JPH0154105B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing and painting a heat-resistant resin surface, and more specifically, after a pattern layer is once transferred from a transfer material to a transfer pad, a heat-resistant resin is further transferred from a transfer pad to a transfer pad. The present invention relates to a method for easily dyeing and painting a multicolor pattern on a heat-resistant resin surface, particularly on a heat-resistant resin surface exhibiting a three-dimensional curved surface, by transferring the pattern onto the surface and then subjecting it to a heat dyeing treatment.

Conventionally, in order to dye and paint a desired pattern on the surface of a heat-resistant resin, methods for forming a pattern layer containing a dye on the resin surface include direct printing methods such as screen printing, and indirect printing methods such as roll transfer printing. , a tacho printing method in which ink is once printed on the surface of an elastic body from an intaglio printing plate and then transferred to a printing medium, and a slide transfer method using a slide transfer material. However, all of the above methods have the following drawbacks. That is, the method cannot print on objects exhibiting a three-dimensional curved surface, and furthermore, when printing in multiple colors, registration is required for each color, making the process extremely complicated. This method also cannot print on objects exhibiting three-dimensional curved surfaces.
With this method, registration is difficult when printing in multiple colors. Another method is to swell the transfer material with water, slide the pattern layer, and form the pattern layer by hand-applying, etc., but since most of the steps are manual, it is unsuitable for mass production. It is something.

In view of the various drawbacks mentioned above, the present inventors conducted various research experiments in an effort to find a method for dyeing and painting multicolored patterns on heat-resistant resin surfaces, especially heat-resistant resin surfaces exhibiting three-dimensional curved surfaces, in an easy process. As a result, the present invention has been completed. That is, the present invention involves forming a wax layer 2 on a base sheet 1, heating a transfer material 4 on which a pattern layer 3 is formed with ink containing a heat-transferable dye, and removing the pattern layer of the transfer material 4. 3 and the transfer pad 5, at least the pattern layer 3 is transferred to the surface of the transfer pad 5, and then, by pressing the transfer pad 5 and the surface of the heat-resistant resin 6, at least the pattern layer 3 is transferred to the surface of the transfer pad 5.
is transferred to the surface of the heat-resistant resin 6, and then the heat-transferable dye in the pattern layer 3 is transferred into the heat-resistant resin 6 by dry heating or wet heating. This is a method for dyeing and painting the surface of a heat-resistant resin 6, which is characterized by removing residues on the surface of the heat-resistant resin 6.

The present invention will be explained in more detail below.

Heat-resistant resin surfaces to which the dyeing and painting method according to the present invention can be applied include surfaces of molded objects molded using heat-resistant resin, as well as surfaces of various molded objects such as metal surfaces coated with heat-resistant resin. There is.
In addition, such heat-resistant resins include thermosetting resins such as acrylic resins, epoxy resins, urethane resins, polyester resins, alkyd resins, urea resins, phenolic resins, melamine resins, etc. alone, copolymers, or mixtures, or room temperature resins. hardening resin,
Alternatively, there are heat-resistant thermoplastic resins such as polybutylene terephthalate resin, polyethylene terephthalate resin, and polycarbonate resin.

Next, the transfer material used in the present invention will be explained using the drawings.

The transfer material used in the present invention basically includes a base sheet 1, a wax layer 2, and a pattern layer 3.
(See Figure 1).

The base sheet may be one that can be used as a normal transfer material as long as it does not deform at the temperature at which the wax in the wax layer softens, such as paper such as high-quality paper, coated paper, or kraft paper. ,
As for films, polyester films and the like can be used.

The wax layer 2 is formed by printing and applying wax onto the base sheet 1. The waxes used include, for example, modified montan wax and paraffin wax.

Further, after forming the wax layer, an adhesive layer 7 may be formed if necessary (see FIG. 2).
When forming the adhesive layer, it is preferable to use an adhesive that does not have tackiness at room temperature, but becomes tacky when heated, maintains that tackiness for a certain period of time, and then hardens to achieve complete adhesiveness. It is.
Examples of such adhesives include copolymers of styrene resin and vinyltoluene, butadiene, isoprene, etc., ethylene-vinyl acetate copolymers, rosin and its derivatives, tackifiers such as terpene resins, and dicyclohexyl phthalate. , diphenyl phthalate or the like can be used.

The wax layer may be made of a thermoplastic material that does not have tackiness at room temperature but becomes tacky when heated and maintains its tackiness for a certain period of time. Thermoplastic substances with such properties include synthetic alloy waxes, oxidation-modified waxes, paraffin waxes, animal and vegetable waxes, mineral oils,
Mainly waxy mixtures of animal and vegetable oils, thermoplastic hydrocarbon resins, ethylene copolymers, etc., or thermoplastic latexes, styrene-butadiene latexes,
Nitrile butadiene rubber latex, alkyd emulsion, acrylic ester copolymer emulsion, ethylene vinyl acetate copolymer emulsion, acrylic emulsion, vinyl chloride copolymer emulsion, copolymer emulsion of other thermoplastic resins, hydrocarbon resins and There are mixtures with rosin emulsion, etc. Furthermore, two types of mixtures having different softening points and melting points may be prepared by appropriately selecting from the group of thermoplastic substances mentioned above, and each mixture may be printed and coated to form a two-layer structure. In this case, the steps of peeling off and adhering the wax layer at the time of transfer, which will be described later, are carried out relatively smoothly. Further, it is preferable that the wax layer and the adhesive layer described above are appropriately selected and used so as to have a high permeability to heat-transferable dyes during heat dyeing, so that a large dyeing effect can be obtained.

The pattern layer 3 is formed on the wax layer 2 provided with an adhesive layer 7 if necessary. This pattern layer is formed by printing means such as gravure printing, offset printing, screen printing, or a combination thereof using ink made of a heat-transferable dye, binder, etc. that can dye the surface of the heat-resistant resin. The heat-transferable dyes include disperse dyes, oil-soluble dyes, basic dyes, acid dyes, and other heat-transferable dyes that can be dyed by dry heat or moist heat.For example, disperse dyes include Disperse Yellow 1 and 3. ,8,9,13,16,
23 Disperse Orange 3,7,15,25 Disperse Red 1,4,9,11,13,15 Disperse Violet 1,4,12,18 Disperse Blue 1,3,5,14,19,58 Solvent for oil-soluble dyes Yellow 18, 30 Solvent Orange 7 Solvent Red 23, 24, 25 Solvent Violet 13 Solvent Blue 18 Basic dyes include CIBasic Yellow 1, 2, 11, 13 CIBasic Orange 2, 21 CIBasic Red 1, 2, 9, 12, 23, 25, 35,
49 CIBasic Violet 1, 3, 4, 9, 10, 14,
15, 16 CIBasic Blue 1, 5, 6, 7, 8, 9, 26,
69, 77 CIBasic Green 1, 4, etc.

Further, it is preferable to use a thermoplastic resin having elastomeric properties as the binder.

In addition, for this pattern layer, if the wax constituting the wax layer has poor adhesiveness and no adhesive is provided on the wax layer, a binder must be used that exhibits adhesiveness at a temperature at which the wax layer softens. . For example, 50℃~
There are polyamide-based, neoprene-based, and copolymerized nylons that exhibit adhesive properties at 100°C.

Further, a resin layer 8 is provided above and/or below the pattern layer 3 as required (see FIG. 3). This resin layer is used to prevent the pattern layer from collapsing when pressed by the transfer pad, and is particularly effective for delicate patterns. Therefore, it is preferable to use a resin having elastomeric properties and excellent film-forming properties for this resin layer. Such resins include thermoplastic resins such as acrylic and urethane.

Next, the transfer step in the present invention will be explained.

First, the transfer material is heated. Heating is carried out at a temperature at which the wax layer softens and becomes sticky, or at a temperature at which the adhesive layer or pattern layer exhibits adhesive properties. The heating temperature at this time is preferably as low as possible in order to prevent the transfer pad from being contaminated by the heat-transferable dye. If the wax or adhesive described above is used, it is preferable to heat it at a temperature in the range of 50°C to 200°C. Although the heating means may be selected as appropriate, it is preferable to use the heating plate 9 because it allows the process to immediately proceed to the step of pressing the next transfer pad (see FIG. 4).

After heating the transfer material, the transfer pad 5 and the pattern layer 3 of the transfer material 4 are brought into pressure contact. Due to this pressure contact, the pattern layer etc. is transferred to the surface of the transfer pad (fifth
(see figure). Note that silicone rubber or the like is used as the material for the transfer pad.

Thereafter, the transfer pad 5 and the surface of the heat-resistant resin 6 are brought into pressure contact (see FIG. 6). By this pressure contact, the pattern layer 3 and the like are transferred to the surface of the heat-resistant resin 6 (see FIG. 7). At this time, if necessary, the surface of the heat-resistant resin is preheated.

Thereafter, the heat-resistant resin is subjected to dry heating or wet heating (steaming, heating in boiling water), and the heat-transferable dye contained in the pattern layer 3 is diffused into the heat-resistant resin through the wax layer 2 and the like. The surface of the heat-resistant resin 6 is dyed at a position corresponding to the pattern of the pattern layer 3 (see FIG. 8). The heating dyeing conditions are 130°C to 250°C for dry heating;
10 seconds to 60 minutes, 100℃ to 200℃ for wet heating, 5
minutes to 120 minutes is suitable.

After dyeing, unnecessary residues such as the wax layer, pattern layer, adhesive layer, resin layer, etc. on the surface of the heat-resistant resin are dissolved and removed by cleaning with Trichloride or other solvents, washing with warm water, etc., and the desired residues formed on the transfer material are removed. A heat-resistant resin surface having a dyed pattern corresponding to the pattern is obtained (see FIG. 9).

In addition, the heat-resistant resin object painted according to the present invention is
If surface resistance is particularly required depending on the manner of use, it is preferable to overcoat using a heat-resistant resin, preferably the same type of heat-resistant resin as the material to be transferred (see FIG. 10).

Since the present invention is a method of painting on a heat-resistant resin surface as described above, it is suitable for easily painting a large quantity of multicolored designs even on a heat-resistant resin surface exhibiting a three-dimensional curved surface. . Therefore, it is expected to be widely applied in various fields, and is a dyeing and painting method with extremely high industrial value.

Examples of the present invention will be described below. All parts represent parts by weight.

Example 1 A 128 g/m ² coated paper was used as a base sheet, and a wax layer consisting of a thermoplastic waxy material layer and a thermoplastic material layer having the following composition was formed thereon.

Thermoplastic waxy layer Hydrocarbon resin 38 parts Synthetic alloy Hoechst wax Caw-20 (manufactured by Hoechst) 8 parts Oxidized modified Hoechst wax KPE (manufactured by Hoechst) 12 parts Oxidized modified Hoechst wax R-21 (manufactured by Hoechst) 4 Parts Ethylene copolymer wax 8 parts Beeswax 4 parts Paraffin wax 16 parts White oil 10 parts Thermoplastic material layer Hydrocarbon resin 16 parts Oxidation modified wax KPE (manufactured by Hoechst) 16 parts Ethylene copolymer wax 12 parts Castor wax 8 parts Beeswax 8 parts Parafine wax 24 parts White oil 16 parts A pattern layer was formed on the formed wax layer by gravure printing using an ink having the composition below to obtain a transfer material.

[Seriton Pink SF-7864 (manufactured by BASF) 15 parts Gosenil T-50 (manufactured by Nippon Gosei) 100 parts Toluene 130 parts] [Seriton Yellow SF-7861 (manufactured by BASF)
15 parts Gosenil T-50 100 parts Toluene 130 parts] [Dulanol Blue G (manufactured by ICI) 15 parts Gosenil T-50 100 parts Toluene 130 parts] The obtained transfer material was heated to 120°C on a heating plate. ,
At the same time, a silicone rubber transfer pad was used to transfer part of the pattern layer and wax layer onto the thermosetting acrylic resin-coated surface of an aluminum die-cast tableware plate, and then heated at 170°C for 20 minutes to remove the parts in the pattern layer. The heat-transferable dye was diffused into the thermosetting acrylic resin to dye the surface of the aluminum die-cast tableware. Thereafter, unnecessary residues on the surface of the aluminum die-cast tableware were dissolved and removed using trichlene, and a beautiful multicolored pattern was applied to the surface of the tableware.

Example 2 A 128 g/m ² coated paper was used as a base sheet, and a wax layer having the following composition was uniformly coated thereon.

Hoechst OP (manufactured by Hoechst) 80 parts Bareco Ultraflex Amber (manufactured by Bareco) 20 parts A pattern layer was formed on the formed wax layer by screen printing using an ink having the composition shown below.

[Serethread RB (manufactured by Bayer) 10 parts Gosenil T-50 90 parts Toluene 90 parts] [Fat Yellow 3G (manufactured by Hoechst) 10 parts Gosenil T-50 90 parts Toluene 90 parts] [Oil Blue 2N (manufactured by Bayer) ) 10 parts Gosenil T-50 90 parts Toluene 90 parts] A resin layer was formed on the formed pattern layer using Dianal LR-708 (manufactured by Mitsubishi Rayon Co., Ltd.) to obtain a transfer material.

The obtained transfer material was heated to 120℃ on a heating plate,
At the same time, use a transfer pad to transfer the resin layer, pattern layer, and part of the wax layer onto the thermosetting acrylic resin molded product, and then heat at 180°C for 20 minutes to transfer the heat-transferable dye in the pattern layer. The molded product was dyed by diffusion transfer to a thermoset acrylic resin molded product. Thereafter, unnecessary residues on the surface of the molded product were dissolved and removed using trichlene, and a thermoset acrylic resin molded product with a beautiful multicolored pattern on the surface was obtained.

[Brief explanation of drawings]

FIG. 1 is an enlarged sectional view of a transfer material used in the present invention, and FIGS. 2 and 3 are enlarged sectional views of other embodiments of the transfer material used in the present invention. FIG. 4 to FIG. 9 are schematic cross-sectional views showing the dyeing and painting process of the present invention. FIG. 10 is a schematic cross-sectional view showing a state in which the painted heat-resistant base material obtained according to the present invention is overcoated. In the figure, 1...base sheet, 2...wax layer,
3... Design layer, 4... Transfer material, 5... Transfer pad, 6... Heat resistant resin, 7... Adhesive layer, 8...
Resin layer, 9... heating plate, 10... overcoat layer.

Claims (1)

[Claims] 1. A wax layer 2 is formed on the base sheet 1,
At least the pattern layer 3 is heated by heating the transfer material 4 on which the pattern layer 3 is formed with ink containing a heat-transferable dye and bringing the pattern layer 3 of the transfer material 4 into pressure contact with the transfer pad 5. The pattern layer 3 is transferred to the surface of the transfer pad 5, and then at least the pattern layer 3 is transferred to the surface of the heat resistant resin 6 by pressing the transfer pad 5 and the surface of the heat resistant resin 6, and then dry heating or wet heating is performed. The heat-transferable dye in the pattern layer 3 is transferred into the heat-resistant resin 6, and after dyeing the surface of the resin 6, the heat-transferable dye in the pattern layer 3 is transferred into the heat-resistant resin 6.
A method for dyeing and painting a heat-resistant resin surface, characterized by removing residues on the surface. 2. A method for dyeing and decorating a heat-resistant resin surface according to claim 1, characterized in that a transfer material having an adhesive layer provided between the wax layer and the pattern layer is used. 3. The wax layer according to claim 1, wherein the wax layer is made of a thermoplastic material that does not have tackiness at room temperature but becomes tacky when heated and maintains its tackiness for a certain period of time. A method for dyeing and painting heat-resistant resin surfaces. 4. A method for dyeing and painting a heat-resistant resin surface according to claim 1, wherein the pattern layer is made of heat-sensitive adhesive ink. 5. A method for dyeing and decorating a heat-resistant resin surface according to claim 1, characterized in that a transfer material having a resin layer provided above and/or below the pattern layer is used. 6. A method for dyeing and painting a heat-resistant resin surface according to claim 1, which comprises performing an overcoat using a heat-resistant resin after removing residues on the heat-resistant resin surface.