JPS6014156B2 - Transfer printing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for thermal transfer printing of cellulose-containing materials.

A method is already known in which a design is printed on a temporary support such as paper using a printing ink containing a sublimable disperse dye, this is used as a transfer sheet, and is superimposed on the object to be transferred, followed by applying heat and pressure to transfer lacquer. There is.

However, conventionally used transfer objects are limited to molded products of synthetic or semi-synthetic polymers such as acetate, polyester, and nylon, which have an affinity for disperse dyes, and lack compatibility with sublimable dyes. It was not applied to cellulosic materials.

In order to improve the affinity between cellulose and disperse dyes, there is a method of treating cellulose fibers with a fiber processing resin such as methylol melamine, or a method of treating cellulose fibers with a swelling agent to combine the hydroxyl groups of the cellulose fibers with the reactive groups of the dye. A method of fixing the pigment matrix by covalent bonding has been proposed.

However, the former method has the disadvantage of impairing the unique texture of cellulose fibers, and the latter method has a low reaction rate between the hydroxyl groups of cellulose fibers and the reactive groups of disperse dyes, resulting in poor washing fastness. There are some aspects that I am dissatisfied with.

The present inventors have conducted various studies on transfer printing methods that allow disperse dyes to adhere well to cellulose without impairing the unique texture of cellulose fibers. We discovered that by thermal transfer printing on cellulose using a transfer sheet supporting isatoic acid derivatives, we could obtain dyed products with excellent washing fastness while maintaining the unique texture of cellulose fibers. , has completed the present invention. That is,
An object of the present invention is to provide a method for obtaining dyed products having high washing fastness without impairing the unique texture of cellulose fibers in a transfer printing method for cellulose-containing materials. An azo or anthraquinone sublimable disperse dye having a molecular weight of Z800 or less and having a reactive group containing the general formula [1] [wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom] Or represents a halogen atom.

] A transfer sheet supporting an isatoic acid derivative represented by
This is easily achieved by heating the dye and isatoic acid derivative supported on the transfer sheet to the cellulose-containing material by heating for 1 to 4 minutes under a temperature condition of 00C. The present invention will be explained in detail below.

In the present invention, the cellulose-containing material includes natural cellulose fibers such as Sosuke, hemp, regenerated cellulose fibers such as viscose rayon, copper ammonia rayon, and woven or knitted fabrics, nonwoven fabrics, and films thereof, or the above-mentioned cellulose fibers and polyester or Examples include blended products with polyamide.

In the present invention, the dye supported on the transfer sheet is an azo or anthraquinone sublimable disperse dye having a reactive group containing an active halogen and having a molecular weight of 800 or less. Examples of active halogen-containing reactive groups include substituents represented by the following general formula.

(In the formula, × represents fluorine, chlorine, bromine, or iodine, and R and R represent an alkyl group.) Among them, dihalogeno S triazinyl group, trihalogenopyrimidyl group, dihalogeno maleimide anhydride group, and dihalogenoprobionyl group. and the like are preferably used.

Specific examples of dyes suitably used in the present invention include (wherein A represents a reactive group).

), etc., or azo disperse dyes such as (In the formula, A represents a reactive group.

) and other anthraquinone disperse dyes.

The dye used in the present invention has a molecular weight of 140 to
Particularly suitable are those that sublimate or evaporate in 1 to 4 minutes, preferably 15 to 100 seconds at a temperature of 240:00.

In the present invention, the dye described above is used on the transfer sheet together with the following general formula [1] [wherein R and x are as defined above].

] It is used in support of a cysoxylic acid converter.

Such isatoic acid derivatives include isatoic anhydride, N-methyl isatoic anhydride, N-ethyl isatoic anhydride, N-(n
-propyl) isatoic anhydride, 5-chloroisatoic anhydride, and the like. The transfer sheet used in the present invention is made of paper with an ink containing the dye and isatoic acid promoter.
Patterns, letters, numbers, etc. are printed on a support such as cellophane, metal foil, or plastic film by any printing method such as offset printing, flexographic printing, gravure printing, or screen process, or by ink containing the above dye. It is produced by printing a pattern etc. on a support in the same manner as above and then overcoating with an ink containing the isatoic acid derivative.

The ink used to prepare the transfer sheet may be oil-based or water-based, and usually contains a solvent, a binder, etc. other than the dye, and if necessary, the isatoic acid converter.

Vehicles and auxiliary agents constituting the ink, such as solvents and binders, vary depending on the printing method employed, so those suitable for the printing method are used. The isatoic acid derivative is usually used in an amount of 0.1 to 13 moles, preferably 0.5 to 5 times the mole of the dye, and the ink containing the dye and isatoic acid anhydride has a content of both of the above. Anything within the range will be used. In addition, when a design or the like is printed on a support with a printing ink that does not contain an isatoic acid derivative and then overcoated with an ink that contains an isatoic acid derivative, it is desirable to use a slightly larger amount of the isatoic acid derivative than the above range. In the present invention, ureas such as N-N'-dimethylurea, cellulose-grade vertical swelling agents such as polyhydric alcohols such as polyethylene glycol, or alkyl derivatives thereof, or sodium hydroxide,
Acid absorbers such as sodium carbonate, potassium acetate, sodium trichloroacetate, sodium silicate, trietanoamine, and anthranilic acid amide may be added to the above-mentioned inks.

Further, the cellulose weave total swelling agent or acid absorbent may be included in the cellulose-containing material in advance.

In order to perform transfer printing of a cellulose-containing material according to the present invention, the above-described transfer sheet and cellulose-containing material are overlapped with the printed surfaces of the transfer sheets in contact with each other, and if desired, mechanically pressed together at a temperature of 140 to 240°C. , preferably 170
~220oo for ~4 minutes between 1 bait sand, preferably 15~1
It is sufficient to carry out the heat treatment in the sand bath as described in step 2.

Thermal transfer may be carried out under normal pressure, or good results can be obtained even if it is carried out under reduced pressure, for example, under a pressure of about 15 to 15 Hg. By performing such thermal transfer, the dye and isatoic acid promoter on the transfer sheet are diffused into the cellulose-containing material, some of the hydroxyl groups of cellulose are aminated as shown in the following formula, and the reactive groups of the dye react with the amino groups. Since dyes can be fixed almost quantitatively, wet fastness, which has traditionally been a problem, is significantly improved.

Furthermore, since no particular pretreatment is required for the cellulose-containing material, not only can the transfer printing process be shortened, but the unique texture of cellulose is not impaired.

Hereinafter, 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 departs from the gist thereof.

In addition, "parts" in the examples indicate "parts by weight."

Example 1 Mercerized broad cotton (number 4) was soaked in a treatment solution consisting of 0.2 parts of sodium bicarbonate, 2 parts of polyethylene glycol (average molecular weight 300), and 79.8 parts of water to obtain a squeezing rate of 70%. After squeezing the mixture, it was dried at 8,000 for 5 minutes.

On the other hand, a transfer sheet was prepared by printing on gravure coated paper with an ink consisting of 3 parts of the following dye, 2 parts of N-methyl isatoic anhydride, 8 parts of inpropyl alcohol, and 6 parts of ethyl cellulose.

The above-mentioned cotton cloth was superimposed on this transfer sheet, and transferred and fixed by heating and pressing with lk9/sulfur G between 9-sand at 200:00 using a flat pressure press.

The dyed product obtained was a bright yellow color, and the nonionic surfactant (manufactured by Kao Soap ■, trademark: Score Roll #9)
00) at 80 o'clock for 15 minutes, and even after subsequent extraction with dimethylformamide at 130 o'clock for 20 minutes, no dye was observed to come off.

Example 2 The design portion of the transfer sheet was overcoated with an ink consisting of 6 parts of the following dye*9 parts of pyrualcohol and 6 parts of ethyl cellulose.

A cotton cloth treated as described in Example 1 was overlaid on the thus prepared transfer sheet, and a 2003
The transfer was fixed by heating and pressurizing the sand between 9 and 0, lk9/fence ○. The dyed product obtained was a bright yellow color, and like the results of Example 1, only a small amount of the dye came off during washing.

Example 3: Mercerized line broad (4: false silkworm hand)
0.1 part of sodium trichloroacetate, 2 parts of tetraethylene glycol dimethyl ether and 79 parts of water. It was immersed in a treatment container consisting of $100, squeezed to a squeezing rate of 75%, and then air-dried.

On the other hand, the following dye: 3 parts inpropyl alcohol 88 parts and ethyl cellulose 6 parts
A transfer sheet was prepared by printing on coated paper for gravure using an ink consisting of 2 parts.

Furthermore, 4 parts of N-methyl isatoic anhydride, isopro*5-k.

A transfer sheet was prepared by printing on gravure coated paper with an ink consisting of 2 parts of isatoic anhydride, 8 parts of inpropyl alcohol, and 6 parts of ethyl cellulose. The above-mentioned cotton cloth was superimposed on this transfer sheet, and then 200
The transfer was fixed by heating and pressing 6 inkstone sand with qo, lk9/g.

The dyed product obtained was a bright yellow color, and only a small amount of the dye came off during washing.

Example 4 The same procedure as in Example 2 was carried out except that the following dye was used as the reactive disperse dye and N-ethyl isatoic anhydride was used instead of N-methyl isatoic anhydride. A yellow print was obtained.

Example 5 Polyester/cotton (65/35) blended fabric was mixed with polyethylene glycoyl monomethyl ether (average molecular weight 400)
It was impregnated in a solution consisting of 12 parts of soda, 5 parts of borax, and 870 parts of water when cold, and air-dried.

The blended fabric subjected to the above treatment and the transfer sheet described in Example 1 were stacked together using a flat press machine and
The transfer was fixed by applying heat and pressure for 90 seconds.

The blended fabric on which the dye had been fixed was soaped for a length of 80 qo using the nonionic surfactant described in * in Example 1 to obtain a uniform dark yellow print without flickering.

Example 6 The following dye: 3 parts N-ethyl isatoic anhydride 2 parts, N-methyl urea 28 parts,
Sodium trichloroacetate 0.05 part, ethyl cellulose 5
A transfer sheet was prepared by printing on gravure coated paper with an ink consisting of 62 parts and 62 parts of ethanol.

By combining this transfer sheet and mercerized cotton cloth,
20500, lk9/c 1 using flat press machine
The transfer was fixed by heating and pressurizing the 0-misaki sand.

The obtained cotton cloth was soaped at 80 qo for 15 minutes using the nonionic surfactant described in Example 1 to obtain a yellow printed material with high fastness and resistance to moisture.

Claims (1)

[Scope of Claims] 1. An azo or anthraquinone sublimable disperse dye having a molecular weight of 800 or less and having a reactive group containing an active halogen, and general formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom or a halogen atom. ] A transfer sheet supporting an isatoic acid derivative represented by
A transfer printing method for a cellulose-containing material, characterized in that the dye and isatoic acid derivative supported on the transfer sheet are transferred to the cellulose-containing material by heating for 10 seconds to 4 minutes under a temperature condition of 0°C. 2. In the azo or anthraquinone sublimable disperse dye having a molecular weight of 800 or less and having a reactive group containing an active halogen in the transfer printing method according to claim 1, the reactive group containing an active halogen is dihalogen-S-triazinyl. group, trihalogenopyrimidyl group, dihalogeno maleimide anhydride group, or dihalogenopropionyl group.