JPS6035470B2 - Heat transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat transfer method that allows dry transfer to acidic latent synthetic fibers.

Conventionally, various methods have been developed and proposed for coloring various fibers, one of which is the so-called sublimation transfer method.

Generally, in this sublimation transfer method, a transfer sheet is produced by forming an arbitrary pattern on an arbitrary support using a composition mainly composed of a disperse dye with high sublimability, and then the patterned surface of the transfer sheet is This is a method of sublimating the disperse dye and transferring the desired pattern to the transfer substrate by superimposing the transfer substrate on the substrate and heating the transfer substrate.The method includes an EP printing process and a steaming process. It also has the advantage of being able to color by dry heat while saving labor in the washing process and the like.

However, although it has the above-mentioned advantages, it also has various drawbacks, and various improvement methods have been proposed for this reason. For example, one of the ways to achieve this effect is to improve the disperse dye.
A method of dry transfer printing of acid-modified synthetic fibers has been proposed. However, in practice, the above method is difficult to obtain clearly colored products because indolenine-based methine-type disperse dyes not only have poor sublimation properties but also have poor dyeability on woven fabrics, etc. Indolenine-based methine type disperse dyes are not preferred because they are sensitive to changes in pH and have drawbacks such as instability of the ink. As a result of various studies in order to improve the above-mentioned drawbacks, the present inventors have developed a method in which acidic modified fibers are treated with a solution containing one of an ammonium compound, an amine compound, an acid amide compound, an inorganic acid, or an organic acid. On the other hand, a pattern layer of a composition containing an indolenine-based methine type disperse dye and an alkaline agent is formed on the base sheet to form a transfer sheet, and then the above-mentioned treatment of the acidic waste fibers is performed. When the surface and the pattern layer surface of the transfer sheet were overlapped, and then the transfer sheet was peeled off by heating and pressurizing both, the indolenine-based methine type disperse dye in the pattern layer of the transfer sheet was exposed to acidic acid. The present invention was completed by discovering that it is possible to transfer and dye fibers to obtain dry transfer colored products with clear color tone and good fastness.

The above-mentioned present invention will be explained in more detail below.

First, in the present invention, the acid-modified fibers used as the transfer substrate include, for example, acid-modified polyacrylic fibers, acid-modified modacrylic fibers, acid-modified polyester fibers, and acid-modified polyester fibers. Examples include nylon fibers, and blends, interwovens, cross-wire products, etc. with other fiber materials including these acidic synthetic fibers can be used. Therefore, in the present invention, for the above-mentioned various acidic modified fibers, ammonium compounds containing ammonium groups such as aqueous ammonia, ammonium chloride, ammonium acetate, ammonium sulfate, and ammonium nitrate, and amino groups such as methylamine and ethylamine are added. 5g containing one or more of these amine compounds, formic acid amide, saddleamide compounds containing acid amides such as urea, or inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as formic acid, acetic acid, and propionic acid. '〆～Immediate g'Solution 80 ○～5 at 98℃
It uses fibers that have been heat-treated for between 60 minutes and 60 minutes. Next, in the above-described present invention, the transfer sheet will be explained. First, the base sheet is preferably one that is not affected by various conditions such as the conditions for forming the pattern layer or the heat transfer conditions. For example, Use various papers or processed papers, cellophane, various heat-resistant resin films or sheets, various metal foils or plates, or lamination films made by laminating these in any manner according to conventional methods. can do. Next, in the above-mentioned present invention, the indolenine methine type disperse dye has the general formula {where R, R4 is a hydrogen atom,
A halogen atom, a lower alkyl group having 1 to 3 carbon atoms, or
Represents a lower alkoxy group having 1 to 3 carbon atoms, R2, R3
each independently represents a lower alkyl group having 1 to 4 carbon atoms (including a substituted alkyl group substituted with a non-dissociable substituent), a phenyl group, or an alkyl group.

} can be used. Specifically, for example, it can be easily obtained by heating a 2,3,3-trimethylindolenine derivative and a 4-formylaniline derivative in an acidic medium (eg, acetic acid or 20% sulfuric acid).

Suitable 2,3,3-trimethylindolenine derivatives include, for example, 2,3,3-trimethyl-5-methylindolenine, 2,3,3-trimethyl-5-propylindolenine, 2,3,3-trimethyl-5-ethyl Indolenine, 2,3,3-trimethyl-5-methoxyindolenine "2,3,3-trimethyl-5-ethoxyindolenine, 2,3,3-trimethyl-5-propoxyindolenine, 2,3,3-trimethyl-5-chlorindolenine" Examples include renin, 2,3,3-trimethyl-5-promoindolenine, and 2,3,3-trimethylindolenine.

Suitable 4-formylaniline derivatives include, for example, 4-formyl-N,N-dimethylaniline, 4-formyl-N,N-diethylaniline, and 4-formyl-N-dimethylaniline.
-Methyl-N-(8-cyanoethyl)aniline, 4-formyl-N-methyl-N-(B-k.

ethyl)aniline, 4-formyl-N-methyl-N-(8-methoxyethyl)aniline, 4-formyl-N-
(8-ethoxyethyl)aniline, 4-formyl-N-ethyl-N-(8-cyanoethyl)aniline, 4-formyl-N-ethyl-N-(3-chloroethyl)aniline, 4-formyl-N-ethyl-N-(8-methoxyethyl)aniline , 4-formyl-N-ethyl-N-(6-
ethoxyethyl)aniline, 4-formyl-N-methyl-N-penzylaniline, 4-formyl-N-ethyl-N-penzylaniline, 4-formyl-N-(6-cyanoethyl)-N-benzylaniline, 4-formyl-N
-(8-Chlorethyl)-N-penzylaniline, 4-formyl-N-(8-methoxyethyl)-N-penzylaniline, 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-(3-cyanoethyl)-m-toluidine,
4-formyl-N-methyl-N-(3-methoxyethyl)-1m-toluidine, 4-formyl-N-ethyl-N-
(8-chloroethyl)-m-toluidine, 4-formyl-N-ethyl-N-(8-ethoxyethyl) 1m-toluidine, 4-formyl-N-ethyl-N-(8-cyanoethyl)'' 1m-toluidine, 4-formyl-N -Methyl-N-benzyl-m-toluidine, 4-formyl-N
-Ethyl-N-penzyl-m-toluidine, 4-formyl-N-(8-cyanoethyl)-N-benzyl-m-toluidine, 4-formyl-N-(8-chloroethyl)-N
-Benzyl-m-toluidine, 4-formyl-N-(8
-methoxyethyl)-N-penzyl-m-toluidine,
4-formyl-N,N-diethyl-m-anisidine, 4
-formin-N,N-diethyl-m-chloraninon, 4-formyl-N-methyldiphenylamine and 4
-Formy-N-ethyldiphenylamine and the like. Next, in the present invention, the alkaline agent has the property of acting on the above-mentioned indolenine methine type disperse dye to increase the thermal transferability of the dye and the property of stabilizing it. Specifically, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, and hydroxide. Alkaline earth metal hydroxides such as barium and strontium hydroxide, lithium carbonate, sodium carbonate,
Salts of strong or weak bases and weak acids such as potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, strontium carbonate and sodium acetate; other bases such as amines such as aqueous ammonia, dimethylformamide, ethanolamine and trietanoamine; In addition, DBU (manufactured by Sun Abbott Co., Ltd.) etc. can be used.

In the present invention, the amount of the alkali agent used as described above can be 1/10 to 20 molar equivalent per 1 molar equivalent of dye, but 0.5 to 20 molar equivalent per 1 molar equivalent of dye.
Particular preference is given to using 10 molar equivalents of alkaline agent.

In the present invention, the reason why the thermal transferability of the beam material is increased by the action of an alkaline agent is not clear, but since the dye develops color in an acidic environment and disappears in an alkaline environment, the dye becomes more non-ionized in an alkaline environment. This seems to be for the purpose of

Next, in the present invention, a method for manufacturing a transfer sheet is explained. For example, an ink or coating composition containing a binder, the above-mentioned dye, and an alkaline agent as main components is applied on a base sheet, and A transfer sheet can be manufactured by forming an arbitrary monochrome or multicolor pattern layer, such as letters, symbols, and pictures, using a printing, drawing, or coating method.

In the above method for producing a transfer sheet, known binders may be used, such as methylcellulose, ethylcellulose, hydroxymethylcellulose, cellulose acetate butyrate, cellulose acetate, cellulose derivatives such as sodium alginate and its derivatives, and polyvinyl alcohol. , polyvinyl acetate, polycarbonate resin, polyester resin, polyamide resin, phenolic resin,
Aminoplast resin, acrylic acid, methacrylic acid,
Unsaturated carboxylic acids such as itaconic acid, fumaric acid, and maleic acid, or ester derivatives, nitrile derivatives, or amide derivatives of these unsaturated carboxylic acids, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, vinylpyrrolidone, vinylmethyl Homopolymers of various vinyl monomers such as ether, butadiene, ethylene, and propylene or copolymers thereof, starch powder, gum arabic, gum tragacanth, gelatin, etc. can be used.

It should be noted that the above-mentioned binder used in the present invention is not preferably one that softens or melts due to heating temperatures such as heat transfer conditions, and if the binder softens or melts, the binder itself may also be transferred during heat transfer. This is not preferable because it may transfer onto the surface of the base layer, resulting in a transferred product with inferior texture.

Next, in the present invention, a basic dye can be used in combination with the indolenine methine type disperse dye as the dye.

Specific examples of the basic dye include 3,3-diethyloxathacyanine iotardide and Astrazon Pink FG (manufactured by Bayer AG, C.1.48015).
, 2,2'-Libocyanin (C.1.808), Astraphylloxin FF (C.1.48070), Alastrazone Yellow 70LL (C.1.Basic Yellow 21), Eisen-Chiron Yellow Ship LH ( Methine (cyanine) basic dyes such as monomethine, dimethine, or trimethine, such as Hojitani Kagaku K.K., C.1.48055), Eisen Cachilon Red String Day (C.1.48020), etc. class, auramine (C.1.655
diphenylmethane basic dyes such as ), malachite green (C.1.42000), brilliant
Green (C.1.42040), Mazienta (C.1
．． 42510) Methyl Violet (C.1.425
35), Crystal Violet (C.1.4255
5), triphenylmethane-based basic dyes such as methyl green (C.1.684), Victoria Blue B (C.1.44045), and pyronine G (C.1.739).
), xanthine basic dyes such as Rhodamine B (C.1.45170) and Rhodamine 6G (C.1.45160), acrazine. Yellow G (C.1.785), Leonine AL (C.1.46075), Benzoflavin (C.
．． 1.791), Phosphine (C.1.46045)
, acridine basic dyes such as Neutral Red (C.1.50040), Astrazone-Flu-8GE
Basic dyes such as quinone imine basic dyes such as / can be used.

Therefore, in the present invention, when a basic dye is used in combination, since the indolenine methine type disperse dye alone does not provide sufficient hue expression, the present invention is intended to compensate for this.
It can produce all hues including black. In the present invention, the basic dye can be used in any proportion with the indolenine methine disperse dye.

In addition to the above-mentioned binder, dye, alkaline agent, etc., in the method for manufacturing the transfer sheet described above, if necessary, for example, when the dye is transferred onto the transfer substrate, the base material may be added. A coloring aid that penetrates into materials and has the effect of swelling between micelles and increasing the permeability of dyes, or various additives that adjust the state of compositions containing binders, dyes, alkaline agents, etc. etc. can be used arbitrarily.

Examples of the above-mentioned coloring aids include urea, naphthalene,
Various surfactants such as ammonium tartrate, glycine A, oxalates of aliphatic amines such as cyclohexylamine, ammonium acetate, benzylamine, anionic, nonionic or amphoteric surfactants, etc. can be used. In addition, the above additives include, for example, plasticizers, stabilizers, waxes/greases, desiccants/auxiliary desiccants, curing agents, emulsifiers, thickeners,
Fillers, dispersants, etc. can be used.

In addition, in the method for manufacturing the transfer sheet as described above, the composition containing the binder, dye, alkaline agent, etc. is in the form of a solution,
It may be in any form such as emulsion, suspension, or sol. Next, in the above-mentioned present invention, to explain the method of heat transfer using the above-mentioned transfer sheet, firstly, in the present invention, the above-mentioned transfer sheet and the acidic modified fiber which is the transfer target base material are The patterned layer surface and the treated surface of the latter are placed one on top of the other so that they are in contact with each other, and then both are heated and pressurized with a heated hot-pressing plate or the like, or passed between heated rollers to be heated and pressurized, and then After that, by peeling off the transfer sheet, only the dye in the pattern layer on the transfer sheet is transferred onto the acidic modified fiber, resulting in a transfer that has an extremely clear color tone and is rich in various fastness properties. In the above thermal transfer method for obtaining a product, the heating temperature varies depending on the type of dye, etc., but is preferably selected arbitrarily from a range of about 80° to 250 qo.

In addition, in the above description, the pressurization conditions are approximately 50 g/~20
K9/c bamboo is preferred.

Furthermore, the time for performing the heating and pressure treatment in the above is about 1
A range between current sand and 9 inkstone sand is preferred.

According to the present invention as described above, it is possible to satisfy a red hue using an indolenine methine type disperse dye.

In other words, with conventional basic dyes, there are no red-based dyes that have good ink storage and transfer paper storage properties, and when producing black, the dyeing speed does not match with other hues. There is a phenomenon of red floating dyeing, and this is to be improved. Furthermore, by making the ink using the indolenine methine type disperse dye alkaline with an alkaline agent, the ink storage stability and the transfer paper storage stability can be improved. Furthermore, since it is stable even when mixed with a cationic dye, it is very effective for dry transfer to acidic waste fibers. Further, in the present invention, by being able to use an indolenine-based methine type disperse dye, the range of application of the transfer substrate can be expanded to a wide range.

For example, in the conventional sublimation transfer method, only disperse dyes can be used as the coloring agent, and the substrate to be transferred is also limited to corresponding polyester fibers. According to the method of the invention, acid-modified synthetic fibers such as acid-modified polyacrylonitrile fibers can be colored by using indolenine-based methine-type disperse dyes and basic dyes in combination with them as dyes. It is possible.

Furthermore, in the method of the present invention, the thermal transferability of the indolenine-based methine-type disperse dye, which exhibits small phenomena such as melting, evaporation, or sublimation due to heat, can be significantly increased by applying an alkali agent to the dye. Moreover, once the transfer color is transferred to the transfer substrate, the color develops due to bonding or dissolution with the fibers and eliminates sublimation. It is possible to obtain a transfer product that is extremely excellent in various fastness properties such as durability.

In addition, in the ink composition for producing the transfer sheet of the present invention, the indolenine-based methine type disperse dye is very stable under alkalinity using an alkaline agent, and has a long shelf life of the ink.
The transfer sheet has excellent storage stability, and is unstable in acidic or medium-temperature ovens. In this case, the acidic substance mixed into the basic dye makes it extremely unstable, but the alkaline agent makes both extremely stable, resulting in excellent ink storage stability, transfer sheet stability, and storage stability. It is something.

The present invention will be described in more detail below with reference to Examples.

Note that the middle part of the examples is parts by weight.

Examples 1 to 16 Ethylcellose N-7 (manufactured by Hercules) 8 parts xylene 6 parts butanol
25 parts Sodium monohydroxide
Part 2 Dyes shown in Table 1
5 parts △ Total 10 sides Put the above ingredients into a stainless steel container and completely dissolve them using a fly speculator to prepare gravure ink, and use this ink to gravure print any pattern on processed paper coated with an aqueous polyvinyl alcohol solution. I made transfer paper.

This transfer paper and Cashmilon CA-5160 (manufactured by Asahi Kasei Co., Ltd.)
The transfer cloth was layered and heated with a hot iron of 20,000 yen between sands of 5 yen to obtain a transfer cloth. In addition, Mitsubishi Rayon Co., Ltd. treated Bonnel and ammonium sulfate treated Cashmilon CA-516
0 (manufactured by Asahi Kasei Co., Ltd.) was transferred using the above transfer paper under the same conditions as above, and a clearer transfer cloth was obtained. Also, its friction, wet and light fastness properties were improved. When a gravure ink with the above example and the following ingredients was prepared by the above method and compared under the same conditions as above, it was found that the use of the gravure ink with the following ingredients was inferior in terms of color development and various fastnesses (friction, wetness, light resistance, etc.). Ta. Ethyl cellulose 8
xylene 62 butanol
25 parts D Dye shown in Table 1 5 parts A Total 10 dark areas Table 1 Examples 17 to 32 Ethyl cellulose N-7 (11-manufactured by Kyures) 8 parts xylene 6 parts butanol
25 parts m Sodium hydroxide
3 parts Dyes shown in Table 1 2
Crampons Carotene Yellow 80LH Raw Powder 2 parts Total 10 legs. A gravure ink was prepared using the above ingredients under the same conditions as in the previous example, and then EO printing and transfer were performed to obtain a transfer cloth with good machine color.

Furthermore, as a result of preparing a gravure ink with a composition in which sodium hydroxide was omitted from the above composition, it was inferior in terms of color development and various fastnesses (friction, wetness, light fastness, etc.) than those containing sodium hydroxide.

Furthermore, ink compositions without sodium hydroxide were not as good as those containing sodium hydroxide in terms of ink storage stability and transfer paper storage stability. Example 33 The following ink compositions (N) to (skin) had the same results as in the above example.

Claims (1)

[Scope of Claims] 1 Acidic modified fibers are heat-treated by being treated with a solution containing one of an ammonium compound, an amine compound, an acid amide compound, an inorganic acid, or an organic acid; A transfer sheet is formed by forming a pattern layer of a composition containing a renin-based methine type disperse dye and an alkaline agent, and then the treated surface of the acid-modified fiber and the pattern layer surface of the transfer sheet are overlapped, and then A heat transfer method characterized in that both are then heated and pressed to transfer the indolenine methine type disperse dye in the pattern layer of the transfer sheet to the acidic modified fibers and dye them. 2. The heat transfer method according to claim 1, wherein the pattern layer contains a basic dye.