JPS6035468B2 - Transfer printing method - Google Patents

Description

[Detailed description of the invention] The present invention relates to a transfer printing method.

In order to improve the vaporization or migration properties of cationic dyes in transfer printing of beamable materials, the cationic dyes are treated with an alkali to form a free base, or the counterions of the cationic dyes are treated with various types. Transfer sheets are created using weak acid ions instead. However, the transfer sheet prepared in this manner has poor stability over time, and a significant decrease in density is observed in the transfer printed fabric obtained using the sheet, especially when stored in a high temperature atmosphere. Generally, transfer sheets are used for a long period of time, so this decrease in density poses a major obstacle in the industrialization and commercialization of transfer printing. Various studies have been conducted on the causes of the decrease in concentration, including the cationic dye penetrating and adsorbing into the transfer sheet in a high-temperature, high-humidity atmosphere, adsorption to the binder resin, or decomposition of the cationic dye itself over time. is becoming clear. For this reason, various proposals have been made, including a method of pre-treating the transfer sheet support with a silicone-based or paraffin-based water repellent, a method of using a specific binder resin for ink, and a method of using a dye stabilizer. There is.

However, although these methods have some effects, the current situation is that they are not fully satisfactory. In view of this, the present inventors conducted intensive research and found that a transfer sheet with good storage stability can be obtained by using a specific acid salt of a water-resistant cationic dye. We have discovered that this can be done and have arrived at the present invention.

That is, the gist of the present invention resides in a transfer printing method characterized in that a cationic dye dyeable material is transfer printed using an aromatic sulfonate of a cationic dye.

The present invention will be explained in detail below.

In the transfer printing method of the present invention, the aromatic sulfonate of a cationic dye as the dye, in other words, the counter ion has the general formula (1)A-(S03e)n...
- A sulfonic acid residue represented by (1) (in the formula, F represents an aromatic hydrocarbon residue that may have a substituent, and n represents a number of 1 or more and usually 3 or less) Use elutriation-soluble cationic dyes.

In the general formula (1), specific examples of Ar include a benzene nucleus and a naphthalene nucleus which may have a substituent.

Preferred substituents that may be bonded to the nucleus include hydroxyl, nitro, amino, carboxyl, alkyl or alkoxy groups having 3 or less carbon atoms, and halogen atoms such as chlorine and bromine. A general formula like this (
Specific examples of the sulfonic acid residues shown in 1) are:
Benzenesulfonic acid, phenolsulfonic acid, aniline sulfonic acid, toluenesulfonic acid, benzoic acid sulfonic acid, chlorobenzenesulfonic acid, benzenedisulfonic acid,
Examples include residues of aromatic sulfonic acids such as benzenetrisulfonic acid, naphthalenesulfonic acid, naphthalenesulfonic acid, aminonaphthalenesulfonic acid, naphthalenedisulfonic acid, naphtholdisulfonic acid, aminonaphthalenedisulfonic acid, and naphthalenetrisulfonic acid. On the other hand, the cationic dye component of the dye used in the present invention may be any type of cationic dye (basic dye) as long as the counterion is a sulfonic acid residue represented by the general formula (1). Examples include cationic dyes such as mono- or diazacarbocyanine-based, hemicyanine-based, xanthene-based, triallylmethane-based, oxazine-based, and naphthostyryl-based dyes, or cationic light brighteners. Such an aromatic sulfonate of a cationic dye can be prepared in a conventional manner, for example, by forming a salt of a water-soluble cationic dye and a corresponding aromatic sulfonic acid with an inorganic base such as sodium, potassium, or calcium in an aqueous medium, or an alkyl amine. It can be easily obtained by reacting a salt with an organic base such as. In the present invention, the transfer sheet is produced by an offset method on a support such as paper, processed paper, cellophane, or heat-resistant plastic film, using an ink containing one or more aromatic sulfonates of the cationic dyes, according to a conventional method. , gravure method, flexo method, screen method, etc.
It is created by printing designs, letters, numbers, etc. using the leakage method.

As a printing method, a gravure method is particularly suitable because continuous patterns are possible. The ink used to create the transfer sheet may be oil-based or water-based, and contains a binder resin for printing ink and the like in addition to the dye and solvent.

Any of a variety of well-known binder resins can be used as printing ink binder resins, but ethyl cellulose and alcohol-soluble cellulose esters are particularly suitable for oil-based inks, and for water-based inks, Styrene-maleate copolymer emulsion and gum arabic are particularly suitable. In the present invention, transfer printing is carried out by bringing the transfer sheet and the cationic dye dyeable material into close contact for 30 to 12 hours at a temperature of 100 to 220 degrees, preferably 150 to 200 degrees when carried out under normal pressure.

When carried out under reduced pressure, transfer printing can be performed at lower temperatures or for a shorter time. In transfer printing, known basic substances such as caustic soda, caustic potash, calcium hydroxide, and sodium methylate can also be used as transfer accelerators for cationic dyes.

The transfer accelerator may be mixed with the ink at the time of preparing the transfer sheet. Alternatively, the transfer sheet support may be undercoated in advance, or the transfer sheet may be overcoated. Examples of cationic dye-dyeable materials to which the transfer printing of the present invention is applied include acrylic fibers such as Cashmilon F (trademark of Asahi Kasei Co., Ltd.) and Bonnell V (trademark of Mitsubishi Rayon Co., Ltd.) modacrylic fibers such as Kanekalon S (trademark of Kaneka Co., Ltd.) Modified polyester fibers such as Dacron T-64
, T-65 and T-92 (U.S. DuPont trademark) acidic modified polyamide fibers, such as nylon T-120 (UK ICI
(manufactured by DuPont, USA) and nylon 844 (manufactured by DuPont, USA).

Of course, blending with other fiber materials containing a large amount of these fibers,
It may be a mixed weave or a mixed knit product. The method of the present invention has been described in detail above. According to the method of the present invention, transfer printing can be performed with good reproducibility over a long period of time since a transfer sheet having good storage stability is used. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In addition, in the following examples, all "parts" indicate "parts by weight." Example 1C. 1. Basic blue 69 to 44
100 parts of warm water was dissolved.

While pouring this solution, sodium naphthalene-2-sulfonate was gradually added, and a sparingly soluble dye complex precipitated. After sacrificing it thoroughly, separate it and dry it.C. 1 Basic Blue 69 naphthalene-2-sulfonate 6 fat B was obtained. C. obtained by the above method. 1
．． 1 part of Basic Blue 69 naphthalene-2-sulfonate, 1 part of ethyl cellulose N-7 (manufactured by Hercules, USA), inpropyl alcohol/toluene mixture (
A mixture consisting of 89 parts (volume ratio 1:1) of 1 to 3 parts of Fat B
The mixture was placed in a suitable container along with 10 glass beads of ◇ and made into ink using a paint shaker (manufactured by Toyo Seiki Co., Ltd.).

Next, this ink was used to print on gravure paper using a gravure printing machine to create two copies of transfer paper.

One part of the transfer paper was heated to a temperature of 400℃ as an accelerated aging test.
The sample was left for one week in an atmosphere of 0.0 and 90% relative humidity, and then dried. When these two types of transfer papers (one subjected to accelerated aging test and the other not) were stacked with Dacron T-64 and transferred using a heat press under the conditions of 20,000 and 3 mm, in both cases, A transfer printed fabric with vivid colors was obtained.

The rate of decrease in the surface density of a transfer printed fabric obtained when using a transfer paper that has been subjected to an accelerated aging test compared to the surface density of a transferred printed fabric that is obtained when a transfer paper that has not been subjected to an accelerated aging test (see below) (simply referred to as surface concentration reduction rate) is io
% was extremely low.

The surface concentration was measured using a spectrophotometer (manufactured by Hitachi, EPR-
It was measured using a For comparison, C. 1. When similar evaluation was performed using Basic Blue 69 (counterion Cso), the surface concentration reduction rate was 52%.

Example 2 In Example 1, C. 1. C.I. in place of naphthalene mono-2-sulfonate in Basic Blue 69. 1. Two types of transfer paper were prepared in the same manner as in Example 1 except that Basic Yellow 66 naphthalene-2-sulfonate was used.

0.2 of an overcoat agent with the following composition was applied to these transfer papers.
Coated using 5 mil Bar Coke.

(Overcoating agent composition) Potassium hydroxide 2.5 parts Ethyl cellulose (manufactured by Hercules, USA) 8-0 parts Inpropyl alcohol 89.5 parts 100 parts Next, using these transfer papers, under the conditions of 20,000 and 30 seconds. When transferred to Kanekalon S using a heat press,
In all cases, transfer printed fabrics with vivid colors were obtained.

Further, the surface concentration reduction rate was determined in the same manner as in Example 1, and was found to be 15%. For comparison, C. 1. When Basic Yellow 66 was used as it was and a similar evaluation was conducted, the surface density reduction rate was 55%. Example 3~
10 In Example 1, C.I. 1. Instead of Nafrin-2-sulfonate in Basic Blue 69, C.I. 1. Two types of transfer paper were prepared in the same manner as in Example 1, except that the aromatic sulfonate of Thick Violet 16 shown in Table 1 was used.

0.2 of an overcoat agent with the following composition was applied to these transfer papers.
It was coated using a 5 mil bar coater and dried.

(Overcoat composition) Sodium hydroxide 2.5 parts Ethylcellulose N-7 (manufactured by Hercules, USA) 8-0 parts Inpropyl Allure 89.5 parts 100 parts Next, using these transfer papers, 19yC, When the transfer was carried out on Cashmilon F using a hot press for 30 seconds, a transferred printed fabric with vivid colors was obtained in all cases.

Further, the surface concentration reduction rate was determined in the same manner as in Example 1 and is shown in Table 1. For comparison, the counterion is C. or C. 1. A similar evaluation was conducted using Basic Violet 16, and the results are shown in Table 1.

Table 1 Example 12 C. 1. 1.5 parts of 1,5-naphthalenedisulfonate of Basic Red 35, ethyl cellulose N-7 (manufactured by Hercules, USA)7. 8 parts of inpropyl alcohol
6.5 parts, calcium hydroxide5. Mixture 1 consisting of anchorage
Two types of transfer papers were prepared in exactly the same manner as in Example 1 except that the 0-sheet portion was used.

When these two types of transfer paper were used to transfer to nylon 884 using a hot press at 195° C. and 45% sand, transfer printed fabrics with vivid colors were obtained in both cases.

Claims (1)

[Claims] 1. A transfer printing method characterized in that a cationic dye dyeable material is transfer printed using an aromatic sulfonate of a cationic dye.