JPS595627B2 - Senriyoyouki - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to solutions of plastic soluble dyes that can be sublimed and to the production of inks or paints from these solutions, which are particularly relevant for the production of felt-tip pens, pens, fountain pens, etc., or for the production of woven or non-woven fabrics. Alternatively, it relates to the production of paints capable of transfer printing of films of synthetic materials.

It is now well known to use dispersed or plastic-soluble sublimable dyes in the dyeing and transfer printing of fibers made of synthetic materials.

Transfer printing uses a temporary support that has no affinity for dyes.
This is carried out by heating the fiber to 120 to 230° C. while keeping it in close contact with the fiber to be transferred using an appropriate method. The dye sublimes and dissolves into the synthetic material. Synthetic materials that can be dyed with dispersed dye compositions include cellulose diacetates or triacetates, polyesters, acrylic and methacrylic polymers, polyamides or mixtures of these materials with each other;
Further examples include fibers and films in which small amounts of natural materials are mixed with these materials.

Temporary supports that have no affinity for dyes are generally somewhat pure cellulose paper, cellulose film or sheets of aluminum or other metals. However, as the name suggests, disperse dyes are insoluble in water and most common solvents such as alcohol, perchlorethylene, trichlorethylene, benzene, toluene and xylene.

The inks that are commonly used are also fine particles of dyes finely dispersed in an insoluble medium. These inks cannot be used in felt tip pens or markers because they fade very quickly once the dye settles on the felt. It precipitates and clumps in fountain pens, making it difficult to use and changing the color density during use. Finally, the dye in the dispersion is present in a crystalline state as opposed to dissolved in the polymer, so that the color of the temporary support is very different from the color obtained after transfer.

As stated in the description and claims of this specification,
The term "dye" refers to dyes that are sublimable and insoluble in water and many of the common solvents used in transfer printing processes.

According to one embodiment of the invention, the solvent consists of at least one liquid organic substance having at least one keto group and/or at least one liquid derivative of ethylene glycol having at least one ether group, When both coexist, a dye solution is provided which is a liquid having different boiling points.

The invention also relates to inks and paints obtainable by the use of binders soluble in the above solutions.

The dye solutions of the invention are used for the production of felt tip markers, felt tip pens or feather pens and paints.

Preferred dyes are felt chips, impregnated sponge bodies (St
oragewads) and pens, the materials forming the markers and the bristles of brushes.

Dye solvents such as dimethylformamide, dimethyl sulfoxide, hexamethyl phosphorotriamide, tetrahydrofuran and Piczine may have too high a boiling point, require very long drying times, vacuum drying, or cause problems with pens, workers, etc. It is unsuitable because it acts on certain materials or is toxic.

Furthermore, the solvent must in no case have a significant effect on these synthetic materials which are intended to be drawn or applied directly onto fibers or films.
It has been found that materials with keto groups generally have sufficient solvent capacity for disperse dyes.

In practice, it is not necessary for the solvent to have very high solvent power. This is because the invention does not require the use of very concentrated solutions. Experiments have shown that a dye concentration of 20 to 309/l is usually sufficient. The following keto compounds are preferred in terms of solvency, price, and boiling point. Acetone Boiling Point 56.2 Methyl Ethyl Ketone 79 Methyl Isobutyl Ketone 1169C Diacetone Alcohol 162℃ Ethylene Glycol Some ethers have lower solvent power than ketones, but
It is selectively used in addition to ketones.

Ethylene glycol monomethyl ether 125 C Ethylene glycol monoethyl ether 135 C Ethylene glycol monobutyl ether 171 C Ethylene glycol monomethyl ether acetate 142 Ethylene glycol monoethyl ether acetate 155 The color of dye solutions in these solvents or solvent mixtures can be applied to synthetic materials. The color is very similar to the color after transfer.

A way to almost exactly determine the color obtained after transfer is to touch it on paper or film and store it between two glass plates to avoid evaporation of the solvent. The color at that time is
As long as the dye remains in solution, it approximates the actual color. In order to avoid premature discoloration of the deposited color, it is advantageous to use a mixture of solvents of different boiling points. It is desirable that the felt of the felt tip pen not dry too quickly without its cover.

On the other hand, the ink must contain sufficient volatile solvent to prevent run-off or water repellency and to allow vapor re-penetration even if it happens to be exposed uncovered and becomes too dry. It has been found that derivatives of ethylene glycol have better solubility for binders than the commonly used ketones.

The binder must not have the ability to retain the dispersed dye during transfer, ie it must not have any affinity for the dye. Furthermore, it is not fusible and advantageously has a sticking temperature higher than the transfer temperature to prevent thermal sticking to the temporary support during transfer.

These binders must be soluble in the solvent or mixed solvents.

I found the following binder to be satisfactory. Ethylcellulose, preferably with a high degree of substitution (at least 47%)
It is contained in an amount of 0.5 to 10%.

Preferably, the binder is dissolved in one or more ethylene glycol derivatives before addition of the other ingredients.

Acrylic copolymers such as Gelol TSR (manufactured by Soprozoa) or acrylate D. I. P (manufactured by Bayer AG) binder, particularly 1 to 10%, is preferred.

Gum latch (preferably 1-10%).

A solid polymer obtained from the condensation of ethylene oxide with an aromatic base such as Skudru S (manufactured by Lorne Poulenc).

The proportion of these binders must be sufficient to ensure a good content of dye on the temporary support and to prevent powdering.

For pens and markers it is advantageous to use binders that do not increase viscosity significantly, whereas for paints some increased viscosity is preferred. When ethylcellulose is used in paint, the proportion of ethylcellulose is preferably 2 to 10% by weight.

The desired viscosity can be obtained by varying the molecular weight of the binder.

In order to produce the desired variety of shades, it is advantageous to use and coordinate the three basic dyes yellow, red and blue, which have very similar sublimation curves.

These dyes must be suitable for use in non-aqueous media. In practice the following dyes have been found to be quite satisfactory.

Acetoquinone Yeroichi Liumière 4JL Muesterquinone Red, Dispersion Blue CIl4 Liumière 4BLL
(Flancolor) and Yellow Regiran TR-P1 Red Regiran TB-P1 Blue Regiran TR-P, and Blue Regiran TG-P. (Bayer).

By mixing solutions of yellow, red and blue dyes,
Black, orange, brown, green, khaki colors etc. can be easily obtained.

Although the formulation of these primary colors is done by the user, the mixture is preferably made by the supplier.

It has been found that felts of wool or massed polyester fibers may be used for felt tip pens and markers.

The impregnated sponge body that stores ink and controls ink flow within the pen can be made from polyester viscose or wool fibers. The body and filler of the pen or marker are made from a solvent resistant material, such as metal or polypropylene.

Next, examples will be given, but the present invention is not limited thereto.

Example 1 The following solvents were mixed:

Methyl isobutyl ketone 2 parts (by volume) Diacetone alcohol 1 Ethylene glycol monomethyl ether 2 Ethyl cellulose TlO (Hercules Inc. registered trademark) is contained in the above solvent mixture as a 5% by weight solution.

This mixture contains 209/l of Dispersed Blue CIl4 (Flancolor) and Esteroquinone Red Lumiere and Acetoquinone Erolli Lumiere 4J.
An equal amount of LZ is present.

After filtration under pressure, each of these dye solutions was injected into a felt torch tip marker.

This marker has an aluminum body with a wool fiber tip and a polyester fiber impregnated sponge body. A picture was drawn with this marker on a coated paper weighing 809/I, and the green shading obtained by the yellow and blue color scheme was easily transferred onto a polyester film using an iron heated to 210°C. .

Example 2 The method of Example 1 was carried out except that the following solvent mixture was used.

Methyl ethyl ketone - 1 part (by volume) Methyl isobutyl ketone 3 Ethylene glycol monoethyl ether acetate 1 Ethylene glycol monomethyl ether acetate 1 Acrylate DIP (manufactured by Bayer) Binder 1/4 Yellow Resiren TR-S1 as dye
Red Resilan TB-P (manufactured by Bayer) was used.

When a felt tip pen was impregnated with this ink in the same manner as in Example 1, excellent results were obtained.

Example 3 A fountain pen ink was prepared by mixing 8 parts by volume of yellow dye, 2 parts by volume of red dye, and 9 parts by volume of blue dye with the solution of Example 2.

A pen using this ink was able to transfer drawings onto polyamide 6.6 tissue. Example 4 Scroll acrylate DIP binder
The same mixture as in Example 2 was prepared, except that 2% (by weight) of Ol)S (manufactured by Lone Poulenc) was added.

Appropriate heating is required to dissolve this binder. Disperse dyes include Dispersed Blue CIl4, Esteroquinone Red Lumiere 4BL
L and acetoquinone yellow Lumier
e) 4JLZ (Flancolor) was used. After transferring the drawing drawn with a pen (Marker) made using this composition, the fabric was washed with warm soapy water to remove any traces of the Scroll S.

This binder was fusible at 50°C and stained the fabric somewhat. Example 5 A tricolor paint of yellow, red and blue is made with the following formulation.

Methyl isobutyl ketone 1 part (volume) Ethylene glycol monoethyl alcohol 1 Diacetone alcohol 1 Dissolve 4% by weight of Hercules N22 ethyl cellulose (based on the total weight of the solvent) in this mixture, and add the following three base paints, Dispazol AGTP Yellow. (ICI) Dispazol B3 BTP Red (ICI) Dispazol B2 GTP Blue (ICI) were dissolved in 259 parts each to prepare three types of base paints.

A design representing a stained glass window from these three primary colors was applied onto coated paper weighing 1009/I.

In addition to yellow, red and blue, mixed colors of base colors and colors diluted with the above base mixture were obtained.

This painted design was successfully transferred onto a film of ethylene glycol polyterephthalate (trade name: Terphane, manufactured by Cellophane Co.).

Although the present invention has been described in detail above, specific examples of the configuration of the present invention can be summarized as follows. 1) An ink or paint comprising a solution according to the claims and a soluble binder. 2) The binder is ethyl cellulose with a degree of substitution of at least 47% and is contained in an amount of 0.5 to 10% by weight of the ink. 3) The binder is lactic gum, and the weight of the ink is 1 to 10? The ink of 1) 4) binder is polyacrylate and contains 1 to 10% by weight of the ink. 5) The ink of 1) above, wherein the binder is a solid polymer obtained by concentrating ethylene glycol with a substance containing one aromatic group 6) The binder contains at least 47% 7) Any of the above 1) to 6) containing a plurality of dyes having substantially equal sublimation curves. 8) Dye solutions of the embodiments substantially as described above; 9) Inks and paints of the embodiments substantially as described above; 10) Inks and paints according to any of the foregoing. Transfer printing method to transfer.

Claims (1)

[Claims] 1. One or more sublimable, water-insoluble dyes that can be used in transfer printing and a substance selected from the group consisting of: a) acetone, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol; b) ethylene glycol monomethyl ether; consisting essentially of one or more liquid substances selected from the group consisting of substances selected from the group consisting of ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate. A dye solution characterized by: