JP2001526995A - Fibrous inkjet printing media - Google Patents

Abstract

  (57) [Summary] Ink jet printing media are provided that improve the waterfastness of the ink on the media, improve the absorption of the aqueous ink into the media, and make the ink jet printed images on the media chromatic and clear. An ink / media set is also provided. The print media is a fibrous cloth or sheet substrate that is treated with a positively charged species to firmly bind the pigment in the ejected ink to the fibers of the media. Where appropriate, the print media also includes a wetting agent, such that the media immediately absorbs the ejected ink. This medium has high tensile and tear strength and is suitable for outdoor signs and banners.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION

The present invention relates to print media, and more particularly to a fibrous sheet material that has been treated to improve the quality of images printed on the sheet material by an inkjet printer.

[0002]

BACKGROUND OF THE INVENTION

Ink jet printing is a non-impact method that records information in response to electrical signals such as signals generated by a computer.
od). In an ink jet printer, an electric signal generates ink droplets to be coated on a print medium such as paper or a film sheet. Inkjet printers offer reliability, relatively quiet operation, graphic performance, print quality,
And is widely accepted in the market due to its low cost.

In current ink jet printers, some primary color inks (usually,
(Black, cyan, magenta, and yellow) are used to print text and graphic information on print media. These inks are composed primarily of water and contain a colorant that is a dye or pigment dispersion. Dye-based inks tend to fade when exposed to sunlight. Pigment-based inks exhibit good light stability, especially when used in outdoor applications. Most ink jet printing inks also include polyhydric alcohols to prevent nozzle clogging and also include various other minor additives. U.S. Pat. No. 5,085,698 (EI du Pont de
Nemours & Company (hereinafter "DuPont") discloses a pigment ink suitable for use in ink jet printing.

[0004] Inkjet printed images consist of discrete dots of ink. In order to print colored image information such as photographs or complex graphics, it is important that dots have sharp boundaries. Breeding or wicking of the ink on the print medium reduces the resolution of the image. This also occurs when the printed image is brought into physical contact with the ink before the ink is sufficiently dried. However, if the printed image easily bleeds, the image printed by the inkjet is deteriorated. Occasionally, printed colors are obtained by combining primary color inks with an ink coverage greater than that required for 100% coverage. When printing inks at such high densities, it is very important that the ink be quickly absorbed into the media and dried before it bleeds.

[0005] Ink jet printing is often performed on plain paper. Paper is a suitable medium for many desktop publishing applications if it is not exposed to physical adverse conditions such as wind, rain and sunlight. Print the printed sheet on a map, packaging material, or outdoor sign and banner (b
In applications where the print medium must be durable under physical adverse conditions for long periods of time, such as when used in an anner, a strong, durable print medium is needed. Print media used in outdoor applications or under physical adverse conditions must be strong and capable of receiving and maintaining high resolution images even after prolonged exposure to wind, rain and sunlight. There must be. Ink jet printable media suitable for use under adverse physical conditions, such as outdoor applications, must not shrink or deform when wet. The strength of the medium must also be maintained for long periods of time despite exposure to wind, rain and sunlight. On the other hand, ink-jet printable media must rapidly absorb the water present in the ink-jet printing ink, even when printing the ink at high density and high speed, so as not to flood the ink on the media surface. At the same time, the ink-jet printable media must not promote ink wicking at the media surface, or the printed image would be blurred and more transparent than desired.

[0006] Synthetic fibrous sheets, such as sheets made of spunbonded polyolefin, are tough, durable, and flexible. However, when conventional inkjet printing inks are jetted directly onto synthetic fibrous sheets, the printed images are very poor. The colors are washed out and the sharpness of the image is poor (ie, poor boundaries between colors as well as wicking of colors into non-printed areas). Thus, ink jet print media currently used in printed products that must withstand physical adverse conditions are made up of two or more layers. Such materials generally include a support layer made of a high strength sheet material such as vinyl or nylon, and an ink-receiving layer of one or more printable hydrophilic layers coated on the support layer.
PCT Publication No. WO 97/01448 discloses an inkjet printed substrate consisting of a film or nonwoven web coated with a second layer containing a latex binder, hydrophilic silica, a cationic polymer, and a surfactant. U.S. Pat. No. 4,775,594 discloses a polyester film coated with a clear coating comprising a clear polymer resin and a non-volatile organic acid.
An inkjet printable transparency material is disclosed. US Patent No. 5
No. 4,429,860 (assigned to DuPont) discloses an ink-jet printable sheet comprising a support sheet coated with a hydrophilic polymer binder containing a reactive component such as an acid or base group, which assists in binding the ink to the sheet material. Is disclosed.

[0007] Coated printed sheets are taller than desired and expensive to manufacture. What is needed is a single layer sheet material that is not bulky, tough, durable, and still inkjet printable, but not expensive. This single layer sheet material must also rapidly absorb water-based ink jet printing inks, even when printing inks at high density and high speed. Also, for such inkjet printable sheet materials to be suitable for outdoor applications, the single layer sheet material must retain the inkjet printed ink even after exposing the printed sheet to wind, rain and sunlight. Must.

[0008]

SUMMARY OF THE INVENTION

The present invention provides an inkjet printable media comprising a fibrous polymer substrate having a positively charged species on a surface. The inkjet printable media of the present invention has a tensile strength of at least 20 N / 2.54 cm, a basis weight of less than 8 oz / square yard, and a TAPPI T558 pm of at least 0.01 microliter / mm ² / sec. It is an integral sheet structure having a water absorption rate of -95 and an IJE color washout of less than 50%. Preferably, the fibrous polymer substrate is a nonwoven sheet, such as a spunbonded polyolefin sheet. Fibrous substrates consist of fibers having on their surface positively charged colloidal silica and a wetting agent. Alternatively, the fibrous substrate comprises a positively charged proton, metal ion, or cationic polymer on the surface, and
If necessary, consist of fibers with wetting agents.

The invention also relates to an ink / print comprising (a) an ink comprising an insoluble colorant in an aqueous carrier medium, and (b) an ink-jet printable medium such as those described above. Provide a set of media. The invention also provides (1) forming a solution comprising water and a source of a positively charged species; (2) wetting a fibrous polymer substrate with the solution; / 2.
Has a basis weight of strength and less than 8 oz / tensile 54cm, (3) drying the substrate, dried substrate is at least 0.01 microliters / mm ² / sec TAPPI T558pm- Providing an ink jet printable medium comprising having a water absorption rate according to 95 and a color washout according to the IJE method of less than 50%. The source of the positively charged species is preferably selected from the group of positively charged colloids, acids, cationic polymeric materials, and water-soluble compounds of calcium, aluminum, magnesium and zirconium. If the fibers of the substrate do not readily wet, the process includes an additional step of adding a wetting agent to the solution before wetting the fibrous substrate with the solution. The print medium processed by the method of the present invention is measured by the OD method,
It has a four color optical density that is at least 8% greater than the four color optical density of the fibrous polymer substrate before wetting the substrate with the treatment solution.

A more detailed description of the invention is provided in the following detailed description of the preferred embodiments.

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an inkjet printing medium that improves the waterfastness of the ink on the medium and improves the absorption of the aqueous ink into the medium. The present invention also provides a method for making inkjet printed media appear chromatic (because the colorant is kept near the surface of the media) so that the lines and edges of the image and the image are sharp and distinct. Provide both media on which images can be printed. The print media of the present invention has a fibrous texture that has been treated so that the media readily absorbs the ejected ink and the pigments and dyes in such ejected inks are strongly bonded to the media fibers. Cloth or sheet substrate. Preferably, the media has high tensile and tear strength to provide utility of the media for outdoor applications such as signs and banners.

[0012] The present invention also provides a set of inks and print media. The inks in this ink / medium set are dye-based or pigment-based aqueous inkjet printing inks. Preferred pigment inks maintain their color even after prolonged exposure to sunlight. Dye-based or pigment-based inks are described in US Pat. No. 5,429,860, assigned to DuPont, which is hereby incorporated by reference. The preparation of more preferred pigment-based inks is described in the examples below. The print media of the ink / medium set is the print media described herein.

[0013] The inkjet printing medium of the present invention is a fibrous substrate that has been treated to make the substrate significantly inkjet printable. The fibrous substrate is preferably a woven or non-woven sheet or cloth. More preferably, the fibers of the fibrous substrate are polymer fibers. As used herein, a "fibrous polymer substrate" is a substantial portion of a synthetic polymer fiber such as a polyamide fiber, polyester fiber, or polyolefin fiber, or a blend of such synthetic fibers, or natural and synthetic fibers. Woven or non-woven fabric or sheet made of a blend of More preferably, the print medium is an integral structure. As used herein, "monolithic structure" means a coated layer or lamination made of the same type of fiber or blend of fibers in the thickness direction of the fabric or sheet structure, where the fibers are distinguishable. Used to indicate a woven or non-woven fabric or sheet that forms a substantially uniform layer that does not.

According to a preferred embodiment of the present invention, the fibrous substrate of the inkjet print media is a nonwoven sheet or sheet that is tough, tear-resistant, and does not degrade quickly when exposed to rain and sunlight. It is an integral structure made of woven fabric. A preferred fibrous substrate is a fibrous polyolefin sheet. Suitable polyolefin fibrous sheet materials include spunbond webs of polypropylene and polyethylene, scrims, woven slit films, carded webs, flash spun webs,
And woven or non-woven sheets of polyolefin fibers or blends of polyolefin fibers and other fibers. Woven fabrics for fibrous substrates include fibers made up substantially of polyamide, polyester and polyolefin fibers. Preferred woven fabrics for print media include nylon 6,6, DACRON (TM) polyester, and blends of polyester and natural fibers such as cotton. Dacron ™ is a registered trademark of DuPont.

US Pat. Nos. 3,169,899 and 3rd, incorporated herein by reference.
, 532,589 (both assigned to DuPont),
Flash-spun polyethylene plexifilament
ary) is a particularly preferred fibrous base material for use in the ink jet printable media of the present invention. The term "plexi-fiber" refers to a three-dimensional, multi-layer, thin, ribbon-like film-fibril element of random length, with an average film thickness of about 4 microns or less, and a medium fibril width of about 25 microns or less. Means a single mesh. In a plexi-fibre structure, the film-fibril elements are generally co-extensive with the long axis of the structure to provide a length of the structure,
It intermittently joins and separates at irregular intervals at various locations across the width and thickness to form a continuous three-dimensional network.

One such plexifibre sheet material is TYVEK ™, a spunbond polyolefin sheet sold by DuPont. TYVEK (
(Trademark) is a registered trademark of DuPont. The TYVEK ™ sheet is made from heat bonded flash spun polyethylene and forms a lightweight sheet with excellent strength while also exhibiting good resistance to normal weathering conditions. In addition, TYVEK ™ sheet material is easily recycled because it is made of high density polyethylene. TYVEK ™ sheet material is made by adding stabilizers to polyethylene to improve the sheet's resistance to degradation by prolonged exposure to heat or UV light. Antioxidants (such as Irganox 1010 also manufactured by Ciba-Geigy) and acid neutralizers (such as calcium stearate) are also added to the polymer fibers of the sheet to reduce degradation during prolonged weathering. To stabilize the TYVEK ™ sheet against UV degradation, a hydroxylamine stabilizer may also be added to the fibers of the sheet.

Particularly suitable for the fibrous substrate of the inkjet printable media of the present invention is TYVEK ™ type 1082C sheet material due to its high tensile and tear strength. TYVEK (TM) 1082C sheet material has a basis weight thickness of about 255 microns and about 101g / m ² (3.0 oz / yd). The TYVEK ™ 1082C sheet material has an Elmendorf tear strength between 5.0 and 9.2 Newtons and a tensile strength of about 360 N / 2.54 cm.

According to the present invention, the fibrous substrate is treated with a positively charged species that functions to bind the colored pigment or dye in the ink jet printing ink to the fibers of the fibrous substrate. When the fibrous substrate is composed of hydrophobic fibers, such as most synthetic polymer fabrics and sheets, it is also preferred that the fibrous substrate be treated with a wetting agent. Preferably, the positively charged species and the wetting agent are applied to the fibrous substrate in the form of a liquid mixture or solution. The wetting agent allows the liquid mixture or solution to come into full contact with the fibrous substrate,
Positively charged species in the treatment mixture or solution can reach as many fibers of the fibrous substrate as possible. Hereinafter, the term "treatment liquid" is defined to include both true solutions and colloidal dispersions.

The fibrous substrate is immersed in the treatment liquid with a treatment liquid containing a positively charged species and, if appropriate, a wetting agent, and then drying the substrate. Is handled by Preferably, the fibrous substrate is immersed in the treatment liquid long enough to saturate the substrate. When removing the substrate from the processing solution, excess solution is squeezed out of the substrate, and then the substrate is air-dried or oven-dried. Alternatively, the treatment liquid is applied to the fibrous substrate by an applicator roll, spray applicator, air knife, or Meyer rod. Even after the treatment liquid has been dried on the fibrous substrate, the positively charged species and wetting agent remain on the fibers of the substrate. The wetting agent makes the fibers more hydrophilic (ie, more receptive to aqueous inkjet printing inks). As used herein, "aqueous printing ink"
It is defined as a water-based ink containing other liquids such as alcohol. It is believed that the positively charged species form protonated sites in the fibers near the surface of the fibrous substrate that function to trap the pigment or dye of the aqueous ink.

The preferred ink jet printing ink is a pigment ink, since the pigment ink retains color better than other inks, especially in outdoor applications. Ink jet printable pigment inks are dispersions of the pigment in an aqueous carrier medium manufactured as described in the Examples below. Ink jet printable pigment inks are usually anionic, but may be cationic. If the pigment is cationic, the positively charged species of the print medium are preferably replaced by negatively charged species.

[0021] The stability of the pigment ink dispersion depends on the ability of the dispersant to dissolve or disperse in the carrier medium. When reducing the dispersibility or solubility of the dispersant in the carrier medium, or when rendering the dispersant insoluble, the pigment dispersion becomes unstable.
As a result, the pigment dispersion precipitates. This precipitate is also commonly known as flocculation or coagulation. Without wishing to be bound by theory, the positively charged species on the surface of the treated fibrous print media of the present invention can: (1) destabilize the pigment dispersion to cause aggregation of the charged pigment; (2) attracts the oppositely charged pigment in the ink to the substrate fibers; and (3) captures the pigment near the surface of the substrate as the aqueous portion of the ink is rapidly absorbed into the fibrous substrate. Yes function. When the print media of the present invention is used with a dye-based inkjet printing ink, the positively charged species of the print media of the present invention insolubilize the dye and precipitate the dye on the fibrous substrate. Cause This precipitate is commonly referred to as dye fixation.

Sources of positively charged species that have been found to enhance ink jet printability of fibrous substrates include positively charged colloids, strong acids, aluminum chlorohydrate, aluminum zirconium tetrachlorohydrex glycine , Calcium chloride, and combinations thereof. Cationic coagulants and flocculants, such as calcium, aluminum, magnesium, and zirconium metal ions and polymeric materials with positively charged sites (ie, amine and amide sites), also serve as sources of positively charged species. I do. The positively charged species is applied to the fibers of the fibrous substrate by the treatment liquid.

It has been found that the addition of a wetting agent to the treatment liquid makes the fibrous substrate more ink jet printable. Such wetting agents include ionic, amphoteric, and non-ionic surfactants. The wetting agent in the treatment liquid helps to ensure that treatment liquids that are difficult to reach the fibers of the print media substrate penetrate and are treated. Other minor components are added to the processing liquid to improve mixing and application of the liquid to the print media substrate. For example, a known defoamer is added to the treatment liquid to reduce foaming during application of the liquid to the print medium substrate. In order to improve the miscibility of the components in the liquid and make the liquid more stable,
A small amount of a soluble solvent such as isopropyl alcohol is also added to the processing solution.

The concentration of the active ingredient in the processing solution is determined by the desired level of image vividness and vividness (measured as optical density), the desired resistance of color washout, and the desired level of ink-jet print on the print medium. Depends on rub resistance. The actual concentration of the active ingredient on the print medium depends on the absorption of the liquid during processing of the medium with the treatment liquid and the concentration of the active ingredient in the treatment liquid. The active ingredient on the print medium can be made to have a higher concentration even by multiple treatments with the treatment liquid. If the treatment liquid is applied with a spray, roll, air knife, or Meyer rod applicator, it is expected that the treatment liquid will be applied more than once to the same surface of the print medium to make the treatment more uniform. If the user of the print medium desires to print on both sides of the print medium, it is also expected that the treatment liquid will be applied to both sides of the print medium.

According to one preferred embodiment of the present invention, the treatment liquid for treating the fibrous polymer substrate to increase the inkjet printability of the substrate includes calcium chloride, positively charged colloidal silica. And one or more surfactants (Examples 4-8)
See). One positively charged colloidal silica that has been found to dramatically improve the inkjet printability of polyolefin-based substrates is DuPo
LU of positively charged colloidal silica (40% solids) marketed by nt
DOX (TM) CL-P. LUDOX ™ is a registered trademark of DuPont. Colloidal silica is particularly effective for treating fibrous polymer substrates to produce ink-jet printable media when the treatment liquid also includes calcium chloride as an additional source of positively charged species. I found it to be. Two surfactants combined with colloidal silica and calcium chloride in the processing solution are alcohol ethoxylate propoxylate (MERPO sold by DuPont)
L (trademark) LF-H) and polyalkylene oxide-modified heptamethyltrisiloxane (WITCO Corporation (Greenwich, Conn.)
SILWET (TM) L-77) sold by E.I.

According to another embodiment of the present invention, a liquid for treating a fibrous polymer substrate to produce an ink-jet printable medium is prepared from an acid used alone or in combination with a surfactant. Become. One acid that has been found to be particularly effective in improving ink jet printability of fibrous substrates is phosphoric acid, especially when used in combination with citric acid and a surfactant (Examples 10-16). It is.

According to another embodiment of the present invention, a treatment liquid for treating a fibrous polymer substrate to increase the inkjet printability of the substrate comprises calcium chloride, positively charged colloidal silica, Consist of aluminum chlorohydrate, aluminum zirconium tetrachlorohydrex glycine, and one or more surfactants in water (Examples 17-20). Preferred surfactants are Union
Carbide Corporation (Danbury, Connecti
cut), a nonionic alcohol ethoxylate surfactant, TERGITOL ™ TMN-6. Other non-acid sources of positively charged species for print media include n-butyl phosphate (Example 21) and polymer complexing agents (Examples 22 and 23).

As can be seen in Examples 38-62, treating various fibrous substrates with various acids can reduce the optical density of inkjet printed images, even when no surfactant is present in the processing solution. Be improved. When the acid has a pH of 2.2 or less, using only the acid improves the optical density of the ink-jet printed image on the treated fibrous substrate. Treatment with such a liquid also reduces bleed observed in printed images on acid-treated substrates. The effects of the acids used in Examples 38-62 on reducing image bleed and improving optical density ("OD") are summarized below.

[0029]

[Table 1]

Sulfuric acid and various inorganic acids have also been found to improve the ink jet printability of fibrous substrates. One disadvantage of the acid treatment is that the acid degrades the substrate or reacts with those in contact with the treated substrate. For this reason, Example 4
Print media -7 and 17-20 are further preferred embodiments of the present invention.

Processing the fibrous substrate as described above produces a print medium in which the inkjet printed image is sharp and chromatic. Images on the print media of the present invention exhibit low color washout when wet and very good wet and dry rub resistance. Wet and dry rub resistance is expected to be further improved by applying a commercial water-based or solvent-based coating to the printed image. Such coatings include Rohm & Haas (Philade
IPHIA, Pennsylvania) and RHOPLEX ™ Emulsion E-2321 and Water-Mat, Inc. (Syracuse, New
York) WATER-MAT.

The print media of the present invention is an economical, monolithic inkjet printable media that holds inkjet printed inks and has the strength and durability required for demanding applications. As exemplified below, the print media of the present invention can be affixed to a solid surface, cloth or other substrate such as a reinforcing scrim material.

The following non-limiting examples are intended to illustrate the products and methods of the present invention and are not intended to limit the invention in any way.

[0034]

【Example】

In the following examples, a sample of the sheet material is saturated with various processing solutions,
Excess treatment liquid was squeezed out between rubber-coated nip rollers. Next, the sample was oven dried. The dried samples were tested for water absorption, washout of inkjet printed colors, readability of inkjet printed barcodes, and optical density properties of inkjet printed colors as described in the Examples below. . Production of Ink Production of Dispersant 1 A 1 liter flask was equipped with a mechanical stirrer, thermometer, nitrogen inlet, drying tube outlet, and addition funnel. 164 g of tetrahydrofuran (THF), 0.5 g of tetrabutylammonium m-chlorobenzoate (TBACB), and 15 g of 1,1-bis (trimethylsiloxy) -2-methylpropene were charged into a flask.
Feed 1 (THF, 20 g; TBACB 0.5 g) was started and added over 120 minutes. Feed 2 (trimethylsilyl methacrylic acid, 102 g) was started simultaneously and added over 30 minutes. 30 minutes after the addition of feed 2, feed 3 (n-butyl methacrylate, 92 g; methyl methacrylate, 3
2g) was started and added over the next 30 minutes. One hour after the completion of Feed 3, 50 g of methanol was added and 100 g of volatiles were removed by distillation. Preparation of Dispersant 2 A 1 liter flask was equipped with a mechanical stirrer, thermometer, nitrogen inlet, drying tube outlet, and addition funnel. THF, 194 g, TBACB, 1.2 g, 1, 1
-Bis (trimethylsiloxy) -2-methylpropene, 14 g, was charged to the flask. Feed 1 (THF, 20 g; TBACB 1 g) was started and added over 120 minutes. Feed 2 (trimethylsilyl methacrylic acid, 95 g) was started simultaneously and added over 30 minutes. Thirty minutes after the addition of Feed 2, Feed 3 (benzyl methacrylate, 138 g) was started and added over the next 30 minutes. One hour after the completion of Feed 3, 25 g of methanol was added,
75 g of volatiles were removed by distillation. Preparation of Black Concentrate A black dispersion was prepared using the following procedure.

[0035]

[Table 2]

The above mixture was placed in a two-roll mill and processed for 45 minutes. This produced a pigment chip containing 67% pigment and 33% polymer. 42g of this chip 300g
And diluted with 1658 g of deionized water,
A 10% pigment solids black concentrate was prepared. Preparation of Cyan Concentrate A cyan dispersion was prepared using the following procedure.

[0037]

[Table 3]

The mixture was placed in a two-roll mill and processed for 45 minutes. This produced a pigment chip containing 60% pigment and 40% polymer. 38g of this chip 250g
And diluted with 1212 g of deionized water,
A 10% pigment solids cyan concentrate was prepared. Preparation of Magenta Concentrate A magenta dispersion was prepared using the following procedure.

[0039]

[Table 4]

The above mixture was placed in a two-roll mill and processed for 45 minutes. This produced a pigment chip containing 60% pigment and 40% polymer. 38g of this chip 250g
And diluted with 1212 g of deionized water,
A 10% pigment solids magenta concentrate was prepared. Preparation of Yellow Concentrate A yellow dispersion was prepared using the following procedure.

[0041]

[Table 5]

The mixture was placed in a two-roll mill and processed for 45 minutes. This produced a pigment chip containing 55% pigment and 45% polymer. 330g of this chip is 57
g of 45% caustic solution and diluted with 1413 g of deionized water to produce a 10% pigment solids yellow concentrate. Preparation of primary color inks Black used in Examples 1-37 by mixing together the following components:
Four primary color inks of cyan, magenta and yellow were produced.

[0043]

[Table 6]

The following components were mixed together to produce the four primary color inks used in Examples 38-62: black, cyan, magenta, and yellow.

[0045]

[Table 7]

Liponics ™ EG-1 is available from Lipo Chem. Co. (Pate
rson, New Jersey). Zony ™ FSO is a surfactant sold by DuPont. Surfynol 440 is available from Air Products, Inc.
. (Allentown, Pennsylvania). In Printing Examples 1-37, inkjet printing of the inks used for color washout and optical density measurements was performed by Encad, Inc. (San Die
go, California) Encad Novajet Pro-50 (Enc)
ad Novajet Pro-50) Color inkjet printer. With this encad printer, 300 over a 50 inch print width
Color printing was performed at dpi × 300 dpi. Print pattern is black, cyan,
There was a series of seven 0.5 inch squares of the colors yellow, magenta, red, green and blue. X-Rite ™ Densitometer, Model 41
8 (X-Rite Inc. (Grandville, Michigan)) was used to measure the optical density on this color square.

In Example 1-25, the ink jet printing of the black barcode for the barcode readability test was performed at 300 dpi × 300 dpi color and 600 dpi.
Hewlett Packard Deskjet 560c (Hewlett Packard Deskjet 560c) for black printing at pi × 600 dpi (He
Wlett Packard (Palo Alt, CA)) printer.

In Examples 38-62, using Hewlett Packard 560c
A series of seven 0.5 inch squares of black, cyan, yellow, magenta, red, green and blue colors used for optical density measurements were printed. In Examples 38-62, an X-Rite ™ densitometer, model 41
Using No. 8, the optical density was measured on the color square. The printed pattern also includes an array of colored lines on a yellow background, indicating control of ink spreading, and therefore line sharpness and image resolution. Test Methods In the above description and in the following non-limiting examples, the following test methods were used to determine the various performance and properties noted. ASTM refers to American Society for Testing Materials, TAPPI refers to American Pulp and Paper Technology Association, and ANSI refers to American National Standards Institute. Basis Weight The basis weight is determined according to ASTM D-3776, which is incorporated herein by reference, and is stated in g / m ² . The basis weights noted for the examples below are each based on the average of at least 12 measurements made on the sheet. Absorption AST Products (Billerica, Massachusetts)
es) The absorption was measured using a video contact angle system, VCA 2500XE from TAPPI, according to TAPPI method T558pm-95. Three unprinted test samples, each 1 inch by 0.25 inch, were cut from the sample to be tested. Drops of deionized water were sequentially deposited on each specimen using a motor-driven syringe programmed to deposit 0.8 microliters of water. The needle was removed from the drop by lowering the sample. Depending on the rate of absorption, the absorption of water droplets into the test samples was recorded using a video camera programmed to record at a rate of 14.5 frames per 3 seconds or 5 frames per 12 seconds. The drop volume was determined at the first and last frames where the drop was clearly visible as the difference between the measurements of the two drops. The absorption rate was determined by dividing the drop volume difference between the first and last frames where the drop was clearly visible by the elapsed time between the first and last frames. The absorption rate was recorded in microliters per second (microliter / mm ² / sec) per unit area of the sample covered by the water droplets. Optical Density The optical density was measured by a method developed by DuPont (hereinafter referred to as "OD method"). The optical density is a measure of the amount of reflected light from the test sample. The optical density is a logarithm of which the base of the reciprocal of the amount of reflected light is 10. Optical density = log ₁₀ (1 / reflected light) 7 of black, cyan, yellow, magenta, red, green and blue colors
0.5 printed as above with a series of two 0.5 inch square printed squares
The optical density was measured for a sample piece of inch × 4 inch. Red, green and blue squares were printed with a combination of the four primary color inks.

X-Rite ™ model 418 densitometer (X-Rite ™
, Inc. (Gndville, Michigan)) was used to measure the optical density of each color square. Status E density
) (ANSI / ISO 5-3-1995, ANSI / NAAPM IT2.1)
8-1996). For each sample, the optical density of the non-printed section of the sample was measured. This measurement was stored in a densitometer. The optical density was measured individually for each of the seven colors of the sample. The optical density recorded for each color was obtained by subtracting the optical density measured at the non-printed part of the sample from the optical density measured at the printed part.

The optical densities measured for the four primary colors (black, cyan, yellow, magenta) are described dimensionlessly for the following examples. The average of the optical densities of the four primary colors is also shown. Using the average optical density calculated for each sample and the average optical density for the untreated control sample, the percentage improvement in optical density was determined. The percent improvement in optical density was calculated as follows. Percent improvement = [(average optical density (treated sample)-average optical density (control)) (optical density) / average optical density (control)] x 100 Color washout and later called "IJE method", DuPont's Ink Jet Enterpri
Color washout was measured by the following method devised by Se. According to the IJE method, a series of seven 0.5 inch × 0.5 inch squares of black, cyan, yellow, magenta, red, green and blue colors were printed 0
. Washout was measured on a 5 inch × 4 inch specimen. Printing was performed by the above-described inkjet printing method using the pigment-based ink as described above.
The optical density of each of the printed squares was measured using an X-Rite model 418 densitometer. Next, the printed piece was submerged in the water of the beaker. Next, a magnetic stir bar was placed and the beaker was placed on a standard laboratory magnetic stirrer. The stirrer was turned on and the sample was stirred for 30 minutes. Next, the test sample was removed from the beaker and air-dried. Using a X-Rite model 418 densitometer, the optical density of each of the seven washed test samples was measured.

The percent color washout was determined from the optical densities measured for each of the seven colors before and after washing the sample. The percent washout for each of the seven colors was averaged to give the overall color washout described in the Examples below. The percent color washout for each color was calculated as follows. Percent washout = [((optical density (before washing))-optical density (after washing)) (color) / optical density (before washing)] x 100 barcode readability ANSI X3, here incorporated by reference. The bar code readability was measured according to .182-1990.The ANSI X3.182-1990 test measures the print quality of bar codes for the purpose of code readability, which tests contrast, modulation and defects. And evaluate the print quality of the barcode symbol for decodeability and assign a rating of A, B, C, D or F to each category, where the rating "A" is the highest rating and requires the least mathematical calculations. Represents a highly readable code that can be decoded by the scanner unit.
"F" is the lowest grade for a barcode for which the scanner produces a response and represents a barcode that requires a large amount of mathematical calculations by the scanner unit to interpret. The overall grade of the sample is the lowest grade obtained in any of the above categories. At least 7 out of 10 barcode scans are grade "F"
Otherwise, the barcode is considered readable.

Seagull Scientific Systems (Redmond,
Barton Tender, a software marketed by Washington, DC
Full ASCII code 3-9 and UP generated using for Windows
The test was performed using a CA barcode. Using the above black ink, 600
Hewlett Packard 560c for printing at dpi x 600 dpi (black)
The barcode was inkjet printed by a printer. Scanner is Pho
graphical Science Corporation Inc. (W
and a 6 mil bandwidth PSC QuickCheck 650 scanner from Ebster, New York. Automat
ic Identification Systems (Westerville)
e, Ohio) software Scanalst. Frazier porosity Frazier porosity is a measure of the air permeability of a porous material and is expressed in units of ft ³ / ft ² / min. Fresia porosity measures the volume of air flow through a material at a differential pressure of 0.5 inches of water. An orifice is attached to the vacuum system to limit air flow through the sample to a measurable amount. The size of the orifice depends on the porosity of the material.
Sherman W. Frazier Co. Porosity is measured in ft ³ / ft ² / min using a dual manometer with a calibration orifice of Example 1-9 about 101g / m ² (3.0 oz / yd) of the average basis weight of TYVEK (trademark) samples a surfactant spunbonded polyethylene sheet of 1082C, calcium chloride, colloidal silica and de Ionized water was immersed in the treatment solution containing the weight percentages listed for Examples 1-8 in Table 1. Example 9 is a control sample of the same sheet material that was not treated with the treatment liquid. Surfactants are alcohol ethoxylate propoxylate (MER sold by DuPont)
POL ™ LF-H) or polyalkylene oxide-modified heptamethyltrisiloxane (WITCO Corporation (Greenwich,
SILWET (TM) L-7 sold by J. Connecticut))
7) or a combination thereof. Calcium chloride solution is 5 to 1 of processing solution
5 weight percent was formed (from 37.5 weight percent technical grade liquid). Positively charged colloidal silica is a colloidal silica liquid (40% solids) (D
LUDOX ™ CL-P sold by uPont.

Excess treatment liquid was squeezed out by passing the wet sample between rubber-coated nip rollers. Liquid absorption by the sheet was approximately equal to the weight of the sheet (about 3 ounces on a square yard basis). The samples were oven dried at 90 ° C to 95 ° C and then tested for water drop absorption. The above-described seven color blocks were inkjet-printed on the dried sheet sample using the above-described encad inkjet printer. Optical density and color washout were measured for each of the above samples. The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the ink) for the treated sample of the example and the untreated control sample (Example 9). Also print a black barcode (using Hewlett Packard 560c) on the dried sample and scan with a barcode scanner as described above to see if the printed image is clear enough to be read by the barcode scanner. Was examined. The results are shown in Table 1 below.

[0054]

[Table 8]

As can be seen from Examples 4-7, 20% colloidal silica liquid (40% solids)
5% calcium chloride solution (37.5 weight percent CaCl ₂ ); A treatment solution of between 5% and 2% of the surfactant significantly improved the inkjet printability of the spunbond polyethylene substrate as compared to an untreated sample of the same sheet material (Example 9). The treated sample absorbed water seven times faster than the untreated sample. The untreated sample of Example 9 was five times less waterfast than any of the treated samples of Examples 4-7. The barcode printed on the treated sample was clear enough to be read with a barcode scanner, but the same printed barcode on the untreated sample could not be read with a barcode scanner. Finally, the average optical density of the four primary inks printed on the treated samples was 28% to 46% greater than on the untreated control samples.

Examples 1-3 illustrate an alternative embodiment of the present invention, wherein calcium chloride is the only source of positively charged species on the print media. Examples 1 and 2 show that increasing the weight percent of the calcium chloride solution (37.5% CaCl ₂ ) improves the optical density of the printed image. Examples 1 and 3 show that when the weight percent of the calcium chloride solution was kept at a constant 5%, only a slight improvement in the optical density was obtained as a result of reducing the pH of the processing solution. Example 2 shows that significant improvement in optical density is obtained with calcium chloride as the sole source of positively charged species, but the printed image of Example 2 shows a relatively high color wash of 15.7%. Show out. It was also observed that the print image of Example 2 was more chalk-like than the print image of Example 4-7. The mechanical properties of the printed image of Example 2 were inferior and were more easily rubbed than the printed images of Examples 4-7, using colloidal silica as another source of positively charged species on the print medium. Dropped. If calcium chloride is the only source of positively charged species on the print media,
White spots were often observed in the printed images when calcium chloride was removed from the media with the printed ink.

Without wishing to be bound by theory, the positively charged colloidal silica forms spheres or clumps that are more mechanically entangled with the fibers of the print media than are the positively charged ions of calcium chloride. It is thought that. Thus, when the anionic ink pigment adheres to the surface of the colloidal silica spheres, the fibrous substrate and the printed image are less than when calcium chloride is the only source of positively charged species on the print media. And the mechanical properties are more satisfactory. On the other hand, if some calcium chloride is present on the print medium, the pigment in the anionic ink will agglomerate on the surface and the pigment will contribute the most to a vivid and lively image, so that the It is believed that the colors look vivid and clear. Examples 10-16 Similar to the sheets used in Examples 1-9, TYVEK ™ 1082C sheets were prepared by combining surfactant, acid, and deionized water with the weight percentages listed for Examples 10-16 in Table 2. Immersed in the treatment solution contained in The surfactant was potassium butyl phosphate (ZELAC ™ -TY sold by DuPont)
) Or octylphenoxypolyethoxyethanol nonionic surfactant (U
Nion Carbide Corporation (Danbury, Conn.)
TRITON (TM) X-100 sold by Necticut))
It is. The acid is phosphoric acid or a combination of phosphoric acid and citric acid. A treatment solution was prepared by first adding a surfactant to the deionized water and then adding a small amount of 80% reagent grade phosphoric acid to adjust the pH. In Example 16, which also used citric acid, the liquor was first adjusted to pH 1.7 with phosphoric acid and then to pH 1.64 with citric acid. The pH was measured with a Brinmmann, model 691, pH meter.

Excess treatment liquid was squeezed out by passing the wet sample between rubber-coated nip rollers. Liquid absorption by the sheet was approximately equal to the weight of the sheet (about 3 ounces on a square yard basis). The samples were oven dried at 90 ° C to 95 ° C and then tested for water drop absorption. The above-described seven color blocks were inkjet-printed on the dried sheet sample using the above-described encad inkjet printer. Optical density and color washout were measured for each of the above samples. The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the ink) to the treated sample of the example and the untreated control sample (Example 9). Also, the dried sample is printed with a black barcode (using Hewlett Packard 560c) and scanned with a barcode scanner as described above to determine whether the printed image is clear enough to be read by a barcode scanner. Was evaluated. The results are shown in Table 2 below.

[0059]

[Table 9]

[0060] Examples 10 and 16, comprising an acid used in combination with a potassium butyl phosphate ester (ZELAC ^R -TY), processing the fibrous polymer substrate, a good medium for ink jet printability 3 shows a liquid for production. In particular, when citric acid and potassium butyl phosphate are used in combination, phosphoric acid has been found to be particularly effective in improving the inkjet printability of fibrous substrates. Without wishing to be bound by theory, both the phosphoric acid and the acidified potassium butyl phosphate ester form positive pigments in the anionic inkjet printing ink on the print media that aggregate and bind near the surface of the print media. It is thought to function as a charged species. The acidified potassium butyl phosphate has a hydrophobic end that is believed to bind to the fibrous substrate of the print medium and a hydrophilic end that is believed to bind to the pigment of an anionic inkjet printing ink. Potassium butyl phosphate is
It is believed that in an acid environment, the print medium acts as a wetting agent to make the aqueous inkjet printing ink more readily absorbed.

First, potassium butyl phosphate (6% by weight) is added to deionized water,
Next, a small amount of phosphoric acid was added to this solution to adjust the pH of the solution to 1.7, and further, the pH of the solution was adjusted to 1.64 with citric acid (Example 16). Was manufactured. The inkjet printed image printed on the print medium of Example 16 had a more uniform appearance than the image printed on the medium of Example 10 where the only acid was phosphoric acid. It is believed that the presence of citric acid results in improved spreading of the ink on the surface of the print media. The fibrous sheet treated as described in Example 16 absorbed water more than 200 times faster than the untreated sample of Example 9. When tested for waterfastness, the untreated sample of Example 9 faded more than 13 times the inkjet printed image than the treated sample of Example 16. The barcode printed on the processed sample of Example 16 was clear enough to be read by a barcode scanner, but the same printed barcode on the unprocessed sample could not be read by the barcode scanner. In addition, the average optical density of the four primary color inks printed on the treated sample of Example 16 was 29% greater than on the untreated control sample of Example 9.

In Example 11, when the pH of the processing solution was increased, potassium butyl phosphate (ZELAC ™ -TY) was reduced in the absorbency of the print medium, and the color wash of an image printed on the medium was reduced. Indicates a less effective wetting agent with increased out. Example 12 demonstrates that reducing the amount of potassium butyl phosphate in the processing solution to 4% by weight has a detrimental effect on both the absorbency of the print media and the optical density of the image printed on the media. Show. Examples 13-15 use a nonionic surfactant (TRITON ™ X-100 instead of potassium butyl phosphate).
) Shows that the improvement in the optical density of the image printed on the medium is significantly less. Examples 17-20 A sample of 101 g / m ² (3.0 oz / sq. Yard) basis weight TYVEK ™ Type 1082C spunbond polyethylene sheet was prepared by charging a positively charged colloidal silica, calcium chloride, aluminum chlorohydride. The sample was immersed in a treatment solution containing a rate, aluminum zirconium tetrachlorohydrex glycine, a surfactant, and deionized water. The positively charged colloidal silica liquid was prepared in Example 4-
LUDOX ™ CL-P (40% solids) used in Example 8 and calcium chloride was in the form of a 37.5 weight percent technical grade liquid. Aluminum chlorohydrate is in the form of a 50 weight percent liquid sold as Chlorhydrol ™, and aluminum zirconium tetrachlorohydrex glycine is sold as REZAL ™ 36G.
Weight percent liquid form, both of which are available from Reheis Inc. (Berke
ley Heights, NJ). The surfactant was a nonionic alcohol ethoxylate solution containing 10% water (TERGITOL ™ TMN-6 (90% AQ) sold by Union Carbide),
From 1.5% by weight. The concentrations of colloidal silica, calcium chloride, aluminum chlorohydrate and aluminum zirconium tetrachlorohydrex glycine were kept constant in Examples 17-20. At first,
A treatment liquid was prepared by adding a humectant to deionized water while mixing. Next, the remaining components were gradually added to the water containing the wetting agent while mixing was continued to produce a treatment liquid.

The excess processing solution was squeezed out by passing the wet sample through a rubber-coated nip roller. Liquid absorption by the sheet was approximately equal to the weight of the sheet (about 3 ounces on a square yard basis). The samples were oven dried at 90 ° C to 95 ° C and then tested for water drop absorption. Seven color blocks (described above) were inkjet printed on the dried sheet sample using an Encad inkjet printer (described above). Optical density and color washout were measured for each of the above samples. The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the ink) to the treated sample of the example and the untreated control sample (Example 9). The results are shown in Table 3 below.

[0064]

[Table 10]

Examples 17-20 illustrate another preferred embodiment of the present invention. Except for the surfactant, the weight percentages of the components of the processing solutions of Examples 17-20 were kept constant. Without wishing to be bound by theory, it is desired that the positively charged colloidal silica, calcium chloride,
It is believed that aluminum chlorohydrate and aluminum zirconium tetrachlorohydrex glycine each serve as a source of positively charged species on the processing medium. As discussed with respect to Examples 4-8 above, the positively charged colloidal silica is mechanically entangled with the fibers of the print media, and the anionic ink pigment adheres to the surface of the colloidal silica sphere or sphere. It is thought to form a lump. The presence of the divalent calcium chloride on the print medium makes the colors in the ink jet printed image on the medium vivid and clear. As discussed with respect to Examples 4-8 above, the presence of calcium chloride ions on the media surface causes the pigment in the anionic ink to agglomerate near the surface of the print media, resulting in a vivid, lively image. Will give. The trivalent aluminum zirconium tetrachlorohydrex glycine and aluminum chlorohydrate compounds of the processing solution act as a strong complexing agent to produce pigment aggregates larger than calcium chloride, resulting in the mechanical integrity of inkjet printed images. It is thought to improve. By treating the print media with the combination of positively charged species of Examples 17-20, excellent optical density, low color washout,
In addition, it is possible to manufacture an ink jet printable medium capable of ink jet printing an image having good rub resistance.

Examples 17-20 also demonstrate that increasing the weight percent of the nonionic alcohol ethoxylate surfactant (TERGITOL ™ TMN-6) in the processing solution does not sacrifice image quality. The following shows that the absorbability of an ink-jet printable medium can be improved. Examples 17 and 18 range from 0.5% to 1.
The presence of 5% alcohol ethoxylate surfactant indicates that the absorbency of the media is significantly improved while maintaining the optical density of the printed image. Examples 21-22 In Examples 21-22, a cross-laminated reinforcing scrim material having a basis weight of 23 g / m ² (0.68 oz / square yard) thermally laminated to one side of a TYVEK ™ sheet was used. CLAF ™ S1510 sheet (Amoco N
isseki CLAF, Inc. A sample of TY VEK ™ type 1070P spunbond polyethylene sheet material having a basis weight of 71 g / m ² (2.1 oz / sq. Yard) reinforced with (available from Atlanta, GA) was prepared in the Examples. Tested as described in 17-20. The sample of Example 21 was replaced with the sample of Example 1.
7 and then oven dried at 90 ° C. to 95 ° C. prior to testing. The sample of Example 22 did not undergo any treatment prior to testing. As described above, the above-described seven color blocks were inkjet-printed on the sample using the Encad inkjet printer. Optical density and color washout were measured for each sample as described above. The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the inks) for the untreated control sample of Example 22 and the treated sample of Example 21. The results are shown in Table 4 below.

[0067]

[Table 11]

Example 21 demonstrates the use of a reinforcing scrim material by treating a sheet with a combination of positively charged colloidal silica, calcium chloride, aluminum chlorohydrate, aluminum zirconium tetrachlorohydrex glycine, and a surfactant. It shows that a print medium comprising a spunbond polyethylene sheet laminated with the above can be an excellent inkjet printable medium. It is expected that alternate printing media can be produced by heat laminating a spunbond sheet material sheet on the opposite side of the reinforcing scrim material sheet. Examples 23-25 Examples 23-25 illustrate alternative print media treatment solutions containing sources other than the positively charged species of acid. A sample of TYV EK ™ type 1082C spunbond polyethylene sheet having a basis weight of 101 g / m ² (3.0 ounces per square yard) was treated with a treatment solution containing one of the following compound combinations in deionized water: Dipped. n-Butyl phosphate + sulfuric acid alkoxylate of oil-in-water emulsifier (Unio
n TRITON ™ W-30 sold by Carbide (Example 23), positively charged colloidal silica + nonionic alcohol ethoxylate surfactant (TERGITOL ™ TMN-6 (90% AQ) )) + Liquid cationic polydadomac (polydimethyldiallylammonium chloride) coagulant (All
PERCOL ™ 4 from ied Colloid 3 (Sufflok, VA)
06-F) (Example 24), and positively charged colloidal silica + nonionic alcohol ethoxylate surfactant + highly cationic polyacrylamide derivative flocculant (Chemtal, Inc.)
. (Riceboro, Georgia) C411) (Example 25).

The concentrations of the components in the deionized water are shown in Table 5 below. The treatment liquid of Example 23 was prepared by first adding TRITON ™ W-30 to deionized water and then gradually adding n-butyl phosphate to adjust the pH.
The liquid was continuously mixed while adjusting the pH using a laboratory dispenser of the model IKA model Ultra Turrax T25 / S1. The treatment liquids of Examples 24 and 25 were prepared by first adding a surfactant, and then gradually adding other components to the liquid.

The excess liquid was squeezed out by passing the wet sample between rubber-coated nip rollers. Liquid absorption by the sheet was approximately equal to the weight of the sheet (about 3 ounces on a square yard basis). The samples were oven dried at 90 ° C to 95 ° C and then tested for water drop absorption. Seven color blocks (described above) were inkjet printed on the dried sheet sample using an Encad inkjet printer (described above). Optical density and color washout were measured for each of the above samples. The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the ink) to the treated sample of the example and the untreated control sample (Example 9). The results are shown in Table 5 below.

[0071]

[Table 12]

Example 23 shows that by treating the media with n-butyl phosphate as a source of positively charged species, only a very slight improvement in the optical density of the printed image on spunbond polyethylene print media was obtained. Indicates no. Example 24 demonstrates that treating the media with a cationic polydadomac coagulant (PERCOL ™ 406-F) resulted in a slight improvement in the optical density of printed images on spunbond polyethylene print media. Is shown. No such improvement was found with the cationic polyacrylamide derivative flocculant of Example 25 (C411).
The printed images of Examples 23 and 24 are described in Examples 4-8, 10, 16, and 17-20.
Are more vivid and lively than ink jet printed images on the more preferred print media. Examples 26-28 Samples of nonwoven spunbond polypropylene sheet material were processed and evaluated for water drop absorption, color washout and optical density of the printed color. The polypropylene sheet is hot calendered and 229 microns (9 mils) thick and 126
It was made of multilayer melt-spun polypropylene fibers having a basis weight of 3.7 g / m ² (3.7 ounces / square yard).

One sample of this sheet material was immersed in treatment liquid A, one sample of this sheet material was immersed in treatment liquid B, and a control sample of this sheet material was not treated.
Treatment solution A contained surfactant, acid, and deionized water at the weight percent listed for Example 16 (6% Zelac.TM.-TY, deionized water, pH 1.64 with a combination of phosphoric acid and citric acid). (Adjusted to). Treatment B was composed of colloidal silica, calcium chloride, surfactant, and deionized water in the weight percentages listed for Example 4 (20% colloidal silica liquid (40% solids), 5%
(37.5% CaCl ₂ ), 1% MERPOL ™ LF-H, 0.8% SILWET ™ L-77).
Excess liquid was squeezed out by passing the wet sample between rubber-coated nip rollers. The samples were oven dried at 90 ° C to 95 ° C.

Each sample was tested for water drop absorption as described above. The above-described seven color blocks were inkjet-printed on the dried sheet sample using the above-described encad inkjet printer. Optical density and color washout were measured for each of the above samples. Treated sample of Example and untreated control sample (Example 28)
The average optical density (based on the primary colors of the four inks) was compared against the average density to determine the percent improvement in optical density. The results are shown in Table 6 below.

[0075]

[Table 13]

In Examples 26-28, treatment solution A (pH adjusted to 1.64 with a combination of 6% Zelac ™ -TY, deionized water, phosphoric acid and citric acid) or treatment solution B
(20% colloidal silica liquor (40% solids) in deionized water, 5% calcium chloride liquor (37.5% CaCl ₂ ), 1% MERPOL ™ LF-H, 0.8% SILWET ™ L-77) dramatically improves the ink jet printability of the nonwoven spunbond polypropylene sheet material. By applying the processing liquids A and B to the non-woven polypropylene sheet material,
The sheet's absorbency, color washout, and optical density properties were all dramatically improved. Examples 29-31 Samples of polyester woven material were processed and evaluated for water drop absorption, color washout and optical density of the printed color. 0.386mm for polyester cloth
And a woven DACRON polyester having a basis weight of 3.27 oz / sq. Yard (101 g / m ² ).

One sample of this cloth was immersed in treatment liquid A and this cloth was immersed in treatment liquid B, and a control sample of this cloth was not treated. Treatment solution A was a solution containing colloidal silica, calcium chloride, and deionized water in the weight percentages listed in Example 16 (
PH was adjusted to 1.64 with 6% Zelac ™ -TY, deionized water, a combination of phosphoric acid and citric acid). Treatment solution B was a solution (20% colloidal silica solution (40% solids), 5% solution of calcium chloride (37.5% of CaCl _2), was 1% of MERPOL (TM) LF-H, 0. of ^{8% SILWET R L-77)} . Liquid absorption by the sheet was approximately equal to the weight of the cloth. Excess liquid was squeezed out by passing the wet sample between rubber-coated nip rollers. The samples were oven dried at 90 ° C to 95 ° C.

Next, each sample was tested for water drop absorption as described above. The above-described seven color blocks were inkjet-printed on the dried sheet sample using the above-described encad inkjet printer. Optical density and color washout were measured for each of the above samples. The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the ink) to the treated sample of the example and the untreated control sample (Example 31). The results are shown in Table 7 below.

[0079]

[Table 14]

Examples 29-31 were treated with treatment solution A (pH adjusted to 1.64 with a combination of 6% Zelac ™ -TY, deionized water, phosphoric acid and citric acid) or treatment solution B.
(20% colloidal silica liquor (40% solids) in deionized water, 5% calcium chloride liquor (37.5% CaCl ₂ ), 1% MERPOL ™ LF-H, 0.8% treatment with SILWET ^R L-77 surfactant) for indicating that the ink-jet printability of Poriesu Tel fabric is dramatically improved. The sheet absorbency, color washout, and optical density properties were all dramatically improved by applying treatments A and B to the polyester woven fabric. Examples 32-34 Samples of cotton fabric material were processed and evaluated for water drop absorption, color washout and optical density of the printed color. The cotton cloth was made of 100% woven cotton and had a thickness of 0.439 mm and a basis weight of 137 g / m ² (4.06 ounces per square yard).

One sample of the cloth was immersed in the treatment liquid A, the cloth was immersed in the treatment liquid B, and the control sample of the cloth was not treated. Treatment solution A was a solution (6% Zelac ™ -TY, deionized water, a combination of phosphoric acid and citric acid, containing a surfactant, an acid, and deionized water in the weight percentages listed in Example 16). To 1.64
Was adjusted). Treatment solution B was a solution containing colloidal silica, calcium chloride, a surfactant, and deionized water at the weight percentages listed in Example 4 (20% colloidal silica solution (40% solids), 5% calcium chloride solution (37.5% of CaCl _2), was 1% of MERPOL (TM) LF-H, of ^{0.8% SILWET R L-77)} . Liquid absorption by the sheet was approximately equal to the basis weight of the cloth. Excess liquid was squeezed out by passing the wet sample between rubber-coated nip rollers.
The samples were oven dried at 90 ° C to 95 ° C.

Next, each sample was tested for water drop absorption as described above. The above-described seven color blocks were inkjet-printed on the sheet sample using the above-described encad inkjet printer. Optical density and color washout were measured for each of the above samples. The treated sample of Example and the untreated control sample (Example 3
The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the ink) to 4). The results are shown in Table 8 below.

[0083]

[Table 15]

In Examples 32-34, treatment solution A (pH adjusted to 1.64 by a combination of 6% Zelac ™ -TY, deionized water, phosphoric acid and citric acid) or treatment solution B
(20% colloidal silica solution (40% solids), 5% calcium chloride solution (3
CaCl ₂₎ 7.5% of the ink-jet printing of cotton fabric material is improved by treatment with 1% MERPOL (TM) LF-H, 0.8% of the S ILWET (TM) L-77) It indicates that. The physical properties of sheet absorbency, color washout and optical density were all improved by applying treatments A and B to a woven cotton fabric. Examples 35-37 Samples of a 50/50 blend of polyester and cotton were treated and evaluated for water absorption, color washout and optical density of the printed color. This mixed woven fabric is 5
It was made of 0% cotton and 50% polyester. This mixed woven cloth is 0.165m
m and a basis weight of 113 g / m ² (3.35 oz / square yard).

One sample of the cloth was immersed in the treatment liquid A, the cloth was immersed in the treatment liquid B, and the control sample of the cloth was not treated. Treatment solution A was a solution (6% Zelac ™ -TY, deionized water, a combination of phosphoric acid and citric acid, containing a surfactant, an acid, and deionized water in the weight percentages listed in Example 16). To 1.64
Was adjusted). Treatment solution B was a solution (20% colloidal silica solution (40% solids), 5% Calcium chloride solution (37.5% CaCl ₂ ), 1% MERPOL ™ LF-H, 0.8% SILWET ™ L-77. Liquid absorption by the sheet was approximately equal to the basis weight of the cloth. Excess liquid was squeezed out by passing the wet sample between rubber-coated nip rollers. The samples were oven dried at 90 ° C to 95 ° C. Each sample was then tested for water drop absorption as described above. The above-described seven color blocks were inkjet-printed on the sheet sample using the above-described encad inkjet printer. Optical density and color washout were measured for each of the above samples. The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the ink) to the treated sample of the example and the untreated control sample (Example 37). The results are shown in Table 9 below.

[0086]

[Table 16]

Examples 35-37 were treated with treatment solution A (pH adjusted to 1.64 with a combination of 6% Zelac ™ -TY, deionized water, phosphoric acid and citric acid) or treatment solution B.
(20% colloidal silica liquor (40% solids) in water, 5% calcium chloride liquor (37.5% CaCl ₂ ), 1% MERPOL ™ LF-H, 0.8% SILWET (TM) L-77 surfactant) shows a dramatic improvement in inkjet printability of woven polyester / cotton mixed woven material. The sheet absorbency, color washout, and optical density properties were all dramatically improved by applying treatments A and B to a polyester / cotton blend. Examples 38-62 Examples 38-62 show how treating three different fabrics with various acids improves the ink jet printability of the fabric. The following cloth was used. 1. 100% polyester. The polyester cloth has a thickness of 0.386 mm and 101
It was g / m ² (3.27 oz / yd) DACRON ^R polyester woven having a basis weight of (hereinafter "polyester cloth"). 2.100% nylon. The nylon cloth has a basis weight of 74.5 g / m ² (2.21 oz / square yard) and a thickness of 0.132 mm, and is washed and free of sizing agent. Taffeta (Milliken Style 670922/198) (Or later"
Nylon cloth "). 3. 70% polyester / 30% cotton. The 70% polyester / 30% cotton blend was a blended fabric (hereinafter "blend").

The cloth was dipped in one of the acid solutions listed below. The cloth sheet was dried at 20-40 ° C. by dripping off excess liquid. The dried cloth was stuck on the backing paper, and the above-described primary color ink jetted by a Hewlett Packard 560c inkjet printer was printed. An untreated control sample of each of the three fabrics was also printed. As described above, seven color square patterns used to measure optical density were printed on the samples. In addition, a printed pattern containing an array of colored lines on a yellow background was printed for the purpose of visually comparing the sharpness of the lines with the resolution of the image. The optical density was measured for each of the samples described above.

The percent improvement in optical density was determined by comparing the average optical density (based on the four primary colors of the inks) for the treated sample of the example and the untreated control sample.

The control of the spread of the dots was visually evaluated. Uncontrolled ink spreading is a “suction” where ink colors migrate to adjacent non-printing areas
Or it leads to a "bleed" effect. Often, such "wicking" or "bleeding" occurs along the fibers of the sheet or fabric. Uncontrolled dot spreading results in blurred lines and poorly defined edges between colored regions.
A score of "Poor"("P") for the dot spread control indicates a print that shows little sharpness of the boundary between one color and an adjacent color or non-printed area. A score of "Fair"("F") for the dot spread control represents a print that shows a sharp definition of the boundary between one color and an adjacent color or non-printed area, , Represents the migration of a color between one color and an adjacent color. A score of "Good"("G") for the dot spread control represents a print that shows a clear, sharp definition of the boundary between one color and an adjacent color or non-print area.

The results for the polyester fabric samples are set forth in Table 10 below. The results for the nylon cloth samples are set forth in Table 11 below. The results for the blended fabric samples are shown in Table 12 below.
It writes in.

[0092]

[Table 17]

[0093]

[Table 18]

[0094]

[Table 19]

[0095]

[Table 20]

[0096]

[Table 21]

It will be apparent to those skilled in the art that modifications and variations can be made to the print media of the present invention. Therefore, the present invention is not limited in broad terms to the specific details or illustrative embodiments described above. Thus, all matter contained in the foregoing description and examples are illustrative and should not be construed in a limiting sense.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) D06M 11/79 D06M 11/12 13/224 D06P 5/00 111 (31) Priority claim number 09/140, 081 (32) Priority Date August 25, 1998 (August 25, 1998) (33) Priority Country United States (US) (81) Designated Country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), CA, CN, JP, KR (72) Inventor Held, Robert P. 19713 Newark, Delaware, United States of America・ Douglas Day Array Drive 449

Claims (25)

[Claims] 1. An ink-jet printable medium comprising a fibrous polymer substrate having positively charged species on a surface thereof, wherein said ink-jet printable medium has an integral structure and a tensile strength of at least 20 N / 2.54 cm. is a basis weight of less than 8 oz / yd, when printing absorbing speed by at least 0.01 microliters / mm ² / sec TAPPI T558p m-95, and the IJE method in inkjet, less than 50% of the color washout An inkjet printable medium having: 2. The ink-jet printable medium of claim 1, wherein the ink-jet printable medium has an IJE color washout of less than 25% and a water absorption rate according to TAPPI T558 pm-95 of at least 0.2 microliter / mm ² / sec. Ink jet printable media. 3. The ink-jet printable medium according to claim 1, wherein the fibrous polymer substrate is a non-woven sheet. 4. The nonwoven sheet is a spunbonded polyolefin sheet, and when tested according to ANSI X3.182-1990, a barcode that is ink-jet printed on this medium using black pigment ink is printed using a barcode scanner. 4. The ink jet printable medium of claim 3, wherein the medium is readable and has a four color optical density of at least 0.85 as measured by the OD method. 5. The ink-jet printable medium of claim 2, wherein the fibrous substrate comprises fibers having positively charged colloidal silica and a wetting agent on the surface of the fibers. 6. The ink-jet printable medium according to claim 5, wherein said fibrous base material comprises fibers having calcium chloride on the surface of said fibers. 7. The fibrous base material comprises fibers having a wetting agent and at least one compound selected from the group consisting of water-soluble compounds of calcium, aluminum, magnesium and zirconium on the surface of the fibers. 4. The ink-jet printable medium according to claim 1. 8. The ink-jet printable medium of claim 2, wherein the fibrous substrate comprises fibers having positively charged protons and wetting agents on the surface of the fibers. 9. A composite sheet comprising the ink-jet printable medium of claim 1 laminated to a reinforcing scrim material. 10. An ink-jet printable medium comprising a monolithic sheet of polymer fibers having positively charged colloidal silica and a wetting agent on the surface of the sheet fibers, wherein said ink-jet printable medium comprises at least: 20 N / 2.54 cm tensile strength, less than 8 oz / square yard, at least 0.01 microliter / m
An inkjet printable medium having a water absorption rate according to TAPPI T558 pm-95 of m ² / sec and a color washout according to IJE method of less than 50%. 11. The ink jet printable medium according to claim 10, wherein the fibers of the fibrous base material have calcium chloride, aluminum chlorohydrate, and aluminum zirconium tetrachlorohydrex glycine on the surface thereof. 12. The ink jet printable medium of claim 10, wherein the polymer fibers comprise flash spun polyolefin fibers. 13. An ink-jet printable medium comprising: (a) an ink containing an aqueous carrier medium and a dye or pigment colorant; and (b) a fibrous polymer substrate having a positively charged species on its surface. Wherein the medium is of unitary construction, at least 20N
/2.54cm tensile strength, color by 8 ounces / basis weight of less than square yard, at least 0.01 microliters / mm ² / sec TAPPI T558pm-95 that by the water absorption speed, and less than 50% Ije method A set of ink / print media, comprising: having a washout. 14. The ink / print media set according to claim 13, wherein said ink comprises an anionic pigment colorant dispersed in an aqueous carrier medium. 15. The ink jet printable medium of claim 14, wherein the ink jet printable medium has an IJE color washout of less than 25% and a water absorption rate according to TAPPI T558 pm-95 of at least 0.2 microliter / mm ² / sec. Set of ink / print media. 16. The ink / print media set of claim 15, wherein said fibrous polymer substrate comprises fibers having positively charged colloidal silica and a wetting agent on the surface of said fibers. 17. The ink / print media set of claim 15, wherein said fibrous polymer substrate comprises fibers having positively charged protons and wetting agents on the surface of said fibers. 18. A method comprising forming a solution comprising water and a source of a positively charged species, wetting a fibrous polymer substrate with said solution, wherein said substrate comprises at least 20 N /
Drying the substrate, having a tensile strength of 2.54 cm and a basis weight of 8 oz / square yard or less, wherein the dried substrate has at least 0.01 microliter / mm ² / sec. A method of making an inkjet printable medium comprising the steps of having a water absorption rate according to TAPPI T558 pm-95 and a color washout according to the IJE method of less than 50%. 19. The method of claim 18, wherein the source of the positively charged species is selected from the group of positively charged colloidal silica, acids, and water-soluble compounds of calcium, aluminum, magnesium, and zirconium. 20. The dried fibrous polymer substrate, as measured by the OD method, at least 8% greater than the optical density of the four colors of the fibrous polymer substrate before wetting the substrate with the treatment liquid. 20. The method of claim 19 having four colors of optical density. 21. The liquid according to claim 1, wherein the liquid contains an acid, and the pH of the liquid is less than 2.5.
10. The method according to 9. 22. The method of claim 21, wherein said liquor comprises between 2% and 10% by weight of potassium butyl phosphate and said acid comprises phosphoric acid. 23. The method according to claim 19, wherein said liquid comprises at least 2% by weight of colloidal silica and at least 0.4% by weight of a surfactant. 24. The method of claim 23, wherein said surfactant is selected from the group consisting of alcohol ethoxylate, alcohol ethoxylate propoxylate, and polyalkylene oxide modified heptamethyltrisiloxane. 25. The liquid according to claim 1, wherein the liquid comprises at least 4% and 12% by weight of colloidal silica, 0.4% and 5% by weight of a surfactant and 1% and 10% by weight of calcium chloride. 24. The method of claim 23 comprising comprising.