JPS6024865B2 - 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 a cellulose-reactive disperse dye having a sulfonyl fluoride group.

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. .

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 has hardly been applied to cellulose-based materials.

However, for cellulose fibers, in order to slightly improve the affinity between cellulose fibers and disperse dyes, there are two methods: treating cellulose fibers with a fiber processing resin such as methylolmelamine, or treating cellulose fibers with a swelling agent. However, methods have been proposed in which the dye matrix is fixed by covalent bonding between the hydroxyl groups of the cellulose fibers and the reactive groups of the dye. However, the former method has the disadvantage of impairing the unique texture of cellulose fibers, and the latter method has the disadvantage that the reaction rate between the hydroxyl groups of the cellulose fibers and the reactive groups of the disperse dye is low, resulting in poor washing fastness. There are some unsatisfactory points in practical terms.

The present inventors have conducted various studies on a transfer printing method that allows disperse dyes to adhere to cellulose without impairing the unique texture of cellulose fibers. We found that by applying heat transfer printing to cellulose-containing materials using a transfer sheet supporting disperse dyes, dyed products with excellent washing fastness can be obtained while maintaining the unique texture of cellulose fibers. , and completed the present invention.

That is, an object of the present invention is to provide a method for obtaining a dyed product having high washing fastness without impairing the unique texture of cellulose fibers in a transfer printing method for cellulose-containing materials. The general formula [1]DfS02F)n [1
] (In the formula, D represents a dye matrix containing no sulfonic acid group or carboxylic acid group, and n represents an integer of 1 to 4.

) 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 woven fabrics thereof. Examples include knitted fabrics, nonwoven fabrics, films, and blended fabrics of the above-mentioned cellulose fibers with polyester and polyamide.

In the thermal transfer printing method of the present invention, a sublimable disperse dye having a molecular weight of 800 or less and having one or two to four fluorinated sulfonyl groups 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, as the dye matrix D- in the general formula [1], an azo dye matrix such as , or an anthraquinone pigment matrix such as , etc. can be mentioned.

The dye used in the present invention has a molecular weight of 140 to
Preferably for 1 to 4 minutes at a temperature of 24030°C.
Particularly preferred are those which sublimate or evaporate between 5 and 10 sands. 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 that have been passed through the printing method are used. To carry out the invention advantageously, N, N
-Ureas such as dimethyl urea, polyhydric alcohols such as polyethylene glycol or their alkyl derivatives, and cellulose fiber swelling agents that do not react with reactive groups of dyes such as tetraethylene glycol dimethyl ether are desirable.

) and other cellulose fiber swelling agents and sodium hydroxide,
It is desirable that an acid absorbent such as sodium carbonate, potassium acetate, sodium trichloroacetate, or sodium silicate be included in the cellulose-containing material in advance. The content of swelling agent and acid absorbent in cellulose fiber is 10 to 10, respectively.
Approximately 20% by weight, approximately 0.02 to 0.2% by weight.

Further, the above-mentioned cellulose grade vertical 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 by a coercive 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 sheets in contact with each other, and if desired, mechanically pressed together at a temperature of 140 to 240°C. Preferably 170~
Pine wood may be heat-treated at 0° C. for 1 to 4 minutes, preferably 15 to 12 inkstone steps.

Thermal transfer may be carried out under normal pressure, or may be carried out under reduced pressure, for example at a pressure of about 15 to 150 skin days, 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, compared to the conventional method, the method of the present invention improves wet fastness, which is the biggest problem with cellulose fibers, because covalent bonding between cellulose-containing materials and sulfonyl fluoride groups occurs almost quantitatively. becomes solvable.

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 by alkali.

3 Methi.

Since the disperse dye can be fixed to the cellulose fiber without using a fiber processing agent such as melamine or dihydroxydimethylolethylene urea, the unique feel of the cellulose fiber is not impaired. Its industrial value is extremely large. 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 addition, "parts" in the examples indicate "parts by weight."

Example 1 Mercerized cotton broad (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 squeezing rate was 70. %, and then dried at 50 qo for 5 minutes.

Next, prepare an ink by grinding 6 parts of the dye of the above structural formula, 8 parts of ethyl cellulose, and 86 parts of isopropanol with a paint conditioner, and print this ink on gravure coated paper using a bar coater (0.5 side). A transfer sheet was created.

The above-mentioned cotton cloth was placed on top of this transfer sheet, and transferred and fixed by heating and pressing at 200° C. and lk9/G for 60 seconds using a flat plate press. The dyed product obtained was a rich, vivid orange color. Spread this product for 2 days/The nonionic surfactant (manufactured by Kao Soap, trademark: Score Roll #900)
) and soaping at 990 for 20 minutes with a Yu ratio of 1:50, very little dye came off.

Furthermore, when extraction was subsequently performed using dimethylformamide at 130° C. for 20 minutes, no loss of the dye was observed.

Example 2 A polyester/cotton (65/35) blended fabric was soaked in the treatment described in Example 1 and squeezed to a squeezing rate of 75%.
0 for 5 minutes.

The blended fabric subjected to the above treatment and the transfer sheet described in Example 1 were superimposed and heated at 200°C using a flat press machine at lk9.
When the blended fabric with the dye fixed on it was heated and pressed for 6 spacings with G to fix the transfer and was soaped under the conditions described in Example 1, almost no dye was observed to come off, and there was no flickering. A uniform deep orange print was obtained.

Example 3 Mercerized cotton broadcloth (4 fleas) was immersed in a treatment solution consisting of 0.2 parts of sodium bicarbonate, 25 parts of polyethylene glycol (average molecular weight 300), and 74.8 parts of water to give a squeezing rate of 70%. After squeezing it out, it was air-dried.

Next, 6 parts of the dye of the above structural formula, 6 parts of ethyl cellulose, and 88 parts of inpropyl alcohol were crushed in a ball mill to prepare an ink. ) to create a transfer sheet.

The above-mentioned cotton cloth was superimposed on this transfer sheet, and transferred and fixed by heating and pressing at 200 qo, lk 9/lump G between 6 layers using a flat pressure press. The obtained dyed product had a rich reddish orange 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 parts) was soaked in a treatment bath consisting of 0.25 parts of sodium carbonate, 2 parts of tetraethylene glycol dimethyl ether, and 79.8 parts of water to achieve a squeezing rate of 75%. After squeezing it out, it was air-dried.

Next, 6 parts of the dye of the above structural formula, 8 parts of ethyl cellulose, and 86 parts of inpropyl alcohol were ground with a paint conditioner to prepare an ink, and this ink was applied onto gravure coated paper using a bar coater (0.5 side). A transfer sheet was created by printing. The above-mentioned cotton cloth was superimposed on this transfer sheet and 21,000 liters was pressed using a flat plate press.
The transfer was fixed by heating and pressing between 6 inkstone sands at a G of kg/kg.

The obtained dyed product had a deep blue color, and when it was soaped under the same conditions as in Example 1, only a small amount of the dye came off.

Examples 5 to 22 When thermal transfer printing was carried out in the same manner as in Example 1 except that the dyes shown in Table 1 were used, fast dyed products with the hues shown in the right column of Table 1 were obtained.

Table 1

Claims (1)

[Claims] 1 A cellulose-containing material has the general formula D-(SO_2F)_n [wherein D represents an azo or anthraquinone pigment matrix that does not contain a sulfonic acid group or a carboxylic acid group,
n represents an integer of 1 or more and 3 or less. ] A method for thermal transfer printing of cellulose-containing materials, characterized by thermal transfer printing using a reactive disperse dye shown in .