JPH11277996A - Metal plate for sublimation printing and decorative metal plate - Google Patents

Abstract

(57) [Problem] To provide a metal plate for sublimation printing and a decorative metal plate which is excellent in light resistance and does not need to cover an image receiving surface with an ultraviolet blocking layer. In addition, the present invention provides a metal plate for sublimation printing and a decorative metal plate capable of forming a high-density image without causing heat fusion with sublimation printing paper, in addition to being excellent in light resistance. SOLUTION: A dye-receiving layer containing a high heat-resistant ultraviolet inhibitor for reducing discoloration of a sublimation dye due to ultraviolet rays is provided on a metal substrate of a metal plate for sublimation printing. Further, by using a polyester-based resin, an acrylic-based resin, or a urethane-based resin having a glass transition temperature of 120 ° C. or more as the binder resin for the dye-receiving layer, thermal fusion is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative metal plate (decorative metal plate) and a metal plate for sublimation printing used for producing the same. More specifically, the present invention relates to a decorative metal plate which does not require an ultraviolet blocking layer on an image receiving surface, and a metal plate for sublimation printing.

[0002]

2. Description of the Related Art A decorative metal plate, especially a decorative steel plate, having an image such as a picture or a grain pattern is used for kitchen utensils such as system kitchens, furniture such as storage furniture, architectural interior materials, cabinets for light electrical equipment, and the like. ing. As a method of forming an image such as a pattern or pattern on the surface of a metal plate to produce a decorative metal plate, an image is directly printed on the surface of a metal base material by offset printing, gravure printing, or the image is printed. For example, laminating the resin film thus formed on the surface of the metal substrate via an adhesive layer. JP-A-6-247097 describes a method of forming an image on a surface of a metal substrate using an on-demand printer such as an electrostatic plotter or an inkjet printer without using a printing plate. . Also, JP-A-6-246870 discloses that an image is output on the surface of a resin film by using an on-demand printer such as an electrostatic plotter or an ink jet printer, and the resulting patterned resin film is coated with a metal substrate. The method of lamination is described above.

[0003] As another method, an image is formed on a recording paper for textile printing using a pigment ink by offset printing, gravure printing, or an on-demand type printing method, and the obtained pigment printed paper is adhered to a metal substrate. It is also known to transfer an image to the surface of a metal substrate by heating or pressurizing. However, pigments are not transparent. For this reason, when performing pigment printing on a metal substrate, the color and texture of the base are concealed due to the formed image. Cannot be expressed sufficiently.

In JP-A-49-17450, an image is gravure-printed on a recording paper for printing using a sublimation dye, and the obtained sublimation printing paper and a metal substrate are brought into close contact with each other and heated. A method for transferring a highly transparent image to the surface of a metal substrate has been proposed. The metal substrate is
No dyeing property for sublimation dyes. For this reason, in order to perform sublimation printing on a metal substrate, a dye receiving layer is provided on the metal substrate. Then, the dye receiving layer forming surface of the metal substrate and the image printing surface of the sublimation printing paper face each other and are brought into close contact with each other,
The image is transferred by heating. Since the sublimation dye has high transparency, the sublimation printing can produce a decorative metal plate that makes full use of the metallic luster of the base. In addition, when the transparency of the image is high, the intermediate color reproduced by overlapping the colors becomes beautiful.

[0005]

[0005] Metal decorative boards are often used as parts of durable consumer goods. However, sublimation dyes have poor light fastness as compared with pigments, and are easily discolored when irradiated with light rays. Therefore, in order to perform sublimation printing on a printing metal plate, it is necessary to enhance the light resistance of an image. It is conventionally known that after performing sublimation thermal transfer to a thermal transfer image receiving sheet, an ultraviolet blocking layer containing an ultraviolet absorbent is formed on the image receiving surface to improve the light fastness of the printed matter. However, if the ultraviolet blocking layer can be omitted, it is preferable.

In addition, if an organic solvent is used when forming the ultraviolet blocking layer, problems such as damage to the dye receiving layer and blurring of the image on the receiving layer are likely to occur. Therefore, in order to form an ultraviolet shielding layer, for example, a resin composition containing a binder resin and an ultraviolet absorbent for an ultraviolet shielding layer is melted and extruded or laminated, or a similar resin composition is formed into an aqueous emulsion. It is necessary to form an ultraviolet blocking layer without using an organic solvent by a method such as coating. For this reason, a special device and a drying system are required, and the number of steps is increased. From the viewpoint of cost, it is desirable to omit the coating after image formation as much as possible.

Further, the present inventors output images on recording paper using an on-demand type printing system using an electrostatic action such as an electrostatic plotter or an ion printer, using a wet developer in which a sublimation dye is dispersed. Thus, a sublimation printed paper was produced. Then, using the obtained sublimation printing paper, sublimation printing was performed on the dye receiving layer of the metal substrate.

However, when the dye receiving layer forming surface of the metal substrate and the image output surface of the sublimation printing paper face each other and are closely contacted and heated, the result is that the sublimation printing paper and the dye receiving layer are likely to be thermally fused. became. When the printed paper is forcibly removed from the metal substrate, in a severe case, the so-called abnormal transfer occurs in which the image output surface of the printed paper is thinly peeled off and remains on the dye receiving layer. In addition, when the heating temperature at the time of transfer is reduced to avoid thermal fusion between the sublimation printing paper and the dye receiving layer, the transfer of the sublimation dye is reduced, and the density of the transferred image becomes insufficient. .

The present invention has been accomplished in view of the above circumstances, and a first object of the present invention is to provide a metal plate for sublimation printing which does not require the formation of an ultraviolet shielding layer after sublimation printing, and An object of the present invention is to provide a decorative metal plate which is excellent in light resistance even without a blocking layer. Further, a second object of the present invention is to provide a sublimation printing metal plate capable of forming a high-density image without causing thermal fusion with a sublimation printing paper, in addition to not requiring an ultraviolet blocking layer, and The object of the present invention is to provide a decorative metal plate having an image formed of a sublimation dye and having a high density, and having excellent light resistance even if the image of the sublimation dye is not protected by an ultraviolet blocking layer. .

[0010]

In order to solve the above-mentioned first object, in the present invention, a highly heat-resistant UV inhibitor which reduces discoloration of a sublimation dye due to ultraviolet rays is contained on a metal plate substrate. And a decorative metal plate formed by performing sublimation printing on the metal plate for sublimation printing, wherein the metal plate has at least a dye receiving layer formed thereon.

When a dye-receiving layer forming the image receiving surface of a metal plate for sublimation printing is added with an ultraviolet blocking agent for reducing discoloration of the sublimation dye due to ultraviolet light, the light resistance of the printed and transferred image is improved. Discoloration is less likely. As a result, there is no need to cover the image receiving surface of the finished decorative metal plate with the ultraviolet blocking layer. As the ultraviolet blocking agent, for example, an ultraviolet absorbing substance and / or an ultraviolet reflecting substance can be used.

When performing sublimation printing, the dye-receiving layer comprises:
Since the dye is heated to a temperature close to or higher than the sublimation temperature of the dye, the ultraviolet blocking agent must also have high heat resistance. It is preferred that the UV-blocking agent is such that it still retains the ability to reduce discoloration of the sublimation dye, even after heating during sublimation printing. When performing sublimation printing, the printed paper is often heated to 160 ° C. or higher. Therefore, it is preferable to use an ultraviolet blocking agent which has a capability of reducing discoloration of a sublimation dye even after being heated to a high temperature of 160 ° C. or more. An inorganic ultraviolet blocking agent is suitably used as the high heat resistant ultraviolet blocking agent as described above. Among them, zinc oxide and / or titanium oxide are particularly preferable. The ultraviolet blocking agent is preferably added at a ratio of 10 to 50% by weight based on the weight of the solid content of the dye receiving layer.

[0013] Further, by forming an underlayer to which a pigment is added between the metal plate substrate and the dye receiving layer, it is possible to adjust the feel and the ground color of the base of the decorative metal plate. When sublimation printing is performed, the transparency of the sublimation dye is high, so that the metal plate substrate below the image may be seen through. Therefore, in the case of sublimation printing, it is extremely effective to add a pigment to form an underlayer whose ground color and texture are adjusted.

In the present invention, in order to solve the above-mentioned second object, a polyester resin, an acrylic resin, or a urethane resin having a glass transition temperature of 120 ° C.
The above is used as a binder resin for the dye receiving layer. These resins may be used alone or in combination of two or more. Since these resins have good dye-dyeability and are less likely to thermally fuse with sublimation printed paper,
In order to increase the transfer amount of the sublimation dye to the dye receiving layer, the transfer heating temperature can be set sufficiently high. As a result, an image having a high density can be formed.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. FIG. 1 is a diagram schematically showing a cross section of an example (1) of a metal plate for sublimation printing according to the present invention. In FIG. 1, the metal plate 1 for sublimation printing of the present invention has a base layer 3 provided on the surface of a metal plate base 2 and a dye receiving layer 4 containing an ultraviolet blocking agent provided on the base layer. It was done.

The metal plate substrate 2 is a known metal plate conventionally used as a decorative metal plate, for example, a steel plate such as a stainless steel plate, a plated steel plate, a cold rolled steel plate, or a non-ferrous metal such as an aluminum plate. A plate can be used. Further, a metal molded body having a three-dimensional shape can also be used as the metal plate base material. The metal plate for sublimation printing of the present invention may be a three-dimensional molded body.

The dye receiving layer 4 containing an ultraviolet blocking agent is
It may be formed directly on the surface of the metal plate substrate 2,
Etc. may be formed via an intermediate layer. When the adhesion between the metal plate substrate 2 and the dye-receiving layer 4 is poor, it is preferable to interpose an underlayer for assisting the adhesion between the two. Further, even when the adhesion between the metal plate substrate 2 and the dye receiving layer 4 is good, it is possible to form a ground layer to which a pigment is added to adjust the texture and ground color of the ground of the decorative metal plate. it can.

When sublimation printing is performed, the transparency of the sublimation dye is high, so that the metal plate substrate under the transferred image may be seen through, and the design of the decorative metal plate may be impaired. In such a case, if the receiving layer is formed via a white underlayer, for example, a beautiful image can be formed without being affected by the color and texture of the substrate. Therefore, in the case of sublimation printing, it is extremely effective to add a pigment to form an underlayer whose ground color and texture are adjusted.

As the binder for the underlayer, a resin having high adhesiveness is used for both the metal plate substrate and the image receiving layer. For example,
Examples thereof include a vinyl chloride resin, a polyester resin, an acrylic resin, a fluorine resin, and a urethane resin. Known pigments can be added to the underlayer.

As the black pigment, for example, an inorganic coloring agent such as carbon black or triiron tetroxide, or an organic coloring agent such as cyanine black can be used.

As the yellow pigment, inorganic pigments such as graphite, cadmium yellow, yellow iron oxide, titanium yellow, and ocher can be used. As a yellow colorant,
The following poorly soluble metal salts (azo lakes) can also be used.
That is, an acetoacetic acid arylide monoazo pigment,
Hansa Yellow G (CI No. pigment Yellow 1), Hansa Yellow 10G (CI No. pigment Yellow 3),
Hansa Yellow RN (CI No. pigment Yellow 6
5), Hansa Brilliant Yellow 5GX (CI No. p
igment Yellow 74), Hansa Brilliant Yellow 10
GX (CI No. pigment Yellow 98), Permanent Yellow FGL (CI No. pigment Yellow 97), Shimura Lake Fast Yellow 6G (CI No. pigment Ye)
llow 133), Lionol Yellow K-2R (CI No.
pigment Yellow 169); disazo yellow G (CI No. pigment
Yellow12), Disazo Yellow GR (CI No. pigmen)
t Yellow 13), Disazo Yellow 5G (CI No. pig
ment Yellow 14), Disazo Yellow 8G (CI No.p
igment Yellow 17), Disazo Yellow R (CI No.
pigment Yellow 55), permanent yellow HR (C.
I. No. pigment Yellow 83); Chromophthal Yellow 3G (CI No. pigment Yellow 9) which is a condensed azo pigment
3), Chromophthal Yellow 6G (CI No. pigment Y
ellow 94), Chromophthal Yellow GR (CI No. pi
gment Yellow 95); Hosta Palm Yellow H3G (CI No. pi), a benzimidazolone monoazo pigment
gment Yellow 154), Hosta Palm Yellow H4G (C.
I. No. pigment Yellow 151), Hosta Palm Yellow H2G (CI No. pigment Yellow 120), Hosta Palm Yellow H6G (CI No. pigment Yellow 175),
Hosta Palm Yellow HLR (CI No. pigment Yell
ow 156); Irgazine Yellow 3RLTN (CI No. pigment Yellow 11), which is an isoindolinone pigment.
0), Irgazin Yellow 2RLT, Irgazin Yellow 2GLT (CI No. pigment Yellow 109), Fastogen Super Yellow GROH (CI No. pigment)
Yellow 137), Fastogen Super Yellow GRO
(CI No. pigment Yellow 110) and Sandrin Yellow 6GL (CI No. pigment Yellow 173) can be used.

The following are examples of other yellow pigments. That is, flavantron (CI No. pigment Yellow 2
4), anthramirimidine (CI No. pigment Yellow)
108), phthaloylamide type anthraquinone (CI No.
pigment Yellow 123), Heliofast Yellow E3
R (CI No. pigment Yellow 99): an azo-based nickel complex pigment (CI No. pigment Gr) which is a metal complex pigment
een 10), Nitroso-based nickel complex pigment (CI No.pig
ment Yellow 153), azomethine-based copper complex pigment (CI N
o. pigment Yellow 117); a quinophthalone pigment,
Phthalimidoquinophthalone pigment (CI No. pigment Ye
llow 138) can be used.

As the magenta pigment, inorganic pigments such as cadmium red, red iron oxide, silver vermilion, lead red and antimony vermilion can be used. The following azo lake pigments can also be used as the magenta colorant. That is, Brilliant Carmine 6B (CI No. pigment Red 57:
1), lake red (CI No. pigment Red 53: 1),
Permanent Red F5R (CI No. pigment Red 4
8), Risor Red (CI No. pigment Red 49),
Persian orange (CI No. pigment Orange 17),
Black orange (CI No. pigment Orange 18),
Helio Orange TD (CI No. pigment Orange 1
9), Pigment Scarlet (CI No. pigmentRed
60: 1), Brilliant Scarlet G (CI No. pigm
ent Red 64: 1), Helio Red RMT (CI No. pigm)
ent Red 51), Bordeaux 10B (CI No. pigment Red)
63), Helio Bordeaux BL (CI No. pigment Red 5
4) etc. can be used.

As the magenta colorant, the following insoluble azo pigments (monoazo, disazo and condensed azo) can also be used. That is, para red (CI No. pigment), which is a monoazo or disazo pigment,
Red 1), Lake Red 4R (CI No. pigment Red)
3), permanent orange (CI No. pigment Orang
e5), permanent red FR2 (CI No. pigment
Red 2), permanent red FRLL (CI No. pi
gment Red 9), permanent red FGR (CI No.
pigment Red 112), Brilliant Carmine BS (C.
I. No. pigmentRed 114), permanent carmine FB
(CI No. pigment Red 5), P.E. V. Carmin HR
(CI No. pigment Red 150), permanent carmine FBB (CI No. pigment Red 146), Nova Palm Red F3RK-F5RK (CI No. pigment Red 17)
0), Nova Palm Red HFG (CI No. pigment Ora
nge 38), Nova Palm Red HF4B (CI No. pigment)
Red 187), Nova Palm Orange HL. HL-70 (C.
I. No. pigment Orange 36), P.I. V. Carmin HF4
C (CI No. pigment Red 185), Hosta Balm Brown HFR (CI No. pigment Brown 25), Vulcan orange (CI No. pigment Orange 16), pyrazolone orange (CI No. pigment Orange 13), pyrazolone red (CI No. pigment Red 38); Chromophtal Orange 4R (CI No.
pigment Orange 31), Chromophtal Scarlet R
(CI No. pigment Red 166), Chromophtal Red BR (CI No. pigment Red 144) and the like can be used.

As the magenta pigment, the following condensed polycyclic pigments can also be used. That is, pyranthrone orange (CI No. pigmen) which is an anthraquinone pigment
t Orange 40), Anto Anthrone Orange (CI No.
pigment Orange 168), dianthraquinonyl red (CI No. pigment Red 177); a thioindigo-based pigment, thioindigo magenta (CI No. pigment Vi
olet 38), thioindigo violet (CI No. pig)
ment Violet 36), Thioindigo Red (CINo. pig)
ment Red 88); perinone pigment, perinone orange (CI No. pigment Orange 43); perylene pigment, perylene red (CI No. pigment Red 19)
0), perylene vermillion (CI No. pigment Red 1
23), Perylene Maroon (CI No. pigment Red 17)
9), Perylene scarlet (CI No. pigment Red 1)
49), perylene red (CI No. pigment Red 17)
8); Quinacridone pigments such as quinacridone red (CI No. pigment Violet 19), quinacridone magenta (CI No. pigment Red 122), quinacridone maroon (CI No. pigment Red 206), and quinacridone scarlet (CI No. pigment Red) 207); pyrocholine pigments; red fluorbin pigments can be used.

Other magenta pigments include rhodamine 6G lake (CI No.
pigment Red 81) can be used. Dyeable lake pigments are obtained by reacting a water-soluble dye with a precipitant to form a lake and fix it.

As the cyan pigment, inorganic pigments such as ultramarine blue, navy blue, cobalt blue and cerulean blue can be used. The following can also be used as the cyan colorant. That is, a phthalocyanine pigment,
First Gemble-BB (CI No. pigment Blue 1
5) Sumiton Cyanine Blue HB (CI No. pig
ment Blue 15), cyanine blue 5020 (CI No.
pigment Blue 15: 1), Monastral Blue FBR (C.
I. No. pigment Blue 15: 2), Palomar Blue B-48
10 (CI No. pigment Blue 15: 3), Monastral Blue FGX (CI No. pigment Blue 15: 4), Lionol Blue ES (CI No. pigment Blue 15: 6), Heliogen Blue L6700F (CI No. pigment) Blue
15: 6), Sumika Print Cyanine Blue GN-O
(CI No. pigment Blue 15), Heliogen Blue L
7560 (CI No. pigment Blue 16), Fast
Sky Blue A-612 (CI No. pigment Blue 1
7), cyanine green GB (CI No. pigment Gre
en 7), cyanine green S537-2Y (CINo. p
igment Green 36), Sumiton Fast Violet RL (CI No. pigment Violet 23); Indanthrone blue (PB-60P, PB-22, PB-2) which is a slender pigment
1, PB-64); a basic dye lake pigment, such as methyl violet phosphorus phosphorus molybdate lake (PV-3), can be used.

Among the above-mentioned various pigments, it is preferable to use a pigment having high heat resistance. The following can be exemplified as the high heat-resistant pigment.

First, examples of high heat-resistant black pigments include carbon black, acetylene black, black iron oxide, and iron black.

The high heat resistant yellow pigments include inorganic pigments such as graphite, yellow iron oxide, cadmium yellow, nickel titanium yellow, chromium titanium yellow and metal oxide pigments, isoindolinone pigments, condensed azo pigments, and the like. Organic pigments such as system pigments can be exemplified. Examples of the isoindolinone pigment include Irgazine Yellow 3RLTN.
(CI No. pigment Yellow 110), Irgazin Yellow 2RLT, Irgazin Yellow 2GLT (CI No.
pigment Yellow 109), Fastogen Super Yellow GROH (CI No. pigment Yellow 137), Fastogen Super Yellow GRO (CI No. pigment Yell)
ow 110), Sandrin Yellow 6GL (CI No. pigme
nt Yellow 173) can be used. Chromophthal Yellow 3G (CI No. pigment
Yellow 93), Chromophthal Yellow 6G (CI No. p
igment Yellow 94), Chromophthal Yellow GR (C.
I. No. pigment Yellow 95) can be used. Further, as the metal oxide pigment, dipyroxide color yellow # 9110, # 9121 (manufactured by Dainichi Seika Kogyo) can be used.

Examples of magenta pigments having high heat resistance include organic pigments such as condensed azo pigments and inorganic pigments such as cadmium red, molybdenum red and metal oxide pigments. Examples of the condensed azo pigments include Chromophtal Orange 4R (CI No. pigment Orange 31), Chromophtal Scarlet R (CI No. pigment Red 166), and Chromophtal Red BR (CI No. pigment Red 14).
4) etc. can be used. Also, as the metal oxide pigment,
Die peroxide color brown # 9220 (manufactured by Dainichi Seika Kogyo) can be used.

Examples of the highly heat-resistant cyan pigments include organic pigments such as phthalocyanine pigments and anthraquinone pigments, ultramarine (ultramarine blue), cobalt blue,
Examples thereof include inorganic pigments such as chromium oxide, spinel green, and metal oxide pigments. As phthalocyanine pigments,
Phthalocyanine Blue (Pigment Blue 15, Pigment Blu
e 15: 3, Pigment Blue 15: 1), chlorinated phthalocyanine (Pigment Green 7), brominated phthalocyanine (Pig
ment Green 36) can be used. As an anthraquinone pigment, sllen blue (Pigment Blue 60) or the like can be used. Dipoxide color blue # 9453 (manufactured by Dainichi Seika Kogyo) can be used as the metal oxide pigment.

In the present invention, a coloring agent, which is a so-called processed pigment, in which a resin is coated on the surface of the pigment particles, may be used. Further, a mixture of the above-described pigments or a pigment having an intermediate color such as green, orange, or purple may be added. Further, additives such as a surface roughening agent and an adhesion enhancer may be added to the underlayer as needed. When the pigment is added to the underlayer, the pigment is usually added in an amount of 5 to 200 parts by weight per 100 parts by weight of the underlayer.

In order to form an underlayer on a metal plate base material, components such as a binder resin and other necessary pigments are mixed with an organic solvent such as toluene, methyl ethyl ketone, ethanol, isopropyl alcohol, cyclohexane, and DMF. A base layer coating solution is prepared by dissolving or dispersing in a mixed solvent of a solvent and water. Then, the obtained coating liquid may be applied and dried on the surface of the metal plate substrate by a known method such as gravure printing, screen printing, or reverse coating printing using a gravure plate. The coating amount of the underlayer is usually about 1 to 100 μm.

On the image receiving surface of the metal plate for sublimation printing of the present invention,
The dye receiving layer 4 is provided with or without the underlayer 3 interposed therebetween. Since the metal plate substrate does not have a dyeing property to the sublimation dye, a dye receiving layer must be provided in order to perform sublimation printing on the metal plate substrate. This dye receiving layer is formed of a binder resin having dye-dyeing properties, an ultraviolet blocking agent for reducing discoloration of the sublimation dye due to ultraviolet rays, and other additives.

As the binder resin having dyeability to the sublimation dye, a known resin used for forming an image receiving surface of an image receiving sheet for sublimation thermal transfer can be used.
Specific examples include orthophthalic acid, isophthalic acid,
Terephthalic acid-based, bisphenol-based, vinyl ester-based polyester resins; ethylene-acrylic acid, ethylene-acrylate ester, acrylic ester-vinyl,
Acrylic copolymer resins such as methacrylate-vinyl; tolylene diisocyanate (TDI);
4'-diphenylmethane diisocyanate (MDI),
Urethane resins formed by the reaction of various isocyanate derivatives and isocyanurate derivatives such as lysine ester triisocyanate with various polyols such as polyester polyol, polyether polyol, acrylic polyol and phenolic polyol; polyvinyl chloride, polyvinylidene chloride, etc. Halogenated polymers of vinyl acetate; vinyl resins such as polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyacryl ester, polystyrene, polystyrene acryl; polyvinyl formal, polyvinyl butyral, polyvinyl acetal, etc. Acetal resin; Polycarbonate resin; Cellulose resin such as cellulose acetate;
Polyolefin resins; urea resins, melamine resins, amino resins such as benzoguanamine resins and the like can be exemplified. The binder resin may be used alone or in combination of two or more.

Among them, polyester resins,
Acrylic resins or urethane resins are preferable because they have good dyeing properties. Further, among these resins, those having a glass transition temperature of 120 ° C. or higher are more preferable because they do not easily undergo thermal fusion with sublimation printed paper. In the case of sublimation printing, if the heating temperature of the printing is lowered in order to avoid the thermal fusion of the printed paper, the transfer of the sublimation dye is reduced and the density of the transferred image tends to be insufficient. On the other hand, if the dye-receiving layer is formed using these preferred binder resins, even if the transfer heating temperature is sufficiently increased to increase the transfer amount of the sublimation dye to the dye-receiving layer, And the thermal fusion between the dye and the sublimation printed paper can be prevented. As a result, an image having a high density can be formed.

Sublimation dyes have poor light fastness compared to pigments, and are liable to undergo discoloration such as fading and hue change when exposed to light, especially ultraviolet light. When an ultraviolet blocking agent that reduces discoloration of the sublimation dye due to ultraviolet rays is added to the dye receiving layer, the light resistance of an image formed on the surface of the dye receiving layer is improved, and the color is hardly discolored. As a result, there is no need to provide an ultraviolet light blocking layer on the dye receiving layer, and it is possible to omit the step of forming the ultraviolet light blocking layer which has been conventionally performed after sublimation printing.

The ultraviolet blocking agent for reducing the discoloration of the sublimation dye due to ultraviolet rays is a component capable of attenuating or completely preventing the discoloration action due to ultraviolet rays. As such an ultraviolet blocking agent, for example, a component having an ultraviolet absorbing property such as benzophenone or benzotriazole, or a component having an ultraviolet reflecting property such as zinc oxide or titanium oxide can be used. A conventionally used ultraviolet absorber may be used in the ultraviolet shielding layer for coating the surface of the dye receiving layer. As the ultraviolet blocking agent, one type may be used alone, or two or more types may be used in combination.

In sublimation printing, the dye layer of the printed paper is heated to a temperature higher than the dye sublimation temperature. Therefore, the temperature of the dye-receiving layer, which is brought into close contact with the dye layer of the printed paper, also rises to a temperature equal to or higher than the dye sublimation temperature or slightly lower than the sublimation temperature. For this reason, the UV blocking agent added to the dye-receiving layer must be of a high heat resistance such that even after being heated during sublimation printing, the ability to reduce discoloration of the sublimation dye is still left. . When performing sublimation printing, the printed paper is often heated to 160 ° C. or higher. Therefore, it is preferable to use an ultraviolet blocking agent which has a capability of reducing discoloration of a sublimation dye even after being heated to a high temperature of 160 ° C. or more. It is preferable that the discoloration reducing ability of the ultraviolet blocking agent after sublimation printing is not deteriorated at all as compared with before sublimation printing, but it is sufficient if the discoloration reducing ability that is practically satisfactory remains.

As the preferred ultraviolet blocking agent having the above-mentioned ultraviolet blocking ability and high heat resistance, inorganic ultraviolet blocking agents are preferable, and among them, zinc oxide and titanium oxide are particularly preferable. As the titanium oxide, a rutile pigment having low photocatalytic activity is preferable. By coating the active sites on the titanium oxide surface with an inorganic surface treatment agent such as alumina, it works as a good ultraviolet ray cut agent.

If necessary, additives such as a light fastness improver such as a radical scavenger, an antibacterial agent and a deodorant may be added to the dye receiving layer 4 together with a binder resin and an ultraviolet ray inhibitor.

The ultraviolet blocking agent is preferably added to the dye receiving layer at a ratio of 10 to 50% by weight based on the solid content of the dye receiving layer. UV blocking agent content is 10
If the amount is less than 10% by weight, the function as an ultraviolet blocking agent may not be sufficient. On the other hand, if the content is more than 50% by weight, the dispersibility, the transparency, and the strength of the coating film tend to be reduced.

In order to form a dye receiving layer on a metal plate substrate or a base layer, first, a binder resin, an ultraviolet ray blocking agent,
Then, other necessary additives are mixed, and the obtained mixture is dissolved or dispersed in an appropriate amount of a solvent to prepare a coating liquid for a receptor layer. Then, the obtained coating liquid is applied to the surface of a metal plate substrate or a base layer by a known method such as gravure printing, a reverse coater, a screen coater, or a flow coater, and dried to obtain a dye receiving layer. The coating amount of the dye receiving layer is not particularly limited.
It is preferably about 20 g / m ² . If the coating amount of the image receiving layer is less than 0.1 g / m ² , poor coating is likely to occur. On the other hand, if the coating amount is more than 20 g / m ² , the cost tends to increase.

As described above, a metal plate for sublimation printing was prepared in which a dye-receiving layer containing a highly heat-resistant ultraviolet blocking agent was provided on a metal plate substrate with or without an underlayer. You. Then, a decorative metal plate can be produced by subjecting the metal plate for sublimation printing of the present invention to sublimation printing by a known method. For example, a wet developer in which a toner of a sublimation dye is dispersed and an electrostatic recording paper for sublimation printing are prepared, a sublimation printing paper is prepared using these, and the sublimation of the present invention is performed using the obtained sublimation printing paper. When printing is performed on a printing metal plate, a decorative metal plate is completed.

To prepare a wet developer in which a sublimation dye toner is dispersed, for example, a mixture of a sublimation dye, a copolymer resin for improving fixability or charging characteristics, and a charge control agent is prepared by electrically insulating the mixture. What is necessary is just to introduce | transduce into a dispersion medium and to fully disperse | distribute. As the sublimation dye, a disperse dye is preferably used. These dyes have a molecular weight of about 150 to 550, and are selected in consideration of sublimation or melting temperature, hue, light resistance, solubility in resins and developers, and the like.

For example, diarylmethane, triarylmethane, thiazole, methine, azomethine,
Xanthine, oxazine, azo and azo derivatives,
Anthraquinone derivatives, quinophthalone derivatives, spirodipyran-based, indolinospiropyran-based, fluoran-based,
Rhodamine lactam dyes are used.

For example, C.I.
I. Disperse Yellow 51, 3, 54, 79, 6
0, 23, 7, 141; I. Disperse Blue 2
4, 56, 14, 301, 334, 165, 19, 7
2, 87, 287, 154, 26, 359; I. Disperse threads 135, 146, 59, 1, 73, 6
0, 167; I. Disperse Violet 4, 1
3, 26, 36, 56, 31; I. Solvent Violet 13; C.I. I. Solvent Black 3;
I. Solvent Green 3; I. Solvent Yellow 56, 14, 16, 29, 105; C.I. I. Solvent Blue 70, 35, 63, 36, 50, 49, 11
1, 105, 97, 11; I. Solvent Red 1
35, 81, 18, 25, 19, 23, 24, 143,
146, 182 and the like.

For example, 3,3-diethyloxacyanine iodide, Astrazone Pink FG (CI.48)
015, manufactured by Bayer AG), 2,2-carbocyanine (C.I. 808), Astraphyloxine FF (C.I.
I. 148070), Astrazon Yellow 7GLL
(CI Basic Yellow 21), Aizen Carotene Yellow 3GLH (CI.48055, manufactured by Hodogaya Chemical Co., Ltd.), Aizen Carotene Red 6BH (CI.48
020) and the like; methine (cyanine) -based basic dyes such as dimethine-based and trimethine-based; diphenylmethane-based basic dyes such as auramine (CI.655); malachite green (CI.42000);
Brilliant green (C.I. 42040), magenta (C.I. 42510), methyl violet (C.I.
I. 42535), crystal violet (C.I.
42555), methyl green (C.I.684), Victorian blue B (C.I.44045) and other triphenylmethane-based basic dyes, and pyronin G (C.I.73).
9), xanthene-based basic dyes such as rhodamine B (CI. 45170) and rhodamine 6G (CI. 45160), acridine yellow G (CI. 785), and leonine AL (CI. 46075). Benzoflavin (CI.791), affine (CI.46045)
Acridine-based basic dyes, neutral red (CI.50040), Astrazone Blue BGE /
Xl 25% (CI. 50005), quinone imine-based basic dyes such as methylene blue (CI. 52015), and other basic dyes such as anthraquinone-based basic dyes having a quaternary amine. These dyes can be used as they are or in a form in which these dyes have been treated with alkali, and a counter ion exchanger or a leuco form of these dyes can also be used. When a colorless or light-colored leuco dye or the like is used in a normal state, a developer may be included in the image forming sheet side.

Further, these disperse dyes are used not only by one component but also by mixing two or more kinds. In particular, when mixed and melted, the thermal behavior greatly differs depending on what kind of mixture they form, and the vapor pressure also changes depending on the composition ratio accordingly. When it occurs, the activation energy is small and the sublimation sensitivity can be improved.

The resin for improving the fixing property includes a monomer effective for controlling the charging characteristics of the wet developer and a monomer effective for controlling the solubility and dispersibility of the wet developer in a solvent. In particular, the resin is a (meth) acrylic monomer (however, this expression expresses both acryl and methacryl, and the same applies to the following (meth) acryl). It is a resin obtained by copolymerizing a contained vinyl monomer mixture. Specific examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Having a short methylene chain such as butyl acrylate (meth)
Acrylates and the like, and nitrogen-containing acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
Acrylamide, isopropylacrylamide, methylenebisacrylamide, N-allylacrylamide, N
Acrylamide derivatives such as diacetone acrylamide, N, N-dimethylacrylamide, (meth) acrylic acid-2-hydroxyethyl ester, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, methylstyrene, Examples include monomers such as vinyl acetate. Particularly preferably, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Hexyl acrylate, methylstyrene and vinyl acetate are mentioned.

Particularly, vinyl monomers effective for adjusting solubility and dispersibility in a solvent include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. (Meth) acrylate having a long methylene chain. Particularly preferred is 2-ethylhexyl (meth) acrylate.

The copolymer resin is obtained by copolymerizing at least one of each of a monomer suitable for controlling the charging characteristics and a monomer effective for controlling solubility and dispersibility in a solvent. However, the copolymerization ratio of both is 5 to 30.
% By weight, more preferably 10 to 20% by weight. If the amount is less than this, sufficient improvement in charging characteristics cannot be obtained, and if it is more than this, aggregation of the wet developer and a decrease in image density occur.

In particular, since the molecular weight of the copolymer resin affects the OD value and image fogging due to yellow, the preferred molecular weight of the copolymer resin is 50,000 to 200,000 in terms of polystyrene in terms of weight average molecular weight measured by GPC. is there. More preferably, it is 80,000 to 170,000. When the molecular weight is larger than this, fogging, that is, background stain is liable to occur, and when the molecular weight is smaller than this, the image density is reduced and image deletion is liable to occur.

As the resin for improving the charging characteristics, it is possible to use such a resin that when the resin is used as a fixing agent, the charge amount becomes too large to cause a decrease in image density. Specific examples include a monomer effective for adjusting the charging characteristics and a copolymer resin effective for adjusting the solubility and dispersibility of the wet developer in a solvent, and particularly, the resin has a basic group. It is a resin obtained by copolymerizing a vinyl monomer mixture containing a vinyl monomer.

Vinyl monomers having a basic group particularly good for controlling charging characteristics include nitrogen-containing acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; acrylamide; Isopropylacrylamide, methylenebisacrylamide, N-allylacrylamide, N-
Monomers such as acrylamide derivatives such as diacetone acrylamide and N, N-dimethylacrylamide.

Vinyl monomers effective for controlling the solubility and dispersibility in a solvent include (meth) acrylic acid-2
(Meth) acrylates having a long methylene chain, such as ethylhexyl, lauryl (meth) acrylate, and stearyl (meth) acrylate.

The copolymerization ratio of the resin is preferably such that the content of the vinyl monomer having a basic group is 5 to 40% by weight, more preferably 10 to 20% by weight. If the amount is less than this, the charging characteristics cannot be sufficiently improved, and if it is more than this, aggregation of the wet developer and a decrease in image density occur.

The preferred molecular weight of the resin used as the resin for improving charging characteristics is from several thousand to several hundred thousand in terms of styrene in terms of weight average molecular weight measured by GPC.
The content of the charge property improving resin is preferably 1 to 1000% by weight of the charge control agent contained in the wet developer. Particularly preferably, it is 10 to 100% by weight. If it is less than this, the effect of the charge control is small, and if it is more than this, the image density is reduced.

As the charge control agent, any charge control agent that decomposes under sublimation thermal transfer conditions and does not harm the human body can be used as it is used in a wet developer. For example, dialkyl sulfosuccinate metal salts; manganese naphthenate, calcium naphthenate, zirconium naphthenate, cobalt naphthenate, iron naphthenate, lead naphthenate, nickel naphthenate, chromium naphthenate, zinc naphthenate, magnesium naphthenate, octylate Manganese, calcium octylate, zirconium octylate,
Iron octylate, lead octylate, cobalt octylate, chromium octylate, zinc octylate, magnesium octylate, manganese dodecylate, calcium dodecylate, zirconium dodecylate, iron dodecylate, lead dodecylate,
Metal soaps such as cobalt dodecylate, nickel dodecylate, chromium dodecylate, zinc dodecylate, magnesium dodecylate; metal salts of alkylbenzenesulfonic acid such as calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, barium dodecylbenzenesulfonate; lecithin And organic amines such as n-decylamine. Preferably,
Examples thereof include metal salts of naphthenic acid and octylic acid, and particularly preferred is zirconium naphthenate.

As the electrically insulating dispersion medium, for example, n-
Examples include paraffinic hydrocarbons, iso-paraffinic hydrocarbons, halogenated aliphatic hydrocarbons, and branched-chain aliphatic hydrocarbons. Particularly preferred are branched chain aliphatic hydrocarbons. Branched-chain aliphatic hydrocarbons are supplied by Exxon under the trade name Isopar. There are grades of Isopar E, Isopar G, Isopar H, Isopar L, Isopar M, etc.
An appropriate resin is selected according to the type of the copolymer resin.

In order to prepare an electrostatic recording paper for sublimation printing, for example, a conductive material such as a polymer electrolyte such as a quaternary ammonium salt polymer or a surfactant is coated on the surface of paper or a heat-resistant plastic film. Prepare a conductive base paper by coating or impregnating, acrylate resin, butyral resin,
It is obtained by applying and drying a coating liquid in which an insulating resin such as a silicone resin is dissolved or dispersed to form a dielectric layer.

An electrostatic latent image is formed on the surface of the electrostatic recording paper on which the dielectric layer is formed by using an ion printer or an electrostatic plotter, and then the above-described toner of the sublimation dye is dispersed. When development is performed using the wet developer thus formed, an image of the sublimation dye is formed on the electrostatic recording paper, and a sublimation printing paper is completed. Then, the image forming surface of the obtained sublimation printing paper and the receiving layer forming surface of the metal plate for sublimation printing of the present invention face each other and overlapped, and heating is performed at an appropriate temperature and time. The image is transferred, and a decorative metal plate is completed. The decorative metal plate thus prepared is excellent in light resistance even if the image receiving surface is not covered with the ultraviolet shielding layer.

[0064]

Hereinafter, the metal plate for sublimation printing and the decorative metal plate according to the present invention will be described in more detail through examples.

Example 1 (1) Production of Wet Developing Agent A cyan wet developing agent Cy having the following composition was produced.
First, the respective materials other than the dispersion medium for dilution were mixed, and the mixture was placed in a mixing container together with the glass beads for dispersion, and dispersed for 3 hours with a disperser (RC-5000 manufactured by Red Devil Co.), and then the glass beads for dispersion were removed. It was removed to obtain a master toner. Furthermore, 60 parts by weight of the obtained master toner was diluted with 660 parts by weight of a diluting isoper to adjust the total amount to 720 g to obtain a wet developer Cy. Further, the following cyan dye was mixed with the same amount of magenta dye (CI Di).
magenta wet developer Mg was obtained in the same manner as described above except that sparse red 60) was used. Further, the following cyan dye was replaced with the same amount of yellow dye (C.I.
I. Disperse Yellow 54) was carried out in the same manner as above, except that the yellow wet developer Y was used.
e was obtained.

<Composition of Wet Developer Cy> Varnish of 2-ethylhexyl methacrylate (EHMA) -ethyl acrylate (EA) copolymer resin (solid content: 40% by weight, dispersion medium: Isopar G (manufactured by Exxon)) , Weight ratio: EHMA / EA = 70/30, weight average molecular weight: 150,000): 10.0 parts by weight Cyan dye C.I. I. Disperse Blue
60: 4.0 parts by weight-Charge control agent Zirconium naphthenate (Nikka Naphtex Zr, manufactured by Nippon Chemical Industry Co., Ltd.): 6.0 parts by weight-Dispersion medium for master toner Trade name: Isopar G (manufactured by Exxon): 40. 0 parts by weight (subtotal: 60.0 parts by weight) Dispersion medium for dilution Isopar G (manufactured by Exxon): 660.0 parts by weight (total: 720.0 parts by weight)

(2) Measurement of charge amount The charge amount of the toner particles was measured by the following method. A wet type developer is filled between a brass electrode plate having a spacing of 1.0 cm, a length of 5.0 cm, and a width of 4.5 cm, and a high voltage generator (type 237 manufactured by KEITHLEY) is used to fill the space between the two electrodes.
A voltage of 0 V was applied, and a current value was measured over time until 60 seconds had elapsed from the start of energization. First, based on the measured value, the current value (I ₀ ) after a lapse of 60 seconds from the initial current amount (I ₀ )
₆₀ ) to calculate the initial total electric charge Q ₀ spent 60 seconds after the start of energization. Then, based on the current value after 60 seconds from the start of energization, and calculating a charge amount Q ₆₀ spent 60 seconds in the steady state. Then, to calculate the total charge amount Q _t of the toner particles by calculating the difference between the two charge amount. The equation for the above calculation is expressed as follows.

[0068]

[Equation 1] Q _t = Q ₀ −Q ₆₀ = Q ₀ −I ₆₀ × 60 seconds

Thereafter, the electrode plate on which the wet type developer was adhered was taken out of the current value measuring cell, dried, and the toner adhesion amount (M) on the electrode plate was measured. On the basis of the adhesion amount (M) and the total charge amount Q _t, toner specific charge i.e. toner 1g
Per charge Q _t / M (μc / g) was calculated. Table 1 shows the measurement results.

[0070]

[Table 1]

(3) Development Wet developer C for sublimation printing produced as described above
y, Mg, Ye and electrostatic plotter (VERSATEC
8900, manufactured by Xerox Co., Ltd.), solid images of Cy, Mg and Ye were respectively formed on the electrostatic recording paper to obtain a sublimation printed paper.

(4) Preparation of a steel sheet for transfer printing On a steel sheet having a thickness of 2 kg / m ^2, a coating solution for an underlayer having the following composition was applied using a miller bar (# 24), dried, and dried under a white color. Formations formed. The coating amount after drying of the underlayer is 20 g /
It was m ^2. Next, a coating solution for an image receiving layer having the following composition is prepared, and is coated on the underlayer using a Miyabar (# 12).
Dried. The amount of coating after drying of the coating layer was 10 g / m ² . Then, it was cured by annealing at 230 ° C. for 10 minutes to form a receiving layer, thereby producing a steel sheet for sublimation printing.

<Coating liquid for base layer> Acrylic resin (BR85, manufactured by Mitsubishi Rayon Co., Ltd.): 10
Parts by weight-Titanium white (R-820, manufactured by Ishihara Sangyo): 2 parts by weight-Toluene: 100 parts by weight <Coating liquid for image receiving layer>-Polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.): 10 parts by weight Methylol melamine (Cymel 320, manufactured by Mitsui Syamide): 10 parts by weight Ultraviolet ray inhibitor Ultrafine zinc oxide (manufactured by Sumitomo Cement): 9 parts by weight Methyl ethyl ketone: 74 parts by weight

(5) Sublimation printing The sublimation printing paper obtained as described above and a steel plate for transfer printing are overlapped and heated at 200 ° C. for 30 seconds using a thermal transfer machine (HP-54A, manufactured by Hashima Co., Ltd.). , Cy, M on steel plate
Each pattern of g and Ye was printed and transferred, respectively, to obtain a sample of a decorative metal plate.

(6) Light Resistance Test A sample of the decorative metal plate was subjected to a light resistance test using a sunshine weather meter (Suga tester) equipped with a carbon arc lamp with an irradiation time of 200 hours. For each color pattern formed on the steel plate, the hue (L (0), a (0), b (0)) and 20 before irradiation start.
Hue after irradiation for 0 hour (L (200), a (200), b
(200)) with a Gretag spectrophotometer (SPM100-
II, manufactured by Gretag). Then, based on the measurement result, ΔE was calculated by the following equation. Light resistance was also evaluated. The evaluation criteria for light fastness are as follows. Tables 2 to 4 show the measurement results of the hue and the evaluation results of the light fastness.

[0076]

ΔE = {(L (0) −L (200)) ² + (a
(200) -a (0)) 2 + (b (200) -b
(0)) ² } ^1/2

<Evaluation Criteria> Good: Hue change was small. Bad: A remarkable change in hue was observed.

Example 2 A sample of a decorative metal plate was prepared and tested in the same manner as in Example 1 except that the blending ratio of the ultrafine zinc oxide as an ultraviolet ray inhibitor was changed to 5 parts by weight. The light resistance of the obtained sample was good. The test results are shown in Tables 2 to 4.

Comparative Example 1 A sample of a decorative metal plate was prepared and tested in the same manner as in Example 1 except that no ultraviolet ray blocking agent was used. The light resistance of the obtained sample was poor. The test results are shown in Tables 2 to 4.

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

According to the metal plate for sublimation printing of the present invention,
A decorative metal plate excellent in light resistance and resistant to discoloration can be obtained. In addition, it is not necessary to form an ultraviolet shielding layer on the image receiving surface, so that it is possible to improve production efficiency, reduce costs, and the like.

According to the present invention, there is also provided a metal plate for sublimation printing which is not only excellent in light resistance but also hardly causes thermal fusion with printing paper. When such a metal plate for sublimation printing is used, the transfer heating temperature can be sufficiently increased in order to increase the transfer amount of the sublimation dye to the dye receiving layer. As a result, a decorative metal plate excellent in light resistance and having a good image with high density can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing a cross section of a metal plate for sublimation printing of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Sublimation printing metal plate 2 ... Metal plate base material 3 ... Underlayer 4 ... Dye receiving layer

Claims (12)

[Claims] 1. A metal for sublimation printing, wherein at least a dye-receiving layer containing a highly heat-resistant UV-blocking agent for reducing discoloration of the sublimation dye due to ultraviolet rays is provided on a metal plate substrate. Board. 2. The metal plate for sublimation printing according to claim 1, wherein the ultraviolet ray blocking agent contains an ultraviolet ray absorbing substance and / or an ultraviolet ray reflecting substance. 3. The sublimation printing according to claim 1, wherein the ultraviolet blocking agent still has a capability of reducing discoloration of the sublimation dye even after being heated during sublimation printing. For metal plate. 4. The method according to claim 3, wherein the ultraviolet blocking agent still has a capability of reducing discoloration of the sublimation dye even after being heated to a temperature of 160 ° C. or higher.
The metal plate for sublimation printing described in 1. 5. The metal plate for sublimation printing according to claim 1, wherein the ultraviolet ray blocking agent contains an inorganic ultraviolet ray blocking agent. 6. The metal plate for sublimation printing according to claim 5, wherein the inorganic ultraviolet blocking agent contains zinc oxide and / or titanium oxide. 7. The method according to claim 1, wherein the dye receiving layer further contains at least one binder resin selected from a polyester resin, an acrylic resin, and a urethane resin. The metal plate for sublimation printing described in 1. 8. The metal plate for sublimation printing according to claim 7, wherein the binder resin has a glass transition temperature of 120 ° C. or higher. 9. The metal plate for sublimation printing according to claim 1, wherein the content of the ultraviolet blocking agent is 10 to 50% by weight based on the weight of the solid content of the dye receiving layer. 10. The coating amount of the dye-receiving layer when dried,
Characterized in that it is a 0.1 to 20 g / m ^2, sublimation printing metal plate according to claim 1. 11. The metal plate for sublimation printing according to claim 1, wherein the dye receiving layer is formed on the metal plate base via a base layer containing a pigment. 12. A decorative metal sheet formed by performing sublimation printing on the metal sheet for sublimation printing according to any one of claims 1 to 11.