JPS5857552B2 - Dry transfer printing method for acid-modified synthetic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dry transfer printing of acidic modified synthetic fibers using an ink composition containing an indolenine methine type disperse dye.

More specifically, the present invention is based on the following general formula (wherein R1 represents a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 3 carbon atoms, or a lower alkoxy group having 1 to 3 carbon atoms,
2 and R3 each independently represent a lower alkyl group having 1 to 3 carbon atoms, R4 represents a hydrogen atom, a methyl group, or a cyano group, and Q represents a general formula (wherein R5 is a lower alkyl group having 1 to 3 carbon atoms). R6 represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms, R7 represents a hydrogen atom or a non-dissociable substituent, and R8JR9 and RIO represent a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. Represents a lower alkyl group, R11
j R12 each independently represents a hydrogen atom, a lower alkyl group having 1 to 3 carbon atoms, or a lower alkoxy group having 1 to 3 carbon atoms.

).

This is a method of dry transfer printing acidic modified synthetic fibers, particularly acidic modified polyac IJ lonitrile fibers or acidic modified polyester fibers, using an ink composition containing the dye represented by ().

Over the past few years, transfer printing has gradually become popular, and in particular transfer printing, which takes advantage of the sublimation properties of dyes, has responded to social demands for labor saving in the dyeing process and pollution prevention. It has grown to the point where it now occupies 15 staff.

The main reason why transfer printing has attracted worldwide attention and is being rapidly put into practical use in various fields is that it is possible to reproduce delicate designs and prints can be easily obtained. The treatment of wastewater, that is, the post-treatment of the dyeing process, such as soaping and washing, can be completely eliminated, making it extremely streamlined.

Against this background, dry transfer printing on polyester fibers using disperse dyes has already been put into practical use industrially, but dry transfer printing using cationic dyes on acrylic fibers is difficult because cationic dyes have poor sublimation transfer properties. Tame and
Since the light fastness of sublimation transfer printed materials is inferior to that of materials dyed using normal dyeing methods, they have not yet been put into full-scale practical use.

However, various proposals have recently been made regarding application to acrylic fibers, such as a method of transferring under reduced pressure as a method to improve the poor transferability of cationic dyes, and a method of transferring basic dyes to improve the transferability of free dyes. Examples include a method of converting it into a base and applying it to transfer printing.

However, in the former case, there are often restrictions not only in terms of the equipment but also in terms of the dye used, and in the latter case, the free base is often extremely unstable and difficult to add to the ink composition as it is. However, even if such an ink composition could be added, the stability over time of a transfer paper made using such an ink composition would not be completely satisfactory.

As a result of intensive research by the present inventors into dyes for transfer printing that can dye acid-modified synthetic fibers, particularly acid-modified polyacrylic fibers or acid-modified polyester fibers, in vivid, deep colors and have excellent light fastness, The present invention has been completed by discovering that the above performance can be satisfied by using the dye represented by the general formula (1).

In the method of the present invention, the dyeing mechanism between the dye and the fiber is that a tetraton from the acidic group bonded in the fiber is formed on the tertiary nitrogen atom of the dye represented by the general formula (1). It is thought that this salt-formed dye further forms salt with the dissociated acid phase group in the fiber and dyes it. Therefore, when the dye of general formula (1) is dyed on the fiber by transfer printing, it becomes a cationic dye. It will be converted into type dye.

This is fully supported by the fact that the hue of the dyed product is more bathochromic than the hue of the dye before transfer, further increasing its Western-style appearance.

The phenomenon in which the dye represented by general formula (1) is converted into a cationic dye by the method of the present invention is not observed in similar multi-ring disperse dyes having a tertiary nitrogen atom; This is one of its major features.

Furthermore, the fact that the dye according to the present invention is transferred to fibers in the form of a disperse dye greatly improves the poor transferability, which is a drawback of transfer using conventional cationic dyes. There are major features of the present invention.

The first method for obtaining the dye represented by the general formula (1) used in the present invention is to use the following general formula (wherein X1 represents a hydrogen atom, a methyl group or a cyano group, and R1, R2 and R3 are As defined.

) and the following general formula (wherein R5, R6, R,, R8, Ro, R, o+ R,.

and R12 are as defined above.

) in an acidic medium (for example, acetic acid or 20% sulfuric acid), and a second method is to heat the formyl compound represented by
and Xl are as defined above.

) and the following general formula (wherein R5, R6, R7, R8, R9 and RIG are as defined above).

) in an acidic medium (for example, acetic acid or 20% sulfuric acid), and in either case, the desired dye can be obtained easily and in good yield.

Suitable indolenine derivatives represented by general formula (5) include, for example, 2, 3, 3. -) lynchylindolenine, 2,3,3.5-tetramethylindolenine,
2,3,3-trimethyl-5-propylindolenine,
2,3.3-trimethyl-5-ethylindolenine,
2,3,3-1-1) Methyl-5-methoxyindolenine, 2,3.3-4limethyl-5-ethoxyindolenine, 2,3゜3-trimethyl-5-chlorindolenine, 2゜3 .3-trimethyl-5-bromoindolenine, 2.3-dimethyl-3-ethylindolenine, 2
-ethyl-3,3-dimethylindolenine, 2methyl-
Examples include 3,3-diethylindolenine and 2-cyanomethyl-3,3-dimethylindolenine.

Further, as a suitable formylated indole derivative represented by the general formula (6), for example, 2-methyl-
3-formylindole, 2-ethyl-3-formylindole, 2-phenyl-3-formylindole, 1-methyl-2-phenyl-3-formylindole, ■-ethyl-2-phenyl-3-formylindole, 1,2-
Dimethyl-3-formylindole, 1,2-diethyl-3-formylindole, 1.5-'; Methyl-2-phenyl-3-formylindole 2-methyl-3-formyl-5-methoxyindole, 2-phenyl-3-
Formyl-5-chloroindole and 1,2.5-1
-rifutyl-3-formylindole and the like.

Suitable formylated indoline derivatives represented by general formula (7) include, for example, 1-formyl-2-methylindoline, 1-formyl-2-ethylindoline, and 1-formyl2.3.3- Examples of preferable benzaldehyde derivatives represented by the general formula (8) include 2,4-dimethoxybenzaldehyde, 2,4-dimethylbenzaldehyde, and 4-methoxybenzaldehyde. , 4-methylbenzaldehyde, 4-proboxybenzaldehyde and 4-ethoxybenzaldehyde.

Suitable formylated indolenine derivatives represented by general formula (9) include, for example, 2-formylmethyl-3,3-dimethylindolenine, 2-formylmethyl-3,'3,5-trimethyl Indolenine, 2
-Formylmethyl-3,3-dimethyl-5-propylindolenine, 2-formylmethyl-3,3-dimethyl-
5-ethylindolenine, 2-formylmethyl-3,3
-dimethyl-5-methoxyindolenine, 2-formylmethyl-3,3-dimethyl-5-ethoxyindolenine, 2-formylmethyl-3,3-dimethyl-5-chlorindolenine, 2-formylmethyl-3, 3-dimethyl-5-bromoindolenine, 2-formylmethyl-3-
Methyl-3-ethylindolenine, 2-(α-formylethyl)-3°3-dimethylindolenine, 2-formylmethyl3,3-diethylindolenine and 2-formylcyanomethyl-3,3-dimethylindolenine etc.

In addition, suitable indole derivatives represented by the general formula (■0) include, for example, 2-methylindole, 2-
Ethylindole, 2-phenylindole, 1-methyl-2-phenylindole 1-ethyl-2-phenylindole, 1,2-dimethylindole, 2-methyl-5-methoxyindole 2-phenyl-5-chlorindole and 1 .

Examples include 3-trimethylindoline.

Acid-modified synthetic fibers that can be applied to dry transfer printing by the method of the present invention include acid-modified polyacrylic fibers,
For example, Cashmiron F (Asahi Kasei product), Exlan DK (
Nippon Exlan product) Bonnel■ (Mitsubishi Rayon product)
, acid-modified modacrylic fibers such as Kanekalon S
(Kanebuchi Chemical Products), acid-modified polyester fibers such as Dacron T-65, T-92 (DuPont products),
Tetron K (Toshi product), acid-modified nylon fibers, such as nylon 544 (DuPont product) Nylon T
-120 (ICI product), blended with other fiber materials including these acid-modified synthetic fibers,
Mixed woven and mixed knitted products can also be transfer printed by the method of the present invention.

The transfer paper used in the practice of the present invention is prepared by producing an aqueous or oil-based coloring composition (ink, printing paste, etc.) by a conventional method using the dye represented by the general formula (1), and
This can be obtained by applying this to a base sheet such as paper or film on the entire surface or in a pattern by an appropriate printing method, textile printing method, handwriting, dipping or spraying method.

In order to obtain a suitable transfer print, the transfer paper is brought into close contact with the object to be dyed and heated in accordance with a conventional method.

Transfer conditions are 120-210 under normal pressure or reduced pressure.
The conditions may be selected from the range of heating at a temperature of 'C for 20 seconds to 5 minutes.

In addition, the dyed products obtained by carrying out the present invention generally have sufficient performance for practical use as they are, but in some cases, steaming treatment may further improve the dyeing properties and produce even more excellent dyeing. It can be dyed with fastness.

The dye represented by the general formula (1) has good transferability under the transfer printing conditions described above, so that a deep-colored dyed product can be obtained, and the dyed product has various fastness properties such as light fastness, washability, etc. Excellent.

The reason for this is that the dye contains tertiary esters contained in its molecules.
This is because they are ionically dyed with the acidic groups contained in acidic modified synthetic fibers due to the action of nitrogen atoms, and in this point they are different from disperse dyes in polyester fibers.

Furthermore, since the transfer speed of these dyes has little temperature dependence, it is hardly affected by slight temperature irregularities during heating, and therefore uniformly dyed products can be obtained.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the following Examples.

Note that Chubu and Section mean parts by weight and weight % unless otherwise specified.

A gravure ink is prepared by homogeneously dispersing the above components using a ball mill, and this ink is used to gravure print a pattern on wood-free paper to produce transfer paper.

This transfer paper was placed in close contact with Bonnell (2) and placed in a heating device A-JAX (manufactured by American Laundry Machinery Co.), and heated under normal pressure at 190° C. and humidity for 30 seconds to obtain a dyed product.

The color density of this dyeing was high and its side light and wet fastness were good.

Examples 9 to 16 When dyes represented by the general formula were used in place of the dyes used in the previous examples, prints with similar performance were obtained.

The substituents shown in Table 2 correspond to formula (1), and the color tones are those on polyacrylonitrile fibers.

The above components were sufficiently dispersed using a sand mill to prepare a water-based gravure ink.

Using this ink, gravure printing was carried out on the above-mentioned paper to make a transfer paper, and this transfer paper and Cashmilon F were brought into close contact with each other and heated for 30 seconds at a humidity of 190°C under normal pressure. I got a print.

Example 18 The above components were sufficiently dispersed using three rolls to form a silk screen ink, and this ink was screen printed on high quality paper to produce transfer paper.

This transfer paper and Dacron T-92 are brought into close contact, and the heating device A
・Heating was performed for 30 seconds at a humidity of 190° C. under normal pressure using a JACKS to obtain an excellent dyed product similar to that of Example 9.

Claims (1)

[Scope of Claims] 1 The following general formula (wherein R1 represents a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 3 carbon atoms, or a lower alkoxy group having 1 to 3 carbon atoms, and R2 and R3 are the same or different) Carbon number 1-3
represents a lower alkyl group, R4 represents a hydrogen atom, a methyl group or a cyano group, and Q represents the following general formula (wherein R5 represents a lower alkyl group having 1 to 3 carbon atoms or a phenyl group, R6 represents a hydrogen atom or Represents a lower a/L/kyl group having 1 to 3 carbon atoms, R7 represents a hydrogen atom or a non-dissociable substituent, and R6゜Ro and R10 are a hydrogen atom or the same or different lower alkyl group having 1 to 3 carbon atoms. R11°R12 represents a hydrogen atom, the same or different lower alkyl group having 1 to 3 carbon atoms, or lower alkoxy group having 1 to 3 carbon atoms. ) A dry transfer printing method for acid-modified synthetic fibers, characterized by using an ink composition containing a dye represented by: