JPS6338223B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a painted heat-resistant base material, and its purpose is to provide a method for manufacturing a painted heat-resistant base material that can efficiently utilize dyes without requiring special effort. . Conventionally, a method of applying colloidal alumina, colloidal silica, etc. to the surface of a heat-resistant base material and baking it to form a protective film is well known. Since the formed alumina layer and silica layer are active layers, various methods have been considered for coloring these layers using dyes. One of them is, for example, the invention disclosed in Japanese Unexamined Patent Application Publication No. 107493/1985 filed by the present applicant, which is a heat-sensitive pressure-sensitive adhesive with a pattern layer formed using an ink containing a heat-transferable dye. There is a method in which the pattern layer is once transferred onto the active alumina layer using a transfer material, and then heated to dye the heat-transferable dye into the alumina layer. However, with this method, there is a risk that the heat-transferable dye in the pattern layer will diffuse not only into the alumina layer but also into the outside air on the opposite side during heating, and therefore the dye cannot be used efficiently. . In order to improve this point, the applicant further invented and applied for a method of coloring an activated alumina layer or activated silica layer with an ink containing a dye, and then forming a resin layer thereon and heating the layer. (Gan Sho 55-32250). According to this method, the above-mentioned drawbacks are improved and the dye can be used efficiently, but a new problem arises in that it is time-consuming because the step of forming a resin layer after coloring the activated alumina layer or activated silica layer is increased. Ta. In view of the various shortcomings of the conventional methods as described above, the present inventors conducted various studies and studies to improve these problems, and as a result, the present invention was completed.
That is, in the present invention, at least one of colloidal alumina or colloidal silica is coated on the surface of a heat-resistant base material, fired to form an active film layer, and a heat-transferable dye is dyed with the heat-transferable dye. A pattern is formed on the surface of the active film layer using an ink consisting of a water-soluble resin binder and a water-soluble resin binder by a spray method, a dipping method, a transfer printing method, a direct printing method, a hand drawing method, etc., and then heating the pattern. The method for producing a painted heat-resistant substrate is characterized in that after the dye is transferred into the active film layer, the resin binder is removed by washing with water, and then a pore-sealing treatment is performed. The present invention will be explained in more detail below. The heat-resistant substrates targeted in the present invention include glass, ceramics, metals, and the like. At least one of colloidal alumina and colloidal silica is applied to a base material by a spray method, a dipping method, etc., and then fired. Firing is performed at 350°C to 850°C for 10 to 180 minutes. By this firing, a transparent active film layer with excellent dyeing ability is formed on the surface of the substrate. A pattern is applied to the surface of the formed active film layer. In this case, an ink consisting of a heat-transferable dye and a water-soluble resin binder that is not dyed by the heat-transferable dye is used. As heat transferable dyes, disperse dyes, oil-soluble dyes, mordant dyes, acid dyes, dyes for aluminum, etc. can be used. For example, CI as a disperse dye
Despers Yellow 3, 8, 16, 51, 54, 60,
64, 119 CI Despers Orange 1, 3, 7, 25
CI Despers Thread 1, 4, 11, 13, 15, 60,
65, 73, 78, 191 CI Desperse Violet 1, 4, 17, 23, 26, 28 CI Desperse Blue 1, 3, 14, 19, 26, 35, 54, 55, 56, 72, 81,
There are 134, 180, etc. Oil-soluble dyes include CI Solvent Yellow 14, 16, 77, 98, 116 CI Solvent Red 1, 3, 23, 24, 25, 27, 146, 147
CI Solvent Violet 13 CI Solvent Blue 11, 35, 83, etc. CI as a mordant dye
Mordant Yellow 1, 5, 38 CI Mordant Red 3, 11 CI Mordant Blue 1, etc.
As acidic dyes, CI Acid Yellow 17, 23,
There are 25 CI Assisted Red 14, 37 CI Assisted Blue 25, 43, etc. Dyes for aluminum include Aluminum Red GLW (S) Aluminum Blue LLW (S) Aluminum Blue BW (S)
etc. Examples of water-soluble resin binders that are not dyed by heat-transferable dyes include hydroxypropyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, modified vinyl acetate derivatives, polyvinyl methyl ether, and polyvinyl pyrrolidone-vinyl acetate copolymers. , acrylic copolymer, etc. Examples of means for forming a pattern include a spray method, a dipping method, a transfer printing method, a direct printing method, and a hand-drawing method. When a printing means is used, it is preferable to use an alcohol-soluble resin as the resin binder, since this improves the printability of the ink.
Also, in the case of a spray method or a dipping method, the ink dries quickly, so it is desirable that the ink is soluble in an organic solvent. After forming a pattern on the surface of the active film layer, it is heated. This heating is performed in order to cause the heat-transferable dye to migrate into the active film layer. 1 at 100℃~250℃
The active film layer is dyed by heating for 60 minutes to 60 minutes.
Since the resin binder in the ink is not dyed by the heat-transferable dye, almost all of the dye in the ink is transferred into the active film layer due to the dye adsorption property of the active film layer.
After dyeing, the resin binder remaining on the active film layer is removed by washing with water. The reason why the water washing method is applied is that washing with a solvent may cause the dye in the active membrane layer to be eluted. For this purpose, a water-soluble resin binder is used and the resin binder is washed with water. After removing the resin binder by washing with water, sealing treatment is performed. Pore sealing treatments include thermosetting acrylic, melamine, epoxy, and other resins, sodium silicate,
An inorganic material such as lithium silicate or a chemical such as phosphotungstic acid, phosphomolybdic acid, or tannic acid is applied onto the active film layer and heated as appropriate. Since the present invention is a method for manufacturing a painted heat-resistant substrate as described above, dyes can be used efficiently without requiring any special effort. Therefore, it is easy to dye a predetermined dye into the active film layer especially for patterns, colored parts, etc. with high color density. Glass, ceramics obtained by applying the present invention,
Painted heat-resistant substrates such as metal are used for cosmetic containers, vases,
It is suitable for various uses such as painted enamel containers and tiles. Examples of the present invention will be described below. Example 1 Colloidal silica (Snowtex-0 manufactured by Nissan Chemical Industries, Ltd.) was spray coated on the surface of a transparent glass bottle, and after drying, it was baked at 550°C for 40 minutes to form an active film layer of activated silica with a thickness of 3.0 μm on the glass bottle surface. Established. Thereafter, the surface of the active film layer was colored with ink of the following composition by a spray method. Metrose 60SH (Shin-etsu Daigaku) 5 parts Hostasam Blue HBL (FH) 2 parts Hostasam Yellow H/3GL (FH) 1 part methanol 82 parts water 10 parts After coloring, heat at 200℃ for 10 minutes, and cool down. The glass bottle was washed with water to remove the resin binder in the ink. Next, spray coat the pore sealant with the following composition, dry at 100℃ for 10 minutes, and then dry at 200℃ for 30 minutes.
After heating for 1 minute, a highly concentrated blue-green glass bottle with a surface hardness of 4 on the Mohs scale was obtained. Sodium silicate No. 3 (Asahi Denka Kogyo) 20 parts Silane coupling agent SZ6072 (Toray Silicone)
0.068 parts water 80 parts Example 2 Colloidal alumina (Alumina Sol 200 manufactured by Nissan Chemical) was coated on the surface of the enamel plate by dipping, and fired at 450°C for 50 minutes to coat the surface of the enamel plate with activated alumina with a thickness of 2.8 μm. An active film layer was provided. Thereafter, characters were printed on the enamel plate using the screen printing method using ink of the following composition. Britetsu Gum White (Nippon Star Chemical) 50 parts Aluminum Blue LLW (S) 5 parts Thioethylene glycol 2 parts Ammonium tartrate 3 parts Water 40 parts Next, the enamel board was subjected to a moist heat treatment at 102°C for 30 minutes, and then washed with water. , the resin binder of the ink was removed by washing with water. After that, spray coat the pore sealant with the following composition, dry at 100℃ for 5 minutes, and then dry at 180℃.
The sealing process was completed by heating for 30 minutes. As a result, a highly concentrated blue enamel plate was obtained. EpoMitsuku R-304 (Mitsui Petrochemicals) 5 parts EpoMitsuku T-440 (Mitsui Petrochemicals) 2.8 parts DCZ-6040 Silane (Toray Silicone) 0.1 parts Diacetone alcohol 44 parts Xylene 30 parts Cellsolve Acetate 18.1 parts Example 3 Transparent glass bottle An active film layer was formed in the same manner as in Example 1. Next, a pattern layer is printed on the polypropylene of the polyester/polypropylene laminate film using inks having the following compositions (a), (b), and (c), and on top of that, a water-soluble and methanol-soluble ink shown in the following composition (d) is printed. Using a transfer sheet with an adhesive layer formed using an adhesive, heat and pressure transfer was performed on the active film layer surface of the transparent glass bottle using a roller transfer machine at 200°C and 10cm/sec, and then the transparent glass bottle was heated at 200°C. , heated for 10 minutes. (B) Nisso HPC-SL (Nippon Soda) 8 parts Kayasetoflavin FG (Nippon Kayaku) 4 parts Isopropyl alcohol 88 parts (B) Nisso HPC-SL (Nippon Soda) 8 parts Siketone Polyester Red FB 6 Part Isopropyl alcohol 86 parts (c) Nisso HPC-SL (Nippon Soda) 8 parts Kayaset Blue A-2R (Nippon Kayaku) 6 parts Isopropyl alcohol 86 parts (d) Coponyl PK-40 (Nippon Gosei) 20 parts Rubiskol DA28E 20 parts Methanol 60 parts After that, the resin binder and adhesive in the ink were washed away with warm water at 40°C, and after drying, a pore sealant of the following composition was spray coated and heated at 180°C for 30 minutes. A transparent glass bottle with a beautiful pattern of density was obtained. Cymel #300 (Mitsui Toatsu) 15 parts Almatex (Mitsui Toatsu) 15 parts DC-6020 (Toray Silicone) 0.05 part DC-6040 (Toray Silicone) 0.05 part Water 69.9 parts Example 4 Example 2 on the surface of a transparent glass plate An active film layer was formed in the same manner as described above. Next, a transfer sheet was prepared on polypropylene-polyester laminated paper using an ink composition and an adhesive layer composition having the following compositions. The design was printed using gravure printing to obtain uniform color density. Ink composition Hydroxypropyl cellulose 8 parts Kayaset Blue A-2R 5 parts Isopropyl alcohol 87 parts Adhesive layer composition Coponil PK-40 (40% methanol solution)
(Nippon Gohsei) 15 parts Rubiscol VA28E (40% ethanol solution)
(Yuka Verteishu) 15 parts Methanol 70 parts Next, cut the transfer sheet into a size of 25 cm ² .
After extraction in 100 ml of cold methyl ethyl ketone for 2 hours, the mixture was transferred to a 250 ml volumetric flask, and further cold methyl ethyl ketone was added to bring the total volume to 250 ml. The transmittance of this solution at its maximum absorption wavelength (584 nm) was measured using a spectrophotometer, and the results were as shown in Table 1. Next, transfer printing was performed on the active film layer surface of the transparent glass plate in the same manner as in Example 3 using the above transfer sheet. Thereafter, the glass plate was heated to dye the active film layer, and then washed with 500 ml of warm water. Next, the glass plate was sealed in the same manner as in Example 3, and then the light transmittance of the blue-colored glass plate was measured using a transmission measuring device. The results are shown in Table 1. Next, as a comparative example, a transfer sheet prepared using an ink composition and an adhesive layer composition having the following composition was used on a transparent glass plate on which an active film layer was formed in the same manner as in Example 4. Transfer printing was applied. Ink composition Cellulose acetate butyrate 8 parts Kayaset Blue A-2R 5 parts Toluene 43.5 parts Methyl ethyl ketone 43.5 parts Adhesive layer composition Almatex 894 (50% toluene solution) 24 parts Methyl ethyl ketone 76 parts The design on the transfer sheet is The transfer sheet, which has the same uniform density as the transfer sheet used in Example 4, was cut into 25 cm ² pieces in the same manner as above, extracted in 100 ml of cold methyl ethyl ketone, and measured using a spectrophotometer under the same conditions. When the transmittance was measured, the results were as shown in Table 1. heating the transparent glass plate with transfer printing;
After the active membrane layer was dyed, it was washed with 500 ml of trichlene solution. Next, after performing the same pore sealing treatment as described above, the light transmittance of the blue-colored transparent glass plate was measured, and the results were as shown in Table 1.

[Table] As is clear from Table 1, it was recognized that Example 4 had a higher dyeing efficiency than Comparative Example.

Claims (1)

[Claims] 1 Coat at least one of colloidal alumina or colloidal silica on the surface of a heat-resistant base material and bake it to form an active film layer, and add a heat-transferable dye and a water-soluble material that is not dyed by the heat-transferable dye. A spray method using an ink consisting of a resin binder,
Forming a pattern on the surface of the active film layer by a method such as a dipping method, a transfer printing method, a direct printing method, or a hand-drawing method,
A method for manufacturing a painted heat-resistant inspection material, which comprises heating the material to transfer the dye into the active film layer, washing away the resin binder with water, and then performing a sealing treatment.