JPH0141755B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resist dyeing agent, and an object thereof is to provide a high quality resisting agent that is oil-soluble and particularly has excellent printability.

Resistants have traditionally been used to form cut-out patterns, cut-out characters, etc. when dyeing textile products, plastic molded products, anodized aluminum molded products, etc. As a means for forming such a punched pattern, there is a method of providing a resisting layer on the surface of the chromosome to be dyed at the punched pattern portion by using a dye resisting agent and a method such as screen printing or gravure printing. This method is especially suitable for mass-producing delicate and precise punched patterns. However, most of the conventional resist dyes are water-soluble or alcohol-soluble, and are unsuitable for ink formation or printing using organic solvents. In addition, oil-soluble resist dyes also exist, but conventional ones have a mechanism that physically prevents dye from passing through, and it is difficult to say that they have sufficient resist dyeing ability.
In particular, when a thin resist dye layer is formed, its resist dye effect is not satisfactory, and it is particularly unsuitable for providing a resist dye layer for cutting patterns using high-speed continuous printing methods such as gravure printing. It was hot.

The present inventor has completed the present invention as a result of various research and considerations in view of the above-mentioned drawbacks of conventional resist dyes. That is, in the present invention, the chlorine content is
This resist dye is characterized by containing as a main component a mixture of 45% or more of a polymer and an alkoxide, acylate or chelate compound of a metal of a group or a group.

Hereinafter, the resist dyeing agent according to the present invention will be explained in more detail.

The polymer used in the present invention contains 45% or more of chlorine, and includes, for example, chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene, chlorinated vinyl chloride, and the like. The reason for limiting the chlorine content will be described later.

Group or group metals include, for example, aluminum,
These include zirconium, titanium, germanium, etc.
If necessary, an organic solvent is added to the mixture of the alkoxide, acylate or chelate compound of these metals and the polymer. The mixing ratio of the polymer and the alkoxide, acylate or chelate compound is not particularly limited, but is 5% to the solid content of the polymer.
% or more is often used, especially for reasons of economy and efficiency.
It is preferably 30 to 60%, and is adjusted as appropriate depending on the amount of dye to be resist-dyed.

When using the resisting agent having the above structure, it is necessary to apply a resisting layer to the surface of the plastic molded product, anodized aluminum molded product, etc. by direct printing such as screen printing or gravure printing, or by transfer printing means. By forming this, it is possible to provide a resist dyeing layer that can form delicate and precise punched patterns. It can also be applied to textile products by providing a resist dyeing layer on dry heat transfer printing paper. The types of dyes that can be used for resist dyeing are heat transferable dyes such as disperse dyes and oil-soluble dyes.

Although the mechanism by which the resist dye according to the present invention prevents dye staining is not clear, it can be considered, for example, as follows. That is, due to the steric hindrance of chlorine molecules in the polymer, it takes time for the dye to pass through the resisting layer, and during that time the dye is
A reaction between the acylate or chelate compound and the dye occurs, preventing staining of the chromosome, or a dehydrochlorination reaction occurs in the polymer, causing a reaction in the resist layer.
It is thought that resistance to dyeing may be achieved by lowering the pH, promoting the reaction of the group or group metal alkoxide, acylate, or chelate compound with the dye, and preventing staining of the chromosomes. It will be done. After repeated research and consideration, the present inventors discovered that in order to obtain a sufficient resisting effect with a resisting layer thin enough to be printed, the chlorine content in the polymer should be 45% or more. It is something that

Since the present invention is a resist dyeing agent having the above-mentioned structure, when it is applied, it has excellent printability, and a resist dyeing layer as thick as that formed by printing means is sufficient for resist staining. effect can be obtained. Therefore, when dyeing textile products, plastic molded products, anodized aluminum molded products, etc.
It is an industrially valuable resisting agent that can be used to form particularly delicate and precise punched patterns and characters.

Examples of the present invention will be described below.

Example 1 A floral pattern was formed on a 55 g/m ² pure white roll paper by gravure process printing using ink of the following composition.

Yellow ink (parts by weight) Yellow oil-soluble dye (Kayaset Yellow A-G (Nippon Kayaku)) 4 Ethyl cellulose 6 Polymerized rosin ester resin 10 Toluene 74.2 Ethanol 15.8 Red ink (parts by weight) Red oil-soluble dye (Kayaset Yellow A-G (Nippon Kayaku) 6 Ethyl cellulose 6 Polymerized rosin ester resin 10 Toluene 73.2 Ethanol 14.8 Blue ink (parts by weight) Blue oil-soluble dye (Kayaset Blue TD-R (Nippon Kayaku)) 7 Ethyl cellulose 6 Polymerized rosin ester resin 10 Toluene 73 Ethanol 14 Furthermore, letters were printed on the above-mentioned floral printed paper using a resisting agent of the following composition to prepare a sublimation transfer paper having a resisting layer.

Resistants (parts by weight) Chlorinated rubber 12 Tetra-1-propoxy titanium 6 Toluene 41 Methyl ethyl ketone 41 Next, the sublimation transfer paper was overlapped with a polyester fabric and heat transfer was performed at 210°C for 20 seconds. White letters were formed on the patterned printed fabric.

Example 2 A floral pattern was formed on the polypropylene surface of a polyester-polypropylene laminate film by gravure process printing using ink having the following composition.

Yellow ink (parts by weight) Yellow disperse dye (Hostatherm Yellow H3GL-R
(FH)) 5 Ethyl cellulose 10 Isopropyl alcohol 85 Pink ink (parts by weight) Pink disperse dye (Seriton Pink SF7864
(BASF)) 6 Ethyl cellulose 10 Isopropyl alcohol 84 Blue ink (parts by weight) Blue disperse dye (Despasol Blue GTP (ICI))
7 Ethyl cellulose 10 Isopropyl alcohol 83 Next, an adhesive layer was printed using an adhesive having the composition shown below, and characters were further printed on the floral pattern using a resist dye having the composition shown below.

Adhesive (parts by weight) Acrylic resin 30 Toluene 35 Methyl ethyl ketone 35 Resistant (parts by weight) Chlorinated hydrocarbon resin 30 Di-1-propoxy bis(acetylacetonite) zirconium 10 Toluene 30 Methyl ethyl ketone 30 Prepared in this way Transfer was performed on an anodized aluminum plate using a transfer sheet at a transfer temperature of 220°C and a transfer speed of 10 cm/sec. Next, the aluminum plate was heated and dyed in a dry oven at 190°C for 10 minutes, and then sealed in boiling water for 15 minutes.
When the remaining surface layer was washed with Triclean, silver letters were formed in the beautiful floral pattern.

Example 3 Characters were screen printed on a stainless steel bar coated with epoxy resin using a resist dye prepared in the following formulation. Thereafter, the stainless steel rod was spray coated with a dye solution having the following composition.

Resistant (parts by weight) Aluminum tris acetylacetonate
12 High molecular weight chlorinated rubber 10 Low molecular weight chlorinated rubber 30 Chlorinated hydrogen solvent 48 Dye solution (parts by weight) Blue oil-soluble dye (Kayaset Blue TD-R (Nippon Kayaku)) 5 Hydroxypropyl cellulose 5 Isopropyl alcohol 90 After drying The stainless steel rod was dyed in a dry oven at 170°C for 30 minutes. Thereafter, when the stainless steel rod was washed with trichlene to remove the resist dye layer and the spray dye layer, letters with silvery luster appeared on the stainless steel rod.

Claims (1)

[Claims] 1. A resist dye for disperse dyes and oil-soluble dyes, characterized in that the main component is a mixture of a polymer having a chlorine content of 45% or more and an alkoxide, acylate, or chelate compound of a group metal or group metal.