WO2006130144A1

WO2006130144A1 - Nanoparticle containing, pigmented inks

Info

Publication number: WO2006130144A1
Application number: PCT/US2005/019162
Authority: WO
Inventors: Konghyun Sunwoo; Sujin Moon; Jeonggook Cho; Juhyung Lee
Original assignee: Kimberly-Clark Worldwide, Inc.
Priority date: 2005-05-31
Filing date: 2005-05-31
Publication date: 2006-12-07
Also published as: CN101184812A; MX2007015131A; JP2008545847A; EP1885807A1

Abstract

There is provided a new composition, printed fabrics and method for improving color strength and crock fastness on printed or coated polymeric, silk and cotton fabrics. The novel printing composition is an aqueous mixture having silica nanoparticles and silane coupling agents in addition to pigments and a relatively small amount of binder. The nanoparticles and coupling agent are preferably in a ratio of from about 1:3 to 3:1. The binder may be present in an amount between about 0.1 and 10 weight percent. A number of other optional ingredients like humectants, dispersants, biocides and the like may be present. Also provided is a method of making the printed fabric including the steps of mixing nanoparticles and coupling agent, adding water, pigment and binder and milling the mixture to a particle size between about 150 and 200 nm, applying the composition and drying the printed fabric.

Description

NANOPARTICLE CONTAINING, PIGMENTED INKS

BACKGROUND OF THE INVENTION

5

The color strength and fastness of pigmented ink on textiles is generally controlled by the amount of polymeric binder added to the ink mixture. It is very difficult, however, to achieve good fastness of pigmented inks onto printed or coated fabric through increased binder addition without a detrimental change of the fabric o "hand" or softness. When the amount of polymeric binder is high enough to demonstrate good durability (or fastness), fabric hand becomes stiff or harsh. If the amount of binder is reduced to keep fabric hand constant, good fastness, especially fastness to crocking, cannot be achieved.

Textiles, either woven or nonwoven, are used for a wide variety of applications s from clothing, wipers and diapers to automobile covers. These applications call for materials having diverse properties and attributes. Some applications call for fabrics which are highly wettable, e.g. liners for diapers and feminine hygiene products, and which are soft like clothing, or are absorbent like wipers and towels, while others require strength, e.g. protective fabrics like car and boat covers, and still others require o repellency and barrier properties like medically oriented fabrics such as, for example, sterilization wraps and surgical gowns.

Though the myriad applications for fabrics may seem unrelated and diverse, a common feature is the desire to have them printed in some manner. This printing may be for the purpose of advertisement, product identification, decoration, obscuring stains, 5 etc. Unfortunately, because of the conditions under which many fabrics are used, completely successful printing systems have not been developed, most particularly printing systems which may be carried out at room temperature.

It is therefore an object of this invention to provide a printing (ink) composition which is easy to apply, cures at room temperature, and which will remain on the fabric o when exposed to most common cleaning chemicals and under most conditions of use, i.e., which has a high color strength and crock fastness. It is another objective of this invention to provide a textile which is printed with the printing composition provided and to provide a method of printing a textile with the composition. SUMMARY

This invention is generally directed toward a new composition, and method for improving color strength and crock fastness on printed or coated polymeric, silk and cotton fabrics.

The novel printing composition is an aqueous mixture having silica nanoparticles and silane coupling agents in addition to pigments and a relatively small amount of binder. The nanoparticles and coupling agent are preferably in a ratio of from about 1:3 to 3:1. The binder may be present in an amount between about 0.1 and 10 weight percent. A number of other optional ingredients like humectants, dispersants, biocides and the like may be present.

The composition may be applied to a fabric through a myriad of techniques and dried. The fabric may be a composite fabric of hydroentangled pulp and spunbond fibers, spunbond fabrics, meltblown fabrics, woven fabrics and laminates of spunbond and meltblown fabrics. The woven fabric may be cotton, silk, polyester or nylon.

The invention further includes printed fabric having thereon the dried residue of an aqueously applied composition, where the composition has nanoparticles, silane coupling agent, binder and ink.

Also provided is a method of making the printed fabric including the steps of mixing nanoparticles and coupling agent, adding water, pigment and binder and milling the mixture to a particle size between about 150 and 200 nm, applying the composition and drying the printed fabric.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have found that good color fastness and strong color strength for inks can be achieved by using a small amount of polymeric binder with silica nanoparticles and a silane coupling agent. The inventors have found that about 0.1 to 10 weight percent of silica nanoparticles with 0.5 to 20 weight percent of a silane coupling agent can improve fastness to crocking and color strength in pigmented ink systems with acrylic or polyurethane polymeric binders.

The inventive composition may be applied by any of a myriad of means known in the art like screen printing, digital printing, dip coating, spin coating or spraying on hydrophobic and hydrophilic fabrics such as polyesters, polyolefins, cotton, nylon, silks etc and the fabrics may be woven or nonwoven.

There is no constraint on the basis weight or components of the fabric used with the novel inks. Woven and nonwoven fabrics, therefore, may be used, including bonded carded webs, spunbond fabrics or meltbiown fabrics and fabrics containing pulp like those described in US Patent 5,284,703, one embodiment of which is known commercially as Hydroknit® material. Such fabrics may be a single layer embodiment or as a component of a multilayer laminate which may be formed by a number of different laminating techniques including using adhesive, needle punching, thermal o point bonding, through air bonding and any other method known in the art.

Without wishing to be bound by any particular theory, the inventors believe that a silane coupling agent can be crosslinked between an organic polymer and inorganic silica nanoparticles and that the addition of the coupling agent can enhance the durability of coated fabrics, with higher color strength. Traditional ink formulations s rely on improving fastness properties by adding polymeric binder such as acrylic and polyurethane binder. The inventors found no significant relationship, however, between the amount of binder added and the amount of crock fastness improvement. The inventors likewise found that polymeric binders with only silica nanoparticles would not significantly improve crock fastness. Silica particles and silane coupling 0 agents, however, can improve the binding effect of polymeric binder such as acrylic and polyurethane binder as shown below. The inventors believe that silica nanoparticles with silane coupling agents can promote the binding of polymeric binder by cross-linking between polymer and polymer or between polymer and pigment or between polymer and fabric surface. 5 Colorfastness to crocking is measured according to AATCC Test Method 8-

1996 by placing a 5 inch by 7 inch (127 mm by 178 mm) piece of the material to be tested into a Crockmeter model CM-5 available from the Atlas Electric Device Company of 4114 Ravenswood Ave., Chicago, IL 60613. The crockmeter strokes or rubs a cotton cloth back and forth across the sample a predetermined number of times with a o fixed amount of force. The color transferred from the sample onto the cotton is then compared to a scale wherein 5 indicates no color on the cotton and 1 indicates a large amount of color on the cotton. A higher number indicates a relatively more colorfast sample. The comparison scale is available from the American Association of Textile Chemists and Colorists (AATCC), PO Box 12215, Research Triangle Park, NC 27709. Color strength (K/S) was. measured using a Hunterlab Miniscan XE-Plus spectrophotometer, available from Hunter Associates Laboratory, Inc. of Reston, VA (hunterlab.com). Differences between similar colors can amount to a contrast if they demonstrate a ΔE* value greater than 3. In this regard, L*a^*b* color value measurements and ΔE^* calculations (CIE 1976 Commission Internationale de

I'Eclairage) may be made using an Hunterlab Miniscan XE-Plus spectrophotometer, in accordance with the operator's manual. Average optical densities are generally taken as the sum of the average of three measurements using each filter. Delta E* is calculated in accordance with the following equation:

ΔE^*=SQRT [(L^*standard - L* sample)² + (a^*standard - a^* sample)² + (b*standard - b*sample)²]

The higher the ΔE*, the greater the change in color intensity. Testing may be conducted in accordance with ASTM DM 224-93 and ASTM E308-90. Where values for ΔE^* are less than 3.0 for a substrate with a matte finish, it is generally accepted that such color change/difference cannot be observed with the human eye. A detailed description of spectrodensitometer testing is available in Color Technology in the Textile Industry, 2^nd Edition, Published 1997 by AATCC (American Association of Textile Chemists & Colorists).

The nanoparticles used herein are silica nanoparticles that have been modified by the addition of metal molecules like aluminum, silver, copper, nickel and gold in order to give specific properties desired by the user. These include water repellency, antimicrobial activity and surface tension modification.

Metal modified silica nanoparticles are made by mixing nanoparticles with solutions containing metal ions. Such solutions are generally made by dissolving metallic compounds into a solvent, resulting in free metal ions in the solution. The metal ions are drawn to and adsorbed onto the nanoparticles due to the electric potential differences. Further discussion of the modification of nanoparticles may be found in US patent application 10/137052, filed on April 30, 2002, which is incorporated by reference.

Numerous techniques may be utilized to form a stronger bond between the transition metal and silica particles. Silica sols, for example, are generally considered stable at a pH of greater than about 7, and particularly between a pH of 9-10. When dissolved in water, salts of transition metals are acidic (e.g., copper chloride has a pH of approximately 4.8). Thus, when such an acidic transition metal salt is mixed with a basic silica sol, the pH is lowered and the metal salt precipitates on the surface of the silica particles. This compromises the stability of the silica particles. Further, at lower pH values, the number of silanol groups present on the surface of the silica particles is reduced. Because the transition metal binds to these silanol groups, the capacity of the particles for the transition metal is lowered at lower pH values. It is also possible to bond metal and silica particles to form a "coordinate" and/or "covalent bond." This may have a variety of benefits, such as reducing the likelihood that any of the metal will remain free during use (e.g., after washing).

In order to ameliorate the pH-lowering affect caused by the addition of an acidic transition metal salt (e.g., copper chloride), it is desirable to employ selective control over the pH of the silica particles during mixing with the transition, metal. The selective control over pH may be accomplished using any of a variety of well-known buffering systems known in the art.

A number of suitable metal motified silica nanoparticles are commercially available. These include SNOWTEX®-C, SNOWTEXΘ-AK and SNOWTEX®-OXS nanoparticles from Nissan Chemical Industries, Ltd., Inorganic Materials Division, of Tokyo, Japan. Generally speaking, the silane coupling agents may be covalently linked to the silica particles through the silanol groups (Si-OH) present on the surface thereof. Specifically, the silicon atom of the silane coupling agent may form a covalent bond with the oxygen of the silanol group. Once the silane coupling agent is covalently linked to the silica particles, the organofunctional group may form a coordinate bond with the transition metal. Copper, for example, may form a coordinate bond with different amino groups present on aminopropyltriethoxysilane coupling agents.

Silanes are known in the art as being useful coupling agents in binding various materials to glass. For example, silane coupling agents have long been used in the glass fiber industry to form a bond between the glass fiber surface and the resin into which the glass fibers are added for reinforcement. In such bonding, it is generally believed that the silicon atom of the silane coupling agent forms a bond or attraction with the silicon atoms of the glass, while the hydrocarbon portion of the silane coupling agent forms a bond or attraction with the hydrocarbon resin. This covalent bonding theory is further explored in Silane Coupling Agents by Edwin P. Pluedemann, Plenum Press, NY, NY, second edition, 1991 , p 18-22. It is somewhat surprising, therefore, that silane coupling agents would enhance or improve the colorfastness of an ink.

The silanes useful in this invention are those which contain hydrocarbon moieties, i.e.; organosilanes, including organoalkoxysilanes and are of the following formula;

R₁

I Z-Si-R₂ I

R₃

wherein Z represents a vinyl, allyl or other double bonded group capable of reaction under radical polymerization conditions, R₁, R₂, and R₃ are reactive such as methoxy, ethoxy and other alkoxy groups, amino, epoxy, ureido, and vinyl groups, Cl or Br halogens, esters such as acetoxy groups, or -O-Si or unreactive groups such as alkyl or aryl hydrocarbon groups. The three R groups may all be the same or different but at least one R group must be reactive in order to function as a hydrolytically reactive agent. Some examples of suitable organofunctional silane coupling agents that may be used include, but are not limited to, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3- (meth)acryloxypropylmethyldimethoxysilane, 3-

(meth)acryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxysilane, 3-(4- vinylphenyl)propyltrimethoxysilane, 4-vinylphenylmethyltrimethoxysilane, 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-(2- aminoethyl)aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- mercaptopropylmethyldiethoxysilane, and partial hydrolyzates thereof. A number of suppliers exist for these silanes, including HuIs America Inc., Chisso Corp., OSI Specialties Inc., and Dow Corning Corporation. Exemplary silanes for use herein include 3-glycidyloxypropyltrimethoxysilane (GPTS) (CAS 2602-34-8), available under the trade designation SILO-ACE S-510® from Chisso Corporation of Japan and (3-aminopropyl) triethoxysilane (APTES) (CAS 919-30-2) available from Sigma-Aldrich Chemical of Milwaukee, Wl.

The silane used in this invention should be present in an amount between 0.01 and 10 weight percent of the thermoplastic polymer into which it is being mixed. More particularly, an amount between about 0.1 and 2.5 weight percent has been found to be satisfactory and still more particularly, an amount of about 1 weight percent.

The silanes useful in this invention are usually liquid at room temperature and pressure though may also be a solid in the form of a powder or granule, thus making the mixing process relatively straightforward.

Binders suitable for use herein include acrylic, polyurethane and polyester binders, though more generally, any suitable binder known tp those skilled in the art of formulating printing inks may be used. Exemplary binders include Soluryl R40 and the Snowtex series of binders (see Table 2 below). The binders may be present in an amount between 0.1 and 10 weight percent, more particularly between about 4 and 7 weight percent, of the mill base. Pigments refer to compositions having particulate color bodies, not liquid as in a dye. Pigments that may be used in the practice of the invention include any which may be found to positively interact with the nanoparticles, coupling agents and binders used in the formulation. Non-exclusive examples of such pigments include carbon black, emacol blue, emacol carmine, the irgaphore pigments, carbojet yellow and printofix red. The method of preparing the novel ink composition of the invention may begin with the surface addition of coupling agent to the silica nanoparticles. This is accomplished by exposing the nanoparticles to silane coupling agents in a ratio of from 3:1 to 1 :3, more particularly between 2:1 and 1 :2, most particularly about 1 :1 , at room temperature at a pH of from 6 to 8 or more particularly about 7. The mixing of the nanoparticles and coupling agents results in an exothermic reaction that will proceed at a temperature of 60 to 70 ⁰C for a number of hours depending on the amount of reactants present, eventually returning to room temperature.

A pigment mill base is then prepared by mixing the coupling agent-modified nanoparticles prepared above with pigment, a dispersing agent if necessary, a binder and water and any desired optional ingredients. Milling beads, often 0.3 or 0.4 mm diameter Zr beads, are added to the pigment mill base and the mixture is milled until the particle size is between about 150 and 200 mm. The final concentration of the mixture is about 15 to 20 weight percent ink.

The mill base is then generally mixed with more water, a humectant, a biocide, corrosion inhibitors and a surfactant to adjust surface tension, if necessary. Humectants include polyethylene glycol (PEG) 200, 400, 600, glycerine, diethyleneglycol (DEG), and 2-pyrolididone. After this step the ink has a concentration of about 3 to 5 weight percent.

The ink may then be applied to a textile or fabric and dried at about 110 to 120 ⁰C. The curing process may proceed without a drying step though it is recommended to have a separate drying step because better fabric heat setting can be achieved after removing water thoroughly. ,

There are numerous methods of applying inks to fabric that may be used in the practice of this invention. Any other suitable method known to those skilled in the art may be used. Exemplary methods non-exclusively include pre-metered and post- metered systems as described briefly as follows:

Pre-Metered Systems (no excess of ink applied initially):

Slot die: This method utilizes a head with a slot in it. The coating material is metered through this slot directly onto the substrate. Direct G ra vu re: The coating material is in small cells in a Gravure roll. The substrate comes into direct contact with the Gravure roll and the coating material in the cells is transferred onto the substrate.

Offset Gravure with reverse roll transfer: Similar to the direct Gravure except the Gravure roll transfers the coating material to another roll. This second roll then comes into contact with the substrate.

Curtain coating: This is a coating head with multiple slots in it. The coating materials, which are of different compositions, are metered through these slots and drop a given distance prior to coming into contact with the substrate.

Slide (Cascade) coating: This method is similar to the curtain coater except the multiple layers of coating material come into direct contact with the substrate upon exiting the coating head. There is no open gap between the coating head and the substrate.

Forward and reverse roll coating (also known as transfer roll coating): This consists of a stack of rolls which transfers the coating material from one roll to the next for metering purposes. The final roll comes into contact with the substrate. Depending upon the moving direction of the substrate and the rotation of the last roll, this will be either forward or reverse roll coating.

Extrusion coating: This technology is similar to the slot die except the coating material is a solid at room temperature. The material is heated to melting temperature in the coating head and metered as a liquid through the slot directly onto the substrate. Upon cooling, the material becomes a solid again.

Rotary screen: The coating material is pumped into a roll which has a screen surface. A blade inside the roll forces the coating material out through the screen and then transfers it to the substrate. Spray nozzle application: The coating material is forced through a spray nozzle directly onto the substrate. The desired amount of coating can be applied (Pre-Metered method). Or the substrate can be saturated by the spraying nozzle and then the excess material can be squeezed out by going through a nip-roller (Post- Metering method). Flexographic printing: The coating material is transferred onto a raised patterned surface of a roll. This patterned roll then transfers the coating material onto the substrate.

Digital Textile printing: The coating or printing inks are in an inkjet cartridge. The fabric substrate is brought under the printing inkjet head and ink is jetted onto the substrate to make a printed image.

Post-Metering (an excess of ink is initially applied and subsequently removed):

Rod coaters: The coating material is applied to the surface of the substrate and the excess material is removed by a rod. A Mayer rod is the dominate method used to meter off this excess coating.

Air knife coating: The coating material is applied to the surface of the substrate and the excess material is removed by blowing it off using high pressure air.

Knife coating: The coating material is applied to the surface of the substrate and the excess material is removed by a head in the configuration of a knife.

Blade coating: The coating material is applied to the surface of the substrate and the excess material is removed by a head in the configuration of a flat blade.

Dip coating (saturating) followed by squeeze roll: The substrate is submersed in the material to be applied. The saturated substrate is then pulled through two rollers to squeeze out the excess material. Spin coating: The substrate to be coated is rotated at high speed. The coating material is applied to the rotating substrate and the excess material spins off the edge.

Fountain coating: The coating material is applied to the substrate by means of flooded fountain head. The excess material is removed by a blade.

Brush application: The coating material is applied to the substrate by a brush. The excess material is regulated by the movement of the brush across the surface of the substrate.

In order to promote the crockfastness of the ink, the printed fabric must then be

"cured". Curing is the process of exposing the fabric to sufficient moisture at a temperature and for a time sufficient to cause the increase in crockfastness. Curing takes place for a sufficient time at about 150 - 200 ⁰C, depending on type and thickness of the textile substrate and environmental factors. Cotton, for example, needs a curing time of 3 minutes at 180 ⁰C. Nylon requires 3 minutes at 150 ⁰C and PET needs a curing time of 3 minutes at 180 ⁰C. (It should be noted that times are approximate.)

Examples of Pigment Mill Base: ink, binder, nanoparticles, without coupling agents

A Pigment Mill Base (Table 1 ) was made for comparison of fastness after the addition of five different binders. In these examples, no coupling agent was added to the mixture. These binder polymers are listed below in Table 2.

Table 1

Table 2

The five different polymers from Table 2 were added into the Pigment Mill

Base (Table 1 above), each at 1 weight percent, and the color strength (K/S) and crocking fastness were evaluated. A control example having no binder polymer was also tested. The polymer was added into pigment mill base (pigment + Solsperse(dispersant) + Snowtex AK as shown in Table 1) and Polyester Twill Fabric was dipped into the pigment mill base with/without polymeric binder, dried at 120 ⁰C and cured at 180 ⁰C for 3 minutes each.

After curing, the fabric was washed in tap water to removed unfixed pigment from the surface of the polyester fabric. Crock fastness and color strength (K/S) were evaluated using the washed polyester fabrics. The results in Table 3 show that there was no significant improvement in crocking fastness nor in color strength as compared to the Pigment Mill Base without a binder.

Table 3

Another example of polymer addition into pigment in order to improve crocking fastness is shown in Table 4 below. Solutions were made with Emacol Blue pigment from Sanyocolor Inc. of Japan, Snowtex®-AK silica nanoparticles (in some examples) and Soluryl R-40 acrylic binder from Hanwha Chemical Co. of Korea, in the weight percentages as shown. These various solutions were coated onto PET, cotton and silk fabrics by dip coating, dried at 120 ⁰C and cured at 180 ⁰C for 3 minutes. Crock fastness was evaluated in AATCC Test Method 8-1996 and K/S values were measured using a Hunter lab Miniscan XE-Plus as discussed above.

Table 4

It should be noted that 6 weight percent of Soluryl R-40 and 1.1 weight percent of Snowtex®-AK gave the highest fastness in silk fabric, for example but fabric hand with 6 weight percent of acrylic binder was not good. The effect of the amount of acrylic polymer on crock fastness was not significant as shown in Table 4. The presence of silica nanoparticles appeared to improve color strength but not to reliably improve crock fastness.

A Pigment Red solution (Emacol carmine mixture) was prepared by mixing

23.5 g of Emacol carmine (30%) from Sanyocolor of Japan, 46.1 g of Soluryl S372 pigment dispersant from Hanwha Chemical Co. of Korea and 277.8 g of water. Soluryl R-40 acrylic binder in the weight percentages shown and Snowtex®-AK (in some examples) were added as detailed in Table 5 below. Fabrics were dip coated and heat treated at 18O⁰C for 3 minutes. These results show that there are no significant relationships between the amount of acrylic binder, the presence of nanoparticles and crock fastness properties.

Table 5

Fabric Dip Coating Tests with and without nanoparticles and silane coupling agent

PET, cotton and silk fabrics were dipped into inks as described Table 6 and dried in the open air overnight. The dried fabrics were cured at 180 ⁰C for 3 minutes using a small lab scale stentering machine, washed under running tap water and dried. The ingredients were added and milled for 2 hrs using Zr bead milling machine prior to dipping. After milling, the mixtures were filtered using Whatmann filter paper (No 1 and No 5).

Table 6

Color values (K/S, L, a, b ) and color fastness to crocking were evaluated. The results are shown in Tables 7, 8 and 9.

Table 7

Table 8

Table 9

As shown in Tables 7, 8 and 9 above, Snowtex®-AK and silane coupling agent were added to the pigment ink with polymeric binder system and improvement of color strength and crock fastness were more apparent than with the addition of polymeric binder alone.

Commercial inks with and without nanoparticles and silane coupling agent

Four commercially available pigment inks were tested with and without Snowtex®-AK and 3-glycidyloxypropyltrimethoxysilane (GPTS). Three different fabrics were dipped into the pigment ink formulations and dried/heat-treated at 180 ⁰C for 3 minutes and washed under running tap water. Color strength and crockfastness were compared and Tables 10, 11 , 12 and 13 show the results. Table 10

Table 11

Table 12

All four colors of pigment inks showed a large improvement in crock fastness or color strength by addition of Snowtex®-AK and GPTS. Significant improvement was not found in silk fabric but improvement in polyester fabrics was distinguishable in color strength or crock fastness.

Digital ink jet printer tests for inks having nanoparticles and silane coupling agent

Inks for digital inkjet printers with wide format were prepared and ink jetting test were carried out on polyester, cotton and silk. The Mill Base ingredients were ball milled using a high speed bead mill with 0.3 mm diameter Zr beads for 2 hours. Table 13

Mill base preparation

Ink Formulation

After milling, the following chemicals were added to the Base of Table 13 to make the final ink formulation. Table 14

The printer used for printing the formulations from Table 14 was a Mimaki Textile-jet TX2-1600. There were no major problems printing the formulated inks. There were no adverse effects from the silica nanoparticles and silane coupling agents on ink jetting from the ink-jet cartridge for the textile printer. Including CYMK (Cyan, Yellow, Magenta, Black), 8 colors of pigmented ink with silica nano particles were prepared with same manner as shown in Table 14.

The color fastness of pigment ink are shown in following Tables 15, 16 and 17.

Table 15

Fastness results on Cotton Fabric

As will be appreciated by those skilled in the art, changes and variations to the invention are considered to be within the ability of those skilled in the art. Examples of such changes are contained in the patents identified above, each of which is incorporated herein by reference in its entirety to the extent it is consistent with this specification. Such changes and variations are intended by the inventors to be within the scope of the invention.

Claims

What is claimed is:

1. A printing composition comprising water, ink, binder, silica nanoparticles and silane coupling agent

2. The composition of claim 1 wherein said nanoparticles and coupling agent are present in a ratio of from 3:1 to 1 :3.

3. The composition of claim 2 wherein said nanoparticles are present in an amount between 0.1 and 10 weight percent

4. The composition of claim 1 wherein said binder is present in an amount between about 0.1 and 10 weight percent.

5. The composition of claim 1 further comprising a dispersing agent.

6. The composition of claim 1 wherein said silane coupling agent is selected from the group consisting of vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3- (meth)acryloxypropylmethyldimethoxysilane, 3-

(meth)acryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxysilane, 3-(4- vinylphenyl)propyltrimethoxysilane, 4-vinylphenylmethyltrimethoxysiIane, 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- aminopropylmethyldimethoxysilane, 3-aminopropyImethyldiethoxysilane, 3-(2- aminoethyl)aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3- mercaptopropylmethyldiethoxysilane, and mixtures and partial hydrolyzates thereof.

7. The composition of claim 1 wherein said nanoparticles have metal ions selected from the group consisting of aluminum, copper, nickel, silver, gold and mixtures thereof.

8. The composition of claim 1 which has been printed onto a substrate selected from the group consisting of composite fabrics of hydroentangled pulp and spunbond fibers, spunbond fabrics, meltblown fabrics, woven fabrics and laminates of spunbond and meltblown fabrics.

5

9. The composition of claim 8 wherein said substrate is a woven fabric made from cotton, silk, polyester or nylon.

10. A printed fabric having thereon the dried residue of an aqueously applied o composition comprising between 0.1 and 10 weight percent nanoparticles, between 0.1 and 10 weight percent silane coupling agent, between 0.1 and 10 weight percent binder and ink.

11. The printed fabric of claim 10 wherein said silane coupling agent is selected s from the group consisting of 3-glycidyloxypropyltrimethoxysilane and 3- aminopropyltriethoxysilane and mixtures thereof.

12. The printed fabric of claim 10 selected from the group consisting of composite fabrics of hydroentangled pulp and spunbond fibers, spunbond fabrics, o meltblown fabrics, woven fabrics and laminates of spunbond and meltblown fabrics

13. The printed fabric of claim 10 wherein, prior to drying, said composition is applied to said fabric my a method selected from the group consisting of slot die, direct gravure, offset gravure with reverse roll transfer, curtain coating, slide coating, 5 forward and reverse roll coating, extrusion coating, rotary screen, spray nozzle application, flexographic printing, rod coating, air knife coating, knife coating, blade coating, dip coating followed by squeeze roll, spin coating, fountain coating, brush application.

0 14. A method of making a printed fabric comprising the steps of: mixing silica nanoparticles and silane coupling agents in a ratio from 1 :3 to 3:1 , adding water, binder and pigment thereto, milling to a particle size of from 150 to 200 nm to make a milled composition, applying said composition to said fabric; and, 5 drying said fabric.