JP2000318391A - Transfer film for curved surface printing and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer film for curved surface printing capable of printing the surface with an excellent design without craze or the like of an image layer for constituting a design in the case of transferring step by curl fitting in the transfer film for printing the surface formed with the layer for constituting the design by an electrophotographic type. SOLUTION: In the transfer film for curved surface printing obtained by laminating an image layer for constituting a design printed by an electrophotographic type on one surface of a support film to be swelled in a predetermined solvent, the layer is printed by using a toner containing a swelling accelerator for facilitating elongation spreading of the layer in the case of transferring the layer to a printing material surface to be curved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention mainly relates to the curved surface of various printed materials such as metal products, plastic molded products, ceramic molded products, etc. 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 or a box shape. Printing on unsuitable flat shapes, screen printing suitable for printing requiring a thick ink layer, and printing using transfer paper consisting of a base material, wax layer, printing ink layer, and thermoplastic resin layer Clock printing is performed by transfer printing, in which the ink layer is transferred by heating from the substrate side while being in close contact with the body, and then transferring the ink from the intaglio to a pad of silicon rubber and pressing it against the printing material (a kind of offset printing). Dial printing, pad printing used for precision products such as marking of electronic parts, and the like.

Among such printing methods for curved surfaces, curl fitting (special curved surface printing) can be mentioned as a printing method capable of painting (printing) on 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 printed is provided. The image layer of the transfer film is transferred to the outer peripheral surface of the printing medium using water pressure by pushing the printing medium from above (see Japanese Patent Publication No. Sho.
2-41683, JP-A-54-33115).

[0004]

In preparing a transfer film for curved surface printing used for the curl fitting, a printing step of forming an image layer on a support film has been conventionally performed by gravure printing. However, in order to form an image layer for painting by gravure printing, 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 which can perform printing without using a printing plate has been attracting attention. On-demand printing such as an ink jet method and an electrophotographic method has been attracting attention. Various printed materials have been produced. The present inventors have already attempted to incorporate such an on-demand printing method into the printing process of Carlfit, and thereby, transfer of curved surface printing capable of responding to recent demands of small lots and many kinds. It has become possible to produce films quickly and at low cost.

[0006] Among such on-demand systems, the electrophotographic system is a typical one.
Due to its cost advantage over gravure printing, this electrophotographic method is beginning to be used mainly for printing small numbers of booklets, flyers, posters, and the like. Recently, a device capable of printing on a special material such as a film for flexible packaging has been proposed, and it is expected that the field of application thereof will be further expanded in the future.

The present inventors have studied the use of the electrophotographic method in a printing process of an image layer of a transfer film for curved printing used for the curl fit in order to apply such an electrophotographic method to the curl fitting. However, since the toner used in the electrophotographic method is greatly different from the gravure ink used in the conventional curl fitting, when the image layer of the transfer film for curved surface printing is attempted to be printed by the electrophotographic method, A variety of problems have arisen. As one of the problems, the image layer of the transfer film for curved printing printed by the electrophotographic method in this way,
When the transfer film for curved surface printing is floated on a predetermined solvent, and the curved surface printing body is lowered onto the curved surface printing body to transfer the curved surface printing body surface to the surface of the curved surface printing body by a liquid pressure, there is a problem that the picture (image layer) is difficult to extend. Therefore, in such a transfer processing step, there is a problem that cracks may occur in a picture (image layer) at the time of transfer or thereafter.

This problem is largely due to the solubility of the toner resin in the activator and the viscosity after dissolution. That is, in the transfer processing step in the usual curl fitting, before floating the transfer film for curved printing on a predetermined solvent, the activator is used so that the image layer swells with the swelling of the support film of the transfer film for curved printing. Apply. Here, since the chargeability and dispersion stability of the toner resin forming the image layer vary greatly depending on the material, the range of material selection is extremely small. Therefore, it is difficult to select a toner resin according to the activator, and a toner resin having insufficient solubility in the activator may be selected.

[0009] On the other hand, the activator also has a low degree of freedom in selecting a solvent due to the required physical properties such as the fact that it must be slow-drying, and in some cases, it is necessary to select a material that cannot sufficiently dissolve the toner resin. Furthermore, in a toner, it is important how to coat a pigment with a resin so as to obtain a stable property. Therefore, even if the toner resin alone has a high solubility in an activator, it is dissolved after the toner is formed. Sometimes it took longer to do. In such a case, even if the activator is applied to the image layer, the support film swells with a predetermined solvent in the transfer processing step, and when the transfer processing is performed, the image layer expands with the elongation of the support film. It cannot spread, and cracks or the like may occur in the image layer at the time of transfer or thereafter.

The present invention has been achieved in view of the above-mentioned problems, and a transfer film for curved surface printing on which an image layer constituting a pattern is formed by an electrophotographic method, the pattern is formed in a transfer processing step by curl fitting. It is a main object of the present invention to provide a transfer film for curved surface printing capable of performing curved surface printing excellent in design without generating cracks or the like of a constituent image layer.

[0011]

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 an electrophotographic method is provided on one surface of a support film which swells in a predetermined solvent. In the transfer film for curved surface printing formed by laminating, the image layer smoothes the movement of the toner particles in the image layer when performing the transfer processing to the curved surface printed body, to facilitate the spread of the image layer. A transfer film for curved surface printing, which is an image layer printed using a toner containing a swelling accelerator.

As described above, in the transfer film for curved printing according to the present invention, since the image layer is an image layer printed using a toner containing a swelling accelerator having the above-described characteristics, the transfer processing step In the above, when the transfer film for curved surface printing is floated on a predetermined solvent and is transferred to a curved surface printed body, the image layer can also be extended and extended according to the elongation accompanying the swelling of the support film. Therefore, problems such as cracking of the image layer during and after the transfer processing do not occur. That is, when the image layer expands and spreads along with the expansion of the support film due to swelling, the swelling accelerator is interposed between the toner particles, so that the toner particles can spread evenly without agglomeration. Therefore, problems such as cracking of the image layer during or after transfer do not occur.

In this case, as described in claim 2, it is preferable that the swelling accelerator is a substance which is in a solid state before being transferred to a curved surface printed body and which is in a liquid state during the transfer processing. . The solidification of the swelling agent before transfer processing, that is, for example, during formation (printing) of the image layer or storage after formation of the transfer film for curved surface printing, causes problems such as disturbing the pattern of the image layer. There is no. In addition, when the swelling accelerator becomes liquid at the time of transfer processing, a liquid swelling accelerator is interposed between the toner particles,
When the image layer expands and spreads during the transfer processing, the toner particles can be easily moved without agglomeration, and the above-described problems such as cracking of the image layer can be prevented.

In the present invention, it is preferable that the swelling accelerator is a substance which is heated during transfer processing to be in a liquid state. If it is a substance that liquefies by heating during transfer processing, for example, floating transfer film for curved printing on a heated predetermined solvent,
This is because the swelling accelerator can be easily liquefied by a method such as using a heated curved printed body, and problems such as cracks in the pattern of the curved printed body can be easily prevented.

In this case, as described in claim 4, it is preferable that the swelling accelerator is a substance having a melting point lower than the temperature of the predetermined solvent at the time of transfer processing. As described above, by using a swelling accelerator having a melting point lower than the temperature of the predetermined solvent at the time of transfer processing, the transfer of the curved surface printing transfer film to the predetermined solvent at the time of transfer processing enables the image layer to be formed without special heating. This is because the swelling accelerator therein can be liquefied, and defects such as cracks generated in the image layer during the transfer step and thereafter can be prevented.

In particular, in the present invention, as described in claim 5, the swelling accelerator preferably has a melting point of 30 ° C. or more and 100 ° C. or less. From the viewpoints of cost and safety, water is usually used as the predetermined solvent. Since the boiling point of water is 100 ° C., the temperature of the water at the time of transfer processing is 100 ° C. or less. Since the melting point of the swelling accelerator is preferably lower than the temperature of water at the time of the transfer processing, the melting point of the swelling accelerator is preferably 100 ° C. or less. On the other hand, as described above, the swelling accelerator used in the present invention is preferably in a solid state before transfer processing. In general, before performing the transfer processing, that is, the production of the transfer film for curved printing, and the storage of the produced transfer film for curved printing, are performed at room temperature, that is, 30 ° C.
Made at lower temperatures. Therefore, a substance having a melting point of 30 ° C. or more is in a solid state during the production and storage of the transfer film for curved printing, and does not cause a problem such as flowing of a picture of an image layer during the production and storage. For such a reason, it is preferable that the melting point of the swelling accelerator used in the present invention is 30 ° C. or more and 100 ° C. or less.

Further, in the present invention, as described in claim 6, it is preferable that the swelling accelerator has a melting point of 35 ° C. or more and 60 ° C. or less. This is usually performed at a temperature of 60 ° C. or less from the viewpoint of the stability and workability of the transfer process. Therefore, it is preferable to use a swelling accelerator having a lower melting point, that is, having a melting point of 60 ° C. or lower. Further, when the melting point is 35 ° C. or more, the image layer during printing and during storage is more stable.

In the present invention, it is preferable that an intermediate layer is disposed on one surface of the support film which swells in the predetermined solvent, and the image layer is disposed on the surface or inside the intermediate layer. And claim 14).

As described above, when the intermediate layer is formed, by selecting the material of the intermediate layer, the toner material does not need to be changed depending on the type of printing machine used in the electrophotographic system. Even toner can be firmly fixed. Further, the image layer can be protected in the step of washing and removing the support film after the transfer processing step.

Further, in the present invention, as described in claim 8, it is preferable that the intermediate layer is insoluble in the predetermined solvent. This is because if the intermediate layer is insoluble in the above-described predetermined solvent, it is possible to prevent the pattern of the image layer from being disturbed due to the elongation of the film in the curl-fit transfer processing step.

Further, in the present invention, claim 9
As described in above, the support film swelling in the 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.

In the present invention, it is preferable that the image layer of the transfer film for curved printing is formed by an electronic printing method using a wet toner.
3). The toner used for the image layer temporarily adheres to the support film, easily forms a dry film, further adheres to the surface of the curved printed body, and easily swells with an activator described below. Those containing as a vehicle are preferred. Examples of such a resin include those having a glass transition temperature of room temperature or less. 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, the solvation of the resin and the ζ potential of the particle surface are performed. As a result, an appropriate repulsion acts between the particles, so that no blocking occurs. On the other hand, when such a resin having a low glass transition temperature is used as a vehicle for the dry toner, a problem of blocking may occur. Therefore, in order to use a resin having curl fit property, it is preferable that the toner used for printing is a wet toner rather than a dry toner.

Further, according to the present invention, as set forth in claim 11, a step of preparing a support film which swells in a predetermined solvent, and printing an image layer constituting a pattern by electrophotography on one surface of the support film. And a step of printing the image layer, wherein the step of printing the image layer comprises the step of promoting swelling comprising a substance having a melting point lower than the temperature of the predetermined solvent during transfer processing to the curved surface printed body. The present invention provides a method for producing a transfer film for curved surface printing, which is a step of printing using a toner containing an agent.

As described above, in the method for producing a transfer film for curved printing according to the present invention, the step of printing the image layer is performed by printing using the toner containing the swelling accelerator as described above. In the step of transferring the obtained curved printing transfer film to the curved printing body, the swelling agent is liquefied just by floating the curved printing transfer film of the present invention on the predetermined solvent, and the toner in the image layer Since the movement is smoothed by preventing the aggregation of the particles, the image layer expands and spreads without any problem with the expansion of the swollen support film.
As a result, problems such as cracking of the image layer during or after transfer do not occur.

Further, in the method for producing a transfer film for curved surface printing according to the present invention,
It is preferable to use a toner having a swelling accelerator having a melting point in the range of 30 ° C. or more and 100 ° C. or less, and to perform the step of printing the image layer at a temperature lower than the melting point. As described above, it is preferable that the melting point of the swelling accelerator be 30 ° C. or more and 100 ° C. or less for the reason described above.
In the printing step of the image layer, it is preferable that the image layer is printed at a temperature equal to or lower than the melting point of the swelling accelerator, since the swelling accelerator in the toner has better printing characteristics when the swelling accelerator is in a solid state. It is.

Further, according to the present invention, as described in claim 15, (1) a step of preparing a transfer film for curved surface printing by the production method according to any one of claims 11 to 14 And (2) an image of the transfer film for curved surface printing obtained in the previous step with an activator capable of swelling the image layer or, when an intermediate layer is formed, either the image layer or the intermediate layer. (3) applying the transfer film for curved surface printing on the predetermined solvent heated to a temperature higher than the melting point of the swelling accelerator with the surface on which the image layer is printed facing up; The process of floating on
(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. Extending and adhering the transfer film for printing; (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 surface printed body from which the support film has been removed.

As described above, the image layer is formed (printed) by using the toner containing the above-described swelling accelerator, and is transferred to a curved surface printing body at a temperature higher than the melting point of the swelling accelerator. Therefore, the swelling accelerator becomes liquid at the time of transfer processing, and smoothens the movement of the toner particles in the image layer. Therefore, even when the image layer expands and spreads when the image is transferred onto the curved surface print, there is no problem that the toner particles are aggregated and cracks are generated.

According to the present invention, as described in claim 16,
Another object of the present invention is to provide a curved printed body characterized in that the transfer film for curved surface printing as described above is transferred onto the surface of the curved surface printed body. Such a curved surface printed body can be manufactured quickly and at low cost by utilizing the features of the image layer printed by the electrophotographic method, and also uses the specific toner as described above. Thereby, it is possible to make the design excellent in design without cracking. Therefore, the curved surface printed body of the present invention has an effect that it can be used at low cost to print many kinds of small lots and has excellent design without defects such as cracks in the picture.

Further, the present invention provides a wet toner used for forming an image layer of a transfer film for curved printing by electrophotography by forming the image layer on the curved printing. Provided is a wet toner comprising, as a swelling accelerator, a substance which is heated to be in a liquid state when transfer processing is performed on a curved surface print using a transfer film. By forming the transfer film for curved surface printing using such a wet toner, problems such as cracking of the pattern of the image layer during or after transfer processing to the curved surface print body as described above do not occur. In this case, for the same reason as described above, the swelling accelerator is used at 30 ° C to 1 ° C.
The substance preferably has a melting point in the range of 00 ° C.

[0030]

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 according to the present invention is a transfer film for curved surface printing comprising a support film swelled in a predetermined solvent and an image layer constituting a pattern printed by an electrophotographic method laminated on one surface of the support film. The image layer facilitates movement of the toner particles in the image layer when performing transfer processing to the curved surface printed body, using a toner containing a swelling accelerator for facilitating the expansion and spread of the image layer. This is characterized by being a printed image layer, and particularly has a great feature in that a toner containing a swelling accelerator is used in electrophotographic printing. Hereinafter, this swelling accelerator will be described first.

(Swelling Accelerator) The swelling accelerator used in the present invention is to be added to an electrophotographic toner and kneaded to improve the fluidity between the toner particles. A substance that can be produced. By adding such a swelling agent to the electrophotographic toner, it is possible to prevent aggregation of the toner in the transfer processing step, and when transferring the transfer film for curved surface printing to a curved surface print, such a method is used. The image layer printed with the appropriate toner can be uniformly stretched and spread, and the problem that the image layer is cracked during or after the transfer processing can be prevented.

As the swelling accelerator used in the present invention,
Any material may be used as long as it has a function of smoothing the movement of the toner particles interposed between the toner particles, but it is preferably a solid before transfer processing to the curved surface printed body. It is preferable that the material be a liquid during transfer processing. For example, when printing an image layer on a support film, or when the toner particles of the image layer have fluidity during storage after being formed into a transfer film for curved surface printing, a problem occurs during printing, or a pattern is disturbed during storage. Or there is a possibility. Therefore, it is preferable that the toner particles forming the image layer have no fluidity during printing or storage, and have fluidity during transfer processing. From such a viewpoint, before performing the transfer processing on the curved surface printed body, that is, at the time of printing on the support film, further, in a state where it is stored as a support film for curved surface printing, the swelling accelerator is solid. However, it is preferable that the material be a liquid during transfer processing to a curved surface print that actually requires fluidity of toner particles.

As described above, as a substance which is in a solid state before the transfer processing to the curved surface printed body and is in a liquid state at the time of the transfer processing, for example, a substance which is very soluble in a certain solvent, etc. Such a substance can be liquefied by applying the solvent to the image layer before the transfer processing to convert the solid swelling accelerator into a solution during the transfer processing. In addition, a substance that liquefies when a certain kind of energy ray is added can be used, but a substance that is liquefied by heating during transfer processing is preferable from the viewpoint of easiness of operation and the like.

When a substance which is liquefied by heating is used as a swelling accelerator, it is necessary to heat and use a transfer film for curved surface printing during transfer processing. Various heating methods can be used. For example, a method of irradiating infrared rays on the image layer side of a transfer film for curved surface printing,
A method in which a transfer film for curved surface printing is floated on a predetermined solvent and the heated curved surface print body is lowered from above the transfer film can be used. However, from the viewpoint of uniformity and stability of the heating temperature, and further, easiness of operation, etc., the above-mentioned predetermined solvent is heated to a predetermined temperature, and the transfer layer for curved printing is floated on this solvent to form an image layer. A method is preferred in which the swelling accelerator therein is heated to be in a liquid state.

In the case where a method of heating the swelling accelerator by such a method is employed, the swelling accelerator must be a substance having a melting point lower than the temperature of the predetermined solvent at the time of transfer processing. Therefore, in the present invention, it is preferable that the swelling accelerator is a substance having a melting point lower than the temperature of the above-mentioned predetermined solvent when the transfer film for curved surface printing is transferred to the curved surface printed body.

In this case, since the transfer processing step cannot be performed at a temperature higher than the boiling point of the predetermined solvent, the melting point of the swelling accelerator is lower than the boiling point of the predetermined solvent. It is preferred that Generally, water is used as a predetermined solvent used in the transfer processing step from the viewpoint of cost and safety. Therefore, when water is used, the upper limit of the melting point of the swelling accelerator is the boiling point of water. That is, in the present invention, the melting point of the swelling accelerator is preferably 100 ° C. or less, which is the boiling point of water. Further, transfer processing to a curved surface printed body using the transfer film for curved surface printing is usually performed at a liquid temperature of a predetermined solvent of 60 ° C. or less from the viewpoint of the stability and workability of the transfer process. . Therefore, it is particularly preferable to use a substance having a melting point of 60 ° C. or less as the swelling accelerator.

On the other hand, as described above, it is preferable that the swelling accelerator used in the present invention has no fluidity before transfer processing, ie, during printing of the image layer and during storage after that. It is preferred that the accelerator be solid. Usually, since the printing of the image layer and the storage of the obtained transfer film for curved surface printing are performed at a temperature lower than 30 ° C., the melting point of the swelling accelerator used in the present invention is preferably 30 ° C. or more, It can be said that it is preferably 35 ° C. or higher.

The swelling accelerator used in the present invention is not particularly limited. Animal waxes such as beeswax and spermaceti, vegetable waxes such as carnauba wax, candelilla wax, wood wax, and paraffin. Waxes, petroleum waxes such as microcrystalline wax, synthetic hydrocarbons such as Fischer-Tropsch wax, low molecular weight polyethylene, wax compounds such as n-paraffin having 21 or more carbon atoms, and other stearic acid, myristic acid, palmitic acid, etc. Fatty acids, stearyl alcohol, higher alcohols such as polyvinyl ether, polyhydric alcohol fatty acid esters such as sorbitan monostearate, polyolefin resins, epoxy resins, polyamide resins, polyester resins, urethane resins and the like. It is.

Among such substances, the following substances can be mentioned as substances having a melting point in the most preferable range, that is, 35 ° C. or more and less than 60 ° C. The numerical values in parentheses of the following substances indicate the melting points.

That is, 1-octadecanol (57.
9), perbenzoic acid (41.3-42), kaurene (50
-51), ethyl carbamate (52), ethyl carbamate (48.2), methyl carbamate (55-5
6), camphenilone (38.4), (-)-camphene (51.5-52), 3,4-xylidine (51),
4,6-xylenol (49), m-xylene-α,
α'-diol (46-47), quinazoline (48),
Guanidine (about 50), 18-Fraun-6 (39.5)
-40.5), glyoxal (58), glycerin =
α-nitrate (54), glycerin = β-nitrate (58-59), chromone (59), α-chloroacetophenone (59), 2-chloroquinoline (38), 2-
Chloronaphthalene (59.5), p-chlorophenol (43), m-chloronitrobenzene (45), 5-chloro-2-nitrophenol (40), 3-chloropropionic acid (43-44), p-chloro Benzaldehyde (49), benzyl silicate (38), methyl silicate (3
6), germacrone (56-57), 1-naphthyl acetate (49), salicylaldehyde = oxime (57),
Phenyl salicylate (41.9), diacetanilide (37-37.5), cyanamide (46), cyclooctanone (40-41), trans-1,2-cyclopentadiol (50), α, α′- Dichloroacetone (4
2.5), 2,5-dichloroaniline (50), α,
α'-dichloro-o-xylene (55), 1,2-dichloronaphthalene (37), 1,6-dichloronaphthalene (49), 3,4-dichloronitrobenzene (43),
2,3-dichlorophenol (58), 2,4-dichlorophenol (45), 2,5-dichlorophenol (59), 2,3-dichloropropionic acid (50), p
-Dichlorobenzene (54), dicyclohexylcarbodiimide (34-35), 1,3-dithiane (53-5)
4), dithioerythritol (45-47), 2,5-
Dinitrotoluene (51.2), di-2-pyridylnidisulfide (58), diphenylamine (55), 1,
2-diphenylethane (53), 1,3-diphenyl-
2-propanone (37), dibromoacetic acid (48), 2,
4-dibromophenol (40), 2,6-dibromophenol (56-57), N, N'-dimethylthiourea (56-58), N, N-dimethyl-2-naphthylamine (46), N, N- Dimethyl-p-phenylenediamine (40.5), N, N'-dimethyl-o-phenylenediamine (34-35), N, N'-dimethyl-p-phenylenediamine (53), 2,2-dimethyl- 1-propanol (55-56), 2,3-dimethyl-p-benzoquinone (58), 2,6-dimethoxyphenol (55-56), 2,3-dimethoxybenzaldehyde (54), 2,5-dimethoxybenzaldehyde (5
3), 3,4-dimethoxybenzaldehyde (56),
p-Dimethoxybenzene (57-58), dimethyl oxalate (53.3), m-jodvencene (36.
5), zingerone (40-41), cinnoline (38-
39), succinonitrile (57.15 to 57.2)
0), scopolamine (59), methyl stearate (3
7.78), stearolic acid (46-46.5), spiropentane (38.3-38.5), ethylene carbonate (3
9), -o-ethyl thiocarbamate (40-41),
Benzyl thiocyanate (43), thiobenzophenone (53-54), deoxybenzoin (59-60),
(±) -trans-decahydroquinoline (48.2-
48.5), tetraethylammonium dichloride (3
7.5), 1,2,3,4-tetrachlorobenzene (4
6.5), 1,2,3,5-tetrachlorobenzene (5
4.5), 1-tetradecanol (38.26), tetrabromoethylene (56.5), 1,2,3,4-tetrabromobutane (39), N, N, N ', N'- Tetramethyl-p-phenylenediamine (51), (+)-α
-Terpineol (37), o-terphenyl (58-
59), diethyl terephthalate (44), docosan (4
4.4), triethylphosphine oxide (46),
Trioctalphosphine oxide (50-54),
2,2,2-trichloro-1-ethoxyethanol (4
7.5), trichloroacetic acid (57.4), 2,3,6-
Trichlorophenol (58), tris (2-hydroxypropyl) amine (48-52), trinitroacetonitrile (41.5), 1,1,1-trinitroethane (57), 1,2,4-tribromo Benzene (44-4
5), trimyristin (56.5), 1,3,5-trimethoxybenzene (54-55), o-tolylhydrazine (59), o-toluidine (43.5), p-toluenethiol (44) , Tropacocaine (49), tropolone (51-52), 1-naphthylamine (49.2-
49.3), 2-naphthaldehyde (58), nicotinonitrile (50-51), m-nitroanisole (3
9), p-nitroanisole (53.9), N-nitroaniline (46-46.5), ethyl p-nitrobenzoate (57-57.5), 2-nitro-p-cresol (36), ethyl o-nitrocinnamate (42), N-nitrodimethylamine (57), 4-nitrosodiphenylamine (43), 2-nitrobiphenyl (37.2),
3-nitropyridine (37.2), o-nitrophenol (45.8), p-nitrobenzylidene dichloride (48), o-nitrobenzyl chloride (49.
5), m-nitrobenzyl chloride (47), o-nitrobenzaldehyde (46), m-nitrobenzaldehyde (56-57), nitromesitylene (44), norbornene (44-44.5), paraconic acid (57) ~ 5
8), 8-parerolactone (58-60), 1,8-bis (dimethylamino) naphthalene (47-48), bis (phenylthio) methane (39.5-40.5), bis (methylthio) methane (41 ), Ethyl α- (hydroxyimino) acetoacetate (58-58.5), o-hydroxybenzophenone (41), 5-hydroxymethyl-
2-furaldehyde (35), 2-hydroxyacetic acid (4
1), 3-hydroxyacetic acid (49), hydrocinnamic acid (50.5-51), pinacol (43.2-43.
4), hinokitiol (52-52.5), pivalic acid (35.4), 2-biphenylylamine (49-5)
0), 4-biphenylylamine (55), biphenyl-
2-ol (58), biphenyl-2,4'-diamine (45), 2-piperidinone (39-40), piperonal (37), piperonyl alcohol (56), pyrazine (57), 2-pyridylamine (58.1), phenyl cyanamide (47), 4-phenylbutyric acid (52),
m-phenylene diisocyanate (51), phenoxathiin (58), phenol (40.95), o-phenolsulfonic acid (about 50), pseudoperetieline (54), phthalaldehyde (58), phthalate Ethyl hydrogen oxide (47-48), 2-butyne-1,4-diol (58), furfurylidene acetone (39-40), p
-Bromoacetophenone (51.2), α-bromoacetophenone (53-54), α-bromo-p-xylene (36-37), bromoacetic acid (49-50), bromocyan (52), bromodiphenylmethane (45) , P-
Bromo-N, N-dimethylaniline (58), 2-bromonaphthalene (59), o-bromonitrobenzene (4
3-44), m-bromonitrobenzene (56), 1-
Hexadecanol (49.5), 1,6-hexanediol (42.8), 1-heptadecanol (53.9-
54), 2,4,6-heptanetrione (49), behenolic acid (58), henycosan (40.5), benzylideneacetone (43), N-benzylideneaniline (54), benzylidene-diacetate (46), o-
Benzylaniline (54-55), p-benzylaniline (34-35), 1-benzylisoquinoline (55-55)
56), 1-benzylnaphthalene (57.5-58),
2-benzylnaphthalene (58), N-benzylhydroxylamine (57), benzenesulfonic acid (50-5
1), N-benzoylpiveridine (49), benzophenone (48-48.5), 1-pentadecanol (4
3.9-44), pentabromoethane (56-57),
Pentamethylbenzene (54.3), formanilide (47.9), formohydrazide (54), manool <53), myristic acid (54.1), maleic anhydride (52.6), mesitylenesulfonyl dichloride ( 5
8), mescaline (35-36), methacrolein (50), 4-methylimidazole (56.5), N-
Methyl-p-phenylenediamine (35-36), p-
Methylbenzophenone (59-60), 1-methyleneindene (37), p-methoxyacetophenone (3
9), p-iodoanisole (53), p-iodotoluene (36), 2-iodonaphthalene (54.2), o
Iodonitrobenzene (49.5), m-iodonitrobenzene (37), o-iodophenol (42),
m-iodophenol (40), 2-iodopropionic acid (45-47), lauric acid (44.8), rimene (55.5), dibenzyl sulfide (50), triphenyl phosphate (50.3-50) .7), levulinic acid (37.
2), acetaldehyde = oxime (47), acetaldehyde = phenylhydrazone (56), acetoacetic acid (36-37), azoxybenzene (38-38.
5), 2,2'-azotoluene (55.4), o-anisaldehyde (39), 2-amino-2-ethyl-1,
3-propanediol (37.5-38.5), o-aminobenzaldehyde (39-40), p-aminobenzenethiol (46), o-aminobenzonitrile (4
7), m-aminobenzonitrile (53-53.5),
Icosan (36.8), isoapiol (55-5
6), methyl isothiocyanate (36), 2-isopropyl-5-methylphenol (51.5), 2-isopropyl-5-methyl-p-benzoquinone (46-4)
7), 1-indanone (42.5), 2-indanone (60-61), indan (51.4), indole (53), α-ethylcrotonic acid (45-46), ethyl styryl ketone ( 41), ethyl phenyl sulfone (42), p-ethylphenol (47), ethyl methyl sulfone (36), 2-ethoxynaphthalene (37-38), ephedrine (34-40), elaidic acid (44) .5), α-eleostearic acid (49
-49.2), Eremophilon (42-43), cinnamoyl chloride (35-86) and the like.

The swelling accelerator used in the present invention can be used irrespective of the solubility in the activator applied in the transfer step. However, if the substance is soluble in the activator, the image layer can be fluidized quickly in the transfer step, and further, if it is insoluble, poor adhesion may occur during printing or curved surface transfer. For that reason, the swelling accelerator is more preferably a substance soluble in the active agent. The swelling accelerator used in the present invention is preferably a substance that is insoluble in a toner solvent. This is because a substance soluble in the toner solvent may deteriorate the stability over time of the toner.

The swelling accelerator used in the present invention is preferably a substance which does not affect the chargeability of the toner or a substance which effectively contributes to the chargeability of the toner. For example, an ionic compound is not preferred because the electrical conductivity of the toner may be unnecessarily increased in some cases. Therefore, in the present invention, it is preferable to use a nonionic compound as the swelling accelerator.

Specifically, as the swelling accelerator, a substance which has little influence on the chargeability of the toner is preferably a saturated or unsaturated hydrocarbon such as docosan or icosane, or an alkylbenzene such as pentamethylbenzene. , Esters such as methyl stearate, polyethylene glycol and the like. Further, as the swelling accelerator used in the present invention, which contributes to the positive charging property of the toner, preferred substances include amines such as N-methyl-p-phenylenediamine, 1-naphthylamine and o-aminobenzaldehyde; Examples include pyridines such as nitropyridine, pyrazines, anilines such as p-benzylaniline, and azo compounds such as 2,2'-azotoluene. Furthermore, lauric acid, acetoacetic acid, lauric acid, acetoacetic acid,
Carboxylic acids such as 3-chloropropionic acid; phenols such as phenol and p-chlorophenol; halides such as pentabromoethane and 1,2,3,4-tetrachlorobenzene; sulfonic acids such as benzenesulfonic acid; Alcohols such as octadecanol and 1,6-hexamethylenediamine can be exemplified.

It is preferable that the swelling accelerator is added to the toner in an amount of 5 to 100 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the binder resin of the toner. When the amount is less than 5 parts by weight, the effect of promoting swelling is hardly obtained, and the pattern of the image layer may be cracked. When the amount exceeds 100 parts by weight, there is a problem in the adhesiveness to the curved surface print. This is because there is a possibility.

By using such a swelling accelerator, the toner particles in the image layer constituting the picture have fluidity, and the curl fit transfer step is performed in this state, so that the toner can be used in a normal electrophotographic toner. It is possible to provide a transfer film for curved surface printing which is excellent in design without causing cracks due to the elongation of the pattern of the image layer, which is a problem when printed. Therefore, 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.

(Support Film) The transfer film for curved surface printing of the present invention is obtained by printing an image layer on a support film using a toner containing the above-mentioned swelling accelerator. Such a support film used in the present invention, in the printing process of the curl fit, at the time of transfer on a solvent, swells sufficiently on the solvent, and has multicolor printing suitability, further transferability, that is, curved surface printing It is preferable that the material has sufficient properties to be attached to the body surface. 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.

Thus, 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 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 preferable 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 moisture of 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.

(Image Layer) In the present invention, an image layer is formed on the above-mentioned support film by electrophotographic printing using a toner containing a swelling accelerator characteristic of the present invention. Here, the electrophotographic printing method used in the present invention is not limited to an electrophotographic method in a narrow sense in which a photoconductive surface of a photoreceptor is charged and subjected to imagewise exposure to form an electrostatic latent image. An electrostatic recording method that forms an electrostatic latent image by scanning the surface of a dielectric with a needle electrode or the like. A bias is applied to a photoconductor, and imagewise exposure is performed on this to form an electrostatic latent image. This means all copying methods including a step of electrostatically forming a latent image, such as a method of performing a copying operation. Further, the pattern formed on the image layer is not limited to one having a design property, but includes various patterns and solid coating.

(Wet toner) The image layer is formed by printing toner by the above-mentioned electrophotographic method.
There are two types of electrophotographic toners used for the image layer, a wet toner and a dry toner. The toner used for such an image layer is temporarily adhered to the support film, easily forms a dry film, adheres to the surface of the curved surface printed body, and easily swells with an activator described later. It is preferable to use a resin containing the resin as a vehicle. Examples of such a resin include those having a glass transition temperature of room temperature or less. 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, the solvation of the resin and the ζ potential of the particle surface are performed. As a result, an appropriate repulsion acts between the particles, so that no blocking occurs. On the other hand, when such a resin having a low glass transition temperature is used as a vehicle for the dry toner, a problem of blocking may occur. Therefore, in order to use a resin suitable for curl fitting, the toner used for printing is preferably a wet toner rather than a dry toner. In the case of a wet toner, the toner is fixed by drying the solvent after development. Therefore, from the viewpoint of fixability, it is preferable that the glass transition temperature of the binder resin is equal to or lower than room temperature, and it can be said that the use of a wet toner is preferable.

As described above, the above-mentioned wet toner is basically a toner in which toner particles composed of a resin and a colorant are dispersed in a dispersion medium. In the present invention, a swelling accelerator is added to this. . Therefore, when printing is performed on a support film by an electrophotographic method using such a wet toner, the image layer is composed of toner particles composed of the resin and the colorant and a swelling accelerator interposed between the toner particles. You.

Examples of the resin used for such toner particles include 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-2-hydroxyethyl methacrylate copolymer, 2-ethylhexyl methacrylate-diacetone acrylamide copolymer, etc. Among the above acrylic resins and the like, those having a glass transition temperature of room temperature or lower can be used alone or in combination with those having a glass transition temperature of room temperature or higher depending on the necessity such as film strength.

In such a wet toner, as a means for stably dispersing the toner particles in a solvent, the pigment particles in the toner are generally coated with a resin having a solvent affinity. One of the indexes indicating the solvent affinity is a solubility parameter (SP value). Taking the relationship between a resin and a solvent as an example, the SP value can indicate the degree of solubility of the resin in the solvent. 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 types of monomers A and B, and the SP value (δ) of each homopolymer. Satisfy the following relationship.

[0059]

(Equation 1)

The adsorption of the resin onto 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 located on the outermost shell of the pigment-resin particles and stabilizes the dispersion. To contribute. 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.

As a toner solvent, a highly insulating solvent such as isoparaffin is generally used. Examples of the highly insulating solvent that can be used include n-hexane (7.3), n-heptane (7.5), n-octane (7.5), and nonane (7.5.
6), decane (7.7), dodecane (7.9), cyclohexane (8.2), perchloroethylene (9.3),
Trichloroethane (9.9) and the like. The numbers in parentheses of the above compounds indicate the SP value of each solvent.

For example, when Isopar L (SP = 7.1) manufactured by Exxon, which is an isoparaffinic hydrocarbon solvent, is used as a toner solvent, monomer A (SP value of a homopolymer) is used.
Examples of are: 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 the like, and monomer B (homopolymer S
Examples of (P value) include vinyl acetate (9.4), styrene (9.1), methyl acrylate (9.7), ethyl acrylate (9.2), and 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 the monomer A is not lower than room temperature, and the Tg of the homopolymer of the monomer B is not higher than room temperature. ) And (2) are set so that the copolymer has a glass transition temperature of room temperature or lower. More preferably,
In order to sufficiently coat the pigment particles in the toner, it is set so as to be insoluble or hardly soluble in the toner solvent as a whole.

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 volume fractions of components 1 and 2, W ₁ and W ₂ are weight fractions, and the temperatures are both absolute temperatures.

As a colorant for a wet toner, a known organic 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 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), 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) can 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); a thioindigo pigment, thioindigo magenta (CI No. pigment Vi)
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 (CIN) which is a dyeing lake pigment.
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);
1, PB-64); a basic dye lake pigment, such as methyl violet phosphorous molybdate (PV-3), 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, more specifically, a scaly shape obtained by baking titanium oxide or iron oxide on the inner part of a shell, crushed pearl, or mica fine particles (2) metal powder, more specifically, powder of aluminum, brass, bronze, gold, silver, or the like, preferably 1-120 μm fine particles or scale-like foil pieces (3) Pieces 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 forming a transparent yellow color after the deposition. Gold powder crushed after painting; (4) 2 with 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 matte pigments, 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. Note that the swelling accelerator may also have the effect of these additives.

The method for producing such a wet toner used in the present invention may be in accordance with any known method, but is preferably produced by a solvent replacement method or a cooling granulation method.

In the solvent replacement method, a bead mill comprising 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, is used. Ball mill, pulverize the pigment with a high-speed disperser, add a toner solvent to this dispersion, remove the solvent used for pigment dispersion with a rotary evaporator, etc., perform re-dispersion to make the particle size uniform It consists of steps. When producing a wet toner by this method, the timing of addition of the swelling accelerator used in the present invention,
When the swelling accelerator is insoluble in the volatile solvent, it may be added at any time as long as it is before the above-described pigment dispersion step, and when the swelling accelerator is soluble in the volatile solvent, It may be added at any time before the solvent replacement (granulation) step.

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. Solid content slurry, knead well with a planetary mixer, etc., cool to around room temperature with stirring to precipitate the resin, dilute with toner solvent, use a bead mill, ball mill, high speed disperser, etc. It is a process of making uniform. The swelling accelerator may be added at any time before the above-mentioned cooling (granulation) step when the wet toner is produced by this method.

It is considered that the form of resin granulation is different depending on the method of producing a wet toner, and the physical properties of the toner such as particle diameter, dispersibility, and chargeability actually differ depending on the production method. Therefore, the selection of the toner manufacturing method is determined by carefully examining the properties of the starting materials and the physical properties required of the toner.

When the swelling accelerator used in the present invention greatly affects the chargeability of the toner, the charge control agent is granulated, that is, before and after the step in the solvent replacement method, and in the step of cooling granulation. It is preferable to add them before and after.

(Dry Toner) On the other hand, a dry toner can be used as the toner for forming the image layer of the transfer film for curved surface printing of the present invention. As such a 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 control agent, an additive, and a swelling accelerator which is a feature of the present invention. iron,
Including magnetic powder such as magnetite. The binder resin needs to be selected in consideration of the chargeability and heat fixing property of the toner. The main binder resins are polystyrene, hydrogenated styrene resin, styrene / isobutylene copolymer, styrene / butadiene copolymer, styrene / butadiene / chlorinated paraffin copolymer, and other polystyrene resins; polymethyl methacrylate, polyethyl Methacrylate,
Acrylic resins such as polybutyl methacrylate, polyglycidyl methacrylate, methyl methacrylate / butyl methacrylate copolymer, 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 / n-butyl methacrylate / maleic anhydride copolymer, styrene / n-butyl methacrylate・ Styrene such as acrylic acid copolymer ・ (meth) acrylate copolymer resin: polyester resin such as fumaric acid / etherified diphenol polyester; epoxy resin; polyurethane resin; silicone resin; butyral resin; Polyolefin resins such as high molecular weight polyethylene, ethylene / vinyl acetate copolymer, low molecular weight polypropylene; polyamide resins; polyvinyl alcohol resins; fluorine resins such as polyvinylidene fluoride; , It can be used an imide resin, ketone resin, cellulose, rosin, and alkyd resin.

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 liquid 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. The swelling accelerator may have the function of these additives, as in the case of the liquid toner.

The process for producing such a dry toner, except for a part of toner such as a microcapsule toner, usually includes a process of dispersing a colorant and a charge controlling agent in a binder resin (thermal kneading and the like). The process can be broadly divided into two processes. The swelling accelerator, which is a feature of the present invention, is added during the former dispersion step, and is mixed or dispersed in the binder resin.

(Intermediate Layer) In the transfer film for curved printing according to the present invention, an intermediate layer may be provided between the support film and the image layer. The intermediate layer is provided for fixing and fixing the image (image layer) on the support film when the image layer is printed directly on the support film and the pattern (image layer) is difficult to fix and fix, 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, it is necessary that the intermediate layer has such a property that the toner used for image recording can be fixed on the surface or inside thereof. Further, it is preferable that the film is insoluble in a predetermined solvent for swelling and dissolving the support film, and has a swelling property with respect to an activator to be described later, an adhesive property with respect to a curved printed body, and the like.

The intermediate layer provided in the present invention has a resin as a main component, and is mixed with various additives as required. As the resin used for the intermediate layer, a resin having a low Tg is preferable similarly to the resin used for the toner vehicle, since it has appropriate adhesiveness.

Examples of such a resin include a pure frame or a modified alkyd resin such as a fatty acid-modified phthalic acid alkyd and a maleic acid alkyd; (meth) acrylic resins such as polyethyl acrylate and methacrylic acid / lauryl methacrylate copolymer; Metal salts thereof; acrylamide / acryl copolymer resins such as acrylamide / 2-ethylhexyl methacrylate copolymer; styrene resins such as styrene / butadiene copolymer and styrene / isoprene copolymer; styrene / n-butyl methacrylate copolymer Styrene acrylic resins such as styrene resins; various saturated and unsaturated polyester resins; polyolefin resins such as polyisobutylene; polyacetal resins such as polyvinyl formal, polyvinyl butyral, and polyvinyl acetal; Polyethylene resins such as ethylene / vinyl acetate copolymers and ethylene / ethyl acrylate copolymer resins; polyvinylpyrrolidone and its copolymers; alkylene oxide resins such as polyethylene oxide and carboxylated polyethylene oxide; polyether polyols; Sodium alginate; natural or semi-synthetic resin such as gelatin and its derivatives, casein, trolloay, tragacanth gum, pullulan, vectin, carrageenan, glue, albumin, various starches, paste, soybean protein; terpene resin; ketone resin Rosin and rosin ester can be used. 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 fixability 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 the filler used 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; zinc carbonate; Tin; 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. Which of the above-mentioned materials is selected and what kind of structure of the intermediate layer is selected is appropriately designed according to the image forming mode.

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 and the like can be used. It is formed by, for example, dissolving a 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 .

(Adhesive Layer) In the transfer film for curved surface printing of the present invention, an adhesive layer may be provided on the image layer. 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 type of toner constituting the image layer. Especially when the addition amount of the swelling accelerator is large,
In some cases, the adhesion to the curved surface print may be reduced. In such a case, by providing the adhesive layer on the image layer, it is possible to maintain good adhesiveness with the curved surface print.

Such an adhesive layer is made of one or more resin materials which swell in a specific solvent and exhibit 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 .

(Method of Manufacturing Transfer Film for Curved Surface Printing) Next, an example of a method of manufacturing the transfer film for curved surface printing described above will be described with reference to the drawings. The method for producing a transfer film for curved surface printing of the present invention includes at least 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. In the method for producing a transfer film for curved surface printing, the step of printing the image layer contains a swelling accelerator composed of a substance having a melting point lower than the temperature of the predetermined solvent during transfer processing to the curved surface printed body. It is characterized by printing using toner.

First, a support film 1 is prepared as shown in FIG. Next, a recording drum formed by the recording unit 6 using an electrophotographic printer 7 including a toner tank 2, a developing unit 3, a recording drum 4, an impression cylinder 5, and a recording unit 6 as shown in FIG. The toner A attached according to the electrostatic latent image on 4 is electrostatically transferred onto the support film 1.

The developing section 3 includes a roller developing device,
The developing unit is not particularly limited as long as it is a developing unit for wet toner such as a slit developing unit or a dish developing unit. As the recording drum 4, a photoconductor, a dielectric drum, or the like can be used. When the recording drum 4 is a photoconductor, the recording unit 6 is a laser light emitting device. When the recording drum 4 is a dielectric drum, the recording unit 6 is a needle for forming an electrostatic latent image instead of the laser light emitting device. An electrode, an ion flow head, or the like is used. The transfer of a toner image from a recording drum such as a photoreceptor to a support film is usually performed by electrostatic transfer. However, when an adhesive layer is used, simple pressure fixing can be used. In this case, when the glass transition temperature Tg of the adhesive layer resin is higher than the temperature in the printing press, it is preferable to heat the support film to a temperature equal to or higher than the adhesive layer resin Tg in order to obtain sufficient adhesiveness.

In this way, a transfer film 9 for curved surface printing having the image layer 8 formed on the support film 1 as shown in FIG. 1C is formed. Obtained transfer film for curved surface printing 9
As shown in FIG. 1D, an activator 10 described later is applied on the image layer 8 and sent to a transfer process by curl fitting.

As described above, according to the method for producing a transfer film for curved surface printing of the present invention, at least a step of preparing a supporting film and forming a pattern by electrophotography using a specific wet toner on one surface of the supporting film. It consists of a step of printing the image layer, if necessary, an intermediate layer may be formed between the support film and the image layer,
Further, an adhesive layer may be formed on the image layer as needed.

(Method of Manufacturing Curved Printed Body) (Application of Activator) Next, an example of a method of manufacturing a curved printed body using the above-described transfer film for curved printing will be described with reference to the drawings. In the method for producing a curved printing body of the present invention, as shown in FIG. 1D, after preparing a transfer film 9 for curved printing, first, an activator 10 is applied to the image layer 8 side of the transfer film 9 for curved printing. Apply. Here, when an adhesive layer is formed on the image layer 8, the activator 10 is applied on the adhesive layer.

The activator is applied in this manner unless the activator is applied to swell the image layer or the like unless the transfer film for curved printing is floated on the solvent and then swelled. This is because the image layer or the like cannot follow the elongation of the film, and there is a possibility that image cracking may occur. Further, when the curved printed body is pressed from above onto the transfer film for curved surface printing and transferred, the transfer film for curved surface printing cannot be in close contact with the surface of the curved printed body, and transfer is not successful. When such an activator is applied, when the swelling accelerator present in the image layer is soluble in the activator,
Since the swelling accelerator can be easily liquefied, problems such as image cracking of the image layer can be more effectively prevented.

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, and does not dissolve the pigment of the image layer and evaporates until transfer is performed. In addition, it is desirable that the curved printed body is not eroded or that the paint is not rapidly dissolved when the curved printed body is transferred with the paint when the curved printed body is undercoated with the paint. Further, from the above-mentioned reason, it is preferable that the swelling accelerator contained in the toner forming the image layer can be dissolved.
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 spirit, petroleum naphtha and other aliphatic hydrocarbons, 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 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, 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 thereof, and N- 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 alcohol Thermosetting resins such as polyamide resins, polyester resins, phenol resins, melamine resins, urea resins, epoxy resins, diallyl phthalate resins, silicon resins, polyurethane 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 are preferably added to the above-mentioned solvents to form an activator for reasons such as easy adjustment of viscosity, irrespective of application method, long retention time of toner, and long transfer time. The addition amount is preferably in the range of 5 to 60% by weight.

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 Ethylene glycol monobutyl ether: 14 parts by weight -Butyl cellosolve acetate: 52 parts by weight-Maleic acid: Small amount

[0109] As the gravure coating, offset gravure, roller coating, bar coating, spray coating, can be applied and ultrasonic coating, the coating amount of the active agent coating means for such active agents, 2 to 30 g / m ² And preferably 3 to 15 g / m ² .

In the present invention, it is particularly preferable that the swelling accelerator in the toner is soluble in the above-mentioned activator.
In the case of insolubility, it is preferable that the temperature of the activator to be applied is set to be equal to or higher than the melting point of the swelling accelerator in the toner, and the low-melting substance is melted immediately after application.

(Transfer Processing Step) 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 9 for curved surface printing on which an image layer 8 constituting a pattern is printed on a support film 1 is floated on a solvent. At this time, the temperature of the predetermined solvent is higher than the melting point of the swelling accelerator contained in the toner constituting the image layer 8.
By setting the temperature of the predetermined solvent to a temperature higher than the melting point of the swelling accelerator, the swelling accelerator in the image layer 8 is melted and liquefied, and the image layer 8 expands as the support film 1 swells. When it spreads, aggregation of the toner particles in the image layer 8 can be prevented, and problems such as image cracking can be prevented.

Since the support film 1 swells in this solvent, the support film 1 swells and spreads as shown in FIG. 2 (a). At this time, since the image layer 8 on the support film 1 also contains the swelling accelerator liquefied as described above and is coated with an activator, the image layer 8 also spreads along with the spread of the support film 1. Thereby, the transfer film for curved surface printing is in a spread state.

Then, in the state where the transfer film 9 for curved surface printing is spread as described above, as shown in FIG. Then, a part or the whole thereof is settled in the solvent 11, and the transfer film 9 for curved surface printing is spread and adhered to the surface of the curved surface printed body 12 by the pressure of the solvent 11.

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 concave portions or convex portions, 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 print 12 is removed from the solvent 11.
The support film 1 is removed. In order to remove the support film 1, as shown in FIG. 2C, it is preferable to shower-swell the swollen support film using the same solvent as the solvent 11 because it is 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 supporting film. For example, when polyvinyl alcohol (PVA) is used as the supporting 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. 2D, the curved surface molded body 12 from which the support film has been removed is dried by means such as an air blow or a drying oven. After drying, curved surface print 1
2 is coated with a paint for a protective layer using a paint gun or the like (FIG. 2).
(E)), after application, the coating is dried in a drying oven (FIG. 2 (f)) to form a protective layer to obtain a curved print.

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 composed of 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-described ionizing radiation-curable composition include unsaturated polyesters, polyester acrylates, epoxy acrylates, and urethane acrylates. Polyol acrylate, various acrylates such as melamine acrylate, polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyol methacrylate, and various methacrylates such as melamine methacrylate, 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, according to the method for producing a curved printing body of the present invention, a transfer film for curved printing having the same design as conventional gravure printing can be obtained quickly and at low cost by using an electrophotographic method. Since transfer processing can be performed by using the same, a curved surface print can be obtained quickly and at low cost. At this time, since the swelling accelerator is contained in the image layer of the transfer film for curved surface printing, it is possible to prevent problems such as cracking of the image layer in the transfer processing step.

Accordingly, it is possible to use a curved printed body free from defects such as cracks in an image, for example, for producing various prototypes, and it is possible to sufficiently cope with recent trends in small lots and many kinds. Is the way.

Further, a curved print body obtained by transferring the above-described transfer film for curved print of the present invention onto the surface of a curved print body is manufactured promptly by utilizing the features of the image layer printed by the electrophotographic method. Not only is it possible to achieve a low cost, but also by using the specific toner as described above, it is possible to obtain an excellent design without cracks in the picture. Therefore, such a curved printed body of the present invention has an effect of being inexpensive and capable of printing many kinds of small lots, and having excellent design without defects such as cracks in the picture. .

[0124]

EXAMPLES Example 1 (Preparation of Wet Toner) Preparation of Cyan Wet Toner VR-101: 15 parts by weight (modified ethylene copolymer resin) manufactured by Du Pont-Mitsui Polychemicals Co., Ltd. Polyethylene glycol 1500: 7.5 parts by weight (manufactured by Junsei Chemical Co., Ltd., melting point 44 to 48) ° C) C. I. Pigment Blue 15: 1: 15 parts by weight (PALOMAR BLUE B-4806, manufactured by Bayer)-Isoparper L (manufactured by Exxon): 30 parts by weight 500 g of a composition consisting of 30 parts by weight is ripened to 120 ° C while a double planetary mixer. , And slowly cooled to room temperature at a rate of 0.5 ° C./min with continuous stirring.
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
16.7 g of basic calcium penelonate (manufactured by Witco) as a charge control agent was added to 00 g, and further diluted with Isopar L to 2700 g to obtain a cyan wet toner. 2. Preparation of magenta wet toner C.I. I. Pigment B
lu 15: 1 to C.I. I. Pigment Red
A magenta wet toner was prepared in the same manner except that 176 (PV Carmine HF-3C, manufactured by Clariant) was used. 3. Preparation of Yellow Wet Toner C.I. I. Pigment Blu
e 15: 1 as C.I. I. Pigment Yellow
180 (PV FAST Yellow HG, manufactured by Clariant) 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: 1.

Each of the obtained toners was uniformly negatively charged, and exhibited good dispersion stability.

(Adjustment of Intermediate Layer) 1 part by weight of acrylamide / n-butyl acrylate / lauryl acrylate copolymer resin 9 parts by weight of MEK Was coated with a wire bar to a dry coating amount of 7 g / m ² and dried to form a water-resistant intermediate layer.

(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 had excellent resolution and was firmly fixed to the intermediate layer on the PVA film.

(Transfer Processing) An activator (C, P, AH NORMAL EX, Ohashi Chemical Industry Co., Ltd.) was applied on the printed image layer of the obtained transfer film for curved surface printing with a wire bar at 13 g / m ^2. , And immediately floated on a water surface at a temperature of 60 ° C. with the image layer facing upward so that the temperature of the activator did not fall below the melting point of the wax.

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 outer surface of the curved printed material is removed. A transfer film for curved printing was adhered to the surface. The curved surface printed body was pulled 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. 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.

[Example 2] The polyethylene glycol in Example 1 was replaced with paraffin wax (No. 115,
A transfer film for curved surface printing and a curved surface printed body were obtained in the same manner as in Example 1 except that the temperature was changed to Nippon Seiro Co., Ltd., melting point 47 ° C.

Example 3 The polyethylene glycol in Example 1 was replaced with 1,6-hexanediol (melting point 4
A transfer film for curved surface printing and a curved surface printed body were obtained in the same manner as in Example 1 except that the temperature was changed to 2.8 ° C.).

Example 4 The polyethylene glycol in Example 1 was replaced with 3-chloropropionic acid (melting point: 43 to
A transfer film for curved surface printing and a curved surface printed body were obtained in the same manner as in Example 1 except that the temperature was changed to 44 ° C.).

Example 5 Example 1 was repeated except that the polyethylene glycol in Example 1 was changed to 2-amino-2-ethyl-1,3-propanediol (melting point: 37.5 to 38.5 ° C.). Similarly, a transfer film for curved surface printing and a curved surface printed body were obtained.

Example 6 The polyethylene glycol in Example 1 was replaced with 1-octadecyl alcohol (melting point 5
7.9 ° C.) to obtain a transfer film for curved surface printing and a curved surface printed body in the same manner as in Example 1.

Example 7 A transfer film for curved surface printing and a curved surface printed body were obtained in the same manner as in Example 1 except that polyethylene glycol was replaced with n-icosane (melting point: 36.8 ° C.). Was.

Comparative Example 1 A transfer film for curved surface printing and a curved surface printed body were obtained in the same manner as in Example 1 except that polyethylene glycol was not added.

Comparative Example 2 Curved surface printing was performed in the same manner as in Example 1 except that the addition amount of polyethylene glycol in Example 1 was changed to 0.7 parts by weight (4.7 wt% with respect to the binder resin). Transfer film and a curved print were obtained.

Comparative Example 3 A transfer film for curved surface printing was prepared in the same manner as in Example 1 except that the addition amount of polyethylene glycol in Example 1 was changed to 20 parts by weight (133 wt% based on the binder resin). A curved print was obtained.

[Evaluation] The transfer films for curved printing and the curved printed products obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 1.

(Evaluation of Transfer Film for Curved Surface Printing) The density ratio (OD ₍ after the test ₎ / OD ₍ before the test ₎ ) of the cyan image before and after the cyan toner image was rubbed with an eraser was measured using a Macbeth densitometer. Was evaluated.

OD ₍ after test ₎ / OD ₍ before test ₎ = 1-0.7: ○ OD ₍ after test ₎ / OD ₍ before test ₎ = 0.7-0.4: ΔOD ₍ after test ₎ / OD ₍ Before test ₎ = 0.4 to 0: ×

(Evaluation of Curved Printed Body) The presence or absence of cracks and white spots in the image was evaluated according to the following criteria.

：: Cracks observed with a 20 × magnifier
No white spots are observed. Δ: Cracks and white spots cannot be confirmed with the naked eye, but can be confirmed with a magnifier of 20 times magnification. ×: Cracks and white spots can be confirmed with the naked eye.

[0144]

[Table 1]

As is clear from the results shown in Table 1 above,
The transfer film for curved surface prints and the curved surface prints using the wet toner to which an appropriate amount of the swelling accelerator was added had good results.

[0146]

According to the present invention, there is provided a transfer film for curved surface printing, wherein an image layer constituting a pattern printed by electrophotography is laminated on one surface of a support film which swells in a predetermined solvent. An image printed using a toner containing a swelling accelerator for smoothing the movement of the toner particles in the image layer and facilitating the expansion and spreading of the image layer when performing transfer processing to a curved surface printed body. A transfer film for curved surface printing, which is a layer.

As described above, since the image layer of the transfer film for curved printing according to the present invention is an image layer printed using a toner containing a swelling accelerator having the above-described characteristics, the transfer processing step In, when the support film is floated on a predetermined solvent and transferred to the curved surface print,
Since the image layer can also be expanded and expanded with the expansion of the swollen support film, there is no problem such as cracking of the image layer during and after the transfer processing.

Therefore, as compared with a conventional transfer film for curved surface printing which is printed by gravure printing which requires a printing plate, a transfer film for curved surface printing having the same design and transferability without causing cracks in the pattern is obtained. Since it can be obtained at low cost and in a short time, it can be used for prototypes, calibration, and the like, and has an effect that it can sufficiently cope with recent trends in many kinds and small lots.

[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 electrophotographic printing.

FIG. 2 is an explanatory diagram illustrating an example of a printing process using curl fitting.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Toner tank, 3 ... Developing part, 4 ... Recording drum, 5 ... Impression cylinder, 6 ... Recording part, 7
... Electrophotographic printer, 8 ... Image layer, 9 ... Transfer film for curved surface printing, 10 ... Activator, 11 ... Solvent, 12 ...
Curved surface print, A: toner.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H113 AA03 AA04 BA18 BA22 BB07 BB09 BB10 CA31 DA25 DA45 DA47 EA03 FA10 FA36 3B005 EB01 EB03 EC16 EC17 FA03 FA04 FA12 FA17 FB40 FD05Z FG02X GA28

Claims (18)

[Claims] 1. A transfer film for curved surface printing, comprising an image layer constituting a pattern printed by an electrophotographic method laminated on one surface of a support film which swells in a predetermined solvent,
When the image layer performs a transfer process to a curved surface printed body, printing is performed using a toner containing a swelling accelerator for facilitating movement of toner particles in the image layer and facilitating expansion and spreading of the image layer. A transfer film for curved surface printing, characterized in that the transfer layer is a processed image layer. 2. The curved surface printing material according to claim 1, wherein the swelling accelerator is a substance which is in a solid state before being subjected to transfer processing to the surface to be printed, and which is in a liquid state during transfer processing. Transfer film. 3. The swelling accelerator is a substance that is heated to be a liquid during transfer processing.
The transfer film for curved printing according to the above. 4. The transfer film for curved surface printing according to claim 3, wherein the swelling accelerator is a substance having a melting point lower than the temperature of the predetermined solvent at the time of transfer processing. 5. The method according to claim 1, wherein the swelling accelerator is at least 30.degree.
The transfer film for curved surface printing according to claim 4, having the following melting point. 6. The transfer film for curved printing according to claim 5, wherein the swelling accelerator has a melting point of 35 ° C. or more and 60 ° C. or less. 7. The image forming apparatus according to claim 1, wherein an intermediate layer is disposed on one surface of the support film swelling in the predetermined solvent, and the image layer is disposed on or in the surface of the intermediate layer. The transfer film for printing on a curved surface according to claim 6. 8. The transfer film for curved printing according to claim 7, wherein the intermediate layer is insoluble in the predetermined solvent. 9. 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 8. 10. The transfer film for curved printing according to claim 1, wherein the toner is a wet toner. 11. Production of a transfer film for curved surface printing, comprising at least a step of preparing a support film which swells in a predetermined solvent, and a step of printing an image layer constituting a pattern on one surface of the support film by electrophotography. In the method, the step of printing the image layer is a step of printing using a toner containing a swelling accelerator consisting of a substance having a melting point lower than the temperature of the predetermined solvent at the time of transfer processing to the curved surface printed body. A method for producing a transfer film for curved surface printing, comprising: 12. The method according to claim 1, wherein a step of using a toner containing a swelling accelerator having a melting point in the range of 30 ° C. or more and 100 ° C. or less and printing the image layer at a temperature lower than the melting point is performed. 12. The method for producing a transfer film for curved surface printing according to item 11. 13. The method for producing a curved transfer film according to claim 11, wherein a wet toner is used. 14. The method according to claim 11, further comprising a step of forming an intermediate layer between the step of preparing the support film and the step of printing the image layer.
A method for producing a transfer film for curved surface printing according to any one of claims 1 to 4. 15. A step of (1) preparing a transfer film for curved surface printing by the production method according to any one of claims 11 to 14, and (2) forming the image layer by:
Or if an intermediate layer is formed, applying an activator capable of swelling either the image layer or the intermediate layer to the surface on the image layer side 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 heated to a temperature higher than the melting point of the swelling accelerator, with the surface on which the image layer is printed facing up; The curved printed body is lowered from above the swollen transfer film for swelling, and a part or the whole thereof is settled in the solvent, and the pressure-sensitive solvent applies the curved printed transfer film to the surface of the curved printed body. Extending and adhering; (5) removing the curved printed body from the solvent; washing and removing the support film from the curved printed body; and (6) protecting layer on the curved printed body from which the support film has been removed. Form Method of manufacturing a curved printed body characterized by having a degree. 16. A curved printing body, wherein the transfer film for curved printing according to claim 1 is transferred to a surface of a curved printing body. 17. A wet toner used when an image layer of a transfer film for curved surface printing is formed by printing by an electrophotographic method, wherein transfer processing to a curved surface printing body is performed using the transfer film for curved surface printing. A liquid toner comprising a substance which is heated to be in a liquid state at the time of performing as a swelling accelerator. 18. The liquid toner according to claim 17, wherein the swelling accelerator is a substance having a melting point in a range of 30 ° C. to 100 ° C.