JP2000280694A - Transfer film for curved surface printing and its manufacture, and curved surface printing body using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the bonding to a curved surface body to be printed, the extending/ developing property of a picture and the fixation of the picture to a supporting film at the time of a curl fit transfer by an electronic photographing method by using a wet toner of a resin wherein the glass transition temperature of at least one component of the binder resin is a room temperature or lower. SOLUTION: A toner image 8 which is image-developed by a wet toner having the same polarity with, or an opposite polarity from a static electricity image in an developing section 7, and is transferred to a transfer section 10 when an induction drum 5 is rotated, is transferred to a material to be recorded by applying a bias or a static electric charge having an opposite polarity from the wet toner 9. For the wet toner 9, a toner particle basically comprising a resin and a coloring agent, is dispersed in a dispersion medium, and even when a resin of which the glass transition temperature is low is used, a proper repulsive force works between the particles, and a blocking is not generated. Also, in the wet toner 9, the toner is fixed by the drying of a solvent after a development, and from a viewpoint of the fixation as well, the glass transition temperature of at least one component of the binder resin is preferably set at a room temperature or lower.

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. Including the flat part.)
The present invention relates to a transfer film for curved surface printing for performing printing by a transfer method and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a method of printing on various printing materials having a curved surface includes dry offset printing through printing on a simple shape such as a conical shape or a box shape. Printing using flat paper that does not pass through, screen printing through printing requiring a thick ink layer, and further using transfer paper consisting of a base material, wax layer, printing ink layer, thermoplastic resin layer, Transfer printing, in which the ink layer is transferred by heating from the substrate side while being in close contact with the printing material, and then transferring the ink from the intaglio to a pad of silicone rubber and pressing it against the printing material (a kind of offset printing) And pad printing which is also used for precision products such as clock faces and marking of electronic parts.

Among such printing methods for a curved surface, a special curved surface printing (hereinafter referred to as a "curl fit") is one of the printing methods capable of applying a picture (printing) to a printing medium having a complicated shape. it can. The printing on a curved surface by this curl fit is performed by transferring 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, wherein the image layer has an upper surface. The printing medium is floated on the water surface, and the printing object to be painted is pushed in from above, and the image layer of the transfer film is transferred to the outer peripheral surface of the printing medium by using water pressure. No. 41683, JP-A-54-331
No. 15).

[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 types of products in recent years, on-demand printing that enables printing without using a printing plate has been attracting attention.
Various printed materials are produced by on-demand printing such as an inkjet method and an electrophotographic method. The present inventors have already invented such an on-demand type printing method into the print process of the call fit, and have applied for the application. As a result, a transfer film for curved surface printing that can respond to recent demands for small lots and many kinds can be manufactured quickly and at low cost.

The electrophotographic system is a typical on-demand system, and has begun to be used mainly for printing a small number of booklets, flyers, posters, etc. due to its cost advantage over conventional offset and gravure printing. . Recently, a device capable of printing on a special web such as a film for flexible packaging has been announced, and it is expected that the field of application will be further expanded in the future. The present inventors have considered incorporating the electrophotographic method into the print process of the color fit, but the toner normally used in the electrophotographic method is different from the ink used in the conventional color fit. The properties were very different, which caused various problems. One of the drawbacks is a lack of adhesive strength between the pattern and the printed surface when the film on which the pattern is printed by the electrophotographic method is used for hydraulic transfer.
Another drawback is the difficulty in elongating the picture during hydraulic transfer. Still another disadvantage is that toner has poor fixability to a support film. In this case, if the toner image is heated, and the binder resin is once softened and then cooled, a fixing property can be obtained, but the applied heat may cause shrinkage, deformation, and crosslinking of the support film. Is not preferred.

[0006] These disadvantages are largely caused by the thermal properties of the binder resin of the toner, and occur when the material does not have appropriate tackiness or fluidity at the working temperature, that is, when Tg is higher than room temperature. Cheap. In dry toner, the Tg of the binder resin is 5 to prevent blocking at room temperature.
The temperature must be 0 ° C. or higher, and even in a wet toner, when a binder resin that requires heat fusion fixing is used, the Tg is high, and the above-mentioned disadvantages are notable. The present invention has been accomplished in view of the above situation, and uses an electrophotographic method to adhere to a curved surface print at the time of transfer of a card fit, spread the pattern, and fix the pattern to a support film. It is an object of the present invention to provide a transfer film for curved surface printing having excellent properties.

[0007]

In order to achieve the above object, according to the present invention, there is provided an image forming apparatus according to claim 1, wherein an image layer constituting a pattern printed by electrophotography is provided on one surface of a support film which swells in a predetermined solvent. A transfer surface for curved printing, wherein a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower is used as the electrophotographic toner. A transfer film for printing is provided, and a transfer film is provided.
In the process of preparing a support film that swells in a predetermined solvent, and a method of manufacturing a transfer film for curved surface printing having at least a process of printing an image layer constituting a pattern by electrophotography on one surface of the support film, A method for producing a transfer film for curved surface printing, wherein a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower is used as the electrophotographic toner.

[0008] As described above, by using a wet toner in which at least one component of the binder resin is a resin having a glass transition temperature of room temperature or lower, the toner image has good tackiness. It is possible to obtain a transfer film for curved surface printing that is firmly bonded. Further, a transfer film for curved surface printing in which a toner image is fixed on a support film can be obtained without applying excessive heat. Further, since the toner image has good fluidity, it is possible to obtain a transfer film for curved surface printing having excellent spreadability during hydraulic transfer. By performing curved surface printing by curl fitting using the transfer film for curved surface printing, a curved surface printed body excellent in design can be obtained quickly and at low cost.

According to the present invention, an adhesive layer is disposed on one surface of a support film which swells in a predetermined solvent, and the surface of the adhesive layer is printed by an electrophotographic method. In a transfer film for curved surface printing formed by laminating image layers constituting a pattern, a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower is used as the electrophotographic toner. This is a transfer film for curved surface printing. When the adhesive layer is thus formed, the toner can be firmly fixed without changing the toner material for each type of printing machine to be used. This adhesive layer may be insoluble in the predetermined solvent as described in claim 3. This can prevent the toner image from being disturbed due to the elongation of the film in the transfer process of the call fit.

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 as 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, the present invention provides, as described in claim 6, (1) a step of preparing a transfer film for curved surface printing by the production method of any one of claims 4 to 5, and (2) A step of applying an activator capable of swelling at least one of the image layer and the adhesive layer to a surface on the image layer side of the transfer film for curved printing obtained in the previous step; (4) lowering the curved print from above the transfer film for curved print swollen on the solvent, and floating a part or all of the print on the surface with the layer printed thereon. Setting the transfer film for curved surface printing on the surface of the curved surface printed body by the pressure of the solvent, and (5) taking out the curved surface printed body from the solvent and setting the support film on the curved surface. Wash off from print A step for a method of manufacturing a curved printed body characterized by having a step of forming a protective layer on the curved surface printing material which is removed (6) support film.

In the step of floating the transfer film for curved surface printing on the predetermined solvent with the surface on which the image layer is printed facing upward, the temperature of the predetermined solvent may be adjusted by a wet process. By setting the glass transition temperature of at least one component of the binder resin of the toner or higher, the extensibility of the picture layer in the transfer step and the adhesiveness to the curved surface print can be further improved.

[0013]

As described above, the curved print body is manufactured using the transfer film for curved print having the image layer constituting the picture, which is printed by the above-described electrophotographic printing method. By utilizing the above, not only can a curved printed body be manufactured quickly and at low cost, but also by using a specific toner, a curved printed body excellent in design can be manufactured.

[0014]

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 printing according to the present invention is a transfer film for curved printing formed by laminating image layers constituting a pattern printed by an electrophotographic method, wherein a binder is used as the toner of the electrophotographic method.
A wet toner in which at least one component of the resin is a resin having a glass transition temperature of room temperature or lower is used. (Fig. 1)

As described above, by using a wet toner in which at least one component of the binder resin is a resin having a glass transition temperature of room temperature or lower, a problem arises when printing with a normal electrophotographic toner. -It is possible to provide a transfer film for curved surface printing which is excellent in adhesiveness to a curved surface printed body, spreadability of a pattern, and fixability of a pattern to a support film at the time of LeFit transfer. Therefore, as compared with a conventional transfer plate for curved printing which is printed by gravure printing which requires a printing plate, a transfer film for curved printing having the same design and transferability can be obtained at low cost and in a short time. Therefore, it can be used for prototypes, proofreading, and the like, and can sufficiently cope with recent trends in many kinds and small lots.

The electrophotographic printing method used in the present invention is not limited to a narrowly defined electrophotographic method in which a photoconductive surface of a photoreceptor is charged and subjected to imagewise exposure to form an electrostatic latent image. The electrostatic recording method of forming an electrostatic latent image by scanning the surface of a dielectric with a needle electrode, an image-like ion stream, etc., and applying a bias to the photoconductor and subjecting it to imagewise exposure The present invention covers all copying methods including a step of electrostatically forming a latent image such as a method of forming a latent image.

FIG. 3 shows an example. In FIG. 3, ions are emitted from a recording unit 5 that emits ions corresponding to an electric signal of image information to a dielectric drum 5, and an electrostatic image is recorded. Next, the dielectric drum 5 rotates, and the electrostatic image is developed in the developing unit 7 with toner of the same polarity as the electrostatic image (in this case, so-called reversal development is performed) or with the opposite polarity, to visualize the electrostatic image. Then, the visualized toner image is transferred to the transfer portion, and a bias or an electrostatic charge having a polarity opposite to that of the toner is applied across the recording material, so that the toner image recorded on the dielectric drum 5 is applied to the recording material. Transcribed. Thereafter, the dielectric pair drum 5 removes residual toner, electrostatic charge, and the like in the cleaner portion, and returns to the initial state. To obtain a color image, the toner is sequentially switched to, for example, Y, M, C, and Bk in correspondence with each color image signal, and these are changed to 4 in this case.
By repeating the transfer to the recording material one time, a full-color image can be obtained.

The support film used in the present invention is a car
In the printing process of Le Fit, when transferred on a solvent, it swells sufficiently on the solvent, and has multicolor printing suitability,
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, polyacrylic acid soda, and polyvinyl methyl ether. -Ter, a copolymer of methyl vinyl ether and maleic anhydride, a copolymer of vinyl acetate and itaconic acid, polyvinylpyrrolidone,
Or cellulose derivatives such as cellulose, acetyl cellulose, acetyl butyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, sodium alginate, and the like.
These can be used alone or as a mixture.

In the present invention, the above-mentioned predetermined solvent, that is, the solvent that causes the transfer film to float and swell in the Calfit is not particularly limited, but may be water in terms of cost and safety. preferable. When the predetermined solvent is water as described above, it is preferable to use a film that swells in water as the support film,
Specifically, among the above-mentioned films, starch-based films, polyvinyl alcohol-based films, films composed of a mixture of polyvinyl alcohol and starch, or liquids such as paper, non-woven fabric, various porous films, etc. Examples thereof include a film coated on a permeable base and a film coated with a laminate.

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 electrophotographic printing, the hygroscopicity during handling, the speed of softening by absorbing water after floating, the time required for spreading or diffusion, the transfer It is possible to control the ease of deformation at the time. An example of a preferred film mainly composed of polyvinyl alcohol (PVA) resin is composed of 80% by weight of PVA, 15% by weight of a high molecular weight water-soluble resin, and 5% by weight of starch, and has an equilibrium water content of about 3%. is there. The thickness of such a support film is preferably in the range of 10 to 100 μm, more preferably in the range of 20 to 60 μm.

The transfer film for curved surface printing of the present invention is formed by forming an image layer constituting a pattern on one surface of such a support film as a seed layer. Here, the pattern is not limited to one having a design property, but includes various patterns and solid coating. The toner used for the image layer is
It is preferable to use a resin which temporarily adheres to the above-mentioned support film, easily forms a dry film, further adheres to the surface of the transfer body, and swells easily with an activator described later as a vehicle. Such resins include at least one
Those having a glass transition temperature of a component of room temperature or lower are particularly preferably used. Since such a resin has tackiness at room temperature, a problem of blocking between toner particles occurs when used for dry toner. For this reason, dry toner
The binder resin must have a glass transition temperature of 50 ° C. or higher, and therefore, the resin having the above-mentioned preferable glass transition temperature cannot be used.

On the other hand, a wet toner is basically a toner in which toner particles composed of a resin and a colorant are dispersed in a dispersion medium. Even when a resin having a low glass transition temperature is used, a solvent for the resin is used. Blocking does not occur because an appropriate repulsive force acts between the particles due to the sum and the ζ (zeta) potential of the particle surface.
Therefore, in order to use a resin having a suitable color fit, the toner used for printing must be a wet toner. In a wet toner, the toner is fixed by drying the solvent after development. Therefore, from the viewpoint of fixability, it is preferable that at least one component of the binder resin has a glass transition temperature of room temperature or lower.

The wet toner preferably used in the present invention.
Are 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, 2-ethylhexyl acrylate-methacrylic acid copolymer, lauryl methacrylate Among acrylic resins such as g-2-hydroxyethyl methacrylate copolymer and 2-ethylhexyl methacrylate-diacetone acrylamide copolymer, those having a glass transition temperature of room temperature or lower are used alone. Or mixed with glass transition temperature above room temperature according to the necessity such as film strength It can be used Te.

The glass transition temperature (Tg) of the present invention means that an amorphous polymer liquid which cannot be crystallized structurally is supercooled and solidified into a glassy state as the temperature is lowered. However, it refers to the temperature at this time. An amorphous polymer having a glass transition temperature or higher usually behaves as a viscous liquid, and has tackiness and fluidity. The glass transition temperature can be determined not only by examining the temperature characteristics of the specific volume, but also by a change in temperature such as specific heat, refractive index, dielectric constant, diffusion constant, and elastic modulus.
However, different transition temperatures are often obtained depending on the measurement method, and it is considered that the glass transition is not a second-order transition of a thermodynamically equilibrium phase but rather a relaxation phenomenon with a large time effect. As the wet toner resin used in the present invention, one obtained by copolymerizing two or more monomers is basically used so that one molecule has a plurality of functions. The glass transition of the random copolymer occurs in between the glass transition temperatures of the respective homopolymers. That is,

Tg = V ₁ Tg ₁ + V ₂ Tg ₂ (1) 1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ (2) where V ₁ and V ₂ are the volume fractions of components 1 and 2, W ₁ and W ₂ are weight fractions, and the temperatures are both absolute temperatures. For example, when the Tg is desired to be 25 ° C. or less, the T
The resin is designed by either copolymerizing monomers having a g of 25 ° C. or less, or copolymerizing a monomer having a Tg of a homopolymer of 25 ° C. or less and a monomer having a Tg of 25 ° C. or more. As will be described later, preferred toner resins are those whose homopolymer is toner.
It is a copolymer of a monomer soluble in a solvent and an insoluble or hardly soluble monomer.Generally, a resin soluble in a highly insulating solvent such as a toner solvent has a low intermolecular force and therefore has a room temperature or less. Insoluble or poorly soluble resins often have a Tg of room temperature or higher. Therefore, in the case described above, in order to obtain a desired Tg, it is necessary to determine the ratio between the high Tg component and the low Tg component by the above equations (1) and (2).

Tg = 25 ° C., high Tg monomer / low T
The combination of g monomers is, for example, styrene (100
° C) / butadiene (-58 ° C) = 66/34, styrene (100 ° C) / isoprene (-58 ° C) = 66/34,
Styrene (100 ° C) / 2-ethylhexyl methacrylate (-10 ° C) = 40/60, vinyl acetate (32 ° C)
/ 2-ethylhexyl methacrylate (-10 ° C) = 8
5/15, acrylic acid (106 ° C) / 2-ethylhexyl methacrylate (-10 ° C) = 38/62, methyl methacrylate (105 ° C) / 2-ethylhexyl methacrylate (-10 ° C) = 39/61, isobonyl methacrylate (110 ° C) / 2-ethylhexyl methacrylate (-10 ° C) = 37/63, N-isopropylacrylamide (85 ° C) / 2-ethylhexyl methacrylate ( −10 ° C.) = 44/56, methacrylic acid (228
° C) / 2-ethylhexyl acrylate (-50 ° C) =
45/55, 2-hydroxyethyl methacrylate (8
6 ° C) / 2-ethylhexyl acrylate (-50 ° C)
= 66/34, methacrylic acid (228 ° C) / lauryl methacrylate (65 ° C) = 52/48. In order to make the Tg of the copolymer resin 25 ° C. or lower, it is only necessary to design a lower Tg component and a higher Tg component more than the copolymer composition exemplified here.

As a means of stably dispersing toner particles in a solvent in a wet toner, it is common practice to coat pigment particles in the toner with a resin having a solvent affinity. One of the indices indicating the solvent affinity is a solubility parameter (SP value). When the relationship between a resin and a solvent is taken as an example, the SP value indicates the degree of solubility of the resin in the solvent. If the difference between the SP values is small, the solubility of the resin in the solvent is large, and if the difference is large, the solubility is small and the resin becomes insoluble. From the viewpoint of dispersion stability of the toner particles, the toner resin preferably used in the present invention is a copolymer resin of at least two kinds of monomers A and B, and the SP value (δ) of each homopolymer. Satisfy the following relationship. Adsorption of the resin to the pigment surface occurs at the portion (A) insoluble in the dispersion medium of the resin, and the portion (B) soluble in the dispersion medium is in the outer shell of the pigment-resin particles and contributes to the dispersion stabilization. Therefore, such a wet developer can obtain high dispersion stability and fixability even when the solubility of the fixing agent resin in the dispersion medium is low.

| Δ _A -δ _toner solvent | ≧ 1.5, | δ _B -δ _toner solvent | ≦ 1.5, | δ _A -δ _B | ≧ 1.0 The toner solvent has high insulation such as isoparaffin. A neutral solvent is generally used. Examples of the highly insulating solvent that can be used include n-hexane (7.3) and n-heptane (7.
5), n-octane (7.5), nonane (7.6), decane (7.7), dodecane (7.9), cyclohexane (8.2), perchloroethylene (9.3), Trichloroethane (9.9) and the like. The number in parentheses is the SP value of each solvent. When Isopar-L (SP = 7.1) manufactured by Exxon, which is an isoparaffinic hydrocarbon solvent, was used as the toner solvent, monomer A (SP of homopolymer) was used.
As examples of (value), ethylene (8.1), butadiene (8.4), isoprene (8.15), isobutylene (7.7), lauryl methacrylate (8.2), stearyl methacrylate (7.8), isobonyl methacrylate (8.2), t-butyl methacrylate monomer
(8.2), and monomer B (homopolymer SP)
As examples of (value), vinyl acetate (9.4), styrene (9.1), methyl acrylate (9.7), ethyl acrylate (9.2), propyl acrylate (9.
0), methyl methacrylate (9.3), ethyl methacrylate (9.1), methacrylic acid (9.4) and the like.

Usually, the Tg of the homopolymer of monomer A is above room temperature, and the Tg of the homopolymer of monomer B is below room temperature. According to (1) and (2), the copolymer is set so as to have a glass transition temperature of room temperature or lower. More preferably, it is set so as to be insoluble or hardly soluble in the toner solvent in order to sufficiently coat the pigment particles in the toner.
As described above, the room temperature in the present invention means a temperature in a range in which the transfer film of the present invention does not require temperature control by external control, and there is no particular limitation as long as such a temperature is used.
Specifically, it means a range of 10 to 30 ° C.

As the colorant for the wet toner, a known organic pigment or inorganic pigment is usually 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, titanium 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 oker can be used. As the yellow colorant,
The following Nada-soluble metal salts (azo lakes) can also be used.
That is, an acetoacetic acid arylide monoazo pigment,
Hanzaiello-G (CI No. PigmentYe)
lllow 1), Hansayero-10G (CIN)
o. Pigment Yellow 3), Hansayello-RN (CI No. Pigment Yellow)
65), Hansa Brilliant Toyero-5GX (C.I.
I. No. Pigment Yellow 74), Hansa Brilliant Toyero-10GX (CINo.P.
pigment Yellow 98), permanent yellow-FGL (CI No. Pigment Yellow).
low 97), Shimurare-Kifastastero-6G
(CI No. Pigment Yellow 13
3), Riono-Louiero-K-2R (CI No. P
disazoyello-G (C.I. yellow 169); acetoacetic arylide-based disazo pigment.
I. No. Pigment Yellow 12), Disazoyello-GR (CI No. Pigment)
Yellow 13), Disazoiello-5G (C.I.
I. No. Pigment Yellow 14), Disazoiello-8G (CI No. Pigment)
Yellow 17), Disazoyello-R (C.I.
No. Pigment Yellow 55), permanent yellow-HR (CI No. Pigment)
Yellow 83); Chromophthaliello-3G (CI No. Pigment Y) which is a condensed azo pigment
yellow 93), Chromophthaluiero-6G (C.I.
I. No. Pigment Yellow 94), Chromophthaliero-GR (CI No. Pigment)
Yellow 95); Penstaimidazolone-based monoazo pigment, Hostapa-muyero-H3G (CI.
No. Pigment Yellow 154), Hostapa-Muero-H4G (CI No. Pigmen)
t Yellow 151), Hostapa-Muyello-H
2G (CI No. Pigment Yellow)
120), Hostapa Muyello-H6G (CIN)
o. Pigment Yellow 175), Hostapa-Muyello-HLR (CI No. Pigment)
Yellow 156); Irgazin yellow-3RLTN (CI No.
Pigment Yellow 110), Irgazine Yellow-2RLT, Irgazine Yellow-2GLT (C.I.
I. No. Pigment Yellow 10),
Fastgens-Per-Yero-GROH (C.I.N.
o. Pigment Yellow 137), Fastgens-Per-Yellow-GRO (CI No. Pig.
ment Yellow 110), Sandrin Yellow-6GL (CI No. Pigment Yellow)
w 173) can be used.

The following are examples of other yellow colorants. That is, flavantron (CI No. Pigment, which is a sllen pigment).
Yellow 24), anthramirimidine (C.I.
No. Pigment Yellow 08), a phthaloylamide type anthraquinone (CI No. Pig.
ment Yellow 123), Heliohusto Ystello I E3R (CI No. Pigment Yellow)
low 99); an azo-based nickel complex pigment which is a metal complex pigment (CI No. Pigment Green)
10), a nitroso-based nickel complex pigment (CIN)
o. Pigment Yellow 153), an azomethine-based copper complex pigment (CI No. Pigment Y)
phthalimide quinophthalone pigment (CI No. Pigmen) which is a quinophthalone pigment.
t Yellow 138) can be used.

As the magenta colorant, inorganic pigments such as cadmium red, red bengal, silver vermilion, lead red, and antimony vermilion can be used. As the magenta colorant, the following azo lake pigments can also be used. That is, Brilliant Carmine 6B (CI No. Pigment
Red 57: 1), lake red (CI No. P)
pigment Red 53: 1), permanent red F5R (CI No. Pigment Red 4).
8), Resource Red (CI No. Pigment)
Red 49), Persian orange (CI No.
Pigment Orange 17), Black Orange (CI No. Pigment Orange 1)
8), Helio Orange TD (CI No. Pigmen)
t Orange 19), pigment scarlet (CI No. Pigment Red 60: 1), brilliant scarlet G (CI No. Pigme).
ntRed64: 1), Helio Red RMT (C.I.
I. No. PigmentRed 51), Bold-
10B (CI No. Pigment Red 6)
3), Heliobold-BL (CI No. Pigme)
nt Red 54) 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. Pi.) Which is a monoazo or disazo pigment.
gment Red 1), Lake Red 4R (C.I.
I. No. Pigment Red 3) and permanent orange (CI No. Pigment T Or).
angel 5), permanent red FR2 (CI.
No. Pigment Red 2) and permanent red FRLL (CI No. Pigment Red).
9), permanent red FGR (CI No. P
Pigment Red 11) and Brilliant Carmine BS (CI No. Pigment Red 11).
4), permanent cumin FB (CI No. Pi)
gment Red 5), P.E. V. Cummin HR
(CI No. Pigment Red 150),
Permanent Cumin FBB (CI No. Pigm
ent Red 146), Novapa-Murred F3RK
-F5RK (CI No. Pigment Red)
170), Nova-Mulled HFG (CI No. P
pigment Orange 38), Novapa Murred HP4B (CI No. Pigment Red)
187), Nova Palm Orange HL. HL-70 (C.I.
I. No. Pigment Orange 36),
P. V. Carmine HF4C (CI No. Pigme)
nt Red 185), Hosta Bum Brown HFR
(CI No. Pigment Brown 2
5), Vulcan orange (CI No. Pigmen)
t Orange 16), pyrazolone orange (C.I.
I. No. Pigment Orange 13), pyrazolone red (CI No. Pigment Re)
d 38); Chromophthal Orange 4R (CI No. Pigment Orange) which is a condensed azo pigment.
ge 31), Chromophthal scarlet R (C.I.
I. No. Pigment Red 166) and Chromophthal Red BR (CI No. Pigment)
Red 144) can be used.

As the magenta colorant, the following condensed polypyrrole pigments can also be used. That is, pyranthrone orange (CI No. 1) which is an anthraquinone pigment.
Pigment Orange 40), Anthroneth Orange (CI No. Pigment Ora)
nage 168), dianthraquinonyl red (C.I.
I. No. Pigment Red 177); a thioindigo magenta (C.I.
No. Pigment Violet 38), thioindigo violet (CI No. Pigment)
Violet 36), Thioindigo Red (CIN)
o. Pigment Red 88); Perinone orange (CI No. Pigme) which is a perinone pigment.
nt Orange 43); which is a perylene pigment.
Perylene Red (CI No. Pigment Re)
dl90), peryleneba-million (CI No.
Pigment Red 123), perylene marne (CI No. Pigment Red 179),
Perylene scarlet (CI No. Pigment)
Red 149), perylene red (CI No.
Pigment Red 178), a quinacridone-based pigment, quinacridone red (CI No. Pig.
ment Violet 19), quinacridone magenta (CI No. Pigment Red 12)
2), quinacridone marne (CI No. Pigm
ent Red Pigment 06), quinacridone scarlet (CI No. Pigment Red)
207); pyrocholine pigments; red fluorbin pigments can be used.

Other magenta colorants include Rhodamine 6G lake (C.I.
No. Pigment Red 81) can be used.
Dyeable lake pigments are obtained by reacting a water-soluble dye with a precipitant to form a lake and fix it. As the cyan-based coloring agent, inorganic pigments such as ultramarine blue, navy blue, cobalt blue, and celerian blue can be used. The following can also be used as the cyan colorant. That is, Fast Gemble-BB which is a phthalocyanine pigment
(CI No. Pigment Blue 15),
Sumiton Cyanine Bull-HB (CI No. Pi
gment Blue 15), Cyanimble-502
0 (CI No. Pigment Blue 15:
1), Monastral Bull-FBR (CI No. Pi)
gment Blue 15: 2), Palomar B-B-
4810 (CI No. Pigment Blue)
15: 3), Monastral Bull-FGX (CIN)
o. Pigment Blue 15: 4), Riono-
Ruble-ES (CI No. Pigment Blu)
e 15: 6), Heliogenble-L6700F (C.I.
I. No. Pigment Blue 15: 6), Sumika Print Cyanine Blu-GN-O (C.I.N.
o. Pigment Blue 15), Heliogenble-L7560 (CI No. Pigment BL 15).
ue 16), Fast Sky Bull-A-612
(CI No. Pigment Blue 17),
Cyanine Green GB (CI No. Pigmen)
t Green 7), cyaning lean S537-2
Y (CI No. Pigment Green 3)
6), Smiton Fast Violet RL (CI.
No. Pigment Violet 23); a slender pigment, indanthromble- (PB-60P,
PB-22, PB-21, PB-64); a basic dye lake pigment, methyl violet phosphorus molybdate lake (CI No. Pigment Viol)
et3) can be used.

In addition, a glitter pigment or a mat pigment can be used if necessary. As the glitter pigment, for example, (1) what is called a pearl pigment, and more specifically, titanium oxide or iron oxide is baked on the inner part of a shell, crushed pearl, or mica fine particles. Scaly foil pieces (titanium dioxide-coated mica) and the like; (2) metal powders, more specifically powders of aluminum, brass, bronze, gold, silver, etc., preferably fine particles or scaly foils of 1 to 120 μm (3) Pieces of a plastic film deposited, more specifically, a silver powder obtained by depositing and crushing the above metal, usually aluminum, on a polyethylene terephthalate film; Golden powder crushed after painting in a transparent yellow color later; (4) 2 having a different refractive index
More than one kind of resin layers, for example, a polyester resin layer and an acrylic resin layer, each having a thickness of several μm or less are laminated in large numbers, and the composite film that causes iris color due to light interference is cut finely. And the like can be exemplified.

As the mat pigment, kaolinite,
Viscous minerals such as smectite, hallocite, muscovite, and talc; and synthetic achromatic pigments such as anhydrous silica, anhydrous alumina, calcium carbonate, magnesium carbonate, and barium carbonate. If necessary, additives such as a charge control agent, a dispersant, and a fixing agent may be added to such a toner. The method for producing the wet toner of the present invention may be in accordance with any known method, but production by a solvent replacement method or a cooling granulation method is preferably performed. The solvent replacement method comprises dissolving the toner resin in a volatile solvent in which the toner resin is soluble and compatible with the toner solvent, and further adding a pigment and, if necessary, a dispersant. Particles obtained by pulverizing the pigment with a sum mill, ball mill or high speed disperser, adding a toner solvent to the dispersion, removing the solvent used for the pigment dispersion with a rotary evaporator, etc. Redispersion to make the diameter uniform. On the other hand, the cooling granulation method involves dissolving the toner resin in a toner solvent heated to a temperature at which the toner resin becomes soluble to a concentration close to the saturation concentration, and further adding a pigment and, if necessary, a dispersant and the like to obtain a high solid state. Mix well with a planetary mixer, etc. to form a slurry of a partial concentration, cool to around room temperature with stirring to precipitate the resin, dilute with a toner solvent, and use a bead mill, ball mill, high speed disperser. -Uniformizing the particle size by means of a laser or the like. It is considered that the form of the resin granulation is different depending on the manufacturing method, and the toner properties such as the particle diameter, dispersibility, and chargeability actually differ. The selection of the preparation method must be carefully considered in consideration of the properties of the starting material, the physical properties required for the toner, and the like.

Next, a transfer film for curved surface printing provided with an adhesive layer, which is a different aspect of the present invention, will be described.
This is a transfer film for curved printing, wherein an adhesive layer is provided between the support film and the image layer.
(FIG. 2) This adhesive layer is provided for fixing and fixing a picture when it is difficult to fix and fix the picture on the support film when the image layer is directly printed on the support film. Another object is to prevent the image from being disturbed due to non-uniform swelling of the image layer when the printed film is floated on a predetermined solvent. From the above-mentioned point, this adhesive layer needs to have a property capable of fixing the toner used for image recording to the surface or inside thereof. Furthermore, the support film swells,
It is preferably insoluble in a predetermined solvent for dissolution, and has swelling properties with respect to an activator described later, adhesive properties with respect to a curved-surface printed body, and the like.

The adhesive layer provided in the present invention contains a resin as a main component, and is mixed with various additives as necessary. As the resin used for the adhesive layer, a resin having a low Tg like the toner resin is preferable because it has appropriate tackiness. For example, pure frames or modified alkyd resins such as fatty acid-modified phthalic acid alkyd and maleic alkyd; (meth) acrylic resins such as polyethyl acrylate, methacrylic acid / lauryl methacrylate copolymer and metal salts thereof; acrylamide Acrylamide / acrylic copolymer resin such as / 2-ethylhexyl methacrylate copolymer; styrene-based resin such as styrene / butadiene copolymer and styrene / isoprene copolymer; styrene / n
Styrene acrylic resins such as -butyl methacrylate copolymer; various saturated and unsaturated polyester resins; polyolefin resins such as polyisobutylene; polyvinyl formal, polyvinyl butyral, and polyvinyl acetate
Polyethylene resins such as ethylene / vinyl acetate copolymers and ethylene / ethyl acrylate copolymer resins; polyvinyl virolidones and their copolymers; alkylenes such as polyethylene oxide and carboxylated polyethylene oxide Oxide resins; polyetherpolyols; polyvinyl ether resins such as polyvinyl methyl ether; sodium alginate; gelatin and its derivatives; Natural or semi-synthetic resins such as seaweed and soybean proteins; terpene resins; ketone resins; rosin and rosin esters can be used. These resins are not only homopolymers,
They may be blended and used within a compatible range.

Further, in order to improve the fixing property of the toner, an appropriate surface unevenness or void may be provided in the adhesive layer. For this purpose, a filler is mixed into the adhesive layer. Examples of usable materials include silica; alumina; kaolinite; natural or synthetic smectite clay minerals such as montmorillonite, organic montmorillonite, saponite, teniolite, hectorite and derivatives thereof; talc; calcium carbonate; magnesium carbonate; Barium sulfate; various zeolites; titanium oxide; cerium oxide; magnesium oxide; zirconium oxide; sodium silicate; calcium silicate; potassium silicate; magnesium silicate; aluminum silicate; diatomaceous earth; zinc sulfide; zinc hydroxide; Tin oxide; magnesium sulfate;
Inorganic pigments such as aluminum hydroxide, hydrotalcite, lithobon, and carbon resin pigments; polystyrene resin; urea resin; penzoquanamine plastic pigment; melamine resin; silicone resin; polyurethane resin; polyester resin; Organic pigments such as polyacrylic resin; polyacrylamide resin; polypropylene; polyvinyl chloride; and polyvinylidene chloride.

The means for forming such an adhesive layer on the support film is not particularly limited, but includes gravure coat, offset gravure, roll coat, bar coat, spray coat. Means such as a coat and an ultrasonic coat can be used, and it is formed by dissolving the forming material such as the resin described above in an appropriate solvent. The thickness of such an adhesive layer varies depending on the material used for the adhesive layer, but is preferably in the range of 2 to 30 g / m 2. Next, a method for manufacturing the transfer film for curved printing described above will be described. The method for producing a transfer film for curved printing of the present invention includes a step of preparing a support film that swells in a predetermined solvent, and a step of printing an image layer constituting a pattern by electrophotography on one surface of the support film. And a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower as the electrophotographic toner.

Since the support film swelling in the predetermined solvent is as described above, the description of the step of preparing the support film is omitted. Hereinafter, an example of a process of printing an image layer constituting a pattern on the support film by an electrophotographic printing method will be described. First, a support film 2 is prepared as shown in FIG. Next, as shown in FIG. 4B, a toner tank 13, a developer 14, and a photosensitive member 1 filled with a wet toner.
5, using a wet electrophotographic printer 17
The toner particles adhered in accordance with the electrostatic latent image on the photoconductor 15 formed by the laser 18 are electrostatically transferred to the supporting film 2. As the developer, a developing device for a wet toner such as a roller developing device, a slit developing device, and a dish developing device is preferably used. It is also effective to use a dielectric drum in place of the photoreceptor and form an electrostatic latent image with a needle electrode or an ion flow head instead of the laser. The transfer of a toner image from a recording drum such as a photoreceptor to a supporting film is usually performed by electrostatic transfer. However, when an adhesive layer is used, simple pressure fixing can be used. When the Tg of the adhesive layer resin is higher than the internal temperature, it is preferable to heat the support film to a temperature equal to or higher than the Tg of the adhesive layer resin in order to obtain sufficient adhesiveness.

The transfer film for curved surface printing in which the image layer 3 is formed on the support film as shown in FIG.
1 is formed. Obtained transfer film for curved surface printing 1
As shown in FIG. 4 (d), an activator 19 described later is applied onto the image layer 3 and sent to a transfer step by a call fit. As described above, the method for producing a transfer film for curved printing according to the present invention comprises, at least, a step of preparing a support film and an image layer forming a pattern by electrophotography using a specific wet toner on one surface of the support film. Is printed. If necessary, an adhesive layer may be formed between the support film and the image layer (see FIG. 2). Next, a method for manufacturing a curved surface 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,
After preparing the transfer film 1 for curved printing (as shown in the figure), first, the image layer 3 of the transfer film 1 for curved printing is prepared.
Activator 19 is applied to the side. If the activator is applied in this manner, if the activator is not applied and the image layer or the like is swollen, when the transfer film for curved printing is floated on the solvent and then swollen, the elongation of the support film is increased. This is because an image layer or the like cannot follow the image, resulting in image cracking. Also,
This is because, when the curved print is pressed against the transfer film for curved printing from above, the transfer film for curved print cannot adhere to the surface of the curved print, and the transfer is not successful. Such an activator may be any as long as it can swell the image layer, or the image layer and the adhesive layer, and does not dissolve the pigment of the image layer, does not evaporate until transfer is performed, and further prints the curved surface. When the body surface is eroded or when the curved surface printed body is undercoated with a paint, it is desirable that the paint should not be rapidly dissolved during 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 activators 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. , Aromatic hydrocarbons such as toluene, xylene, cyclohexane, ethylbenzene, halogenated hydrocarbons such as trichloroethylene, perchloroethylene, chloroform, carbon tetrachloride, methyl alcohol, ethyl alcohol
Monovalent alcohols such as alcohol, propyl alcohol, butyl alcohol, amyl alcohol, and benzyl alcohol;
Polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cyclohexanone and isophorone, ethyl ether, isopropyl ether, ethylene glycol −
Mono-methyl ether, ethylene glycol, mono-
Ethers such as ethyl ether and diethylene glycol, esters such as acetates and butyrate,
Examples include nitrohydrocarbons, nitriles, amines, other acetals, acids, furans, and the like, which are used alone or as a mixed solvent.

Further, a mixture of such a solvent and a resin having an affinity for the solvent can be used as the activator. Such resins include, for example, vinyl chloride monomers such as vinyl chloride and vinylidene chloride, styrene and derivatives thereof, vinyl ester monomers such as vinyl acetate, allyl alcohol and allyl esters, acrylic acid, methacrylic acid , Unsaturated carponic 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 thereof, N of acid amide derivatives of the above unsaturated carboxylic acids -Methylol derivatives and N-alkylmethylol 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 monomethacrylate, ethylene glycol monomethacrylate, ethylene glycol diacrylate, ethylene Glycodimethacrylate
G, maleic anhydride, itaconic anhydride, methyl vinyl ketone, butadiene ethylene, propylene, dimethylaminoethyl methacrylate, vinyl pyridine, tert-
Thermoplastic resins such as homopolymers or copolymers of monomers such as butylaminoethyl methacrylate and monoallyl ether of polyhydric alcohols, polyamide resins, polyester resins, and phenol resins. , Melamine resins, urea resins, ethoxy resins, diallyl phthalate resins, silicon resins, thermosetting resins such as polyurethane resins, or modified resins or precondensates thereof, natural resins, rosin and its derivatives, cellulos -Derivatives, natural or synthetic rubbers, petroleum resins and the like.

These resins are 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 wt%. Is preferred. Preferred examples of such an activator composition are shown below, but the composition of the activator is designed according to the material to be swollen, and the activator of the present invention is not limited to this. . (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-Phthalate 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-ethylene glycol monobutyl ether: 14 parts by weight-butyl cellosolve acetate: 52 parts by weight-maleic acid: small amount

As the means for applying such an activator, gravure coat, offset gravure, roll coat, harcoat, spray coat, ultrasonic coat, etc. can be applied. The application amount of the activator 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 1 having an image layer 3 constituting a pattern printed on a support film 2 is floated on a solvent. Since the support film 2 swells in this solvent, the support film 2 swells and spreads as shown in FIG. At this time, the image layer 3 on the support film 2 also spreads along with the spread of the support film 2 because the activator is applied. Thereby, the transfer film for curved surface printing is in a spread state. The temperature of the solvent when the transfer film for curved printing is floated on the solvent is preferably equal to or higher than the glass transition temperature of at least one component of the toner resin forming the image layer. Thereby, the toner resin has appropriate fluidity and tackiness,
This is because the spread of the image layer and the adhesiveness to the curved surface print are improved.

In the state where the transfer film for curved printing 1 is spread as described above, as shown in FIG. 5B, the curved printed body 21 is lowered from above the transfer film 1 for curved printing on the solvent 20. Then, a part or the whole thereof is settled in the solvent 20, and the transfer film 1 for curved surface printing is extended and adhered to the surface of the curved surface printed body 21 by the pressure of the solvent 20.
Here, the material to be curved is not particularly limited in both material and form 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 adhere. Examples of the material that can be used for the curved surface print include acrylonitrile-butadiene-styrene (ABS) resin, polystyrene resin, polycarbonate resin, AES resin (ABS resin with improved resistance), polypropylene resin , A polyethylene resin, a polyolefin oxide resin, a homopolymer such as a polyvinyl chloride resin, or a synthetic resin comprising a copolymer or a mixture selected from these, a melamine resin,
Injection molded products such as phenolic resin, formalin resin, urea resin and cellulose resin, extrusion molded products, hollow molded products, vacuum molded products, etc., as well as metal products, ceramic molded products, etc. Can be mentioned.

In terms of form, most forms such as those having concave or convex parts, flat ones, two-dimensional or three-dimensional curved surfaces, ones having through holes, and lattices 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 printed body 21 is taken out from the solvent 20, and the support film is removed. In order to remove the support film, it is preferable to shower-swell the swollen support film using the same solvent as the solvent 20, as shown in FIG. By performing the shower cleaning as described above, the support film can be completely removed, and the stain generated during transfer can also be removed. Here, the temperature of the solvent, the washing time, etc. are greatly different depending on the solvent and the support film used,
For example, as a supporting film, polyvinyl alcohol (PV)
When A) is used and water is used as a solvent, it is generally preferable to wash at a water temperature of 15 to 60 ° C. for about 1 to 10 minutes.

Then, as shown in FIG. 5D, the curved surface molded body 21 from which the support film has been removed is dried by means such as an air blower or a drying oven. After drying, the protective layer 23 is formed on the curved surface print using the protective layer coating device 22 and a drying step is further performed to obtain a curved surface print (FIGS. 5E and 5).
(F)). 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 an oligomer having an ethylenically unsaturated bond in a molecule, or an ethylenically unsaturated polymer in a molecule. Examples thereof include an ionizing radiation-curable composition comprising a composition having a monomer having a saturated bond or a mixture thereof as a main component.

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 resins and the like. Various acrylates such as acrylate, urethane acrylate, polyol acrylate, melamine acrylate, polyester methacrylate, epoxy methacrylate, urethane methacrylate, and polyol Methacrylates, melamine methacrylates, and other various methacrylates. Examples of monomers having an ethylenically unsaturated bond in the molecule include styrene-based monomers such as styrene and α-methylstyrene. Methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, acrylic 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 diol acrylate, propylene glycol acryl acrylate G, neopentyl glycol diacrylate,
1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate
Polyfunctional compounds such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or polythiol compounds having two or more thiol groups in the molecule, for example, Trimethylolpropane trithioglycolate, trimethylolpropane trithiopropione
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, according to the method for producing a curved printed body of the present invention, a curved printed body having excellent design similar to that of conventional gravure printing can be obtained quickly and at low cost by using an electrophotographic method. Therefore, the manufacturing method can be used, for example, for preparing and correcting various prototypes, and can sufficiently cope with recent trends in small lots and many types. This effect is similarly exerted on a curved printed body obtained by this manufacturing method.

(Example 1) (Preparation of Cyan Wet Toner) Lauryl methacrylate / N-isopropylamide copolymer resin 3 parts (lauryl methacrylate / N-isopropylamide (weight ratio) = 50 / 50, weight average molecular weight 125,000, Tg = -10 ° C) I. No. Pigment Blue 15: 4 (MONASTRALBLUEFGX, manufactured by Zeneca Corporation) 3 parts ・ Non-drying oil type alkyd resin (phthalkid 926-70 (nonvolatile content 70%), manufactured by Hitachi Chemical Co., Ltd.) 1.5 parts ・ Tetrahydrofuran 40 parts 47.5 g of a glass bead 5 having a diameter of 1 mm
The mixture was placed in a mixing container together with 0 g, and dispersed with a paint shaker (RC-5000, manufactured by Red Devil Co.) for 3 hours.
After filtering off the glass beads, 200 g of Exxon Isopar L was charged while irradiating with an ultrasonic homogenizer (US-300T manufactured by Nippon Seiki Seisaku-sho, Ltd.), and tetrahydrofuran was added by a rotary evaporator. Was evaporated off. After dispersing again with an ultrasonic homogenizer, zirconium naphthenate (manufactured by Nippon Chemical Industry Co., Ltd.)
0.2 g was added, and the mixture was put again in a mixing container together with 150 g of a glass bead, and dispersed by a paint shaker for 3 hours. The glass beads were removed from the resulting dispersion, and the dispersion was diluted with Isopar L to 360 g to obtain a wet cyan toner.

(Preparation of Magenta Wet Toner) C.I. I. No. Pigment Blue
15: 4 as C.I. I. No. Pigment Red5
7: 1 (No. 587 Carmine 6B TON)
Magenta wet toner was prepared in the same manner except that ER was replaced by Daido Kasei Kogyo Co., Ltd.). (Production of Yellow Wet Toner) C.I. I. No. Pigment Blue 15: 1 as C.I. I. Pigment Yellow 17 (Seika Fast Yellow-No. 19, manufactured by Dainichi Seika Co., Ltd.) was prepared in the same manner as above except that Pigment Yellow 17 was manufactured. (Production of Black Wet Toner) C.I. I. No. Pigment Blue 15: 1 in carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation)
A black wet toner was prepared in the same manner as above except that All of the obtained toners were uniformly positively charged and exhibited good dispersion stability.

(Preparation of Transfer Film for Curved Surface Printing) An electrostatic latent image of -150 V was formed in a pattern on a dielectric drum by an ion flow head, and was subjected to roller development using the above toner. went. The toner image on the drum was sequentially transferred onto a 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. (Transfer) An activator (Ohashi Chemical Industry Co., Ltd. C, P, AH) was formed on the printed image layer of the obtained transfer film for curved surface printing.
NORMAL EX) with a wire bar at 13 g /
Coating was performed at a rate of 2 m 2, and the image layer was floated on the water surface at a temperature of 25 ° C. before the activator was dried, with the image layer facing upward.

After confirming that the transfer film for curved printing has been sufficiently swollen by the 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 outside of the curved printed material is removed. A transfer film for curved printing was adhered to the surface. The curved surface print was lifted out of water, and the polyvinyl alcohol remaining on the outermost surface was washed away with water at room temperature, and dried at 70 ° C. for 20 minutes. To protect the image layer, the two-component urethane paint was spray-coated on the dried curved printed body, and then dried at 70 ° C. for 40 minutes to obtain a curved printed body. The resulting curved printed body had good design throwing power during transfer, and was excellent in design without peeling or white spots during PVA washing removal.

Example 2 (Preparation of Cyan Wet Toner) 2-Ethylhexyl acrylate / 2-hydroxyethyl methacrylate copolymer resin (2-ethylhexyl acrylate / 2-hydroxyethyl methacrylate) Tacrylate (weight ratio) = 70/30, weight average molecular weight 178,000, Tg = -22 ° C) 15 parts · Linseed oil-modified alkyd resin (Hariphthal 3100, manufactured by Harima Chemicals, Ltd.) 7.5 Part ・ C. I. No. Pigment Blue 15: 1 (PALOMARB LUEB-4806, manufactured by Bayer AG) 15 parts • Kneading with a double planetary mixer for 3 hours while heating 500 g of a composition consisting of 30 parts of ISOPAR-L (manufactured by Exxon Corporation) to 120 ° C, While continuing to stir, slowly cool to room temperature at a rate of 0.5 ° C / min.
A strike-like pigment dispersion was obtained. Isopar L was added at a ratio of 25 parts to 15 parts of the pigment dispersion, and a paint shade was added.
Car (Red Devil RC-5000) for 12 hours
And dispersed to form a master toner. Master Toner 400
g in the form of a basic barium petronate (W
Itco) (16.7 g) was added and Isopar-L was added.
To 2700 g to obtain a cyan wet toner.

(Preparation of Magenta Wet Toner) C.I. I. No. Pigment Blue
15: 1 to C.I. I. No. Pigment Red 1
Magenta wet toner was prepared in the same manner except that 76 (PV Cumin HF-3C, manufactured by Clariant) was used. (Production of Yellow Wet Toner) C.I. I. Pigment Blue 15: 1 as C.I.
I. No. Pigment Yellow 180 (P
VFAST Yellow HG (manufactured by Clariant)), except that yellow wet toner was prepared. (Production of Black Wet Toner) C.I. I. No. Pigment Blue 15: 1 in carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation)
A black wet toner was prepared in the same manner as above except that All the obtained toners were uniformly negatively charged, and exhibited good dispersion stability.

(Preparation of Adhesive Layer) ・ Acrylamide / n-butyl acrylate / lauryl acrylate copolymer resin 1 part ・ MEK 9 parts A water-resistant adhesive layer was formed on a thin film of a metal layer using a wire bar so that the dry coating amount was 7 g / m ² . (Preparation of Transfer Film for Curved Surface Printing) An electrostatic latent image of +300 V was formed in a pattern on a dielectric drum by a needle electrode, and was subjected to roller development using the above toner. The toner image on the drum was sequentially transferred onto the PVA film coated with the above adhesive layer 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 has excellent resolution, and P
It was firmly fixed to the adhesive layer on the VA film. (Transfer) Using the obtained transfer film for curved surface printing, a curved surface printed body was obtained in the same manner as in Example 1. The resulting curved printed body had good design throwing power during transfer, and was excellent in design without peeling or white spots during PVA washing removal.

(Comparative Example) (Preparation of Cyan Wet Toner) The composition in Example 1 was prepared as follows: a 2-ethylhexyl methacrylate / methacrylic acid copolymer resin (2-ethylhexyl methacrylate / methacrylic acid ( (Weight ratio) = 50/50, weight average molecular weight 140,000, Tg = 72 ° C) 3 parts I. NO. Pigment Blue 15: 4 (MONASTRAL BLUE FGX, manufactured by Zeneca Co., Ltd.) 3 parts. A cyan wet toner was obtained in the same manner as in Example 1, except that 40 parts of tetrahydrofuran were used. (Preparation of Magenta Wet Toner) C.I. I. No. Pigment Blue 15: 4 as C.I. I. No. Pigment Red 57: 1 (N
o. A magenta wet toner was prepared in the same manner except that 587 Carmine 6B TONER (manufactured by Daido Kasei Kogyo Co., Ltd.) was used. (Production of yellow wet toner)

C. in cyan toner I. No. Pi
gment Blue 15: 4 as C.I. I. No. Pi
gment Yellow 109 (Irgazine Yellow-2GLTE, manufactured by Ciba Specialty Chemicals Co., Ltd.) was prepared in the same manner as above to prepare a yellow wet toner. (Production of Black Wet Toner) C.I. I. No. Pigment Blue 15: 4 is carbon black (MA-100, manufactured by Mitsubishi Chemical Corporation).
A black wet toner was prepared in the same manner as above except that All the obtained toners were uniformly negatively charged, and exhibited good dispersion stability.

(Preparation of Transfer Film for Curved Surface Printing) A full color transfer film for curved surface printing was obtained in the same manner as in Example 1. The obtained image had poor fixability, and peeled off from the PVA film when strongly rubbed with a finger. (Transfer) Using the obtained transfer film for curved surface printing, a curved surface printed body was obtained in the same manner as in Example 1. Since the toner could not be fixed on the PVA, peeling of the image occurred when the activator was applied with a wire bar. Further, in the transfer step, the picture did not adhere firmly to the ABS, and peeling and white spots occurred during PVA washing and removal.

[0065]

As described above, according to the present invention, transfer for curved surface printing is performed by laminating an image layer constituting a pattern printed by an electrophotographic method on one surface of a support film which swells in a predetermined solvent. In the film, as an electrophotographic toner, a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or less is utilized, thereby utilizing the on-demand method and the features to quickly and quickly reduce the toner. Not only can a curved printed body be manufactured at a low cost, but also by using a specific toner, it is possible to manufacture a curved printed body excellent in design. In addition, an adhesive layer is disposed on one surface of a support film that swells in a predetermined solvent, and a transfer film for curved surface printing is formed by laminating an image layer constituting a pattern printed by an electrophotographic method on the surface of the adhesive layer. In the electrophotographic method, by using a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower, the on-demand method is utilized, and the toner is quickly and inexpensively manufactured. Not only can produce a curved printed body, but also a wider range of use of the toner, making it possible to produce a curved printed body that is more excellent in image performance and excellent in design.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a transfer film for curved surface printing of the present invention.

FIG. 2 is a conceptual diagram of another embodiment of the transfer film for curved surface printing of the present invention.

FIG. 3 is a conceptual diagram illustrating an image forming process of electrophotography.

FIG. 4 is a conceptual diagram showing a process of printing an image layer constituting a picture by the electrophotographic printing method of the present invention.

FIG. 5 is a conceptual diagram illustrating a process of transferring an image onto a curved transfer target using a transfer film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transfer film for curved surface printing 2 Support film 3 Image layer 4 Adhesive layer 5 Dielectric drum 6 Recording part 7 Developing part 8 Toner image 9 Wet toner 10 Transfer part 11 Cleaner part 12 Image forming apparatus by electrophotographic process 13 Toner tank 14 Developer REFERENCE SIGNS LIST 15 photoconductor 17 wet electrophotographic printer 18 laser 19 activator B toner particle 20 solvent 21 curved surface print 22 protective layer coating device 23 protective layer

Claims (9)

[Claims] 1. A transfer film for curved printing, comprising an image layer constituting a pattern printed by electrophotography on one surface of a support film which swells in a predetermined solvent, wherein the electrophotographic toner is used as the toner. A transfer film for curved surface printing, wherein a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower is used. 2. A curved-surface printing method in which an adhesive layer is disposed on one surface of a support film which swells in a predetermined solvent, and an image layer constituting a pattern printed by an electrophotographic method is laminated on the surface of the adhesive layer. In the transfer film for use, at least one of a binder resin is used as the electrophotographic toner.
A transfer film for curved surface printing, wherein a wet toner whose component is a resin having a glass transition temperature of room temperature or lower is used. 3. The transfer film for curved surface printing according to claim 2, wherein said adhesive layer is insoluble in said predetermined solvent. 4. The transfer film for curved surface printing according to claim 1, wherein the support film swelling in the predetermined solvent is a water-soluble film. 5. Production of a transfer film for curved surface printing having at least a step of preparing a support film swelling in a predetermined solvent and a step of printing an image layer constituting a picture on one surface of the support film by an electrophotographic method. A method for producing a transfer film for curved surface printing, wherein a wet toner in which at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower is used as the electrophotographic toner. 6. A step of preparing a support film which swells in a predetermined solvent, arranging an adhesive layer on one surface of the support film, and printing an image layer constituting a picture by electrophotography on the surface of the adhesive layer. And a process for producing a transfer film for curved surface printing having at least one step, wherein at least one component of a binder resin is a resin having a glass transition temperature of room temperature or lower as the electrophotographic toner.
A method for producing a transfer film for curved surface printing, comprising using: 7. A process for preparing a transfer film for curved printing by the method according to any one of claims 5 and 6, and (2) swelling at least one of the image layer and the adhesive layer. (C) applying the activator to the image layer side surface of the transfer film for curved printing obtained in the preceding step; and (3) applying the transfer solvent for curved print to the predetermined solvent with the surface on which the image layer is printed facing up. (4) Lowering the curved printed body from above the transfer film for curved printing swollen on the solvent, and settling a part or all of the body in the solvent, and printing the curved surface by the pressure of the solvent. (5) a step of extending and adhering the transfer film for curved printing on the surface of the body, (5) a step of removing the curved print body from the solvent, and washing and removing the support film from the curved print body, and (6) a support film. Curved surface from which And forming a protective layer on the printed body. 8. In the step of floating the transfer film for curved surface printing on the predetermined solvent with the surface on which the image layer is printed facing upward, the temperature of the predetermined solvent is adjusted to at least one of the binder resin of the wet toner. 8. The method for producing a curved printed body according to claim 7, wherein the temperature is equal to or higher than the glass transition temperature of the components. 9. A curved printed body obtained by the method according to claims 7 and 8.