JP2000296359A - Thermal transferring coated metallic plate excellent in the infiltration of subliming dye and printing coated metallic plate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing coated metallic plate, which is free from the generation of pattern ununiformity even if grinding a transferred coating film and on which a high clarity printed pattern is capable of being imparted. SOLUTION: The sublimating thermal transferring coated metallic plate is constituted so that an under coating layer composed of 60-100 wt.% acrylic resin and 40-0 wt.% polyvinylidene fluoride resin and exhibiting dyeing property to a sublimating dye and a transparent or semi-transparent top coating film layer composed of 60-90 wt.% polyvinylidene fluoride resin and 40-10 wt.% acrylic resin are formed on the surface of a metallic plate. The printing coated metallic plate making the best use of the material feeling of the base and having unique deep feeing is obtained by superposing the printing surfaces of a transfer paper containing the sublimating dye and heat-treating to infiltrate the sublimating dye permeated through the top coating film layer. A triazine based ultraviolet absorbent and a benzotriazol based ultraviolet absorbent can be formulated singly or in combination in top coating film layer or the under coating film layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a panel material for an elevator, an interior material for a decoration, an outer panel of an electric appliance or a furniture, and has a sublimation property suitable for a small lot multi-type application in which various printing patterns are provided. The present invention relates to a coated metal plate for thermal transfer having excellent dye permeability and a printed coated metal plate using the same.

[0002]

2. Description of the Related Art Masking coating, silk screen printing, printed PVC film lamination, and the like are used for manufacturing a coated metal plate having a multicolor pattern excellent in design.
In particular, for applications requiring extremely high clarity, such as elevator interior wall panels and building entrance interior materials,
Multi-color pattern is applied by masking painting and silk screen printing. In a method of manufacturing a high-definition printed metal plate using masking coating or silk screen printing, a masked or pre-printed silk screen is placed on the coated metal plate, and ink is stretched over the metal plate to enhance the design. Give. Next, in order to protect the design surface, a clear coating made of urethane, acrylic, or the like is applied, and the clear coated surface is roughly polished and finally buffed. As a result, the painted surface is smoothed, and an appearance with high sharpness is obtained.

[0003] It is also known to produce printed coating metal plates with high image clarity using sublimable dyes. In this case, transfer paper printed by offset, silk, gravure, or the like using a sublimable dye is superimposed on the metal coating surface, and subjected to a heat-compression treatment to allow the sublimable dye to penetrate into the top coating film.
A clear coating film is further formed on the top coating film into which the sublimable dye has penetrated, and the clear coating film is polished to obtain a printed metal plate having a smooth surface. Japanese Patent Application Laid-Open No. 5-78988 introduces dyeing a metal plate on which a fluororesin film is laminated with a sublimable dye via a bonding agent. The fluororesin film is not dyed with a sublimable dye,
In addition, it utilizes the property of easily transmitting a sublimable dye. When transfer paper on which a sublimable dye is printed by offset, silk, gravure or the like is superimposed on a film surface of a laminated metal plate and heated and pressed, a printed surface in which the sublimable dye penetrates the adhesive is obtained. The obtained printed laminated metal sheet has characteristics excellent in weather resistance and stain resistance.

[0004]

The sharpness of a printed metal plate is improved by smoothing the top coating layer. However, since the top coating film in which the sublimable dye has penetrated is polished, a decrease in the concentration of the sublimable dye and unevenness in design are likely to occur. Therefore, in general, a clear coating film is further formed on a printed metal plate printed with a sublimable dye, and the clear coating film is polished to impart sharpness. However, since a thermal transfer step is inserted between the painting steps, it is not preferable in terms of work efficiency and cost. In this regard, when a laminated metal plate on which a fluororesin film is laminated is used as a printing base plate as described in JP-A-5-78988, the fluororesin film can be polished, so that the concentration of the sublimable dye is hardly reduced. Vividness is imparted. However, fluororesin films are more expensive than fluororesin paints, and wrinkles occur during lamination, and there is a lower limit to the film thickness that can be used in terms of film strength. It is used. From the perspective of permeation of sublimable dyes, the thicker the fluororesin film, the longer it takes to permeate the sublimable dyes, and the more bleeding due to dot gain tends to increase. Thickening is not preferred. In the case of a printed laminated metal plate, it is necessary to increase the thickness of the adhesive layer to about 10 μm in order to increase the density of the pattern, which causes an increase in cost.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been devised to solve such a problem, and a transparent or translucent fluororesin paint having no dyeing property on a sublimable dye is overcoated. The use of a sublimable dye that does not require a clear coating after infiltration printing and does not cause a decrease in density or design unevenness even when the top coating is polished as it is, and presents a surface with high sharpness. An object of the present invention is to provide a coated metal plate for thermal transfer having excellent permeability and a printed coated metal plate using the same.

[0006] The coated metal sheet for thermal transfer of the present invention having excellent permeability of the sublimable dye and the printed metal sheet using the same exhibit dyeability to the sublimable dye in order to achieve the object. A transparent or translucent undercoat film layer composed of 60 to 100% by weight of an acrylic resin and 40 to 0% by weight of a polyvinylidene fluoride resin, a transparent or semi-transparent undercoat layer composed of 40 to 10% by weight of an acrylic resin and 60 to 90% by weight of a polyvinylidene fluoride resin. By applying a heat-transfer coated metal plate having a translucent top coat layer formed on the surface of the metal plate, and superposing the printed surface of a transfer paper containing a sublimable dye on the heat-transfer coated metal plate, and performing heat treatment. The sublimable dye penetrated to the undercoat layer to form a printed metal plate. A triazine-based ultraviolet absorber and a benzotriazole-based ultraviolet ray having a weight loss of not more than 10% by weight at 300 ° C. under an air atmosphere in a heating condition of 5 ° C./min under heating conditions in an air atmosphere. The absorbent may be used alone or in combination.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A printed metal plate according to the present invention uses a plated steel plate, a stainless steel plate, an aluminum plate or the like as a base metal plate 1 as shown in FIG. A transparent or translucent undercoat film layer 4 is formed on the surface of the base metal plate,
A transparent or translucent top coat layer 5 is provided on the outermost layer (a). A white base coat layer 2 (b) and a primer layer 3 are provided between the base metal plate 1 and the undercoat layer 4.
(C) may be provided. The base coat layer 2 is not limited to white, and may have another color tone including a clear coating film. In any case, the color tone of the base metal plate 1 and the base coat layer 2 becomes a ground pattern, and a printed design steel plate having a unique depth feeling utilizing the texture of the base material is manufactured. Further, in order to further increase the sense of depth, one to three clear coating films made of urethane resin or the like can be provided on the top coating film layer 5.

[0008] The undercoat layer 4 must receive the sublimable dye transferred from the transfer sheet and be well dyed, and must have sufficient adhesion to the overcoat layer. Top coat layer 5
However, since a part of the coating film is crystallized with the lapse of time, it is difficult to sufficiently secure the coating film adhesion when using an undercoating film of a resin completely different from the coating film. Therefore, the resin system of the undercoat film must be the same as or close to the resin system of the overcoat film. The undercoating layer 4 contains 60 to 100% by weight of an acrylic resin with respect to 40 to 0% by weight of the polyvinylidene fluoride resin, and the overcoating layer 5 has a ratio of 60 to 90% by weight of the polyvinylidene fluoride resin. Then, 40 to 10% by weight of an acrylic resin was blended. When the blending amount of the polyvinylidene fluoride resin contained in the undercoat film 4 exceeds 40% by weight and the blending amount of the acrylic resin is less than 60%, the coating film is less likely to be dyed with a sublimable dye and the storage stability of the image is reduced. The bleeding occurs due to deterioration of the property. The undercoating film 4 contains 10 to 30% by weight of a polyvinylidene fluoride resin in order to secure adhesion to the overcoating film 5 and storage stability of the image.
Those containing 90 to 70% by weight of an acrylic resin are preferred.

Top coat layer 5 of transparent or translucent resin
Is preferably a coating film having a property of easily permeating a sublimable dye without being dyed, and a coating material having a large amount of a polyvinylidene fluoride resin mixed with an acrylic resin is used. As a result, the sublimable dye permeates deep into the top coating film to be polished without remaining in the top coating film, and dyes the undercoating film layer 4 having good coloring properties, thereby exhibiting an even design. In the overcoat film, 40 to 10% by weight of an acrylic resin is blended with respect to 60 to 90% by weight of a polyvinylidene fluoride resin. If the compounding amount of the polyvinylidene fluoride resin is less than 60% by weight and the compounding amount of the acrylic resin exceeds 40% by weight, the acrylic resin in the overcoat film is dyed with a sublimable dye, and design irregularities occur after polishing. It will be easier. Conversely, if the compounding amount of the polyvinylidene fluoride resin exceeds 90% by weight and the compounding amount of the acrylic resin is less than 10% by weight, adhesion to the undercoat film 4 cannot be obtained. The acrylic resin blended in the overcoat film is not limited in material as long as it is compatible with the polyvinylidene fluoride resin, and methyl methacrylate, a copolymer of methyl methacrylate and butyl methacrylate, or the like is used. A thermosetting acrylic resin obtained by adding a thermosetting component such as melamine or isocyanate to an acrylic resin containing a functional group can also be used.

When a transfer sheet preliminarily patterned with a sublimable dye is brought into contact with a printed metal plate and heated, the sublimated dye passes through the transparent or translucent top coat layer 5 to form a transparent or translucent undercoat. A pattern penetrating into the coating layer 4 and dyed in the thickness direction is formed. The transfer sheet is produced by printing such as gravure, offset, and screen. For small lot printing, a transfer sheet may be prepared by an electrophotographic method using a computer graphic which does not require a plate making process, an electrostatic recording method, an ink jet method, a thermal transfer method, or the like. The sublimable dye is a dye that can be sublimated and volatilized when heated and transferred to the undercoat coating layer 4,
For example, quinophthalone derivatives, anthraquinone derivatives,
A disperse dye such as an azo dye is used. Dyes conventionally used for sublimation heat transfer, sublimation transfer printing, etc.
It can be used without any restrictions.

The yellow sublimable dyes include Kaya
Cet Yellow AG, Kayacet Yel
low TDN (manufactured by Nippon Kayaku Co., Ltd.), RTY52,
Dianix Brilliant Yellow 5
GE (Mitsubishi Chemical Corporation), Blast Yellow
8040, DY108 (manufactured by Arimoto Chemical Co., Ltd.), Sum
ikaron Yellow EFG, Sumikar
on YellowE-4GL (manufactured by Sumitomo Chemical Co., Ltd.), FORON Brilliant Yellow
SGGLPI (Sand), PS Yellow GG
(Made by Mitsui Toatsu Dye Co., Ltd.).

As magenta sublimable dyes, Kay is used.
Acet Red 026, Kayacet Red
130, Kayacet Red B (Nippon Kayaku Co., Ltd.), Oil Red DR-99, Oil Red
DK-99 (manufactured by Arimoto Chemical Co., Ltd.), Diaceli
ton Pink B (Mitsubishi Chemical Corporation), Sum
ikaron Red E-FBL (Sumitomo Chemical Co., Ltd.), Latyl Red B (Du Pont), Sudan Red 7B (BASF), R
esolin Red FB, Ceres Red 7
B (manufactured by Bayer).

As the cyan-based sublimable dye, Kaya
lon Fast Blue FG, Kayacet
Blue FR, Kayacet Blue 136,
Kayacet Blue 906 (manufactured by Nippon Kayaku Co., Ltd.), Oil Blue 63 (manufactured by Arimoto Chemical Co., Ltd.), HSB9, RTB31 (manufactured by Mitsubishi Chemical Corporation),
Disperse Blue # 1 (manufactured by Sumitomo Chemical Co., Ltd.), MS Blue 50 (manufactured by Mitsui Toatsu Dye Co., Ltd.), Ceres Blue GN (manufactured by Bayer), Duanol Brilliant Blue
2G (manufactured by ICI) and the like. The sublimable dye for each color is
They may be used alone or in combination of two or more. Black is
It can be obtained by appropriately mixing yellow, magenta and cyan sublimable dyes. When a sublimable dye having a color tone other than the above is used, a dye having a sublimation temperature (including a case of volatilizing from a liquid) of 60 ° C. or more is preferable.

When the transfer sheet is heated while being in contact with the base metal plate 1, the sublimable dye contained in the transfer sheet sublimates, and the transparent or translucent top coat layer 5 as shown in FIG. Transparent or translucent undercoat layer 4
Penetrates in the thickness direction. Therefore, a three-dimensional printed pattern is developed in the undercoating film layer 4 dyed almost uniformly in the thickness direction. Since the obtained printed pattern is provided on the undercoating film 4, it is not affected even if the topcoating film layer 5 is polished to improve the sharpness, and it has a sense of depth, three-dimensional appearance, glossiness and freshness. A printed pattern with excellent cinematography is obtained. In addition, since the printed pattern has penetrated into the resin layer, a pattern strong in abrasion resistance and scratch resistance is formed.

An ultraviolet absorber may be added to the undercoat layer 4 and the overcoat layer 5 in order to prevent discoloration of the sublimable dye and decrease in gloss of the resin layer due to transmission of ultraviolet rays of sunlight. . As the ultraviolet absorber, a benzotriazole type or a triazine type is used alone or in combination. The ultraviolet absorber is preferably 1 to the nonvolatile matter of the paint.
１８18% by weight is blended into the paint. When the amount of the ultraviolet absorbent exceeds 18% by weight, stain resistance, workability, appearance of the coated film and the like are deteriorated, and coloring of the overcoat film by the ultraviolet absorbent is also observed. The UV absorber preferably has a weight loss of 10% by weight or less at 300 ° C. under a heating condition of 5 ° C./min in an air atmosphere in order to prevent weight loss during baking of the coating film. Film baking condition is 200 ~
When the temperature reaches 240 ° C., the generally used benzophenone-based or benzotriazole-based ultraviolet absorber is inferior in heat resistance and sublimation resistance, so the ultraviolet absorber contained in the coating film is reduced by sublimation, and the initial amount is reduced. Action is impaired.

The benzotriazole-based ultraviolet absorber includes octyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propinate (TINUVIN manufactured by Ciba Geigy).
384), 2- [2-hydroxy-3,5-bis (α, α'dimethylbenzyl) phenyl] -2H-benzotriazole (TINUVIN manufactured by Ciba Geigy)
900), methyl-3- [3-t-butyl-5- (2H
-Benzotriazol-2-yl) -4-hydroxyphenyl] propinate and polyethylene glycol (molecular weight: about 300) (TINU manufactured by Ciba Geigy)
VIN 1130), 2- [2'-hydroxy-3'-
(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] -benzotriazole (Kyoyaku Co., Ltd. Biosorb 590).

The triazine-based ultraviolet absorber includes, for example,
2- [4 [(2-hydroxy-3-didecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- [4 [(2-hydroxy-3-tridecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,6 -Bis (2,4-dimethylphenyl-
Mixture of 1,3,5-triazine (Ciba-Geigy)
TINUVIN 400). The above ultraviolet absorbers can be used alone or in combination of two or more. Further, in order to improve the light resistance of the undercoat film 4 and the overcoat film 5, a hindered amine-based light stabilizer may be added as necessary. The light stabilizer is compounded in an amount of 3.0% by weight or less based on the nonvolatile content of the paint.

The hindered amine light stabilizers include the following. Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Sankyo Corporation S
ANOL LS770), screws (1,2,2,6,6-
Pentamethyl-4-piperidyl) sebacate (SANOL LS765 manufactured by Sankyo Co., Ltd.), 1- {2- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Provionyloxy] ethyl} -4- [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine (SANOL LS2626 manufactured by Sankyo), 4-
Benzoyloxy-2,2,6,6-tetramethylpiperidine (SANOL LS744 manufactured by Sankyo Co., Ltd.),
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione (SANOL LS manufactured by Sankyo Corporation)
440), bis (1,2,2,6,2- (3,5-di-t-hydroxybenzyl) -2-n-butylmalonate)
6-pentamethyl-4-piperidyl) (TINUVIN 144 manufactured by Ciba-Geigy), bis (2
2,6,6-tetramethyl-4-piperidyl) ester (TINUVIN 780FF manufactured by Ciba-Geigy),
Dimethyl succinate and 1- (2-hydroxyethyl)-
Polycondensate of 4-hydroxy-2,2,6,6-tetramethylpiperidine (TINUVIN manufactured by Ciba-Geigy)
622LD), poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6
6-tetramethyl-4-pyridyl) imino]} (CHIMASSORB 944LD manufactured by Ciba-Geigy),
N, N'-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6
Polycondensate of -chloro-1,3,5-triazine (CHIMASSORB 119FL manufactured by Ciba Geigy), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (TINUVIN manufactured by Ciba Geigy)
292), bis (1-octaoxy-2,2,6,6-
Tetramethyl-4-piperidyl) sebacate (TINUVIN 123 manufactured by Ciba-Geigy), HA-70G
Adekastab LA-52, Adekastab LA-57, Adekastab LA-62, Adekastab LA-63, Adekastab LA-67, Adekastab LA-68, Adekastab LA-82,
ADK STAB LA-87 (made by Asahi Denka Kogyo Co., Ltd.)

The above light stabilizers can be used alone or in combination of two or more. The compounding amount of the light stabilizer is 3.0% by weight or less. Even if it is added in excess of 3.0% by weight, the effect of improving the light fastness of the sublimable dye penetrated into the coating film is saturated, and the appearance of the coating tends to deteriorate. The light stabilizer is desirably added in the range of 0.5 to 1.5% by weight. The undercoat film 4 and the overcoat film 5 may be formed via the base coat layer 2 (FIG. 1b), may be formed via the base coat layer 2 and the primer layer 3 (FIG. 1c), or may be formed on the base metal. Formed directly on plate 1 (FIG. 1a)
May be. In any case, the color tone of the base metal plate 1 and the base coat layer 2 becomes a ground pattern, and is observed through the sublimable dye dyeing layer 6. As a result, a printed metal plate having a unique sense of depth and excellent design can be manufactured utilizing the base material.

[0020]

Example 1 A 0.5 mm thick galvanized steel sheet was subjected to a pre-coating treatment, and a white polyester resin paint (FLC-600 manufactured by Nippon Paint Co., Ltd.) was dried to a dry film thickness of 19 μm. After painting, at a plate temperature of 220 ° C, 1
A white basecoat resin coating was baked for a minute. Next, a triazine-based ultraviolet absorber (Tiba Geigy T
INUVIN 400) and a benzotriazole UV absorber (TINUVIN 38 manufactured by Ciba Geigy)
4) was added in an amount of 0 to 4.0% by weight based on the non-volatile content of the paint, and a hindered amine light stabilizer (manufactured by Ciba Geigy)
TINUVIN 123) to the paint non-volatile content.
A fluororesin-based clear paint containing 0 to 70% by weight of polyvinylidene fluoride resin and 100 to 30% by weight of an acrylic resin to which 5% by weight has been added is applied to a dry film thickness of 12 μm, and the sheet temperature is 230 ° C. for 1 minute. By baking, an undercoat film layer was formed.

Next, a triazine-based ultraviolet absorber (TINUVIN 400 manufactured by Ciba-Geigy) and a benzotriazole-based ultraviolet absorber (TINUGE manufactured by Ciba-Geigy)
VIN 384) is 0-
3.0 to 50% by weight, 95 to 50% by weight of polyvinylidene fluoride resin to which 1.5% by weight of a hindered amine-based light stabilizer (TINUVIN 123 manufactured by Ciba Geigy Co., Ltd.) is added based on the nonvolatile matter of paint, and 5 to 50% by weight of acrylic resin % Of a fluororesin-based clear paint (Uniflon K, manufactured by Nippon Paint Co., Ltd.) to a dry film thickness of 15 μm.
By baking at a plate temperature of 250 ° C. for 1 minute, a top coat layer was formed. Note that a triazine-based ultraviolet absorber (TINUVIN 400 manufactured by Ciba-Geigy) and a benzotriazole-based ultraviolet absorber (TINUGE manufactured by Ciba-Geigy)
VIN 384), as a result of thermogravimetric analysis, showed a weight loss of 3.5% by weight and 5.0% by weight at 300 ° C under heating conditions of 5 ° C / min in an air atmosphere, respectively. The transfer of the pattern using the sublimable dye is performed by using a sublimable dye toner (sublimation printing toner manufactured by Nippon Steel Chemical Co., Ltd.) and electrostatically using an electrostatic plotter-type image printing system (Juana manufactured by Exis). Solid cyan, magenta, and yellow patterns were output on recording paper. The obtained electrostatic recording paper was superimposed on the coated surface of the coated steel sheet, and heated and pressed at a temperature of 150 ° C. and a pressure of 0.5 kg / cm ² for 150 seconds. After the completion of the pressure bonding, the electrostatic recording paper was peeled off from the coated steel sheet to produce a printed coated steel sheet (Examples 1, 3, 5, 7, 9, 11, 13, Comparative Examples 1, 5, 7,
9, 11, 13).

Example 2 A pre-coating treatment was applied to a stainless steel sheet (SUS304 HL) having a thickness of 0.5 mm to form an undercoat layer and an overcoat layer under the same conditions as in Example 1. Next, the same sublimable dye as in Example 1 was used and transferred to a coated steel sheet in the same manner to produce a printed coated steel sheet (Examples 2, 4, 6, 8, 10, 12, 14, Comparative Examples) 2, 6, 8, 10, 12, 14). Example 3 Polyvinylidene fluoride resin 20 in which a triazine-based UV absorber and a benzotriazole-based UV absorber were each added in an amount of 4.0% by weight based on the coating nonvolatile matter.
An undercoat film layer was formed using a fluororesin clear paint containing 80% by weight of an acrylic resin, and a print-coated steel sheet was produced under the same conditions as in Example 1 except that the overcoat film layer was not provided ( Comparative example 3). Example 4: a stainless steel plate having a thickness of 0.5 mm (SUS3
04 HL) was subjected to pre-coating treatment to form an undercoat film layer under the same conditions as in Example 3. Next, the same sublimable dye as in Example 1 was used and transferred to a coated steel sheet in the same manner to produce a printed coated steel sheet (Comparative Example 4).

Example 5: An undercoat layer was formed under the same conditions as in Example 3, and then a triazine-based UV absorber and a benzotriazole-based UV absorber were each added in an amount of 1.5% by weight based on the nonvolatile matter of the paint. A transparent or translucent Lumiflon-based fluororesin paint (Cefralcoat M.SUS manufactured by Central Glass Co., Ltd.) or a polyester-based resin paint (Nippon Paint Co., Ltd.) in which a hindered amine-based light stabilizer is added at 1.5% by weight based on the nonvolatile content of the paint. FL Co., Ltd.
C-5100) or an acrylic resin paint was applied to a dry film thickness of 15 μm, and baked at a plate temperature of 230 ° C. for 1 minute to form a top coat layer. Then, the same sublimation dye as in Example 1 was used and transferred to a coated steel sheet in the same manner to produce a printed coated steel sheet (Comparative Examples 15, 17,
19). Example 6: An undercoating layer was formed under the same conditions as in Example 4, and then a topcoating layer was formed under the same conditions as in Example 5 to produce a printed steel sheet (Comparative Examples 16, 18, and 2).
0).

Example 7: After forming a white base coat resin coating under the same conditions as in Example 1, an undercoat coating layer was formed under the same coating conditions and conditions as those used in Example 5 for forming a top coating layer. Next, a polyfluorene containing 1.5% by weight of a triazine-based UV absorber and 1.5% by weight of a hindered amine-based light stabilizer based on the nonvolatile matter of the paint was added to each of the nonvolatile matter of the paint. A fluororesin clear paint containing 70% by weight of vinylidene fluoride resin and 30% by weight of an acrylic resin is applied to a dry film thickness of 15 μm and baked at a plate temperature of 250 ° C. for 1 minute to form an overcoat film layer. did. Next, the same sublimable dye as in Example 1 was used and transferred to a coated steel sheet by the same method to produce a printed coated steel sheet (Comparative Examples 21 and 23). Example 8: An undercoat layer was formed under the same conditions as in Example 6 except that a transparent or translucent polyester resin paint or a Lumiflon-based fluororesin clear paint was used, and an overcoat film was formed under the same conditions as in Example 7. After forming the layers, printed painted steel sheets were produced in the same manner (Comparative Examples 22 and 24).

Each of the printed coated steel sheets manufactured as described above was polished with # 1500 abrasive paper, and further buffed with an abrasive to give sharpness. The color tone of the printed coated steel sheet before and after polishing, coating film adhesion, light resistance, coating appearance, and dye transferability under a wet environment were examined. The results of the investigation are shown in Table 1 (Example of the present invention) and Tables 2 to 4 (Comparative Examples). Each property in Tables 1 to 4 was evaluated by conducting tests as follows. 1) Color before and after polishing Color difference between printed painted steel sheet before polishing and printed painted steel sheet after polishing (ΔE for cyan, magenta and yellow respectively)
Was displayed. 2) Coating film adhesion Printed steel sheet before polishing.
The test was performed by inserting a grid defined in G3320 and extruding by 6 mm), and the coating film peeled off with the peeling of the adhesive tape was evaluated on a 5-point scale. 3) Light resistance The color difference ΔE between the test plate and the non-irradiated plate after 240 hours was displayed in a sunshine carbon arc weather meter (sprayed with fresh water for 12 minutes during irradiation for 60 minutes) at a test temperature set to 63 ° C. Note that if the color difference ΔE ≧ 7 after 240 hours, it is difficult to put it into practical use for interior use. Comparing the light fastness of the cyan, magenta and yellow dyes sublimating under substantially the same conditions, the cyan light has the lowest light fastness. Therefore, the effect of adding the ultraviolet absorber and the light stabilizer was evaluated by the light resistance of cyan.

4) Appearance of the coating An index for obtaining a smooth and uniform appearance is shown as an index.
Those with color unevenness / cloudiness were evaluated as “△”, and those with clear yuzu skin / color unevenness / cloudy were evaluated as “x”. 5) Transferability of dye Magenta color on electrostatic recording paper using an image printing system of electrostatic plotter system (Juana by Exis) using a sublimable dye toner (sublimation printing toner by Nippon Steel Chemical Co., Ltd.). Was output. The obtained electrostatic recording paper was superimposed on the painted surface of the coated steel sheet, and the temperature was 150 ° C.
Thermocompression bonding was performed at 150 ° C. and a pressure of 0.5 kg / cm ² for 150 seconds. After the completion of the pressure bonding, the electrostatic recording paper was peeled from the coated steel sheet to obtain a printed coated steel sheet. The printed coated steel sheet was heated to a temperature of 4
J adjusted to 9 ± 1 ° C and 95% or more relative humidity
Insert into a wetness tester according to IS K 2246, 500
After the time, the magenta halftone dot% was measured. The dot gain was determined from a comparison between the dot percentage of the printed coated steel sheet before the test and the dot percentage after 500 hours. A dot gain of 30% or less is indicated by ◎, a dot gain of 30 to 50% is indicated by ○, 50 to 100
%, And 100% or more were evaluated as x, and the transferability of the sublimable dye was evaluated. If the dot gain is equal to or larger than the mark, the level is considered to be usable.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

As is clear from the comparison between Table 1 and Tables 2 to 4, in Table 1 according to the present invention, the color difference before and after polishing, coating film adhesion, light resistance, coating appearance, and dye transferability are shown. All exhibited sufficiently satisfactory characteristics. On the other hand, in Comparative Examples 1 and 2 in Table 2, since the content of the acrylic resin in the overcoat film was large, the color difference before and after polishing was large, and it was difficult to reproduce the color tone before polishing. The transferability of the sublimable dye was also large. In Comparative Examples 3 and 4, it was difficult to reproduce the color tone before polishing, as in Comparative Examples 1 and 2, since the film was transferred and polished without the top coat. In Comparative Examples 5 and 6, there was no problem with the color difference before and after polishing, but the adhesion between the top coat and the undercoat was insufficient. Comparative Examples 7-1
In the case of 0, since the content of the polyvinylidene fluoride resin contained in the undercoating film was as large as 50 to 70% by weight, there was a problem in the migration stability of the sublimable dye. In Comparative Examples 11 and 12, since no ultraviolet absorber was added to both the top coat and the undercoat, the color tone fluctuation after 240 hours of sunshine carbon arc weather meter (63 ° C.) was large. In Comparative Examples 13 and 14, since the ultraviolet absorber was changed to a benzophenone-based material having poor heat resistance, the color tone fluctuation after 240 hours of sunshine carbon arc weather meter (63 ° C.) was large. In Comparative Examples 15 to 20, the color difference before and after polishing was large, and the color tone before polishing was reproduced because the Lumiflon-based fluororesin paint, polyester-based resin paint, or acrylic-based resin paint was used, in which the sublimable dye was difficult to pass through the top coat. It was difficult to do. In Comparative Examples 21 to 24, the polyester resin paint or the Lumiflon-based fluororesin paint was used for the undercoat film, so that the adhesion to the overcoat film could not be sufficiently ensured.

[0032]

As described above, the printed metal plate of the present invention is a transparent and dyeable sublimable dye composed of 60 to 100% by weight of an acrylic resin and 40 to 0% by weight of a polyvinylidene fluoride resin. Alternatively, since a transparent or translucent top coat layer composed of 60 to 90% by weight of polyvinylidene fluoride resin and 40 to 10% by weight of an acrylic resin is formed on the translucent undercoat layer, a clear coat is formed. It is not necessary to improve the sharpness by polishing the top coat itself. For this reason, a printed metal plate excellent in sharpness and design without any unevenness in design can be easily manufactured at low cost.

[Brief description of the drawings]

FIG. 1 shows a cross section of a surface layer portion of a printed metal plate according to the present invention; (a) a base metal plate provided with an undercoat film and an overcoat resin layer; (b) an undercoat film via a base coat layer And a base metal plate provided with a top coat resin layer. (C) Explanation of printing using a sublimable dye on a base metal plate provided with an undercoat film and a top coat resin layer via a primer layer and a base coat layer. Figure

[Explanation of symbols]

 1: base metal plate 2: base coat layer 3: primer layer 4: undercoat coating layer 5: overcoat coating layer 6: sublimation dye dyeing layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/30 B32B 27/30 A D C09D 5/00 C09D 5/00 D 127/16 127/16 133 / 04 133/04 (72) Inventor Toshio Nagatomo 1st day new steelmaking at 7 Takayashinmachi, Ichikawa-shi, Chiba Coating and Composites Research Dept., R & D Co., Ltd. (72) Inventor Hiroshi Enya 7 Takamachishinmachi, Ichikawa-shi, Chiba No. 1 Day New Steel Works Co., Ltd. F-term (reference) 4D075 AC43 AE03 CA02 CB04 DA06 DB02 DC18 EA05 EB16 EB22 EB56 EC17 EC47 4F100 AB01C AB03 AB18 AH03A AH03B AK19A AK19B AK25BAK07B BA10B BA10C CA13A CA13B CC00A CC00B EH71 GB08 GB48 HB01 JL00 JM02A JM02B JN01A JN01B YY00A YY00B 4J038 CD111 CD112 CG112 CG141 JB35 JB36 PA07 PC02

Claims (3)

[Claims] 1. A transparent or translucent undercoat film layer comprising 60 to 100% by weight of an acrylic resin exhibiting dyeing properties to a sublimable dye and 40 to 0% by weight of a polyvinylidene fluoride resin, and acrylic resins 40 to 10%. A coated metal sheet for thermal transfer, having a transparent or translucent top coat layer composed of 60% by weight and 60 to 90% by weight of a polyvinylidene fluoride resin and having excellent permeability of a sublimable dye formed on the surface of the metal sheet. 2. A printing method in which the sublimable dye penetrates to the undercoat film layer by superimposing the printed surface of the transfer paper containing the sublimable dye on the coated metal plate for thermal transfer according to claim 1 and subjecting it to heat treatment. Painted metal plate. 3. The weight loss of the top coat layer and / or the undercoat layer of the coated metal sheet for thermal transfer according to claim 1 at 300 ° C. under a heating condition of 5 ° C./min in an air atmosphere. The printed metal plate according to claim 2, wherein a triazine-based UV absorber and a benzotriazole-based UV absorber are contained singly or in combination of 10% by weight or less.