BACKGROUND OF THE INVENTION
(Field of the Invention)
[0001] The present invention relates to an image-receiving sheet for use in a sublimation-type
heat-sensitive transfer recording process.
(Description of the Related Art)
[0002] A sublimation-type heat-sensitive transfer recording process is characterized by
a low noise output, small-sized, low priced apparatus having a short output time and
which is easily conserved. In addition, as a result of using a sublimable dye, high
gradation recording characterized by such qualities as a high density and a high definition
can be carried out by means of continual fluctuation of the heat generating energy
amount. As a result in comparison with other recording processes, it is particularly
advantageous in obtaining full color copies. Accordingly, it is widely employed as
the recording process in color printers, video printers, and the like.
[0003] A prior art image-receiving sheet for use in sublimation-type heat-sensitive transfer
recording processes which is comprised of a dye-receiving layer formed on top of a
laminated substrate, which in turn is formed of a synthesized paper (mainly polypropylene
paper) laminated on top of conventional paper, as disclosed in U.S. Patent 4,778,782,
has come to be employed.
[0004] However, with this type of image-receiving sheet, because the smoothness of the synthesized
paper is insufficient, the smoothness of the dye-receiving layer on top of this synthesized
paper is also insufficient. Additionally, there is also a problem in that as a result
of the high cost of the synthesized paper, the laminated paper is very costly. As
well, it is possible to consider an image-receiving sheet formed by placing the dye-receiving
layer directly on top of the conventional paper. However, as a result of the insufficient
smoothness of the conventional paper surface, there exists drawbacks such as a similar
insufficient smoothness of the dye-receiving layer, formed on top of the conventional
paper, and a decrease in the recording sensitivity of the image-receiving sheet.
[0005] When the smoothness of the dye-receiving layer is insufficient, the image cannot
be precisely transferred in accordance with the signal to be inputted to the thermal
head, which leads to the occurrence of irregularities such as dot errors and dot omissions
of the image, as well as disturbances in the image quality, which bring out a rough
impression in the intermediate gradation.
SUMMARY OF THE INVENTION
[0006] The purpose of the present invention is to improve on the disturbances in the recording
image quality caused by poor surface smoothness of the dye-receiving layer, as well
as to improve the coloring sensitivity of the image-receiving sheet.
[0007] In order to achieve this objective, the image-receiving sheet for use in a sublimation-type
heat-sensitive transfer recording process according to the present invention incorporates
a high polymer layer in between the substrate and dye-receiving layers. The dye-receiving
layer has a surface roughness degree defined by a center line average roughness (R
a) of 0.3 µm or less, and a maximum height (R
max) of 5 µm or less.
[0008] In the present invention, the surface roughness degree of the dye-receiving layer
was measured by means of JIS-B-0601. In accordance with the image-receiving sheet
for use in a sublimation-type heat-sensitive transfer recording process of the present
invention, the recording sensitivity is improved, disturbances of the recording image
quality can be greatly reduced, and high projection vividness, as well as superior
intermediate gradation reproductivity can be obtained.
A BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Figure 1 is a sectional view outlining an example of an image-receiving sheet for
use in a sublimation-type heat-sensitive transfer recording process according to the
present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] In the following the present invention will be described in detail.
[0011] Figure 1 is a sectional view showing an example of an image-receiving sheet for use
in a sublimation-type heat-sensitive transfer recording process according to the present
invention (hereinafter referred to as "an image-receiving sheet"). In the figure,
numeral 1 represents the substrate, numeral 2 represents the high polymer layer and
numeral 3 represents the dye-receiving layer. As the substrate 1, use of conventional
paper such as baryta paper, art paper and coat paper having a thickness of preferably
10∼200 µm. In view of the heat durability, paper with a large thickness and a smooth
surface is preferred.
[0012] On one surface of this substrate 1, a high polymer layer 2 is provided. This high
polymer layer 2 is formed from thermoplastic resins such as polyethylene, polypropylene,
polyethylene terephthalate, polystyrene, polymethylmethacrylate, acryl-based copolymers,
polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinylidene chloride,
ionomer resins, butyral resins, and the like, thermosetting resins such as epoxy resins,
unsaturated polyester resins, and the like, ultraviolet ray curable resins, and electron
ray curable resins.
[0013] When necessary, inorganic materials, dyes, pigments, stabilizing agents, fluorescent
whitening agents, and the like having minute particle diameters can be incorporated
into the high polymer layer 2.
[0014] It is necessary for the image-receiving sheet of the present invention, in order
to have an even (smooth) surface, to possess a dye-receiving layer 3 with a surface
roughness degree, as stated above, defined by an R
a of 0.3 µm or less and an R
max of 5 µm or less. However, in order to obtain a smooth dye-receiving layer 3 from
coating, the existence of a high polymer layer 2 likewise possessing an even (smooth)
surface is preferred: for example, it is preferred that the surface roughness degree
of the high polymer layer 2, measured also by means of JIS-B-0601, be defined by center
line average roughness (R
a) of 0.3 µm or less, and a maximum height (R
max) of 5 µm or less. At this time, the cut off value of is 0.8 mm and the measured length
is 8 mm. If the R
a of high polymer layer 2 exceeds 0.3 µm, or if R
max exceeds 5 µm, obtaining a dye-receiving layer with a smooth surface tends to become
difficult, and irregularities during recording, such as dot errors and dot omissions
of the image, as well as disturbances in the image quality occur, bringing out a rough
impression in the intermediate gradation.
[0015] The high polymer layer 2 has a thickness of preferably 1∼100 µm, more preferably
5∼70 µm. If the thickness of high polymer layer 2 is less than 1 µm, leveling the
substrate unevenness becomes very difficult, and as a result it becomes difficult
to obtain a dye-receiving layer, to be applied on top of the substrate, with a sufficient
surface smoothness, and thus the image quality when recording is degraded. Additionally,
the recording sensitivity has a tendency to decrease as well. On the other hand, if
the thickness exceeds 100 µm, there are cases when the time required for drying as
well as curing the high polymer layer 2 with ultraviolet rays or electron rays as
well as for thermosetting becomes longer, and the cost becomes greater.
[0016] As the coating method for providing high polymer layer 2 on top of substrate 1, methods
in which resin solutions, formed by dissolving the above mentioned thermoplastic resins,
thermosetting resins, ultraviolet ray curable resins, electron ray curable resins,
and the like in a suitable solvent are formed, coated on the substrate using roll
coating methods, blade coating methods, flow coating methods, lip coating methods
and the like, and then dried, as well as methods in which heat is applied to the above
mentioned thermoplastic resins forming a melt which is then applied as a coat onto
the substrate and cooled, or methods in which films formed from the above mentioned
resins are pasted onto substrate 1 using an adhesive agent can be used. Among these
methods, it is preferred that methods be employed in which resin solutions are coated
using comma roll coating methods, lip coating methods and flow coating methods, through
which a high surface smoothness as well as a high thickness precision can be obtained.
[0017] On top of this high polymer layer 2, a dye-receiving layer 3 is provided. This dye-receiving
layer 3 receives and develops the sublimable dye which is transferred from the transfer
sheet. The raw material for forming the dye-receiving layer 3 is not limited to anything
in particular, so long as it is a material which can be well dyed with a sublimable
dye, and also, at the time of recording, does not cause blocking with the transfer
sheet. For example, as the dyeable resin, the following can be used: cellulose resins
such as methyl cellulose, ethyl cellulose, ethylhydroxy cellulose, hydroxyethyl cellulose,
hydroxypropyl cellulose, cellulose acetate and the like, vinyl resins such as polyvinyl
alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl acetate, polyvinyl chloride,
polyvinyl pyrrolidone, polystyrene and the like, acrylate resins such as polymethyl(meth)acrylate,
polybutyl(meth)acrylate, polyacrylamide, polyacrylonitrile and the like, polyester
resins, polycarbonate resins, polyurethane resins, polyamide resins, urea resins,
polycarprolactone resins, polyarylate resins, polysulfone resins and the like as well
as their copolymers and mixtures. Among these resins, since polyester resins are well
dyed by the sublimable dye and the maintenance stability of the projection image which
can be obtained is excellent, it is preferred that at least one component of the dyeable
resin be a polyester resin.
[0018] As the above mentioned polyester resin, there can be mentioned linear thermoplastic
polyester resins obtained by polycondensation between a dicarboxylic acid and a diol,
and/or unsaturated polyester resins obtained by polycondensation between an unsaturated
polybasic acid having a reactive double bond and a polyhydric alcohol. In view of
the solubility in an organic solvent, the dyeing ease and the light resistance, a
linear thermoplastic polyester resin having a molecular weight of 2,000 to 40,000
and a crystallization degree of not higher than 1%, which is obtained by polycondensation
between at least one dicarboxylic acid and at least one diol, is preferred.
[0019] As specific examples of the linear thermoplastic polyester resin obtained by polycondensation
between at least one dicarboxylic acid and at least one diol, there can be mentioned
a polyester resin obtained from terephthalic acid, isophthalic acid, ethylene glycol
and neopentyl glycol, a polyester resin obtained from terephthalic acid, isophthalic
acid, ethylene glycol and a bisphenol A/ethylene oxide adduct, a polyester resin obtained
from terephthalic acid, isophthalic acid, ethylene glycol and 1,6-hexanediol, a polyester
resin obtained from terephthalic acid, isophthalic acid, sebacic acid, ethylene glycol
and neopentyl glycol, a polyester resin obtained from terephthalic acid, sebacic acid,
ethylene glycol and neopentyl glycol, and a polyester resin obtained from terephthalic
acid, isophthalic acid, adipic acid, ethylene glycol and neopentyl glycol. These polyester
resins can be used singly, or in the form of mixtures of two or more thereof. In order
to improve the stability against light, heat, water or others, preferably two or more
of these polyester resins are used in combination. For example, when two polyesters
A and B are used, preferably the A/B weight ratio is from 20/80 to 80/20.
[0020] Additionally, in place of terephthalic acid, isophthalic acid, and the like, it is
also possible to use esterificated dimethylterephthalate, dimethylisoterephthalate,
and the like in the condensation polymer raw material.
[0021] As the unsaturated polyester resin obtained by the polycondensation of an unsaturated
polybasic acid possessing a reactive double bond, and a polyalcohol, there can be
mentioned resins obtained from the following: maleic anhydride/phthalic anhydride/propylene
glycol, maleic anhydride/isophthalic acid/propylene glycol, maleic acid/fumaric acid/isophthalic
acid/1,3-butane diol, maleic acid/isophthalic acid/neopentyl glycol, maleic anhydride/tetrahydrophthalic
anhydride/dipropylene glycol, and the like.
[0022] In order to further improve the releasing property between the dye-receiving layer
3 and the transfer sheet, incorporation of a crosslinking component into the dye-receiving
layer 3 of the present invention is preferred. For example, a thermosetting component
of isocyanate and polyol are incorporated, and the formation of the dye-receiving
layer is carried out followed by thermocrosslinking, or the dye-receiving layer can
be obtained by coating a crosslinking agent which can be cured with active energy
rays, as disclosed in Japanese Patent Application (Kokai) 62-46689 and in EP-0261505-A2,
for example the dye-receiving layer can be obtained by coating a resin composition
incorporating a monomer or oligomer possessing an acryloyloxy group or a methacryloyloxy
group on top of the substrate, followed by curing with active energy rays. In particular,
the method in which the dye-receiving layer is obtained by incorporating a component
which can be crosslinked with active energy rays, followed by curing with active energy
rays, has a high productivity. Moreover, the dye-receiving layer which can be obtained
is easily dyed with a sublimable dye, has a superior stability and an excellent luster
maintenance, and thus this method is more preferred.
[0023] The amounts of the dyeable resin and the crosslinking agent to be used are not in
particular limited, however it is preferred that the amount of the dyeable resin incorporated
range from 40∼95% by weight, and the amount of the crosslinking agent incorporated
range from 60∼5% by weight per 100 parts by weight of the total amount of the dyeable
resin and crosslinking agent. If the amount of the dyeable resin incorporated is less
than 40% by weight, it becomes difficult to both dye the dye-receiving layer obtained
with the sublimable dye, and to obtain a sufficient dyeing density. On the other hand,
if the amount incorporated exceeds 95% by weight, the dye-receiving layer obtained
adheres easily to the transfer sheet during heat transfer.
[0024] As specific examples of the crosslinking agent, in the case of thermosetting, there
can be mentioned reactive setting silicon oils such as cured amino modified silicon
oils and epoxy modified silicon oils. In the case of lightsetting, there can be mentioned
light setting silicon oils and polyfunctional monomers or polyfunctional oligomers
possessing (meth)acryloyloxy groups, however, among these, polyfunctional monomers
or polyfunctional oligomers possessing (meth)acryloyloxy groups are preferred. Ultraviolet
rays that can be easily handled as the active energy rays can be used for these agents,
and these agents can be set in a short time period, and are therefore advantageous
from a productivity standpoint.
[0025] As specific examples of monomers possessing (meth)acryloyloxy group there can be
mentioned polyether acrylate-based or polyether methacrylate-based (hereinafter, "acrylate
or methacrylate" will be abbreviated singly as "(meth)acrylate"), polyester (meth)acrylate-based,
polyol (meth)acrylate-based, epoxy(meth)acrylate-based, urethane amide (meth)acrylate-based,
urethane (meth)acrylate-based, spiroacetal (meth)acrylate-based, polybutadiene (meth)acrylate-based
monomer or oligomers.
[0026] As specific examples of this type of monomer or oligomer, there can be mentioned
polyether (meth)acrylates such as those synthesized from 1,2,6-hexanetriol, propylene
oxide and acrylic acid and from trimethylolpropane, propylene oxide and acrylic acid;
polyester (meth)acrylates such as those synthesized from adipic acid, 1,6-hexanediol
and acrylic acid and from succinic acid, trimethylolethane and acrylic acid; (meth)acrylates
or polyol (meth)acrylates such as triethylene glycol diacrylate, hexapropylene glycol
diacrylate, neopentyl glycol diacrylate, 1,4-butane diol dimethacrylate, 2-ethylhexyl
acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, ethylcarbitol
acrylate, trimethylolpropane triacrylate, pentaerythritol tetra-acrylate, dipentaerythritol
tetra-acrylate, dipentaerythritol penta-acrylate, 2,2-bis(4-acryloyloxydiethoxyphenyl)propane,
and 2,2-bis(4-acryloyloxydipropoxyphenyl)propane; epoxy (meth)acrylates such as those
synthesized from diglycidyl-etherified bisphenol A and acrylic acid, from diglycidyl-etherified
polybisphenol A and acrylic acid, and from triglycidyletherified glycerol and acrylic
acid; amideurethane (meth)acrylates such as those synthesized from γ-butyrolactone,
N-methylethanolamine, bis(4-isocyanatocyclohexyl)methane and 2-hydroxyethyl acrylate,
and from γ-butyrolactone, N-methylethanolamine, 2,6-tolylenediisocyanate, tetraethylene
glycol and 2-hydroxyethyl acrylate; urethane acrylates such as 2,6-tolylenediisocyanate
diacrylate, isophorone diisocyanate diacrylate, and hexamethylenediisocyanate diacrylate;
spiroacetal acrylates such as those synthesized from diallylidene pentaerythritol
and 2-hydroxyethyl acrylate; and acrylated polybutadienes such as those synthesized
from epoxidized butadiene and 2-hydroxyethyl acrylate. These monomer and oligomers
may be used singly or in the form of mixture of two or more thereof.
[0027] Of the above-mentioned monomers and oligomers, compounds represented by the following
general formulae (I),(II) and (III) are especially preferred as the crosslinking agent
because they have an excellent quick-drying property in air when ultraviolet rays
are used as the active energy rays.
[0028] Compounds represented by the following general formula (I):

(in which n is an integer from 1 to 4, at least three of the groups X are groups represented
by the general formula CH₂=CH-COO-R₁-(in which R₁ represents single bond, an alkylene
group having 1 to 8 carbons or a polyoxyalkylene group having an alkylene group having
1 to 8 carbon atoms), and the remaining groups X are selected from an alkyl group
having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a group represented
by the formula -(OR₂)
m-H (in which R₂ represents an alkylene group having 1 to 8 carbon atoms and m is positive
integer), a group represented by the formula-(OR
2)
m-OH (in which R₂ and m are as defined above), or a group represented by the formula
-(OCOR
2)
m-H (in which R₂ and m are defined above).
[0029] As specific examples of this type of compound, there can be mentioned dipentaerythritol
tetra-acrylate, dipentaerythritol penta-acrylate, dipentaerythritol hexa-acrylate,
tripentaerythritol penta-acrylate, tripentaerythritol hexa-acrylate and tripentaerythritol
hepta-acrylate.
[0030] Polybisphenol A polyacrylates represented by the following general formula (II):

(wherein n is a positive integer from 1 to 10 and X' is optionally -OH or -OCOCH=CH₂).
As specific examples of this type of compound, there can be mentioned diglycidyletherified
bisphenol A diacrylate and a diacrylate of Epikote #1001 (n=3, supplied by Shell Chemicals).
[0031] Compounds represented by the following general formula (III):

(wherein X₁,X₂,...and X
n, which may be the same or different, represent an alkylene group having up to 6 carbon
atoms, in which one hydrogen atom may be substituted by a hydroxyl group, and n is
an integer from 0 to 5). As specific examples of this type of compound, there can
be mentioned 2,2-bis(4-acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-acryloyloxytriethoxyphenyl)propane
and 2,2-bis(4-acryloyloxydipropoxyphenyl)propane.
[0032] Additionally, in the present invention in order to further improve the anti-blocking
property between the recording media and the transfer sheet (anti-sticking property),
it is preferred that a releasing agent be incorporated into the dye-receiving layer.
As the releasing agent to be used, there can be mentioned at least one member selected
from the group consisting of silicon-containing surface active agents, fluorine-containing
surface active agents, and graft polymers with polyorganosiloxane in the main stem
or in a branch. These aforementioned compounds can also be used jointly as well.
[0033] The amount of releasing agent incorporated is 0.01 to 12 parts by weight, preferably
0.05 to 10 parts by weight, per 100 parts by weight of the total amount of the dyeable
resin and the crosslinking agent.
[0034] If the amount of releasing agent incorporated is less than 0.01 parts by weight,
improvement of the anti-blocking property is decreased, while on the other hand, if
the amount incorporated exceeds 12 parts by weight, the dye-receiving layer becomes
opaque.
[0035] As the silicon-containing surface active agents, a polydimethylsiloxane/polyoxyalkylene
block compound (which may be modified with another functional group) is effective,
in particular silicon-containing surface active agents in which the ratio of the group
CH₃-(SiO)
1/2- to the group -OR- (in which R represents an alkylene residue) is CH₃-(SiO)
1/2- / -OR- = 1/10 ∼ 1/0.1, preferably from 1/5 ∼ 1/0.2, are effective in improving the
anti-blocking property, leveling property and dyeing density.
[0036] As specific examples of the silicon-containing surface active agent, there can be
mentioned compounds represented by the following general formulae (IV) and (V):

wherein P is:

and m and n represent a positive integer, x and y represent 0 or a positive integer,
with the proviso that m, n, x and y satisfy the requirement of
and R₃ represents a hydrogen, an alkyl group, an acyl group, or an aryl group.)

wherein Q is:

wherein m and n represent a positive integer, x and y represent 0 or a positive integer,
with the proviso that m, n, x and y satisfy the requirement of
and z is 0 or an integer from 1 to 5. Additionally, R₄ represents -Si(CH₃)₃, a hydrogen,
an alkyl group, an acyl group or an aryl group, and R₅ represents a hydrogen, an alkyl
group, an acyl group, or an aryl group.)
[0037] One or more members selected from non-ionic, anionic, cationic, or amphoteric fluorine-containing
surface active agents which are soluble to some extent in the mixture of the dyeable
resin and the crosslinking agent can be used as the fluorine-containing surface active
agent. For example, there can be mentioned anionic surface active agents such as fluoroalkoxypolyfluoroalkyl
sulfates, fluorocarbon-sulfonic acid salts and fluorocarbon-carboxylic acid salts;
cationic surface active agents such as N-fluoroalkylsulfonamide alkylamine quaternary
ammonium salts, N-fluoroalkylsulfonamide alkylamine salts, N-fluoroalkylamide alkylamine
quaternary ammonium salts, N-fluoroalkylamide alkylamine salts and N-fluoroalkylsulfonamide
alkylhalomethyl ether quaternary ammonium salts; non-ionic surface active agents such
as fluorocarbon sulfonamides, fluorocarbon aminosulfonamides, fluorocarbon carboxysulfonamides,
fluorocarbon hydroxysulfonamides, fluorocarbon sulfonamide/ethylene oxide adducts,
fluorocarbon hydroxysulfonamide sulfates, fluorocarbon amino acid amides, fluorocarboxylic
acid amides, fluorocarbon hydroxy-acid amides, fluorocarbon acid amide/ethylene oxide
addition condensates, fluorocarbon hydroxy-acid amide sulfates, fluorocarbon sulfonic
acids, fluorohydrocarbon carboxylic acids, fluorohydrocarbon alkyl esters, fluorohydrocarbon
alkyl ethers, fluorohydrocarbon carboxyalkyl esters, fluorohydrocarbon hydroxyamides,
fluorohydrocarbon alkyl sulfates and fluoroalkyldiamines; and amphoteric surface active
agents such as alkylamines having a betaine type fluorocarbon sulfonamide linkage
and alkylamines having a betaine type fluorocarbon acid amide linkage. When considering
such things as the leveling property and the improvement of the blocking property
of the dye-receiving layer, even among the above mentioned surface active agents,
non-ionic surface active agents are preferred.
[0038] As the graft polymer possessing polyorganosiloxane in the main stem or in a branch,
there can be mentioned graft polymers having in the main stem polymers or copolymers
obtained from vinyl polymerization, condensation polymerization, ring-opening polymerization,
and the like, and polyorganosiloxane in a branch. As specific examples of these graft
polymers there can be mentioned, graft polymers obtained from the polymerization of
at least one monomer such as alkyl (meth)acrylate, (meth)acrylic acid, (meth)acrylic
acid derivatives possessing functional groups, vinyl acetate, vinyl chloride, (meth)acrylonitrile,
styrene and the like to a polysiloxane (macromonomer), to which a single terminal
metacryloyloxy group, vinyl group or mercapto group has been added; graft polymers
obtained from the reaction of a dicarboxylic acid and a diol with a macromonomer,
possessing two hydroxyl or carboxyl groups near the polysiloxane end; and graft polymers
obtained from the reaction of a diepoxy or a diisocyanate compound with a macromonomer
possessing two hydroxyl or carboxyl groups near the polysiloxane end.
[0039] As the other graft polymer possessing polyorganosiloxane in the main stem or in a
branch, there can be mentioned graft polymers having polyorganosiloxane in the main
stem, and polymers or copolymers obtained from vinyl polymerization, condensation
polymerization, ring-opening polymerization, and the like, in a branch. As specific
examples of these graft polymers there can be mentioned graft polymers obtained from
the polymerization of at least one monomer such as alkyl (meth)acrylate, (meth)acrylic
acid, (meth)acrylic acid derivatives possessing functional groups, vinyl acetate,
vinyl chloride, (meth)acrylonitrile, styrene and the like to a polysiloxane having
a methacryloyloxy group in its side chain, synthesized by the condensation of organosilane
and silane possessing vinyl polymerizable groups such as 3-methacryloylxypropyl-dimethoxymethylsilane,
methylvinyldimethoxysilane, ethylvinyldiethoxysilane, and the like; graft polymers
obtained from the polymerization of a monomer possessing a (meth)acryloyloxy group
which was obtained through the reaction of (meth)acrylic acid and a polysiloxane possessing
a glycidyl group in its side chain, synthesized by the condensation of organosilane
and diethoxy-3-glycidoxypropylmethylsilane; and graft polymers obtained by polycondensation
of a dicarboxylic acid and a polysiloxane possessing a hydroxyl group in its side
chain, synthesized by polycondensation of organosilane and hydroxyethylmethyl-dimethoxysilane.
[0040] When synthesizing a polysiloxane to be incorporated into the main stem or a branch
of the graft polymer, it is best to perform the polymerization at a temperature of
70∼150°C using a cyclic silane as the main raw material, in particular a cyclic dimethylpolysiloxane
with 3∼8 repeating units, and a silane compound as the molecular weight modifier such
as a trimethylmethoxysilane or a trimethylethoxysilane with one alkoxy group per molecule,
and reacting this cyclic silane and a silane compound with a silane possessing a functional
group under strong acid or strong base catalyst.
[0041] By incorporating these graft polymers into the dye-receiving layer, there is a tendency
for the blocking to a transfer sheet to be drastically eliminated together with the
improvement of the dark color fastness of the dye-receiving layer.
[0042] The weight ratio of the polyorganosiloxane component to polymers or copolymers other
than polyorganosiloxane is preferably (polyorganosiloxane component)/(polymer or copolymer
component) = 95/5 to 10/90, more preferably from 90/10 to 20/80. If this ratio exceeds
95/5, there is a tendency for the dark color fastness to be degraded, and if the ratio
is less than 10/90, there is a tendency for both the anti-blocking property as well
as the dark color fastness to be degraded. Additionally, it is preferred that the
polyorganosiloxane containing graft polymer having a molecular weight of 1000 or greater
be used. If the molecular weight of the graft polymer is less than 1000, it becomes
difficult to improve the dark color fastness.
[0043] Where a compound having a high polymer solubility and a low viscosity, such as tetrahydrofurfuryl
acrylate monomer, is used as a component of the crosslinking agent, the resin composition
to form the dye-receiving layer 3 can be directly coated using coating methods such
as roll coating, bar coating or blade coating. However, in order to improve the adaptability
to the coating operation, preferably a solvent such as ethyl alcohol, methyl ethyl
ketone, toluene, ethyl acetate or dimethylformamide is incorporated to adjust the
viscosity to an adequate level. In this case, the composition can be easily coated
by spray coating, curtain coating, flow coating or dip coating.
[0044] Additionally, fine inorganic particles having a particle size smaller than several
µm, such as those of silica, alumina, talc and titanium oxide, may be incorporated
in the resin composition in accordance with usage objectives.
[0045] The resin composition incorporating a crosslinking agent curable with active energy
rays, can be cured by active energy rays such as electron rays, ultraviolet rays,
and the like. When ultraviolet rays are used as the active energy rays, preferably
a widely known photopolymerization initiator is incorporated into the composition.
The amount of the photopolymerization initiator is not in particular limited, however
0.1 to 10.0 parts by weight per 100 parts by weight of the total amount of the above
mentioned dyeable resin and the crosslinking component, to form the dye-receiving
layer, is preferred.
[0046] As specific examples of the photopolymerization initiator, there can be mentioned
carbonyl compounds such as benzoin, benzoin isobutyl ether, benzyldimethylketal, ethylphenyl
glyoxylate, diethoxyacetophenone, 1,1-dichloroacetophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone,
1-hydroxycyclohexyl-phenylketone, benzophenone, benzophenone/diethanolamine, 4,4'-bisdimethylamino-benzophenone,
2-methylthioxanthone, tert-butylanthraquinone and benzyl; sulfur compounds such as
tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azo compounds such
as azobisisobutylonitrile and azobis-2,4-dimethyl-valeronitrile; and peroxides such
as benzoyl peroxide and di-tert-butyl peroxide. These compounds can be used singly
or in the form of mixture of two or more thereof.
[0047] The dye-receiving layer is formed after the aforementioned resin composition is coated
on top of the high polymer layer 2 using the aforementioned coating method, followed
by drying of the solvent and curing with heat and light as necessary. The thickness
of the dye-receiving layer obtained is appropriately 1 µm or greater. If the thickness
is less than 1 µm, it becomes difficult to deeply dye the dye-receiving layer.
[0048] It is necessary that the dye-receiving layer formed in this manner have a surface
roughness degree as defined in JIS-B-0601 wherein the center line average roughness
R
a and maximum height R
max are shown as 0.3 µm or less and 5 µm or less, respectively. When the surface roughness
degree falls outside of this range, dot errors and dot omissions of the image, as
well as disturbances in the image quality occur during recording, bringing out a rough
impression in the intermediate gradation. The cut off value at this time was 0.8 mm,
and the measured length was 8 mm.
[0049] In order to form this type of dye-receiving layer, among the aforementioned coating
methods for the dye-receiving layer, comma roll coating, lip coating and flow coating
methods are preferred.
[0050] In the image-receiving sheet of the present invention obtained in this manner, due
to the smooth surface of the dye-receiving layer, the recording image quality and
the projection vividness are improved.
[0051] In the following, examples will be given: note, all of the "parts" in the examples
and comparative examples are by weight. Further, in the examples the following are
represented:
2P6A is dipentaerythritol hexa-acrylate;
2P5A is dipentaerythritol penta-acrylate;
2P4A is dipentaerythritol tetra-acrylate;
A-DEP is 2,2-bis(4-acryloyloxydiethoxyphenyl)propane;
Resin A is a polyester resin obtained by polycondensation of terephthalic acid,
isophthalic acid and sebacic acid with ethylene glycol and neopentyl glycol (molecular
weight: 20,000 to 25,000, Tg: 10°C); and
Resin B is a polyester resin obtained by polycondensation of terephthalic acid,
isophthalic acid and sebacic acid with ethylene glycol, neopentyl glycol and 1,4-butane
diol (molecular weight: 20,000 to 25,000, Tg: 47°C).
[0052] Silicon containing surface active agent A is represented by the following structural
formula (VI):

Example 1
[0053] To the surface of one side of a coat paper of thickness 150 µm, a solution of polymethylmethacrylate
and acetone (resin portion 30% by weight) was coated using a comma roll coater, and
then dried to produce a high polymer layer of thickness 30 µm. The surface roughness
degree of this high polymer layer showed an R
a of 0.09 µm, and an R
max of 1.5 µm. On top of this high polymer layer, a composition consisting of 3 parts
of 2P6A, 4 parts of 2P5A, 3 parts of 2P4A, 10 parts of A-DEP, 20 parts of Resin A,
60 parts of Resin B, 0.1 parts of silicon-containing surface active agent A, 5 parts
of 1-hydroxycyclohexylphenylketone, 300 parts of methylethylketone and 100 parts of
toulene was coated using the comma roll coating method, the solvent was removed, followed
by curing of the composition by irradiation with ultraviolet rays to produce a dye-receiving
layer of thickness 7 µm, with an R
a of 0.05 µm and an R
max of 1.2 µm, thereby completing the formation of an image-receiving sheet.
Example 2
[0054] To the surface of one side of an art paper of thickness 100 µm, a solution consisting
of 20 parts of a methylmethacrylate/methylacrylate copolymer in a weight ratio of
90/10, 2 parts of 2P6A, 2 parts of 2P5A, 1 part of 2P4A, 2 parts of benzyldimethylketal
and 73 parts of methylethylketone was coated by a lip coating method, dried and cured
with ultraviolet rays to produce a high polymer layer of thickness 40 µm, with an
R
a of 0.11 µm and an R
max of 2.0 µm. A dye-receiving layer was formed on top of this high polymer layer in
the same manner as example 1, and an image-receiving sheet was obtained. The dye-receiving
layer obtained had a thickness of 6 µm, with an R
a of 0.09 µm and an R
max of 1.7 µm.
Example 3
[0055] To the surface of one side of a coat paper of thickness 150 µm, a solution consisting
of 20 parts of a copolymer of vinyl chloride/vinyl acetate in a weight ratio of 85/15,
40 parts of methyl ethyl ketone and 40 parts of toulene was coated using the flow
coating method, and dried to produce a high polymer layer of thickness 25 µm, with
an R
a of 0.22 µm and an R
max of 3.8 µm. Onto the top of this high polymer layer, a composition consisting of 10
parts of a polyester resin (VYLON #200 manufactured by Toyobo Co., Ltd.), 0.5 parts
of an amino-modified silicon (KF-393 manufactured by Shin-Etsu Chemical Co., Ltd.),
0.5 parts of an epoxy-modified silicon (X-22-343 manufactured by Shin-Etsu Chemical
Co., Ltd.) and 89 parts of a solvent (toulene/methylethylketone: in a weight ratio
of 1/1) was coated using a dipping method and dried to produce a dye-receiving layer
of thickness 6 µm, with an R
a of 0.26 µm and an R
max of 4.6 µm. In this manner the image-receiving sheet was formed.
Example 4
[0056] An image-receiving sheet was obtained in the same manner as in example 3 except that
the high polymer layer of thickness 25 µm, with an R
a of 0.26 µm and an R
max of 4.8 µm, was formed from polyethylene on the surface of one side of a coat paper
using a melt coating method. The dye-receiving layer obtained had a thickness of 6
µm, with an R
a of 0.28 µm and an R
max of 4.8 µm.
Comparative example 1
[0057] An image-receiving sheet was obtained in the same manner as in example 1 except that
a high polymer layer was not formed. The dye-receiving layer obtained had a thickness
of 7 µm, with an R
a of 1.2 µm and an R
max of 9.5 µm.
Comparative example 2
[0058] An image-receiving sheet was obtained in the same manner as in example 3 except that
a high polymer layer was not formed. The dye-receiving layer obtained had a thickness
of 6 µm, with an R
a of 2.2 µm and an R
max of 11.7 µm.
Comparative example 3
[0059] Using an adhesive agent, polypropylene synthetic paper YUPO FPG (thickness 60 µm)
manufactured by Ozi Yuka Synthetic Paper Co., Ltd. was laminated onto one surface
of an art paper of thickness 100 µm. The surface roughness degree of the polypropylene
synthetic paper was defined by an R
a of 0.62 µm and an R
max of 11.8 µm. The dye-receiving layer was then formed on top of this polypropylene
synthetic paper and an image-receiving sheet was obtained in the same manner as in
example 1. The dye-receiving layer obtained had a thickness of 7 µm, with an R
a of 0.51 µm and an R
max of 8.5 µm.
[0060] Using the image-receiving sheets obtained from these examples and comparative examples,
the anthraquinone-based sublimable dispersing dye was sublimated under conditions
in which 13 V of impressed voltage was applied by a 6 dot/mm thermal head for 5∼20
ms, following which a color image was recorded. In the image-receiving sheet of examples
1∼4, smooth intermediate gradations lacking a rough impression were obtained, in addition
to a superb projection vividness. However, in comparative examples 1∼3, disturbances
of the image, as well as a rough impression of the image quality were observed. Furthermore,
in comparative examples 1 and 2, the image dyeing density was remarkably degraded.