JPS6143474B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer sheet for resist dyeing used in dry textile printing.

Conventionally, as a transfer sheet for resist printing used in dry printing, a resin with high gas-shielding properties (for example, Japanese Patent Publication No. 10854/1983) is printed on a thermal transfer sheet that has been printed using ink containing a sublimable dye. Alternatively, there are methods in which an adsorbent (for example, JP-A-50-55412) is applied to trap the dye vapor during thermal transfer and prevent dyeing onto the cloth. The ability to physically prevent dye vapor from reaching the fabric depends on the thickness of the shielding agent coating, and it is clear that the thicker the coating, the better. Therefore, when the amount of dye is used to give a high color density on cloth that can be used practically, in order to obtain complete resistance, the dry coating of the screening agent film after printing must be 10 to 10%. It needs to be 100μ thick. Considering various printing methods, only screen printing methods are capable of such thick-embossed printing, gravure printing has a maximum thickness of a few microns, and offset printing cannot produce thick-walled printing.

In addition, as a method to improve the shortcomings of such physical methods, a method has been proposed in which, for example, a water-repellent agent is applied to the transfer base paper and then a water-based ink containing a sublimable dye is printed. (Tokukai Akira
48-4118). According to this method, water-based ink does not adhere to the water-repellent areas, so that resist dyeing is achieved. However, this method has many practical difficulties. That is, since water swells cellulose, the water in the water-based ink expands the paper during printing, impeding dimensional stability in multicolor printing and causing misregistration.
Wrinkles occur. Furthermore, since water has a high surface tension, it is difficult to wet the printing plate surface. That is, in the case of a gravure plate, the cells are not uniformly filled with ink.

In addition, water-based ink has poor wettability on the paper surface, and its printing performance is far inferior to that of oil-based ink in terms of uniform printability. This is a fatal drawback in dry printing methods intended for dyeing expensive textiles. Furthermore, the long-term storage stability of the ink is poor, and in the case of dye precipitation or insoluble dyes, a large amount of dispersant is required, resulting in changes in gelation, separation, and flow characteristics, and after the transfer sheet is stored, it may not be the same again as it was immediately after printing. It is extremely difficult to use it. Furthermore, water causes rust in ink storage cans, printing plates, printing machines, etc., and maintenance thereof is much more difficult than with oil-based inks.

As a result of various studies to improve the conventional method as described above, the present inventors have developed an ink containing an oil-based ink repellent agent (hereinafter simply referred to as oil-repellent ink).
By printing or coating a combination of 100% and an oil-based ink containing a sublimable dye, we have completed a transfer sheet for resist printing that has excellent reproducibility and expressiveness of designs such as delicate, gradation, and multicolor.

The present invention will be explained in detail below. First, the transfer sheet of the present invention will be explained with reference to the drawings. FIG. 2 is a cross-sectional view schematically showing the transfer sheet 1 of the present invention. The printing layer 3 has a printing layer 3 made of the above printing layer, and further has a printing layer 5 made of an oil-based ink containing a sublimable dye 4 on a base sheet other than the printing layer.

As shown in FIG. 1, the transfer sheet 1 is prepared by coating or printing a part of the base sheet 2 with an oil-repellent ink to form a printing layer 3 of the oil-repellent ink, and then applying a sublimation dye. When solid printing or coating is done with an oil-based ink containing It is formed. In addition, the printing layer 5
is not necessarily provided in all parts other than the printed layer 3, and may be provided in a part thereof. Further, in FIG. 2, the printed layers 3 and 5 are shown to have the same thickness for convenience, but it goes without saying that they may have different thicknesses.

In the present invention, all base sheets that can be used in normal heat transfer printing can be used, but the effect may vary depending on various conditions such as conditions for forming patterns or resin coatings, heat transfer conditions, etc. It is preferable to use materials that do not accept heat, such as various papers or processed papers, cellophane, various heat-resistant metal foils or thin plates, or lamination films made by arbitrarily laminating these materials according to conventional methods. can be used.

Furthermore, in view of the aspect of the present invention, it is desirable that the surface has a high degree of smoothness. In other words, if paper or processed paper is fluffed by pulp fibers, the smoothness of the surface of the printed part of the oil-based ink repellent material will decrease, which may cause contamination when printing or applying oil-based ink containing sublimable dyes. Easy to occur. In particular, sublimable dyes have the property of forming a strong color on a material to be transferred such as cloth, even if they are not noticeable on transfer paper, so the smoothness of the surface is important.

Next, the oil-repellent ink basically consists of 5 to 99 wt% of an oil-based ink-repellent agent and a solvent.
The above agents may act as a binder, but if necessary, synthetic resins such as phenol resin-modified alkyd resins or alkyd resins modified with natural resins, cellulose resins such as methyl cellulose, ethyl cellulose, and ethyl hydroxyethyl cellulose, acrylic resins, and polyvinyl resins may be used. A binder such as a vinyl resin such as butyral can be used in combination or added. Furthermore, stabilizers, waxes, greases, desiccants, auxiliary desiccants, hardeners, emulsifiers, thickeners, fillers, dispersants, gelling agents, PH regulators, antifoaming agents, activators, etc. may be added. . Further, when it is desired to color the resist-dyed portion, about 0.01 to 30 wt% of a sublimable dye can be added to the above ink. This sublimable dye can be selected from among the dyes contained in the oil-based ink described below.

As the oil-based ink repellent agent, silicon compounds having siloxane bonds, surfactants with fluorine introduced into their lipophilic groups, aliphatic amides, and the like can be used. For example, various types of silicone can be used as long as they are ink repellent.
Specific product names include KF96, KF69,
There are KF412, KS707, KR261, and KP354 (manufactured by Shin-Etsu Chemical). In any of these, a catalyst can be used as necessary to increase the speed of the curing reaction. Examples of fluorides include FC-95,
FC−98, FC−126, FC−128, FC−134, FC−
170, FC−176, FC−430, FC−431, FC−
706, FC-806 (manufactured by Sumitomo 3M), and oil barrier FP81, 82, and 85 (manufactured by Sumitomo Chemical Industries). Also, examples of aliphatic amides include ARMID
-HT, ARMID-O, ARMOSLIP-CP (manufactured by Lion Armor).

Examples of solvents constituting the oil-repellent ink include aromatic solvents such as toluene, xylene, and benzene; alcoholic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-butyl alcohol; and ethyl acetate, propyl acetate, and acetic acid. One type or a mixture of two or more types of esters such as n-butyl can be used.

There are no particular restrictions on the method of applying or printing the oil-repellent ink, but if the base sheet is paper with low smoothness, the coating thickness must be 1 to 50 μm, and screen printing or gravure printing may be used. Law is preferable.

Next, the oil-based ink containing the above-mentioned sublimable dye contains 0.01 to 30 wt% of the sublimable dye and 5 to 50 wt% of the binder.
%, and 20 to 99.99 wt% of solvent. If the above-mentioned sublimable dye has sublimation property,
Although any dye can be used, disperse dyes, oil-soluble dyes, and triphenylmethane basic dyes are preferred.

As the binder, one or more of cellulose resins such as methylcellulose, ethylcellulose, and ethylhydroxyethylcellulose, acrylic resins, and vinyl resins such as polyvinyl butyral can be used. Further, the above-mentioned solvents include, for example, aromatic solvents such as toluene, xylene, and benzene; alcoholic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-butyl alcohol; and ethyl acetate, propyl acetate, and n-butyl acetate. One or more types of esters can be used.

There are no particular restrictions on the method of applying or printing the oil-based ink, but in view of contamination of non-image areas, it is preferable that the ink has a high tack value and a high flow value. In this sense, offset printing is preferred. Tack value is 11 to 16
(400PRM), flow is preferably 12-15. The printing layer made of this oil-based ink has a dry coating thickness of about 1 to 50 μm.

Further, known means such as providing an overcoat layer on the entire surface of the transfer sheet according to the present invention can be added as appropriate.

As is clear from the above description, the transfer sheet of the present invention can be produced extremely easily by printing or coating a combination of oil-repellent ink and oil-based ink containing sublimation dye, and can achieve a delicate resisting effect. It is something that can be done. Transfer sheets with such excellent resist dyeing effects are polyacrylonitrile-based,
It can be used for printing various textile products such as polyester and polyamide, polyester films, and various synthetic leathers.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, in the following text, "part" means "part by weight"
shows.

Example 1 (a) Oil-repellent ink composition ARMID-O (manufactured by Lion Armor Co., Ltd., anti-blocking agent) 5 parts Butyral (manufactured by Sekisui Chemical Co., Ltd., BL-1) 15 parts Solvent (xylene: n-butanol = 2 :1)
More than 80 parts were mixed and kneaded in a ball mill for 48 hours.

(b) Oil-based ink composition Celliton Fast Yellow G (manufactured by BASF, CI
Disperse Yellow 3) 10 parts ethyl hydroxyethyl cellulose (manufactured by Hercules, EHEC-EL) 10 parts solvent (toluene: isopropyl alcohol =
1:1) More than 80 parts were mixed and kneaded in a ball mill for 48 hours.

Above, on kraft paper using oil-repellent ink,
The floral pattern was printed using a gravure plate with a cell depth of 80μ. On top of this, apply the above oil-based ink to a cell depth of 20μ.
It was printed on a solid gravure plate and made into a transfer sheet. The sheets were overlapped with the polyester taffeta so that the painted part was sandwiched between them, and the sheets were heated at 180°C and passed around a 1m diameter drum of a continuous heating transfer machine at 8m/min.
When the sheet was removed, a cloth with a white resist dyed floral pattern on a yellow background was obtained.

Example 2 (a) Oil-repellent ink composition silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.,
KS705) 80 parts Catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., PS-1) 4 parts Toluene 16 parts The above ingredients were stirred and mixed using a stirrer.

(b) Oil-based ink composition Duranol Brilliant Blue G (manufactured by I.C.I.,
C.I.Disperse Blue 14) 25 parts rosin-modified alkylphenol resin 24 parts wax compound 7 parts cobalt naphthenate 2 parts aluminum octate 2 parts spindle oil 20 parts tung oil 20 parts Knead the above using a three-roller did.

Using the oil-repellent ink described above, polka dots were printed on art paper using a silk screen printing method with a film thickness of 100 μm. If necessary, the sheet was placed in an oven at 120° C. for several minutes to complete the silicone curing reaction.

A solid pattern was printed on this using the above-mentioned oil-based ink using a lithographic printing machine in a conventional manner.

The sheet was layered with nylon twill so that the painted part was sandwiched between them, and after applying heat pressure of 200g/cm ² for 30 seconds at 200℃ using a flatbed heat press machine for thermal transfer, when the sheet was removed, a blue background was created. A cloth with white polka dots was obtained.

Example 3 In Example 2, the oil-repellent ink composition (a) was
Ceres Red BB (manufactured by Bayer, Solvent Red
25) was added and mixed and kneaded using a ball mill.
When printing and thermal transfer were performed in the same manner as in Example 2 using the oil-repellent ink that can be colored in this way, the white polka dot pattern in Example 2 was dyed red. Moreover, there was no deviation from the blue background, and the so-called colored resist dyeing had been completed. This is extremely difficult when registering two colors using a printing method.

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view for explaining one step of manufacturing the transfer sheet of the present invention, and FIG. 2 is a schematic cross-sectional view showing an example of the transfer sheet of the present invention. 1 ...Transfer sheet for resist dyeing, 2...Base sheet,
3...Printed layer with oil-repellent ink, 4...Sublimable dye, 5...Printed layer with oil-based ink.

Claims (1)

[Scope of Claims] 1. On the base sheet, there is partially a printed layer made of ink containing an oil-based ink-repellent agent, and the other part has a printed layer made of oil-based ink containing a sublimable dye. Transfer sheet for resist dyeing. 2. Claim 1, which includes a sublimable dye in the printing layer made of an ink containing an oil-based ink-repellent agent.
Transfer sheet for resist dyeing as described in section.