JPS61225387A - Printing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] 〔Technical field] The present invention relates to a textile printing method.

[Prior Art] Conventional textile printing methods can be roughly divided into four types: roll printing, screen printing, photosensitive printing, and transfer printing.

Roll printing and screen printing have a major drawback in that it is almost impossible to print and reproduce delicate, graphic patterns and designs because rolls and screens are used.

Photosensitive printing methods are described, for example, in German Patent No. 901495, German Patent No. 958787, and US Patent No. 2111479.
No. 2,541,178, U.S. Pat. No. 2,628
This method is also shown in the specifications of No. 821 and U.S. Pat. No. 2,756,144, but when printing with this method, it is necessary to use a water-soluble dye, so the transfer paper cannot be lithographically printed. The major drawback is that it is completely impossible to create, and in order to reproduce delicate, graphic-like patterns and designs, gravure printing must be used. As is well known, gravure printing requires an extremely expensive plate-making process (mold cost), making it unsuitable for small lofts and the demand for a wide variety of products, making it an extremely uneconomical method, and it is by no means desirable from an industrial perspective. It's hard to say.

Transfer printing is a printing method that utilizes sublimation of disperse dyes, as shown in British Patent No. 647105, French Patent No. 1228880, Japanese Patent No. 415618, or Japanese Patent No. 4401559. Transfer printing can reproduce delicate and graphic patterns and designs. However, this method has a major drawback in that the type of fabric is limited to synthetic fibers and is completely impossible to use with natural fibers.

In addition, as a special transfer printing, for example, JP-A-49-86
Transfer printing on acrylic fabric using cationic dyes, as shown in Japanese Patent Application Laid-Open No. 49-12917 and IFII Publication No. 58-110286, as well as British Patent No. 670174 and British Patent No. 1284824. , German Patent No. 2122805, US Patent No. 1954451
No., U.S. Patent No. 2,588,286, Special Publication No. 148-1973
No. 65, Special Publication No. 18194, Special Publication No. 48-18194, and Special Publication No. 18194, Special Publication No. 45-2
Wet transfer printing shown in the specification of No. 1447 is known.

However, all of these transfer printing methods have the same drawbacks as photosensitive printing methods.

[Purpose and Summary of the Invention] The Ministry of the Invention has been researching textile printing methods for some time, and in this research, we have solved each of the drawbacks of each conventional textile printing method, and created delicate and graphic patterns and designs. We have continued our intensive research with the aim of developing a printing method that can be economically and easily reproduced for a wide range of fabrics, both natural fibers and synthetic fibers. In this research, I came up with the idea of printing without using gravure printing using lithographic inks or water-soluble dyes that could not be used at all in lithographic printing, and continued research based on this idea. As a result, by insolubilizing the water-soluble dye to improve its properties as a pigment, and kneading this with a general lithographic ink vehicle, lithographic printing or lithographic offset printing becomes possible, and then steaming, soaping, and They discovered that the intended purpose could be achieved by subjecting whales to post-treatments such as water dyeing, and completed the present invention on whales. That is, in the present invention, a water-insoluble dye is subjected to a water-insolubilization treatment, and an ink prepared by kneading this with a lithographic ink vehicle is used to perform lithographic printing or lithographic offset printing on the surface of a fabric, followed by steaming, soaping and This relates to a textile printing method characterized by (1) performing post-treatments such as washing with water.

According to the method of the present invention, all the drawbacks of conventional textile printing methods can be overcome. That is, in the method of the present invention, water-soluble dyes include direct dyes, reactive dyes, acid dyes, acidic metal-containing dyes,
Basic dyes are insolubilized to give them properties as pigments, and this is kneaded with a normal lithographic ink vehicle to enable lithographic printing or lithographic offset printing. Patterns and designs can be easily and economically reproduced on both natural and synthetic fabrics. Furthermore, since it does not rely on gravure printing, it can be economically and quickly adapted to the production of small lots and a large number of products.

[Structure of the invention]

The ink used in the method of the present invention is produced by subjecting a water-soluble dye to water-insolubilizing treatment and kneading this with a lithographic ink vehicle. There are various types of water-soluble dyes used in this case, such as direct dyes, reactive dyes, acid dyes, acid alloy dyes, and basic dyes, which can all be used in a wide range of ways.

As the πth treatment to make these water-soluble dyes water-insoluble,
Examples include metal chelation or lakeing methods, or agglomeration or adsorption methods. The means for insolubilizing the dye itself is well known, and the above-mentioned water insolubilizing treatment itself in the present invention may be carried out by any known means. For example, the chelation or lake formation means may be any means in which chelation or lake formation occurs between the metal and the dye and the metal becomes water-insoluble. The latter aggregation or adsorption means include, for example, a method that utilizes the cohesive force of a condensate of benzaldehyde and polyhydric alcohol, and adsorption of porous adsorbent materials such as zirconium complex, carbon black, activated carbon, graphite, and γ-alumina. A preferred specific example is a method that utilizes this ability.

These water insolubilization treatments are appropriately selected and used depending on the type of dye used, printing conditions, etc.

Particularly, a major feature of the present invention is that such a water-soluble dye is made water-insoluble, a lithographic ink is prepared using this, and this lithographic ink is used to print on a fabric using lithographic printing or a lithographic offset printing machine. After the ink on the fabric has dried, it is subjected to the usual steaming, soaping, and washing processes to obtain a printed product. This has never been the case in the past.In fact, the conventional use of technology for water-insolubilizing water-soluble dyes is, for example, metal chelation and lake formation in the areas of paints, printing inks, cosmetics, and dyeing wastewater treatment. Already in use, acidic or basic dyeing lakes are used as colorants in paints and printing inks to achieve colorful tones that cannot be achieved with ordinary pigments, and to remove traces left after wiping lipstick on the lips. The purpose was to use an insolubilized dye lake so as not to leave any residue, or to treat wastewater by turning the dye dissolved in water into a lake to clarify dyeing wastewater.

As the vehicle for the lithographic ink used in the present invention, a wide range of vehicles that have been conventionally used as vehicles for the Kusunoki lithographic ink can be used as they are, such as rosin, rosin-modified phenolic resin, alkyd resin, and oil f6. Note: Acrylic resin, petroleum resin, or any other resin that can be used as a lithographic vehicle, or tung oil without resin,
Fess consisting only of natural drying vegetable oils such as linseed oil or synthetic drying oils can also be used.

The thin leather invention does not preclude the addition of other usual additives used in lithographic inks, such as thickeners, thickening agents, gelling agents, dryer paints, and anti-back transfer agents. etc. can be exemplified.

In the present invention, this lithographic ink vehicle and the water-insolubilized product of the above-mentioned water-soluble dye are used in a conventional manner [ζ, therefore, an ink is prepared. In this case, the ink and the means used may be in accordance with conventional methods.

Using the ink thus obtained, lithographic offset printing is performed on the surface of the fabric. In this case, not only synthetic fibers but also natural W4 fibers can be used.For example, synthetic A fibers include nylon, polyester, acrylic, and various other synthetic fibers; , linen, wool, etc. Any conventional method of lithographic printing or lithographic offset printing can be effectively used.

The thus printed fabric is then dried.

This drying is preferably dry to the touch or completely dry.

This is then followed by the usual steaming, soaping and rinsing.

The printed material obtained by the method of the present invention reproduces the w@ type and graphic design in rich colors and vividly, making it an extremely excellent printed material.

According to the method of the present invention, in addition to the various features and effects described above, the following effects can also be expected.

(b) As mentioned above, the dye insolubilized product itself is suitable for use in dyeing wastewater treatment, and the amount of dye-colored wastewater generated during post-treatments such as steaming, soaping, and washing is extremely small, which helps prevent water pollution. It is also very helpful.

(C)) Yet another feature is that the problem of hot water contamination often seen in general textile printing hardly occurs in the present invention. In the third aspect of the present invention, the mechanism by which the dye, which has been made into a pigment, is restored to a water-soluble dye during steaming and dyes the fabric is not clear, but it is probably due to chemical decomposition or This is thought to be due to physical migration (bleed).

[Example] The method of the present invention will be explained below with reference to Examples, in which the numbers indicating the ratios in the formulation ([all indicate the ratios unless otherwise specified).

Example 1 Two types of dye insolubilized products are prepared using the following formulations.

[Dye insolubilized compound]

The insoluble residue obtained by filtering, washing, and drying these is used to formulate the following inks to obtain inks of two colors, yellow and red.

[Ink formulation]

Insolubilized dye from above 1. Super glossy medium (Dainippon Ink) 1. Linseed oil varnish
0.2 extra festival
0.1 This mixture is milled using a three-roll mill to form an ink.

Lithograph printing is carried out on cotton cloth using the two-color ink of yellow and red produced in this way, and after drying, steaming, soaping, and subsequent washing with water, a delicate two-color yellow and red ink is created. A printed T-shirt that faithfully reproduces the pattern and exhibits a variety of textures and stiffness.

Example 2 First, make the following blending trowel with the dye insolubilized product of the 4 poles.

[Dye insolubilized compound]

Using the residue obtained by passing through, washing, and drying these four types of formulations, four color inks are made with the following formulations.

Knead it with a three-roll mill, turn it into ink, and use a lithographic offset printing machine to print a color photo design on cotton fabric.
Print in color. After drying, steaming, soaping, and washing processes produce a colorful photographic print. The printed material thus produced has good abrasion and wet fastness, good wash fastness, light fastness, and a rich texture.

Example 8 [Dye insolubilized material blend] 5olophenyl Red 6BL 160% (C
IBA-Geigy) (C, 1, Direct Red
79) Sodium sulfate (Na2SO4”l0H20)
15 Sodium chloride (Na(J)
10 Zirconium Complex ZSP-100 (Kigenso Kagaku Kogyo) Barium chloride (BaCA'2 anhydride) 20 heat
400ml of hot water was passed through, washed, dried and made into a pigment, and the remaining water was used in the following ink formulation.

[Ink formulation]

The above dye insolubilized 1. Super glossy medium (Dainippon Ink) 1. Linseed oil varnish
0.2 extra festival 0.
The ink made with 13 rolls is printed on cotton cloth using a lithographic offset printing machine and dried.

The printed material obtained by steaming, soaping, and washing with water is dyed in the same color on both sides of the cotton fabric, and can be used as an effective banner or flag for outdoor advertising that can be observed from both sides of the cotton fabric.

Example 4 [Dye insolubilized material formulation] (CIBA-GeigyXC, 1, Direct Re
d 79) Soda lime 8 Aluminum sulfate Al2 (SO4) 3 anhydride 20
800 ml of boiling water This material is passed through, washed and dried, and the remaining dye insolubilized product is used in the following ink formulation.

[Ink formulation]

The above dye insolubilized 1. Super glossy medium (Dainippon Ink) 1. Linseed oil FES
0.2 extra varnish 0
．． 1 Knead this in a three-roll mill to make ink.

Lithographic offset printing is carried out on cotton fabric, followed by drying layer, steaming, soaping and washing treatment.

The obtained printed material faithfully reproduced the delicate dark red pattern, had a good texture, and had a high degree of fastness.

Example 5 Insolubilization treatment in water was carried out using four types of dyes in the following formulation.

[Dye insolubilized compound]

The insolubilized dyes of the four grades can be obtained by passing through, washing and drying as shown in Examples 1 to 4.

These are blended as inks of four colors.

These are ground in a three-roll mill and made into ink.

The yellow, red, blue and black inks produced in this way are used to print cotton,
A landscape color photograph design is printed on the surface of linen or silk fabric using lithographic offset printing and dried. The steamed, soaped, and water-washed prints faithfully reproduce delicate, deep-colored designs, with no hot water contamination, and a finish with good abrasion, wet and washing fastness, and a nice texture. When comparing the density of the prints of these silk, hemp, and cotton fabrics using a densitometer, we found that: Silk: 1.24 Linen: 1.24 Hemp: 1.24
・・・・・・ 1.22 cotton ・・・・・・・・・
1.12, which indicates a concentration sufficient for practical use, but among them, the concentration in silk is the highest.

Regarding sunlight fastness, regardless of the type of ink or the type of fabric, all of them showed light fastness with no fading when irradiated with a fade meter for 48q. This is how it was done 1
Zeta-printed materials are used, for example, for cotton cloth, interior decorations, linen for tablecloths, and silk for clothing.

Example 6 [Dye insolubilized product formulation] Am1nyl Red E-8BL (Sumitomo Chemical) (C,1, Ac1d Red 257
) Sodium sulfate (Na2SO4-10H20)
15 Sodium chloride CNaC1)
10 Silicic acid (Sin2)
Barium octachloride (BaCJ2 anhydrous) 20 liters of hot water
400 is treated as in Examples 1 to 5 and blended into an insolubilized dye and a pear ink.

[Ink formulation]

The above dye insolubilized l Super gloss medium (Dainippon Ink) l Linseed oil varnish
0.2 extra varnish 0
．． It is ground in a 13-roll mill and made into ink. This ink is used to print on silk and wool fabrics on a lithographic offset printing press. After drying, steaming, soaping and washing with water result in a print with a colorful red pattern.Example 7 [Dye insolubilized compound] (CIBA-Geigy) (C, 1, Direct
Black 22) Sodium sulfate (Na2SO4”l0H
20) l 5 Sodium chloride (Na
CJ? ) 10 Ken 52 Carbon blank (Mitsubishi Kasei) Barium dichloride (BaCA'2 anhydride) 20 Hot water
400 was treated in the same manner as in Examples 1 to 6 above to obtain an insolubilized dye.

[Ink formulation]

The above dye insolubilized 1. Super glossy medium (Dainippon Ink) 1. Linseed oil varnish
0.2 extra festival 0
．． It is ground in a 13-roll mill and made into ink. Using this ink, lithographic blocks are printed on cotton cloth using a block with a sumi-e design. After drying, a process of steaming, soaping, and washing produces a replica of the ink painting that is faithful to the original.

Example 8 The carbon black used in Example 7 was replaced with graphite CPB (Nippon Graphite)! Exactly the same result as in Example 7 was obtained by simply changing the structure.

Example 9 [Dye insolubilized material formulation] Sumilight 5upra Blue BRRc
onc.

(Sumitomo Chemical) (C, 1, Direct Blue 71
) Sodium sulfate (Na2SO4-10H20)
15 Sodium chloride (NaCJ)
10 power〉Hepeuremina A-IHγ-
AJ208) (Sumitomo Aluminum Smelting) Barium chloride (BaCJ?2 anhydride)
20 fever #40
0 Obtain insolubilized dye by treatment in the same manner as in the above example O [Ink formulation] Insolubilized dye 1 Super gloss medium (Dainippon Ink) 1 Linseed oil Fes
0.2 extra festival 0.
1 This is ground in a three-roll mill and made into ink.

Lithographic offset printing is performed on cotton fabric using this ink. After drying the ink, steaming, soaping and washing are performed. The resulting printed material faithfully reproduces the delicate dark blue pattern.

Example 10 Commercially available lake pigment 4 obtained by lake-forming acidic or basic dye
Each color ink is made using the seeds.

[Ink formulation]

The above formulations are milled using a three-roll mill and made into ink. Print on various fabrics using lithographic offset printing.

In this case, 10-1 and 10-2 inks are applied onto silk;
Inks 10-8 and 10-4 print in two colors on silk and acrylic fabrics, respectively. After the ink dries, steaming, soaping, and washing can change the pattern to create a very vivid and delicate pattern. Among these, there are two types: those printed on silk cloth using ink 10-8 and 10-4 before post-processing such as steaming, and those after post-processing such as steaming. and conduct a - week sun exposure test (facing south). With both types of ink, prints before steaming slightly change and fade noticeably within two days, but prints with post-treatment such as steaming do not change color or fade even after a week. do not have. This means that when these lake pigments are used as a conventionally known general printing ink, the light fastness Gζ is extremely poor, but when used as a printed material as in the present invention, that is, by printing or dyeing, the light fastness is significantly improved and is sufficient. This shows that results with practical value can be obtained. All of the lake pigments used in Example 1O were used in powder form, but many are currently commercially available in paste form. If such a paste is used in the present invention, the process of kneading with a three-roll mill can be omitted, and the advantage of reducing the cost of ink production is that only a simple mixing is required, which is even more convenient. It is.

〔Effect of the invention〕

The method of the present invention exhibits the following effects compared to conventional methods.

■Delicate and graphic ink (photo) color designs can be easily reproduced.

■It is possible to efficiently obtain printed products in small lots and in a wide variety of types economically and quickly.

■Applicable to most types of fabrics.

■Does not cause hot water pollution.

■It helps prevent water pollution by producing almost no dyeing wastewater.

(that's all)

Claims (1)

[Claims] (1) Using an ink prepared by subjecting a water-soluble dye to water-insolubilization treatment and kneading this with a lithographic ink vehicle,
Perform lithographic direct printing or lithographic offset printing on the surface of the fabric,
A textile printing method characterized by subsequent post-treatments such as steaming, soaping, and water washing.