JPS5911716B2 - 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 disperse dye.

More specifically, the present invention relates to the general formula [wherein R1 represents a hydrogen atom, a chloro atom, a bromine atom, a lower alkyl group or a lower alkoxy group, R2,
R3 represents the same or different lower alkyl groups, R
4 represents a hydrogen atom, a methyl group, or a cyano group, and A represents a general formula (wherein R5 represents a hydrogen atom, a chloro atom, a lower alkyl group, or a lower alkoxy group; an alkoxy group, or a general formula (wherein R7 is a hydrogen atom, a lower alkoxy group, a hydroxyl group, a lower alkyl group which may be substituted with a cyan group or a chloro atom, and R8 is a lower alkoxy group, a hydroxyl group, a cyan group) Alternatively, it represents a lower alkyl group, phenyl group or benzyl group which may be substituted with a chloro atom.

).

), or the general formula (wherein Rg r Rlo represents a lower alkyl group and R1, R2 and R3 are as defined above).

).

This is a method of dry transfer printing acidic modified synthetic fibers, particularly acidic modified polyacrylonitrile fibers or acidic modified polyester fine fibers, using an ink composition containing the dye represented by the following.

Over the past few years, transfer printing has gradually become popular, and in particular, transfer printing that uses 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 is now in charge.

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. This means that the wastewater treatment, 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 of polyester fibers using disperse dyes has already been put into practical use industrially, but a method of dry transfer printing of acrylic fibers using cationic dyes has been developed. has not yet reached full-scale practical use because cationic dyes have poor sublimation transfer properties and the light fastness of dyes dyed by sublimation transfer is inferior to those dyed by ordinary dyeing methods.

However, various proposals have been made recently regarding the application to ACRIS 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 free dyes to improve the transferability of basic 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 ink compositions could be added, the stability over time of transfer paper prepared using such ink compositions would not be completely satisfactory.

The present inventors have conducted extensive research 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 was completed by discovering that the above performance can be satisfied by using the dye represented by the general formula (1).

The dyeing mechanism between the dye and the fiber according to the method of the present invention is that protons from the acidic group bonded in the fiber are used to form a dye on the tertiary nitrogen atom of the dye represented by the general formula (1). It is thought that the salt-formed dye further forms salts with the dissociated acidic groups in the fibers and dyes. Therefore, the general formula (
When the dye 1) is dyed onto fibers by transfer printing, it is converted into a cationic dye.

This is fully supported by the fact that the hue of the dyed product is more bathochromic and more vivid than the hue of the dye before transfer.

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 heterocyclic disperse dyes having a tertiary nitrogen atom, and 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 dye represented by general formula (1) used in the present invention is
It can be obtained by any of the following three manufacturing methods.

The first method of preparation is based on the general formula (where R1, R2, R3 and R4 are as defined above).

) and an aniline derivative represented by the general formula (where R5 and R6 are as defined above) in an acidic medium (for example, acetic acid or 20% sulfuric acid). can be obtained easily.

Suitable formylated indolenine derivatives represented by general formula (9) include, for example, 2-formylmethyl-
3,3-dimethylindolenine, 2-formylmethyl-
3,3,5-trimethylindolenine, 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-ethyloxyindolenine, 2-formylmethyl-3,3-; methyl-5-chloroindolenine, 2-formylmethyl-3,3-dimethyl-5-bromoindolenine, 2- Formylmethyl-3-methyl-3
-Ethylindolenine, 2-(α-formylethyl)-
3,3-dimethylindolenine, 2-formylmethyl-
Examples include 3,3-diethylindolenine and 2-formylcyanomethyl-3,3-dimethylindolenine.

Furthermore, suitable aniline derivatives represented by the general formula Cl0) include, for example, aniline, p-anisidine, 2-chloro-4-ethylaniline, 2,4-dimethoxyaniline, 0-phenetidine, 4-n-7' Lopylaniline, cleansin, 4-amino-N-ethylaniline, 4-
Amino-dimethylaniline, 4-amino-N-ethyl-
N-β-hydroxyethylaniline, 4-amino-3-
Methyl-diethylaniline, 4-amino-N-methyl-N-β-cyanoethylaniline, 4-amino-3-methoxy-diethylaniline, 4-amino-N-ethyl-N
-benzylaniline, 4-amino-diphenylamine,
Examples include 4-amino-N-methyl-diphenylamine, 4-amino-N-ethyl-N-β-methoxyethylaniline, and 4-aminobenzylaniline.

Further, the second method for producing the dye represented by the general formula (1) used in the present invention is to combine the formylated indolenine derivative represented by the general formula (9) and the general formula (in the formula R1t R2
y R3+ Rg and RIO are as previously defined and B■ represents an anion derived from an inorganic acid.

) and/or a heterocyclic compound represented by general formula I
, α2), (13), (14) and (15) in an acidic medium (for example, acetic acid or sulfuric acid); The third production method uses the general formula (wherein X represents a hydrogen atom, a methyl group or a cyan group, and R1*R2 and R3 are as defined above.

) and the general formula (wherein R1
+ R2+ R3+ Rg and R□.

is as defined previously.

) and a formylated heterocyclic compound represented by the formula (2) are heated in an acidic medium in the same manner as the first method.

In this case, the desired dye can be obtained easily and in good yield by any method.

General formula aυ used in the second production method, (12), (1
3).

Suitable heterocyclic compounds represented by α(a) and (L5) include, for example, the following structural formulas, (represented by general formula αυ) (represented by general formula (14)) (general formula 〇5 ) can be expressed as ).

In addition, suitable indolenine derivatives represented by the general formula (16) used in the third production method include, for example, 2,3
．． 3-trimethylindolenine, 2,3,3.5-tetramethylindolenine, 2,3.3-)dimethyl-5-
Probilintrunin, 2,3.3-)limethyl~5-
Ethylindolenine, 29313-)! J)'f-5-methoxyindolenine, 2,3.3-) 1) Methyl-5-ethoxyindolenine, 2,3.3-)
'J Methyl-5-chlorindolenine, 2.3.3-)
Dimethyl-5-bromoindolenine, 2,3-dimethyl-3-ethylindolenine, 2-ethyl-3,3-dimethylindolenine, 2-methyl-3,3-diethylindolenine, and 2-cyanomethyl-3. Examples include 3-dimethylindolenine.

Furthermore, general formula (17), α8), (19)',
Suitable formylated heterocyclic compounds represented by (20) and (21) include, for example, compounds represented by the following structural formula (general formula (1r) 1 (general formula (2υ)) I can give what I can.

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 (Caseikasei Products), Exlan DK (
Bonnell V (Mitsubishi Rayon product), acid-modified modacrylic fibers such as Kanekalon S (Value product).

Acid-modified polyester fibers such as Dacron T-
65, T-92 (DuPont product), Tetron K (Toshi product), acid-modified nylon fibers such as nylon 844 (DuPont product), nylon T-120 (ICI product), etc. Blends, interwovens, and cross-knitted products with other fiber materials, including acid-modified synthetic fibers, 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 above-mentioned general formula (1),
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 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 provide even more excellent dyeing fastness. It can be dyed with 5 degrees.

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 excellent fastness such as light fastness and washing resistance. ing.

The reason for this is that the dye contains secondary
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 almost unaffected by slight temperature differences during heating, and therefore uniformly dyed products can be obtained.

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

In addition, unless otherwise specified, "middle part" and "chi" mean parts by weight.

Examples 1 to 8 Ethyl cellulose N-7 (manufactured by Vercules) 9 parts - 5 parts A gravure ink was prepared by uniformly dispersing it, and a pattern was gravure printed on high-quality paper using this ink to make a transfer paper.

This transfer paper was placed in close contact with Bonnell V (Mitsubishi Rayon), placed in a heating device A-JAX (American Laundry Machinery Company), and heated at a temperature of 190° C. for 30 seconds under normal pressure to obtain one dyed product.

The color density of this dyed product was high, and its light fastness and wet fastness were good.

Examples 13-20 When the dyes shown in Table 2 were used in place of the dyes used in the previous examples, prints with similar performance were obtained.

Example 21 Water/isopropyl alcohol (1:1) solution of water-soluble acrylic resin (solid content 45%) 40 parts Water 30 parts Isopropyl alcohol 20 parts Dye in the example process 10 parts 100 parts The above ingredients were thoroughly mixed using a sand mill. to prepare an aqueous gravure ink.

A transfer paper was made by gravure printing on high quality paper using this ink, and this transfer paper and Cashmilon F (chemical-free product) were closely attached and heated at a temperature of 190°C for 30 seconds under normal pressure. Similarly, excellent prints were obtained.

Example 22 Ethyl cellulose N-1006, 5 parts (manufactured by Cures) - 8.0 parts Ethylene glycol monobutyl polymer 80.5 parts Dye in Example 13 5.0 parts i o o, Part o The above ingredients were sufficiently dispersed using three rolls to form a silk screen ink, and this ink was screen printed on high quality paper to make a transfer paper.

This transfer paper and Dacron T-92 (DuPont product) were brought into close contact and heated to 190°C under normal pressure using a heating device A/JAX.
After heating for 30 seconds at a temperature of .degree. C., an excellent dyeing similar to that of Example 9 was obtained.

Claims (1)

[Claims] 1. General formula [wherein R1 is a hydrogen atom, a chloro atom, or a hydrogen atom]. 4, represents a lower alkyl group or a lower alkoxy group, R2tR3 represents the same or different lower alkyl group, R4 represents a hydrogen atom, methyl group or cyan group, A is a general formula (in the formula, R5 is a hydrogen atom , a chloro atom, a lower alkyl group, or a lower alkoxy group, R6 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a general formula (wherein R7 is a hydrogen atom, a lower alkoxy group, a hydroxyl group, a cyan group, or a chloro a lower alkyl group which may be substituted with an atom, R8 represents a lower alkyl group, a phenyl group or a benzyl group which may be substituted with a lower alkoxy group, a hydroxyl group, a cyano group or a chloro atom; ), or the general formula (wherein R9 and RIO represent lower alkyl groups and 1R1, R2 and R3 are as defined above). ) A dry transfer printing method for acid-modified synthetic fibers, characterized by using an ink composition containing a dye represented by: