications, white opacifying pigments also help provide the desired white color. If opaque, yellow areas are to be printed, suitable colored pigments are used in conjunction with the opaque printing Neri formulation.

In this case, the white pigment serves as an opacifying agent and the colored pigment provides the desired color. When formulating colored printing pastes, it is convenient to use a white printing paste formulation similar to Example 1 or 2 as a starting material. A suitable coloring pigment is added to this raw material. The color pigment used depends on the desired hue. In order to obtain dark colors, the amount of colored pigment used may be equal to or greater than the base of the white printing paste. Additionally, an aqueous crosslinkable latex polymer is also added to act as a vehicle for the primary pigment and as a binder in the cured state. If the background color is white or light, commercial
A transparent printing paste thickener called "clearconcentrate" may also be included in the paste to reduce unnecessary opacity in bright background colors.

In colored print formulations, as opposed to white formulations, the binder consists primarily of an aqueous, film-forming, crosslinkable latex, with a small amount of thermoset to enhance washfastness and durability. Preferably, a crosslinkable resin is added. The following examples describe suitable aqueous opaque colored printing paste formulations.

Example 4 I made red printing paste with the following composition.

Uniflint Scarlet NDL 23
4 Ultrabond Red 2B 5
．． 4 White formulation of Example 2 1
7.8 Hiker 2679 Acrylic Latex
17.8 A rotating screen printing range was used to print a red spot pattern of the above printing paste formulation on freely dyed printing fabrics of white printing stock and various background colors.

Multicolor opaque printing Water-based printing paste 1 of the present invention capable of printing clear colors with sharp contrast even on yarn-dyed fabrics of any color
Because of the excellent opacity of the compound and because the Mokuzumo Ming printing paste formulation can be easily applied using conventional rotating screen printing equipment, the present invention allows for the production of a variety of colors not previously possible. This made it possible to create patterns. Another aspect of the invention is therefore the production of printed fabrics formed from dyed yarns that are yarn-dyed, in particular of a predetermined color, wherein specific areas of the fabric are of a predetermined color that contrasts with the color of the yarn. the printed pattern areas are actually opaque and therefore unaffected by the color of the thread, and the pattern and pattern areas are mutually and It is made up of a number of threads that contrast with the predetermined color, and one of the colors is lighter than the thread dyed in the predetermined color.
The coating consists of a film-like corrugation that covers the exposed surface of the yarn; the corrugation provides an opaque layer to the coating; frame fi
It consists of a latex polymer binder.

One such multicolored dyed fabric is described in the following example.

Example 5 Eight prints of five different colors were made using a formulation similar to that of Example 4, but the color pigments were varied. Colors were green, yellow, pale blue, melon and royal blue. These printing pastes were used in a continuous printing station of a rotating screen printing range to create multicolored flower and dot patterns.

Two multicolored flower and dot patterns were printed on navy blue, royal blue, and a vast amount of red dyed fabric. Each trial: 1! The five printed colors are vivid and contrast with the background color of the fabric.

The next example is the durability of the fabric? Tl: i? ? ! The effect of cure rjlN degree, latex 8 degree, catalyst, and crosslinking resin on fastness is shown.

Example The content of the latex was basically the same as Example 2, but the content of the latex was varied from 0 to 30% by weight (the solid content of the latex was varied from 0 to 15% by weight). ) Test specimens of red fabric dyed fabrics were printed using an opaque white printing paste formulation.

Test specimens of each printing paste formulation were tested at 160'F.
Cure for 90 seconds at 182°C (below 360°C). The specimens were then tested using the standard AATCC, which simulates five commercial laundering methods.
Washing fastness test (AATCC Test Method 61-1980 Test No. 1i-A) was carried out and then tested on an arbitrary scale from 0 to 5 and isoabsorbed. In the rating, O indicates zero washfastness (no printed pattern remains on the fabric) and 5 indicates perfect washfastness (little loss of washout pattern; unacceptable).

The results are shown in Table 1.

Table ■ 0 0 0 501 3 1 2 5 l 4+ 7 1 5 9 4 5 555 When the latex content is 0 to 1.5%, there is no washing fastness at low curing temperatures, but only slight fastness at high temperatures. Indicated. At 3% latex, washfastness is still quite low at both curing temperatures. Good washing fastness with 5% latex and high temperature curing. and 1 kg at low temperature curing at 9%.

Example 7 A fabric test specimen similar to that used in Example 6 was printed with a white print paste formulation similar to Example 2. However, the concentration of Aerotex resin was 0°2.4.8 and 16%. The specimens were dried, cured and tested as in the previous example.

None of the samples produced satisfactory wash fastness at the reverse curing temperature, but a slight improvement in fastness was observed at the 8% resin concentration. Samples cured at 182°C (below 360°C) showed considerable fastness despite no added resin. Optimal fastness was obtained at the 4% level, but adding more resin at this level did not result in further improvement.

At the 16% level, the fastness decreased slightly.

These tests demonstrate that although the presence of resin helps improve wash fastness, the resin is not essential to wash fastness, especially at high curing temperatures. It shows.

Example 8 Using a white printing paste formulation similar to that in Example 2,
Fabric test specimens were prepared and tested as in the previous example, except that the QuickSet P catalyst (DmU was 0.0.2
．． 1.2 and 5%.

At lower curing temperatures, no clear trend in fastness was observed with increasing catalyst levels. For printed products cured at high temperatures, no increase in fastness was observed above the 1% level.

The following examples illustrate various non-crosslinkable polymeric binder systems that can be used to make the opaque prints of the present invention.

Example 9 Pioneer white BS 6
0 propylene glycol
3 block out B
15779°a
] Zeon Latex/', 60-6
20 Thickener Concentrate T1 This mixture was printed in the manner described in Example 1 and heat cured.

Example 10 Chipeonia white 13S 6
0 propylene glycol
3 block out B 15
Polyvinyl alcohol (15% aqueous solution) 2
0 ammo 0 a
1 Thickener Concentrate T1 This formulation was incorporated into a water-soluble binder using polyvinyl alcohol. This formulation was printed and cured as described in Example 1. Subsequent passage of a dilute solution of sodium hydroxide followed by steaming and washing resulted in improved performance due to reduced dissolution of polyvinyl alcohol.

Example 11 % Bionea White BS 5
Q Propylene glycol
3 block out B
i.

Eastman size WD
25a″3a 1
Thickener Concentrate T1 This non-crosslinkable binding formulation was incorporated into a water-dispersible polyester size, Eastman/ID. dilute caustic solution,
Subsequent steaming rendered the sizing compound insoluble and the print was cured to provide improved durability.

While the drawings and specification depict preferred embodiments of the invention and certain terminology is used, it is used in a general and descriptive sense and not in a restrictive sense.

[Brief explanation of drawings]

Figure 1 shows the opaque area produced by the invention.
- It is a micrograph showing the fabric which has. Figures 2 and 3 are microscopic t:χ photographs showing similar fabrics with opaque areas thereon produced by the commercially practiced aqueous printing technique and the known solvent-based Terakar printing technique, respectively. It is a ingredient. Hio (

Claims (1)

[Scope of Claims] 1. A printed textile fabric formed from intertwined threads of a predetermined color, wherein selected areas of the fabric are of a predetermined color that contrasts with the color of the threads. the printed pattern area is substantially opaque and is therefore unaffected by the color of the thread, and the pattern area covers the exposed surface of the intertwined threads; an opaque coating of said predetermined color that hides the color of the underlying yarn, said coating comprising an opacifying pigment that imparts opacity to said coating and curing that adheres to said yarn and binds said opacifying pigment to said yarn. A printed textile product fabric characterized by containing a water-insoluble polymer binder. 2. The printed textile product of claim 1, wherein the opaque coating including the patterned area covers each of the yarns in the printed areas such that the intertwined yarns of the fabric remain visible. fabric. 3. The printed textile fabric of claim 2, wherein the opaque coating individually confines and covers exposed fibers on the surface of the yarn such that the individual surface fibers of the yarn remain visible. 4. The printed textile fabric according to claim 1, 2 or 3, wherein the predetermined color of the printed pattern area is obtained by the color of the opacifying pigment. 5. The printed textile fabric according to claim 4, wherein the opacifying pigment comprises a white pigment. 6. The printed textile product according to any one of claims 1 to 5, wherein the coating further contains a colored pigment to impart a predetermined desired color to the printed pattern area. fabric. 7. The printed textile fabric according to any one of claims 1 to 6, wherein the coating further contains a dye to impart a predetermined desired color to the printed pattern area. . 8. The printed textile fabric of claim 7, wherein said polymeric binder contains reactive dye moieties available for binding with reactive dyes, and said dyes chemically react with said dye moieties. 9. Claim 7 or 9, wherein the dye is at least one selected from the group consisting of acid stone dyes, cationic dyes, direct dyes, disperse dyes, fiber-reactive dyes, mordant dyes, and solvent dyes; The printed textile fabric according to clause 8. 10 The printed pattern area is formed from a plurality of colors that contrast with each other and a predetermined color of the yarn, and at least one of the colors of the printed pattern area is a predetermined color of the yarn. The printed textile fabric according to any one of claims 1 to 9, which is brighter than the predetermined color. 11. Claim 1, wherein the polymer binder comprises crosslinked latex. 12. The printed textile fabric according to any one of claims 1 to 10. 12.
The printed textile product fabric according to any one of Item 1. 13. Any of claims 1 to 12, wherein the opaque coating contains an opacifying pigment, a crosslinked acrylic latex polymer, a heat-reactive acrylic resin crosslinked with the acrylic latex polymer, and a curing catalyst. The printed textile product fabric described in one of the above. 14. The printed textile fabric of claim 13, wherein the density of said opacifying pigment in said coating is greater than the total amount of said acrylic latex polymer and said acrylic resin. 15 The entire fabric is formed of dyed yarn of a predetermined color, selected areas of the fabric have a printed pattern area of a predetermined color that contrasts with the color of the thread, and the printed pattern area is 1) substantially opaque and therefore unaffected by the color of the thread, the patterned areas being formed from a plurality of colors that contrast with each other and with the predetermined dyed color of the thread;
of a color (one of which is lighter than the predetermined color in which the yarn was dyed, the patterned area extends beyond the exposed surface of the yarn, and includes a covering that conceals the underlying color; !
1. A printed textile fabric according to claim 1, comprising an opacifying pigment that imparts opacity to the inkstone and a hardened water-resistant polymer binder that binds the opacifying pigment to the yarn. 16. The printed pattern area is formed from a plurality of colors that contrast with each other and with the predetermined color of the thread, and at least one of the colors is lighter than the predetermined color of the thread. The printed fiber product fabric according to any one of Items 1 to 15. 17. The above opaque I71! A coating colors an opacifying pigment, a cross-linked acrylic latex polymer, a heat-reactive acrylic resin cross-linked with said acrylic latex polymer, a curing catalyst, and said latex polymer, thereby coloring said predetermined area in the printed area. A printed textile fabric according to any one of claims 1 to 16, which contains a color-giving dye. 18. Applying a printing paste containing a pigment and a thermoset binder to selected areas of the fabric, 7 then applying the printing paste to a substantially opaque solution of a predetermined color unaffected by the color of the underlying thread. A method of producing a printed textile fabric by drying and curing to obtain printed areas, the method comprising: applying to a fabric a printing paste comprising a stable dispersion of an opacifying pigment and an aqueous curable polymeric binder; in a dried and cured fabric in an amount sufficient to form an opaque coating of a predetermined color covering the exposed surface of the yarn and obscuring the underlying color. . 19. A method according to claim 18 in which the printing paste has a low solids content of 30% by weight. 20. The amount of the opacifying pigment in the printing paste is greater than or equal to the amount of the water-based curable polymeric binder. 21. The method according to claim 18 or 19, wherein the printing paste further contains a heat-reactive crosslinking agent. 22. Any one of claims 18 to 21, wherein the opaque pigment contains a white pigment.
the method of. 23. The method according to any one of claims 18 to 22, including the addition of a dye to provide the defined color. 24. The aqueous printing paste further contains a coloring pigment. 25. The step of applying an aqueous printing paste to the fabric comprises printing the paste onto the fabric at a printing station of a rotary stencil printing machine. 26. A patent in which the step of applying an aqueous printing paste to a fabric is carried out in a plurality of colors at successive stations of a rotating screen printing device. Claims (711, Paragraph 25). 27. Claims 18 to 26, wherein the step of applying an aqueous printing paste to the fabric comprises applying the printing paste to a previously colored fabric. Which of the following is the method described in one of the claims?28゜The pre-blued fabric is a relatively dark colored fabric, and the printing paste is a contrasting bright (white) paste.
The method according to item 27. In addition, according to any one of claims 18 to 28, wherein the aqueous printing paste further contains a curing catalyst; 30. The method of claim 29, wherein said catalyst comprises a sulfonic acid catalyst. 31. Any one of Clauses 18 to 30 of the clause in which the printing paste consists of the above-mentioned non-lightening pigment, an aqueous crosslinkable acrylic latex polymer, a heat-reactive crosslinkable acrylic surface, and a curing catalyst. The method described in.