JPS5831435B2 - cellulose - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of printing a cellulose fiber-containing structure using a transfer sheet printed with a printing ink containing a sublimable disperse dye in a fast and uniform manner.

The method of printing a design on a temporary support such as paper using printing ink containing a sublimable disperse dye, superimposing this as a transfer sheet on the object to be transferred, and applying heat and pressure for transfer printing was developed in the 3rd year of the Tokko Showa era.
8-15013, Special Publication No. 39-18793, Special Publication No. 43
-28426, etc., and is well known.

Moreover, the materials to which transfer has been applied have been limited to molded articles made of artificial or synthetic polymers such as acetate, polyester, nylon, and polyurethane, which are dyeable with disperse dyes and have good heat resistance.

When the above method is applied to natural or regenerated cellulose fiber structures such as cotton, linen, rayon, etc., it is expected that there will be almost no dyeing, or that the dyeing will be only staining.

Therefore, even when the above method is applied to a mixed structure of cellulose fibers and synthetic fibers or semi-synthetic fibers, the synthetic fiber portion or semi-synthetic fiber portion will be dyed, but the cellulose fiber portion will hardly be dyed, so the entire structure will be dyed. However, it was not suitable for practical use, as it was only dyed in a very light color, and it was almost impossible to obtain prints with delicate photographic designs with sharp edges, which are the characteristics of these transfer printing methods.

The object of the present invention is to transfer print a cellulose fiber-containing structure using a transfer sheet printed with a printing ink containing a sublimable disperse dye, thereby producing a delicate photographic-like print that is fast, uniform, and has sharp edges. To obtain printed products.

Other fibers mixed with cellulose fibers are polyamide,
In the case of synthetic or semi-synthetic fibers that can be dyed with disperse dyes such as polyurethane, acetate, polyacrylonitrile, etc., a method of uniformly dyeing both the cellulose fiber part and the synthetic or semi-synthetic fiber part of the cellulose fiber-containing structure to the same color is recommended. This is what we provide.

Another objective is to develop a method for obtaining delicate photographic printed products with sharp edges that can be applied to coarsely woven fabrics such as lawn voile, which are normally impossible to print, and highly elastic knitted fabrics. This is what we provide.

The present inventors have applied for a transfer printing method (Japanese Patent Application No. 47-74845) for a 100% cellulose fiber structure or a cellulose/polyester fiber mixed structure, but this method is not suitable for synthetic or semi-synthetic materials other than cellulose and polyester. They discovered that it can also be applied to mixed structures with fibers.

The method of the present invention involves treating a cellulose fiber-containing structure with a chemical having a swelling effect on cellulose and having a boiling point of 150°C or higher;
For example, after pretreatment with polyhydric alcohol and its derivatives, the cellulose fiber-containing structure treated with the swelling agent is superimposed on a transfer sheet that has been preprinted with a printing ink containing a sublimable disperse dye, and the structure is sublimated by heating and pressing. The method consists of the steps of sublimating and condensing the dye from the transfer sheet into the cellulose fiber-containing structure, and further subjecting it to crosslinking treatment if necessary.

The cellulose fiber-containing structure to which the present invention is applied includes:
Natural or regenerated cellulose fibers such as cotton, linen, viscose rayon, viscose cotton, polynosic rayon, copper ammonium rayon, etc., and synthetic or semi-synthetic fibers such as polyamide, polyurethane, polyacrylonitrile, cellulose diacetate, cellulose triacetate (excluding polyester) ), mixed spinning, mixed weaving, mixed knitting products, mixed papers, mixed nonwoven fabrics, etc.

In the swelling agent pretreatment in the present invention, the cellulose fiber-containing structure is immersed in a chemical having a swelling effect on cellulose and a boiling point of 150°C or higher, such as a polyhydric alcohol and its derivatives, or an aqueous solution or dispersion thereof. After soaking and removing excess liquid, the process is usually followed by intermediate drying.

Of course, spraying, coating, etc. can be used as a pretreatment method.

The amount of swelling agent used is usually 3% or more, preferably 5 to 40% by weight, based on the weight of the fibers.

In the present invention, specific examples of the cellulose swelling agent having a boiling point of 150°C or higher include the following polyhydric alcohols and derivatives thereof.

That is, alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, butanediolbentanediol, hexylene glycol, octylene glycol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol diethyl ether lz, diethylene glycol monoethyl ether, diethylene glycol motsupyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene Glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether,
Propylene glycol monobutyl ether, alkylene glycol mono- and diethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tetrapropylene glycol monomethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol formate diester, ethylene glycol Mono- and diesters of alkylene glycols such as formic acid diester, ethylene glycol butyric acid monoester, ethylene glycol propionic acid diester, diethylene glycol monoacetate, diethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol monomethyl ether acetate , ethers of alkylene glycols such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol monohexyl ether acetate Esters, polyethylene glycol with an average molecular weight of 200 to 4000, average molecular weight of 400 to 5000
Polypropylene glycol with an average molecular weight of 400-5
Polyalkylene glycols such as polyethylene glycol block copolymers with an average molecular weight of 200
Monomethyl ether of polyethylene glycol with an average molecular weight of ~4000 and polypropylene glycol with an average molecular weight of 400-5000 Mono- and Diethers, polyethylene glycol with an average molecular weight of 200 to 4000, and average molecular weight of 400 to 500
Mono- and diesters of polyalkylene glycols such as monoacetate, diacetate, monoacrylate, diacrylate, monomethacrylate, diacrylate of polypropylene glycol of 0, substituted 7' JL such as methoxymethoxyethanol, 1-butoxyethoxypropanol / ml-ols, chrycerin, trimethylolpropane, polyglycerin (glycidol/
In addition to polyhydric alcohols such as glycerin adducts, mono-, di-, and triesters of polyhydric alcohols such as glycerin monoacetate, diacetate, and triacetate, adducts of polyhydric alcohols and alkylene oxides, Examples include adducts of polyhydric alcohols and lactones, but particularly preferred are polyethylene glycol monomethyl ether (average molecular weight 250 to 100.0").
), polyethylene glycol monoethyl ether (average molecular weight 250-1000), polyethylene glycol monopropyl ether (average molecular weight 250-1000), polyethylene glycol monobutyl ether (average molecular weight 250-1000), and the like.

In the method of the present invention, 0.1. Disperse Yellow 1.3, 8, 9.42.
60.

C, 1, Disperse Orange 3, 15.0.1. Disperse Red 1.11, 17, C, 1, Disperse Violet 12.0.1. Deine Perne Blue-3,5
, 9 The pretreated structure is superimposed on a transfer sheet that has been printed in advance with a printing ink containing at least one sublimable disperse dye selected from 9, and the sublimable dye is condensed by heating and pressing. .

The transfer sheet used uses paper such as gravure printing paper (printing coated paper), polyolefin, polyester film, etc. as a temporary support, and after coating this support with a release layer, sublimation is applied. Disperse dye and a binder that disperses this dye and does not have too strong an affinity for the dye, such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, gelatin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, carboxymethylcellulose, acrylic ester It is created by printing with a printing ink made of resin, methacrylic acid resin, etc. by silk screen, letterpress printing, flexo printing, gravure printing, etc., and if necessary, by overcoating with a protective film. The sublimable dye may be applied in a pattern to the temporary support by vacuum deposition, or a currently commercially available dry sublimable transfer paper may be used.

In the method of the present invention, after the dye is sublimated and condensed on the cellulose fiber-containing structure by heating and pressurizing, the pretreatment agent is removed by washing with water as necessary, and the dye is condensed and stabilized.

In particular, in the case of a high boiling point swelling agent, washing with water is preferred since the swelling agent is difficult to evaporate during transfer.

Furthermore, in the method of the present invention, in order to improve the washing fastness of the disperse dye sublimated and condensed on the cellulose part, post-treatment with a crosslinking agent is performed as necessary.

As the crosslinking agent, the following crosslinking agents can be applied.

Namely, dimethylol urea, dimethylol ethylene urea, dimethylol propylene urea, dimethylol dihydroxy ethylene urea, partially methoxylated dimethylol dihydroxy ethylene urea, dimethylol uron,
trimenalol melamine, trimethoxymethyl melamine, hexamethoxymethyl melamine, dimethylol ethyl triazone, dimethylol ethyl triazone, dimethylol hydroxyethyl triazone, dimethylol methyl carbamate, dimethylol methyl carbamate, dimethylol hydroxyethyl carbamate, Examples include N-methylol acrylamide, 4-methoxy-5-dimethyldimethylolpropylene urea, glyoxal, formaldehyde, tetraoxane, glitaraldehyde, and epoxy compounds, but particularly preferred are dimethylol dihydroxyethylene urea and partially methoxylated dipropylene urea. Methyloldihydroxyethylene urea.

The above-mentioned crosslinking agents are used according to the usual formulation examples for cellulose.

In this case, a catalyst must also be used.

Examples of the catalyst used include compounds such as inorganic acids, organic acids, ammonium salts of strong acids, polyvalent metal salts of strong acids, hydrochlorides of organic amines, etc., and particularly preferred are hydrochlorides of organic amines. .

Furthermore, commonly used softeners, hand improvers, and the like may be added to the crosslinking agent treatment bath as necessary.

In the present invention, the sublimable disperse dye used is a sublimable disperse dye with high hydrophobicity, that is, low polarity, and
It is preferable that the molecular weight is also relatively small.

By the method of the present invention, cellulose fibers, which could not be dyed with conventional disperse dyes, can be dyed. Both fiber parts can be dyed uniformly in the same color.

Furthermore, the method of the present invention is characterized in that it can be applied to lawns, voiles, etc., which are normally impossible to print due to their coarse texture, and good results can be obtained.

The reason why cellulose fibers can be dyed with disperse dyes is unknown, but pre-treatment with a swelling agent causes the cellulose fibers to take on a swollen structure, giving them the ability to absorb all the dyes, and also due to the affinity between the swelling agent and the dye. This is thought to be because the sublimated disperse dye is modified to diffuse into the interior of the cellulose fiber.

Therefore, inorganic swelling agents that have no affinity with dyes are unsuitable.

Furthermore, after dyeing, when the swelling agent is removed, the cellulose fibers recover close to their original structure, and only the disperse dye that has diffused inside remains, so that the cellulose fibers and the synthetic fibers or semi-synthetic fibers can be dyed with the same uniform color.

When the water absorption swelling property of the cellulose fibers is reduced by post-treatment with a crosslinking agent, the dispersed dyes that have diffused into the fibers will not come off during washing, and the washing resistance will be further improved.

The dyed product to which the present invention was applied was a printed product with a sharp edge and a fibrous design, and could fully meet the demands of consumers.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the examples.

In addition, parts or % in Examples indicate parts by weight or % by weight.

Example 1 A viscose rayon/nylon 6 (50150) blend fabric was immersed in a 15% aqueous solution of polyethylene glycol monomethyl ether (molecular weight 340), squeezed to a squeezing rate of 75%, and dried at 60°C for 10 minutes.

On the other hand, on gravure printing paper (S Perrin M, manufactured by Tokushu Paper Co., Ltd.), the coating amount of polyvinyl alcohol was measured using a solution of 10 parts of polyvinyl alcohol dissolved in 90 parts of a mixture of ethyl alcohol/water (1/1). After overcoating to a coating density of about 2 g/m2, it was dried.

The surface of the paper coated with vinyl alcohol was coated with a mixed solvent of Improper Tool/Ethyl Alcohol (1/1). I.

17.10 parts of Disbird's Red and 6 parts of ethyl cellulose
The paper was printed using a gravure printing machine using ink made from a mixture of 1 and 2, and dried to make transfer paper.

On top of this transfer paper, the blended fabric pretreated with the polyethylene glycol monomethyl ether (molecular weight 300) was superimposed, and heat and pressure treatment was performed using a flat press machine at 200°C, 30 seconds, 1 hour/day. Then, the disperse dye was condensed and dyed onto the blended fabric.

This dyed blended fabric was mixed with 10% dimethylol dihydroxyethylene urea and 1,3-diaminopropanol hydrochloride (3
After immersion in an aqueous solution containing 0% aqueous 1ffl) 2%,
It was squeezed at a squeezing rate of 70%, dried at 100°C for 4 minutes, then subjected to dry heat treatment at 155°C for 4 minutes, then washed with water, soaped, and finished by drying.

As a result, both the rayon part and the nylon part were printed uniformly in the same color, and a print with good washing fastness was obtained.

This is a great improvement compared to conventional untreated blended fabrics in which the rayon portion was hardly dyed or had only staining properties.

Example 2 A cotton/nylon 6 (85/15) blend fabric was immersed in a 10% aqueous solution of polyethylene glycol (molecular weight 300) and squeezed to a squeezing rate of 75%.

Thereafter, a transfer paper was prepared and transferred in the same manner as in Example 1.

Next, 5% dimethylol dihydroxyethylene urea,
1,3-diaminopanol hydrochloride (30% aqueous solution)
After immersing in an aqueous solution containing 2%, it was squeezed at a squeezing rate of 75%, dried at 80°C for 5 minutes, then subjected to dry heat treatment at 160°C for 4 minutes, and then heated at 80°C for 15 minutes with chip soap 29/l. Soaped for a minute, washed with water, and dried.

The resulting print faithfully reproduced the design of the transfer paper and had good wet fastness.

Example 3 In a mixed aqueous solution of 10% triethylene glycol and 5% ethylene glycol monoacetate, cotton/nylon 6.
6 (85/15) blend fabric was dipped, squeezed to a squeezing rate of 75%, and then dried.

Transfer paper was prepared and transferred in the same manner as in Example 1, and resin processing was performed in the same manner as in Example 2.

The resulting printed material had sharp edges and faithfully reproduced the design on the transfer paper.

Example 4 Polyethylene glycol monomethyl ether (molecular weight 3
40) in a 10% aqueous solution of cotton/nylon 6.6 (85/
15) The blended fabric was dipped, squeezed to a squeezing rate of 75%, and then dried.

Using the dye groups shown below (conch, cake), dye transfer papers were created in the same manner as in Example 1,
Transfer, washing, and drying were carried out in the same manner as in Example 1.

The obtained printed product was divided into two parts, and one part was processed with resin in the same manner as in Example 2.

The other side was washed with 2g/l of chip soap at 60℃ for 3 hours.
Soaped for 0 minutes.

As a result, most of the dye in the line parts of the prints that were not treated with resin fell off and the sharp design could not be maintained, but the prints that were treated with resin did not lose the dye even when soaped under the same conditions. was barely noticeable, maintaining its sharp design.

C, 1, Day Nupers Yellow 1, 3, 8, 9°42;
0.1. Day Nupers Orange 3,15;C! , 1. Disbirds Red 1, 11, 17: 0.1. Disverse Violet 12; 0. I.

Day Nupaz Blue - 3, 5, 9, 71° Example 5 A nylon/rayon (50/60) blended fabric was immersed in a 15% aqueous solution of triethylene glycol, and the squeezing rate was 10.
After narrowing down to 0%, it was dried at 60°C for 10 minutes.

This pre-treated blended fabric and the transfer paper used in Example 1 were superimposed and subjected to pressure heat treatment and resin processing in the same manner as in Example 1.

The resulting printed product faithfully reproduced the design of the transfer paper, and both the nylon portion and the line portion were uniformly dyed in the same color.

Furthermore, the washing fastness was also good. Example 6 A cellulose triacetate/cotton (65/35) blended fabric was pretreated with a swelling agent in the same manner as in Example 1, and the pretreated blended fabric and the transfer paper used in Example 1 were superimposed and heated at 195°C.
After transferring by heating and pressing at Kt: 1/cr/l for 30 seconds, resin processing was performed in the same manner as in Example 1.

The resulting printed product faithfully reproduced the design of the transfer paper, and both the cellulose triacetate portion and the line portion were uniformly dyed in the same color.

Furthermore, the washing fastness was also good.

Claims (1)

[Claims] 1. A mixed structure of cellulose fibers pretreated with a cellulose swelling agent having a boiling point of 150°C or higher and other fibers (excluding polyester fibers) is treated with the following sublimable dye. A cellulose fiber-containing structure characterized in that it is laminated with a transfer sheet printed with a printing ink containing at least one kind, and heated and pressed to transfer the vapor on the transfer sheet to the above-mentioned swelling agent-pretreated mixed structure. Transfer printing method for objects. 0.1. Disbirds Yellow 1.3.8.9.42.
60. 〃 Orange 3, 15, 〃 Red 1, 11, 17, 〃 Violet 12, 〃 Blue 359