JP3142726B2 - Fabric for inkjet printing, printing method, and printed matter - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing method for printing on a cloth using an ink jet printing method, a printing cloth and a printed material.

[0002]

2. Description of the Related Art Conventionally, as a method of ink-jet recording on a cloth, a cloth is temporarily adhered to a non-stretchable flat support coated with an adhesive and printed by a printer (Japanese Patent Laid-Open No. 63-6183). And a method of inkjet dyeing a cloth pretreated with an aqueous solution containing any of a water-soluble polymer substance which is non-dying to the dye to be used, a water-soluble salt, and water-insoluble inorganic fine particles (Japanese Patent Publication No. 31594), a method of pre-treating cellulose fibers with an aqueous solution containing an alkaline substance, urea or thiourea and a water-soluble polymer substance, ink-jet dyeing with an ink containing a reactive dye, and performing dry heat fixing treatment (Japanese Patent Publication No. 4-35351). ) And so on. The purpose of these prior arts is to prevent bleeding of an image, to obtain a sharp picture, and to obtain a clear print with high density. However, the same color density and sharpness as those of the printed matter obtained by the conventional printing method (screen printing) have not yet been obtained. Furthermore, because of poor penetration in the thickness direction of the cloth, color depth and uniform color loss on the back surface were insufficient. Therefore, the application range of the printed matter has been narrowed.

[0003]

As a result of various studies to solve the above problems, the present inventor has improved the color density by attaching a specific polyethylene oxide resin and boehmite-based granular alumina to a cloth. The present invention has been accomplished by knowing that the above problems can be solved, and an object of the present invention is to provide an ink jet textile printing fabric, a printing method, and a printed material which solve the above problems. It is in.

[0004]

In order to solve the above-mentioned problems, the present invention relates to a method of fabricating a fabric, wherein the fabric has at least an average primary particle diameter of 10%.
0.5 to 10% by weight of boehmite-based granular alumina having a specific gravity of 1.17 to 1.20 and an average molecular weight of 1
0.1 to 2.5 million polyethylene oxide resin
The present invention proposes a fabric for ink jet printing, characterized in that the fabric is adhered to an amount of up to 30% by weight.

[0005] The present invention is also a fabric for ink jet printing, characterized in that at least one selected from the group consisting of a water-soluble inorganic salt, a hydrotrope and a chelating agent is further adhered to the above-mentioned fabric.

Further, the present invention is a printing method and a printed material, characterized in that the above ink jet textile is subjected to ink jet recording, then subjected to a color development treatment, washed, and then dried.

Hereinafter, the present invention will be described in detail.

[0008] As described above, the ink jet textile printing fabric of the present invention is prepared by adding boehmite-based granular alumina having an average particle size of 10 to 20 mμ and a specific gravity of 1.17 to 1.20 to the total weight of the fabric. Polyethylene oxide resin having a molecular weight of 0.5 to 10% by weight and an average molecular weight of 100,000 to 2.5 million is attached in an amount of 0.1 to 30% by weight based on the total weight of the cloth.

The above-mentioned boehmite-based granular alumina used in the present invention is advantageous in operation because it has a low viscosity even when dispersed in a large amount in water or the like, as compared with amorphous feathered alumina.

As a specific example of the boehmite-based granular alumina, there is alumina sol-520 manufactured by Nissan Chemical Industries, Ltd. (average primary particle diameter 10-20 μm, specific gravity 1.17-1.20). In addition, boehmite-based alumina and alumina sol are used. Such alumina, alumina sol has the function of keeping the dye in the ink near the surface of the fabric,
Although it is effective in improving the color density, bleeding occurs because alumina sol alone does not have an ink absorption and holding power.

The polyethylene oxide resin used in the present invention is not only a resin that does not cause viscosity increase or gelation when mixed with the above-mentioned alumina dispersion, but also has an ink holding property and an effect of preventing bleeding. . Therefore, the effect of the present invention is highly achieved by using the above-mentioned alumina sol in combination. This resin has a molecular weight of about 100,000 to 5,000,000, but a resin preferably used in the present invention has a molecular weight of about 100,000 to 2.5,000,000. Molecular weight 25
Those having a molecular weight of 100,000 or more are not preferred because the viscosity of the aqueous solution becomes too high. Those having a molecular weight of 100,000 or less have insufficient ink retention and bleeding prevention effects.

JP-A-6-184954 discloses a cloth containing alumina boehmite sol. However, in this cloth, alumina boehmite is permanently attached to the cloth to form a cloth, and the dye in the ink jet ink is adsorbed to the cloth-formed boehmite to form a high-density color. On the other hand, in the present invention, boehmite is different in that it is removed by washing after coloring.

JP-A-2-300377 discloses an ink-jet printing method in which a cloth is pretreated with silica or alumina having a particle diameter of 0.2 to 10 μm. This technique prevents the occurrence of bleeding by increasing the ink absorbency by utilizing the porosity of silica or alumina. In the present invention, the boehmite-based alumina adsorbs the dye and stays on the surface of the fabric to improve color development, but does not prevent bleeding. Therefore, in the present invention, the polyethylene ink resin is used to hold ink and prevent bleeding. Therefore, the mechanism for preventing bleeding is different.

The fabric for ink jet printing according to the present invention is basically obtained by applying an aqueous slurry comprising the above-mentioned alumina sol and polyethylene oxide resin to a cloth by a method such as coating or impregnating spray. The optimum is 0.5 to 10% by weight of alumina and 0.1 to 30% by weight of polyethylene oxide resin. The mixing ratio of the alumina of the present invention and the resin is 2 by weight.
0: 1 to 1:10, more preferably 15: 1 to 1: 5. In order to improve the solution stability and coating suitability of the aqueous slurry, a pH adjuster, an activator, an aqueous solvent, an aqueous resin, and the like can be added to the aqueous slurry.

In particular, in order to improve the color developability and the effect of preventing bleeding when performing ink-jet printing,
It is preferable to add a water-soluble inorganic salt, a hydrotroping agent, a chelating agent and the like.

The amount of these additives varies depending on the type, but is preferably 0.05 to 10% by weight based on the total amount of the aqueous slurry.

Examples of the water-soluble inorganic salt include potassium sulfate,
Sodium sulfate, magnesium sulfate, potassium fluoride,
Sodium chloride, potassium bromide, potassium iodide and the like.

Examples of the aqueous solvent include alcohols and glycols.

As the activator, an anionic, cationic or nonionic activator is appropriately selected and used.

Specific examples of the pH adjuster include phosphoric acid, boric acid, silicic acid, acetic acid, carbonic acid, citric acid, tartaric acid,
Maleic acid, phthalic acid and their alkali metal salts,
Ammonium salt, triethylamine salt, triethanolamine salt, caustic soda, triethanolamine and the like.

Urea as a hydrotropic agent,
Specific examples thereof include thiourea, tannic acid, lignin sulfonic acid, a sodium salt of EDTA as a chelating agent, and a cationic polymer as an aqueous resin.

The type of cloth used in the present invention is cotton,
Silk, hemp, nylon, rayon, acetate, polyester and their blended fabrics. It is necessary to change the pH of the treating agent depending on the type of these fabrics, for example, cotton,
Silk, hemp, and rayon are recorded with a reactive dye while controlling the alkaline pH with sodium bicarbonate or sodium carbonate. In the case of nylon, the pH is controlled with an acid and recorded with an acid dye. In the case of acetate and polyester, the pH is preferably near neutral.

Next, a method of performing ink jet recording using the fabric of the present invention will be described. Usable inks may be inks of any of reactive dyes, acid dyes, direct dyes and disperse dyes, and the most suitable dye ink can be used according to the type of fabric. The recording may be performed by scanning the cloth of the present invention using an ink jet print head to apply the ink in an image form. After recording, the object is achieved by performing a heat color development treatment as necessary, followed by washing and drying.

For the heat coloring process, a known method used in a conventional printing process is applied as it is. That is, a high-temperature steam method or a thermosol method is used.
The actual processing conditions vary depending on the type of cloth, but when dyeing cotton or silk with reactive dye ink, use a high-temperature steam method.
Treat at 0-105 ° C for 5-30 minutes. When the polyester is dyed with the disperse dye ink, the treatment is performed at 160 to 180 ° C. for several minutes to several tens of minutes by the high-temperature steam method, and is performed at 190 to 230 ° C. for several seconds to several tens of seconds by the thermosol method.

After the color development treatment, a washing step is performed. In general, washing with water and soaping with an aqueous solution containing an alkali agent are performed. In the case of a polyester cloth, it is standard that after washing with water, reduction washing is performed with an aqueous solution containing an alkali agent and hydrosulfide, followed by further washing with water.

The components of the ink for ink jet recording used in the present invention include a dye, water, a water-soluble organic solvent, p
An H adjuster, a fungicide, a surfactant, a dispersant, a water-soluble resin and the like are appropriately used. Acid dyes, direct dyes,
Basic dyes, reactive dyes, disperse dyes, and pigments are used. Examples of the water-soluble organic solvent include glycols, glycol ethers, nitrogen-containing solvents, alcohols, and the like.
As examples of the surfactant, any of nonionic, anionic, cationic and amphoteric surfactants can be used, and they are used properly according to the purpose. In addition, a hydrotrope such as urea may be used.

A dispersant is essential for the disperse dye ink, and specific examples thereof include lignin sulfonic acid salt, naphthalene sulfonic acid formalin condensate, and polyoxyethylene monophenyl ether.

Water, which is an essential component of the liquid medium constituting the ink used in the ink jet printing method of the present invention, accounts for 30 to 90% by weight, preferably 40 to 90% by weight based on the total amount of the ink.
It is used in an amount of 90% by weight, more preferably 50 to 85% by weight.

The above is an essential component of the ink jet textile printing ink used in the method of the present invention, but a common organic solvent can also be used as a liquid medium of the ink. For example, ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; oxyethylene such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol Or an oxypropylene addition polymer; alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, and hexylene glycol; 1,2,6-hexanetriol and the like Triols; thiodiglycol; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol Lower alkyl ethers of polyhydric alcohols such as methyl (or ethyl) ether and triethylene glycol monomethyl (or ethyl) ether; polyhydric such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether Lower dialkyl ethers of alcohols; sulfolane, N-methyl-2-pyrrolidone,
1,3-dimethyl-2-imidazolidinone and the like.

The content of the water-soluble organic solvent as described above is
Generally, 3 to 60% by weight based on the total weight of the ink,
Preferably it is in the range of 5 to 50%.

When the above liquid mediums are used in combination, they can be used alone or as a mixture. The most preferable liquid medium composition is one in which the solvent contains at least one kind of polyvalent alcohol. Among them, thiodiglycol alone or a mixed system of diethylene glycol and thiodiglycol is particularly preferable.

The ink-jet printing method of the present invention is a method of printing on the ink-jet printing cloth of the present invention using the above-described printing ink. As the ink jet recording method to be used, any conventionally known ink jet recording method may be used.
According to the method described in Japanese Patent Application Laid-Open No. 4-59936, the ink subjected to the action of thermal energy causes a rapid volume change,
The method of ejecting ink from the nozzles by the action force due to the state change is most effective. In such a system, stable printing can be performed by performing recording on the ink jet textile printing fabric of the present invention.

The conditions for obtaining a particularly effective print are preferably such that the ejected droplets are in the range of ²⁰ to 200 pl and the ink ejection amount is in the range of 4 to 40 nl / mm ² .

As an example of an apparatus suitable for performing printing using the ink-jet printing fabric of the present invention, thermal energy corresponding to a recording signal is applied to ink in a room of a recording head, and droplets are generated by the thermal energy. And a device for causing the above.

FIGS. 1, 2 and 3 show examples of the structure of a head which is a main part of the apparatus.

The head 13 includes a glass, ceramics or plastic plate having a groove 14 through which ink passes, and a heat generating head 15 used for dry heat recording (a head is shown in the figure, but is not limited to this. ) Are adhered. The heating head 15 includes a protective film 16 made of silicon oxide or the like and aluminum electrodes 17-1 and 17-.
2, a heating resistor layer 18 made of nichrome or the like, a heat storage layer 19, and a substrate 20 having good heat dissipation properties such as alumina.

The ink 21 has a discharge orifice (fine hole) 2
The meniscus 23 is formed by the pressure P.

When an electric signal is applied to the electrodes 17-1 and 17-2, the area of the heating head 15 indicated by n rapidly generates heat, and bubbles are generated in the ink 21 in contact with the area.
The meniscus 23 protrudes by the pressure, the ink 21 is ejected, and becomes a recording droplet 24 from the orifice 22 and flies toward the fabric 25 of the present invention.

FIG. 3 is an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described with reference to FIG. In addition,
FIG. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a cross-sectional view taken along line AB in FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head.

In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, and forms a cantilever. The blade 61 is provided at a position adjacent to a recording area of the recording head, and in the case of this example, is held in a form protruding into the movement path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61, and has a configuration in which the cap moves in a direction perpendicular to the moving direction of the recording head to come into contact with the discharge port surface to perform capping. Further, an absorber 63 is provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding into the movement path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove moisture, dust, and the like from the ink ejection port surface.

Reference numeral 65 denotes a recording head which has discharge energy generating means and discharges ink on a fabric facing the discharge port surface where discharge ports are arranged to perform recording, and 66 denotes a recording head on which the recording head 65 is mounted. This is a carriage for moving. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and the adjacent area.

Numeral 51 denotes a cloth feeding section for inserting the cloth of the present invention, and numeral 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the fabric of the present invention is supplied to a position facing the discharge port surface of the recording head, and is discharged to a discharge section provided with a discharge roller 53 as recording proceeds.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the cap 62 of the head recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. I have. As a result, the ejection port surface of the recording head 65 is wiped. When capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62 moves so as to protrude into the movement path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of wiping described above. As a result, the ejection port surface of the recording head 65 is also wiped during this movement. The above-described movement of the print head to the home position is performed not only at the end of printing or at the time of ejection recovery, but also at a predetermined interval while the print head moves through the printing area for printing to the home position adjacent to the printing area. Then, the wiping is performed with this movement.

[0046]

Next, the present invention will be described more specifically with reference to examples.

% Is based on weight.

EXAMPLE 1 Polyethylene oxide (Alcox E-60 manufactured by Meisei Chemical Co., Ltd., molecular weight: 100) was applied to cotton (thickness: 250 μm).
2.0%), 2.0% urea, 2.0% sodium carbonate, and 6.0% alumina sol-520 (impact: 80%), dried and dried. An inventive fabric was obtained. Alumina in the obtained fabric was 4.8%, polyethylene oxide was 1.6%, urea was 0.16%,
Sodium carbonate was 1.6%. The obtained fabric of the present invention was cut out to the size of A4 size plate, and multicolor printing was performed using the following ink using a commercially available inkjet color printer (BJC-820J manufactured by Canon). Immediately after the printing was completed, steam heating treatment was performed at 102 ° C. for 8 minutes, followed by sufficient washing with water and drying. A color image of a deep and sufficient density was printed vividly on the cotton. In addition, a sharp image was obtained without stain on the white portion where no ink was attached.

Ink Composition Cyan Ink C.I. I. Reactive Blue 15 12 parts Thiodiglycol 22 parts Ethylene glycol 13 parts Ion exchange water 53 parts Magenta ink C.I. I. Reactive Red 226 11 parts Thiodiglycol 22 parts Ethylene glycol 13 parts Ion exchange water 54 parts Yellow ink C.I. I. Reactive Yellow 95 10 parts Thiodiglycol 22 parts Diethylene glycol 13 parts Ion-exchanged water 55 parts Black ink C.I. I. Reactive Black 399 parts Thiodiglycol 22 parts Ethylene glycol 13 parts Ion-exchanged water 56 parts After mixing and stirring the above four inks, adjust the pH to 7.0 with sodium hydroxide, and then filter with a Fluoropore filter. Used.

Example 2 Pad with an aqueous solution containing 0.5% of polyethylene oxide (Alcox E-75, viscosity average molecular weight: 200 to 250), 2.0% of sodium sulfate and 5% of alumina sol-520 Thickness 2 after processing (drawing ratio: 90%)
A 00 μm polyester fabric was prepared. Alumina in the obtained fabric was 4.5%, polyethylene oxide was 0.45%, and sodium sulfate was 1.8%. Next, the sheet was cut into a roll having a width of 42 cm, and full-color printing was performed with an ink containing the following disperse dye using a commercially available inkjet color printer (BJC-440, manufactured by Canon Inc.). Immediately after the printing was completed, the printed portion was cut off and subjected to a color development treatment with superheated steam at 180 ° C. for 5 minutes. Next, it was reduced and washed with an alkaline solution containing hydrosulfide, and then dried after being washed with water. A deep and sufficient density color image was printed vividly on the obtained polyester fabric. In addition, a sharp image was obtained without staining of a white portion where ink did not adhere. Further, the image density on the back surface was also sufficient.

Ink Composition Cyan ink C.I. I. Dipper's Blue 87 7 parts Lignin sodium sulfonate 2 parts Thiodiglycol 15 parts Triethylene glycol 15 parts Ion-exchanged water 56 parts Magenta ink C.I. I. Disperse Red 92 6 parts Sodium ligninsulfonate 2 parts Thiodiglycol 15 parts Triethylene glycol 15 parts Ion exchange water 62 parts Yellow ink C.I. I. Disperse Yellow 93 6 parts Sodium ligninsulfonate 2 parts Thiodiglycol 15 parts Triethylene glycol 15 parts Ion-exchanged water 62 parts Black ink C.I. I. Disperse Black 18 8 parts Sodium ligninsulfonate 2 parts 15 parts thiodiglycol 15 parts Triethylene glycol 15 parts Ion-exchanged water 60 parts Each of the above components was mixed and dispersed using a sand grinder, and filtered and used with a filter.

Example 3 2.0% of polyethylene oxide (Alcox R-1000), 1% of urea and 6.0 of alumina sol-520
%, EDTA4Na and an aqueous solution containing 0.1% were subjected to pad treatment (squeezing ratio: 90%), and dried to prepare a new synthetic fiber polyester cloth (fiber thickness: 0.8 denier). It contained 1.8% polyethylene oxide, 0.9% urea, 5.4% alumina sol, and 0.09% EDTA4Na.

The subsequent operation was performed in exactly the same manner as in Example 3 to obtain a final print. A deep and sufficient density color image was printed vividly on the obtained polyester fabric. Further, sharp images were obtained on the front and back without any stain on the white portion where no ink was attached.

Example 4 A silk feather doubled with polyethylene oxide (Alcox®
(400%, molecular weight: 180 to 250,000), an aqueous solution containing 4.0% of alumina sol-520 and 3% of urea (squeezing rate: 70%) was prepared. It contained 2.8% polyethylene oxide, 2.1% alumina sol and 2.1% urea. This was cut out to the size of A3 plate, and multicolor printing was performed using the same ink as in Example 1 using a commercially available inkjet color printer (BJC820J manufactured by Canon). Immediately after the printing was completed, the substrate was treated with superheated steam at 102 ° C. for 8 minutes, then washed with water and dried. On the obtained silk feather double cloth, a color image having a sufficient density without unevenness was printed vividly. In addition, a sharp image was obtained without staining of a white portion where ink did not adhere.

Examples 5 to 8 The polyethylene oxide of Example 2 (Alcox E-
75) was replaced with the polyethylene oxide shown in Table 1, and a polyester cloth was pretreated in the same manner as in Example 2. After ink jet recording, a printed product was obtained through the same color development and washing steps as in Example 2. The results obtained are summarized in Table 1. As a comparative example, those other than the present invention are also shown.

[0056]

[Table 1] * Sharpness: ◎: No bleeding, no color mixing in the picture ○: No bleeding, slight color mixing in the picture at a large amount of ink △: No bleeding, but slight color mixing in the picture ×: bleeding * Color density: ○: clear and deep color density Δ: clear but not deep color density ×: unclear and colorless color density Comparative Example 4 Instead of alumina sol-520 used in Example 2, alumina sol-200 (manufactured by Nissan Chemical Industries, specific gravity: 1.09 to
1.14, except that 2.0% of (average primary particle size: 100 μm, amorphous) was used to obtain a printing fabric in the same manner as in Example 2. Multicolor printing was performed on the fabric using the same ink and printer as in Example 2. After completion of the printing, the same treatment as in Example 2 was performed to obtain a printed material. Although a color image with a relatively vivid color tone was obtained on the cloth, an image with a deep, sharp, and sufficient density was not obtained.

[0057]

As described above, according to the present invention,
It is possible to record a high-density image with no bleeding on the fabric. Further, according to the present invention, a fabric for ink jet printing having a sufficient color density on the back surface of the fabric can be obtained.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a head section of an ink jet recording apparatus.

FIG. 2 is a cross-sectional view of a head section of the inkjet recording apparatus.

FIG. 3 is an external perspective view of a head obtained by multiplying the head shown in FIG. 1;

FIG. 4 is a perspective view illustrating an example of an ink jet recording apparatus.

[Explanation of symbols]

 Reference Signs List 61 wiping member 62 cap 63 ink absorber 64 discharge recovery section 65 recording head 66 carriage

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomoya Yamamoto 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Takafumi 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Mariko Suzuki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-6-184954 (JP, A) JP-A-7-238467 ( JP, A) JP-A-2-300377 (JP, A) JP-A-3-59177 (JP, A) JP-A-61-55277 (JP, A) JP-A-63-85188 (JP, A) 63-31594 (JP, B2) JP 4-35351 (JP, B2) JP 44-15596 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06P 5 / 00

Claims (4)

(57) [Claims] 1. A fabric having an average primary particle diameter of at least 1
0.5 to 10% by weight of boehmite-based granular alumina having a specific gravity of 1.17 to 1.20 and a polyethylene oxide resin having an average molecular weight of 100,000 to 2,500,000 is used.
1 to 30% by weight of an ink-jet textile fabric. 2. A textile for ink jet printing, characterized by adhering at least one selected from the group consisting of a water-soluble inorganic salt, a hydrotrope agent and a chelating agent to the textile for ink jet textile printing of claim 1. 3. A textile printing method, wherein the textile for ink jet textile printing according to claim 1 or 2, is subjected to ink jet recording, then subjected to a color development treatment, washed, and then dried. 4. A printed matter obtained by the printing method according to claim 3.