JP3464974B2 - Painted metal plate for sublimation dye transfer printing with excellent light resistance - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated metal plate for sublimation dye transfer printing, which is provided with various printing patterns by dyeing a sublimation dye by thermal transfer.

[0002]

2. Description of the Related Art When a printed coated metal plate is produced using a sublimable dye, the sublimable dye is printed on the top clear layer of the coated metal plate by a printing method such as offset, silk, gravure or transfer, and then heated. The sublimation dye is permeated into the clear coating by the treatment. For pattern printing using sublimable dyes,
A method in which a transfer sheet is brought into contact with a coating film of a curable synthetic resin layer and heated (JP-A-51-24313), after forming a printing layer on a coated metal plate by transfer printing using a sublimable dye, A method of forming a top coating film on the surface and then infiltrating a sublimable dye from the inside of the coating by heat treatment (JP-A-54-104907), and forming a primer coating film and a colored top coating film on the steel plate surface A method of impregnating a thermally sublimable ink into a coating film of a prepainted metal plate (JP-A-7-31).
931), a method of permeating a sublimation type colorant into the inside of an opaque resin layer provided on a metal plate substrate (JP-A-7-102733).

In any pattern printing method, a pattern is developed by infiltrating a sublimable dye into the top coating film.
However, ordinary sublimation dyes are disperse dyes or oil dyes having a small polarity, and are easily deteriorated by plasticizers, organic chemicals and the like. It is also a dye that is easily decomposed or discolored by light such as ultraviolet rays. Therefore, it is difficult to maintain a stable color and pattern in a usage environment that is exposed outdoors for a long period of time. Discoloration or fading due to light irradiation is prevented by blending the ultraviolet absorber in the paint at a ratio of 0.5 to 3 mass% with respect to the nonvolatile content of the paint.

[0004]

However, the pre-coated steel sheet used for printing has a baking temperature of 200 to 240 ° C. and a holding time of 1 to 2 minutes, and the sublimable dye is applied to the coating film. The transfer conditions for permeation are 160 to 190 ° C ×
1 to 4 minutes. That is, the ultraviolet absorber is exposed to the high temperature atmosphere at least twice by the time production of the printed metal plate is completed. Therefore, generally used benzophenone-based or benzotriazole-based ultraviolet absorbers are inferior in heat resistance and sublimation resistance, and the amount of the ultraviolet absorber contained in the coating film is reduced by sublimation. The decrease in the amount of the ultraviolet absorber not only adversely affects the discoloration and fading of the ultraviolet absorber, but also causes the sublimation of the ultraviolet absorber to cause the surface of the coating film to become dull and yellow. The yellowing phenomenon becomes more prominent as the thickness of the original coating plate becomes more severe under both coating baking conditions and transfer conditions.

In this regard, in JP-A-9-206678, a benzotriazole-based or triazine-based UV absorber having good thermal stability and solubility is added at a ratio of 6 to 18% by mass with respect to the nonvolatile content of the paint. is doing. The addition of benzotriazole-based or triazine-based UV absorbers is effective for many types of sublimable dyes, but some sublimable dyes, especially those with poor lightfastness, reach levels that can be used for outdoor applications. Discoloration and fading cannot be suppressed. It may be possible to change to a sublimation dye that is more excellent in light resistance, but it is not easy to change the sublimation dye considering the suitability according to the type of printer used for output and the restriction of color tone. By the way, of the four basic inks used (cyan, magenta, yellow, black), even if only one of them has poor light resistance, it cannot be used outdoors.

[0006]

The present invention has been devised to solve such problems, and a top coat film is formed by using a resin having excellent light resistance. An object of the present invention is to provide a coated metal plate for sublimation dye transfer printing, in which discoloration / fading of the sublimation dye permeated into the substrate is significantly suppressed and various printed patterns are provided by thermal transfer of the sublimation dye.

In order to achieve the object, the coated metal plate for sublimation dye transfer printing of the present invention has a number average molecular weight of from 1,000 to 1,000.
10000, glass transition temperature (Tg) 20 to 60 ° C, ratio of melamine to 100 parts by mass of resin solid content is 20 to 1
50 parts by mass, heat containing a 1,2-benzene-dicarbonyl structure derived from a dicarboxylic acid-based monomer and / or a 2,2-dimethyltrimethylene structure derived from a dialcohol-based monomer as part of the molecular structure A top coating film formed from a transparent or semi-transparent paint containing a curable polyester resin as a main component is provided on the surface of the metal plate.

The top coat may preferably contain 3 to 22 parts by mass of a triazine-based UV absorber and a benzotriazole-based UV absorber with respect to 100 parts by mass of the nonvolatile content of the paint, either alone or in combination. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A coated metal plate for sublimation dye transfer printing according to the present invention is a base metal plate 1 such as a plated steel plate, a stainless steel plate or an aluminum plate, and a base coat layer 2 and a primer layer 3 are provided if necessary. A transparent or semi-transparent top coat film 4 is formed on the surface layer (FIG. 1). As long as there is a top coat film 4 on the surface layer, a print coat metal plate (a) having a base coat layer 2 provided between the base metal plate 1 and the top coat film 4, and a print coat metal plate having a primer layer 3 (b). ), A print-coated metal plate (c) in which the top coating film 4 is directly provided on the base metal plate 1
Either of them may be used. In this specification, the term "top coating film" is used to mean a clear coating film,
Further, an aggregate such as silica may be added to the topcoat paint in order to develop a matte appearance. The base coat layer 2 is not limited to white, and may have another color tone.

The base coat layer 2 is preferably formed with a film thickness of 10 to 20 μm in order to hide the base metal plate 1 and the primer layer 3. Base coat layer 2 having a film thickness of less than 10 μm
Then, the hiding power with respect to the base metal plate 1 and the primer layer 3 is weak, and the coating surface has a mixed color tone of the base metal plate 1 and the primer layer 3. On the contrary, in the thick base coat layer 2 having a thickness of more than 20 μm, the solvent remaining in the coating film is rapidly vaporized during baking, which may cause a pinhole-shaped coating film defect called “side”.

The top coat film 4 is required to be a resin which receives the sublimable dye transferred from the transfer sheet and is dyed well. In this respect, the number average molecular weight is 1000 to 100.
00, glass transition temperature (Tg) 20 to 60 ° C., and a thermosetting polyester resin having a melamine ratio of 20 to 150 parts by mass with respect to 100 parts by mass of resin solid content is excellent in dyeability to sublimable dyes, and an image obtained Also has good storage stability.

The thermosetting polyester resin is a resin synthesized by polycondensation of a dibasic acid and a polyhydric alcohol. The dibasic acid is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or an acid anhydride thereof, specifically, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, maleic acid, maleic anhydride, fumaric acid. , Adipic acid, etc. are used alone or in admixture of two or more. In order to obtain good light resistance, it is particularly preferable that phthalic anhydride and / or orthophthalic acid which form a 1,2-benzene-dicarbonyl structure after polycondensation are contained. Adipic acid containing no phenyl group is also used as a suitable dibasic acid.

Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
There are propylene glycol, pentyl glycol, neopentyl glycol, trimethylolethane and the like, which can be used alone or in combination of two or more kinds. In order to obtain good light resistance, it is preferable to use a glycol having a long aliphatic chain such as pentyl glycol, and it is more preferable to use neopentyl glycol which forms a 2,2-dimethyltrimethylene structure after polymerization.

The number average molecular weight of the thermosetting polyester resin used in the present invention is adjusted to 1,000 to 10,000. Top coat film 4 with a number average molecular weight of less than 1000
Since the elongation is lost, the workability is inferior. On the contrary, when the number average molecular weight exceeds 10,000, the ratio of the cross-linked portion due to melamine is reduced, and thus it is easily decomposed by ultraviolet irradiation or the like. Melamine used as a curing agent itself has high light stability, and when it is mixed with a polyester resin, the light resistance of the resin is improved. The effect of improving the light resistance becomes remarkable with 20 parts by mass or more of melamine, but if the excess amount of melamine exceeds 150 parts by mass, the crosslink density becomes too high and the coating film becomes liable to crack during processing. Further, when the glass transition temperature (Tg) is less than 20 ° C, the coating film hardness is low and the coating film is easily scratched. On the contrary, when the glass transition temperature (Tg) exceeds 60 ° C, the hardness is too high and the workability is significantly deteriorated. To do.

When a transfer sheet pre-patterned with a sublimable dye is brought into contact with the base metal plate 1 and heated, the sublimated dye permeates into the transparent or semitransparent top coat film 4 to dye the sublimable dye. The layer 5 is formed, and a pattern dyed in the thickness direction is developed. The transfer sheet can be produced by gravure printing, offset printing, screen printing or the like. For small lot printing, an electrophotographic method using computer graphics which does not require a plate making process, an electrostatic recording method, an ink jet method, a thermal transfer method and the like can be adopted.

The sublimable dye is a dye which can be transferred to the top coating film 4 by a phenomenon such as sublimation or volatilization when heated. In the present specification, "sublimation" is used in the sense that it also includes volatilization from the liquid phase. As the sublimable dye, disperse dyes such as quinophthalone derivatives, anthraquinone derivatives, and azo dyes are preferably used. Further, sublimation dyes conventionally used for sublimation thermal transfer, sublimation transfer printing and the like can be used for printing the top coat film 4 without particular limitation.

Among the sublimable dyes that can be used, yellow dyes include Kayaset Yellow AG, Kayaset Yellow TDN
(Above, manufactured by Nippon Kayaku Co., Ltd.), RTY 52, Dianix Yell
ow 5R-E ， Dianix Yellow F3G-E ， Dianix Brilliant Yel
low 5G-E (above, Mitsubishi Chemical Corporation), Blast Yel
low 8040, DY108 (above, Arimoto Chemical Co., Ltd.), Sumi
karon Yellow EFG, Sumikaron Yellow E-4GL (above,
Sumitomo Chemical Co., Ltd.), FORON Brilliant Yellow SGGLP
I (manufactured by Sand), PS Yellow GG (manufactured by Mitsui Toatsu Dye Co., Ltd.) and the like.

Magenta sublimation dyes include Kayaset Re
d 026, Kayaset Red 130, KayasetRed B (Nippon Kayaku Co., Ltd.), Oil Red DR-99, Oil Red DK-99
(Above, Arimoto Chemical Co., Ltd.), Diacelliton Pink B
(Manufactured by Mitsubishi Chemical Co., Ltd.), Sumikaron Red E-FBL (manufactured by Sumitomo Chemical Co., Ltd.), Latyl Red B (manufactured by Du Pont), Sud
an Red 7B (manufactured by BASF), Resolin Red FB, Ceres Red
7B (above, manufactured by Bayer).

For cyan sublimation dyes, Kayalon Fast
Blue FG, Kayalon Blue FR, Kayaset Blue 136, Kayas
et Blue 906 (above, Nippon Kayaku Co., Ltd.), Oil Blue
63 (Arimoto Chemical Co., Ltd.), HSB9, RTB31 (above, Mitsubishi Chemical Co., Ltd.), DisperseBlue # 1 (Sumitomo Chemical Co., Ltd.), MS Blue 50 (Mitsui Toatsu Dyestuff Co., Ltd.), Cere
s Blue GN (manufactured by Bayer), Duranol Brilliant Blue 2G
(Made by ICI), etc.

The sublimable dyes for each color may be used alone or in 2
It is also used as a mixture of two or more species. The black color tone is obtained by appropriately mixing sublimation dyes for yellow, magenta and cyan colors. As the sublimable dye having a color tone other than yellow, magenta and cyan, a dye having a sublimation temperature of 60 ° C. or higher is preferable. In selecting a sublimable dye, a dye having a high sublimation temperature is preferable because it has a relatively high molecular weight and imparts excellent light resistance and heat resistance to the coating film.

When the transfer sheet is heated while it is in contact with the underlying metal plate 1, the sublimable dye contained in the transfer sheet sublimes and, as shown in FIG.
Permeate in the thickness direction. Therefore, the sublimable dye dyeing layer 5 dyed almost uniformly in the thickness direction is formed on the transparent or semi-transparent top coat film 4, and a three-dimensional printed pattern can be obtained. Since the obtained print pattern does not have the sublimation dye concentrated in only the surface layer of the top coating film 4, the print fading due to rubbing does not occur, and the transfer print layer after the design is applied by thermal transfer is formed. A post process of protecting with a transparent resin is also omitted. In this way, the required pattern can be easily applied when needed, so that small-lot production of the designed steel sheet with various patterns corresponding to various needs is facilitated. Moreover, since it is not necessary to stock the designed steel sheets with a predetermined pattern in stock, the inventory burden is reduced. Further, since the dye layer does not exist alone between the transparent or semi-transparent resin layer and the metal layer, delamination unlike the conventional laminated steel sheet does not occur.

An ultraviolet absorber may be added to the top coat film 4 in order to prevent fading of the sublimable dye and reduction of gloss of the top coat film 4 due to transmission of sunlight or ultraviolet rays. As the ultraviolet absorber, preferably in the atmosphere,
10 at 300 ° C under a heating condition of a heating rate of 5 ° C / min.
A benzotriazole-based or triazine-based resin that can reduce the weight by not more than mass% is used. Specifically, top coating film 4
3 to 22 parts by mass relative to 100 parts by mass of the nonvolatile content of the coating composition of Triazine type alone or a combination of triazine type and benzotriazole type is added to the top coat film 4. In addition, the light resistance is further improved by adding 3.0 parts by mass or less of a hindered amine light stabilizer.

The benzotriazole type ultraviolet absorber includes octyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propinate (TINUVIN 384 manufactured by Ciba Geigy). , 2- "2-hydroxy-3,5-
"Bis (α, α'dimethylbenzyl) phenyl" -2H-benzotriazole (TINUVIN 900 manufactured by Ciba-Geigy), methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl)
Condensation product of 4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight about 300) (TINUVIN 1130 manufactured by Ciba-Geigy), 2- [2'-hydroxy-3 '-(3 ", 4", 5 ",
6 "-Tetrahydrophthalimidomethyl) -5'-methylphenyl] -benzotriazole (Kyoyaku Co., Ltd. Viosor
b 590) and the like.

Examples of the triazine-based ultraviolet absorber include
2- [4-[(2-hydroxy-3-didecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2- [4-[(2-hydroxy-3-tridecyloxypropyl) -oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine mixture (TINUVIN 400 manufactured by Ciba Geigy) and the like.

These ultraviolet absorbers can be used alone or in admixture of two or more. The blending amount of the ultraviolet absorber is preferably adjusted to 3 to 22% by weight with respect to 100 parts by mass of the nonvolatile component of the coating material. The improvement of light resistance becomes remarkable by adding 3 parts by mass or more of an ultraviolet absorber, but 22% by weight
If the blending amount exceeds, the stain resistance, workability, and appearance of the coating film deteriorate. In addition, coloring of the coating film due to the ultraviolet absorber is also observed. In order to further improve the light resistance of the transparent or semi-transparent top coating film 4, it is preferable to add a hindered amine light stabilizer in an amount of 3% by weight or less based on the non-volatile components of the coating material, if necessary. Examples of the hindered amine light stabilizer include the following substances.

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (SANOL LS770 manufactured by Sankyo Co., Ltd.), bis
(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) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] -2,2,6,6-tetramethylpiperidine (SANOLLS2626 manufactured by Sankyo Co., Ltd.), 4-benzoyloxy-2,2,6,6-tetramethylpiperidine (manufactured by Sankyo Co., Ltd.)
SANOL LS744), 8-Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione (SANOL LS440 manufactured by Sankyo Co., Ltd.) , 2- (3,5-di-t-hydroxybenzyl-2-n-butylmalonate bis (1,2,2,6,6-
Pentamethyl-4-piperidyl) (TIN manufactured by Ciba Geigy)
UVIN 144), succinic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester (TINUVIN 780F manufactured by Ciba Geigy)
F), a polycondensation product of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine (TINUVIN 622LD manufactured by Ciba-Geigy), 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-piperidyl) imino]] (Ciba Geigy CHIMASSORB 944L
D), N, N'-bis (3-aminopropyl) ethylenediamine
2,4-Bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine polycondensate (Ciba Geigy) CHIMASSORB 119FL), screws (1,2,
2,6,6-Pentamethyl-4-piperidyl) sebacate (TINUVIN 292 manufactured by Ciba Geigy), bis (1-octaoxy-2,
2,6,6-Tetramethyl-4-piperidyl) sebacate (TINUVIN 123 manufactured by Ciba Geigy), HA-70G (manufactured by Sankyo Co., Ltd.), ADEKA STAB LA-52, ADEKA STAB LA-57, ADEKA STAB LA-62, ADEKA STAB LA- 63, ADEKA STAB LA-6
7, ADEKA STAB LA-68, ADEKA STAB LA-82, ADEKA STAB LA-87 (manufactured by Asahi Denka Co., Ltd.)

These light stabilizers may be used alone or in combination with 2.
It is also possible to use a mixture of two or more species. Even if a light stabilizer is blended in a large amount exceeding 3.0% by weight, the effect of improving the light resistance of the sublimable dye that has penetrated into the top coating film 4 is saturated and the improvement commensurate with the increase in the amount cannot be seen. The paint appearance tends to deteriorate. The light stabilizer is preferably 0.5 to 1.5.
It is compounded in the range of weight%.

The transparent or semi-transparent top coat film 4 is formed through the base coat layer 2 (FIG. 1a), the base coat layer 2 and the primer layer 3 (FIG. 1b), or the base metal plate 1.
Directly (FIG. 1c). In either 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 dyeing resin layer 5. Therefore, it is possible to obtain a printed and painted metal plate that has a unique sense of depth by utilizing the texture of the base material.

[0029]

[Example] Manufacture of coated steel plate used for transfer original plate A zinc-plated steel plate having a thickness of 0.5 mm is degreased and surface-conditioned, and then coated chromate treatment is applied to obtain a dry film thickness of 14
White polyester resin paint (manufactured by Nippon Paint Co., Ltd.) was applied at a coating amount of μm, and the maximum plate temperature reached 220 ° C.
The white base coat layer 2 was formed by baking for 1 minute. Then, the clear resin coating material was applied to the white base coat layer 2 in an application amount such that the dry film thickness was 18 μm. The clear resin paint has a number average molecular weight of 500 to 20,000,
Glass transition temperature (Tg) 10-80 ℃, resin solid content 100
A polyester resin coating containing 5 to 70 parts by weight of melamine was used. In this polyester resin coating, one or two kinds selected from adipic acid, orthophthalic acid, isophthalic acid and terephthalic acid were used as dicarboxylic acid type monomers. The invention examples 1 to 9 and 1
In 1, 13, 15, 17 and Comparative Examples 1 to 7, neopentyl glycol was added as a dialcohol-based monomer.

Further, Examples 9 and 19 of the present invention and Comparative Examples 7 and 9
Other than the above, a clear paint for the top coating film 4 mixed with a triazine-based UV absorber and a benzotriazole-based UV absorber at a ratio of 1: 1 was used as the non-volatile component of the paint.
Mass% was added. Furthermore, a hindered amine light stabilizer was added to all the clear resin coating materials in an amount of 1.5% by mass. Steel plate coated with clear resin paint reaches the maximum reaching plate temperature of 230 ℃ 1
The top coating film 4 was formed by heating for a minute. The composition of the formed top coating film 4 is shown in Table 1 (Examples of the present invention) and Table 2.
(Comparative example).

[0031]

[0032]

Transfer Printing A sublimation dye ink prepared from cyan sublimation dye was used to output a solid pattern of cyan on an output paper with an inkjet printer. The obtained transfer paper is overlaid on the coated surface of the coated steel plate, and the temperature is 160 ° C. and the pressure is 4 × 10 ⁴ Pa.
It was crimped for 0 seconds. After completion of the pressure bonding, the transfer paper was peeled off from the coated steel sheet. When comparing the light resistance of cyan, magenta, and yellow sublimation dyes that sublimate under almost the same conditions, cyan has the lowest light resistance. Therefore, by using the light resistance of cyan as a reference, the resin composition You can clearly know the effect on.

Performance test of printed coated steel sheet A test piece is cut out from each manufactured printed coated steel sheet, and a light resistance test, a coating film adhesion test, a workability test, a moisture resistance test, a stain resistance test, and a flaw resistance test are performed. I went to In the light resistance test, the test piece was left for 240 hours in a sunshine carbon arc weather meter set at a test temperature of 63 ° C. under the condition that fresh water was sprayed for 12 minutes during irradiation for 60 minutes. 24
The color tone of the test piece after the lapse of 0 hours was measured, and the light resistance was evaluated by the color difference ΔE from the unirradiated test piece. If the color difference ΔE after 240 hours is 10 or more, it is not suitable for outdoor use, and for a long-term use of 3 years or more, the color difference Δ is less than 7
E is desired.

In the coating film adhesion test, the state of peeling of the coating film was observed by a cross-cut Erichsen test (a cross-cut specified in JIS G3320 was inserted and extruded by 6 mm). And, when the coating film is completely peeled off, the mark is 1, the peeling which is close to the peeling is the score 2, the significant peeling is the score 3, the slight peeling is the score 4, and the peeling is What did not occur was rated 5
The coating film adhesion was evaluated as 5 levels.

In the workability test, 0 to 6 t in a room at 20 ° C.
(1t if one plate with the same thickness as the test piece is sandwiched) 1
80 degree bending processing was performed, and the crack generation state of the coating film according to the degree of bending was investigated. Those with no cracks in the coating film and those with cracks in the coating film at 0 to 2t are ⊚, those with cracks in 3 to 4t are ◯, 5t.
The sample with cracks was rated Δ, and the sample with cracks was rated x. Generally, if the evaluation score is ◯ or more, it can be put to practical use for a precoated steel sheet.

In the moisture resistance test, the wetting test set at a test temperature of 49 degrees was continued for 500 hours in accordance with JIS Z0208. After the test, the coating film was observed, and the one in which no blistering occurred was evaluated as ◯, and the one in which blistering was detected was evaluated as x. In the stain resistance test, a red line and a black line were drawn on the surface of the coating film with an oil-based ink, and after standing at 20 ° C for 24 hours
The red and black lines were wiped off with methanol. The one that was wiped off without any marks had a score of 5, and the one with some traces left had a score of 3,
The stain resistance was evaluated with a score of 1 showing a marked trace.
Usually, if the red line drawn with the oil-based ink has a rating of 2 or more, it can be put to practical use as a steel sheet for precoating. In the scratch resistance test, in accordance with JIS K5400-8.4,
The paint film surface was scratched using a pencil (manufactured by Mitsubishi Uni-Mitsubishi Pencil Co., Ltd.), and the scratch resistance was evaluated by the pencil hardness which is the limit at which the scratch does not occur.

As can be seen from the survey results in Table 3, the printed coated metal sheet according to the present invention has any of light resistance, coating adhesion, workability, scratch resistance, stain resistance and moisture resistance. Also, satisfactory characteristics were obtained. Especially, when orthophthalic acid and / or neopentyl glycol was used as a monomer, the light resistance was further excellent.

On the other hand, the printed metal sheet of Comparative Example was inferior to any one or more of light resistance, coating adhesion, workability, scratch resistance and stain resistance (Table 4). . That is, test number 1 using a polyester resin having a small molecular weight was inferior in coating film adhesion and processability, and conversely, test numbers 2 and 7 to 9 using a polyester resin having a large molecular weight had insufficient light resistance. . Also, glass transition temperature (Tg)
The coating film surface of Test No. 3 having a low glass number was easily scratched, and the workability of Test No. 4 having a high glass transition temperature (Tg) was poor.
Further, Test No. 5 with a low melamine content is inferior in light resistance and stain resistance, and conversely Test No. 6 with a high melamine content.
Then there was a problem in workability.

[0040]

[0041]

[0042]

As described above, the coated metal plate for sublimation dye transfer printing of the present invention is made of a thermosetting polyester resin having specified molecular weight, glass transition temperature (Tg) and melamine content. The top coating film is provided on the base metal plate directly or via the base coat layer and the primer layer. Since the top coating film has excellent light resistance and processability and is easily dyed with a sublimable dye, a clear and deep printed pattern having excellent light resistance can be provided. When the coated metal plate for sublimation dye transfer printing of the present invention is used in this way, it is suitable for small-lot production of a wide variety of products and has a good design, full-color advertising signs, decorative interior materials, decorative flooring materials, and decorative covering materials. Designed steel sheets used in a wide range of fields such as materials, elevator door materials, outer panels for home appliances, outer panels for furniture, etc. are manufactured.

[Brief description of drawings]

FIG. 1 shows a cross section of a coated steel sheet for sublimation dye thermal transfer according to the present invention, in which an example (a) in which an overcoat coating film 4 provided through a base coat layer 2 is dyed, a primer layer 3 and a base coat layer 2 are shown. Example (b) in which the top coating film 4 provided through the above is dyed, and example (c) in which the clear coating film 4 directly provided on the base steel plate 1 is dyed.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09D 167/02 C09D 167/02 (56) References JP-A-6-287509 (JP, A) JP-A-8-318592 (JP , A) JP 2000-204483 (JP, A) JP 11-1148047 (JP, A) JP 4-150976 (JP, A) JP 6-157979 (JP, A) JP 9 -206678 (JP, A) Actual development Sho 55-23770 (JP, U) Special table HEI 9-507094 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B05D 1/00- 7/26 B32B 1/00-35/00 C09D 167/00-167/08

Claims (2)

(57) [Claims] 1. A number average molecular weight from 1,000 to 10,000, a glass transition temperature (Tg) 20 to 60 ° C., the ratio of melamine relative to the resin solids 100 parts by Ah at 20 to 150 parts by weight
Therefore, 1,2-benzes derived from dicarboxylic acid type monomers
-Dicarbonyl structure and / or dialcohol-based monomer
2,2-dimethyltrimethylene structure derived from
Sublimation dye with excellent light resistance, characterized in that a top coating film formed from a transparent or semitransparent coating containing a thermosetting polyester resin as a main component contained in a part of the structure is provided on the surface of the metal plate. Painted metal plate for transfer printing. 2. A triazine-based ultraviolet absorber and benzot
Topcoat with lysol-based UV absorbers alone or in combination
The coated metal plate for sublimation dye transfer printing according to claim 1, which is contained in a coating film .