JPS6035467B2 - Thermal transfer printing method for cellulose-containing materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for thermal transfer printing of cellulose-containing materials using cellulose-reactive disperse dyes having di- and monofluoro-1,3,5-triazinyl groups.

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, and this is used as a transfer sheet, overlaid on the object to be transferred, and then heated and pressed to perform transfer EO printing. .

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 in which cellulose fibers are treated with a fiber processing resin such as methylolmelamine, or a method in which cellulose fibers are treated with a resinous agent and the hydroxyl groups of the cellulose fibers react with the dye. A method has been proposed in which the dye matrix is fixed by bonding with a group.

However, the former method has the disadvantage of impairing the unique texture of cellulose fibers, and the latter method has practical disadvantages such as low reaction rate with cellulose fibers and low washing fastness. .

As a result of various studies on reactive groups that significantly increase the reaction rate with cellulose fibers, the present inventors found that di- and monofluoro-1,3,5-triazinyl groups were the best, and thus completed the present invention. It is. That is,
An object of the present invention is to provide a method for obtaining dyed products with high washing fastness without impairing the delicate texture of cellulose in a transfer printing method for cellulose-containing materials. General formula [1] (
In the formula, D represents a dye matrix containing no sulfonic acid group or carboxyl group, and x represents fluorine or an alkoxy group having 1 to 5 carbon atoms.

) can be easily achieved by thermal transfer printing using a reactive disperse dye shown in . The present invention will be explained in detail below.

Cellulose-containing materials in the present invention include natural cellulose fibers such as cotton and hemp, regenerated cellulose fibers such as viscose rayon and copper ammonia rayon, partially aminated or partially acylated modified cellulose fibers, and these. Examples include woven or knitted fabrics, nonwoven fabrics, films, or blended products of the above cellulose fibers with polyesters and polyamides.

In the thermal transfer printing method of the present invention, a sublimable divided dye having a di- or monofluoro-1,3,5-triazinyl group and having a molecular weight of 800 or less is used as the dye. As the matrix structure of the dye having the reactive group, azo-based, anthraquinone-based, berynone-based, quinophthalone-based, nitro-based, stilbene-based, methine-based, azamethine-based, and polymethine-based dyes are suitably used in the present invention.

Specifically, in the general formula [1], the pigment matrix * body D-
Examples include azo pigment matrices such as , and anthraquinone pigment matrices such as .

The dye used in the present invention has a
Particularly preferred are those which sublimate or evaporate in 1 to 4 minutes, preferably 15 to 100 seconds, at a temperature of 1 to 24,000 ℃. The transfer sheet used in the present invention is a pattern that can be printed on a support such as paper, cellophane, metal foil, or plastic film using an ink containing the above dye by any printing method such as offset printing, flexo printing, gravure printing, or screen process. Created by printing letters, numbers, etc.

The ink used to create the transfer sheet may be oil-based or water-based, and usually contains a solvent, a binder, etc. in addition to the dye.

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. To carry out the invention advantageously, N, N
Desirable are cellulose fiber resins that do not react with ureas such as '-dimethylurea, polyhydric alcohols such as polyethylene glycol or their alkyl derivatives, and reactive groups such as tetraethylene glycol dimethyl ether (particularly tetraethylene glycol dimethyl ether).

) and other cellulose fiber lubricants and sodium hydroxide,
It is desirable that the cellulose-containing material contains an acid absorbent such as sodium carbonate, potassium acetate, sodium trichloroacetate, or sodium lotus acid in advance. The content of the resin lubricant and acid absorbent in the cellulose fibers is 10 to 10, respectively.
Approximately 20% by weight, approximately 0.02 to 0.2% by weight.

Further, the above-mentioned cellulose fiber swelling agent and an alkali precursor such as sodium trichloroacetate may be present in the ink.

Furthermore, a crosslinking agent that binds the pigment matrix and cellulose fibers together by a crosslinking effect, such as 1,4-butanediol diglycidyl ether, may be used in combination.

To carry out 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 sheet in contact with each other, and if desired, mechanically pressed together at a temperature of preferably 140 to 240°C. is 170o
~22030 for ~4 minutes, preferably 15
It is sufficient to perform a heat treatment between ~12 inkstone sands.

Thermal transfer may be carried out under normal pressure or may be carried out under reduced pressure, for example under a pressure of about 15 to 150 Yanagi Hg, to obtain good results. The dyed product thus obtained may be subjected to commonly used post-treatments such as resin processing or fixing.

As detailed above, the method of the present invention is 1.
Cellulose-containing material and di- or monofluor 1,3,5
Since covalent bonding with triazine groups occurs almost quantitatively, it becomes possible to solve the biggest problem regarding cellulose fibers, which is wet fastness.

2. Since the amount of acid absorbent used can be reduced, there is no problem of yellowing of cellulose fibers, and clear prints can be obtained without decomposition of disperse dyes caused by alkali.

3. Disperse dyes can be fixed to cellulose fibers without using fiber processing agents such as methylolmelamine or dihydroxydimethylol-lethylene urea, so the unique feel of cellulose fibers is not impaired.

Its industrial value is extremely high. Yes, it is a thing. EXAMPLES The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

In the examples, "parts" refer to "parts by weight."

Example 1 Mercerized cotton broadcloth (No. 4 flea) was soaked in a treatment solution consisting of 0.14 parts of sodium carbonate, 2 parts of tetraethylene glycol dimethyl ether, and 79.8 parts of water, and the print rate was determined. After drying to 70%, it was dried at 50°C for 5 minutes.

On the other hand, 6 parts of Nago self-cleaning detergent, 8 parts of ethyl cellulose, and 86 parts of inbropyl alcohol.
The sample was ground with a paint conditioner to prepare ink, and this ink was printed on gravure coated paper using a bar coater (0.5 skin) to prepare a transfer sheet.

The above-mentioned cotton cloth was superimposed on this transfer sheet, and transferred and fixed by heating and pressing at 200° C. and 1 kg/G for 60 seconds using a flat pressure press.

The dyed product obtained was a bright reddish yellow. 95% of this product at a bath ratio of 1:50 using a nonionic surfactant (manufactured by Kao Soap ■, trademark: Score Roll #900).
00 for 2 minutes, no dye was observed to come off.

Further, using dimethylformamide, 1300
When extracted for 20 minutes at 0, no loss of dye was observed. Comparative Example 1 The procedure was as described in Example 1 except that the following dyes were used.

When the dyed article to which the dye had been transferred was soaked under the same conditions using the nonionic surfactant described in Example 1, the dye fell off significantly, with over 70% of the dye coming off.

Example 2 A polyester/cotton (65/35) blend fabric was soaked in the same manner as described in Example 1 to reduce the print rate to 75%, and then dried at 5000 for 5 minutes.

The blended fabric subjected to the above treatment and the transfer sheet described in Example 1 were stacked together using a flat pressure press to produce a 20,000 lk sheet.
The transfer was fixed using 9/c Tora G for 9 nights under heat and pressure.

When the blended fabric with the dye fixed thereon was soaped under the conditions described in Example 1, almost no dye was observed to come off, and a uniform dark yellow print without flickering was obtained.

Example 3 Mercerized cotton broadcloth (4 anti-flea) was treated with 0.0% sodium bicarbonate. The mixture was immersed in a solution consisting of 25 parts of polyethylene glycol (average molecular weight 300) and 74.8 parts of water, squeezed to a squeezing rate of 70%, and then air-dried.

On the other hand, 6 parts of the following dye, 6 parts of ethyl cellulose, and 88 parts of inpropyl alcohol.
Prepare an ink by grinding the part with a ball mill, and apply this ink onto coated gravure paper using a gravure printing machine (groove depth 3
A transfer sheet was created by EO printing using 0 French).

The above-mentioned cotton cloth was superimposed on this transfer sheet, and transferred and fixed by heating and pressing at 210 qo, lk9/g, between 6 inkstone sands using a flat pressure press. The obtained dyed product had a clear blue color, and when soaping was carried out under the same conditions as in Example 1, very little dye came off. Example 4 Mercerized cotton broadcloth (4 pieces of sericulture) was soaked in a treatment solution consisting of 0.25 parts of sodium carbonate, 2 parts of tetraethylene glycol dimethyl ether, and 79.8 parts of water to obtain a squeezing rate of 75. After narrowing down to %, it was air-dried.

On the other hand, an ink was prepared by grinding the following dye, 6 parts ethyl cellulose, 8 parts, and 86 parts inpropyl alcohol with a paint conditioner, and this ink was printed on gravure coated paper using a bar coater (0.5 bar). , a transfer sheet was created.

The above-mentioned cotton cloth was superimposed on this transfer sheet, and transferred and fixed by heating and pressing at 205 qo, lk 9/m G between 8 times using a flat pressure press. The resulting dyed product is bright yellow,
When soaping was carried out under the same conditions as in Example 1, very little dye came off.

Example 5 Mercerized broad cotton (4 filtration) was soaked in a treatment solution consisting of 0.014 parts of sodium carbonate, 25 parts of tetraethylene glycol dimethyl ether, and 75 parts of water, and squeezed to a squeezing rate of 70%. After that, it was dried at 50°C for 5 minutes.

On the other hand, an ink was prepared by grinding 6 parts of the following dye, 8 parts of ethyl cellulose, and 86 parts of inpropyl alcohol with a paint conditioner, and this ink was printed on gravure coated paper using a gravure printing machine (groove depth 30 r). A transfer sheet was created.

The above-mentioned cotton cloth was superimposed on this transfer sheet, and transferred and fixed by heating and pressing between 6 inkstone sands at 220,001 k9/cm G using a flat press machine.

The dyed product obtained had a clear reddish blue color. When soaping was carried out under the same conditions as in Example 1, very little dye came off.

Example 6 6 parts of the following dye, 8 parts of ethyl cellulose, and 86 parts of inpropyl alcohol
The ink was ground with a paint conditioner to prepare an ink, and this ink was applied to gravure coated paper using a gravure printing machine (groove depth 30mm) to prepare a transfer sheet.

A cotton cloth treated according to the method described in Example 1 was superimposed on this transfer sheet, and
19 (manufactured by Naomoto Kogyo ■) using lOTorr, 2000
The transfer was fixed by heating and pressing for 6 seconds at 0.100 m/mG.

The dyed product obtained was pink. When soaping was carried out under the same conditions as in Example 1, almost no dye was observed to come off. Examples 7 to 15 The dyeing results obtained by heating and pressing cotton broadcloth according to the method described in Example 1 or Example 5 are listed in Table 1.

Table 1 When the dyed fabrics obtained in Examples 7 to 15 were soaped under the same conditions as in Example 1, very little dye came off.

Claims (1)

[Claims] 1 Cellulose-containing material is defined by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. represents fluorine or an alkoxy group having 1 to 5 carbon atoms. ] A method for thermal transfer printing of cellulose-containing materials, characterized by thermal transfer printing using a reactive disperse dye shown in .