MXPA99001609A - Process for treating a fibrous material and article thereof - Google Patents

Abstract

A process for treating a fibrous material which includes the steps of:1) providing a liquid suspension composed of fibrous material;2) intermixing the liquid suspension of fibrous material with a treatment over a time period T1 - wherein the treatment requires a period of time TR sufficient to treat the fibrous material;3) depositing the liquid suspension of fibrous material and intermixed treatment onto a forming surface to form a layer and removing a substantial portion of the liquid, over a period of time T2;and 4) applying pressurized jets of a liquid to the layer of fibrous material to wash unused treatment from the fibrous material within a period of time T3. Periods of time T1, T2 and T3 are immediately consecutive and amount to a total period of time at least as great as TR. Also disclosed is a hydraulically entangled structure composed of:1) at least one layer of a wet-laid nonwoven web containing fibrous cellulosic material;and 2) colorfast dye imparting color to the fibrous cellulosic material such that the fibrous cellulosic material is colorfast.

Description

PROCESS TO TREAT A FIBROUS MATERIAL AND ARTICLES FACED OF THE SAME FIELD OF THE INVENTION This invention relates to a method for treating a fibrous material. The invention also relates to a cellulosic material having a durable color.

BACKGROUND OF THE INVENTION There is a demand for non-woven materials containing cellulose fiber that are colored, that have a textile aesthetics and function, and that remain fixed under harsh chemical and abrasive use. It is highly desirable that such non-woven materials be washable and durable. It is also desired that such substrates be firm and lightweight.

These non-woven materials can be used to replace traditional textiles in applications that include, but are not limited to, wipes, clothing, equipment protection and bedding. Such products are used in a wide range of industries including manufacturing, medical, printing, spray painting, clothing and food service.

The insoluble coloring pigments are used to color non-woven materials containing cellulose fiber. These pigments are generally inorganic or contain a synthetic organic base. A fixing agent is typically used to improve firmness because these coloring pigments are insoluble in the application medium and do not readily migrate to or attach to the cellulose fibers. Useful binding agents include alum, caseins, starches, acrylics, resin sizing, polyvinyl alcohols, cationic dye mordants. Generally speaking, these mordants only modestly improve durability.

Soft polymeric adhesive binders or resins are also used as fixing agents. These improve the durability by encapsulating and binding the insoluble pigment on the surfaces of the fibers. Binders and resins have limited use because they are a surface treatment and generally only have a moderate firmness. Deeper shades of color require an excess of pigment and binder or resin that tend to be removed or glazed. In addition, high levels of pigment act as fillers and can physically weaken a leaf. Binders or resins also make non-woven materials stiffer and damage textile-like aesthetics while they frequently negatively impact the distribution properties and liquid absorbency.

Binders and resins are often soluble in many common volatile and semi-volatile commercial and industrial solvents and liquids and can run off the non-woven material leaving undesirable residues and scratches. When used on hot surfaces or at a high temperature, the resin or binder on the colored non-woven materials can migrate, soften, degrade, and alter the properties of the non-woven material and / or leave residues. Another disadvantage of the binder and resin coloring systems is that they are often added to the dried leaves using sizing presses, saturation techniques or printing operations and then dried again. Many binders are also applied as a secondary process offline to the production of the base sheet which also increases costs.

Dry dyes are also used to color cellulose fibers and non-wovens containing cellulose fibers. Dyes, dye dyes, or dye materials are generally cataloged in numerous classes according to the application. These categories include: basic, acid, direct (including cationic direct), mordant, azo, dispersed, reactive, of sulfur and of tub. These dyes have a wide range of cost, properties of inking and firmness. In addition, the method for applying such dyes ranges widely from a simple introduction to suspended fabrics and supplies to multi-phase chemical processes.

The dyes are physically or chemically bonded to the fiber to provide a durable color. These are typically linked by one or more forces including physical entrapment, hydrogen bonding, van der Waals forces, coordinate binding, ionic forces or covalent bonds. Generally speaking, the dyes are usually fixed or permanent in only certain aspects or under certain conditions.

It is desirable for dye dyes to be resistant to light and water. It is also desirable that a dye dye support other influences found in industrial commercial applications of nonwovens containing cellulose fibers. These include, but are not limited to, bleaches and detergents used during washing and soaking for stain removal; cleaners include acids such as vinegar and bases; and a long list of industrial chemicals including oils, cutting oils and solvents having a wide range of dipole moments such as: acetone, methylene chloride, 1,1,1 trichloroethane and various alcohols, acetones, benzene, naphthalene and mineral spirits.

Generally speaking, basic dyes have poor light fixation and are susceptible to uneven coloration of cellulose fibers (eg, paper fibers). Acid dyes are easily susceptible to bleeding with water due to their low affinity with cellulose fibers. The direct or substantive dyes will color the cellulose fibers without the use of mordants or dyeing aids. However, they tend to lack the necessary general chemical firmness even with the use of mordant cationic fixing agents, formaldehydes or coupling compounds. Direct dyes generally lack firmness as the forces that bind them break easily.

Generally speaking, mordant dyes have no affinity with cellulose fibers and require the use of a metal oxide treatment for good firmness properties. Azo dyes require coupling of two dye components on the fiber but lack the general chemical binding requirements and are usually limited to only a few cellulosic applications. Disperse dyes are typically used to color the hydrophobic fibers and are fine-sized organic compounds with a peel strength and limited solubility.

The reactive dyes can be described as acid, basic or mordant dye with a reactive reacted group which is capable of covalently binding to a cellulose fiber.

Good firmness is typically obtained by converting the soluble compounds to relatively insoluble compounds within the fiber. Tub and sulphide dyes are insoluble and therefore must be modified before coloring the fiber. With these dyes, the insoluble dye is first reduced to the soluble leuco compound and after integration into the fiber it is oxidized back to the insoluble form using sodium sul typically for sulfur dyes and sodium perborate for dyes of tina.

The cellulose fibers can be dyed using a variety of methods ranging from dyeing the individual fibers to consolidated fabrics and by dyeing at points within the construction process of the non-woven fabric. Exemplary methods include the coloring of materials or beater within the solution or sediment for dyeing fabrics by compensation, jigger embedding, dye baths, squeezing, extraction operations, dyeing of foam curtain, and printing. Many of these methods are off-line textile finishing processes.

Specialized methods of loading-pad, thermoset-pad and steam-pad have been developed and modified versions for continuous operations with numerous steps for reactive dyes by cushioning the fabric with the dye solution. The fabric is then either stored for extended reaction times in a vapor proof cover or heated with steam, further padded, and then the fabric is washed to remove the spent chemical.

Continuous low speed pad-jigger methods and steam pad methods are frequently employed for permanent dyeing of fabrics with tub dyes. Suitable reaction times have been achieved especially at high temperatures. After the chemical dyeing using the reagent and vat dyes, a washing step or steps was added to remove the unreacted spent chemicals since the reaction is not 100 percent complete. More permanent dyes generally require several steps of chemical process and extended reaction times.

While reactive dyes, vat dyes and sulfur dyes seem desirable for use with cellulose fibers, the application of these dyes requires more than one process step and is frequently hindered by slow line speeds necessary to achieve adequate reaction times.

Therefore there is a need for a simple process for applying reactive dyes, tub dyes and sulfur dyes to cellulose fibers and to non-wovens containing cellulose fiber to produce a durable coloration. This need extends to a continuous process or step to apply such dyes to the described substrates so that they are solid in color. This need also extends to a process for applying such dyes that is suitable for high speed manufacturing processes. There is also a need for solid color cellulose fibers, non-woven materials containing solid color cellulose fibers, and solid color nonwoven materials including cellulose fibers that have been prepared in a simple one-step process.

DEFINITIONS As used herein, the term "non-woven fabric" refers to a fabric or fabric having a structure of individual fibers or filaments which are interleaved, but not in a repetitive and identifiable manner. Non-woven fabrics have been formed, in the past, through a variety of processes known to those skilled in the art, such as, for example, meltblowing, spin-bonding, wet-forming and various processes of bonded carded fabric.

The term "pulp" as used herein refers to cellulosic fibers from natural sources such as woody and non-woody plants. Woody plants include, for example, deciduous and coniferous trees. Non-woody plants include, for example, cotton, flax, esparto grass, winnowing, straw, hemp jute, and bagasse.

The terms "solid color" and / or "firmness" refer to the extent to which the color will fade or change with exposure to such an agent, such as, for example, sunlight, reactive gases, chemicals, solvents and the like. Color fastness or firmness can be measured by standard test methods such as, for example, the AATCC 3-1989 test method.

The terms "detachment" or "detachment firmness" refers to the extent to which color can be transferred from the surface of a dyed fabric to another surface by rubbing. The detachment test can be carried out using standard testing methods and equipment such as, for example, the AATCC model release meter CM.5, available from Atlas Electric Devices, Company of Chicago Illinois.

As used herein, the term "sheet" refers to a material that can be a woven fabric, a woven fabric, a non-woven fabric, or a film type material (e.g. a perforated film type material) .

As used herein, the term "spunbonded filaments" refers to small diameter continuous filaments which are formed by extruding a melted thermoplastic material as filaments from a plurality of capillary, usually circular and thin vessels of a spinning organ with the diameter of the extruded filaments then being rapidly reduced as by, for example, the eductive pull and / or other well-known splicing mechanisms. The production of non-woven fabrics bonded by spinning is illustrated in the patents such as, for example, in U.S. Patent No. 4,340,563 issued to Appel et al., And in U.S. Patent No. 3,692,618 issued to Dorschner and others. The descriptions of these patents are incorporated herein by reference.

As used herein, the term "conjugated spun filaments" refers to spun filaments and / or fibers composed of filamentary or fibril elements. Exemplary conjugated filaments may have a sheath / core configuration (e.g., a core part essentially or completely wrapped by one or more pods) and / or a configuration of yarns (for example filaments) from side to side (for example, a plurality of filaments / fibers joined along a common interface). Generally speaking, the different elements that make up the conjugated filament (for example, the core part, the sheath part and / or the side-by-side filaments) are formed from different polymers and from the processes using spinning such as, for example , melt spinning processes, solvent spinning processes and the like. Desirably, the conjugated spun filaments are formed from thermoplastic polymers using a melt spinning process such as a spin-jointing process adapted to produce conjugate spunbond filaments.

As used herein, the term "hydraulic entanglement" refers to a method for mechanically joining a fibrous material by treatment with the pressurized jets of liquid. Exemplary hydraulic entanglement processes are described in, for example, U.S. Patent No. 3,485,706 issued to Evans et al .; U.S. Patent No. 4,939,016 issued to Radwanski et al .; and U.S. Patent No. 5,389,202 issued to Everhart et al.

As used herein, the term "hydraulic drilling" refers to a method for releasing, opening, rearrange and / or modify a relatively compact network of fibrous material using the pressurized jets of a liquid. An exemplary hydraulic drilling process is described in, for example, United States Patent No. 5,137,600 issued to Barnes et al.

As used herein, the term "consisting essentially of" does not exclude the presence of additional materials which do not significantly affect the desired characteristics of a given composition or product. Exemplary materials of this kind may include, without limitation, pigments, antioxidants, stabilizers, surfactants, waxes, flow promoters, particulates or aggregate materials to improve the processability of a composition.

SYNTHESIS OF THE INVENTION The problems described above are examined by the present invention which is directed to a process for treating a fibrous material. The process includes the steps of: 1) providing a liquid suspension composed of fibrous material; 2) between mixing the liquid suspension of the fibrous material with a treatment for a period of time T! - wherein the treatment requires a period of time TR to treat the fibrous material; 3) deposit the liquid suspension of fibrous material and the intermixed treatment on a forming surface to form a layer and remove a substantial part of the liquid, over a period of time T2; and 4) applying pressurized jets of a liquid to the layer of fibrous material to wash the unused treatment of the fibrous material within a period of time T3. According to the invention, the time periods Tt, T2 and T3 are immediately consecutive and constitute a total time period at least as large as TR.

The liquid suspension of fibrous material may be an aqueous suspension and may contain a fibrous material such as, for example, polyester fibers and / or cellulose-containing fibers. Desirably, cellulosic fibers are cellulosic and treated fibers. Generally speaking, the fibrous cellulosic material may be of pulp fibers, synthetic cellulose fibers, modified cellulose fibers, and combinations thereof The fibrous cellulosic material may include particulates, non-cellulosic fibrous materials and / or other materials.

According to the invention, the treatment is desirably a chemically reactive treatment. The chemically reactive treatment may be one or more of reactive dyes, vat dyes and sulfur dyes.

In one aspect of the invention, the deposited layer of fibrous material and intermixed treatment may be formed into a fabric or a sheet-like structure. This fabric may be smooth or it may have patterns, striae, stops, loins or the like.

The forming surface which receives the deposited layer may include at least one layer of sheet material between the forming surface and the deposited layer of fibrous material and an intermixed treatment. This sheet material can be one or more non-woven fabrics, textile fabrics, canvas materials, plexifilamentary films, tow and combinations thereof. For example, non-woven fabrics may be one or more meltblown fabrics, spunbonded fabrics, gauze fabrics and combinations thereof. Additional layers of the sheet material can be placed on the deposited layer of the fibrous material. According to one embodiment of the invention, the deposited layer of the fibrous material can be placed in the form of a sandwich between two layers of the sheet material. Alternatively and / or additionally, the fabric may be formed separately and then joined to another layer of material (e.g., a non-woven fabric bonded by spinning or the like) prior to treatment with pressurized jets of a liquid.

According to the invention, the applied pressurized liquid jets used to wash the unused treatment of the fibrous material may also be sufficient to entangle the fibrous material hydraulically. The hydraulic entanglement can be limited to only the fibrous material or it can involve the fibrous material and one or more layers of the sheet material described above. Alternatively and / or additionally, the applied pressurized liquid jets used to wash the unused treatment of the fibrous material may also be sufficient to hydrolyse the fibrous material. Hydraulic drilling may be limited to only the fibrous material or may involve the fibrous material and one or more layers of the sheet material described above.

- The process of the present invention can include a step (for example at least one) or more secondary or post-processing steps. The post-treatment steps for example include additional washing steps, drying steps, etching steps, drilling steps, adding a setting agent, setting agent, mechanical smoothing, cutting, rolling steps and Similar.

The present invention encompasses a product produced by the process described above. The product is a fabric or a sheet type material composed of the treated fibrous material or including it. For example, the product can be a fabric compound or including a solid color fibrous cellulose material.

In one aspect of the invention, TR may vary from a few minutes to an hour or more. T1, T2 and T3 can each vary individually from less than one second to several minutes to an hour or more as long as they are immediately consecutive (for example without significant time separations, of time without work or of time off line between at minus T2 and T3) and constitute a total time period at least as large as TR.

In one embodiment, the present invention encompasses a process for forming a tissue of a treated fibrous cellulosic material. The process includes the steps of: 1) providing an aqueous suspension including a hydrated fibrous cellulose material; 2) intermixing the aqueous suspension of the hydrated fibrous cellulose material with a reactive treatment over a period of time TI (the treatment requiring a period of time TR sufficient to treat the fibrous cellulose material; 3) depositing the aqueous suspension of the hydrated fibrous cellulose material and intermixing the reactive treatment on a surface to form a weave and remove a substantial part of the aqueous liquid, over a period of time T2; and 3) applying pressurized jets of a liquid to the fabric to wash the unused reactive treatment of the fabric within a T3 period of time; where Tj, T2 and T3 are immediately consecutive and constitute a time period of at least as great as TR.

Desirably, the chemically reactive treatment is selected from reactive dyes, vat dyes and sulfur dyes. If a tub dye is employed, the process is practiced so that the tub dye is reduced to its soluble leuco form and subsequently converted to an insoluble form during the TR time period.

The process can be practiced so that the forming surface includes at least one layer of a sheet material between the forming surface and the deposited layer of fibrous material and the intermixed treatment. Alternatively and / or additionally, the deposited layer of fibrous material can be formed separately and then joined to one or more layers of the same or another material (for example a non-woven fabric bonded by spinning or the like) before treatment with jets of a liquid pressurized The fibrous cellulosic material can be one or more of pulp fibers, synthetic cellulose fibers and combinations thereof.

According to the invention, the jets of a liquid can be adapted to hydraulically entangle the fabric.

Alternatively, the jets of a liquid can be adapted to hydraulically drill the fabric. Of course, the process of the present invention may also include at least one subsequent processing step.

Another embodiment of the invention encompasses a process for forming a fabric of a solid color fibrous cellulosic material. The process includes the steps of: 1) providing an aqueous suspension comprising a hydrated fibrous cellulose material; 2) intermixing the aqueous suspension of the hydrated fibrous cellulose material with a reactive treatment over a period of time Tl t said treatment is selected from reactive dyes, vat dyes and sulfur dyes requiring a sufficient TR time period to treat the fibrous cellulose material; 3) depositing the aqueous suspension of the hydrated fibrous cellulosic material and intermixing the reactive treatment on a surface to form a tissue and remove a substantial part of the aqueous liquid, over a period of time T2; and 3) applying pressurized jets of a liquid to the fabric to wash the unused reactive treatment of the fabric for a period of time T3; where T ^ T2 and T3 are immediately consecutive and constitute a time period of at least as great as TR.

If a vat dye is used, the process is practiced so that the vat dye is reduced to its shape soluble leuco and subsequently converted to an insoluble form during the TR time period.

The forming surface may include at least one layer of a sheet material between the forming surface and the deposited layer of the fibrous cellulose material and the intermixed reactive treatment. Alternatively and / or additionally, the deposited layer of the fibrous cellulosic material can be formed separately and then joined to one or more layers of the same or another material (eg, a non-woven fabric bonded by spinning or the like) before treatment with the jets pressurized of a liquid. The fibrous cellulosic material can be one or more of the pulp fibers, the synthetic cellulose fibers, the modified cellulose fibers and the combinations thereof.

According to the invention, the pressurized jets of a liquid can be adapted to hydraulically entangle the fabric. Alternatively, the pressurized jets of a liquid can be adapted to hydraulically drill the tissue. Of course, the process of the present invention may also include at least one subsequent processing step.

The present invention also encompasses a hydraulically entangled structure composed of a material fibrous solid color. The structure is composed of: 1) at least one layer of a non-woven fabric placed in wet containing a fibrous cellulose material; and 2) dyeing with solid color imparting color to the fibrous cellulose material so that the fibrous cellulosic material is solid in color.

The wet-laid nonwoven fabric component of hydraulically entangled structure may include a layer of a sheet material. The sheet material can be selected from the spunbond fabrics, the meltblown fabrics, the bonded and knitted fabrics, the woven fabrics, the weft fabrics, the canvases and combinations thereof. Alternatively and / or additionally, the hydraulically entangled structure of solid color fibrous material may include a matrix of adhesive material. The adhesive material can be a resin or rubber. The solid color dye component of the hydraulically entangled structure can be selected from reactive dyes, vat dyes and sulfur dyes.

The present invention also encompasses a hydraulically drilled structure composed of a solid colored fibrous material. The structure is composed of: 1) at least one layer of a non-woven fabric placed in wet containing a fibrous cellulose material; and 2) dyeing with solid color to impart color to the fibrous cellulosic material so that the fibrous cellulosic material is solid in color.

The hydraulically drilled structure of the solid colored fibrous material may include a matrix of an adhesive material. The adhesive material can be a resin or a gum. The solid color dye component of the hydraulically drilled structure can be selected from reactive dyes, vat dyes and sulfur dyes.

BRIEF DESCRIPTION OF THE DRAWING Figure 1 is an illustration of an example process for treating a fibrous material.

DETAILED DESCRIPTION OF THE INVENTION Referring now to Figure 1, an illustration (not necessarily to scale) of an example process for treating a fibrous material is shown, Generally speaking, the treatment process can be incorporated into a fiber preparation phase and a high speed wet setting fabric forming operation which is coupled with a pressurized liquid jet operation where the unused or spent treatment and / or the chemicals are washed out of the fibrous material.For example, the treatment process may be incorporated into a pulp-reduction preparation phase and material from a high-speed papermaking operation that is coupled with a tangled operation Hydraulic or hydraulic drilling where unused or worn treatment and / or chemicals are washed from the fibrous material. However, it should be understood that the present invention is not limited to such configuration.

According to one embodiment of the present invention, a fibrous material 10 can be placed in a pulp reducer or prep beater of fiber material for making conventional paper 12 containing a liquid (usually water). If the fibers are of cellulosic nature, said fibers can be refined in the pulp beater or reducer until they are hydrated. The supply of fibrous material is maintained in a continuous agitation to form a liquid suspension.

A treatment is added to the fibrous material in the pulp reducer or beater 12. If the fibrous material is cellulosic, the treatment is desirably added after the fibers have been hydrated. The treatment can be solid, liquid or gaseous or combinations thereof. For example, the treatment may be in the form of pellets that dissolve in the liquid medium used to suspend the fibrous material. Alternatively, and / or additionally, the treatment may be in the form of a liquid added into the liquid medium or a gas that is blown into said liquid medium. The treatment can be composed of one or more components, reagents and / or phases added to the fibrous material at the same time or at different times.

Generally speaking, the fibrous material is maintained in a continuous agitation thereby intermingling the liquid suspension of the fibrous material and the treatment. However, the agitation may be stopped or used intermittently if excessive agitation could be harmful to the treatment or to the fibrous material. For example, agitation can be reduced if the air trapped by the agitation can oxidize or react with the treatment and reduce its effectiveness.

After the fiber treatment (for example, dyeing) inside the beater or reducer. pulp 12, the fibrous material suspension and the intermixed treatment (e.g., the delivery solution) is then diluted and readied for formation in a layer of fibrous or woven material using conventional papermaking or wet laying techniques . The supply solution 14 can be stored in a machine chest 15 before tissue formation. If desired, the pH supply solution can be adjusted for equipment compatibility.

The mordants and additives can be added to the pulp reducer, to the chest of the machine or immediately before the formation. These materials can be added to improve fixation and other properties such as softness and wet strength. If desired, additional fibrous materials may be added. These materials may have the same or a different treatment. For example, these additional materials may have the same color or a different color. Examples of the fibrous materials that can be added include wood finishes, other cellulosic fibers, short fibers that are formed in wet non-cellulosic and synthetic fibers and the like.

These fibrous materials can be added to the supply solution prior to tissue formation to improve strength, aesthetics, and durability properties. These can also be handled as a solution or separate solutions if one or more layers of different fiber types are desired.

Even though the non-cellulose fibrous material (eg short fibers) can be treated or dyed in a separate process, it is contemplated that these can be treated or dyed within the same system as the cellulosic fibrous material. For example, certain conventional vat dyes can be used to dye the fibrous polyester material using heat setting. The short non-cellulosic synthetic fibers include polypropylene, polyester, nylon and polyethylene fibers.

The diluted aqueous suspension (for example the delivery solution) 14 is carried and formed on a mobile foraminous forming wire 16 using a conventional paper making head box 18 or a head box for layers with a forming section such as a Fourdrinier wire. or inclination. The tilt wire is generally used to wet relatively long fibers such as, for example, short fibers. According to the present invention, machine tissue speeds for making high speed paper up to 2,000 feet per minute (fpm) or more can be used. These speeds can be much higher than those of the conventional continuous reactive dyeing and dyeing processes. Fabric speeds in such conventional textile processes can reach up to 360 fpm using improved festoon trajectory paths and washers.

After the aqueous solution (e.g., the supply solution) is formed into a tissue 20 and sufficiently drained (typically at consistencies greater than 18 percent), the pressurized jets of a liquid are applied to the fabric while it is on the forming fabric. Alternatively, the fabric can be transferred to a different moving fabric 22 or to the movable drum (not shown) where the pressurized jets of a liquid are applied using a pressurized liquid jet forming apparatus such as, for example, the conventional hydraulic entanglement 24.

Generally speaking, after treatments such as reagent or tub dyeing, the fibrous colored material must be washed to remove the non-fixed and hydrolyzed dye as well as the spent chemicals. If this washing step is not done, the presentation of fabric, the firmness and the stability of the color can be impaired. In addition, the washing step helps remove undesirable chemical residue that could present safety problems, problems for people who have unprotected skin contact with the residue. Washing also helps to minimize or eliminate the undesirable cleaning residue that could be used by the chemical left on the sheet. With most conventional textile fabric ink and reagent ink coloring systems, the washing step is necessary. A hot detergent bath is frequently used in the wash step of such conventional systems. However, these systems tend to be slow and are often carried out in separate operations not connected to the fabric forming process.

According to the present invention, the spent or unused excess treatment (for example the dyeing chemical) can be effectively removed from the fibrous / woven material by using pressurized jets of a liquid such as, for example, the hydraulic entanglement jets. . This can be attributed to the high speeds and high volumes of liquids (typically water) used. The effective washing it is also due to individual treated fibers that are thoroughly washed with the first multiple of hydraulic entanglement while the fibers are still loose and mobile before being impacted and entangled within the fiber matrix of the fabric.

The soaps and warm detergents can be incorporated into the pressurized liquid jets used to wash the tissues. However, the action of washing and high cutting of the jets can be adapted to remove unused treatments so that washing with soap / detergent is not required. The use of such high pressure liquid jets immediately after tissue formation of a liquid suspension to wash the fabric can eliminate the further washing steps.

In an embodiment of the invention, the hydraulic entanglement or hydraulic drilling steps are combined with the washing steps so that additional washing equipment and / or fabric consolidation equipment can be removed.

For example, the pressurized jets of a liquid may be adapted to hydraulically entangle the fabric. Hydraulic entanglement can be achieved using conventional hydraulic entanglement equipment 24 such as can be found in, for example, United States Patent No. 3,485,706 issued to Evans, whose description it is incorporated here by reference. The hydraulic entanglement of the present invention can be carried out with any suitable working fluid such as, for example, water.

Alternatively, the pressurized jets of a liquid can be adapted to hydraulically drill the tissue. Hydraulic drilling can be accomplished using a process and equipment such as can be found in, for example, U.S. Patent No. 5,137,600 issued August 11, 1992 to Barnes et al., The disclosure of which is incorporated herein by reference. The hydraulic drilling of the present invention can be carried out with any suitable working fluid such as, for example, water.

The aqueous suspensions of the fibrous material and the intermixed treatment can also be wet-formed on a substrate material such as, for example, an unwoven fabric. In some cases, the substrate material is treated with surfactant and divided vacuum drainage areas are used. The treated fibrous material (for example the solid colored fibers) and the preformed synthetic nonwoven fabric can be treated with pressurized jets of a liquid (for example hydraulically entangled) on the forming wire or downstream on another section of wire or a perforated drum. .

Substrates such as, for example, woven or non-woven fabrics 26 can also be easily added upstream of the hydraulic entangling equipment 24 after the fibrous or woven material layer 20 has been formed. Generally speaking, such techniques are described. in, for example, U.S. Patent No. 5,389,202 issued February 14, 1995 to Everhart et al., the disclosure of which is incorporated herein by reference. Other layers can be added on top of the fibrous layer 20 to form a multilayer fabric (for example of three or more layers). A wide variety of substrates are contemplated. For example, if the substrate is a non-woven fabric, it can include continuous filaments such as those joined by spinning and netting, melt blowing fabrics, coform combinations, short fiber fabrics formed by air and carded and combinations thereof. . Such fabrics can be made of elastic or non-elastic yarns. The fibers and / or filaments can be made from thermoplastic or thermoplastic polymers.

Any one or both sides of the materials can be treated with pressurized jets of a liquid. It is contemplated that the liquid jets can be used to form a pattern of materials to produce a cloth type aesthetic using selective entanglement backings.

Water discharged from the first jet streams (eg hydraulic entanglement) of pressurized liquid can be isolated from the multiple streams downstream as these are richer in the washout treatments such as, for example, exhausted dye chemicals. The spent chemical and water can be treated and either reused within the process or sent to another site of the paper machine processes that require less severe water conditions.

After the washing step, additional mechanical and / or chemical treatments may be applied. 28. For example, additional washing or the application of liquid treatments can be achieved by using spraying, embedding and squeezing techniques, liquid curtains Vacuum extraction processes or similar. An example of a suitable process for applying liquid is described, for example, in United States Patent No. 5,486,381 entitled "Liquid Saturation Process" and issued on January 23, 1996 to Cleveland et al. Incorporate here by reference.

Such equipment can also be used to add other types of chemicals or treatments including, for example, biting agents. With fabric washed from treatments such as, for example, exhausted dye, several agents can be used at lower amounts than if they are introduced in the prep phase of fiber supply (for example in the pulp reducer or beater 12) to better fix the treatment since the fugitive treatment has been washed off the fabric. For example, less dye fixing chemical may be required to fix the dye molecules diffused into or attached to the individual fibers since excess dye or fugitive dye has washed away from the surface and interstices of the fibrous material.

Other chemicals can also be added including wet strength resins, binders, brighteners, flame retardants, germicides, softeners, starches, corrosion inhibitors and a wide range of textile finishes. Citric acid and ethylene diamine can also be added to improve the stain properties of the colorant.

The treated and washed material can be dried. Air drying processes and drying processes can be found to work well. Other drying processes which incorporate infrared radiation, Yankee dryers, vacuum dewatering, microwaves and ultrasonic energy can also be used. Subsequent thermal treatments may be used alone or in combination with the drying step to melt a part of any fibers thermally fusible that may be present in the material.

It may be desirable to use certain steps and / or post processing processes to impart selected properties to the material. For example, the material may be lightly pressed by the calendering rollers, creped or brushed to provide a uniform exterior appearance and / or certain tactile properties. Alternatively and / or additionally, subsequent chemical treatments such as adhesives or dyes may be added to the fabric.

The material can also be creped and / or mechanically smoothed wet or dry through other methods to improve softness and feel or the creped adhesive to improve the strength and volume properties. The printed finishes can also be applied to improve aesthetics. Such processes may be in line before the winding of the fabric on the roll 32 or off line.

A variety of fibrous materials can be used in the present invention. Generally speaking, the fibrous material must be capable of withstanding potentially aggressive or deleterious treatments such as, for example, reactive treatments or treatments that require a relatively long residence or exposure time. Some fibers that may be used include, but are not limited to, pulp, cellulosic fibers including natural, synthetic and modified cellulose fibers, and polyester fibers, and combinations thereof.

Cellulose fiber sources for processing (eg dyeing) include virgin wood fibers such as hardwood and softwood bleached and unbleached thermomechanical wood pulp. The secondary or recycled fibers can be used. These fibers can be obtained from sources such as office waste, newspaper, supply of brown paper and cardboard cut-outs. Plant fibers can be used. These include hemp, abaca, flax, benzene, cotton, modified cotton and cotton lint. Synthetic cellulosic fibers such as, for example, rayon and viscose rayon can also be used. Another exemplary type of synthetic cellulose is available under the trade designation "Lyocell" from Cortaulds. Modified cellulose fiber can also be used. For example, the fibrous material can be composed of cellulose derivatives formed by substitution of appropriate radicals (eg, carboxyl, alkyl, acetate, nitrate, etc.) for the hydroxyl groups along the carbon chain. These fibers can also be used alone, in combination with other cellulosic fibers and / or non-cellulosic fibers. The particulates and / or other materials can also be used with fibrous materials.

When wood pulp is used (eg wood fibers), consistencies of supply of up to about 12 percent can be easily treated (eg, dyed). After the cellulosic fibers have been completely hydrated, they are completely loose, and the fiber lumen has swelled by accessibility, the impregnation of a treatment (for example the dye molecule) within the fiber structure is more completely achieved and more effectively. Less treatment (for example less dyeing) may be used under these conditions compared to conventional fabric treatments (for example fabric dyeing). Additional benefits may be realized if the treatment is a dyeing treatment. For example, in situations where excess dye is used to obtain deep levels of color, a better incorporation of the dye into the fibers produces better color fastness.

Although the inventors should not rely on a particular theory of operation, the process of the present invention intermixes individual, agitated and freely suspended fibers with a treatment (a dyeing treatment). It is thought that a more effective and complete coloration can be obtained since the migration of the dye / chemical treatment inside the individual fibers is not impaired.

In contrast, fibers already fixed and embedded within a consolidated fabric are thought to prevent migration of the dye treatment / chemical into individual fibers. In addition, many treatments and dyes have a strong affinity for cellulose which can make a uniform penetration difficult within the already fixed and embedded fibers in consolidated tissues. The process of the present invention is thought to provide a more uniform application of the treatment than many conventional methods such as, for example, compensation methods.

The fiber supply preparation step of the present invention allows control of the long reaction times that may be necessary for some treatments (for example, to properly fix the dye treatments). For example, reaction times typically greater than 60 seconds and often one hour or longer may be performed. According to the present invention, the temperature of the liquid suspension of the fibrous material and of the intermixed treatment can also be controlled to facilitate optimal reaction kinetics.

The present invention contemplates a variety of treatments for fibrous materials. The treatments can interact with the fibrous material in many ways including, but not limited to coating, reaction, diffusion and fixation. Multiple component treatments can be used. The treatments can also be used having several different reagents. In one aspect of the invention, the treatments will react with the surface of the fibrous material. In another aspect of the invention, the treatments can diffuse into the fibrous material and react with the fibrous material. In another aspect of the invention, the treatment can diffuse into the fibrous material or coat the surface of the fibrous material and then react with another treatment component or agent to fix the treatment in the fibrous material or on the fibrous material.

Exemplary treatments include acid treatments, caustic or base treatments, single and multicomponent reagents, reactive dyes and the like can be used, either alone or in combination. Certain types of dye treatments have been found to work well in the process of the present invention. For example, the process of the present invention can be used to dye fibrous materials using reactive dyes, tub dyes or sulfur dyes.

Desirable treatments include reactive dyes. Generally speaking, these dyes are used with fibrous cellulosic materials. Although the inventors do not wish to be bound by a particular theory of operation, it is generally thought that such dyes are covalently bound to the fiber. The reactive functional groups in the dyes are typically designated to react with the cellulosic fiber frequently and preferably after diffusion into the fiber structure. These functional groups are designed to remain stable and not react with the medium used to apply the dye. It is desired that such dyes be able to function when water is used as the means to apply the dye. The functional groups of these dyes can react with the cellulose hydroxyl groups to form the covalent dye-fiber cellulose ester bonds that provide a durable color.

Water hardness may require an adjustment when these dyes are used in aqueous fiber handling systems. The level of adjustment can easily be determined by one with an ordinary skill in the art. The reactive dyes are generally added to the cellulosic fibers in the beater or in the pulp reducer after hydration. An electrolyte salt such as, for example, magnesium sulfate or sodium chloride can be added. Generally speaking, the pH of the liquid suspension of fibers and the dye Intermixed reagent is raised to alkali levels to improve the reactivity between the dye and the fibers. For example, the pH may be raised to about 11 or 12. Alkali material such as, for example, sodium bicarbonate (sodium hydroxide) or sodium bicarbonate may be used. The temperatures of the dye and fiber mixture can be increased and maintained at high levels. The reaction time in general or the period of time necessary to adequately treat / dye the fiber (TR) may vary from less than 60 seconds to more than 120 minutes. Exemplary reactive dyes include the Procion® H and M series (from ICI Americas, Inc.) and the Cibacron® series (Ciba-Geigy). These dyes have desired levels of water solubility.

The reactive dyes have good light and wet firmness but lack bleached fixity. With the use of secondary treatments after dyeing such as the use of urea, cationic fixing agents, and resins, modest improvements can be made. For many applications that need more severe fixation requirements, tub dyes can be used.

When used with the cellulosic fibrous material, tub dyes can be added to the pulper or pulp reducer after the fibrous material is hydrated. When aqueous suspensions or fibers are employed, vat dyes are typically insoluble in water and must first reduce to produce a water soluble form. This can be achieved in the pulper or pulper in conventional conditions. For example, consistencies of up to 12 percent can be used. The hardness of the water can be adjusted to improve the water solubility of the vat dye. Sodium sulfate can be added to facilitate the impregnation of dye inside cellulose fibers. The presence of calcium, magnesium, aluminum and similar polyvalent ions can negatively affect the solubility of a vat dye.

Generally speaking, vat dyes are converted in an insoluble form into water in a water-soluble "colorless" leuco-sodic form. This can be achieved by adding an aqueous alkali solution of caustic soda (sodium hydroxide) and a sodium hydrosulfite reducing agent (sodium dithionite). The specific chemistry may vary with particular tub dyes but carrying out this step can be accomplished by one of ordinary skill in the art of tub dyeing.

After the vat dye is solubilized, the leuco-sodium form has good affinity for the cellulose fibers and therefore impregnates the fiber structure. If it is not in this form, there is very little or no impregnation within the fiber. Tub dyes tend to impregnate fiber less than other dyes so care must be taken in the application to produce good fixity. The consistency of the fiber suspension, the agitation, and the dye, the chemical, the electrolyte concentrations and the addition rates are variables that may require adjustment. Such adjustments can be made by one with an ordinary skill in the art of tub dyeing. The unsuitable addition can produce uneven coloring. If the impregnation within the fiber does not occur properly, when the leuco form is oxidized back to the insoluble pigment, the vat dye will simply wash off. The typical time period or reaction times (TR) for good dye impregnation and depletion in the embodiments of the present invention is about 30-45 minutes. In some interpretations of the present invention, the time needed (TR) for an adequate treatment may still be shorter. For example, the appropriate treatment can be carried out over a period of 10 minutes.

The water-soluble form of the vat dye which is impregnated in the fiber is then oxidized back to the insoluble form in water. This oxidation step is also a component of the time period or reaction time (TR) necessary to treat the fibrous material. The oxidation reaction usually occurs simply by exposing the impregnated fiber to the air and with continued agitation. Materials such as, for example, sodium perborate, sodium bichromate and / or sodium or calcium hypochlorite can added to reduce the oxidation reaction time. In some cases, an acid can be added to achieve high levels of oxidation.

Tub dyes can be classified into two categories: anthraquinonoid and indigoid dyes. Both can be used in the practice of the present invention. Examples of anthraquinone dyes include Cibanone® dyes (from Ciba-Geigy), Sandothrene® dyes (Sandoz) and Caledon® dyes (ICI). Indigoid dyes include dyes Durindone® (ICI) and blue Ciba 2B (Ciba-Geigy). The water-soluble sulfate esters of leuco vat dyes can also be used. i: E E M P L O S 1 - 15. z. . .

Different reactive dyes, vat dyes and direct dyes were used to treat wood fibers. The dyes were used alone or in combination with fixation treatments. Dyes and fixatives are available from Ciba-Geigy Corporation, of Basel, Switzerland. The vat dyes of the Cibanone® series, the reactive dyes of the Cibacron® series, the cationic direct dyes of the Pergasol® series and the NF Tinofix® liquid fixative used in the examples are identified in Table 1.

The wood fiber supply used for the dyeing studies was softwood kraft pulp from the northern bleached Terrace Bay Longlac 19, available from Kimberly-Clark Corporation, of Roswell, Georgia.

The percentage amounts of the formulas or recipes for tub dyes, reactive dyes and fixation treatments are based on pounds of ingredient per ton of wood fiber (eg pounds of ingredient / 2, 000 of wood fiber) where the wood fiber has an estimated moisture content of 7 percent. The percentage amounts for other aggregate materials are based on the grams of ingredient per 100 grams of wood fiber or of another supply (for example, grams of ingredients or 10 grams of "wood fiber or other" supply). ) the reactions were typically carried out at ambient temperatures, under agitation, and the hardness of the water was adjusted to approximately 100 PPM before the addition of the dye unless indicated.The specific amounts of material used in the formulas or recipes are identified for each example in Table 1.

GENERAL PROCEDURE - TINA TIN The supply of wood fiber was soaked in tap water to full hydration and pulped to a Consistency of approximately 3 percent using a laboratory mixer. A caustic solution (for example the NaOH solution) was added to the wood supply. In general, enough caustic solution was added to adjust the pH to around 12. An electrolyte salt (for example sodium sulfate) was also added. The amount of electrolyte salt is listed in Table 1 for each example as a percentage based on pounds of ingredient per tonne of wood fiber (eg pounds of ingredient / 2,000 pounds of wood fiber) where fiber wood has an estimated moisture content of 7 percent.

A vat dye was added to the wood supply together with a reducing agent (for example sodium hydrosulfite) and stirred by a. eriod, time ,. _ Quantity_ is listed in Table 1 for each example as a percentage. The reaction time after the added dye as listed in Table 1 for each example.

After a specific period of time in which the tub dye has impregnated the hydrated cellulose, an oxidizing agent (for example sodium perborate) was added to the mixture under agitation. The amount is listed in Table 1 for each example as a percentage. The agitation time after addition of the oxidizing agent was also listed in Table 1 for each example. After stirring, the mixture it was immediately transferred to a supply chest where it was diluted to an appropriate consistency for the formation of a conventional hand sheet. The handsheets were washed and formed using a conventional handleader former and then entangled hydraulically.

GENERAL PROCEDURE - HYDRAULIC TIGHTENING The wet-formed (wet-laid) fabric of dyed wood pulp was placed on the top of a relatively low weight conventional polypropylene spunbond fabric. The basis weight of the spunbonded fabric was about 17 gsm and the basis weight of the treated pulp fabric formed wet was about 73 grams per square meter as determined from the samples that were dried in the oven.

A conventional hydraulic entanglement system composed of 3 manifolds was used. The basic operating procedure is described, for example, in United States Patent No. 5,389,202 issued February 14, 1995 to Everhart et al., The contents of which are incorporated herein by reference. Each manifold has an orifice size of 0.006 inches in diameter. The holes were placed in a single row at a distance of about 40 holes per linear inch of the manifold. The water pressure of the manifold was 850 psig which generated high energy fine column jets. The hydraulically entangled surface was a single-layer 103AM polyester wire backing manufactured by Albany International of Portland, Tennessi. Spunbond woven fabrics were passed under the manifolds at a line speed of about 20 feet per minute (fpm) where they were washed and consolidated by pressurized water jets. The resulting composite material was dried using a conventional laboratory hand sheet dryer.

GENERAL PROCEDURE - DIRECT TINT A blue Pergasol F3R solution was used to treat a hydraulically entangled polypropylene-entangled spunbond substrate available as rags manufactured by Kimberly-Clark Corporation of Rosel, Georgia, under the WORKHORSE® brand. The wood fiber supply used is about 50 percent Longlac 19, 25 percent kraft of bleached south softwood and 25 percent secondary fiber. The Blue Pergasol F3R solution was applied to the substrate using a liquid landfill arrangement as described in U.S. Patent No. 5,486,381, entitled "Liquid Saturation Process" and issued January 23, 1996 to Cleveland and others, previously incorporated by reference.

PROOF OF SAMPLE Substrate color levels were measured and recorded in Table 2 in the CIELAB coordinates using a Hunter laboratory color difference meter, optical sensor model D25 and manufactured by Hunter Associates Laboratory, of Reston, Virginia. The CIELAB coordinates are a system agreed in 1976 within the "International Commission of Illumination" or CIÉ. The coordinates are designated L *, a *, b *. The system uses an opposing three-axis color scale assuming color is perceived in white to black (L *) or "lightness", from green to red (a *) and yellow to blue (b *) sensations. L * varies from 100 for a perfect white to zero for a perfect black. The a * measures the redness when more (for example positive), -gris when zero, and I know how many times (for example negative). b * measures yellowness when more (for example positive), gray when zero and bluish at least (for example, negative).

The CIELAB measurements "Before the Treatment of Hydraulic Tangle (before HET) "were made using hand sheets from the supply of stained wood." After Hydraulic Tangle Treatment (after HET) "measurements were made with the pulp side acting as the reflecting surface. hydraulically entangled contained a fibrous tissue bonded by pigmented polypropylene yarn. present invention is not limited to a conventional hydraulic entanglement treatment as means for supplying the pressurized jets of liquid for washing the fibrous material. It should be understood that the hydraulic entanglement treatment is an example of a type of a pressurized liquid jet treatment that may be employed.

The firmness of color or "fixity" of the materials produced in the examples was tested to measure the tendency of the color to fade or change with exposure to bleach, vinegar, formula 409, and an industrial solvent. These tests were generally carried out in accordance with the AATCC test method 3-1989 and the recommendation I.S.O. (International Organization for Standardization) as described in Trotman, E.R., dyeing technology and textile fiber chemistry, fifth edition, by Charles Griffen & Co. Limited, of Whitstable, Kent, England, 1975. A color change rating scale of variation of "1-5" was used with "5" being the highest rating with a negligible change or no change in color to "1" being the lowest for a large color change.

In each case, a test sample of approximately 1 inch square in size was soaked for a specified time in 100 mL of the test / solvent solution then dried to ambient conditions overnight.

The test samples were compared to the control samples.

The color fastness with exposure to household bleach (5.25 percent sodium hypochlorite) was studied at various bleaching concentrations. The test samples were soaked for 60 minutes with intermittent gentle agitation.

Domestic distilled vinegar (5 percent acidity) and formula 409 (The Clorox Company, Oakland, California) were used separately on the samples to study the color fixity. Samples were soaked for 5 minutes in vinegar or in formula 409 without dilution.

The color fixity with exposure to an industrial solvent was studied using Auto ash 6000 - a printer solvent available from the Newark, New Jersey printing service. The Autowash 6000 is composed of aliphatic and aromatic petroleum distillates and ethyleneoxy ethanol. The samples were soaked for 5 minutes. The results of these tests were reported in Table 3.

The substrate detachment test was carried out on the samples in both the dry state (see Table 2) and in the wet state (see Table 3) immediately after soaking in bleach, vinegar, formula 409 or Autowash 6000 for the time specified above. The detachment test determines the extent to which the color can be transferred from the surface of a dyed fabric to another surface by the treatment (either while dry or while wet with a specific liquid).

The test was carried out using an AATCC model CM.5 release meter manufactured by Atlas Electric Devices Company, of Chicago, Illinois. Each sample was approximately 4 inches wide by 5 1/2 inches long and oriented along the direction of the machine (eg, along the direction of tissue formation) when mounted on the tester A small square cloth of small size (squares of 2 2 release gauge, part number 12-2592-0000, Test Fabrics Inc., of Middlesex, New Jersey) was mounted on the peel tester peg. Tests were carried out for 30 cycles used (unless fabric damage occurred) and each sample was graded using the AATCC chromatic transfer scale, 1994 edition, from the American Association of Textile and Colorist Chemists, Research Triangle Park, North Carolina. The rating was based on a scale of "1-5" with "5" indicating that there was no color transfer, "4" indicating a pale color transfer, "3" indicating some color transfer, "2"indicating many transfers of color and "1" indicating a large color transfer. A rating of "3" or greater is considered acceptable for most applications.

RESULTS FOR EXAMPLES 1-15 As shown in Table 2, only a small amount of color loss (if any) was measured when the stained wood fibers were subjected to high speed hydraulic entanglement jets which indicates a sufficient fiber substantivity. This is observed by comparing the values L *, a *, b * of CIELAB coordinates "before HET" with the values "after HET". The color differences can be attributed in part to the loss of the unbound and unreacted dye chemical, to the loss of fine fiber through the hydraulic entanglement wire backing and to the white spinning fibers / filaments causing the substrate to clear. consolidated.

A non-woven fabric of polypropylene joined by conventional spinning having a basis weight of about 17 grams per square meter and identified as example 15 served as a control material. The color measurement values are given as a reference to evaluate the clearance of the contribution to the shade due to the white pigment added to the polypropylene used in the manufacture of the non-woven fabric joined by spinning. The non-woven fabric bonded by similar polypropylene yarn was hydraulically entangled with the treated wood fibers (eg dyed) as described above for examples 1-13. The WORKHORSE® Manufactured Rag material of Example 14 also contained an essentially identical non-woven fabric bonded by essentially identical polypropylene yarn.

Table 2 shows that the samples had acceptable dry release results. As can be seen in Table 3, some dyes have a better chemical fixity with respect to certain chemicals and not with respect to others and are rarely equally fixed for all. Examples 1 and 2 both have an excellent color fixity. Yellow 2G Cibanone® is included as a dye, -of high chemical fixation. - • - - -. .-. _ ..,. The different amounts of other vat dyes can be less fixed in color can also be added as toners for different color tones of a highly fixed dye. In this manner, general fixity can be retained as shown by example 3 wherein a color of pizza or salmon is based on a highly fixed yellow color.

As seen in Example 4 of the green shade, higher bleach concentrations (sodium hypochlorite) can negatively affect fixity. The addition of modest amounts of a fixing agent, Tinofix NF, to the dyeing process of pre-supply tub and a longer reaction time did not improve the fixity or the peel strength when comparing examples 4 and 5. Adding fixative agents after the hydraulic entanglement phase rather than during the prep supply it is expected to improve the resistance to detachment.

Colored tub dyes similar in color may have an improved fixity as can be seen, for example, in Example 6.

The blue vat dyes are difficult to make a fixed to the color (for example a fixed color to the bleached).

Using high levels of fixative in the prep-dyeing phase only modestly improved the fixity as can be seen in a comparison of Examples 7, 8 and 9.

By using a combination of different vat dyes, and producing a color fixation system. This is shown by combining the violet BNA DP Cibanone® and the Cibanone® olive B DP (example 6) to produce a light blue which has an improved fixity (example 11) on examples 7, 8 and 9 which are composed of only one type of vat dye. A deep shade of blue can be obtained with the tub dyes with a reasonable fixity as shown in example 12.

As seen in example 13 shown, the fixity of the dye in general of blue reactive dye was not as good as that of the tub dyes. For many applications, such fixity is acceptable.

A direct cationic dye Pergasol® blue F 3R is part of a family of dyes which are commonly used in the paper industry for many applications. Such dyes fall short in many durable applications requiring high chemical resistance. Although the blue Pergosal® F 3R is highly water-fixed at given aggregate levels of example 14, it is highly sensitive to bleach and other chemicals as shown in Table 1.

= E J E M'P-L O S 16-29 GENERAL PROCEDURE - TINA TIN The wood pulp was generally treated according to the procedure used for examples 1-15. The supply of wood fiber was reduced to pulp at a consistency noted for each sample in fresh water or in white water from previous runs using a re-shrinking Voith sediment maker. Certain conditions for each example are noted below in Table 4. The general conditions used in examples 1-15 including the Additional details provided in examples 16 and 17 as well as in Table 4 apply to the remaining examples 18-29 except as given in the abbreviated notes given below.

EXAMPLES 16 AND 17 PIZZA / SALMON - 1 Step 1. 60 pounds.- Terrace Bay LL19 pulped to a 3.3 percent consistency (fresh water) using a re-pulp apparatus from Voith sediment maker.

Step 2. 3 L NaOH (50 percent solution) - ^ stirred for 30 seconds. .- - Step 3. Sodium sulfate 20 percent - (by weight, 400 pounds / tons) ~ 5446 grams. Continuous agitation.

Step 4. Add vat dyes - Cibanone® yellow 2G PST - (40 pounds / ton) ~ 545 gm and Cibanone® red 6B PST, (10 pounds / ton) ~ 136 gm. Continuous agitation.

Step 5. 10 percent sodium hydrosulfite (by weight) ~ 2724 gm. pH = 12.3. Agitated 2 minutes and retain reductive pulp. Remedy pH = 13.5. Color change occurred with dye reduction.

Step 6. 40 minutes total reaction time with 30 seconds of agitation after 15 minutes of reaction, was repeated again a second time. Duration of the interim, the reductive pulp was stopped.

Step 7. After 40 minutes the pulp reducer was re-ignited, 7.5 percent sodium perborate (by weight) - 2043 gm was added, and the pulp reducer ran for 20 minutes before falling into a supply chest for training. . "- .--.." Step 8. Of the 60 pounds of dyed supply, the tank was filled to the 103 inch mark (2,880 gallons) (0.23 consistency) and then discharged, and diluted to a consistency of 0.17 percent. This consistency was then used to form a fabric or layer of treated wood fibers.

Results: Peel test results varied from ratings of "3" to "5" and are acceptable. See Table 5, Examples 16A to 17B. When the The supply is placed in the form of a sandwich between the fabrics joined by non-woven yarn, the detachment fixation improves.

The leucoform of the tub dye is a purple shade of dark color. Tinofix® NF (a fixing agent) was added pressure-treated material using a landfill fluid distributor of the type described, in for example U.S. Patent No. 5,486,381, previously incorporated by reference. No improvement in fixity was noticed.

EXAMPLES 18 AND 19 PIZZA / SALMON - 2 Refer to Example 1-6 for a general dyeing procedure.

Changes are noted in specific steps.

Step 1. Part of the pulp reduction water was white water complementary to example 16.

Step 2. The NaOH was added (50 percent solution). The pH was lowered with sulfuric and hydrochloric acid. The pH was again measured = 13.3.

Step 4. Add yellow Cibanone® 2G PDT - (60 pounds / ton), ~ 717 gm @ 0 reaction time. Red Cibanone® 6B PST - (15 pounds / ton) ~ 204 gm.

After 25 minutes of reaction, another 100 grams of 2G Cibanone® yellow was added and the reaction time was increased by an additional 10 minutes for a total time of 50 minutes.

Results: See Table 5.

EXAMPLES 20 AND 21 - PIZZA / SALMÓN - 4 Step 1. The white water from the previous run was used for re-pulping.

Step 2. 185 mL. NaOH (50 percent solution). pH = 12.5.

Step 3. 25 percent sodium sulfate (by weight) - 6810 gm.

Step 4. Add Cibanone® yellow 2G PST (80 lbs / t) - 1090 grams and red Cibanone® 6B PST (20 lbs / t) -272 grams.

Results: See Table 5.

EXAMPLES 22 AND 23 - ORANGE - 1 Step 1. Fresh water. 50:50 LL19 / SSWK. (For example, a mixture of fibers of equal parts of kraft pulp of soft wood of the north LL19 and pulp kraft of soft wood of the south (SSWK)) 60 pounds of pulp reduction 10 minutes @ 3.3 percent consistency.

Step 2. 3.5 L NaOH (50 percent solution), pH = 12.2.

Step 3. 25 percent sodium sulfate - 6810 gm.

Step 4. Add orange Cibanone® 5G DP (33 lbs / t) - 450 gm. and red Cibanone® 2B PST (54 lbs / t) - 735 gm.

Step 7. After 40 minutes of reaction time, the reductive pulp solution was stirred for 5 minutes to see if there was sufficient autoxidation. Due to insufficient oxidation (no color change), 7.5 percent sodium perborate (2043 g) was added.

Results: The leucoform is a dark chocolate color. The color level of supply was acceptable. The detachment fixity for the sandwich fabric was acceptable with ratings of 4 to 5. See Table 5.

EXAMPLES 24 AND 25 BLUE GRAY - 1 (WSK-21) Step 1. Fresh water. 60 pounds of a 50:50 supply LL19 / SSWK.

Step 2. 2.5 L NaOH (50 percent solution). pH = 12.2.

Step 3. 25 percent sodium sulfate. -.6810 Step 4. Add orange Cibanone® 5G DP - 136 g (10 lbs / ton), Cibanone® navy blue PS PST - 817 g (60 lbs / ton) and blue Cibanone® GFJ DP - 272 g (20 lbs / ton).

Results: See Table 5.

EXAMPLES 26, 27 AND 28 - BLUE GRAY - 2 Step 1. Fresh water. 60 pounds of a 50:50 supply of LL19 / SSWK.

Step 2. 2.5 L NaOH (50 percent solution). pH = 12.3.

Step 3. Orange Cibanone® 5G DP - 82 g (6 lbs / ton), dark blue Cibanone® PS PST - 409 g (30 lbs / ton), and blue Cibanone® GFJ DP - 136 g (10 lbs / ton).

Results: They resulted in a poor color fixation and detachment as shown in Table 5.- A color change occurred when the material was exposed to formula 409.

EXAMPLE 29 - CLEAR BLUE (WSK-9) Step 1. 60 lb. supply, 50:50 LL19 / SSWK. Fresh water.

Step 2. 2.5 L NaOH (50 percent solution) pH = 12.3.

Step 3. 25 percent sodium sulfate - 6810 Step 4. Add marine blue Cibanone® PS PST - 68 g (5 lbs / ton) and blue Cibanone® GFJ DP - 109 g (8 lbs / ton).

Results: See Table 5.

PROOF OF SULPHATE and pH The materials of examples 20-29 were cut into square samples of 10 inches by 10 inches. The individual samples were soaked for 30 minutes in 200 mL of tap water at room temperature. After soaking, each sample was squeezed and rinsed with soaking water through a 5-fold wash squeezer, the liquid in which a single sample was soaked and the liquid squeezed out of that sample were combined.

The pH of the liquid was measured with a conventional pH tester and the results are listed in Table 5. The sulfate levels in the liquid were tested using a Hach DR / 2000 direct reading spectrophotometer and the Hach Sulfaver 4 method (method of Turbidity). The results of the sulfate test are reported in Table 5 in units of mg / L.

As shown in Table 5, the pH levels were at or near neutral and the sulfate levels were between zero and around 3 mg / L indicating effective washing with the hydraulic entanglement jets.

Although the present invention has been described in connection with certain embodiments, it is understood that the subject matter encompassed by way of the present invention should not be limited to those specific embodiments. On the contrary, it is intended that the subject matter of the invention includes all alternatives, modifications and equivalents as may be included within the spirit and scope of the following claims.

TABLE EXAMPLE CLASS OF DYE COLOR PROCEDURE OF ORDER DYE DYE TINA Cibanone Yellow 30 libs Yellow Dye 6.25% Caustic (50% Gold M Soln) PST 10% Sodium Sulphate 10% Sodium Hydrosulfite 20 minutes 7.5 Sodium Perborate 10 minutes TIB Cibanone Yellow 50 pounds Dye 20 Caustic Yellow (10% Soln.) Pounds 2 G PST at pH 12 Tinofix 20% Sodium Sulfate NF 10% Sodium Hydrosulfite 60 minutes 7.5% Sodium Perborate 45 minutes Sulfuric Acid at a pH of 7.5 - 8.5 Additional Mordant 5 minutes TINA Cibanona Pizza or .4Q - Yellow Yellow Salmon 2G + 2G PST 10 pounds Red € B -._ Cibanone Caustic at pH 12 Red 6B 10% Sodium Sulphate ST 10% Sodium Hydrosulfite 20 minutes 7.5% Sodium Perborate 10 minutes TINA Cibanone Green 30 pounds Caustic Green Dye (10% soln) BFD at pH 12 liquid 10% Sodium Sulphate 10% Sodium Hydrosulfite 20 minutes 7.5% Sodium Perborate 10 minutes B (CONTINUED) EXAMPLE CLASS OF TINT COLOR ROCEDIMIENTO DE TENIDO MORDENTE TINTE TINA Green Green 30 libs Tint Sosa 20 BFD LIQ. Caustic pounds Cibanone at a pH of 12 Tinofix 20% Sodium Sulfate NF LIQ. 10% Sodium Hydrosulfite 60 minutes 7.5 Sodium Perborate 45 minutes Sulfuric Acid at a pH of 7.5 - 8.5 Add Fixer 5 minutes TINA Cibanone Green 15 pounds Caustic Olive Olive Dye at pH 12.0 B DP 20% Sodium Sulfate 10% Sodium Hydrosulfite 40 minutes 7.5% Sodium Perborate 30 minutes Sulfuric Acid at a pH of 7.5 - 8.5 TINA Blue Cibanone 50 pounds Blue Dye 2B Caustic at pH 12 PST 20% Sodium Sulphate 10% Sodium Hydrosulfite 20 minutes 7.5% Sodium Perborate 10 minutes TINA Cibanone Blue 40 pounds Dye 40 Blue 2B Caustic at pH 12 pounds PST 20% Sodium Sulfate Tinofix 10% Sodium Hydrosulfite NF LIQ. 60 minutes 7.5% Sodium Perborate 45 minutes Sulfuric Acid at a pH of 7.5 - 8.5 TINA Fixer Cibanone Blue 40 pounds Dye 80 Blue 2B Caustic Soda at 12 pounds PST 10% Sodium Sulphate Tinofix 10% Sodium Hydrosulfite NF LIQ. 20 minutes 7.5 Perborato T A B A 1 (CONTINUED) TABLE COLOR LEVEL - CIELAB DRY REMOVAL EXAMPLE BEFORE HET AFTER HET QUALIFICATION B BALNQUEDOR VINAGRE FORMULA 409 AUTOLAVADO 6000 PRISCO B - Bases of weight for each propensity. 2 - Southern soft wood kraft pulp.

T A B A 5

Claims (37)

R E I V I N D I C A C I O N S

1. A process for treating a fibrous material comprising: provide a liquid suspension comprising fibrous material; intermixing the liquid suspension of fibrous material with a treatment over a period of time T1 (the treatment requires a period of time TR sufficient to treat the fibrous material; depositing the liquid suspension of the fibrous material and the intermixed treatment on a forming surface to form a layer and remove an essential part of the liquid, over a period of time T2; Y applying pressurized jets of a liquid to the fibrous material layer to wash the unused treatment of the fibrous material within a period of time T3; where Tlf T2 and T3 are immediately consecutive and constitute a time period of at least as great as TR.

2. The process as claimed in clause 1 characterized in that the liquid suspension of the fibrous material is an aqueous suspension of hydrated cellulosic fibers.

3. The process as claimed in clause 1 characterized in that the treatment is a chemically reactive treatment.

4. The process as claimed in clause 3 characterized in that the chemically reactive treatment is selected from reactive dyes, vat dyes and sulfur dyes.

5. The process as claimed in clause 1, characterized in that the deposited layer of fiber material and of the intermixed treatment is a fabric.

6. The process as claimed in clause 1 characterized in that the deposited layer of the fibrous material and the intermixed treatment are combined with at least one other layer of a sheet material before the application of the pressurized jets of a liquid.

7. The process as claimed in clause 6 characterized in that at least one layer of the sheet material is selected from non-woven fabrics, textile fabrics, canvas materials, plexifilamentary films, tow and combinations thereof.

8. The process as claimed in clause 1 characterized in that the layer is hydraulically entangled.

9. The process as claimed in clause 1 characterized in that the layer is hydraulically entangled.

; 10. The process as claimed in clause 1, characterized in that it includes at least one subsequent processing step.

11. A process for forming a fabric of a treated fibrous cellulosic material comprising: providing an aqueous suspension comprising a hydrated fibrous cellulosic material; intermixing the aqueous suspension of the hydrated fibrous cellulosic material with a reactive treatment over a period of time T ^ the treatment requires a period of time TR sufficient to treat the fibrous cellulose material; depositing the aqueous suspension of the hydrated fibrous cellulosic material and intermixing the reactive treatment on a surface to form a fabric and removing an essential part of the aqueous liquid, over a period of time T2; Y applying the pressurized jets of a liquid to the fabric to wash the unused reactive treatment of the fabric within a period of time T3; - ~ - where T ,, T2 and T are immediately consecutive and constitute a period of time of at least as great as TR.

12. The process as claimed in clause 11 characterized in that the chemically reactive treatment is selected from reactive dyes, vat dyes and sulfur dyes.

13. The process as claimed in clause 11 characterized in that the deposited layer of fibrous material and intermixed treatment is combined with at least one other layer of sheet material before the application of the pressurized jets of a liquid.

14. The process as claimed in clause 11 characterized in that the forming surface includes at least one layer of a sheet material between the forming surface and the deposited layer of the fibrous material and the intermixed treatment.

15. The process as claimed in clause 14 characterized in that at least one layer of sheet material is selected from non-woven fabrics; textile fabrics, canvas materials, plexifilamentary films, tow and combinations thereof.

16. The process as claimed in clause 15 characterized in that the non-woven fabrics are selected from meltblown fabrics, spunbond fabrics, carded and bonded fabrics, fibrous blocks, air-laid fabrics, wet-laid fabrics, fabrics coformados and combinations thereof.

17. The process as claimed in clause 11 characterized in that the fabric is hydraulically entangled.

18. The process as claimed in clause 11 characterized in that the fabric is hydraulically drilled.

19. The process as claimed in clause 11 characterized in that the fibrous cellulosic material is selected from pulp fibers, synthetic cellulose fibers and combinations thereof.

20. The process as claimed in clause 11, characterized in that it includes at least one subsequent processing step per lp.

21. A process for forming a fabric of a color fixed fibrous cellulose material comprising: providing an aqueous suspension comprising a hydrated fibrous cellulosic material; intermixing the aqueous suspension of the hydrated fibrous cellulose material with a reactive treatment over a period of time Tt, said treatment is selected from dyes reagents, vat dyes and sulfur dyes requiring a period of time TR sufficient to treat the fibrous cellulose material; depositing the aqueous suspension of the hydrated fibrous cellulosic material and intermixing the reactive treatment on a surface to form a fabric and removing an essential part of the aqueous liquid, over a period of time T2; Y applying pressurized jets of a liquid to the fabric to wash the unused reactive treatment of the fabric within a period of time T3; where Tj, -T2 'and- - T3 are immediately consecutive and constitute a period of time at least as large as TR.

22. The process as claimed in clause 21 characterized in that the deposited layer of fibrous material and the intermixed treatment is combined with at least one other layer of sheet material before the application of the pressurized jets of a liquid.

23. The process as claimed in clause 21 characterized in that the forming surface includes at least one layer of a sheet material between the forming surface and the deposited layer of the fibrous material and the intermixed treatment.

24. The process as claimed in clause 23 characterized in that at least one layer of the sheet material is selected from the non-woven fabrics, the textile fabrics, the canvas materials, the plexifilamentary films, the tow and the combinations of the same.

25. The process as claimed in clause 24 characterized in that the non-woven fabrics are selected from melt-blown fabrics, knitted fabrics, carded and bonded fabrics, fibrous blocks, air-laid fabrics, wet-laid fabrics, coformmed fabrics and combinations thereof.

26. The process as claimed in clause 21 characterized in that the fabric is hydraulically entangled.

27. The process as claimed in clause 21 characterized in that the fabric is hydraulically perforated.

28. The process as claimed in clause 21 characterized in that the fibrous cellulosic material is selected from pulp fibers, synthetic cellulose fibers and combinations thereof.

29. The process as claimed in clause 21 further characterized in that it includes at least one subsequent processing step.

30. A hydraulically entangled structure composed of a color fixed fibrous material, the structure comprises: at least one layer of a non-woven wet-laid fabric comprising a fibrous cellulosic material; and a firm color tint that imparts color to the fibrous cellulosic material so that the fibrous cellulosic material is firm in color.

31. The hydraulically entangled structure of fibrous material of firm color as claimed in clause 30 characterized in that the non-woven fabric placed in wet also includes a layer of sheet material.

32. The hydraulically entangled structure of firm colored fibrous material as claimed in clause 31 characterized in that the sheet of material is selected from spunbonded fabrics, meltblown fabrics, carded and bonded fabrics, woven fabrics, woven fabrics, Canvases and combinations thereof.

33. The hydraulically entangled structure of fibrous material of firm color as claimed in clause 31 characterized in that it comprises a matrix of adhesive material.

34. The hydraulically entangled structure of fibrous material of firm color as claimed in clause 35 characterized in that the firm color dye is selected from reactive dyes, vat dyes and sulfur dyes.

35. A hydraulically perforated structure composed of a fibrous material of firm color, the structure comprises: at least one layer of a non-woven wet-laid fabric comprising a fibrous cellulosic material; Y a firm color tint that imparts color to the fibrous cellulose material so that the fibrous cellulosic material is firm in color.

36. The hydraulically perforated structure of fibrous material of firm color as claimed in clause 35 further characterized in that it comprises a matrix of adhesive material.

37. The hydraulically perforated structure of the fibrous material. -solid color as claimed in clause 35, characterized in that the firm color tint is selected from reactive dyes, vat dyes and sulfur dyes. E S U M E N A process for treating a fibrous material which includes the steps of: 1) providing a liquid suspension composed of fibrous material; 2) intermixing the liquid suspension of the fibrous material with a treatment over a period of time Tj - wherein the treatment requires a period of time TR sufficient to treat the fibrous material; 3) deposit the liquid suspension of the fibrous material and intermix the treatment on the forming surface to form a layer and remove a substantial part of the liquid, over a period of time T2; and 4) applying pressurized jets of a liquid to the layer of fibrous material to wash the unused treatment of the fibrous material within a period of time T3. The time periods Tl t T2 and T3 are immediately consecutive and constitute a total period of time of at least as great as TR. Also described is a hydraulically entangled structure composed of: 1) at least one layer of a non-woven fabric placed in wet containing a fibrous cellulose material; and 2) a color firmness dye that imparts color to the fibrous cellulose material so that the fibrous cellulose material is firm in color.