JP3532443B2 - Printed metal plate with excellent slip and abrasion resistance - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a full-color advertising billboard,
It is used for decorative interior materials, decorative flooring materials, elevator door materials, outer panels for home appliances, outer panels for furniture, etc., and is related to printed coated metal sheets with various slip patterns and excellent abrasion and abrasion resistance. .

[0002]

2. Description of the Related Art When manufacturing a printing coated metal plate using a sublimable dye, after printing the sublimable dye on the top clear layer of the coated metal plate by a printing method such as offset, silk, gravure or transfer. , The sublimation dye is permeated into the clear coating film by heat treatment. For pattern printing using a sublimable dye, a method in which a transfer sheet is brought into contact with a coating film of a curable synthetic resin layer and heated (Japanese Patent Laid-Open No. 51-24313), coating by transfer printing using a sublimable dye is performed. After forming a printing layer on a metal plate, a top coating film is formed on the surface, and then a sublimation dye is permeated from the inside of the coating film by heat treatment (JP-A-54-104907). A method of impregnating a thermally sublimable ink into the coating film of a prepainted metal plate having a primer coating film and a colored top coating film formed thereon (JP-A-7-31931), and an opaque resin layer provided on the metal plate substrate. There is a method of infiltrating a sublimation type colorant into the inside of the resin (JP-A-7-102733).
In both methods, a pattern is developed by infiltrating a sublimable dye into the top coating film. However, ordinary clear coatings are smooth and have high gloss and sharpness, but they are prone to scratches and have insufficient scratch resistance, abrasion resistance, and slip resistance. It is difficult to apply it to a markedly flawed area.

The scratch and abrasion resistance of the coating is improved by the addition of inorganic aggregate. For example, a powder coating containing 5 to 70% by weight of fibrous glass to improve wear resistance and scratch resistance (Japanese Patent Laid-Open No. 48-66640),
A paint for precoated steel sheets having a wear resistance and a scratch resistance improved by blending 0.3 to 50% of glass flakes having a thickness of 3 μm or less and passing through a 150-mesh sieve (JP-A-51-
No. 8128), using an acrylic resin coating composition containing 5 to 60 parts by weight of an inorganic aggregate having an average particle size of 3 to 30 μm with respect to 100 parts by weight of the solid content of the color-developing agent in the coating film. A coated metal plate (Japanese Patent Application Laid-Open No. 8-183926) and the like which are excellent in stain resistance are known. However, in both cases, the transparency of the coating film is poor, and it is difficult to make full use of the designability of the underlying metal or the undercoat coating film. Further, although it is excellent in scratch resistance and abrasion resistance, sufficient characteristics are not obtained in terms of slip resistance.

As for the scratch resistance and abrasion resistance, electron beam curable acrylic paints (Japanese Patent Publication No. 55-5422, Japanese Patent Publication No. 56-8070, Japanese Patent Laid-Open No. 1-229622, Japanese Patent Laid-Open No. 2-242863). It is also improved by irradiation with an electron beam or the like. Since the coating film irradiated with the electron beam has a pencil hardness of 9H or higher, the coating film has excellent abrasion resistance, scratch resistance, and stain resistance. However, the processability of the coating film is low, an expensive coating material is required, and a special electron beam irradiation facility for curing the coating film is required, resulting in high manufacturing cost. Another drawback is that the coating film cured by electron beam irradiation is inferior in weather resistance to the thermosetting coating film.

By the way, it is difficult to make a full-color design using a sublimable dye for vinyl chloride tiles, vinyl chloride sheets, etc., which are often used as flooring materials of organic materials, in terms of dimensional stability, heat resistance and the like. It is a good material. On the other hand, there is almost no decorative flooring material that combines the metallic feel of the underlying metal plate and the full-color design. Many table tops are also made of wood, and there are almost no full-color design products with a metallic design on the front. Full-color advertising flooring materials are generally manufactured by simple small-lot post-processing by applying a film. According to this method, since the film end surface is easily peeled off, it is difficult to use it as a signboard for advertising for a long period of half a year or more. In addition, it is difficult to increase the hardness of the film and improve the scratch resistance due to the problem in construction in which the film is attached in the subsequent step. Moreover, since the appearance depends on the texture of the film, it is not possible to give a design expressing a metallic feeling or a ceramic feeling.

[0006]

The present invention has been devised to solve such a problem, and forms a transparent or semitransparent topcoat film containing flaky glass and calcium silicate. In view of the above, it is an object of the present invention to provide a printed and coated metal plate that is capable of full-color printing and that has improved slip resistance and abrasion resistance, making full use of the design properties of the underlying metal or the undercoat coating film. The printing coated metal plate of the present invention,
In order to achieve that purpose, the thickness is 8
A film formed from a top-coat paint containing 5 to 25% by weight of flaky glass having an average diameter in the longitudinal direction of 10 to 70 μm and 0.5 to 10% by weight of calcium silicate having an average primary particle size of 1 to 8 μm. Thickness 5-40 μm, surface roughness Ra1.
A transparent or semi-transparent top coat film having a thickness of 0 to 6.0 μm is provided on the surface layer, and the top coat film is printed by permeation of a sublimable dye. It is preferable that a triazine-based ultraviolet absorber and / or a benzotriazole-based ultraviolet absorber be blended in the coating material that forms the top coat film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A printed metal plate according to the present invention is provided with a base coat layer 2 and a primer layer 3 on the surface of a base metal plate 1 as shown in FIG. A transparent top coat film 4 is formed. As long as there is a top coat film 4 on the surface layer, the base metal plate 1 and the top coat film 4
A printed coating metal plate (a) having a base coat layer 2 provided between the base metal plate 1 and the base metal plate 1 and a base metal plate 1 having a base coat layer 2 and a primer layer 3 provided therebetween. It may be any of the printing coated metal plates (c) in which the top coating film 4 is directly provided. The base coat layer 2 is not limited to white, and may have other color tones including a clear coating film.

The transparent or semi-transparent top coating film 4 has 5 to 4
It is formed with a film thickness of 0 μm. If the film thickness is less than 5 μm, sufficient abrasion resistance cannot be obtained. On the other hand, if the film thickness exceeds 40 μm, the solvent remaining in the coating during evaporation will evaporate rapidly,
There is a risk that pinhole-shaped coating film defects called "sideways" may occur. Further, when the thickness is more than 40 μm, the transparency of the coating film is impaired, and the metallic luster of the base metal plate 1 and when the undercoating film is formed, the designability of the undercoating film cannot be sufficiently exhibited. . The film thickness of the top coating film 4 is preferably in the range of 10 to 25 μm in view of the balance between slip resistance and wear resistance. In applications such as flooring materials where a large amount of wear is expected due to use, a clear coating layer can be further provided as an overcoat in consideration of wear. The hardness of the coating film can be increased by adding a curing agent such as melamine, urea, or isocyanate to the coating film.

The top coat film 4 is made of glass flakes having a thickness of 8 μm or less and an average diameter in the longitudinal direction of 10 to 70 μm.
Weight% is included. 5% by weight of flaky glass
If it does not satisfy the above condition, the pencil hardness of the coating film becomes F or less, and sufficient coating film hardness cannot be secured. Moreover, since flaky glass beads are scattered on the surface of the coating film, unevenness on the surface of the coating film becomes sparse and the appearance is deteriorated. On the contrary, if a large amount of glass flakes exceeding 25% by weight is blended, the opacity of the coating film becomes strong,
The surface roughness also tends to decrease. The glass flakes mixed in the coating film are regulated to have a thickness of 8 μm or less and an average diameter in the longitudinal direction of 10 to 70 μm in consideration of the required properties of the coating film and coating workability. When the glass flakes having a thickness of more than 8 μm are blended, not only the coating film is easily broken when the printed and coated metal plate is bent, but also it is easily removed by abrasion. Thick glass flakes are liable to settle in the paint, which adversely affects the coating workability. When the average diameter in the longitudinal direction of the glass flakes exceeds 70 μm, the glass flakes easily fall off the coating film surface after coating. Conversely 10
If the average diameter is less than μm, it becomes difficult to obtain a coating film having a surface roughness Ra of 1.0 μm or more.

The top coating film 4 has an average primary particle size of 1 to 8 μm.
m calcium silicate is added. Calcium silicate has a particle size of 15 to 50 μ due to the secondary aggregation of primary particles in the paint.
m becomes aggregated particles, and a coating film is formed in the aggregated state, which contributes to improvement of slip resistance. If the average primary particle size exceeds 8 μm, the secondary particles are likely to settle and the coating workability deteriorates.
On the contrary, if the primary particle size does not reach 1 μm, the secondary particle size also becomes small, so that sufficient slip resistance cannot be obtained. Calcium silicate is 0.5 to 10% by weight (preferably 1.5 to 5).
(% By weight) is added to the top coat film 4. If it is less than 0.5% by weight, sufficient slip resistance due to calcium silicate cannot be obtained. On the other hand, if the blending amount exceeds 10% by weight, the transparency of the coating film is impaired, and the metallic luster of the base metal plate 1 or the design of the undercoating film is not sufficiently exhibited in the case where the undercoating film is formed. The topcoat coating film 4 preferably has a coating film hardness of 2H or more in a baked and cured state. In the coating film, a curing agent such as methylated melamine or butylated melamine for increasing the coating film hardness, or a curing catalyst such as a sulfonic acid compound for curing the coating film in a short time may be added. good. The color tone of the top coat film 4 is preferably as transparent as possible so that the metallic luster of the base metal plate 1 or the undercoat film is formed so that the design property of the undercoat paint is sufficiently exhibited.

The type of the coating material for forming the transparent or semi-transparent top coat film 4 is not particularly limited as long as it is a resin that can be dyed well by receiving the sublimable dye transferred from the transfer sheet. Specifically, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl acetate, polyvinyl chloride, polyvinyl pyrrolidone, vinyl resins such as polystyrene, polymethyl (meth) acrylate, polybutyl (meth) acrylate,
Acrylate resins such as polyacrylamide and polyacrylonitrile, polyester resins, polycarbonate resins, polyurethane resins, polyamide resins, urea resins, polycaprolactone resins, polyarylate resins, polysulfone resins, silicone polyester resins, epoxy resins, etc. Polymers or mixtures are used as dyeable resins. Among them, the polyester resin is excellent in dyeability to a sublimable dye, and the storage stability of the obtained print design is also good, so that it is preferable to include it as one component of the dyeable resin.

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 refers to a dye that can be transferred 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 such as Kayaset Yellow AG, Kayaset Ye
llow TDN (Nippon Kayaku Co., Ltd.), RTY 52, Di
anixYellow 5R-E, Dianix Yellow F3G-E, Dianix Bri
lliant Yellow 5G-E (above, Mitsubishi Chemical Co., Ltd.), Blast Yellow 8040, DY108 (above, Arimoto Chemical Co., Ltd.), Sumikaron Yellow EFG, Sumikaron Yellow E-4GL
(Above, Sumitomo Chemical Co., Ltd.), FORON Brilliant Ye
llow SGGLPI (manufactured by Sand), PS Yellow GG (manufactured by Mitsui Toatsu Dye Co., Ltd.) and the like. For magenta sublimation dyes, Kayaset Red 026, Kayaset Red 130, Kayase
tRed B (Nippon Kayaku Co., Ltd.), Oil Red DR-9
9, Oil Red DK-99 (Arimoto Chemical Co., Ltd.), Di
acelliton Pink B (manufactured by Mitsubishi Chemical Corporation), Sumikaro
n Red E-FBL (Sumitomo Chemical Co., Ltd.), Latyl Red B
(Manufactured by Du Pont), Sudan Red 7B (manufactured by BASF), Resolin Red FB, Ceres Red 7B (above, Baye
r company) and so on. For cyan dyes, Kayalo
n Fast Blue FG, Kayalon Blue FR, Kayaset Blue 136,
Kayaset Blue 906 (Nippon Kayaku Co., Ltd.), OilBlue 63 (Arimoto Chemical Co., Ltd.), HSB9, RTB
31 (above, Mitsubishi Chemical Corporation), Disperse Blue # 1
(Sumitomo Chemical Co., Ltd.), MS Blue 50 (Mitsui Toatsu Dyestuff Co., Ltd.), Ceres Blue GN (Bayer Co., Ltd.), Dura
There is nol Brilliant Blue 2G (manufactured by ICI).

The sublimable dyes for each color may be used alone or in two.
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 used. When selecting a sublimable dye, a dye having a high sublimation temperature is preferable because it has a relatively high molecular weight and thus imparts excellent light resistance and heat resistance to the coating film. When the transfer sheet is heated while being in contact with the underlying metal plate 1, the sublimable dye contained in the transfer sheet sublimes and penetrates the transparent or semitransparent top coat film 4 in the thickness direction as shown in FIG. 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. According to this method, a required pattern can be easily applied when needed, so that small-lot production of a design steel sheet having 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.

As the transparent or semi-transparent top coat film 4,
It is preferable to use a thermosetting resin that does not significantly soften at a heating temperature of 150 to 200 ° C. when transferring a printed pattern. The resin having good heat resistance effectively suppresses the reduction of the surface gloss of the printed and coated metal plate after the printed pattern is formed by thermal transfer. When an ultraviolet absorber is added to the transparent or semi-transparent top coat film 4, a decrease in adhesion and discoloration due to the transmission of sun rays, ultraviolet rays and the like are suppressed. The ultraviolet absorber contained in the top coating film 4 is required to have excellent heat resistance, sublimation resistance and solubility. Above all, it is preferable to exhibit heat resistance such that the weight loss at 300 ° C. is 10% by weight or less under heating conditions in an air atmosphere at a heating rate of 5 ° C./min. Ultraviolet absorbers that satisfy the required characteristics include benzotriazole type and triazine type. Preferably, a triazine type alone or a mixture of a triazine type and a benzotriazole type is added to the coating material for the top coat film 4. Further, the hindered amine light stabilizer can be blended in a proportion of 0 to 3.0% by weight.

Examples of the benzotriazole type ultraviolet absorber include 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
Condensate of-[3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propinate 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 (Viosorb 59 manufactured by Kyodo Pharmaceutical Co., Ltd.
0) and the like.

Examples of the triazine-based UV absorber include 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) and the like. These ultraviolet absorbers can be used alone or in admixture of two or more. The amount of UV absorber blended is 1 to 1 with respect to the non-volatile components of the paint.
It is preferably adjusted to 8% by weight. If the blending amount exceeds 18% by weight, the stain resistance, workability, and appearance of the coating film tend to 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 coat 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 paint, if necessary. . Examples of the hindered amine light stabilizer include the following substances. Screw (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 (SANOL LS2626 manufactured by Sankyo Co., Ltd.), 4-benzoyloxy-2,2,6,6-tetra. Methylpiperidine (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 LS440 manufactured by Sankyo Co., Ltd.), 2- (3,5-di-t
-Hydroxybenzyl-2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) (TINUVIN 144 manufactured by Ciba-Geigy), bis (2,2,6,6-tetramethyl-succinate) 4-piperidyl)
Ester (TINUVIN 780FF manufactured by Ciba Geigy), 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]} (manufactured by Ciba Geigy)
CHIMASSORB 944LD), N, N'-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6 A polycondensation product of chloro-1,3,5-triazine (CHIMASSORB 119FL manufactured by Ciba Geigy),
Bis (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.), ADK STAB LA-52, ADK STAB LA
-57, ADEKA STAB LA-62, ADEKA STAB LA
-63, ADEKA STAB LA-67, ADEKA STAB L
A-68, ADEKA STAB LA-82, ADEKA STAB
LA-87 (Asahi Denka Kogyo 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 is saturated and the improvement commensurate with the increase in the amount is not seen, but rather the coating appearance tends to deteriorate. The light stabilizer is preferably added in the range of 0.5 to 1.5% by 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 directly on the base metal plate 1 (FIG. 1c). be able to. In either case, the color tone of the base metal plate 1 and the base coat layer 2 becomes a ground pattern, and a printed and painted metal plate having a unique depth feeling by utilizing the texture of the base material can be obtained.

[0020]

Example 1 The top coating film 4 was directly provided on the base metal plate 1.
Production of printed coated steel sheet (Examples 1 to 11 of the present invention, Comparative examples 1 to 4, 7 to 12: FIG. 1)
c) After degreasing, surface conditioning treatment and coating type chromate treatment on a SUS304HL stainless steel plate having a plate thickness of 0.5 mm, a semitransparent topcoat paint is applied so that the dry film thickness is 16 μm, and the plate temperature is 230 ° C. A semi-transparent resin coating film (top coating film 4) was formed by baking for 1 minute. As the top-coat paint, the thickness is 4-12μ based on the paint non-volatile component.
m, 3 to 30% by weight of glass flakes having an average diameter in the longitudinal direction of 45 to 90 μm, 0.3 to 12% by weight of calcium silicate having an average primary particle size of 3.5 to 8 μm, and a triazine-based UV absorber (Ciba Geigy). A polyester paint containing 6% by weight of TINUVIN 400 manufactured by K.K. was used. A sublimation dye toner (a toner for sublimation printing manufactured by Nippon Steel Chemical Co., Ltd.) is used as a transfer sheet, and a pattern pattern is output on the electrostatic recording paper by an electrostatic plotter type image printing system (Juana manufactured by Exis Co., Ltd.). The transfer sheet produced by the above was used. The transfer sheet is superposed on the top coating film 4 formed on the base metal plate 1, and the temperature is 160 ° C. and the pressure is 0.5 k.
It was thermocompression-bonded for 240 seconds at g / cm ² . After crimping,
The electrostatic recording paper was peeled off from the base metal plate 1.

Form the top coat film 4 through the base coat layer 2
Manufacture of printed and coated steel sheets (Examples 12 to 15 of the present invention, Comparative Examples 5 to 6: FIG. 1b) of hot dip galvanized steel sheets having a thickness of 0.5 mm were subjected to degreasing, surface conditioning treatment, and coating chromate treatment. A white polyester resin coating material was applied so that the dry film thickness was 18 μm, and baked at a plate temperature of 220 ° C. for 1 minute to form a white base coat layer 2. 5 to 25% by weight of flaky glass having a thickness of 4 to 12 μm and an average diameter in the longitudinal direction of 45 to 90 μm on the basis of non-volatile components of the coating, and an average primary particle diameter of 3.5 to 8 μ
0.5-10% by weight of calcium silicate, triazine-based UV absorber (TINUVIN 400 manufactured by Ciba-Geigy)
Was applied to a dry film thickness of 16 μm and baked at a plate temperature of 230 ° C. for 1 minute to form a semitransparent topcoat coating film 4. A pattern was printed on the top coating film 4 formed on the surface of the metal plate by using a transfer sheet in the same manner. The coating film structures of the obtained coated steel sheets are shown in Table 1 (Example of the present invention) and Table 2 (Comparative example).

[0022]

[0023]

Performance Test of Printed Coated Steel Plates The adhesion, coating hardness, workability, slip resistance, abrasion resistance, surface roughness and transparency of the coated films of each of the obtained printed coated metal plates were investigated. . In the coating film adhesion test, a cross-cutting Erichsen (6 mm extruding with a cross-cutting sheet specified in JIS G3320) test was performed, and the peeling state of the coating film layer was evaluated by 5 levels by peeling the adhesive tape. 2 in the workability test
A 180 degree bending process of 0 to 6 t (1 t when one plate having the same thickness as the test piece is sandwiched) was applied in a room at 0 ° C. After observing the surface of the coating film after bending, the cracks were not detected at 0 to 2t, the cracks were generated at 3 to 4t, the cracks were generated at 5t, and the cracks were cracked at 6t. The occurrence of was evaluated as x. Generally, if the evaluation score is ◯ or more, it can be put to practical use for a precoated steel sheet.

The coating film hardness is JIS-K-5400-6-
According to 8.4, a flawing method using Mitsubishi Uni (manufactured by Mitsubishi Pencil Co., Ltd.) was investigated, and evaluation was made with a pencil hardness that is the limit without flaws. In the slip resistance test, the static friction coefficient and the dynamic friction coefficient were measured using a spring type dynamic slip tester. The test piece was attached under the threat metal, and a neoprene rubber plate having a thickness of 5 mm and a Shore A hardness of 60 was attached on the sliding plate. A predetermined weight was placed on the threat metal to adjust the total weight to 800 g, and the weight was moved on the slide plate. Then, according to the following formula, the static friction coefficient was obtained from the maximum static friction force at the moment when the threat metal started to slide, and the dynamic friction coefficient was calculated from the kinetic friction force at the time point 20 seconds after the start of sliding of the threat metal. Static friction coefficient or dynamic friction coefficient = F / P, where F: maximum static friction force or kinetic friction force P: total weight of threat metal and weight

In the abrasion resistance test, a hole having a diameter of 6 mm was made in the center of a test piece having a diameter of 120 mm, and after the weight was measured, it was attached to a Taber abrasion tester. After rotating 200 times, the weight of the test piece was measured, the wear loss was calculated from the weight difference before and after the test, and the Taber index was calculated according to the following formula. Taber index = wear loss (mg) × 1000 / rotation number (200) The surface roughness of the coating film was measured by a contact surface roughness meter to obtain the center line average roughness Ra. The transparency of the coating film is examined by visual observation, and the top coating film 4 has sufficient transparency to utilize the metallic luster of the base metal plate 1 or the design of the base coat layer 2, and there is some cloudiness. The thing which can utilize the designability of the thing was evaluated as △, and the one whose designability was not utilized because it was opaque was evaluated as x.

The examination results of each test are shown in Table 3 (examples of the present invention) and Table 4 (comparative examples). As is clear from the comparison between Table 3 and Table 4, the printed coated steel sheets of the examples of the present invention are all coating film adhesion, pencil hardness, workability, slip resistance, wear resistance,
It exhibited satisfactory performance in terms of surface roughness and transparency. Further, it was shown that when the amount of calcium silicate added was increased, the slip resistance was improved, but the wear resistance and transparency were decreased. From this, it is understood that it is necessary to determine the addition amount of calcium silicate depending on which of designability, wear resistance and slip resistance is important. Also,
As seen in Table 3, when the amount of the glass flakes added was increased, the coating film hardness tended to increase. On the other hand, in the printed coated steel sheet of the comparative example (Table 4), the coating film adhesion,
One or more of pencil hardness, workability, slip resistance, wear resistance, surface roughness, and transparency was inferior. That is, the test number 1 is inferior in transparency, the test number 2 is inadequate in coating hardness, and the test numbers 3 to 6 are inferior in coating adhesion and workability due to different particle sizes of the flaky glass. In No. 7, since flaky glass having a small average diameter in the longitudinal direction was blended, sufficient slip resistance could not be obtained, and in Test No. 8, sufficient slip resistance could not be obtained because the compounding amount of calcium silicate was small. In No. 9, since the calcium silicate was excessively blended, the transparency of the coating film was insufficient.

[0028]

[0029]

[0030]

Example 2 The top coat film 4 is applied through the base coat layer 2.
Manufacture of Printed Painted Steel Sheets Provided (Invention Examples 16 to 27, Comparative Examples 13 to 17: FIG. 1a) After hot-dip galvanized steel sheet having a plate thickness of 0.5 mm was subjected to degreasing, surface conditioning treatment and coating type chromate treatment, A white polyester resin coating material was applied to a dry film thickness of 18 μm and baked at a plate temperature of 220 ° C. for 1 minute to form a white base coat layer 2. Next, a polyester-based top coating composition was applied so that the dry film thickness was 16 μm, and baked at a plate temperature of 230 ° C. for 1 minute to form a semitransparent top coating film 4. In Examples 16 to 27 of the present invention and Comparative Example 13, 20% by weight of flaky glass having a thickness of 4 μm and an average diameter in the longitudinal direction of 45 μm, based on the non-volatile components of the coating,
5% by weight of calcium silicate having an average primary particle size of 3.5 μm, triazine-based UV absorber (TIBA manufactured by Ciba Geigy)
NUVIN 400) and / or benzotriazole type ultraviolet absorber (TINUVIN 384 manufactured by Ciba Geigy) 0 to 9% by weight, hindered amine light stabilizer (Ciba Geigy manufactured by Ciba Geigy)
TINUVIN 123) was added as a top-coat paint in a semi-transparent polyester paint containing 1.5% by weight. Comparative Example 14-
In 17, the same procedure was performed except that a benzophenone-based UV absorber (Viosorb 130 manufactured by Kyodo Yakuhin Co., Ltd.) was used instead of the triazine-based UV absorber and the benzotriazole-based UV absorber in an amount of 1 to 9% by weight based on the nonvolatile content of the paint. To form a top coating film 4.

Each ultraviolet absorber used was placed in an air atmosphere,
Heating to 300 ° C at a temperature rising rate of 5 ° C / min for thermogravimetric analysis,
The weight loss rate at 300 ° C was determined. The weight reduction rate is 3.5% by weight for the triazine-based UV absorber, 5% by weight for the benzotriazole-based UV absorber, and 33% by weight for the benzophenone-UV absorber. The triazine-based UV absorber and the benzotriazole-based UV absorber The excellent weather resistance and heat resistance of the agent were confirmed. Cyan-based sublimation dye RTB31
Using a sublimation dye toner (toner for sublimation printing manufactured by Nippon Steel Chemical Co., Ltd.) made from CIDisperse Blue 26 (manufactured by Mitsubishi Chemical Co., Ltd.), an electrostatic plotter type image printing system (Juana manufactured by Exis Co., Ltd.) was used. A solid pattern of cyan was output on the electrophotographic recording paper. The obtained electrostatic recording paper was superposed on the coated surface of the coated steel sheet and thermocompression-bonded at a temperature of 160 ° C. and a pressure of 0.5 kg / cm ² for 240 seconds. After completion of the pressure bonding, the electrostatic recording paper was peeled off from the coated steel sheet. In addition,
Comparing the light resistance of cyan, magenta, and yellow dyes that sublimate under almost the same conditions, the light resistance of the cyan dye is the lowest. Therefore, the effect of adding an ultraviolet absorber and a light stabilizer is compared with the light resistance of the cyan dye. Compared.

Performance Test of Printed Painted Steel Sheets Produced Test pieces were cut out from each of the produced print coated steel sheets and examined for light resistance. In the light resistance test, the test piece was left for 240 hours under the condition of spraying fresh water for 12 minutes during irradiation for 60 minutes in a sunshine carbon arc weather meter set at 63 ° C. The cyan color tone of the test piece after the test was measured, and the color difference ΔE from the unirradiated test piece was obtained. Further, in the same manner as in Example 1, the test piece after the test was examined for coating film adhesion and workability. The examination results are shown in comparison with Table 5 (Example of the present invention) and Table 6 (Comparative example). The printed coated steel sheet of the present invention (Table 5) exhibited sufficiently satisfactory properties in light resistance, coating film adhesion, and workability. Above all,
The system in which the triazine-based UV absorber and the benzotriazole-based UV absorber were mixed at a ratio of 1: 1 tended to have improved light resistance as compared with the system in which each was blended alone. On the other hand, the printed coated steel sheet of Test No. 13 to which the ultraviolet absorber was not added was inferior in all of light resistance, coating adhesion and workability. Further, Test Nos. 14 to 1 in which a benzophenone-based UV absorber was mixed in place of the triazine-based UV absorber or the benzotriazole-based UV absorber
In the printed coated steel sheet of No. 7, sufficient light resistance was not obtained.

[0033]

[0034]

[0035]

As described above, the printed coating metal plate of the present invention has a transparent or semi-transparent top coating film.
The design characteristics of the underlying metal or the undercoating film can be fully utilized, and it is also excellent in slip resistance and abrasion resistance. Moreover, because it is transfer printing using a sublimable dye, it is possible to produce a large number of small lots, and in combination with it, it becomes a printed coated metal plate with various patterns to meet various needs. . The printing-coated metal sheet thus obtained makes full use of its excellent properties, and is used for full-color advertising signs, decorative interior materials, decorative flooring materials,
It is used for elevator door materials, outer panels for home appliances, and outer panels for furniture.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a surface layer portion of a printed and coated metal plate according to the present invention, showing an example (a) in which a transparent or semitransparent topcoat coating film 4 is provided on a base coat layer 2, a primer layer 3 and a base coat layer 2. Example (b) in which a transparent or semitransparent topcoat coating film 4 is provided on the base metal plate 1
Example with (c)

Front page continuation (51) Int.Cl. ⁷ Identification code FI B32B 15/08 B32B 15/08 G 27/18 27/18 Z 27/20 27/20 Z C09D 5/00 C09D 5/00 Z C09K 3 / 14 540 C09K 3/14 540C 540D (56) Reference JP-A-9-201929 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C23C 26/00 B05D 5/00 B05D 5 / 06 101 B05D 7/14 B05D 7/24 303 B32B 15/08 B32B 27/18 B32B 27/20 C09D 5/00 C09K 3/14 540

Claims (2)

(57) [Claims] 1. A thickness of 8 μm or less on the basis of non-volatile components of a paint,
Flake glass with an average diameter of 10 to 70 μm in the longitudinal direction is 5 to
25% by weight and 0.5-10% by weight of calcium silicate having an average primary particle size of 1-8 μm were mixed to form a film having a thickness of 5-40 μm and a surface roughness Ra of 1.0-6.0.
A printing-coated metal sheet having excellent slip resistance and abrasion resistance, in which a transparent or semitransparent top coat film having a thickness of μm is provided on the surface layer, and the top coat film is printed by permeation of a sublimable dye. 2. The printing-coated metal plate according to claim 1, wherein a triazine-based ultraviolet absorber and / or a benzotriazole-based ultraviolet absorber is incorporated in the topcoat paint.