Image forming process and printed article

Disclosed herein is a process for forming an image on a base material, which comprises the steps of (1) ejecting a liquid ink containing a disperse dye as droplets according to predetermined information to form an image on an ink-absorbent sheet, thereby obtaining an image-printing sheet; (2) bringing the image-printing sheet into close contact with a base material having a dye-receiving layer capable of receiving the disperse dye on its surface and high heat resistance of at least 150.degree. C., heating the printing sheet to transfer and diffuse the disperse dye on the image-printing sheet to and into the dye-receiving layer, and then separating the image-printing sheet from the base material, thereby obtaining an intermediate printed article; and (3) applying an aqueous coating fluid containing a substantially transparent resin to the transferred image on the intermediate printed article to provide a first overcoat layer and then applying a substantially transparent resin to the first overcoat layer to provide a second overcoat layer having a pencil hardness of 2H or harder as determined by the pencil scratch test in accordance with JIS K 5400.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to an image forming process and a printed 
article, and particularly to a process for forming an image having 
excellent image properties on a surface of a base material which has a 
high heat resistance of at least 150.degree. C., but has no ink 
absorbency. 
2. Related Background Art 
As processes for forming images on base materials such as ceramics such as 
earthenware, porcelain and stoneware, glass, plastics, and metals, which 
are not absorbent of liquid ink components, there have heretofore been a 
direct printing process in which printing is performed directly on these 
base materials, and a process of bonding a synthetic resin film, on which 
an image has been printed in advance, to the surfaces of these base 
materials to form an image thereon. 
The former printing process is generally performed by gravure printing or 
offset printing. However, printing presses used in these printing 
processes are expensive, and the processes are required to fabricate a 
plate according to the desired pattern. Therefore, it has been hard to say 
that this process is suitable for small-quantity printing. A process in 
which an image is directly formed on a base material by an ink-jet 
recording system without fabricating a plate is also performed in part. 
Under the circumstances, this process is however applied only to printing 
of lot numbers on products and simple characters up to the present, and 
the color is also limited to a single color. When it is intended to print 
a color image by an ink-jet recording system on the surface of a base 
material having no ink absorbency, overlapped inks remain as ink droplets 
on the base material because the base material has no ink absorbency, so 
that fine color mixing is prevented, and boundaries between different 
colors become indistinct. In addition, the scratch resistance and wear 
resistance of the formed image are insufficient because printing is 
conducted directly on the base material. Namely, it has been difficult to 
form any bright color image excellent in scratch resistance and wear 
resistance directly on the surface of a base material having no ink 
absorbency by the ink-jet recording system. 
On the other hand, the latter process is a process of bonding an 
image-printed synthetic resin film to the surface of a base material 
having no ink absorbency to form an image thereon, but offers a problem of 
adhesion between the image-printed film and the base material. Troubles 
such as peeling of the film have been often caused. 
As a process for solving these problems, Japanese Patent Publication No. 
47-51734 discloses a process in which an ink-receiving layer composed of a 
synthetic resin film is formed on the surface of a base material having no 
ink absorbency in advance, an image-printing sheet, on which an image 
containing a sublimate dye (disperse dye) has been formed, is laid on the 
synthetic resin film, and the printing sheet is then heated to sublimate 
the dye so as to transfer only the dye to the synthetic resin film on the 
base material, thereby forming an image on the resin film. Besides, as a 
process for forming an image containing a sublimate dye on a printing 
sheet, it is disclosed in Japanese Patent Publication No. 60-8959 to use 
an ink-jet recording system. 
Specific examples of such receiving layers for disperse dyes as described 
above are disclosed in Japanese Patent Application Laid-Open Nos. 52-5843, 
5-309956 and 6-143792. According to Japanese Patent Application Laid-Open 
No. 52-5843, however, fiber is intended for a base material, and so the 
principal object in view is to keep the hand feeling of a finished textile 
good. Therefore, any receiving layer having high mechanical strength such 
as high scratch resistance cannot be obtained. In Japanese Patent 
Application Laid-Open Nos. 5-309956 and 6-143792, it is described to use, 
as materials for the formation of receiving layers, polyester resin 
compositions having resistance to various stains which form the cause of 
irregularity of images formed. These resin compositions are believed to be 
excellent as materials for the formation of receiving layers for 
sublimate-transfer image-receiving paper. The sublimate-transfer 
image-receiving paper is generally used in recording systems such as a 
sublimate transfer system and a melt transfer system and attaches 
importance to recording speed. Therefore, as sublimate dyes used, those 
low in sublimation temperature are in use. On the other hand, when an 
image containing a disperse dye formed on an image-printing sheet is 
transferred to heat-resistant base materials such as pottery, glass, 
plastics and metals, it is desirable that the transfer be performed at a 
temperature as high as possible to effectively diffuse the disperse dye 
into the receiving layer. Namely, when the sublimate transfer is performed 
under such conditions, it is possible to form a bright and high-color 
density image, which conforms to the image on the image-printing sheet, on 
the surfaces of the base materials such as pottery and glass. When the 
transfer of the image is performed under such conditions, however, there 
has been problems that the receiving layer composed of the polyester resin 
composition as described above is softened, so that a situation that a 
mark of the image-printing sheet is left on the base materials in the form 
of irregularities, or that the image-printing sheet is not separated from 
the base materials in the worst case may be brought on. 
When the use situation of image-printed articles obtained in the above 
described manner is considered, severe criteria as to properties of the 
images such as mechanical strength, light fastness, stain resistance and 
chemical resistance are not very required of displays and the like used 
indoors. When the printed articles are intended for building materials 
which are used outdoors, for example, external wall materials and floor 
covering materials, considerably severe criteria as to the properties of 
the images are required of them. Even when the printed articles are used 
indoors, it is necessary to take the prevention against the generation of 
mildew on the printed articles into consideration in the case where they 
are intended to use in places easy to generate dew condensation, such as 
bathroom and wall covering materials. 
Further, there is described in Japanese Patent Application Laid-Open No. 
51-116287 a process to add a new function to a printed article after 
conducting textile printing by sublimate transfer to a receiving layer. In 
this method, a flameproofing treatment is conducted by applying an 
overcoat layer to polyester fibers printed by the sublimate transfer. 
However, Japanese Patent Application Laid-Open No. 51-116287 does not 
describe anything about the improvement in mechanical strength, light 
fastness, stains resistance and chemical resistance. As materials for the 
formation of the overcoat layer, those containing a non-aqueous solvent in 
plenty are generally often used because of their good properties. When the 
liquid overcoat materials containing such a solvent in plenty are used, 
however, a disperse dye penetrated into the receiving layer has slightly 
exuded in some cases. Although the amount of the dye exuded is slight, it 
is conspicuous at the contour part of an image when the background of the 
image is white. Therefore, there has been a problem that a clearness of 
the image has been impaired. 
SUMMARY OF THE INVENTION 
It is therefore an object of the present invention to provide an image 
forming process which permits the formation of a clear image without 
fabricating a printing plate on a base material which is not absorbent of 
liquid components and has a high heat resistance, and an image-forming 
material and a printed article obtained by using such a process. 
The above object can be achieve by the present invention described below. 
According to the present invention, there is thus provided a process for 
forming an image on a base material, which comprises the steps of: 
(1) ejecting a liquid ink containing a disperse dye as droplets according 
to predetermined information to form an image on an ink-absorbent sheet, 
thereby obtaining an image-printing sheet; 
(2) bringing the image-printing sheet into close contact with a base 
material having a dye-receiving layer capable of receiving the disperse 
dye on its surface and a high heat resistance of at least 150.degree. C., 
heating the image-printing sheet to transfer and diffuse the disperse dye 
on the image-printing sheet to and into the dye-receiving layer, and then 
separating the image-printing sheet from the base material, thereby 
obtaining an intermediate printed article; and 
(3) applying an aqueous coating fluid containing a substantially 
transparent resin to the transferred image on the intermediate printed 
article to provide a first overcoat layer and then applying a 
substantially transparent resin to the first overcoat layer to provide a 
second overcoat layer having a pencil hardness of 2H or harder as 
determined by the pencil scratch test in accordance with JIS K 5400. 
According to the present invention, there is also provided a printed 
article formed by the process described above. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
In the present invention, a printing sheet containing an image formed with 
a disperse dye is brought into close contact with a dye-receiving layer 
provided on a surface of a base material having no ink-absorbency and a 
high heat resistance of at least 150.degree. C. and heated to transfer and 
diffuse the disperse dye, which forms the image, to and into the 
dye-receiving layer. Thereafter, the image-printing sheet is separated 
from the base material to form an intermediate printed article, and an 
overcoat layer is then formed on the intermediate printed article. The 
overcoat layer is composed of a two-layer structure of first and second 
layers, thereby permitting the formation of a clear and high-color density 
image conforming to the original image and having excellent scratch 
resistance (scuff resistance), wear resistance and the like on the surface 
of the base material having no ink-absorbency. More specifically, bleed of 
the resultant image occurs due to the exudation of disperse dyes, when a 
coating fluid containing a solvent in plenty is used to form an overcoat 
layer. Such exudation is suppressed by the first overcoat layer 
(intermediate layer) composed of a water-soluble resin or a transparent 
resin of an aqueous emulsion. On the first overcoat layer, the second 
overcoat layer containing, for example, an ultraviolet absorbent and a 
mildew-proofing agent therein is provided, thereby obtaining a printed 
article on which an image having far excellent mechanical strength, light 
fastness, stain resistance, chemical resistance and mildew-proofing 
property has been formed on a base material having no ink-absorbency 
selected from the group consisting of ceramics such as earthenware, 
porcelain and stoneware, glass, plastics, and metals without impairing the 
clearness of images. According to the constitution of the present 
invention, further, the dye-receiving layer formed in advance on the base 
material having no ink-absorbency can be composed in view of the 
transferability of image in the first place, so that a beautiful printed 
article having a clear and high-color density image can be obtained. 
The present invention will hereinafter be described in more detail with 
reference to the preferred embodiments. 
The image forming process according to the present invention comprises a 
printing sheet-forming step of forming an image-printing sheet having an 
image formed with a disperse dye; a step of bringing the image-printing 
sheet into close contact with the surface of a dye-receiving layer capable 
of receiving the disperse dye provided on the surface of a base material 
having a high heat resistance of at least 150.degree. C., heating the 
image-printing sheet to transfer and diffuse the disperse dye on the 
image-printing sheet to and into the dye-receiving layer, and then 
separating the image-printing sheet from the base material, thereby 
obtaining an intermediate printed article; and a step of applying a 
substantially transparent resin to the resultant intermediate printed 
article to form an overcoat layer. The feature of the present invention 
resides in that the step of forming the overcoat layer includes applying 
an aqueous coating fluid containing a substantially transparent resin to 
the intermediate printed article to provide a first overcoat layer and 
then applying a substantially transparent resin to the first overcoat 
layer to laminate a second overcoat layer having a pencil hardness of 2H 
or harder, thereby forming a laminated overcoat layer having a two-layer 
structure. 
Disperse dyes contained in inks used in the printing sheet-forming step in 
the present invention are materials known per se in the art, refer to 
water-insoluble or hardly water-soluble dyes used widely in dyeing of 
fibers in a dispersed state and include azo, anthraquinone and other dyes 
from the viewpoint of chemical structure. These disperse dyes have no 
hydrophilic groups such as sulfonic and carboxylic groups in their 
structures, each have a molecular weight within a certain range and are 
used in the form of an aqueous dispersion. They are mainly used in dyeing 
synthetic fibers such as polyester and acetate by heating them at a 
temperature of from 80 to 250.degree. C. after applying them in the state 
of the aqueous dispersions to the fibers or fabrics or during their 
application. In the present invention, all the conventionally known 
disperse dyes may be used. However, preferable disperse dyes in the 
present invention are as follows. 
Examples of disperse dyes preferably used in the present invention include: 
C.I. Disperse Yellow 5, 42, 56, 64, 76, 79, 83, 100, 124, 140, 160, 162, 
163, 164, 165, 186, 192 and 224; 
C.I. Disperse Orange 13, 29, 30, 31, 33, 43, 49, 50, 55, 61, 73, 78 and 
119; 
C.I. Disperse Red 43, 54, 56, 72, 73, 76, 88, 91, 92, 93, 103, 111, 113, 
126, 127, 128, 135, 143, 145, 152, 153, 154, 164, 181, 188, 189, 192, 203, 
205, 206, 207, 221, 224, 225, 227, 257, 258, 288 and 296; 
C.I. Disperse Violet 27, 35, 38, 46, 52 and 56; 
C.I. Disperse Brown 1 and 9; 
C.I. Disperse Blue 54, 60, 73, 87, 94, 113, 128, 139, 142, 143, 146, 148, 
149, 158, 167, 176, 183, 186, 187, 197, 198, 201, 205, 207, 211, 214, 224, 
225, 257, 259, 267, 268, 270 and 301; 
Kayacelon Red E-GL (trade name); and 
Kayacelon Blue E-TB (trade name). 
Among the conventionally-known dispersed dyes as described above, the 
disperse dyes most preferably used in the image forming process according 
to the present invention are those which have a comparatively high 
molecular weight and a transfer temperature of at least about 180.degree. 
C. under normal pressure. The reason for this is that the sublimation and 
transfer at such a high temperature permits effective diffusion of the 
disperse dyes into the receiving layer and hence the formation of a clear 
and high-color density image on the surface of a base material such as 
ceramic or glass becomes possible. When multicolor printing of at least 
two colors is performed in accordance with the image forming process of 
the present invention, it is also preferable that all disperse dyes to be 
used be selected in such a manner that their transfer temperatures are 
within the transfer temperature range as described above with a view 
toward making a degree of coloring upon the transfer even. Incidentally, 
the measurement of the temperature at which a disperse dye effectively 
sublimates and transfers may be carried out by a thermal analytical means 
such as T.G., D.T.A. or D.S.C., or the method prescribed in JIS L 0879. 
The selection of the preferred disperse dyes can be easily made by those 
skilled in the art. 
Inks used in the present invention comprise such a disperse dye as 
described above and a liquid medium dispersing or dissolving the disperse 
dye therein. As the liquid medium used at this time, any of liquid media 
used routinely in general dyeing and liquid media used routinely in 
ink-jet recording inks may be used. For example, water and/or 
water-soluble organic solvents are preferably used. Specific examples of 
preferable water-soluble organic solvents usable in the present invention 
include alkyl alcohols having 1 to 4 carbon atoms, such as methyl alcohol, 
ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, 
sec-butyl alcohol, tert-butyl alcohol and isobutyl alcohol; amides such as 
dimethylformamide and dimethylacetamide; ketones and keto-alcohols such as 
acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; 
polyalkylene glycols such as polyethylene glycol and polypropylene glycol; 
alkylene glycols the alkylene moiety of which has 2 to 6 carbon atoms, 
such as ethylene glycol, propylene glycol, butylene glycol, triethylene 
glycol, hexylene glycol and diethylene glycol; thiodiglycol; 
1,2,6-hexanetriol; glycerol; lower alkyl ethers of polyhydric alcohols, 
such as ethylene glycol monomethyl (or monoethyl) ether, diethylene glycol 
monomethyl (or monoethyl) ether and triethylene glycol monomethyl (or 
monoethyl) ether; N-methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone; 
and the like. 
The liquid media as described above may be used either singly or in any 
combination thereof. However, the most preferred composition of the liquid 
medium is a mixed solvent comprising water and at least one organic 
solvent which comprises at least one water-soluble, high-boiling solvent, 
for example, a polyhydric alcohol such as ethylene glycol, propylene 
glycol or glycerol. These liquid media may preferably be used in such an 
amount that the content of the disperse dye amounts to a range of the 
order of from 0.1 to 15% by weight upon the preparation of an ink 
composition. 
Although the composition of the inks used in the printing sheet-forming 
step in the image forming process of the present invention is as described 
above, conventionally-known various dispersants, surfactants and viscosity 
modifiers may be further added as needed. Examples of the dispersants or 
surfactants which may be added to the inks as needed include anionic 
dispersants or surfactants such as fatty acid salts, salts of 
alkylsulfates, alkylbenzenesulfonates, alkylnaphthalene-sulfonates, 
dialkylsulfosuccinates and alkylphosphates, naphthalenesulfonic 
acid-formalin condensates, and polyoxyethylene alkylsulfates; and nonionic 
dispersants or surfactants such as polyoxyethylene alkylphenyl ethers, 
polyoxyethylene fatty acid esters, sorbitan fatty acid esters, 
polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, 
glycerol esters of fatty acid and oxyethylene-oxypropylene block 
copolymers. 
As the viscosity modifiers, for example, mainly water-soluble natural or 
synthetic polymers such as carboxymethyl cellulose, sodium polyacrylate, 
polyvinyl pyrrolidone, gum arabic and starch are preferably used. The 
viscosity of the ink used in the present invention, which are obtained 
with or without these viscosity modifiers, is preferably 50 cP or lower, 
more preferably within a range of from 1 to 10 cP. 
In the case where an ink-jet recording system of a type that ink is charged 
electrostatically is used in the printing sheet-forming step in the image 
forming process of the present invention, it is preferable to add a 
resistivity regulative agent composed of an inorganic salt, for example, 
lithium chloride, ammonium chloride, sodium chloride or the like upon the 
preparation of the ink. 
In addition to the above three additives, for example, an antifoaming 
agent, a penetrant, a mildew-proofing agent, a pH adjuster, etc. may be 
suitably added to the inks used in the present invention as needed. 
In the printing sheet-forming step in the image forming process of the 
present invention, it is preferable to use inks of such a composition as 
described above to form an image on a medium, which is absorbent of liquid 
ink, by an ink-jet recording method. Therefore, the inks used in the 
present invention may preferably be prepared by the same process as that 
used in the ink-jet recording inks conventionally used. More specifically, 
it is common to mix the above-described components, grind the mixture by 
the conventionally-known grinding means, for example, a ball mill, a sand 
mill or a speed line mill, optionally control the concentration of the 
mixture with a liquid medium and finally adjust its pH to 4 to 10. The 
particle diameter of the disperse dye is generally controlled to about 30 
.mu.m or smaller, preferably about 20 .mu.m or smaller. If the particle 
diameter is too great, problems such as clogging at an orifice may be 
caused upon ink-jet printing in some cases. When a liquid medium 
dissolving the disperse dye therein is selected as the liquid medium, an 
ink usable in the present invention can be obtained by simple dissolving 
operation such as heating. 
As described above, an ink-jet recording method is preferably used in the 
formation of an image in the printing sheet-forming step in the present 
invention. The use of the ink-jet recording method makes an expensive 
printing press, which is required in the conventional printing process, 
useless, and so a printing plate is also unnecessary. This brings about 
the following advantages: An image-printed article can be provided more 
cheaply, and delivery time of the product can also be shortened to an 
extremely great extent. 
As the ink-jet recording method usable in the present invention, any system 
may be used so far as it is a system that an ink-jet recording ink of such 
a constitution as described above can be ejected as droplets according to 
predetermined information to form an image on a printing sheet. Typical 
examples of such systems are described in, for example, IEEE Trans Actions 
on Industry Applications, Vol. JA-13, No. 1 (the February and March, 1977 
issue) and Nikkei Electronics, No. 305 (the Dec. 6, 1982 issue). The 
systems described therein are suitable for the ink-jet recording method 
used in the present invention. Some of them will be described. First, 
there is mentioned an ink-jet recording method of an electrostatic 
attraction system. In this system, there are two methods in one of which a 
strong electric field is applied between a nozzle and an accelerating 
electrode placed several millimeters ahead the nozzle to successively draw 
an ink in the form of droplets out of the nozzle, and information signals 
are applied to deflecting electrodes while the drown ink droplets are 
flown between the deflecting electrodes, thereby conducting recording, and 
in the other of which ink droplets are ejected according to information 
signals without deflecting the ink droplets. Both methods are effective 
for application to the ink-jet printing method used in the present 
invention. 
As the second system, there is an ink-jet recording method of a system in 
which a high pressure is applied to an ink by a small-sized pump, and a 
nozzle is mechanically vibrated by a quartz oscillator or the like, 
thereby forcedly ejecting ink droplets. According to this system, the 
ejected ink droplets are electrically charged according to information 
signals at the same time as the ejection. The charged ink droplets are 
deflected according to the degree of charge while they pass through 
between deflecting electrodes. As another system making good use of this 
system, there is also a system called a microdot ink-jet system. In this 
system, an ink pressure and exciting conditions are kept at optimum values 
within certain ranges, thereby ejecting two kinds of ink droplets of large 
and small sizes from an orifice. Of these ink droplets, only the ink 
droplets of the small size are used in recording. This system features 
that a group of minute ink droplets can be ejected even from an ordinary 
wide orifice. 
As the third system, there is an ink-jet recording method of a 
piezoelectric system. This system uses, as a means for pressurizing an 
ink, a piezoelectric element instead of mechanical means such as a pump 
used in other systems. More specifically, electric signals are applied to 
the piezoelectric element to cause mechanical displacement, thereby 
applying a pressure to an ink to eject the ink from an orifice. 
As the system preferably used in the present invention, there is an ink-jet 
recording method described in Japanese Patent Application Laid-Open No. 
54-59936. In this ink-jet system, an ink undergoes a rapid volumetric 
change by an action of thermal energy applied to the ink by rapidly 
heating a heating element, thereby ejecting the ink out of an orifice. In 
this system, the formation of the heating element and a groove of the 
orifice is made by a photolithography, which is performed in a production 
of semiconductors and the like, upon the production of an ink-jet head 
used. Therefore, the high-density mounting of nozzle and the formation of 
a multi-nozzle are easily performed, and an apparatus of such a system can 
be produced inexpensively. This ink-jet system is hence most suitable for 
the method used in the present invention. 
In the image forming process of the present invention, the disperse 
dye-containing liquid ink ejected by the ink-jet recording method as 
described above is received on a printing sheet having no ink-absorbency 
to obtain an image-printing sheet on which an image of the disperse dye 
has been temporarily formed. As a result, there can be avoided 
disadvantages incurred by direct formation of images on a base material 
having a poor ink-absorbency, as follows: 
First, when an image is directly formed on a base material by the ink-jet 
recording method, ink droplets formed on the base material aggregate each 
other if a base material having no ink-absorbency is used as the base 
material, so that any beautiful image cannot be formed. This problem is 
serious when an image is formed using two or more inks of different colors 
because defective coloring and bleeding at boundaries between different 
colors occur. Second, a disperse dye remaining on the surface of the base 
material after the transfer of the ink by heating must be washed and 
removed. 
As the printing sheet used in the formation of the image with the disperse 
dye in the image forming process of the present invention, any sheet 
generally used in ink-jet recording methods may be used. As preferable 
examples of the sheet, may be mentioned those comprising, as a main 
component, cellulose, which are called plain paper. It goes without saying 
that those provided with a coating layer for controlling an ink 
absorbency, such as glossy paper and OHP, may also be used. However, the 
greatest care must be taken in using them because the coating layer may 
come to adhere to the base material due to heating upon transfer of the 
disperse dye, or the transfer of the disperse dye to the base material may 
be deteriorated. 
The dye-receiving layer, which is formed on the surface of the base 
material having no ink-absorbency in the image forming process of the 
present invention and can receive the disperse dye, will now be described. 
In the present invention, as described above, the surface characteristics 
of the final image-printed article are given by the overcoat layer which 
will be described subsequently. In the present invention, therefore, the 
materials for the formation of the dye-receiving layer can be selected in 
view of the transferability of the disperse dye in the first place. In the 
present invention, however, it should be avoided to use, as a material for 
the formation of the dye-receiving layer, such a resin as a press mark of 
the image-printing sheet is left on the receiving layer when the transfer 
is conducted by the close contact under heat, and the dye-receiving layer 
adheres to the image-printing sheet to fail to separate them from each 
other. It is therefore preferable to select the materials for the 
dye-receiving layer so as to provide a pencil hardness of H or harder as 
determined by the pencil scratch test in accordance with JIS K 5400. 
Specific examples of materials for the formation of such a dye-receiving 
layer include alkyd resins obtained from a polybasic acid (for example, 
azelaic acid, chlorendic acid, succinic acid, trimellitic acid, o-phthalic 
acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, 
adipic acid, sebacic acid or the like), a polyhydric alcohol (for example, 
.alpha.-methyl-glucoside, dipentaerythritol, glycerol, glycols, 
trimethylolmethane, trimethylolpropane, tripentaerythritol or sorbitol) 
and a fatty acid; silicone alkyd resins obtained by copolymerizing an 
alkyd resin with a silicone intermediate such as siloxane; amino resins 
obtained by reacting formaldehyde with urea or melamine, such as 
urea-formaldehyde resins and melamine-formaldehyde resins; epoxy resins 
crosslinked by an amino resin, phenol resin, amine, polyamide, isocyanate 
or the like; and resins such as polyester resins, unsaturated polyester 
resins, silicone resins, urethane resins, polyamide resins, polyimide 
resins and fluororesins. Resins such as acrylic resins obtained by 
polymerization or copolymerization of an acrylic or methacrylic ester may 
also be used. It goes without saying that mixtures and reaction products 
of these resins may also be included. 
Among these resins, the urethane resins, which are reaction products of an 
isocyanate compound with a polyhydroxy compound or an amino 
group-containing compound, are mentioned as the most preferable resins. 
Specific examples of the isocyanate compound include aromatic isocyanates 
such as 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 
m-phenylene diisocyanate, p-phenylene diisocyanate, 2-chloro-1,4-phenylene 
diisocyanate, 1-chloro-2,4-phenylene diisocyanate, 1,5-naphthylene 
diisocyanate and 4,4'-diphenylmethane diisocyanate. Aliphatic and 
alicyclic polyisocyanates may also be used in the present invention. 
Specific examples thereof include hexamethylene diisocyanate, 
hexamethylene triisocyanate, isophorone diisocyanate, etc. Modified 
products and derivatives of these isocyanates may also be preferably used. 
Examples of the polyhydroxy compound include polyether polyols, polyester 
polyols, acrylic polyols, phenol resin polyols, epoxy polyols, polyester 
polyether polyols, carbonate polyols, etc. 
The reaction products of these compounds are generally colorless and 
transparent and easily provided with a dye-receiving layer having a pencil 
hardness of H or harder. Therefore, they are suitable for use in the 
formation of the dye-receiving layer used in the present invention. In the 
case of a reaction using the isocyanate compound, however, it must be 
avoided to mix water except for the case where water is used with 
particular intent because carbon dioxide is generated by its reaction with 
water. The same may be said of carboxyl group-containing compounds. 
It is also effective to add a silane coupling agent to the dye-receiving 
layer as needed. As the effect of the silane coupling agent added, it is 
expectable to improve the adhesion between the base material and the resin 
as generally said. In the system using the isocyanate compound, a coupling 
agent is preferred, because the water content therein can be reduced by 
hydrolysis, and the hydroxyl group formed by the hydrolysis reacts with 
the isocyanate, whereby a dye-receiving layer having higher mechanical 
strength can be formed. 
The amount of the silane coupling agent to be used is of the order of from 
0.1 to 30% by weight based on the total weight of resin. If the amount of 
the silane coupling agent is less than 0.1% by weight, the effect of the 
addition cannot be exhibited. On the other hand, any amount exceeding 30% 
by weight results in a dye-receiving layer which tends to become brittle 
and also deteriorated in adhesion to the base material. 
Specific examples of such a silane coupling agent include 
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 
.gamma.-glycidoxypropyltrimethoxysilane, 
.gamma.-mercaptopropyl-trimethoxysilane, 
.gamma.-mercaptopropylmethyldimethoxysilane, methyltrimethoxysilane, 
dimethyldimethoxysilane, methyl-triethoxysilane, phenyltrimethoxysilane, 
vinyltrimethoxy-silane, 
vinyltriethoxysilane,.gamma.-methacryloxypropyl-trimethoxysilane and 
.gamma.-aminopropyltriethoxysilane. 
As a method of coating the base material such as earthenware with the resin 
as described above to form the dye-receiving layer, the resin may be 
melted at a high temperature and directly applied so far as it is 
thermoplastic. However, precursor unreacted compounds of a resin to be 
coated, or their dilute solution, emulsion or colloid suspension in a 
solvent is generally coated by any of various processes such as spray 
coating, curtain coating, dip coating, wire bar coating, applicator 
coating, spin coating, roll coating, electrodeposition coating and brush 
coating. Thereafter, the coated base material is dried to remove the 
solvent, and a cure reaction is optionally performed, whereby a 
dye-receiving layer can be formed. 
When an isocyanate compound is used to form the dye-receiving layer, the 
removal of the solvent by drying and cure reaction under heat may 
preferably be performed at two steps. Water, which is contained as an 
impurity, is removed together with the solvent by first heating at a 
relatively low temperature, after which the reaction is completed by 
second heating at a high temperature. In particular, when the coating is 
performed by the spray coating, there is a possibility that the 
temperature of the resin may be lowered by rapid vaporization of the 
solvent upon the coating, and water in air may be entrained, thereby 
adversely affecting the reaction. Therefore, this two-step heating is 
particularly effective. The first heating is preferably conducted under 
conditions of 100.degree. C. or lower for from 5 minutes to 2 hours, while 
the second heating is preferably performed under conditions of from 100 to 
250.degree. C. for from 5 minutes to 3 hours. 
Any material may be used as the base material on which the dye-receiving 
layer is to be formed so far as it has heat resistance of at least 
150.degree. C. For example, a material selected from ceramics such as 
earthenware, porcelain and stoneware, glass, plastics, and metals and 
having heat resistance of at least 150.degree. C. is used as the base 
material. Namely, these materials have no ink-absorbency, and it is hence 
difficult to directly form an image on the surfaces of the base materials 
by an ink-jet printing process. On the other hand, any base material 
having a heat resistance lower than 150.degree. C. is required to conduct 
sublimation and transfer of the disperse dye at a low temperature, and so 
it is difficult to obtain a clear image. 
A step of transferring and diffusing the disperse dye from the 
image-printing sheet, on which an image has been formed with the disperse 
dye-containing ink described above, to and into the dye-receiving layer 
formed of the above-described materials will now be described. In this 
step, the image-printing sheet is brought into close contact with the 
dye-receiving layer on the surface of the base material and then heated to 
transfer and diffuse the disperse dye on the image-printing sheet to and 
into the dye-receiving layer on the surface of the base material. 
Thereafter, the image-printing sheet is separated from the base material 
to obtain an intermediate printed article. 
The first importance in this step is to keep the image-printing sheet in 
close contact with the surface (i.e., the dye-receiving layer) of the base 
material. They are generally brought into contact with each other under a 
pressure of the order of from 0.1 to 5 kg/cm.sup.2 using a pressure source 
such as spring or high-pressure air. 
Second, it is effective to preheat the base material with a view toward 
shortening a treating time and obtaining an even temperature distribution. 
Finally, the image-printing sheet and the dye-receiving layer are heated 
at a temperature of 150 to 250.degree. C. for from several seconds to 
several minutes while keeping them in close contact with each other. These 
conditions may be suitably determined from the ranges of the 
above-described conditions taking consideration of the heat resistance of 
the base material, the sublimating tendency of the disperse dye and the 
heat resistance of the dye-receiving layer. If the transfer temperature is 
low, or the heating time is short, the disperse dye is not fully 
transferred and diffused from the image-printing sheet to and into the 
dye-receiving layer, resulting in only an image low in color density. If 
the transfer temperature is raised than the step needs, or the heating 
time is prolonged than the step needs on the other hand, the disperse dye 
is decomposed or vaporized out of the dye-receiving layer, resulting in 
only a faded image. 
After the transfer of the disperse dye as described above, the heating and 
pressurization are completed, and the image-printing sheet is separated 
from the base material, thereby obtaining the intermediate printed article 
on which the intended image has been formed. The intermediate printed 
article itself fully functions as a display. However, satisfactory image 
properties cannot be always achieved when it is intended for use under 
severe conditions in the open air, bathroom or the like. 
Therefore, an overcoat layer is further provided on the intermediate 
printed article in the image forming process of the present invention. The 
feature of the present invention resides in that the overcoat layer is 
composed of two layers of a first overcoat layer and a second overcoat 
layer. First, the first overcoat layer is provided on the intermediate 
printed article for suppressing the exudation of the disperse dye. The 
second overcoat layer is further provided on the first overcoat layer 
serving as an intermediate layer to impart properties such as light 
fastness and mildew-proofing property to the resulting printed article. 
More specifically, it is considered that when an aqueous coating fluid 
composed of, for example, an aqueous solution or emulsion of a resin using 
water as a main medium is used to form an overcoat layer for suppressing 
the exudation of the disperse dye, the exudation of the disperse dye is 
prevented, and so a clear image can be obtained. However, such a resin has 
poor compatibility with additives, in particular, ultraviolet absorbents, 
so that these additives cannot be incorporated into the resin, resulting 
in a failure in obtaining an image-printed article having excellent light 
fastness. Therefore, the first overcoat layer is formed with such a resin 
as described above, and the second overcoat layer is laminated on the 
first overcoat layer. In the second overcoat layer, additives such as an 
ultraviolet absorbent and a mildew-proofing agent are contained, thereby 
satisfying properties such as light fastness and mildew-proofing property. 
Materials for the formation of the overcoat layers will hereinafter be 
described. In the present invention, it is preferable to use, as a 
material for the formation of the first overcoat layer, an aqueous 
solution or emulsion of a resin using water as a main medium. Examples of 
resins applied to the aqueous solution of the resin using water as the 
main medium include water-soluble resins such as poly(meth)acrylic acid 
and salts thereof, polyvinyl alcohol, water-soluble cellulose derivatives, 
carboxymethyl cellulose, starch, polyacrylamide, polyvinyl pyrrolidone, 
acrylic acid-vinyl alcohol copolymers, pectin, glue, casein, polyethylene 
oxide and poly(vinyl methyl ether). 
Besides, examples of resins applied to the aqueous emulsion of the resin 
using water as the main medium include water-dispersible resins such as 
poly(meth)acrylic acid type resins, (meth)acrylate type resins, 
styrene-butadiene type resins, acrylonitrile-butadiene type resins, vinyl 
acetate type resins and vinyl chloride type resins. Examples of products 
of these resins include Voncoat Series 3990, 2310, 6938, 6731, EC-818, 
EC-819, 3980, 3985 and 3986 (all, products of Dainippon Ink & Chemicals, 
Incorporated); Hytec S Series S-3111, S-3121, S-3125, S-3128 and S-3129 
(all, products of Toho Chemical Industry Co., Ltd.); Jurymer AT Series 
AT-210, AT-510, AT-515 and AT-613, and Jurymer ET Series ET-410, ET-530 
and ET-533 (all, products of Nihon Junyaku Co., Ltd.); Polytron Series 
U4431, U4510 and U4630 (all, products of Asashi Chemical Industry Co., 
Ltd.); PVC Latex Series Zeon 150x15, 351 and 576 (all, products of Nippon 
Zeon Co., Ltd.); Primal Series AC-55, AC-261, AC 630, AC-2000, E-2438, 
E-1895, HG-56, TL-5 and E-1630 (all, products of Rohm & Haas Co.); and 
Polysol Series SH-502, HR-G and AP-50 (all, products of Showa Highpolymer 
Co., Ltd.). 
As materials for the formation of the first overcoat layer, water-soluble 
monomers, oligomers and polymers which are cured by exposure to radiation 
having activation energy may also be used. Examples of such materials 
include (meth)acrylates of polyhydric alcohols and their alkylene oxide 
adducts, such as 1,6-hexanediol diacrylate, trimethylolpropane 
triacrylate, Photomer 4061-SN, Nopcomer 4270 and Nopcomer 4510 (all, 
products of San Nopco Limited), and NK Ester A-200, NK Ester A-400, NK 
Ester A-600 and NK Ester A-1000 (all, products of Shin-Nakamura Chemical 
Co., Ltd.); and (meth)acrylates of products obtained by adding glycidyl 
ether to a polyhydric alcohol, such as Denacol Acrylate DA314, Denacol 
Acrylate DA832, Denacol Acrylate DA851, Denacol Acrylate DA911 and Denacol 
Acrylate DA920 (all, products of Nagase Chemicals, Ltd.). When these 
materials are used, it is necessary to conduct a curing treatment. 
Although no curing agent is especially required if the curing is conducted 
by electron beams, it is necessary to add a photo-curing agent to such a 
material in advance if the curing is conducted by ultraviolet rays. 
Examples of photo-curing agents usable at this time and particularly 
suitable for use in an aqueous system include Irgacure 2959, Irgacure 500 
and Irgacure 184 (all, products of CIBA-GEIGY (Japan) Limited). 
The materials for the formation of the first overcoat layer described above 
are preferably colorless and transparent so as not to impair the image of 
the intermediate printed article when laminated with the second overcoat 
layer which will be described subsequently. More specifically, it is 
preferable to limit rise in optical density after the application of the 
first and second overcoat layers to 0.5 or lower in a coating thickness 
described below. Although necessary transparency varies according to the 
pattern of the intermediate printed article, it is unavoidable except for 
a special intention to give a feeling of deteriorated image quality since 
an image is colored or is felt to be opaque, when the rise in optical 
density exceeds 0.5. 
As a method of forming the first overcoat layer, generally a precursor 
unreacted compound of a resin to be applied or a coating fluid in the form 
of its dilute solution, emulsion or colloid suspension in a solvent is 
applied by a process such as spray coating, curtain coating, dip coating, 
wire bar coating, applicator coating, spin coating, roll coating, 
electrodeposition coating or brush coating to form a coating film, and the 
coating film thus formed is then dried to remove the solvent, and 
optionally subjected to a cure reaction, thereby forming the first 
overcoat layer. 
The coating thickness of the first overcoat layer thus formed is preferably 
within a range of from 0.1 to 5 .mu.m in terms of the thickness after the 
drying or curing. If the coating thickness is thinner than 0.1 .mu.m, it 
is difficult to form a complete film, so that frequency of occurrence in 
defective coating becomes high. More specifically, the first overcoat 
layer becomes liable to produce pinholes due to irregularities of the 
surface of the base material and influence of adhered foreign matter. When 
the second overcoat layer is laminated thereon, therefore, the disperse 
dye dispersed and diffused into the dye-receiving layer on the base 
material may possibly exude through the pinholes due to the action of a 
solvent in a coating fluid for forming the second overcoat layer. If the 
coating thickness of the first overcoat layer exceeds 5 .mu.m on the other 
hand, the materials for the formation of the first overcoat layer are used 
more than the layer needs, leading to an economical loss. In addition, 
there is a great possibility that rise in optical density and 
deterioration of mechanical properties may be caused. Therefore, such a 
too thin or thick coating thickness is not preferable. 
When the first overcoat layer is formed, cissing of the coating fluid may 
occur according to its compatibility with the dye-receiving layer serving 
as an undercoating on the base material. In order to prevent the cissing, 
it is effective to subject the surface of the dye-receiving layer to a 
cleaning treatment prior to the formation of the first overcoat layer. As 
an example of a method for the cleaning treatment suitably used at this 
time, may be mentioned a method in which the surface of the dye-receiving 
layer on the base material is cleaned with oxygen plasma or ozone 
generated by ultraviolet-light irradiation in an oxygen-containing gas. 
When the coating fluid is applied to the intermediate printed article 
after conducting such a cleaning treatment, a first overcoat layer 
composed of an even thin film can be formed without causing the cissing of 
the coating fluid. 
In the present invention, the second overcoat layer is provided on the 
first overcoat layer formed in the above-described manner to form a 
laminated overcoat layer composed of two layers. As the materials for the 
formation of the second overcoat layer, materials, which are colorless and 
transparent when laminated on the first overcoat layer, are used so as not 
to impair the image of the intermediate printed article as described 
above. The second overcoat layer is required to have a certain measure of 
mechanical strength because it makes up the top layer on the base 
material. In order to enhance the mechanical strength of the second 
overcoat layer, it is preferable to use materials to give a pencil 
hardness of 2H or harder, more preferably 4H or harder as determined by 
the pencil scratch test in accordance with JIS K 5400. If the surface 
hardness of this degree can be achieved, the resulting printed article can 
be used even in the outdoor application with little problem. 
Example of the materials for the formation of the second overcoat layer, 
which can form a film having the above-described properties, include alkyd 
resins obtained from a polybasic acid (for example, azelaic acid, 
chlorendic acid, succinic acid, trimellitic acid, o-phthalic acid, 
isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic 
acid, sebacic acid or the like), a polyhydric alcohol (for example, 
.alpha.-methyl-glucoside, dipentaerythritol, glycerol, glycols, 
trimethylolmethane, trimethylolpropane, tripentaerythritol or sorbitol) 
and a fatty acid; silicone alkyd resins obtained by copolymerizing an 
alkyd resin with a silicone intermediate such as siloxane; amino resins 
obtained by reacting formaldehyde with urea or melamine, such as 
urea-formaldehyde resins and melamine-formaldehyde resins; epoxy resins 
crosslinked by an amino resin, phenol resin, amine, polyamide, isocyanate 
or the like; and resins such as polyester resins, unsaturated polyester 
resins, silicone resins, urethane resins, polyamide resins, polyimide 
resins and fluororesins. Resins such as acrylic resins obtained by 
polymerization or copolymerization of an acrylic or methacrylic ester may 
also be used. Mixtures and reaction products of these resins may also be 
included. 
As a method of forming the second overcoat layer, generally a precursor 
unreacted compound of a resin to be coated or a coating fluid in the form 
of its dilute solution, emulsion or colloid suspension in a solvent is 
applied by a process such as spray coating, curtain coating, dip coating, 
wire bar coating, applicator coating, spin coating, roll coating, 
electrodeposition coating or brush coating, and the coating film thus 
formed is then dried to remove the solvent, and optionally subjected to a 
cure reaction, thereby forming the second overcoat layer. 
When the second overcoat layer is formed, as with the case where the first 
overcoat layer is formed as described above, cissing of the coating fluid 
may occur according to its compatibility with the materials for the 
formation of the first overcoat layer serving as an undercoating. In order 
to prevent the cissing, it is effective to subject the surface of the 
first overcoat layer to a cleaning treatment prior to the formation of the 
second overcoat layer. As an example of a method for the cleaning 
treatment suitably used at this time, may be mentioned a method in which 
the surface of the first overcoat layer on the base material is cleaned 
with oxygen plasma or ozone generated by ultraviolet-light irradiation in 
an oxygen-containing gas in common with the case where the first overcoat 
layer is formed. 
The coating thickness of the second overcoat layer is preferably within a 
range of from 0.1 to 50 .mu.m, more preferably from 1 to 30 .mu.m in terms 
of the thickness after the drying or curing. If the coating thickness is 
thinner than 0.1 .mu.m, it is difficult to completely cover a necessary 
part of the first overcoat layer due to irregularities of the 
dye-receiving layer and first overcoat layer and influence of foreign 
matter contained upon the formation of the respective layers, so that 
percent occurrence in defective coating becomes high. In addition, 
necessary mechanical strength cannot be achieved. When an ultraviolet 
absorbent and a mildew-proofing agent, which will be described 
subsequently, are contained in the second overcoat layer, their contents 
must be increased for the purpose of developing the effects of such 
agents. Therefore, it is more difficult to obtain the properties required 
of the second overcoat layer, such as mechanical strength. If the coating 
thickness of the second overcoat layer is made thicker than the above 
upper limit on the other hand, a further merit as to the properties can be 
scarcely obtained, leading to an economical loss. Peeling or cracking may 
occur in some cases due to shrinkage of a coating film when the coating 
film is cured upon the formation of the second overcoat layer. Therefore, 
such a too thin or thick coating thickness is not preferable. 
In the present invention, it is preferable to contain an ultraviolet 
absorbent and/or an ultraviolet screening agent in the second overcoat 
layer. As a result, the light fastness of the disperse dyes, which form an 
image, is improved, and deterioration by yellowing of the dye-receiving 
layer and second overcoat layer themselves is prevented, thereby achieving 
good long-term stability of the image. When an image is formed on a base 
material used in a bathroom or the like, it is preferable to further 
contain a mildew-proofing agent in the second overcoat layer. 
The ultraviolet absorbent used in the present invention means an agent 
which absorbs rays having a wavelength (300 to 450 nm) of high energy 
level in an ultraviolet region and discharges the rays as thermal energy, 
and acts to prevent the discoloration and fading of the resulting printed 
image by ultraviolet rays in sunlight and/or illumination light. 
When such an ultraviolet absorbent is added into the second overcoat layer 
in the present invention, it is preferable to add it within limits not 
impeding the transparency of the second overcoat layer and use it in an 
amount ranging from 0.1 to 10% by weight based on the weight of the 
materials for the formation of the second overcoat layer. If the amount of 
the ultraviolet absorbent to be used is less than the above lower limit, 
the effect of improving the light fastness of the resulting image becomes 
insufficient. If it is used in an amount exceeding the above upper limit 
on the other hand, the film-forming property and film properties of the 
second overcoat layer are adversely affected. It is hence not preferable 
to add such an agent in any amount outside the above range. 
As the ultraviolet absorbent used in the present invention, there may be 
used any conventionally-known agents, for example, salicylate-type, 
benzophenone-type, benzotriazole-type, acrylonitrile-type, hindered 
amine-type and metal complex type ultraviolet absorbents. Preferable 
examples thereof include phenyl salicylate, p-tert-butylphenyl salicylate, 
p-octyl salicylate, 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 
2-hydroxy-4-methoxy-benzophenone, 
2-hydroxy-4-methoxy-2'-carboxy-benzophenone, 
2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 
2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 
2-hydroxy-4-methoxybenzo-phenone-5-sulfonic acid, 
2-hydroxy-4-dodecyloxybenzo-phenone, 2,2'-dihydroxy-4-methoxybenzophenone, 
2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2', 
4,4'-tetrahydroxybenzophenone, sodium 
2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 
5-chloro-2-hydroxybenzo-phenone, 
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 
2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzo-triazole, 
2-(2'-hydroxy-3'-tert-butyl-5'-octylphenyl 
propionato)-5-chlorobenzo-triazole, (5'-octylphenyl 
propionato)-5-chlorobenzo-triazole, 
2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 
2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 
2-(2-hydroxy-3',5-di-tert-butylphenyl)benzotriazole, 
2-(2'-hydroxy-3',5-di-tert-butylphenyl)-5-chlorobenzotriazole, 
2-(2'-hydroxy-3',5-tert-amylphenyl)benzotriazole, 
2-[2-hydroxy-3,5-di(2,2-dimethylbenzene)-phenyl]-2H-benzotriazole, 
2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl 
acrylate, nickel bis(octylphenyl) sulfide, nickel 
[2,2'-thiobis(4-tert-octylphenolate)]-n-butylamine, polyethylene glycol 
3-[3-(2H-benzotriazol)-2-yl-5-tert-butyl-4-hydroxyphenyl]-propionate 
monoester and diester, nickel complex of 
3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylate, nickel 
dibutyldithiocarbamate, resorcinol monobenzoate, 
hexamethylphosphoryltriamide, 2,4,5-trihydroxybutyl-phenone, 
di-p-octylphenyl terephthalate, di-p-n-nonylphenyl isophthalate, hindered 
amines such as bis(1,2,2,6-tetramethyl-4-piperidine) 
2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate, and comonomers 
introduced in copolymers together with other monomers, such as 
2-oxy-4-(2-oxy-3-methacryloxy)propoxy-benzophenone and ethyl 
diphenylmethylenecyanoacetate. 
The ultraviolet screening agent used in the present invention means an 
agent which blocks rays having a wavelength in an ultraviolet region, and 
acts to prevent the discoloration and fading of the resulting printed 
image by ultraviolet rays. 
When such an ultraviolet screening agent is added into the second overcoat 
layer in the present invention, it is preferable to add it within limits 
not impeding the transparency of the second overcoat layer and use it in 
an amount ranging from 0.1 to 30% by weight based on the weight of the 
materials for the formation of the second overcoat layer. If the amount of 
the ultraviolet screening agent to be used is less than the above lower 
limit, the effect of improving the light fastness of the resulting image 
becomes insufficient. If it is used in an amount exceeding the above upper 
limit on the other hand, no effects according to the excessive amount can 
be brought about, and moreover opacity increases, so that appreciation of 
the resulting image is impeded. In addition, the film-forming property and 
film properties of the second overcoat layer may be adversely affected in 
some cases. It is hence not preferable to add such an agent in any amount 
outside the above range. Examples of the ultraviolet screening agent used 
in the present invention include silica, talc, mica and cerium oxide. 
As the mildew-proofing agent preferably used in the present invention, 
there may be used any conventionally-known agents. When such a 
mildew-proofing agent is added into the second overcoat layer, it is 
preferable for the agent to account for 0.01 to 10% by weight of the 
weight of the second overcoat layer. If the amount of the mildew-proofing 
agent to be used is less than 0.01% by weight, its effect becomes 
insufficient. If it is used in an amount exceeding 10% by weight on the 
other hand, the mildew-proofing property can not be improved 
correspondingly to the used amount. It is hence not preferable to add such 
an agent in any amount outside the above range. Since the effects of 
mildew-proofing agents vary according to the kinds of fungi, it is also 
effective to use two or more mildew-proofing agents in an amount within 
the above range. 
Preferable examples of such mildew-proofing agents used at this time 
include benzoic acid, sorbic acid, p-hydroxybenzoic esters, 
dihydroxyacetic acid, propionic acid and salts thereof, as well as 
diphenyl, o-phenyl-phenol, copper 8-quinolinolate, PCP, PCP-Na, 
p-chloro-m-xylenol, dihydroxyethylamine pentachlorophenol, 
4-chloro-2-phenylphenol, N-(trichloromethylthio)phthalamide, 
N,N-dimethyl-N'-phenyl(N'-fluorodichloromethylthio) sulfamide, 
N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboxyimide, 
2,4,5,6-tetrachloro-isophthalonitrile, bis(tri-n-butyltin) oxide, 
tributyltin laurate, 10,10'-oxybisphenoxyarsine and thiabendazole. 
In the step of forming the laminated overcoat layer, the coating fluids 
separately containing the resins, which are materials for forming the 
above first and/or second overcoat layers, are applied, and the resins are 
then cured as needed, thereby forming the laminated overcoat layer. Curing 
method of the resins vary according to resins used and include heat curing 
and exposure to radiation having activation energy. In each case, it is 
preferable to perform the curing at a temperature lower than the heating 
temperature upon the transfer of the disperse dye in the ink because the 
image formed with the disperse dye is adversely affected if the 
temperature upon the curing reaction is too high. For example, it is 
preferable to heat it at about 80 to 180.degree. C. for about 5 to 60 
minutes. With respect to the method by the exposure to the radiation 
having activation energy, it is preferable to perform the exposure at an 
exposure rate of about 50 to 3,000 mJ/cm.sup.2 using an ultra-high 
pressure mercury lamp 
The present invention will hereinafter be described more specifically by 
the following Examples and Comparative Examples. Incidentally, all 
designations of "part" or "parts" as will be used in the following 
examples mean part or parts by weight unless expressly noted.

EXAMPLE 1 
First, an intermediate printed article was obtained in the following 
manner. In this example, Inks A to D having the following compositions, 
respectively, were used. 
[Ink A] 
Disperse dye (C.I. Disperse Yellow 76) 5 parts 
Anionic surfactant (Ionet D-2, trade 4 parts name; product of Sanyo 
Chemical Industries, Ltd.) 
Diethylene glycol 15 parts 
Triethylene glycol monomethyl ether 10 parts 
Water 70 parts. 
After all the above components were placed in a ball mill made of alumina 
to prepare a mixture, and the mixture was dispersed for about 36 hours in 
the ball mill, and the pH of the dispersion was adjusted to 7.6 with 
lithium hydroxide, followed by further dispersing it for 2 hours in a 
homogenizer. Thereafter, coarse particles were removed by centrifugation, 
thereby obtaining a water-based Ink A. 
[Ink B] 
Disperse dye (C.I. Disperse Yellow 79) 3 parts 
Disperse dye (C.I. Disperse Blue 60) 3 parts 
Anionic surfactant (Ionet D-2, trade 5.5 parts name; product of Sanyo 
Chemical Industries, Ltd.) 
Ethylene glycol 25 parts 
Glycerol 5 parts 
1,3-Dimethylimidazolinone 5 parts 
Water 60 parts. 
A water-based Ink B was obtained from the above components in the same 
manner as Ink A. 
[Ink C] 
Disperse dye (C.I. Disperse Yellow 56) 3 parts 
Anionic surfactant (Nikkol OPT-100s, 1.5 parts trade name; product of Nikko 
Chemicals Co., Ltd.) 
Nonionic surfactant (Emulgen 911, 0.2 parts trade name; product of Kao 
Corporation) 
Isopropyl alcohol 0.5 parts 
Polyethylene glycol 5 parts 
Water 75 parts. 
After all the above components were placed in a ball mill made of alumina 
to prepare a mixture, and the mixture was dispersed for about 40 hours in 
the ball mill, and the pH of the dispersion was adjusted to 7.4 with 
lithium hydroxide, followed by further dispersing it for 2 hours. 
Thereafter, coarse particles having a particle size of 5 .mu.m or greater 
were removed by a Fluoropore Filter FP-500 (trade name; product of 
Sumitomo Electric Industries, Ltd.), thereby obtaining a water-based Ink 
C. 
[Ink D] 
A water-based Ink D was obtained in exactly the same manner as in Ink A 
except that a disperse dye, C.I. Disperse Red 227 was used in place of the 
disperse dye, C.I. Disperse Yellow 76 in Ink A. 
Inks A to D thus obtained were charged in ink tanks of a BJC-600J (trade 
name; ink-jet printer of bubble jet system; manufactured by Canon Inc.), 
and an image was formed on PB paper (trade name; plain paper; product of 
Canon Inc.), thereby obtaining-an image-printing sheet. The image formed 
was such that a pattern of a bird was printed on a white ground, and the 
remaining white portion was about 70% in terms of area. 
A dye-receiving layer was then formed on a base material for forming an 
image on the base material using the image-printing sheet obtained above. 
The base material used at this time was a white tile of 110 mm square. As 
a material for the formation of the dye-receiving layer, a mixture having 
the following composition was used. 
Sericol SP-3100 (trade name; urethane 100 parts resin; product of Teikoku 
Ink Mfg. Co., Ltd.) 
Sericol 210 (trade name; isocyanate; 13 parts product of Teikoku Ink Mfg. 
Co., Ltd.) 
n-Butyl acetate (diluent solvent; 40 parts. product of Kishida Chemical 
Co., Ltd.) 
The mixture composed of the above components was sprayed on the surface of 
the white tile by a sprayer so as to give a dry coating thickness of about 
10 .mu.m. After the coating, the coating film was heated for 30 minutes at 
90.degree. C. and then for 30 minutes at 150.degree. C., thereby removing 
the solvent and conducting a cure reaction. 
The image-formed surface of the image-printing sheet described above was 
brought into close contact with the dye-receiving layer formed on the 
white tile and treated for 6 minutes at a pressure of 0.3 kg/cm.sup.2 and 
a temperature of 200.degree. C., thereby transferring the disperse dyes to 
the dye-receiving layer. After the transfer treatment, the printing sheet 
was separated from the surface of the dye-receiving layer on the base 
material, thereby obtaining an intermediate printed article. The resultant 
image of the intermediate printed article was clear and sufficient in 
color density, and was such that the original image was faithfully 
reproduced. 
The surface of the intermediate printed article thus obtained was subjected 
to an ultraviolet light/ozone treatment for 30 seconds to clean it. An Eye 
UV/O.sub.3 cleaning machine (Model: OC-253) manufactured by IWASAKI 
ELECTRIC CO., LTD. was used as a cleaner. 
A first overcoat layer was formed on the surface of the intermediate 
printed article cleaned in the above-described manner in the following 
manner. As a material for the formation of the first overcoat layer, a 
coating fluid having the following composition was used. As a process for 
the formation, the coating fluid composed of the following components was 
first applied to the surface of the intermediate printed article by brush 
coating to form a coating film. 
NK Ester A-400 (trade name; 25 parts polyethylene glycol #400 diacrylate; 
product of Shin-Nakamura Chemical Co., Ltd.) 
Irgacure 2959 (trade name; ultraviolet 5 parts curing agent; product of 
CIBA-GEIGY (Japan) Limited) 
Water 70 parts. 
After the coating film was heated at 80.degree. C. for 30 minutes to dry 
it, the resultant first overcoat layer was exposed to radiation having an 
intensity of 1 J/cm.sup.2 from an extra-high pressure mercury lamp to cure 
the resin. The thickness of the first overcoat layer after the cure was 3 
.mu.m. The surface of the resultant first overcoat layer was cleaned by 
the same ultraviolet light/ozone treatment as described above. 
A second overcoat layer was then formed on the first overcoat layer formed 
in the above-described manner. As a material for the formation of the 
second overcoat layer, a coating fluid having the following composition 
was used. This coating fluid was applied by spray coating to form a 
coating film. 
ZPP-N-1000 (trade name; phosphazene 70 parts type methacrylate; product of 
Kyoeisha Chemical Co., Ltd.) 
NK Ester A-9530 (trade name; dipenta- 30 parts erythritol polyacrylate; 
product of Shin-Nakamura Chemical Co., Ltd.) 
Irgacure 184 (trade name; ultraviolet 5 parts curing agent; product of 
CIBA-GEIGY (Japan) Limited) 
Tinuvin 400 (trade name; ultraviolet 3 parts absorbent; product of 
CIBA-GEIGY (Japan) Limited) 
Tinuvin 123 (trade name; hindered 2 parts amine; product of CIBA-GEIGY 
(Japan) Limited) 
Cellosolve acetate (dilute solvent; 200 parts product of Kishida Chemical 
Co., Ltd.) 
Calcium propionate (mildew-proofing 0.3 parts. agent; product of Ueno 
Pharmaceuticals Industry, Ltd.) 
After the coating film was then heated at 80.degree. C. for 30 minutes to 
dry it, the resultant second overcoat layer was exposed to radiation 
having an intensity of 1 J/cm.sup.2 from the extra-high pressure mercury 
lamp to cure the resin, thereby producing a printed article. The thickness 
of the second overcoat layer after the cure was 16 .mu.m. 
No cissing of the coating fluid was observed even upon the formation of 
each of the overcoat layers, and the coating was successfully effected. 
The reflection density of the resultant printed article was measured at 
its white portion and found to be 0.06 after the formation of the overcoat 
layers. Rise in reflection density after the formation of the overcoat 
layers was only 0.01, and the resulting image was hence clear and 
beautiful. 
EXAMPLE 2 
An intermediate printed article was produced in the same manner as in 
Example 1 except that white plate glass of 100 by 100 by 1.1 millimeters 
in dimensions was used as a base material. The surface of the intermediate 
printed article thus obtained was subjected to a washing treatment with 
oxygen plasma under conditions described below to clean the surface. An 
apparatus used at this time was DES-125A (trade name) manufactured by 
Plasma Systems Co., Ltd. The cleaning treatment was performed under 
conditions of RF power of 0.5 kW, a degree of vacuum of 1.2 Torr, an 
oxygen quantity of 300 SccM and treating time of 30 seconds. 
A first overcoat layer was then formed on the surface of the intermediate 
printed article. As a material for the formation of the first overcoat 
layer, Voncoat 9450 (trade name, acrylic-styrene type aqueous emulsion, 
product of Dainippon Ink & Chemicals, Incorporated), which was an aqueous 
emulsion, was used. This aqueous emulsion was applied to the surface of 
the intermediate printed article by brush coating, and the coating film 
formed was then heated at 80.degree. C. for 30 minutes to dry it. The 
thickness of the first overcoat layer after the drying was 1 .mu.m. 
A second overcoat layer was then formed on the thus-obtained first overcoat 
layer on the base material. The second overcoat layer was formed by using 
a coating fluid having the following composition and applying it to the 
first overcoat layer by spray coating. 
BK-80 (trade name; acrylic polymer; 50 parts product of Mitsubishi Rayon 
Co., Ltd.) 
NK Ester A-9530 (trade name; dipenta- 25 parts erythritol polyacrylate; 
product of Shin-Nakamura Chemical Co., Ltd.) 
Arronix M-315 (trade name, highly hard 25 parts acrylic monomer; product of 
Toagosei Chemical Industry Co., Ltd.) 
Irgacure 651 (trade name; ultraviolet 5 parts curing agent; product of 
CIBA-GEIGY (Japan) Limited) 
Tinuvin 400 (trade name; ultraviolet 3 parts absorbent; product of 
CIBA-GEIGY (Japan) Limited) 
Tinuvin 123 (trade name; hindered 2 parts amine; product of CIBA-GEIGY 
(Japan) Limited) 
Cellosolve acetate (dilute solvent; 200 parts product of Kishida Chemical 
Co., Ltd.) 
Sodium dehydroacetate (mildew-proofing 0.4 parts, agent; product of The 
Nippon Synthetic Chemical Industry Co., Ltd.) 
After the coating film composed of the materials for the formation of the 
second overcoat layer was then heated at 80.degree. C. for 30 minutes to 
dry it, the resultant second overcoat layer was exposed to radiation 
having an intensity of 1 J/cm.sup.2 from an extra-high pressure mercury 
lamp to cure the resin, thereby producing a printed article. The thickness 
of the second overcoat layer after the cure was 18 .mu.m. 
No cissing of the coating fluid was observed even upon the formation of 
each of the overcoat layers, and the coating was successfully effected. 
The reflection density of the resultant printed article was measured at 
its white portion and found to be 0.05 after the formation of the overcoat 
layers. Rise in reflection density after the formation of the overcoat 
layers was only 0.01, and the resulting image was hence clear and 
beautiful. 
EXAMPLE 3 
An intermediate printed article was produced in the same manner as in 
Example 1 except that a coating fluid having the following composition was 
used as a material for the formation of a dye-receiving layer to be formed 
on a base material. The surface of the intermediate printed article was 
cleaned in the same manner as in Example 1. 
Desmophen 651-67 (trade name; 162 parts branched polyester; product of 
Sumitomo Bayer Urethane Co., Ltd.) 
Sumidur N75 (trade name; aliphatic 100 parts polyisocyanate; product of 
Sumitomo Bayer Urethane Co., Ltd.) 
n-Butyl acetate (diluent solvent; 100 parts. product of Kishida Chemical 
Co., Ltd.) 
A first overcoat layer was then formed on the surface of the intermediate 
printed article obtained above. The formation of the first overcoat layer 
was performed in accordance with the following process. As a material for 
the formation of the first overcoat layer, Primal B-88 (trade name, 
acrylic type aqueous emulsion, product of Rohm & Haas Co.), which was an 
aqueous emulsion, was used. This aqueous emulsion was applied to the 
surface of the intermediate printed article by brush coating to form a 
coating film, and the coating film thus formed was then heated at 
90.degree. C. for 30 minutes to dry it. The thickness of the first 
overcoat layer after the drying was 5 .mu.m. 
A second overcoat layer was then formed on the first overcoat layer thus 
formed. As a process for the formation of the second overcoat layer, the 
following composition was first applied to the first overcoat layer by 
spray coating to form a coating film. 
Glassca HPC7001 (trade name; silica 90 parts type resin; product of Japan 
Synthetic Rubber Co., Ltd.) 
Glassca 402H (trade name; curing 10 parts agent for Glassca; product of 
Japan Synthetic Rubber Co., Ltd.) 
SERIGUARD S-3018 (trade name; 2.2 parts ultraviolet screening agent; 
product of Nippon Inorganic Chemical Co., Ltd.; 10% by weight based on the 
true weight of Glassca) 
Sodium dehydroacetate (mildew-proofing 0.4 parts. agent; product of The 
Nippon Synthetic Chemical Industry Co., Ltd.) 
After the coating film was then heated at 150.degree. C. for 10 minutes to 
cure the resin, thereby producing a printed article. The thickness of the 
second overcoat layer after the cure was 8 .mu.m. No cissing of the 
coating fluid was observed even upon the formation of each of the overcoat 
layers, and the coating was successfully effected. The reflection density 
of the resultant printed article was measured at its white portion and 
found to be 0.05 after the formation of the overcoat layers. Rise in 
reflection density after the formation of the overcoat layers was only 
0.01, and the resulting image was hence clear and beautiful. 
EXAMPLE 4 
An intermediate printed article was produced in the same manner as in 
Example 1, and a coating fluid having the following composition composed 
of materials for the formation of a first overcoat layer was applied to 
the surface of the intermediate printed article by spray coating. 
Denacol EX-521 (trade name; 10 parts polyglycerol polyglycidyl ether; 
product of Nagase Chemicals, Ltd.) 
Tetramethylammonium chloride (curing 1 part agent for epoxy; product of 
Kishida Chemical Co., Ltd.) 
Water 99 parts. 
After the application of the first overcoat layer, the first overcoat layer 
was heated at 80.degree. C. for 20 minutes and at 150.degree. C. for 10 
minutes to cure the resin. The thickness of the first overcoat layer after 
the cure was 5 .mu.m. Incidentally, the surfaces of the intermediate 
printed article and first overcoat layer were cleaned by the same method 
as in Example 2. 
The following composition, which was a material for the formation of a 
second overcoat layer, was then applied to the first overcoat layer by 
spray coating to form a coating film. 
Glassca HPC7002 (trade name; silica 75 parts type resin; product of Japan 
Synthetic Rubber Co., Ltd.) 
Glassca 402H (trade name; curing 25 parts agent for Glassca; product of 
Japan Synthetic Rubber Co., Ltd.) 
Tinuvin 900 (trade name; ultraviolet 0.66 parts absorbent; product of 
CIBA-GEIGY (Japan) Limited; 3% by weight based on the true weight of 
Glassca) 
Tinuvin 144 (trade name; hindered 0.44 parts amine; product of CIBA-GEIGY 
(Japan) Limited) 
Methyl ethyl ketone (dilute solvent; 30 parts product of Kishida Chemical 
Co., Ltd.) 
Sodium dehydroacetate (mildew-proofing 0.4 parts. agent; product of The 
Nippon Synthetic Chemical Industry Co., Ltd.) 
The coating film was then heated at 150.degree. C. for 10 minutes to cure 
the resin, thereby forming the second overcoat layer to produce a printed 
article. The thickness of the second overcoat layer after the cure was 7 
.mu.m. 
No cissing of the coating fluid was observed even upon the formation of 
each of the overcoat layers, and the coating was successfully effected. 
The reflection density of the resultant printed article was measured at 
its white portion and found to be 0.06 after the formation of the overcoat 
layers. Rise in reflection density after the formation of the overcoat 
layers was only 0.02, and the resulting image was hence clear and 
beautiful. 
Comparative Example 1 
A printed article was produced by producing an intermediate printed article 
in the same manner as in Example 1, the surface of the intermediate 
printed article was cleaned by the same method as in Example 1 and then 
only the same second overcoat layer was provided as that of Example 1 
without providing the first overcoat layer. 
Comparative Example 2 
An intermediate printed article was produced in the same manner as in 
Example 1, and only the same first overcoat layer as that of Example 1 was 
provided without conducting the cleaning treatment of the surface of the 
intermediate printed article. 
Comparative Example 3 
A printed article was produced by producing an intermediate printed article 
in the same manner as in Example 2, the surface of the intermediate 
printed article was cleaned by the same method as in Example 2 and then 
only the same second overcoat layer was provided as that of Example 2 
without providing the first overcoat layer. 
Comparative Example 4 
After producing an intermediate printed article in the same manner as in 
Example 1, a printed article was produced without providing first and 
second overcoat layers. 
The printed articles obtained in the above-described examples and 
comparative examples were evaluated in accordance with the following 
evaluating methods. The results are shown in Table 1. 
(1) Cissing of overcoat layers 
Whether cissing occurred or not upon the formation of the overcoat layers 
was observed visually to rank each sample as "A" where no cissing was 
observed, or "B" where cissing was observed. 
(2) Pencil hardness 
The pencil hardness of each sample was measured by means of a pencil 
scratch tester for film recommended by JIS in accordance with the method 
of JIS K 5400. The pencil hardness was evaluated by the degree of 
scratches on the surface of the coating film in the following manner. 
Namely, a scratch test was conducted 5 times for each sample. When 
scratching on the surface was observed twice or more while the test was 
repeatedly performed 5 times, the pencil used in the test was changed to a 
pencil having a lead hardness lower by one rank to conduct the same test, 
whereby the hardness sign of a pencil used at the time the number of times 
of scratching decreased to less than 2 times was recorded as a pencil 
hardness of the coating film. Alternatively, when scratching was observed 
less than twice while the scratch test was repeatedly performed 5 times, 
the pencil used in the test was changed to a pencil having a lead hardness 
higher by one rank to conduct the same test, whereby the hardness sign of 
a pencil having a lead hardness lower by one rank than a pencil used at 
the time the number of times of scratching increased to twice or more was 
recorded as a pencil hardness of the coating film. 
(3) Scratch resistance 
The surface of each printed article sample was reciprocatorily rubbed 30 
times with a brush for tile joint made of polypropylene (product of Azuma 
Kogyo K.K.) under a load of about 1 kg, and then visually observed as to 
whether scratches were received or not. The scratch resistance was ranked 
as "A" where no scratches were observed, or "B" where scratches were 
observed. 
(4) Sharpness of image 
Particular attention was paid to boundaries between an area in which an 
image was formed with disperse dyes and an area free of any image to 
observe as to whether the sharpness of the image was affected by the 
exudation of the dyes. The sharpness of the image was ranked as "B" where 
the exudation of the dyes was observed, or "A" where no exudation was 
observed. 
(5) Light fastness 
Each printed article sample was left over for 50 hours in a xenon arc 
fade-o-meter (Atlas C, trade name; 35 W, inner filter: quartz; outer 
filter: borosilicate) under conditions of 50.degree. C. and 65% RH. The 
image density of a red solid print area of the sample was measured before 
and after the test to use, as an index to the light fastness, a percentage 
value obtained by dividing an image density after the test by an image 
density before the test. Namely, a greater value indicates better light 
fastness. 
(6) Stain resistance 
Each printed article sample was left over for 2 months with the sample 
stuck on a wall of a bathroom. The bathroom was used once a day. The stain 
resistance was ranked as "B" where appreciation of the image was impeded 
due to generation of mold or mildew, and/or the like, or "A" where no 
stains were observed. 
(7) Evaluation result 
The evaluation results as to the above evaluation items (1) to (6) are 
shown in Table 1. Besides, overall evaluation was conducted from these 
results to also show the results thereof in Table 1. Incidentally, "-" in 
the table means that no evaluation was conducted. With respect to 
Comparative Example 2, the evaluation was conducted as to an area in which 
no cissing was observed. 
TABLE 1 
______________________________________ 
Example Comp. Example 
1 2 3 4 1 2 3 4 
______________________________________ 
Cissing A A A A A B A -- 
Pencil hardness 
8H 
4H 4H 7H 8H H 4H H 
Scratch resistance 
A A A A A B A B 
Sharpness of image 
A A A A B A B A 
Light fastness 
90 
90 88 89 89 55 88 40 
Stain resistance 
A 
A A A A B A B 
Overall evaluation 
A A A A B B B B 
______________________________________ 
According to the present invention, as described above, clear and 
high-color density images faithfully conforming to an original image can 
be formed on base materials such as pottery, glass, plastics and metals, 
which have no liquid ink absorbency. Besides, the printed articles 
obtained in accordance with the present invention have sufficient scratch 
resistance and resistance to marker and good light fastness and also can 
prevent growth of mildew or mold, so that they have excellent image 
properties satisfactorily fit for use in the open air and humid places. 
Therefore, there can be provided printed articles which can be used in 
various purposes. According to the present invention, a clear image can 
also be formed even in, particularly, an image-printed article in which 
its ground is exposed to a great extent, because the sharpness of edges at 
boundaries between dyes forming the image and the exposed portions of the 
ground is good. Even in this sense, printed articles excellent in 
general-purpose properties can be provided. 
While the present invention has been described with respect to what is 
presently considered to be the preferred embodiments, it is to be 
understood that the invention is not limited to the disclosed embodiments. 
To the contrary, the invention is intended to cover various modifications 
and equivalent arrangements included within the spirit and scope of the 
appended claims. The scope of the following claims is to be accorded the 
broadest interpretation so as to encompass all such modifications and 
equivalent structures and functions.