JPS5843038B2 - Non-polluting dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies to aluminium, synthetic resin coating materials, wood, paper, various fiber fabrics, or synthetic resin molded products or sheets containing water-soluble dyes or oil-soluble dyes, or water and organic solvents. Printing or printing using a soluble vehicle and printing ink containing an aldehyde hardener (hereinafter referred to as aldehyde hardener) for forming an ink film or printing paste film, or a printing paste containing dye or pigment. After printing or printing, an aldehyde-based hardener is added to the printed matter or printed fabric without impairing the adsorption of the dye or pigment in the printing ink or printing paste to the printed matter or printed fabric. When completing the dye or pigment dyeing on the printing substrate or printed fabric and at the same time removing excess printing ink or printing paste containing dyes or pigments by washing with water, remove the excess printing ink or printing paste. The present invention relates to a pollution-free dyeing method for printing or textile printing other than offset printing, in which the colored suspension is removed without being eluted in washing water and the washing water is reused.

Conventionally, for example, in dyeing an alumite plate by screen printing, a colored alumite plate is manufactured by washing the alumite plate with water, drying, dyeing by printing, drying, removing excess ink by washing, and sealing process.

Also, in the case of dyeing various fiber fabrics, synthetic resin sheets, paper, etc. by printing, for example, screen printing is performed using a printing paste, and the printed material is produced by drying, fixing, and washing with water.

In the above-mentioned conventional dyeing, when removing surplus ink or surplus printing paste by washing with water, the dyes or pigments in the surplus printing ink or printing paste directly elute or turn into colloids and flow out into the cleaning water, resulting in coloring of the cleaning water. Because colored washing water is discharged as is, it not only consumes a large amount of washing water, but also causes pollution problems as it becomes the subject of pollution control regulations to prevent water pollution caused by colored harmful substances.

In view of the above, the present inventors formed an ink film or a printing paste film using an aldehyde-based hardening agent, and the dye or pigment in the ink or printing paste was formed by a heating reaction due to the action of the aldehyde-based hardening agent. In addition, after printing or printing is completed, dyes or pigments from excess printing ink or printing paste are suspended in the washing water as an insoluble film or lump as a measure to prevent pollution. It was discovered that the clear filtered water could be easily filtered and removed by letting it drain, and the clear filtered water could be recovered and reused as it is without being released, leading to the establishment of the present invention regarding a resource-saving and pollution-free dyeing method. The present invention will now be described in detail.

The present invention uses a normal printing method or textile printing method when printing or textile-printing a synthetic resin film coating material on metal, glass, etc., alumite, wood, various fiber fabrics, paper, or a resin bottom-shaped object or sheet. However, in the printing or textile printing process using printing inks or printing pastes that use water-soluble or water- and organic solvent-soluble vehicles, aldehyde-based hardeners containing formaldehyde, acetaldehyde, glyoxal, etc. as main components are used in printing inks or printing pastes that use water-soluble or water- and organic solvent-soluble vehicles. A film agent is added or used, or after printing with a printing ink or printing with a printing paste, the above-mentioned aldehyde hardener is sprayed or applied with a brush or the like.

In this way, when heating, reaction, and washing with washing water after printing or textile printing, printing or imprinting is completed without any loss in the so-called printability or imprintability of the printing ink or printing paste, and moreover, the printed matter is Alternatively, surplus dyes or pigments from the printed material do not dissolve into the washing water, but are suspended together with the vehicle in the form of colored films, fibers, or lumps that are insoluble in the washing water, and are easily passed through the wash water. It is removable and has no effect on the dyeability or color tone of the printed or printed material.

Any commercially available water-soluble or oil-soluble dyes can be used as the dyes used in printing inks or printing pastes, or the dyes or pigments used in printing pastes. water-soluble natural or synthetic resins for printing inks or printing pastes are used.

Therefore, when the method of the invention is used for printing, it is not used for offset printing.

In the present invention, the suspension containing excess dye or pigment is simply filtered out of the wash water, and the filtered clear wash water can be reused for washing again.

The same effect can be achieved even if the printing or printing material is printed or printed with ordinary printing ink or printing paste, and then the aldehyde-based hardener is sprayed or applied with a brush, reacted with heat, and washed with water. The dye or pigment is suspended in the washing water as a colored solid without being eluted into the washing water, and is easily removed by one filtration in the same manner as above, and the filtrate is reused as clear washing water.

Therefore, in the present invention, printed matter or textiles can be produced without discharging colored wastewater out of the system.

An embodiment of an apparatus for removing film-like or block-like printing ink or printing paste suspended in washing water used in the present invention is shown in FIG.

In FIG. 1, the recovered cleaning water 2 that has been circulated on the printed material or printed material 4 that has been previously treated with hot water at about 45° C. is blown off in the shower 3, and the excess printing ink that is released in the form of a film from the surface of the printed material or printed material Washing water of the printing paste is filtered through a blanket stretched over two feed rollers 5 and 6, and the film-like printing ink or printing paste containing the residual dye or pigment is conveyed on the same blanket, and then conveyed to the roller 6. 7 for dewatering, drying with a heater 8 provided between rollers 6 and 10, and separating the film-like colored ink or printing paste from the blanket with a doctor 9 and storing it in a storage tank 11.

The cleaning water that has passed through the blanket between the rollers 5 and 6 is sent to a cleaning water storage tank 1, where it is recycled by a pump 12 and recycled as cleaning water.

Next, the present invention will be explained in detail by way of examples.

Example 1 After washing an alumite plate with water and drying at 70°C for 7 minutes, a commercially available printing ink using a water-soluble synthetic resin as a vehicle and an oil-based dye as a dye (A and Q inks for alumite dyeing manufactured by Osaka Printing Ink Manufacturing Co., Ltd.) was screen printed and dyed with a printing ink containing 2% by weight of an aldehyde hardener containing formaldehyde, acetaldehyde or glyoxal as a main component of the present invention, and then dyed at 70°C for 1 hour.
A colored alumite plate is produced by a heating reaction for 5 minutes, and then the colored alumite plate is placed in washing water and held for a short time. The printing ink containing excess dye becomes a colored film and is completely removed from the colored alumite plate. In order to peel off the plate, the colored alumite plate is taken out of the water, washed with water, and sealed to obtain an alumite product as usual.

On the other hand, the cleaning water containing colored film-like substances containing surplus printing ink used for cleaning is easily removed by passing it through a normal 1-passing device, and the clear water is recycled and used again for cleaning. Since there is no discharge outside the system, the total amount of washing water used is extremely small and no pollution is caused by the dye.

Table 1 shows a comparison of the amount of ink released to the outside of the system between the method of the present invention using the aldehyde hardener of Example 1 and the conventional alumite printing method.

However, ■ ■ ■ ■ Weight after screen printing on an alumite board and drying at 70°C for 15 minutes, Weight of anodizing board after removing excess ink with 600 cc of water, Passing washing water through a 100 mesh screen once at 70°C,
The weight of the recovered ink film dried for 15 minutes, the amount of ink that flowed into the washing water, and Table 1 show that the conventional method using commercially available AQ ink for alumite dyeing did not remove any colored substances, and the washing water remained colored after passing. However, in the method of the present invention, the printing ink becomes a film,
The colored water was removed by filtration, and the washed water that had been filtrated was clear and not colored, so it could be reused.

The same results as those described above were also obtained by using the cleaning and removing device shown in FIG. 1 and spraying cleaning water to remove excess ink remaining on the alumite plate of Example 1.

In the above, an alumite plate was used, but similar results were obtained with glass, stainless steel plate, iron plate, or zinc plate coated with glass and metal plate coating materials.

Example 2 In the same manner as in Example 1, in the production of a colored alumite plate using an alumite plate, the alumite plate was washed with water, dried and dyed by screen printing, and then dyed with formaldehyde, acetaldehyde or glyoxal as a main component. A 1.5% aqueous solution of a hardening agent was sprayed onto the colored alumite plate using a mist spray at 75°C.
A heating reaction was carried out for 17 minutes, and then the colored alumite plate was placed in washing water and held for a short period of time. Excess printing ink was made into a film and peeled off from the colored alumite plate. Further, the plate was washed with water, passed through the washing water once, and sealed. As a result, a colored alumite plate was obtained in the same manner as in Example 1.

In addition, the washing water was reused as clear water.

In this case, as in Example 1, there was no change in the dyeability or color tone of the colored alumite plate.

Similar results were obtained when the cleaning and removing device shown in FIG. 1 was used to remove excess ink remaining on the screen-printed alumite plate.

Example 3 As in Example 1, a commercially available AQ ink for dyeing alumite was used to test the change in color tone of a colored alumite plate due to changes in the amount of aldehyde hardener added.

The procedure was as in Example 1, except that only an aldehyde hardener was added to the printing ink, varying as shown in Table 2.

By adding 1 to 2% of aldehyde hardener to printing ink, surplus ink becomes a film and is suspended in washing water, and can be removed. It has been found that there is no change in the color tone of the product depending on the amount added, and that adding more than 3% tends to darken the color, and adding more than 5% causes a change in the color tone of the colored alumite plate.On the other hand, if you are looking for a change in color tone. 5% of aldehyde hardener
It has been found that this is also possible by adding the above.

Therefore, in the present invention, in order to achieve non-pollution, the amount of aldehyde hardener added to the printing ink or printing paste is 0 if no change in the color tone of printed matter or printed matter is desired.
．． Approximately 5 to 3% by weight, preferably 1 to 2.5% by weight, if a change in tone is desired, 3% by weight or more is required depending on the degree of desired color tone, but more than 5% by weight is also acceptable. There is little change in color tone, and from an economic standpoint, the upper limit of the amount added is about 5% by weight.

However, the printing inks used were the blue, green, brown, and red colors of the AQ ink for dyeing alumite.

It has been found that colored plates can be obtained using wood, synthetic resin, sheets, or glass plates coated with painted films in the same manner as with alumite plates.

Example 4 A vehicle was prepared by dissolving and mixing 18 parts by weight of polyvinyl pyrrolidone (all parts by weight below) in 47 parts of butyl cellosolve, and to this was added Sudan Blue 2 (5 parts by weight).
ue 2) Dissolve 10 parts of oil-soluble dye (manufactured by Badeish) in 10 parts of water and 25 parts of butylcellosolve and add it to the above vehicle to prepare a printing ink, and add formaldehyde, acetaldehyde or glyoxal as a main ingredient to this. A screen printing ink prepared by adding 2 parts by weight of a hardening agent was used in the same manner as in Example 1, and the same results were obtained.

In this case as well, the excess ink suspension that formed in the wash water in the form of a film was removed by passing through the wash water, and the wash water was reused as clear water.

Instead of anodized aluminum plate, use other metal plates, glass plates, wood plates,
Similar results were obtained using paper, synthetic resin plates or sheets, or other metal plates or glass plates on which painted films were formed.

Example 5 A vehicle was prepared by mixing and dissolving 20 parts of polyvinylpyrrolidone with 45 parts of butyl cellosolve and 5 parts by weight of methyl alcohol, and then adding Isosol Blue B as a water-soluble acid dye.
10 parts of L (manufactured by Ciba Geigy) and 15 parts of butyl cellosolve
Example 1 As a result of treating the alumite plate in the same manner as in Example 1, a colored alumite plate was obtained, and as in the case of Example 1, excess printing ink was suspended in the washing water in the form of a film, and the suspended matter was removed by filtration. The 1 peroxide water was reused as clear wash water.

Other water-soluble acidic dyes include Acitol Yellow M5
RL, orange MRL, dark blue MBR, dark blue MTR, and black MSGL (all manufactured by Badish) were similarly dissolved in water and used.

Additionally, hydroxypropyl cellulose 20 as a vehicle
part and 50 parts of benzyl alcohol or 30 parts of hydroxypropylcellulose and 50 parts of butylcellosolve or 50 parts of maleic acid-modified styrene resin, and further PVA1 or CMC.
50 parts of each can be suitably used.

Example 6 A synthetic resin paint (using AC medium manufactured by Daito Kakai Kogyo Co., Ltd.) was applied to a stainless steel plate and baked at 190°C for 15 minutes. The excess ink suspended in the form of a film was removed by washing with water, followed by a top coat and baking at 190°C for 15 minutes to obtain colored stainless steel.

The filtered washing water was similarly circulated and reused.

Similar results were obtained by direct printing on wood and vinyl chloride resin boards.

Example 7 Screening was carried out using a Tetoron fiber cloth using a water-soluble synthetic resin as a vehicle, a disperse dye, and a printing paste containing a hardening agent containing aldehydes such as formaldehyde, acetaldehyde, or glyoxal as a main component. After printing and heating reaction, the excess printing paste that adhered to the washing water was suspended in the form of a film, and the colored printing paste was removed from the washing water by one filtration. When the washing water was reused, Tetron was obtained. The fabric was not contaminated, and after drying, a Tetoron-printed fabric similar to that in ordinary printing was obtained.

Prints were similarly obtained using the same method for synthetic resin sheets or paper.

As can be seen from the above examples, the present invention prevents dyes or pigments from printing ink or printing paste from being discharged as a water pollution control measure, and allows effective reuse of washing water through a simple pass. This will greatly contribute to printers and textile printers who are subject to pollution regulations due to colored wastewater.

[Brief explanation of the drawing]

FIG. 1 shows an embodiment of a cleaning device for removing surplus printing ink or printing paste from printed matter or textiles used in the present invention and recovering cleaning water for use. 1...Washing water storage tank, 2...Recovered washing water, 3...Shower, 4...Printed matter or printed matter, 5, 6, 7゜8 ...Roller, 9
. . . Doctor, 10 . . . Heating heater, 11 . . . Separation and recovery tank for film-like surplus ink or printing paste.

Claims (1)

[Claims] 1. Printing ink or printing paste prepared by adding dyes or pigments to alumite, synthetic resin coating materials, wood, paper, various fiber fabrics, synthetic resin moldings or sheets using a water-soluble or water- and organic solvent-soluble vehicle. An aldehyde hardener for forming an ink film or printing paste film (hereinafter simply referred to as aldehyde hardener) containing formaldehyde, acetaldehyde, or glyoxal as a main component is added, and printing or textile printing is carried out as usual. Alternatively, the above-mentioned aldehyde-based hardener is sprayed or applied with a brush or the like on the printed matter or printed matter, and then heated and reacted. After washing, the printing ink or printing paste containing excess dye or pigment is suspended as a colored suspension in the washing water, and the colored suspension is removed by filtration. Features a pollution-free dyeing method for printing or textile printing other than offset printing.