JPS5934830B2 - 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 relates to the following general formula (wherein R1,
R4 is hydrogen atom, chloro atom or bromine, carbon number 1-
3 represents a lower alkyl group or a lower alkoxy group having 1 to 3 carbon atoms, and R2 and R3 each independently represent a lower alkyl group having 1 to 4 carbon atoms.
(including substituted alkyl groups substituted with a chlor atom, cyan group, hydroxyl group, or lower alkoxy group having 1 to 3 carbon atoms), phenyl group or benzyl group (including a chloro atom, a lower alkyl group having 1 to 3 carbon atoms), (including substituted benzyl groups substituted with alkyl groups).

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

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 account for %.

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
The light fastness of dyes dyed by sublimation transfer is inferior to those dyed by normal dyeing methods, so they have not yet been put into full-scale practical use.

However, recently various proposals have been made for 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 under reduced pressure 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 cannot be added to the ink composition as it is. It has many drawbacks, such as the fact that it is difficult to add such an ink composition, and even if it were possible to add it, the stability over time of transfer paper made using such an ink composition 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 and wax resistance. The present invention was completed based on the discovery that the above performance can be satisfied by using the dye represented by the general formula (I).

The dyeing mechanism between the dye and the fiber according to the method of the present invention is that a proton from an acidic group bonded in the fiber is used to form a dye on the tertiary nitrogen atom of the dye represented by the general formula (I). It is thought that the dye formed by salting further forms salt with the dissociated acidic groups in the fiber and dyes the fiber.

This relationship is illustrated as follows: When the dye of general formula (I) is dyed onto a fiber by transfer printing, it is converted into a cationic dye.

This can be fully supported by the fact that the hue of the dyed product is more bathochromic than the hue of the dye before transfer, and its clarity is further enhanced.

This phenomenon in which the dye represented by general formula (I) 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 is a major feature of the present invention. This is one of its characteristics.

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.

Dye represented by general formula (1) used in the present invention,
2,3.3-IJ methylindolenine derivative 4-
It can be easily obtained by heating a formylaniline derivative in an acidic medium (for example, acetic acid or sulfuric acid).

Suitable 2,3.3-trimethylindolenine derivatives include, for example, 2,3.3-t-dimethyl-5-methylindolenine, 2,3.3-)dimethyl-5-propylindolenine, 2,3 .3-trimethyl-5-ethylindolenine, 2,3.3-)-rifthyl-5-methoxyindolenine, 2,3.3-toIJmethyl-5-ethoxyindolenine, 2,3.3-trimethyl- Examples include 5-propoxyindolenine, 2,3.3-trimethyl-5-chlorindolenine, 2,3.3-H methyl-5-bromoindolenine, and 2,3.3-MJ methylindolenine.

Further, suitable 4-formylaniline derivatives include, for example, 4-formyl-N, N-dimethylaniline, 4-formyl-N, N-diethylaniline, 4-formyl-N
-Methyl-N-(β-cyanoethyl)aniline, 4-formyl-N-methyl-N-(β-chloroethyl)aniline, 4-formyl-N-methyl-N-(β-methoxyethyl)aniline, 4- Formyl-N-(β-ethoxyethyl)aniline, 4-formyl-N-ethyl-N-(β-ethoxyethyl)aniline, 4-formyl-N-ethyl-N-(β-ethoxyethyl)aniline
-cyanethyl)aniline, 4-formyl-N-ethyl-N-(β-chloroethyl)aniline, 4-formyl-
N-ethyl-N-(β-methoxyethyl)aniline, 4
-Formyl-N-ethyl-N-(β-ethoxyethyl)
Aniline, 4-formyl-N-methyl-N-benzylaniline, 4-formyl-N-ethyl-N-benzylaniline, 4-formyl-N-(β-cyanoethyl)-N-
Benzylaniline, 4-formyl-N-(β-chloroethyl)-N-penzylani+)7.4-formyl-N-
(β-methoxyethyl)-N-benzylaniline, 4-
Formyl-N-methyl-N-(4'-chlorobenzyl)
Aniline, 4-formyl-N=ethyl-N-(4'-methylbenzyl)aniline, 4-formyl-N, N-dimethyl-m-toluidine, 4-formyl-N, N-diethyl-m-toluidine, 4 -Formyl-N-methyl-N-
(β-cyanoethyl)-m-toluidine, 4-formyl-N-methyl-N-(β-methoxyethyl)-m-toluidine, 4-formyl-N-ethyl-N-(β-chloroethyl)m-toluidine , 4-formyl-N-ethyl-
N-(β-ethoxyethyl)-m) luidine, 4-
Formyl-N-ethyl-N-(β-cyanoethyl)-m
-) luidine, 4-formyl-N-methyl-N-benzyl-m=toluidine, 4-formyl-N-ethyl-N-
Benzyl-m-toluidine, 4-formyl-N-(β-
cyanoethyl)-N-benzyl-m-toluidine, 4-
Formyl-N-(β-chloroethyl)-N-benzyl-
m) Luidine, 4-formyl-N-(β-methoxyethyl)-N-benzyl-m-)luidine, 4-formyl-
N, N-diethyl-m-anisidine, 4-formyl-N
.

N-diethyl-m-chloroaniline, 4-formyl-N
-methyldiphenylamine and 4-formyl-N-ethyldiphenylamine.

Acid-modified synthetic fibers that can be applied to dry transfer printing by the method of the present invention include acid-modified polyacrylic fibers,
Takiba Cashmilon F (chemical-free product) Exlan DK (
Nippon Exlan product) Bonnel■ (Mitsubishi Rayon product)
, acid-modified modacrylic fibers such as Kanekalon S
(valued products), acid-modified polyester fibers such as Dacron T-65, T-92 (Dupont products), Tetron K (Toshi products), acidic-modified nylon fibers such as Nylon 844 (Dupont products) Nylon T-
120 (ICI product), and blended, interwoven, and interwoven products containing these acid-modified synthetic fibers with other fiber materials can also be transfer-printed by the method of the present invention.

The transfer paper used in the practice of the present invention uses the dye represented by the above general formula (I) to produce an aqueous or oil-based coloring composition (ink, printing paste, etc.) by a conventional method, and then applies it to paper, film, etc. It can be applied to the entire surface or in a pattern on the base sheet by an appropriate printing method, textile printing method, handwriting, dipping, spraying method, etc.

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 made into a dyed product having the following properties.

The dye represented by the general formula (I) has good transferability under the transfer printing conditions described above, so that a dyed product with high density can be obtained, and the dyed product has excellent various fastnesses such as light fastness and wash resistance. ing.

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 content of the present invention is not limited to the following Examples.

Note that ``parts'' and ``parts by weight'' mean parts by weight unless otherwise specified.

Examples 1 to 8 Gravure ink is prepared by uniformly dispersing the above components using a ball mill, and a pattern is gravure printed on high-quality paper using this ink to produce transfer paper.

This transfer paper was placed in close contact with Bonnell V-110 (Mitsubishi Rayon) and charged into a heating device A-Jacks (American Laundry Machinery Company) for 30 minutes at a temperature of 190°C under normal pressure.
The mixture was heated for seconds to obtain a dyed product.

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

Examples 9 to 16 When dyes represented by the general formulas 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 (I), and the color tones are those on polyacrylonitrile fibers.

Example 21 Water-soluble acrylic resin (1:1) solution (solid content: 45%) The above components were sufficiently dispersed using a sand mill to prepare a water-based gravure ink.

Using this ink, make a transfer paper by gravure printing on high-quality paper.This transfer paper and Cashmilon F (chemical-free product) are brought into close contact and heated at a temperature of 190°C for 30 seconds under normal pressure.
An excellent print similar to that of Example 1 was obtained.

Example 22 Ethylcellulose N-1006, 5 parts (manufactured by Vercules) Clay 8.0 parts The above ingredients were sufficiently dispersed using three rolls to make silk screen ink, and this ink was used to screen print and transfer onto high quality paper. make 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 0.degree. C., an excellent dyeing similar to that of Example 2 was obtained.

Claims (1)

[Scope of Claims] 1 The following general formula (where R, R4 is a hydrogen atom, a chloro atom or a bromine atom, a lower alkyl group having 1 to 3 carbon atoms, or a lower alkyl group having 1 to 3 carbon atoms)
R2゜R3 each independently represents a lower alkyl group having 1 to 4 carbon atoms (a substituted alkyl group substituted with a chloro atom, a cyan group, a hydroxyl group, or a lower alkoxy group having 1 to 3 carbon atoms). ), a phenyl group or a benzyl group (including a substituted benzyl group substituted with a chloro atom or a lower alkyl group having 1 to 3 carbon atoms). ) Dry transfer printing method for acidic modified synthetic fibers characterized by using an ink composition containing a dye represented by 0