JP2000141992A - Transfer film for printing curved face and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a printed matter with a curved face which can deal with demand for a small lot and a variety of grades per lot, rapidly and at a low cost by laminating a pictorial image layer to be printed under an on-demand system, on one of the faces of a supporting film which swells in a specific solvent. SOLUTION: The on-demand system is a printing method by which printing is performed without the use of a printing plate. In detail, an ink jet system, an electronic photography system, a heat fusion-type or a dye sublimation-type heat transfer system and the like are available. After printing an image on a supporting film 1 in ink A using an ink jet printer 2, an image layer 3 which constitutes a pictorial pattern by a drying process is formed to obtain the transfer film 4 for printing a curved face. The supporting film 1 is preferably of such a type that it swells sufficiently in a solvent during transfer in a curl fit printing process and displays the suitability for multicolor printing and transfer printing properties and also has such a property as to stubbornly adhere to the surface of a printed matter with a curved face. Thus it is possible to manufacture the printed matter with a curved face in a short time and at a low cost, compared to the case with the use of a conventional transfer film for printing a curved face by gravure printing which requires a printing plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention mainly relates to curved surfaces of various types of printed materials such as metal products, plastic molded products, ceramic molded products and the like. The present invention also relates to a transfer film for curved surface printing for performing printing by a transfer method with respect to a flat portion.

[0002]

2. Description of the Related Art Conventionally, a method of printing on various printing materials having a curved surface includes dry offset printing suitable for printing on a simple shape such as a conical shape and a box shape. Printing on unsuitable flat shapes, screen printing suitable for printing requiring a thick ink layer, and printing using a transfer paper consisting of a base material, a wax layer, a printing ink layer, and a thermoplastic resin layer. Clock printing is performed by transfer printing in which the ink layer is transferred by heating from the substrate side while in close contact with the body, and then transferring the ink from the intaglio to the pad of silicon rubber and pressing it against the printing medium (a kind of offset printing). Dial printing, pad printing used for precision products such as marking of electronic parts, and the like.

[0003] Among such printing methods for curved surfaces, curl fitting (special curved surface printing) can be mentioned as a printing method capable of applying a picture (printing) to a printing medium having a particularly complicated shape. Printing on curved surfaces with this curl fit
A transfer film having an image layer constituting a pattern activated by an activator on a support film made of a water-soluble or water-swellable film, is floated on the water surface such that the image layer is on the upper surface, and a print to be painted is provided. The image layer of the transfer film is transferred to the outer peripheral surface of the printing medium by using a water pressure by pushing the printing medium from above, and the transfer is performed by using water pressure (Japanese Patent Publication No. Sho 5 (1993)).
2-41683, JP-A-54-33115).

[0004]

In the curl-fit printing process, a printing process for forming an image layer on a support film has conventionally been performed by gravure printing. However, in order to form an image layer for painting by gravure printing as described above, it is necessary to prepare a printing plate, and there is a problem that it takes time, labor, and cost. Therefore, there is a problem that it is difficult to use a curved surface printed body in a short time and at low cost, such as when a prototype is created and evaluated at the development stage.

On the other hand, in the flow of small lots and many kinds in recent years, on-demand printing capable of performing printing without using a printing plate has been receiving attention. On-demand printing such as an ink jet method or an electrophotographic method has been attracting attention. Various printed materials have been produced. However, there has been no example in which such an on-demand printing method is adopted in curved surface printing.

[0006] In the curl-fit printing process, if an ink of a different type from the ink used in the conventional curl-fit is used, the ink or the like may not be fixed on the support film. Further, when such a new kind of ink or the like is directly printed on the support film, there may be a problem that the support film swells. Furthermore, when such a new kind of ink or the like is used, when the image layer formed by these inks or the like is simultaneously washed off when the support film is finally transferred to the printing medium and washed and removed. There is also a problem that there is. These problems are problems that can occur even when the conventional ink is used when it is necessary to change the conventionally used water-soluble support film to another solvent-swellable film.

[0007] Further, when inks of a different type from those used in such conventional curl fitting are used, the transfer properties of the transfer film printed with these inks and the like on a printing substrate are reduced. Can cause problems. Further, when printing is performed on a printing medium made of a new material, a problem may occur in the adhesiveness even when the conventional ink is used.

The present invention has been accomplished in view of the above-mentioned situation, and has been developed at a low cost and at a low cost so that a curved printed body which can respond to recent demands for small lots and many kinds can be manufactured. Providing a transfer film for curved surface printing that can be obtained, and the fixability of these inks to a support film and the transfer in which these inks are printed even under various circumstances such as when a new type of ink is used. It is a main object of the present invention to provide a transfer film for curved surface printing which does not deteriorate the adhesiveness of the film to a printing medium.

[0009]

In order to achieve the above object, according to the present invention, in the first aspect, a picture printed by an on-demand printing method is formed on one surface of a support film which swells in a predetermined solvent. 10. A transfer film for curved printing, characterized by laminating image layers to be formed, wherein a step of preparing a support film swelling in a predetermined solvent according to claim 9; And a method of printing a transfer film for curved surface printing, comprising at least a step of printing an image layer constituting a pattern by a printing method of a system.

[0010] As described above, by printing the image layer constituting the picture on the supporting film by the on-demand printing method, the time, labor and time required to produce a printing plate are reduced as compared with the conventional gravure printing method. Since the cost is not required, a transfer film for curved surface printing can be obtained quickly and at low cost.By performing curved surface printing by curl fitting using this transfer film for curved surface printing, a curved surface printed body can be obtained quickly and at low cost. Obtainable.

Further, according to the present invention, as described in claim 2, an intermediate layer is disposed on one surface of a support film which swells in a predetermined solvent, and an image layer constituting a pattern on the surface or inside of the intermediate layer. Is a transfer film for curved surface printing.

As described above, when the intermediate layer is formed, it is possible to fix any kind of ink or the like by selecting the material of the intermediate layer. It is also possible to protect the support film from the solvent used. Further, in the washing / removing step of the support film after the transfer step, the image layer made of ink or the like can be protected.

According to the present invention, an image layer constituting a picture is disposed on one surface of a support film which swells in a predetermined solvent, and an adhesive layer is disposed on the surface of the image layer. It is a transfer film for curved surface printing characterized by the following. By forming the transfer film on the image layer in this way, for example, due to the properties of the ink or the like forming the image layer and the material of the curved surface print body, even when the adhesion between the image layer and the curved surface print body is poor, An image layer having a picture pattern can be bonded on the curved surface print.

[0014] In this case, it is possible to provide both the intermediate layer and the adhesive layer.

In the present invention, it is particularly preferable that the image layer constituting the picture is a layer printed by an on-demand printing method.
0 and claim 11). This is especially true when the image layer is printed by an on-demand printing method, in which case the image layer is often printed with a different ink, etc., from the viewpoint of fixing properties of the image and adhesion to the curved surface print. Problems often arise. Therefore, it is particularly effective when the image layer is printed by the on-demand method.

In the present invention, in the step of printing the image layer, a pattern is printed by an ink jet method (claims 6 and 12) or a pattern is printed by an electrophotographic method (claims 7 and 13). Is preferred. This is because of the cost among the on-demand printing methods.

In the transfer film for curved printing according to the present invention, the support film swelling in a predetermined solvent is preferably a water-soluble film. By using a water-soluble film for the support film, water can be used as a predetermined solvent when performing curved surface printing by curl fitting, which is preferable in terms of cost and safety.

Further, according to the present invention, as described in claim 14, (1) a step of preparing a transfer film for curved surface printing by the production method of any one of claims 7 to 11, and (2) Applying the activator capable of swelling at least one of the image layer, the intermediate layer and the adhesive layer to the image layer side surface of the transfer film for curved printing obtained in the previous step,
(3) floating the transfer film for curved surface printing on the predetermined solvent with the surface on which the image layer is printed facing up;
(4) The curved surface print is lowered from above the transfer film for curved surface print swollen on the solvent, and a part or the whole thereof is settled in the solvent, and the curved surface is formed on the surface of the curved surface print by the pressure of the solvent. (5) removing the curved print from the solvent and washing and removing the support film from the curved print;
(6) a step of forming a protective layer on the curved printed body from which the support film has been removed.

As described above, by manufacturing a curved printing body using the transfer film for curved printing having an image layer constituting a picture printed by the above-described on-demand printing method, a curved printing body can be manufactured without using a printing plate. Since a curved printed body can be obtained, a curved printed body can be manufactured quickly and at low cost. Therefore, the curved printed body obtained by this manufacturing method as described in claim 15 is:
Can respond quickly to customer demands,
There is an advantage that it is possible to cope with the tendency of a small lot.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the transfer film for curved surface printing of the present invention will be described in detail.

The transfer film for curved surface printing of the present invention is characterized in that an image layer constituting a pattern printed by an on-demand printing method is laminated on one surface of a support film which swells in a predetermined solvent. In particular, the present invention has a great feature in that an image layer constituting a picture is printed by an on-demand printing method.

As described above, by printing the image layer constituting the picture by the on-demand printing method, the image layer constituting the picture can be printed on the support film without producing a printing plate. Therefore, as compared with a conventional transfer plate for curved surface printing printed by gravure printing that requires a printing plate, a transfer film for curved surface printing can be obtained at low cost and in a short time. Therefore,
Since the finally obtained curved printed body can be provided at low cost and in a short time, it can be used for prototypes and the like, and can sufficiently cope with recent trends in many kinds and small lots.

The on-demand printing method used in the present invention means a printing method that can be performed without using a printing plate, and specifically includes, for example, an inkjet method, an electrophotographic method, and a thermal method. Printing methods such as a thermal transfer method of a melting type or a dye sublimation type, and a magnetography method of magnetic head recording or thermomagnetic recording can be used. In the present invention, among others, a printing method using an ink jet method or an electrophotographic method is preferable. This is because these methods are preferable in terms of cost.

The support film used in the present invention swells sufficiently on the solvent when transferred onto the solvent in the curl fit printing step, and has suitability for multicolor printing.
Further, it is preferable that the material has a transfer property, that is, a property of sufficiently wrapping around the surface of the curved surface print. In the present invention, “swells in a predetermined solvent” means that it has either property of dissolving or swelling in a predetermined solvent.

Specific examples of such a support film include, for example, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyvinyl alcohol, polyacrylamide, sodium polyacrylate, polyvinyl methyl ether, Methyl vinyl ether and maleic anhydride copolymer, vinyl acetate and itaconic acid copolymer, polyvinylpyrrolidone, or cellulose, acetylcellulose, acetylbutylcellulose, carboxymethylcellulose, methylcellulose,
Cellulose derivatives such as hydroxyethyl cellulose,
Sodium alginate and the like can be mentioned, and these can be used alone or in combination.

In the present invention, the predetermined solvent, that is, the solvent that causes the transfer film to float and swell in the curl fit is not particularly limited, but is preferably water from the viewpoint of cost and safety.

As described above, when the predetermined solvent is water,
The support film is preferably a film that swells in water.Specifically, among the above-mentioned films, a starch-based film, a polyvinyl alcohol-based film, a film composed of a mixture of polyvinyl alcohol and starch, or a paper made of the above-described material is used. , A nonwoven fabric, a film coated on a liquid-permeable base such as various porous films, or a laminated film.

In the present invention, a film containing a polyvinyl alcohol resin as a main component is most preferable. The film mainly composed of the polyvinyl alcohol resin has a degree of polymerization, a degree of saponification, and the addition of additives such as starch.
By changing various conditions, the mechanical strength required for on-demand printing, moisture absorption during handling,
It is possible to control the speed of softening by water absorption after floating on water, the time required for spreading or diffusion, the ease of deformation during transfer, and the like. An example of a preferable film mainly containing polyvinyl alcohol (PVA) resin is PVA80
% By weight, 15% by weight of a high molecular weight water-soluble resin, and 5% of starch
%, And the equilibrium water content is about 3%.

The thickness of such a support film is 10 to
It is preferably within a range of 100 μm, more preferably 20 to
It is within the range of 60 μm.

The transfer film for curved surface printing of the present invention is obtained by laminating an image layer constituting a picture on one surface of such a support film. Here, the pattern is not limited to one having a design property, but includes various patterns and solid coating.

The ink or toner used for the image layer is not particularly limited as long as it is an ink or toner applicable to on-demand printing, but it is temporarily adhered to the above-mentioned support film to easily form a dry film. And
Further, it is preferable to use, as a vehicle, a resin that adheres to the surface of the transfer member and easily swells with an activator described later.

For example, in the case of the electrophotographic system, wet and dry toners are used. Here, the wet toner is
Basically, toner particles composed of a resin and a colorant are dispersed in a dispersion medium. Therefore, when printing is performed on the support film by an electrophotographic method using such a wet toner, the image layer is formed of toner particles composed of the resin and the colorant. As the resin used for such toner particles, for example, a styrene-butadiene copolymer resin,
Styrene-isoprene copolymer resin, styrene-acrylonitrile copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-methacrylate copolymer resin, ethylene-ethyl acrylate copolymer Resin, vinyl acetate-methyl methacrylate copolymer resin, acrylic acid-methyl methacrylate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, and 2-ethylhexyl acrylate / methacrylic acid copolymer, lauryl methacrylate
A thermoplastic resin such as an acrylic resin such as a 2-hydroxyethyl methacrylate copolymer or a 2-ethylhexyl methacrylate / diacetone acrylamide copolymer can be used.

As the colorant, a known organic pigment or inorganic pigment is generally used. When the molecules of the copolymer resin have a colored atomic group, the copolymer resin itself or the colored atomic group can be used as a coloring agent.
That is, the colorant may be an independent component, or the copolymer resin may function as a colorant.

As the black colorant, for example, an inorganic colorant such as carbon black and iron tetroxide, or an organic colorant such as cyanine black can be used.

As the yellow colorant, 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.

As other yellow colorants, the following can be exemplified. 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. pi
gment Yellow 153), an azomethine-based copper complex pigment (CI
No. pigment Yellow117); a quinophthalone pigment,
Phthalimide quinophthalone pigment (CI No. pigment Yel
low 138) can be used.

As the magenta coloring agent, inorganic pigments such as cadmium red, red iron oxide, silver vermilion, lead red, antimony vermilion and the like 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 pigments) 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 colorant, the following condensed polycyclic pigments can also be used. That is, pyranthrone orange (CI No. pigm) which is an anthraquinone pigment
entOrange 40), ant anthrone orange (CIN)
o. pigment Orange 168), dianthraquinonyl red (CI No. pigment Red 177); thioindigo magenta (CI No. pigment Vi) which is a thioindigo pigment
olet 38), thioindigo violet (CI No. pig)
ment Violet 36), Thioindigo Red (CI No. 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 (CINo. Pigment Red 14
9), perylene red (CI No. pigment Red 178);
Quinacridone red (C.A.
I. No. pigment Violet 19), quinacridone magenta (CI No. pigment Red 122), quinacridone maroon (CI No. pigment Red 206), quinacridone scarlet (CI No. pigment Red 207); pyrocholine pigments; Pigments can be used.

Other magenta colorants include rhodamine 6G lake (CI N
o. 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 colorant, 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.

In addition, if necessary, a brilliant pigment or a matte pigment can be used.

Examples of the glitter pigment include (1)
What is called a pearl pigment, more specifically, the inner part of a shell or a crushed pearl, scale-like foil pieces (titanium dioxide-coated mica) made by baking titanium oxide or iron oxide on mica fine particles; ) Metal powder, more specifically powder of aluminum, brass, bronze, gold, silver, etc., preferably 1 to
Fine particles or scaly foil pieces of 120 μm;
(3) A piece of a plastic film that has been deposited, more specifically, a silver powder obtained by depositing and crushing the above metal, usually aluminum, on a polyethylene terephthalate film, and then painting a transparent yellow color after the deposition. (4) Two or more resin layers having different refractive indices, for example, a polyester resin layer and an acrylic resin layer, each of which has a thickness of several μm or less, are laminated. Examples thereof include foil powder obtained by finely cutting a composite film that produces iris color due to interference.

As the mat pigment, kaolinite,
Examples include clay minerals such as halosite, muscovite, and talc, and synthetic achromatic pigments such as anhydrous silica, anhydrous alumina, calcium carbonate, magnesium carbonate, and barium carbonate.

Additives such as a charge control agent, a dispersant, and a fixing agent may be added to such toner particles as needed.

On the other hand, as the dry toner material, either a two-component toner or a one-component toner can be suitably used. The two-component toner and the non-magnetic one-component toner are basically composed of a binder resin, a colorant, a charge controlling agent, and an additive, and the magnetic one-component toner includes a magnetic powder such as iron and magnetite in addition to the above-described materials. . The binder resin needs to be selected in consideration of the chargeability and heat fixing property of the toner. Principal binder resins include polystyrene, hydrogenated styrene resin, styrene / isobutylene copolymer, styrene / butadiene copolymer, styrene / butadiene / chlorinated paraffin copolymer, and other polystyrene resins; polymethyl methacrylate, polyethyl Methacrylate, polybutyl methacrylate, polyglycidyl methacrylate, methyl methacrylate / butyl methacrylate copolymer,
Acrylic resin such as ethyl methacrylate / acrylic acid copolymer; styrene / n-butyl methacrylate copolymer, styrene / diethylaminoethyl methacrylate copolymer, styrene / methyl methacrylate copolymer, styrene / glycidyl methacrylate copolymer, styrene Methyl methacrylate / n-butyl acrylate copolymer, styrene / methyl methacrylate / butyl acrylate / N-ethoxymethyl acrylamide copolymer,
Styrene / (meth) acrylate copolymer resins such as styrene / n-butyl methacrylate / maleic anhydride copolymer, styrene / n-butyl methacrylate / acrylic acid copolymer: fumaric acid / etherified diphenol-based polyester, etc. Polyester resin; Epoxy resin; Polyurethane resin; Silicone resin; Butyral resin; Polyolefin resin such as low molecular weight polyethylene, ethylene / vinyl acetate copolymer, low molecular weight polypropylene; Polyamide resin; Polyvinyl alcohol resin; Other than fluororesin such as vinylidene,
Terpene resin, imide resin, ketone resin, ethyl cellulose, rosin, alkyd resin and the like can be used.

The charge controlling agent is used for positive charging, such as an electron donating dye such as a nigrosine dye, an alkoxylated amine,
A quaternary ammonium salt, an alkylamide, a simple substance and a compound of phosphorus and tungsten, a molybdate chelate pigment, a fluorine-based activator, hydrophobic silica, and the like are used.
On the other hand, for negative charging, electron-accepting dyes such as metal complex salts of monoazo dyes, electron-accepting organic complexes, chlorinated polyolefins, chlorinated polyesters, polyesters with excess acid groups,
Metal soaps such as sulfonylamine of copper phthalocyanine, oil black and metal salts of naphthenic acid are used.

As the colorant, the same material as that of the wet toner can be used. Other additives include cleaning agents (such as fatty acid metal salts, fluorine-based surfactants, and silicon oxide derivatives), fluidizing agents (such as colloidal silica, silicon varnish, metal soaps, and nonionic surfactants), and fillers (calcium carbonate). , Clay minerals, mica, etc.) are added to the toner as needed.

Next, when the image layer is formed by ink-jet printing, the image layer is composed of ink used in the ink-jet method. Inks used in such an ink-jet method are largely classified into aqueous and oil-based inks, and one of them is selected according to the physical properties of a support film or an intermediate layer described later. In the aqueous ink used in the present invention, the solvent is water alone or a mixed solvent of water and a water-soluble organic solvent. The water is desirably pure water or ultrapure water that has undergone a purification step such as ion exchange or distillation.

The above-mentioned water-soluble organic solvent is a high-boiling-point, low-volatility polyvalent such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol and polypropylene glycol. Alcohols are used or their monoetherified, dietherified, esterified,
For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monobutyl ether and the like are used, and N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, tetrahydrofuran, monoethanolamine, N, N-dimethylethanolamine, N, N-
Diethylethanolamine, diethanolamine, N-
A water-soluble organic solvent such as a nitrogen-containing organic solvent such as N-butyldiethanolamine, triisopropanolamine, and triethanolamine can be added within a range that does not cause printing flow or bleeding.

Further, it has a drying property with respect to water as a main solvent,
For the purpose of improving the permeability, a highly volatile monohydric alcohol such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, and tert-butanol can be added.

On the other hand, the oil-based ink is preferably one based on a solvent having a high boiling point in order to prevent clogging of the head and the like. As the high boiling point solvent, ethylene glycol,
High-boiling and low-volatility polyhydric alcohols such as diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, polyethylene glycol and polypropylene glycol;
Or their monoether, diether,
Esterified products, for example, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, etc .; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin; paraffin-based carbonization such as Exxon Isopar G and Isopar H Hydrogens: petroleum naphtha-based solvents such as Shell Sole manufactured by Shell Petroleum; naphthenic hydrocarbons; and aromatic hydrocarbons.

When quick drying is important, more volatile solvents such as alkyl alcohols such as ethyl alcohol and isopropyl alcohol; acetone,
Ketones such as methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate; amides such as dimethylformamide and dimethylacetamide; and ethers such as dioxane and tetrahydrofuran mixed with the above solvents. Or can be used alone.

Known pigments and dyes are widely used as colorants used in ink jet inks. As the pigment, those described as a colorant for a wet toner can be similarly used. As the dyes, water-soluble direct dyes, acid dyes, basic dyes, food dyes, reactive dyes, and water-insoluble oil-soluble dyes and disperse dyes can be used in the form of being dispersed or dissolved in a solvent.

As the water-soluble dye mainly used in the aqueous ink, for example, the following dyes indicated by a color index are used.

C. I. Acid Yellow 17, 23, 4
2,44,79,142, C.I. I. Acid Red 1,
8, 13, 14, 18, 26, 27, 35, 37, 4
2,52,82,87,89,92,97,106,1
11, 114, 115, 134, 186, 249, 25
4,289, C.I. I. Acid Blue 9, 29, 45,
92, 249, C.I. I. Acid black 1,2,7,
24, 26, 94, C.I. I. Food yellow 3,4,
C. I. Food red 7, 9, 14, C.I. I. Food black 2, C.I. I. Direct Yellow 1,12,2
4, 26, 33, 44, 50, 142, 144, 86,
C. I. Direct Red 1,4,9,13,17,2
0, 28, 31, 39, 80, 81, 83, 89, 22
5,227, C.I. I. Direct orange 26,29,
62, 102, C.I. I. Direct blue 1,2,6
15, 22, 25, 71, 76, 79, 86, 87, 9
0, 98, 163, 165, 199, 202, C.I. I.
Direct plaques 19, 22, 32, 38, 51, 5
6, 71, 74, 75, 77, 154, 168, C.I.
I. Basic Yellow 1,2,11,13,14,1
5,19,21,23,24,25,28,29,3
2,36,40,41,45,49,51,53,6
3, 65, 67, 70, 73, 77, 87, 91, C.I.
I. Basic Red 1,2,12,13,14,1
5,18,22,23,24,27,29,35,3
6,38,39,46,49,51,52,54,5
9, 68, 69, 70, 73, 78, 82, 102, 1
4,109,112, C.I. I. Basic Blue 1,
3,5,7,9,21,22,26,35,41,4
5,47,54,62,65,66,67,69,7
5, 77, 78, 89, 92, 93, 105, 117,
120, 122, 124, 129, 137, 141, 1
47, 155, C.I. I. Basic Black 2,8.

Examples of water-insoluble dyes include diarylmethane, triarylmethane, thiazole,
Methine, azomethine, xanthine, oxazine, azo and azo derivatives, anthraquinone derivatives,
Quinophthalone derivatives, spirodipyran-based, isodrinos-viropyran-based, and fluoran-based dyes are preferably used. For example, C.I. I. Disperse Yellow 51, 3, 54, 79, 60, 23, 7,
141, C.I. I. Day sparse blue 24, 56, 1
4, 301, 334, 165, 19, 72, 87, 28
7, 154, 26, 359, C.I. I. Disperse threads 135, 146, 59, 1, 73, 60, 167,
C. I. Disperse Violet 4, 13, 26, 3
6, 56, 31, C.I. I. Solvent Violet 1
3, C.I. I. Solvent Black 3, C.I. I. Solvent Green 3, C.I. I. Solvent Yellow 66, 1
4, 16, 29, 105, C.I. I. Solvent Blue 7
0, 35, 63, 36, 50, 49, 111, 105,
97, 11, C.I. I. Sol Revent Red 135, 8
1, 18, 25, 19, 23, 24, 143, 146,
182.

In order to improve dispersibility and fixability, a solvent soluble or insoluble in a solvent may be contained. Examples of such resins include polyvinyl alcohols: polyvinylpyrrolidone; ethylene resins such as ethylene / vinyl acetate copolymer; acrylic resins such as polyacrylic acid, acrylic acid / acrylonitrile copolymer; vinyl acetate / acrylic ester; Vinyl acetate copolymer resins such as polymers and vinyl acetate / fatty acid vinyl ethylene copolymers; proteins;
Natural rubbers; glucosides; cellulose derivatives; polyamide resins; rosins and rosin esters; terpene phenolic resins; alkyd resins;
Melamine resins and the like can be mentioned.

In addition, nonionic surfactants such as fatty acid ester type of polyoxyethylene compound and polyethylene oxide condensation type, higher fatty acid salt, higher alkyl dicarboxylate, higher alcohol sulfate, higher alkyl sulfonate, higher fatty acid and Anionic surfactants such as condensates of amino acids, sulfosuccinates and naphthenates; cationic surfactants such as fatty acid amine salts, quaternary ammonium salts, sulfonium salts and phosphonium salts; amphoteric surfactants such as betaine type Surfactants such as preservatives;
A fungicide; a pH adjuster; a defoamer; an ultraviolet absorber; a viscosity adjuster: a surface tension adjuster and the like may be added as needed.

[0060] Ordinary ink-jet inks cannot contain a large amount of binder resin due to low suitable viscosity. For this reason, the ink layer formed in an image form often disappears without being retained during the transfer step in the present invention. This problem can be solved by providing an intermediate layer for fixing the ink layer on the supporting film as described later, but as a method of fixing without providing the intermediate layer, the colorant particles in the ink are wrapped with resin. It is effective to granulate with. According to this method, the colorant itself can have a fixing ability without greatly increasing the viscosity of the ink. The resin for this purpose is a copolymer of at least two kinds of monomers A and B, and the sp value of each monomer and the ing composition is

(Equation 1) Are selected to satisfy the relationship For example, a method of coating pigment particles used in an aqueous ink with a granulating resin is as follows.

1. Pigment dispersing step The granulated resin is dissolved in an organic solvent in which the granulated resin is soluble and compatible with water, and a pigment is further added. This liquid is treated for several hours with a bead mill, a ball mill, a high-speed bead disperser or the like to grind the pigment.

[0062] 2. Solvent replacement step The above dispersion is mixed with water. Dispersion is performed with an ultrasonic homogenizer or the like to prevent aggregation at the time of addition.

3. Organic solvent removal step The organic solvent used for the pigment dispersion is removed from the above dispersion using a rotary evaporator or the like. As the amount of the organic solvent decreases, the portion of the granulated resin caused by the hydrophobic monomer precipitates on the surface of the hydrophobic colorant and covers the colorant. At the same time, the site caused by the hydrophilic monomer of the granulated resin swells in water,
The coated colorant particles are dispersion-stabilized.

4. Post-dispersion step Post-dispersion is performed with an ultrasonic homogenizer or the like to make the particle size uniform.

In this case, the granulated resin is obtained by copolymerization of one or more kinds of hydrophilic monomers and one or more kinds of hydrophobic monomers. And those which are soluble in water and insoluble or hardly soluble in water are preferred.

Examples of the hydrophilic monomer used include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and salts thereof.

Further, vinyl alcohol, ethylene glycol, vinylpyrrolidone, acrylamide, methacrylamide, and a monomer having a salt of a cationic functional group such as a quaternary ammonium or an amino group may be used.

The hydrophobic monomer is not particularly limited. It is preferable to dissolve the organic solvent in the organic solvent.
A solubility parameter value (hereinafter referred to as SP value) is used as an index of solubility.
Is used.

In general, the SP value is known to indicate the compatibility or incompatibility between substances. However, taking the relationship between a resin and its solvent as an example, the degree of solubility of the resin in the solvent is determined by the SP value. The smaller the difference in SP value between the two, the higher the solubility of the resin in the solvent, and the larger the difference, the lower the solubility and the insolubility.

For example, when tetrahydrofuran is used as an organic solvent, a preferable hydrophobic monomer is a homopolymer of a hydrophobic monomer having an SP value of tetrahydrofuran.
It is close to the value (9.1). As such a homopolymer, for example, polyethyl methacrylate (9.
l), polypropyl methacrylate (9.0), polyethyl acrylate (9.2), polymethyl methacrylate (9.3), polypropyl acrylate (9.0),
Polystyrene (9.1), polyvinyl acetate (9.4) and the like can be mentioned.

In order to form a good image on a support film having a poor solvent absorbing ability, a so-called hot melt ink or UV curable ink can be used.

The hot melt ink is a solid or a high-viscosity liquid at room temperature, but is melted and reduced in viscosity by heating during recording. Examples of the solvent include paraffin wax, carnapa wax, candelilla wax, wood wax, beeswax, lanolin, spermaceti, paraffin hooks derivative, microcrystalline wax, Fischer-Tropsch wax, α-olefin maleic anhydride copolymer wax, etc. And fatty acids such as stearic acid, myristic acid and palmitic acid; higher alcohols such as nutearyl alcohol and polypinyl ether; polyhydric alcohol fatty acid esters such as sorbitan monostearate; polyolefins Resins; epoxy resins; polyamide resins; polyester resins; urethane resins.

On the other hand, the UV curable ink contains a prepolymer, a monomer, a photoinitiator and a colorant as main components. As the prepolymer, polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate,
Any of prepolymers such as alkyd acrylate, polyol acrylate, and silicon acrylate can be used without any particular limitation.

Examples of the monomer include vinyl monomers such as styrene and vinyl acetate; monofunctional acrylic monomers such as n-hexyl acrylate and phenoxyethyl acrylate; diethylene glycol diacrylate, 1,6-hexanediol diacrylate, hydroxypiperate ester neopentyl Polyfunctional acrylic monomers such as glycol diacrylate, trimethylolpropane triacrylate, and dipentaerythrol hexaacrylate can be used. The above prepolymer and monomer may be used alone or in combination of two or more.

The photopolymerization initiators include isobutyl benzoin ether, isopropyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, 1-phenyl-1,2-propadione-2-oxime, 2,2-
Dimethoxy-2-phenylacetophenone, benzyl,
Hydroxycyclohexylphenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, chlorothioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2-methylthioxanthone, chlorine-substituted benzophenone, halogen-substituted A material having desired curing characteristics and recording characteristics is selected and used from alkyl-allyl ketones and the like.

In addition, if necessary, a photoinitiating auxiliary such as an aliphatic amine or an aromatic amine; and a photosensitizer such as thiocyanone may be added.

On the other hand, when the image layer is printed by the thermal transfer method, the image layer is made of ink used in the thermal transfer method. Ink materials used in such a thermal transfer method can be classified into materials used for hot-melt transfer and materials used for heat-sensitive sublimation transfer.

First, the ink ribbon used for the hot melt transfer includes an ink layer, a base film, and a heat-resistant (slippery) layer. The ink layer is basically composed of various additives such as a colorant, a wax / ripening thermoplastic resin binder, a softener, and a dispersant.
It is largely determined by the percentage binder. Examples of the thermoplastic resin binder used include polyester resins; polyolefin resins such as polyethylene and polypropylene; ethylene copolymer resins such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer; vinyl chloride resin; (Meth) acrylic resin such as union of acrylic acid and acrylic acid; polyamide; ketone resin; various cellulose derivatives; polyurethane; polystyrene resin; polyacetal resin; epoxy resin;

For the purpose of lowering the melting temperature, animal waxes such as beeswax and spermaceti; carnauba wax;
Vegetable waxes such as candelilla wax and wood wax; petroleum waxes such as paraffin wax and microcrystalline wax; Fischer-Tropsch wax;
Synthetic hydrocarbons such as low molecular weight polyethylene;
The above wax compounds such as n-paraffin can also be used. As the colorant, the same material as that of the wet toner can be used.

The ink ribbon used for the heat-sensitive sublimation transfer is obtained by coating a base film with an ink thin film obtained by mixing a dye having a large heat diffusing ability into a binder. ) Layers.

As the dye, a disperse dye, an oil-soluble dye, and a basic dye are preferably used. These dyes are about 1
It has a molecular weight of about 50 to 550, and is selected in consideration of sublimation or melting temperature, hue, light resistance, solubility in a resin or a developer, and the like. For example, diarylmethane, triarylmethane, thiazole, methine, azomethine, xanthine, oxazine, azo and azo derivatives, anthraquinone derivatives, quinophthalone derivatives, spirodipyran, indolinospyropyran, fluoran, rhodamine Lactam dyeing is preferably used. For example, C shown by a color index
I: Disper Yellow 51, 3, 54, 79, 60,
23, 7, 141; CI Day Sparse Blue 24, 5
6, 14, 301, 334, 165, 19, 72, 8
7, 287, 154, 26, 359; CI: disperse threads 135, 146, 59, 1, 73, 60, 16
7; CI: Disperse violet 4, 13, 26,
36, 56, 31; CI: Solvent Violet 1
3; CI: Solvent Black 3; CI: Solvent Green 3; CI: Solvent Yellow 56, 14, 1
6, 29, 105; CI: Solvent Blue 70, 3
5, 63, 36, 50, 49, 111, 105, 97,
11; CI: Solvent Red 135, 81, 18, 2
5, 19, 23, 24, 143, 146, 182 and the like.

Other examples include 3,3-diethyloxacyanine iodide, Astrazone Pink FG (manufactured by Bayer, CI: 48015), 2,2-carbocyanine (CI: 808), and Astraphyloxine FF ( C
I: 1.48070), Astrazone Yellow 70LL
(CI: Basic Yellow 21), Aizen Carotene Yellow 3GLH (manufactured by Hodogaya Chemical, C1: 4805)
5), Aizen carotene red 6BH (CI: 4802)
Methine (cyanine) -based basic dyes such as monomethine-based, dimethine-based and trimethine-based dyes, such as auramine (C)
I: 655), diphenylmethane-based basic dyes, malachite green (Cl: 42000), brilliant green (CI: 42040), magenta (C
I: 42510), methyl violet (C1: 425)
35), crystal violet (C1: 4255)
5), triphenyllemethane-based basic dyes such as methyl green (CI: 684), victoral blue B (CI: 44045), pyronin G (C1: 739), rotamine B (Cl: 45170), and rotamine 6G ( C1:
45160), acridine yellow G (CI: 785), leonine AL (CI: 4)
6075), acridine-based basic dyes such as benzoflavin (CI: 791) and affine (C1: 46045);
Quinone imine basic dyes such as neutral red (CI: 50040), Astrazone Blue BGE / X125% (CI: 50005), methylene blue (CI: 52015), and other anthraquinone basic dyes having a quaternary amine; And basic dyes. These dyes can be used as they are or in a form in which these dyes have been treated with an 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 color developer may be included in the image forming film side.

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

The binder resin is selected from vinyl chloride resin, polyamide, polycarbonate, polystyrene, acrylic resin, phenol resin, polyester, epoxy resin, polyacetal resin, cellulose resin and the like, which have appropriate heat resistance and dye transfer property. I do.

Finally, the magnetic toner used in the magnetography system is made of a thermoplastic resin, a magnetic substance, and a coloring pigment. The thermoplastic resin and the coloring pigment may be the same as those used in the dry toner for electrophotography. In addition, a conductivity-imparting agent such as tin oxide; a lubricant such as polytetrafluoroethylene; a wax;

[0086] magnetic material _{mainly, Fe 3 0 4, γ-} Fe 2 O 3,
Various ferrites, iron powders, and the like are used, but since the magnetic properties differ depending on the particle shape even with the same composition, particles having a composition and shape matching the characteristics of the printer are selected.

Next, a transfer film for curved surface printing provided with an intermediate layer, which is a different aspect of the present invention, will be described.
This is a transfer film for curved surface printing characterized in that an intermediate layer is provided between the support film and the image layer.

This intermediate layer is provided for fixing and fixing a picture when the image layer is not fixed or fixed on the support film when the image layer is directly printed on the support film. The purpose is to prevent the support film from swelling by the solvent contained in the ink or the toner when the image layer is printed on the support film. The intermediate layer of the present invention, the image layer when the solvent used for removing the support film after the transfer film for curved surface printing is adhered to the curved surface printed body as described later, the image layer has no resistance, etc. It may be provided for protection.

The transfer film for curved surface printing provided with such an intermediate layer is not limited to the printing method in which the image layer is formed, but is particularly suitable when the image layer is formed by on-demand printing. It is valid. This is because the ink or toner used in the on-demand system is highly likely to cause the above-described problems such as the fixability on the support film. However, the present invention is not limited to printing on demand. For example, when it is necessary to perform the curl fit transfer process currently performed with water with another solvent, the type of the support film is changed. In such a case, the intermediate layer may be required even with the ink used in the current gravure printing.

In the present invention, the number of intermediate layers is not limited to one, but may be two or more. In this case, one layer is provided for the purpose of fixing the ink, the other layer is provided for preventing the swelling of the support film by printing, and for protecting the image film in the washing / removing process of the support film after transfer. May be provided for different purposes.

From the above-mentioned point, such an intermediate layer has a property of fixing the ink, toner or colorant used for image recording on the surface or inside thereof, or a property of not dissolving in a predetermined solvent. Must have. Further, it preferably has a swelling property with respect to an activator described later, an adhesive property with respect to a curved-surface printed body, and the like.

The intermediate layer provided in the present invention contains a resin as a main component, and is mixed with various additives as necessary. Examples of the resin used for the intermediate layer include cellulose such as ethyl cellulose, nitrocellulose, cellulose acetate, and hydroxyethyl cellulose and derivatives thereof; alkyd resin; polymethacrylic acid, polymethyl methacrylate, 2-ethylhexyl methacrylate / methacrylic acid copolymer, and lauryl. (Meth) such as methacrylate / 2-hydroxyethyl methacrylate copolymer
Acrylic resins and their metal salts; poly (meth) acrylamide resins such as poly N-isopropylacrylamide and poly N, N-dimethylacrylamide; polystyrene, acrylonitrile-styrene copolymer, styrene
Styrene resins such as maleic acid copolymers and styrene / isoprene copolymers; Styrene / acryl resins such as styrene / n-butyl methacrylate copolymers; various saturated and unsaturated polyester resins; polyolefin resins such as polypropylene; Halogenated polymers such as polyvinyl chloride and polyvinylidene chloride; vinyl resins such as polyvinyl acetate and vinyl chloride / vinyl acetate copolymer; polycarbonate resins; epoxy resins; polyurethane resins; polyvinyl formal, polyvinyl butyral, and polyvinyl acetal. Polyacetal resins such as ethylene / vinyl acetate copolymers and ethylene / ethyl acrylate copolymer resins; amide resins such as benzoguanamine; urea resins; melamine resins; Modified anionic cations; polyvinyl virolidone and copolymers thereof; alkylene oxide homopolymers, copolymers and crosslinked products such as polyethylene oxide and carboxylated polyethylene oxide; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; polyethers Polyol; S
BR, NBR latex; dextrin; sodium alginate; gelatin and its derivatives, casein, trolloay, tragacanth, pullulan, gum arabic, locust bean gum, guar gum, pectin, carrageenan, glue, albumin, various starches, corn starch, konjac, and seaweed Natural or semi-synthetic resins such as agar, soybean protein, etc .; terpene resins; ketone resins; rosins and rosin esters; polyvinyl methyl ether, polyethylene imine, polystyrene sulfonic acid, polyvinyl sulfonic acid, and the like. These resins may be used not only as a homopolymer but also as a blend within a compatible range.

Further, in order to improve the absorbability and fixability of the ink, the toner or the colorant, an appropriate gap may be provided in the intermediate layer. In order to provide voids, a filler is mixed into the intermediate layer. As the filler used, for example,
Silica; alumina; kaolinite; smectite clay minerals such as bentonite and organic bentonite and derivatives thereof: talc; calesium carbonate; magnesium carbonate; calcium sulfate; barium sulfate; zeolite; titanium oxide; cerium oxide; magnesium oxide; zirconium oxide; Soda; calcium silicate; potassium silicate; magnesium silicate; aluminum silicate; diatomaceous earth; zinc sulfide;
Inorganic pigments such as zinc hydroxide; zinc carbonate; zinc oxide; tin oxide; magnesium sulfate; aluminum hydroxide; zeolite; hydrotalcite; pseudoboehmite; lithobon; and carbon resin pigments; polystyrene resin; urea resin; Organic pigments such as plastic pigments, melamine resins, silicone resins, polyurethane resins, polyester resins, fluorine resins, polyacrylic resins, polyacrylamide resins, polypropylene, polyvinyl chloride, and polyvinylidene chloride.

Which of the above-mentioned materials is selected and what kind of structure of the intermediate layer should be selected must be designed by accident according to the type of the on-demand system used for image formation.

When printing is performed using the thermal sublimation transfer system, the intermediate layer must be one that receives the dye transferred from the ink ribbon when heated and maintains the formed image. Furthermore, in order to prevent these intermediate layer resins from fusing to the ink ribbon due to heat during image formation, phosphate esters, surfactants, fluorine compounds, fluorine resins, silicone-containing substances, silicone oils, silicone resins It is preferable to internally add various release agents such as

On the other hand, the intermediate layer suitable for the ink jet system is composed of a resin having a high affinity for the ink in order to have a high ink absorption, or a resin having a affinity for the ink and a filler. Filling material is 10
Although it can be contained in the range of from 80% to 80%, it is more preferably from 15% to 60% in order to have an appropriate ink absorbency and retain an image when swollen.

The means for forming such an intermediate layer on the support film is not particularly limited, but means such as gravure coat, offset gravure, roll coat, bar coat, spray coat, ultrasonic coat, etc. It is formed by, for example, dissolving the forming material such as the resin described above in an appropriate solvent. The thickness of such an intermediate layer varies greatly depending on the type of material used for the intermediate layer, but is preferably in the range of ^{2 to} 30 g / m ² .

Further, as another aspect of the present invention, a transfer film for curved surface printing, in which an adhesive layer is provided on an image layer, can be mentioned. When the transfer film for curved surface printing is transferred to the curved surface print by curl fitting, adhesion to the curved surface print may be poor depending on the kind of ink or the like constituting the image layer. In such a case, by providing the adhesive layer on the image layer, it is possible to maintain good adhesion to the curved surface print.

In the present invention, the method of printing the image layer of the transfer film for curved printing on which the adhesive layer is formed is not particularly limited. However, for example, when an image layer is formed by an ink-jet method and there is no binder resin as a vehicle in the image layer, there are many inks used in on-demand printing which have a problem in adhesiveness. This is particularly effective when the image layer is formed by demand-type printing. In addition, this adhesive layer may have not only the property of improving the adhesiveness to the above-described curved surface print, but also the property of improving the fixing property of the ink of the image layer, for example.

Such an adhesive layer is made of at least one resin material which swells in a specific solvent and develops adhesiveness to a curved surface print. Such resins include, for example, cellulose derivatives such as ethylcellulose, nitrocellulose and cellulose acetate; pure or modified alkyd resins such as fatty acid-modified phthalic acid alkyd and maleic acid alkyd; polymethacrylic acid, polymethyl methacrylate, 2-ethylhexyl methacrylate / methyl methacrylate copolymer, lauryl methacrylate / N, N
-(Meth) acrylic resin such as dimethylacrylamide copolymer; styrene resin such as styrene / n-butyl methacrylate copolymer, polyvinyl toluene, styrene / isoprene copolymer; polyester resin; epoxy resin; polyurethane resin; Polyacetal resin; polyethylene-based resin such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer resin; amide resin; polyvinyl alcohol resin; gelatin, casein;
Natural or semi-synthetic resins such as starch and soybean protein; terpene resins; ketone resins; rosin, rosin esters, and the like can be used. When used in combination with the intermediate layer, it is preferable to select one that can swell in the same solvent as the intermediate layer resin.

The means for forming such an adhesive layer on the image layer is not particularly limited, but means such as gravure coat, offset gravure, roll coat, bar coat, spray coat, ultrasonic coat, etc. Can be mentioned. When forming the adhesive layer, the adhesive layer may be formed by dissolving the resin or the like in an appropriate solvent. further,
The thickness of the adhesive layer varies depending on the type of the material of the adhesive layer, but is preferably in the range of ^{2 to} 30 g / m ² .

Next, a method of manufacturing the above-described transfer film for curved surface printing will be described.

The method for producing a transfer film for curved surface printing according to the present invention comprises the steps of preparing a support film which swells in a predetermined solvent and printing a pattern on one surface of the support film by an on-demand printing method. It has at least.

Since the support film swelling in the predetermined solvent is as described above, the description of the step of preparing the support film will be omitted. Hereinafter, a process of printing an image layer constituting a picture on the support film by an on-demand printing method will be described by taking an ink jet system as an example.

FIG. 1 illustrates a process of forming an image layer on a support film by an ink jet method.
First, as shown in FIG. 1A, a support film 1 is prepared. Next, as shown in FIG. 1B, printing is performed on the support film 1 with the ink A using the ink jet printer 2. FIG. 1C shows a state in which the image is printed and then dried, and an image layer 3 constituting a picture is provided on a support film 1, whereby a transfer film 4 for curved surface printing is formed. Here, the image layer 3 such as a binder resin is not mixed with the ink constituting the image layer 3
If there is no or insufficient adhesiveness between the substrate and a curved surface printing body to be described later, an adhesive layer 5 is provided on the image layer 3 as shown in FIG. The transfer film 4 may be used.

The transfer film 4 for curved surface printing thus formed is coated with an activator 6 described later (see FIG. 1).
(E), (f)), the sheet is transferred to a transfer process by curl fitting.

FIG. 2 shows a process of manufacturing an image layer by an ink jet method and manufacturing a transfer film for curved surface printing in the same manner as in FIG. 1. In this example, a process for fixing and fixing the image layer is shown. The difference is that an intermediate layer is formed.

FIG. 2A shows a state in which the intermediate layer 7 is provided on the support film 1. As shown in FIG. 2B, an image layer of the support film 1 provided with the intermediate layer 7 is printed on the side of the intermediate layer 7 by the ink jet printer 2 using the ink A. FIGS. 2C and 2D show the transfer film 4 for curved surface printing in a dried state after printing. FIG. 2C shows a state in which the ink has penetrated only into the intermediate layer 7, and FIG. 2D shows a state in which the ink has penetrated to the support film 1 through the intermediate layer 7. Show. Further, when the image layer 3 has no or weak adhesion to the curved surface print, the adhesive layer 5 is formed on the image layer 3 as shown in FIG. It may be.

The transfer agent 4 for curved surface printing thus formed is also coated with an activator 6 described later (FIGS. 2 (f) and 2 (g)) in the same manner as in FIG. Sent to.

Next, an example in which an image layer is printed by an electrophotographic method to manufacture a transfer film for curved surface printing will be described with reference to FIG. First, a support film 1 is prepared as shown in FIG. Next, using an electrophotographic printer 12 composed of a toner tank 8, a developer 9, a photoconductor 10 and an impression cylinder 11 as shown in FIG. The toner B attached according to the image is printed on the support film 1. Thus, the support film 1 as shown in FIG.
The transfer film 4 for curved surface printing on which the image layer 3 is formed is formed. Also in this example, as shown in FIG. 3D, the activator 6 is applied on the image layer 3 and sent to a transfer process by curl fitting.

As described above, the method for producing a transfer film for curved surface printing according to the present invention comprises, at least, a step of preparing a support film and printing an image layer constituting a pattern on one surface of the support film by an on-demand printing method. However, if necessary, an intermediate layer may be formed between the support film and the image layer, or an adhesive layer may be formed on the image layer as necessary. Good.

Next, a method for manufacturing a curved printed body using the above-described transfer film for curved surface printing will be described.

In the method for producing a curved surface print according to the present invention,
As shown in FIGS. 1 (e) and (f), FIGS. 2 (f) and (g), and FIG. 3 (d), after preparing the transfer film 4 for curved surface printing, first, the transfer film 4 for curved surface printing is prepared. The activator 6 is applied to the image layer 3 side. Here, when the adhesive layer 5 is formed on the image layer 3, the activator 6 is applied on the adhesive layer 5.

The activator is applied as described above unless the activator is applied to swell the image layer and the like, after which the transfer film for curved printing is floated on the solvent to swell, and then the curved surface is formed. This is because, when the printed body is pressed from above onto the transfer film for curved surface printing and transferred, the transfer film for curved surface printing cannot adhere to the surface of the curved surface printed body, and transfer is not successful. Such an activator may be any as long as it can swell at least one of the image layer, the intermediate layer, and the adhesive layer, does not dissolve the ink in the image layer, does not evaporate until transfer is performed, and When the curved printed body surface is eroded, or when the curved printed body is undercoated with a paint, it is desirable that the paint is not rapidly dissolved at the time of transfer in contact with the paint. In some cases, for example, when the transfer film for curved surface printing is transferred on a solvent before the image layer is completely dried, the activator application step is not necessary.

Examples of such an activator include, for example, pentane, hexane, heptane, octane and the like, or a mixture thereof, such as gasoline, petroleum, benzene, mineral spirits, aliphatic hydrocarbons such as petroleum naphtha, and benzene. , Toluene, xylene, cyclohexane, ethylbenzene, etc., aromatic hydrocarbons, trichloroethylene, perchlorethylene, chloroform, halogenated hydrocarbons such as carbon tetrachloride, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol , Monohydric alcohols such as benzyl alcohol,
Ethylene glycol, propylene glycol, polyhydric alcohols such as glycerin, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone, ketones such as isophorone, ethyl ether, isopropyl ether, ethylene glycol, monomethyl ether, ethylene glycol, Mono-ethyl ether, ethers such as diethylene glycol, acetates, esters such as butyrate,
Examples include nitrohydrocarbons, nitriles, amines, other acetals, acids, furans, and the like, which are used alone or as a mixed solvent.

Further, a solvent obtained by adding a resin having an affinity to the solvent to such a solvent can be used as the activator. Such resins include, for example, vinyl chloride, vinyl halide monomers such as vinylidene chloride, styrene and derivatives thereof, vinyl ester monomers such as vinyl acetate, allyl alcohol and allyl esters, acrylic acid, methacrylic acid, N- of unsaturated carboxylic acids such as itaconic acid, crotonic acid, maleic acid or fumaric acid, ester derivatives of the above unsaturated carboxylic acids, nitrile derivatives or acid amide derivatives, and N- of the acid amide derivatives of the above unsaturated carboxylic acids Methylol derivatives and N-alkyl methylol ether derivatives, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl isocyanate, allyl isocyanate, 2-hydroxyethyl-acrylate,
2-hydroxyethyl-methacrylate, 2-hydroxypropyl-acrylate, 2-hydroxypropyl-
Methacrylate, ethylene glycol-monoacrylate, ethylene glycol-monomethacrylate, ethylene glycol-diacrylate, ethylene glycol-
Dimethacrylate, maleic anhydride, itaconic anhydride,
Thermoplastic resins such as homopolymers or copolymers of monomers such as methyl vinyl ketone, butadiene ethylene, propylene, dimethylaminoethyl methacrylate, vinylpyridine, tert-butylaminoethyl methacrylate, and monoallyl ether of polyhydric alcohols , Polyamide-based resins, polyester-based resins, phenol-based resins, melamine-based resins, urea resins, epoxy-based resins, diallyl phthalate-based resins, silicon resins, thermosetting resins such as polyurethane-based resins, or modified resins or initial resins thereof Condensate, natural resin, rosin and its derivatives, cellulose derivatives,
Natural or synthetic rubber, petroleum resin and the like can be mentioned.

These resins can be easily adjusted in viscosity.
For reasons such as irrespective of application method, long ink holding time, and long transfer time, it is preferable to add the solvent to the above-mentioned solvent to form an activator, and the addition amount is in the range of 5 to 60% by weight. Is preferred.

Preferred examples of such an activator composition are shown below. The composition of this activator is designed according to the material to be swollen, and the activator of the present invention is not limited to this. Not something.

(Activator Composition Example 1) Xylene: 5 to 10 parts by weight Ethylene glycol monobutyl ether: 20 to 30
Parts by weight-butyl carbitol acetate: 30 to 40 parts by weight-phthalic ester (DBP): 20 to 30 parts-cellulose acetate butyrate (CAB): 0.9
Parts by weight Ethyl acetate: 1 to 5 parts by weight (activator composition example 2) Alkyd resin: 15 parts by weight Nitrocellulose: 2 parts by weight Barium bicarbonate: 30 parts by weight Phthalate ester (DBP): 35 parts by weight Parts: ethylene glycol monobutyl ether: 14 parts by weight butyl cellosolve acetate: 52 parts by weight maleic acid: small amount As a means for applying such an activator, gravure coat, offset gravure, roll coat, bar coat,
Spray coat, ultrasonic coat and the like can be applied, and the coating amount of the active agent is ² to 30 g / m ² , preferably 3 to
15 g / m ² .

Next, the transfer film for curved surface printing coated with the activator is floated on a solvent, preferably on water. This state is shown in FIG. A transfer film for curved surface printing 4 having an image layer 3 constituting a pattern printed on a support film 1 is floated on a solvent. Since the support film 1 swells in the solvent, the support film 1 swells and spreads as shown in FIG. At this time, the image layer 3 on the support film 1 also spreads along with the spread of the support film 1 because the activator is applied. Thereby, the transfer film for curved surface printing is in a spread state.

Then, in the state where the transfer film for curved printing 4 is spread as described above, as shown in FIG. 4B, the curved printed body 15 is lowered from above the transfer film for curved printing 4 on the solvent 14. Then, a part or the whole thereof is settled in the solvent 14, and the transfer film 4 for curved surface printing is spread and adhered to the surface of the curved surface printed body 15 by the pressure of the solvent 14.

Here, the material to be curved is not particularly limited as long as it is formed of a material to which the image layer or the adhesive layer of the transfer film for curved surface printing can be adhered. . Examples of the material that can be used for the curved surface printed body include acrylonitrile-butadiene-styrene (ABS) resin, polystyrene resin, polycarbonate resin, AES resin (ABS resin having improved weather resistance), polypropylene resin, polyethylene resin, Injection molded products such as synthetic resins, melamine resins, phenolic resins, formalin resins, urea resins, and fibrous resins consisting of homopolymers or copolymers such as polyolefin oxide resins and polyvinyl chloride resins or mixtures selected from these. And various synthetic resin molded articles such as extrusion molded articles, hollow molded articles and vacuum molded articles, as well as metal products and ceramic molded articles.

In addition, most forms such as those having a concave portion or a convex portion, those having a flat surface, those having a two-dimensional or three-dimensional curved surface, those having a through hole, and those in a lattice shape are applicable. can do. Further, a material such as wood, stone, or woven fabric having a fine emboss for producing a texture can be applied.

Next, the curved surface print 15 is removed from the solvent 14.
Take out and remove the support film. To remove this support film, as shown in FIG.
It is preferable to shower-clean the swollen support film using the same solvent as in No. 4 because it is the most efficient.
By performing the shower cleaning in this manner, it is possible to completely remove the support film and also remove stains generated at the time of transfer. The temperature of the solvent, the washing time, and the like vary greatly depending on the solvent used and the support film. For example, when polyvinyl alcohol (PVA) is used as the support film and water is used as the solvent, generally, It is preferable to wash at a water temperature of 15 to 60 ° C. for about 1 to 10 minutes.

Then, as shown in FIG. 4D, the curved surface molded body 15 from which the support film has been removed is dried by means of an air blow, a drying oven or the like. After drying, a protective layer is formed on the curved surface print to obtain a curved surface print. In addition, for example,
In the case where the intermediate layer is formed and the image layer is sufficiently protected by this, the step of forming the protective layer may not be performed.

Here, the material used for the protective layer may be a thermoplastic resin or a curable resin. Specifically, a thermosetting resin such as a thermosetting acrylic resin, a polyurethane resin, an epoxy resin, a melamine resin, a polyester resin, a prepolymer or oligomer having an ethylenically unsaturated bond in a molecule, or an ethylenically unsaturated molecule in a molecule An ionizing radiation-curable composition comprising a composition containing a monomer having a bond or a mixture thereof as a main component can be used.

Examples of the prepolymer or oligomer having an ethylenically unsaturated bond in the molecule used in the above-mentioned ionizing radiation-curable composition include unsaturated polyesters, polyester acrylates, epoxy acrylates and urethane acrylates. Polyol acrylates, various acrylates such as melamine acrylate, polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyol methacrylate, various methacrylates such as melamine methacrylate, etc., as a monomer having an ethylenically unsaturated bond in the molecule, for example, Styrene monomers such as styrene, α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, Acrylates such as butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; methacrylates such as methyl methacrylate, butyl methacrylate, ethyl methacrylate, and propyl methacrylate; acrylamide; methacrylamide; An unsaturated carboxylic acid amide,
2- (N, N-dibenzylamino) ethyl acrylate,
Substituted amino alcohol esters of unsaturated acids such as (N, N-dimethylamino) methyl methacrylate, 2- (N, N-diethylamino) propyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate Acrylate,
Polyfunctional compounds such as 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or in the molecule And polythiol compounds having two or more thiol groups, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, and pentaerythritol tetrathioglycolate.

Further, examples of the thermoplastic resin used for the protective layer include nitrified cotton, cellulose acetate, cellulose butyrate, acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl butyral resin and the like.

As described above, since the method for producing a curved printed body of the present invention can be obtained without preparing a printing plate, a curved printed body can be obtained quickly and at low cost. Therefore, the manufacturing method can be used, for example, for producing various prototypes, and can sufficiently cope with recent trends in small lots and many kinds. This effect is similarly exerted on a curved printed body obtained by this manufacturing method.

[0130]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 (Formation of Intermediate Layer) A coating solution obtained by sufficiently mixing and dissolving the following composition was coated on a polyvinyl alcohol thin film as a support film by a wire bar. The coating amount was such that the dry coating amount was 8 g / m ² . As a result, an intermediate layer compatible with oil-based inkjet was formed on the support film.

• 2-ethylhexyl methacrylate / methyl methacrylate copolymer resin (2-ethylhexyl methacrylate / methyl methacrylate (weight ratio) = 70/30, weight average molecular weight 383,000): 4 parts by weight • Hydrophobic silica (primary particles) Diameter 12 μm, BET specific surface area 150 m ² / g): 1 part by weight ・ Toluene: 6 parts by weight ・ Methyl ethyl ketone: 9 parts by weight (Production of transfer film for curved surface printing) An ink jet printer (Olympus) using oily ink on this intermediate layer 360 dp by PJ3600 manufactured by Optical Industry Co., Ltd.
(i) Full-color printing was performed to form an image layer to obtain a transfer film for curved surface printing. The obtained image layer was excellent in dot resolution without bleeding, and it was confirmed that the intermediate layer had excellent ink absorbency.

Example 2 (Formation of Intermediate Layer) A thin film of polyvinyl alcohol (PVA) was used as a support film. Nitrocellulose: 14 parts by weight Alkyd resin: 5 parts by weight Phthalate: 6 parts by weight ・ Ethyl acetate: 22 parts by weight ・ Toluene: 26 parts by weight ・ Isopropyl alcohol: 17 parts by weight A coating solution obtained by sufficiently mixing and dissolving a composition comprising: m2 and dried to form a water-resistant first intermediate layer.

Subsequently, a coating liquid obtained by sufficiently mixing and dissolving a composition consisting of: 4 parts by weight of styrene / acrylic acid copolymer resin, 2 parts by weight of calcium carbonate, and 15 parts by weight of ion-exchanged water was used. The coating surface of the first intermediate layer formed on the polyvinyl film is coated with a wire bar so as to have a dry coating amount of 10 g / m 2 and dried, and the second coating layer is compatible with aqueous inkjet printing. An intermediate layer was formed.

(Manufacture of Transfer Film for Curved Surface Printing) Ink jet printer (P manufactured by Seiko Epson Corporation)
M750C), full-color printing was performed on the intermediate layer application surface of the PVA film to produce a transfer film for curved surface printing. The obtained film did not bleed, and no swelling of the supporting film was observed due to the action of the water-resistant intermediate layer.

Example 3 (Preparation of Water-Soluble Pigment Ink for Inkjet) Preparation of cyan ink I. Pigment Blue 15: 4: 5 parts by weight (MONASTRAL BLUE FGX, manufactured by Zeneca Corporation) Polymer dispersant (styrene / acrylic acid copolymer): 1 part by weight Glycerin: 6 parts by weight Ethanol: 8 parts by weight -Ion-exchange water: 50 g of a composition consisting of 80 parts by weight was put into a mixing vessel together with 80 g of glass beads, and a dispersing machine (RC-500 manufactured by Red Devil Co., Ltd.)
In 0), an aqueous pigment cyan ink dispersed for 2 hours was obtained.

2. Preparation of magenta ink C.I. I. Pigment Blu
e 15: 4 as C.I. I. Pigment Red 17
6 (PV Carmine HF-3C, manufactured by Hoechst) was used to prepare an aqueous pigment magenta ink.

[0138] 3. Preparation of Yellow Ink C.I. I. Pigment Blu
e 15: 4 as C.I. I. Pigment Yellow
Aqueous facial yellow ink was prepared in the same manner except that 109 (Irgazine Yellow 2GLTE, manufactured by CHIPA Specialty Chemicals Co., Ltd.) was used.

4. Preparation of black ink C.I. I. Pigment Blu
e An aqueous pigment black ink was prepared in the same manner except that carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) was used instead of 15: 4.

(Production of Transfer Film for Curved Surface Printing) PVA was prepared using the above aqueous pigment ink by an ink jet printer (MJ800C manufactured by Seiko Epson Corporation).
Full color printing was performed on the film. Immediately after the recording, the water in the ink caused swelling of the PVA film, but after drying, the PVA film returned to its original state and no effect on the image was observed. The obtained image tended to have a little poor fixability, and peeled off when rubbed with an eraser or the like.

On the image layer thus formed, nitrocellulose: 12 parts by weight alkyd resin: 4 parts by weight Phthalate ester: 6 parts by weight Ethyl acetate: 32 parts by weight Toluene: 33 parts by weight -Isopropyl alcohol: A coating solution obtained by sufficiently mixing and dissolving a composition consisting of 13 parts by weight was applied by a wire bar so as to have a dry coating amount of 5 g / m2, and dried to form an adhesive layer. No disturbance or discoloration of the image due to the application of the adhesive layer was observed.

The transfer film for curved printing obtained in this manner had good fixability of the image layer and no problem in resolution.

Example 4 (Preparation of Granulated Aqueous Pigment Ink for Inkjet) Preparation of Granulated Cyan Ink In order to impart fixability to the pigment particles, a resin granulated type pigment ink was prepared.

First, a dimethylacrylamide-methyl methacrylate copolymer resin: 12.5 parts by weight (dimethylacrylamide / methyl methacrylate (weight ratio) = 95/15) I. Pigment Blue 15: 4: 5 parts by weight (MONASTRAL BLUE FGX, manufactured by Zeneca Corporation) Tetrahydrofuran: 50 parts by weight Put 67.5 g of a composition together with 130 g of glass beads into a mixing container, and disperser (manufactured by Red Devil Co., Ltd.) RC-
(5000) for 3 hours. Subsequently, 219 g of ion-exchanged water was introduced while irradiating an ultrasonic homogenizer (US-300T manufactured by Nippon Seiki Seisaku-sho, Ltd.), and tetrahydrofuran was removed by evaporation using a rotary evaporator. The dispersion treatment was again performed using an ultrasonic homogenizer to obtain a cyan pigment dispersion. The obtained pigment dispersion was filtered through a mesh, and a cyan ink was prepared by adding 10 parts by weight of polyethylene glycol and 5 parts by weight of ethanol to 85 parts by weight of the cyan dispersion.

[0145] 2. Preparation of granulated magenta ink C.I. I. Pigment
Blue 15: 4 to C.I. I. Pigment Red
A granulated magenta ink was prepared in the same manner except that 176 (PV Carmine HF-3C, manufactured by Hoechst) was used.

[0146] 3. Preparation of Granulated Yellow Ink C.I. I. Pigment
Blue 15: 4 to C.I. I. Pigment Yel
A granulated yellow ink was prepared in the same manner except that low 109 (Irgazine Yellow 2GLTE, manufactured by Chipa Specialty Chemicals Co., Ltd.) was used.

4. Preparation of Granulated Black Ink C.I. I. Pigment
Blue 15: 4 was replaced with carbon black (MA-10).
0, manufactured by Mitsubishi Chemical Corporation) to prepare an aqueous pigment black ink in the same manner.

(Production of Transfer Film for Curved Surface Printing) Using the above-described granulated aqueous pigment ink, full-color printing was performed on a PVA film by an inkjet printer (MJ800C manufactured by Seiko Epson Corporation), and the transfer for curved surface printing was performed. The resulting image was firmly fixed without bleeding, and had excellent resolution.In addition, water in the ink slightly swelled the PVA film immediately after recording, but after drying, It returned and had no effect on the image.

Example 5 (Preparation of Wet Toner) Preparation of Cyan Wet Toner 2-Ethylhexyl acrylate / methacrylic acid copolymer resin: 15 parts (2-ethylhexyl acrylate / methacrylic acid (weight ratio) = 75/25) C.I. I. Pigment Blue 15: 4: 15 parts by weight (MONASTRAL BLUE FGX, manufactured by Zeneca Co., Ltd.)-Isoparper L (manufactured by Exxon): 30 parts by weight A double planetary mixer is ripened to 120 ° C. while 500 g of the composition is ripened. , And slowly cooled to room temperature at a rate of 0.5 ° C./min while stirring continuously.
A paste-like facial dispersion was obtained. Isopar L was added at a ratio of 25 parts by weight to 15 parts by weight of the pigment dispersion, and beads were dispersed with a disperser (RC-5000, manufactured by Red Devil Co.) for 12 hours to obtain a master toner. Master Tona-4
Then, 2.5 g of soybean lecithin (manufactured by Junsei Chemical Co., Ltd.) and 2.5 g of basic calcium petronate (manufactured by Witco) were added to 00 g, and Isopar L was further added.
To obtain a cyan wet toner.

2. Preparation of Magenta Wet Toner I. Pigment Blu
e 15: 4 as C.I. I. Pigment Red 17
6 (PV Carmine HF-3C, manufactured by Hoechst) was prepared in the same manner as above to prepare a magenta toner.

[0151] 3. Preparation of Yellow Wet Toner C.I. I. Pigment Blu
e 15: 4 as C.I. I. Pigment Yellow
109 (Irgazine Yellow 2GLTE, manufactured by Chipa Specialty Chemicals Co., Ltd.) was prepared in the same manner as above to prepare a yellow liquid toner.

4. Preparation of Black Wet Toner C.I. I. Pigment Blu
e A black wet toner was prepared in the same manner except that carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation) was used instead of 15: 4.

All the obtained toners were uniformly negatively charged, and exhibited good dispersion stability.

(Preparation of Transfer Film for Curved Surface Printing) An electrostatic latent image of -200 V was formed in a pattern on a dielectric drum with a needle electrode, and roller development was performed using the above toner. The toner image on the drum was sequentially transferred onto the PVA film by electrostatic transfer, and this process was repeated for four colors to obtain a full-color transfer film for curved surface printing. The obtained image had excellent resolution and was firmly fixed on the PVA film.

Example 6 (Production of a Curved Printed Body) An activator (Ohashi Chemical Industry Co., Ltd., C, Japan) was formed on the printed image layer of the transfer film for curved surface printing obtained in Examples 1 to 5. P, AH NORMAL EX) was coated with a wire bar at a rate of 13 g / m ² , and was floated on a water surface at a temperature of 25 ° C. so that the image layer faced before the activator dried.

Next, after confirming that the transfer film for curved printing has been sufficiently swollen with water and the activator, a curved printed material made of ABS resin is pushed in from above the transfer film for curved printing, and the curved printed material is pressed. A transfer film for curved printing was adhered to the outer surface of the substrate. The curved surface printed body was pulled out of water, the polyvinyl alcohol remaining on the outermost surface was washed away with water at 40 ° C., and dried at 70 ° C. for 20 minutes. The two-component urethane paint was spray-coated on the dried curved printed body to protect the image layer, and then dried at 70 ° C. for 40 minutes to obtain a curved printed body.

[0157] All of the obtained curved prints were less expensive to form a printing plate than the prints produced by the conventional method, and the production time was shorter. Furthermore, it had the same design properties and durability as those of the conventional curved print.

[0158]

According to the present invention, for a curved surface printing, an image layer constituting a picture printed by an on-demand printing method is laminated on one surface of a support film which swells in a predetermined solvent. A transfer film is provided. Therefore, compared with the conventional gravure printing method, the time, labor and cost for preparing a printing plate are not required, so that a transfer film for curved printing can be obtained quickly and at low cost. By performing curved printing by curl fitting using a film, a curved printed body can be obtained quickly and promptly.
Therefore, it is possible to flexibly respond to requests for trial production of various types of curved surface prints, sample preparation for presentation thereof, and launch of products of various types and small quantities.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of a process of forming a transfer film for curved surface printing by inkjet printing.

FIG. 2 is an explanatory diagram showing another example of a process of forming a transfer film for curved surface printing by inkjet printing.

FIG. 3 is an explanatory diagram showing an example of a process of forming a transfer film for curved surface printing by electrophotographic printing.

FIG. 4 is an explanatory diagram illustrating an example of a printing process using curl fitting.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Support film 2 ... Inkjet printer 3 ... Image layer 4 ... Transfer film for curved surface printing 5 ... Adhesive layer 6 ... Activator 7 ... Intermediate layer 8 ... Toner tank 9 ... Developer 10 ... Photoconductor 11 ... Impression cylinder 12 ... Electrophotography Printer 13 Laser 14 Solvent 15 Curved surface print A A Ink B Toner

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H113 AA03 BA22 BB07 BB09 BB10 BB23 DA15 DA25 DA26 DA43 DA48 DA57 3B005 EB01 EB03 FA03 FA04 FA12 FA17 FB01 FB03 FB33 FB40 FC08X FE04 FE20 FG02X GA24

Claims (15)

[Claims] 1. A transfer film for curved surface printing, comprising an image layer constituting a picture printed by an on-demand printing method laminated on one surface of a support film swelling in a predetermined solvent. 2. A curved printing plate, comprising: an intermediate layer disposed on one surface of a support film which swells in a predetermined solvent; and an image layer constituting a pattern disposed on or in the intermediate layer. Transfer film. 3. A transfer film for curved surface printing, comprising: an image layer constituting a picture is disposed on one surface of a support film which swells in a predetermined solvent; and an adhesive layer is disposed on the surface of the image layer. 4. An intermediate layer is disposed on one surface of a support film which swells in a predetermined solvent, an image layer constituting a picture is disposed on the surface of the intermediate layer, and an adhesive layer is disposed on the surface of the image layer. A transfer film for curved surface printing, comprising: 5. The image layer according to claim 2, wherein the image layer forming the picture is a layer printed by an on-demand printing method. Transfer film for curved printing. 6. The image layer according to claim 1, wherein the image layer is an image layer on which a pattern is printed by an ink-jet method.
Or the transfer film for curved surface printing according to claim 5. 7. The transfer film for curved surface printing according to claim 1, wherein the image layer is an image layer on which a pattern is printed by an electrophotographic method. 8. The method according to claim 1, wherein the support film swelling in the predetermined solvent is a water-soluble film.
The transfer film for curved surface printing according to any one of claims 1 to 7. 9. A method comprising: providing a support film swelling in a predetermined solvent; and printing an image layer constituting a picture on one surface of the support film by an on-demand printing method. Of producing a transfer film for curved surface printing. 10. A step of preparing the support film,
The method for producing a transfer film for curved surface printing according to claim 9, further comprising a step of forming an intermediate layer between the step of printing the image layer and the step of printing the image layer. 11. The method according to claim 9, further comprising a step of forming an adhesive layer after the step of printing the image layer.
A method for producing a transfer film for curved surface printing according to claim 10. 12. The transfer for curved surface printing according to claim 9, wherein the step of printing the image layer is a step of printing a picture pattern by an ink jet method. Film production method. 13. The curved surface printing method according to claim 9, wherein the step of printing the image layer is a step of printing a pattern by an electrophotographic method. Production method of transfer film. 14. A process for preparing a transfer film for curved printing according to (1) a method according to any one of claims 9 to 13, and (2) at least one of the image layer, the intermediate layer and the adhesive layer. Applying the activator capable of swelling to the image layer side surface of the transfer film for curved printing obtained in the previous process; and (3) applying the transfer film for curved printing onto the surface with the image layer printed thereon. The step of floating on the predetermined solvent; and (4) lowering the curved print from above the transfer film for curved print swollen on the solvent, causing a part or the whole thereof to settle in the solvent, and (5) a step of extending and adhering the transfer film for curved surface printing on the surface of the curved surface printing body, (5) a step of removing the curved surface printing body from the solvent, and washing and removing the support film from the curved surface printing body. 6) Support film Forming a protective layer on the curved printed body from which the surface has been removed. 15. A curved printed body obtained by the method according to claim 14.