U.S. patent application number 09/153234 was filed with the patent office on 2002-02-21 for ink jet recording material.
Invention is credited to KITAMURA, RYU, MUKOYOSHI, SHUNICHIRO, OHSHIMA, KAZUAKI, TAKAHASHI, TOMOMI.
Application Number | 20020022117 09/153234 |
Document ID | / |
Family ID | 26540365 |
Filed Date | 2002-02-21 |
United States Patent
Application |
20020022117 |
Kind Code |
A1 |
KITAMURA, RYU ; et
al. |
February 21, 2002 |
INK JET RECORDING MATERIAL
Abstract
An ink jet recording material having an excellent ink absorbing
property and capable of recording ink images with superior gloss,
water resistance and light resistance has an outermost ink
receiving layer formed on a support and containing (1) fine pigment
particles selected from amorphous silica secondary particles and
alumina silicate secondary particles which have an average
secondary particle size of 10 to 300 nm and in each of which a
plurality of primary particles having an average primary particle
size of 3 to 40 nm are agglomerated with each other, (2) an
ultraviolet ray absorber and, optionally, (3) an antioxidant.
Inventors: |
KITAMURA, RYU; (CHIBA-SHI,
JP) ; TAKAHASHI, TOMOMI; (TOKYO, JP) ;
MUKOYOSHI, SHUNICHIRO; (ICHIKAWA-SHI, JP) ; OHSHIMA,
KAZUAKI; (YOKOHAMA-SHI, JP) |
Correspondence
Address: |
ARENT FOX KINTNER PLOTKIN & KAHN, PLLC
1050 CONNECTICUT AVENUE, N.W., SUITE 600
WASHINGTON
DC
20036-5339
US
|
Family ID: |
26540365 |
Appl. No.: |
09/153234 |
Filed: |
September 15, 1998 |
Current U.S.
Class: |
428/32.34 |
Current CPC
Class: |
B41M 5/5218 20130101;
B41M 5/5245 20130101; B41M 5/5254 20130101; B41M 5/52 20130101;
B41M 2205/12 20130101; B41M 5/5227 20130101 |
Class at
Publication: |
428/195 |
International
Class: |
B41M 005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 17, 1997 |
JP |
9-251806 |
Oct 3, 1997 |
JP |
9-271571 |
Claims
What we claim is:
1. An ink jet recording material comprising a support and a one or
more ink-receiving layers formed on the support, wherein at least
one of the ink receiving layers comprises: (1) fine colloid pigment
particles selected from fine colloid amorphous silica secondary
particles and fine colloid alumina silicate secondary particles
having an average secondary particle size of 10 to 300 nm and each
consisting essentially of a plurality of primary particles having
an average primary particle size of 3 to 40 nm and agglomerated
with each other; and (2) an ultraviolet ray-absorber.
2. The ink jet recording material as claimed in claim 1, wherein
the at least one ink receiving layer comprising the fine colloid
pigment particles and the ultraviolet ray absorber further
comprises an antioxidant.
3. The ink jet recording material as claimed in claim 1 or 2,
wherein at least one of the ink receiving layers comprises a
cationic compound.
4. The ink jet recording material as claimed in claim 3, wherein
the cationic compound is selected from the group consisting of
polymers of diallyldimethyl ammonium chloride, copolymers of
diallyldimethyl ammonium chloride with sulfur dioxide and
copolymers of at least one amine with at least one carboxylic
acid.
5. The ink jet recording material as claimed in claim 1 or 2,
wherein the ultraviolet ray-absorber comprises at least one member
selected from ultraviolet ray-absorbing benzotriazole
compounds.
6. The ink jet recording material as claimed in claim 1 or 2,
wherein the ultraviolet ray-absorber comprises at least one
inorganic metal oxide selected from the group consisting of zinc
oxide, titanium dioxide, yttrium oxide and cerium oxide.
7. The ink jet recording material as claimed in claims 1, 2, 5 or
6, wherein the ultraviolet ray absorber is in the form of fine
particles having an average particle size of 500 nm or less.
8. The ink jet recording material as claimed in claim 1, 2, 5 or 6,
wherein the ultraviolet ray absorber is in the form of secondary
particles having an average secondary particles of 2 .mu.m or less
and each consisting essentially of a plurality of primary particles
having an average primary particle size of 3 to 100 nm and
agglomerated with each other.
9. The ink jet recording material as claimed in claim 2, wherein
the antioxidant comprises at least one member selected from
antioxidant phenolic compounds.
10. The ink jet recording material as claimed in claim 2, wherein
the antioxidant comprises at least one member selected from the
group consisting of 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol),
4,4'-thiobis(3-methyl-6-tert-butylphenol),
1,1,3-tris-(2-methyl-4-hydroxy- -5-tert-butylphenyl)butane, and
1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexyl- phenyl)butane.
11. The ink jet recording material as claimed in claim 1, 2 or 3,
wherein the ink receiving layer containing the fine colloid pigment
particles and the ultraviolet ray absorber forms an outermost layer
to which an ink jet printing is applied, and at least one
additional ink receiving layer is formed between the outermost ink
receiving layer and the support.
12. The ink jet recording material as claimed in claim 1, wherein
the at least one ink receiving layer is formed by coating a casting
surface with a at least one coating layer corresponding to the ink
receiving layer; transferring and bonding the cast-coated layer on
the casting surface to a surface of the support; and removing the
casting surface from the transferred cast-coated layer.
13. The ink jet recording material as claimed in claim 12, wherein
the at least one ink receiving layer is formed by coating a casting
surface with at least one coating layer corresponding to the ink
receiving layer; transferring and bonding the cast-coated layer to
a surface of an additional ink receiving layer directly formed on
the support; and removing the casting surface from the transferred
cast-coated layer.
14. The ink jet recording material as claimed in claim 1, wherein
the fine colloid pigment particles are fine colloid amorphous
silica particles.
15. The ink jet recording material as claimed in claim 6 or 8,
wherein the ultraviolet ray absorber comprises cerium oxide.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an ink jet recording
material. More particularly, the present invention relates to an
ink jet recording material having high gloss and color density of
recorded images, and excellent water and light resistances.
[0003] 2. Description of the Related Art
[0004] An ink jet recording system is employed to record colored
ink images on a recording material by jetting imagewise ink
droplets through nozzles at a high velocity to cohere the ink
droplets on a surface of the recording material and is advantageous
in that full color printing is easy and in that the printing noise
is low. For this recording system, it is required that no clogging
of the ink jet nozzles occurs, and the printed colored images
exhibit bright colors. Therefore, the ink used for the ink jet
recording system usually contains an acid dye or direct dye, and
thus dyes having a high light fastness cannot be always selected at
the present time.
[0005] As recording paper sheets for the ink jet recording system,
woodfree paper sheets having an enhanced ink absorption and a
coated paper prepared by coating a surface of the woodfree paper
sheet with a porous pigment are widely available. However, these
conventional paper sheets are disadvantageous in that when the ink
images recorded on the conventional recording paper sheets are
stored for long period, the ink images are significantly faded.
Also, the conventional paper sheets are mostly mat-like ink jet
recording sheets having a low surface gloss. Currently, in response
to the rapid popularization of the ink jet printers and to the
requirements for an improved quality of colored images, it is
demanded to provide ink jet recording sheets having a high surface
gloss, an excellent appearance and superior water and light
resistances.
[0006] There are may reports concerning improvements of the light
resistance of printed colored images. For example, Japanese
Unexamined Patent Publications No. 57-87,988 and No. 57-87,989
disclose ink jet recording sheets to which an ultraviolet ray
absorber or an antioxidant is added to improve the light resistance
thereof. Also, Japanese Unexamined Patent Publication No.
63-166,586 discloses an ink jet recording sheet containing silica
particles surface-treated with metal soaps, hydroxides, salts or
oxides of a metal selected from Na, K, Ca, Mg, Al, Zn, Ba, Sr and
Sn to enhance the light resistance of the recording sheet. Further,
as reported in Japanese Unexamined Patent Publication No.
4-201,594, it is known that ultrafine particles of transition metal
oxides are added to the ink receiving layer to support the
inhibition effect of the ultraviolet ray absorbers on
photodeterioration over long period. This type of the recording
material exhibits a certain improvement in light resistance.
However, this ink receiving layer is opaque, and a high gloss, a
high color density of colored images, a high water resistance and a
high light resistance cannot be obtained. This is probably because
of the ink receiving layer formed from pigment particles having a
particle size in the order of several micrometers. To impart a high
gloss, a high color density of colored images and a high water
resistance to the ink receiving layer, Japanese Unexamined Patent
Publication No. 7-68,919 has reported that a support can be coated
with a ultrafine pseudoboehmite sol porous ink receiving layer
containing a mixture of an ultraviolet ray absorber or an
antioxidant with a quencher. However, since the pseudoboehmite
particles exhibit a low ink absorption capacity and a low
ink-absorbing velocity, the above-mentioned ink jet recording sheet
is unsuitable for high resolving power ink jet printers in which a
large amount of ink is jetted to obtain a desired color density of
colored images, and is unappropriate as a recording medium having a
high gloss capable of recording photograph-like colored images.
[0007] The inventors of the present invention have attempted to
provide ink jet recording materials having a high gloss, a high
color density of colored images and a high ink absorption, and
containing pigment secondary colloid particles having an average
secondary particle size of 10 to 300 nm each consisting essentially
of a plurality of primary particles having an average primary
particle size of 3 to 40 nm and agglomerated with each other
(EP-A-803374). The resultant recording material exhibits a high ink
absorption and when ink jet printing is applied to the
above-mentioned recording materials, the resultant colored images
having excellent gloss, color density, water resistance and colored
image quality compared to silver salt photographic images. However,
this recording material is disadvantage in that when the resultant
prints are stored for a long period, and especially when exposed to
strong light, the colored images are faded or discolored.
SUMMARY OF THE INVENTION
[0008] An object of the present invention is to provide an ink jet
recording material capable of recording colored images having
excellent color density, gloss, water resistance and light
resistance.
[0009] The above-mentioned object can be attained by the ink jet
recording material of the present invention which comprises a
support and a one or more ink-receiving layers formed on the
support, wherein at least one of the ink receiving layers
comprises:
[0010] (1) fine colloid pigment particles selected from fine
colloid amorphous silica secondary particles and fine colloid
alumina silicate secondary particles having an average secondary
particle size of 10 to 300 nm and each consisting essentially of a
plurality of primary particles having an average primary particle
size of 3 to 40 nm and agglomerated with each other; and
[0011] (2) an ultraviolet ray-absorber.
[0012] The above-mentioned ink receiving layer containing the fine
colloid amorphous silica and/or alumina silicate particles and the
ultraviolet ray absorber enables the colored images recorded on the
resultant ink jet recording material to exhibit excellent color
density, gloss, water resistance and light resistance. In a
preferable embodiment of the present invention, the ink receiving
layer containing the fine colloid amorphous silica and/or alumina
silicate particles and the ultraviolet ray absorber further
comprises an antioxidant.
[0013] The antioxidant contributes to enhancing the light
resistance of the colored images recorded on the resultant ink
receiving layer.
[0014] In the ink jet recording material of the present invention,
the ink receiving layer preferably contains a cationic compound
which contributes to fixing an anionic dye contained in the ink and
to enhancing the water resistance and long term storage stability
of the printed colored images.
[0015] Also, when the ultraviolet ray absorber comprises at least
one member selected from organic ultraviolet ray-absorbing
compounds, for example, benzotriazole compounds and inorganic
ultraviolet ray-absorbing compounds, for example, zinc oxide,
titanium dioxide, yttrium oxide and cerium oxide, the resultant ink
receiving layer exhibit a significantly enhanced light resistance
of colored images recorded thereon. Also, the above-mentioned
ultraviolet ray absorbing compounds have a relatively good
compatibility with the amorphous silica and alumina silicate
particles. Therefore, a coating liquid containing the
above-mentioned ultraviolet ray-absorbing compounds can be easily
coated on a support to form an ink receiving layer.
[0016] In the ink jet recording material of the present invention,
the ultraviolet ray absorber is preferably in the form of fine
particles having an average particle size of, for example, 500 nm
or less. The ultraviolet ray absorber may be pulverized together
with the silica and/or alumina silicate. When the ultraviolet ray
absorber particles having the above-mentioned particle size are
used, the resultant ink receiving layer can exhibit a high gloss,
color density, water resistance and light resistance of the
recorded colored images, without decreasing the transparency of the
ink receiving layer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] In the ink jet recording material of the present invention,
the support is not limited to specific materials and thus may be
formed from a transparent material or an opaque material. For
example, the substrate preferably comprises a regenerated cellulose
film, a plastic film, for example, polyethylene, polypropylene,
soft polyvinyl chloride, hard polyvinyl chloride, or polyester
film; a paper sheet, for example, a wood-free paper, a coated
paper, an art paper, a cast-coated paper, a foil-laminated paper, a
kraft paper, a polyethylene film-laminated paper, a
resin-impregnated paper, a metalized paper or a water-soluble paper
sheet; a metal foil; or a synthetic paper sheet.
[0018] The ink jet recording material of the present invention has
one or more ink receiving layers formed on the support, and at
least one of the ink receiving layers comprises:
[0019] (1) fine colloid pigment particles selected from fine
colloid amorphous silica secondary particles and fine colloid
alumina silicate secondary particles having an average secondary
particle size of 10 to 300 nm and each consisting essentially of a
plurality of primary particles having an average primary particle
size of 3 to 40 nm and agglomerated with each other; and
[0020] (2) an ultraviolet ray absorber.
[0021] In the present invention, when the fine colloid pigment
secondary particles have an average secondary particle size of 10
to 500 nm, the resultant ink receiving layer has a higher gloss
than that of a conventional ink receiving layer containing pigment
particles with a particle size in the order of .mu.m.
[0022] The ultrafine colloid amorphous silica and alumina silicate
recording particles have a secondary particle size of 10 to 300 nm
preferably 20 to 200 nm, and each consist essentially of a
plurality of primary particles agglomerated with each other and
having an average primary particle size of 3 to 40 nm, preferably 5
to 30 nm. When the primary particle size is too small, the
resultant ink receiving layer exhibits an unsatisfactory ink
absorbing property. Also, when the primary particle size is too
large, the resultant ink receiving layer exhibits an unsatisfactory
transparency and the printed colored images have an unsatisfactory
color density. When the secondary particle size is too small, the
resultant ink receiving layer exhibits a poor film-forming property
and thus numerous cracks may be formed in the ink receiving layer.
Also, when the secondary particles size is too large, the resultant
ink receiving layer has a roughened surface and it becomes
difficult to obtain a high gloss on the ink jet recording material.
To obtain the secondary particles having an average secondary
particle size of 10 to 300 nm or a dispersion thereof, conventional
trade amorphous silica and/or alumina silicate pigment particles
having a particle size of several micrometers are pulverized by
applying a strong shearing force thereto by mechanical means, for
example, a breaking-down method in which a material in the form of
lumps is finely divided. The mechanical pulverizing means include
ultrasonic homogenizers, pressure-type homogenizers, nanomizers,
high speed revolution mills, roller mills, container-driven medium
mills, medium-stirring mills, jet mills, mortars, and sand
grinders. The resultant ultrafine particles may be in the form of
colloid particles or a slurry. In the present invention, the
average particle size is a particle diameter (Martin size)
determined by using an electron microscope (SEM or TEM) (Asakura
Shoten, "Fine Particle Handbook" page 52).
[0023] The fine alumina silicate particles are fine composite
particles prepared by a hydrolysis synthetic method from, as
principal components, of aluminum alkoxide and silicon alkoxide and
contain alumina (Al.sub.2O.sub.3) segments and silica (SiO.sub.2)
segments which cannot be isolated from each other. The weight ratio
of the alumina segments to the silica segments is usually about
6:2. Since the alumina silicate particles have an amorphous
structure, the amorphous alumina silicate particles can be prepared
even in the segment weight ratio in the range from 1:4 to 4:1 and
can be utilized in the present invention.
[0024] Also, a three component metal alkoxide mixture is prepared
from aluminum alkoxide, silicon alkoxide and an other metal
alkoxide, and is subjected to a hydrolysis to prepare fine alumina
silicate particles containing the other metal component.
[0025] The alumina silicate can be synthesized in an alcohol
atmosphere and after the synthesis is completed, the alumina
silicate is in the form of agglomerated particles (secondary
particles). To obtain the alumina silicate secondary particles
having an average secondary particle size of 10 to 300 nm, the
agglomerated particles are pulverized into smaller particles by,
for example, the above-mentioned method.
[0026] The ink receiving layer of the present invention optionally
comprises, in addition to the ultrafine amorphous silica and/or
alumina silicate particles, other trade pigments to enhance the
ink-absorbing property of the ink receiving layer, unless the
smoothness and transparency of the ink receiving layer are
affected.
[0027] The additional pigment includes, inorganic pigments, for
example, silica and alumina silicate different from the specific
ultrafine amorphous silica and alumina silicate particles for the
present invention, kaolin, clay, calcined clay, zinc oxide, tin
oxides, magnesium sulfate, aluminum oxide, aluminum hydroxide,
pseudoboehmite, calcium carbonate, satin white, aluminum silicate,
smectite, magnesium silicate, magnesium carbonate, magnesium oxide
and diatomaceous earth; and organic pigments, for example, styrene
polymer plastic pigments, urea-formaldehyde resin pigments and
benzoguanamine-formaldehyde resin pigments, which are usually used
for coated paper sheets. The additional pigment is preferably used
in an amount of 20 parts by weight or less per 100 parts by weight
of the ultrafine amorphous silica and/or alumina silicate particles
and has a particle size of 2 .mu.m or less.
[0028] The ultraviolet ray absorber usable for the present
invention preferably comprise at least one member selected from
organic and inorganic ultraviolet ray-absorbing compounds as shown
below.
[0029] The ultraviolet ray-absorbing organic compounds include
ultraviolet ray-absorbing salicylate compounds, for example, phenyl
salicylate, p-tert-butyl-phenyl salicylate and p-octylphenyl
salicylate; ultraviolet ray-absorbing benzophenone compounds, for
example, 2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzop- henone, and
2-hydroxy-4-methoxy-5-sulfobenzophenone; ultraviolet ray-absorbing
benzotriazole compounds, for example,
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-5'-tert-butylp- henyl)benzotriazole,
2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chloro-
benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole,
2-[2'-hydroxy-3'-(3",4",5",6"-tetra-hydrophthalimidomethyl)-5'-methylphen-
yl]benzotriazole, and
2,2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-
-benzotriazole-2-yl)phenol; and ultraviolet ray-absorbing
cyanoacrylate compounds, for example,
2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and
ethyl-2-cyano-3,3'-diphenyl acrylate. Among the above-mentioned
compounds, the ultraviolet ray-absorbing benzotriazole compounds
are advantageously employed for the present invention, because they
have a good compatibility to the other components for the ink
receiving layer and cause the colored images printed on the
resultant ink receiving layer to exhibit an excellent light
resistance.
[0030] The ultraviolet ray-absorbing compounds include oxides of
transition metals, for example, cerium oxide, zinc oxide, titanium
oxide and yttrium oxide. Also, cerium acetate is usable as an
ultraviolet ray-absorbing transition metal compound.
[0031] As mentioned above, among the organic ultraviolet
ray-absorbing compounds as mentioned above, the ultraviolet
ray-absorbing benzotriazole compounds are preferably used. Also, to
obtain an ink receiving layer having an enhanced water resistance,
the transition metal oxides are prepared as the ultraviolet ray
absorber. Particularly, cerium oxides exhibit an excellent
ultraviolet ray absorption, and can be obtained in the form of fine
particles having a particle size of 20 nm or less, particularly 10
nm or less, and thus an excellent transparency. Also, cerium oxides
include cationic oxides. Therefore, cerium oxides are
advantageously used for the present invention.
[0032] A trade cerium oxide is available under a trademark of
Needral, made by TAKI CHEMICAL CO., LTD. and has a particle size of
8 nm or less. A trade cationic cerium oxide is available under a
trademark of U-15, made from TAKI CHEMICAL CO., LTD.
[0033] The above-mentioned organic and inorganic ultraviolet
ray-absorbing compounds may be used alone or in a mixture of two or
more thereof, for the present invention.
[0034] Where the ultraviolet ray absorber is in the state of a
liquid, the liquid ultraviolet ray absorber per se can be mixed
into a coating liquid for the ink receiving layer. For example,
2-hydroxy-4-methoxy-benzophenon- e (available under the trademark
of SEESORB 101, made by SHIRAISHI CALCIUM CO.) is soluble in water,
and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (available under
trademark of JF-77, made by JOHOKU CHEMICAL CO., LTD. or of SEESORB
701, made by SHIRAISHI CALCIUM CO., LTD.) is soluble in water at a
high pH value. Of the inorganic ultraviolet ray absorbers, cerium
acetate is soluble in water. Other ultraviolet ray absorbing
compounds are mostly insoluble in water. When is insoluble in
water, the ultraviolet ray absorber particles in the form of a
powder or suspension (emulsion) is preferably controlled to an
average particle size of 500 nm or less not to affect the
transparency and smoothness of the ink receiving layer. There is no
specific lower limit to the average particle size of the
ultraviolet ray absorber. Usually, the average particle size can be
decreased to about 1 nm. To control the average particle size of
the ultraviolet ray absorber particles to 500 nm or less, the
above-mentioned pulverizing method, for example, the breaking-down
method, can be utilized.
[0035] There is no specific limitation to the content of the
ultraviolet ray absorber in the ink receiving layer. Preferably,
the ultraviolet ray absorber is contained in an amount of about 0.5
to about 25 parts by weight per 100 parts of the total amount of
the pigment. When the content of the ultraviolet ray absorber is
too small, the resultant light resistance is unsatisfactory and
when it is too large, the resultant light resistance-enhancing
effect is saturated.
[0036] The ultraviolet ray absorber particles may be in the form of
agglomerated particles which contribute to enhancing the ink
absorbing property of the ink receiving layer. The secondary
particle size of the fine ultraviolet ray absorber can be selected
within the range of 2 .mu.m or less. However, to further enhance
the ink absorbing property of the ink receiving layer and the color
density of the printed images, the secondary particle size of the
fine ultraviolet ray absorber is preferably in the range from 0.1
.mu.m to 1 .mu.m, more preferably 150 nm to 500 nm. When the
particle size of the secondary particles is too small, the
resultant ink-receiving layer may exhibit an unsatisfactory
film-forming property and thus numerous cracks may be formed in the
resultant ink receiving layer. On the other hand, when the particle
size of the secondary particles of the ultraviolet ray absorber is
too large, the resultant ink receiving layer may have a roughened
surface and thus an ink jet recording material having a high gloss
may not be obtained.
[0037] The primary particles which are agglomerated with each other
to form secondary particles of the ultraviolet ray absorber
preferably have an average primary particle size of 3 nm to 100 nm,
more preferably 5 nm to 50 nm. When the primary particle size is
too small, the resultant secondary particles of the ultraviolet ray
absorber may exhibit an insufficient ink-absorbing property, and
when it is too large, the resultant ink received layer may be
disadvantageous in that the transparency of the ink receiving layer
is insufficient, and the colored images printed on the resultant
ink receiving layer are unsatisfactory in color density
thereof.
[0038] The mixing weight ratio of the fine secondary particles of
the pigment to the secondary particles of the ultraviolet ray
absorber is preferably within the range from 50/1 to 2/1, more
preferably from 20/1 to 20/7. When the proportion of the fine
pigment particle is too high, the light resistance-enhancing effect
on the ink receiving layer may be insufficient and when it is too
low, the color brightness of the resultant colored images may be
unsatisfactory and the resultant ink receiving layer may exhibit an
unsatisfactory transparency. The secondary particles of the
ultraviolet ray absorber having an average particle size of 2 .mu.m
or less can be prepared by pulverizing trade ultraviolet ray
absorber agglomerated particles (having, for example, a particle
size of several micrometers) and by mechanical means in which a
strong shearing force is applied to the particles. Namely, the
afore-mentioned breaking-down method which is useful for finely
dividing a lump-formed material may be applied. The mechanical
means include the above-mentioned ultrasonic homogenizers,
pressure-type homogenizers, nanomizers, high speed revolution
mills, roller mills, container-drived medium mill, medium-stirring
mills, jet mills, and sand grinders. The resultant ultrafine
ultraviolet ray absorber particles may be in the state of a
colloidal solution or a slurry.
[0039] In a preferred embodiment of the present invention, to
further enhance the light resistance, the ink receiving layer
further contains an antioxidant. There is no specific limitation to
the content of the antioxidant in the ink receiving layer. Usually,
the antioxidant is preferably used in an amount of 1 to 10,000
parts, preferably 1 to 1000 parts, more preferably 10 to 500 parts
by weight per 100 parts by weight of the ultraviolet ray
absorber.
[0040] Namely, in an embodiment of the ink jet recording material
of the present invention, one or more ink receiving layers are
formed on a support and at least one layer of the ink receiving
layers comprises fine colloid pigment particles selected from
amorphous silica secondary particles and alumina silicate secondary
particles having an average secondary particle size of 10 to 300 nm
and consisting essentially of a plurality of primary particles
having an average primary particle size of 3 to 40 nm and
agglomerated with each other, an ultraviolet ray absorber and an
antioxidant.
[0041] The antioxidant usable for the present invention comprises
at least one member selected from, for example, phenolic
antioxidant compounds, sulfur-containing antioxidant compounds and
phosphorus-containing antioxidant compounds.
[0042] The phenolic antioxidant compounds include monophenolic
antioxidant compounds, for example, 2,6-di-tert-butyl-p-cresol,
butylated hydroxy anisole, 2,6-di-tert-butyl-4-ethylphenol and
stearyl-.beta.-(3,5-di-tert-- butyl-4-hydroxyphenyl)propionate;
bisphenolic antioxidant compounds, for example,
2,2'-methylene-bis(4-metyl-6-tert-butylphenol),
2,2'-methylene-bis(4-ethyl-6-tert-butylphenol),
4,4'-thiobis(3-methyl-6-t- ert-butylphenol) and
4,4'-butylidenebis(3-methyl-6-tert-butylphenol); and poly-phenolic
antioxidant compounds, for example, 1,1,3-tris(2-methyl-4-h-
ydroxy-5-tert-butylphenol)butane,
1,1,3-tris(2-methyl-4-hydroxy-5-cyclophe- xyl-phenyl)butane,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxy--
benzyl)benzene,
tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl-
)propionate]methane,
bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butylic acid]glycol
ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-tri-
azine-2,4,6-(1H,3H,5H)trione and tocopherols.
[0043] The sulfur-containing antioxidant compounds include, for
example, dilauryl 3,3'-thiodipropionate, dimyristyl
3,3'-thiodipropionate and distearyl 3,3'-thiodipropionate.
[0044] The phosphorus-containing antioxidant compounds include, for
example, triphenyl phosphite, diphenylisodecyl phosphite,
phenyldiisodecyl phosphite,
4,4'-butylidene-bis(3-methyl-6-tert-butylphen-
ylditridecyl)phosphite, cyclic neopentane tetraylbis (octadecyl
phosphite), tris(nonylphenyl)phosphite,
tris(monononylphenyl)phosphite, tris(dinonylphenyl)phosphite,
diisodecylpentaeryhritol diphosphite,
9,10-dihydro-9-oxa-10-phosphaphenanthrene=10-oxide,
10-(3,5-di-tert-butyl-4-hydroxy-benzyl)-9,10-dihydro-9-oxa-10-phosphaphen-
anthrene-10-oxide,
10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene,
tris(2,4-di-tert-butylphenyl)phosphite, cyclic
neopentanetetrayl-bis(2,4-- di-tert-butylphenyl)phosphite, cyclic
neopentanetetrayl-bis(2,6-di-tert-by- tyl-4-methylphenyl)phosphite,
and 2,2-methylene-bis(4,6-di-tert-butylpheyl- )octyl phosphite.
[0045] In the ink jet recording material of the present invention,
in consideration of the compatibility with the coating liquid for
the ink receiving layer and the light resistance of the cohered
images recorded in the ink receiving layer, the phonolic compounds
are preferred for the antioxidant. Particularly,
2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) which is available,
for example, under the trademark of ANTAGE W-500, made by KAWAGUCHI
CHEMICAL CO., 4,4'-thio-bis(3-methyl-6-tert-butylphenol which is
available, for example, under the trademark of SUMIRIZER WX, made
by SUMITOMO CHEMICAL CO., LTD.,
1,1,3-tris(2-methyl-4-hydroxy-5-tert- -butylphenyl)butane which is
available, for example, under the trademark of ADECASTAB AO-30,
made by ASAHI DENKA KOGYO K. K., and
1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane which is
available, for example, under the trademark of ARKLS DH-43, made by
ASAHI DENKA KOGYO K. K.
[0046] Where the antioxidant for the present invention is in the
state of a solution, the solution per se can be added to the
coating liquid for the ink receiving layer.
[0047] Where the antioxidant for the present invention is in the
form of a water-insoluble powder or a suspension (emulsion), the
average particle size of the antioxidant particles is preferably
controlled to a level of 500 nm or less. To control the average
particle size to 500 nm or less, the afore-mentioned mechanical
means, for example, a breaking down method, are utilized. There is
no specific limitation to the content of the antioxidant in the ink
receiving layer. Usually, the content of the antioxidant is
preferably 0.5 to 25 parts by weight per 100 parts by weight of the
pigment. When the antioxidant content is too low, the light
resistance-enhancing effect may be unsatisfactory. Also when the
antioxidant content is more than 25 parts by weight, the light
resistance-enhancing effect may be saturated, and thus an
economical disadvantage may occur.
[0048] In the preparation of the ink receiving layer, the ultrafine
amorphous silica and/or alumina silicate particles, the ultraviolet
ray absorber and optionally the antioxidant which have no
film-forming property, are mixed with a binder. The binder
preferably comprises at least one member selected from
water-soluble polymers, for example, polyvinyl alcohol (PVA), and
derivatives thereof such as silyl-modified polyvinyl alcohols and
cation-modified polyvinyl alcohols, casein, soybean protein,
synthetic proteins, starch, and cellulosic compounds, for example
carboxymethyl cellulose and methylcelluloce; and dispersions or
latices of water-insoluble polymers, for example, latices of
conjugated diene polymers, for example, styrene-butadiene
copolymers and methyl-methacrylate-butadiene copolymers, latices of
acrylic polymers, and latices of vinyl copolymers, for example,
styrene-vinyl acetate copolymers, which are usually employed for
coated paper sheets. These polymeric compounds are used alone or in
a mixture of two or more thereof. To obtain a high bonding strength
between the ink receiving layer and the support or between the ink
receiving layers, the water-soluble binder is preferably used.
Particularly, when a PVA having a polymerization degree of 2,000 or
more is used as a binder, the adhesion between the ink receiving
layer and the support or between the ink receiving layers is high,
and thus is useful for obtaining an ink jet recording material
having a high ink-absorbing rate, a high ink absorption capacity, a
high color density of colored images, a high water resistance and a
high light resistance.
[0049] There is no specific upper limit of the polymerization
degree of the PVA.
[0050] Usually, the PVA having a polymerization, degree of about
10,000 or less can be used for the present invention, unless the
PVA causes the resultant coating liquid to exhibit too high a
viscosity.
[0051] Preferably, in the ink receiving layer of the present
invention, the binder is contained in an amount of 2 to 200 parts,
more preferably 5 to 100 parts, by solid weight per 100 parts by
weight of the pigment. When the content of the binder in the ink
receiving layer is too high, pores formed between the solid
particles may become too small and thus the ink-absorbing rate of
the resultant ink receiving layer may be insufficient. When the
binder content is too small, the resultant ink receiving layer may
have large cracks formed due to a poor film-forming property and
may exhibit reduced gloss and color density of printed images.
[0052] For the purpose of enhancing the ink-fixing property of the
ink receiving layer, a cationic compound may be contained in the
ink receiving layer. When the ink receiving layer has a single
layered structure, the single ink receiving layer preferably
contains the cationic compound. Also, when the ink receiving layer
has a multiple layered structure, the outermost ink receiving layer
on which the ink jet printing is applied preferably contains the
cationic compound.
[0053] The cationic compounds usable for the present invention are
preferably selected from cationic polymers. The cationic polymers
include polyalkylenepolyamines, for example, polyethyleneamines and
polypropylenepolyamines and derivatives thereof, acrylic polymers
having tertiary amino groups and/or quaternary ammonium groups, and
diacrylamines.
[0054] There is no limitation to the amount of the cationic
compound in the ink receiving layer. Usually, the cationic compound
is preferably used in an amount of 1 to 30 parts by weight, more
preferably 5 to 20 parts by weight, per 100 parts by weight of the
pigment.
[0055] The ink receiving layer of the present invention optionally
further contains at least one additive selected from dispersing
agents, thickening agents, defoaming agents, coloring agents,
antistatic agents and preservatives which are usually used for
coated paper sheets.
[0056] In a preferred embodiment of the present invention, to
enhance the water resistance and the light resistance of the ink
images formed on the ink receiving layer, the cationic compound is
preferably selected from the group consisting of polymers of
diallyldimethyl ammonium chloride, copolymers of diallyldimethyl
ammonium chloride with sulfur dioxide and copolymers of at least
one amine with at least one carboxylic acid (for example, a
copolymer of diallyl amine with maleic acid). By using the
above-mentioned types of cationic polymers, the light resistance of
the printed ink images can be significantly enhanced, substantially
without degrading the color-forming property of the ink and the
water resistance.
[0057] The reasons of the specific effects of the above-mentioned
cationic polymers are not clear at the present time. However, it is
assumed that the reactivity and stability of the basic segments of
the cationic polymers contribute to the above-mentioned specific
effects. The above-mentioned cationic polymers preferably have a
molecular weight (MW) of 50,000 or more, more preferably 100,000 to
400,000. When the molecular weight is too low, the resultant
cationic polymer may penetrate between the primary particles of the
solid components and may cause a reduction in the ink-absorbing
property of the resultant ink receiving layer. Also, when the
molecular weight is too high, the cationic polymer causes the
resultant coating liquid for the ink receiving layer to exhibit too
high a viscosity and to be difficult to coat. The above-mentioned
types of cationic polymers are preferably contained in an amount of
1 to 30 parts by weight, more preferably 5 to 20 parts by weight,
per 100 parts by weight of the pigment, in the ink receiving layer.
When the amount of the cationic polymer is too low, the resultant
ink images may exhibit an unsatisfactory water resistance-enhancing
effect. Also, the amount of the cationic polymer is too high, the
resultant ink receiving layer may exhibit unsatisfactory
ink-absorbing rate and ink absorption capacity.
[0058] To further enhance the water resistance, trade cationic
resins other than the above-mentioned cationic polymers may be
blended therewith. The cationic resins include
polyalkylene-polyamines, for example, polyethyleneamine and
polypropylenepolyamine, and the derivatives thereof; acrylic resins
having tertiary amino groups and quaternary ammonium groups;
diacrylamines; and other conventional cationic resins.
[0059] The ink receiving layer of the present invention may consist
of the specific ink receiving layer as mentioned above alone.
However, to further enhance the ink-absorbing property, the ink
receiving layer preferably comprises one or more additional ink
receiving layer in addition to the specific ink receiving layer
which will be referred to as a principal ink receiving layer
hereinafter. When two or more ink receiving layers are formed on
the support, at least one of them is the principal ink receiving
layer comprising the specific fine colloid pigment particles and
the ultraviolet ray absorber, and preferably is arranged to form an
outermost layer to which the ink jet printing is applied.
[0060] The additional ink receiving layer comprises a pigment which
may comprise at least one member selected from the above-mentioned
specific amorphous silica and/or alumina silicate and/or other
trade pigments. Also, the additional ink receiving layer may
contain the cationic compound.
[0061] There is no limitation to the amount of the ink receiving
layer. When the ink receiving layer consists of a single principal
ink receiving layer, usually the ink receiving layer is preferably
formed in an amount of 3 to 60 g/m.sup.2, more preferably 10 to 50
g/m.sup.2. When the ink receiving layer has a multiple layered
structure, the principal ink receiving layer containing the
ultraviolet ray absorber and preferably arranged to form an
outermost layer is preferably formed in an amount of 1 to 30
g/m.sup.2, more preferably 3 to 20 g/m.sup.2. When the amount of
the principal ink receiving layer is too low, the light resistance
effect of the resultant ink jet recording material may be
unsatisfactory. Also, when the principal ink receiving layer amount
is too high, the light resistance effect may be saturated.
[0062] The additional ink receiving layer which may contain no
ultraviolet ray absorber is preferably formed in a weight of 1 to
50 g/m.sup.2, more preferably 5 to 40 g/m.sup.2.
[0063] In the production of the ink jet recording material of the
present invention, preferably, at least one coating layer
corresponding to the outermost ink receiving layer is formed on a
casting surface; the resultant cast-coated layer is transferred and
bonded to a surface of the support or to a surface of at least one
additional ink receiving layer directly formed on the support; and
then the casting surface is removed from the transferred
cast-coated layer to form an outermost ink receiving layer. The
resultant outermost ink receiving layer exhibits an excellent
gloss.
[0064] The casting surface has a high smoothness and is formed by a
high smoothness surface of a flexible sheet or film, for example, a
plastic resin film such as regenerated cellulose film, polyethylene
film, polypropylene film, soft polyvinyl chloride film, hard
polyvinyl chloride film or polyester film; a paper sheet, for
example, a polyethylene layer-laminated paper sheet, a glossive
paper sheet, an impregnated paper sheet, or metallized paper sheet;
a metal foil; or a synthetic paper sheet; or a high smoothness
surface of a glass, metal or plastic drum or plate. In
consideration of production process and releasing aptitude of the
resultant ink receiving layer from the casting surface, the polymer
film, for example, polyethylene, polypropylene or polyester film,
and the metallic drum having a high smoothness surface are
preferably employed.
[0065] To impart a high gloss to the ink receiving layer, the
casting surface preferably has a high smoothness. For this purpose,
the casting surface preferably has a surface roughness Ra (in
accordance with Japanese Industrial Standard (JIS) B-0601) of 0.5
.mu.m or less, more preferably 0.05 .mu.m or less. However, the
casting surface may be a semi-gloss surface or a mat surface formed
by controlling the surface roughness.
[0066] The casting surface may be a non-coated surface. To arrange
that the adhesive force between the ink-receiving layer and the
substrate or another ink receiving layer is higher than that
between the casting surface and the ink receiving layer formed on
the casting surface, the casting surface may be coated with a
releasing compound, for example, a silicone compound or a
fluorine-containing resin.
[0067] There is no limitation to the bonding method between the
cast-coated layer formed on the casting surface and the support or
the additional ink receiving layer directly formed on the support,
as long as they can be firmly bonded. Usually, the bonding can be
carried out only by applying a pressure, for example, 5 to 150
kg/cm and by heating, for example, to a temperature of 30 to
100.degree. C. However, preferably, a water vapor or water is
applied to the cast-coated layer on the casting surface and/or to
the surface of the support or the additional ink receiving layer to
an extent such that the water vapor or water-applied layers have a
moisture content of 50 to 350% based on the bone dry weight of the
layers, and the water vapor or water-applied layers are brought
into contact with each other and pressed by, for example, a
calender. Also, the support may be coated with an intermediate
bonding or adhesive layer. The adhesive layer may be
pressure-sensitive. More advantageously, the intermediate layer is
utilized as an additional ink receiving layer. Namely, the support
is coated with the additional ink receiving layer and brought, in
wetted condition, into contact with the cast-coated layer, to bond
them with each other, and then the bonded layers are dried.
[0068] The ink receiving layers and the intermediate layer of the
present invention can be formed by using a conventional coating
device, for example, die coater blade coater, air knife coater,
roll coater, bar coater, gravure coater, rod blade coater, lip
coater or curtain coater.
[0069] The ink applicable to the ink jet recording material of the
present invention comprises, as indispensable components, a
coloring material for forming colored images and a liquid medium
for dissolving or dispersing the coloring material and, as an
optional component, an additive comprising at least one member
selected from dispersing agents, surfactants, viscosity-modifiers,
specific resistance modifiers, pH-modified, mildewproofing agents,
and dissolution or dispersion-stabilizers for the coloring
materials.
[0070] The coloring material for the ink is not limited to specific
dyes or pigments and can be selected from conventional direct dyes,
acid dyes, basic dyes, reactive dyes, food dyes, disperse dyes, oil
dyes and coloring pigments. The content of the coloring material in
the ink is variable depending on the type of the liquid medium and
the derived properties for the ink. In the ink applicable to the
ink jet recording material of the present invention, the content of
the coloring material is preferably 0.1 to 2% by weight which is
similar to that of conventional inks.
[0071] The liquid medium of the ink applicable to the ink jet
recording material of the present invention preferably comprises at
least one member selected from water, and water-soluble organic
solvents, for example, alkyl alcohols having 1 to 4 carbon atoms,
for example, methyl alcohols, ethyl alcohol, n-propyl alcohol,
isopropyl alcohol, n-butyl alcohol and isobutyl alcohol; ketones,
for example, acetone; ketone alcohols, for example, diacetone
alcohol; polyalkylene glycols, for example, polyethylene glycol and
polypropylene glycol; alkylene glycols having 2 to 6 alkylene
groups, for example, ethylene glycol, propylene glycol, butylene
glycol, triethylene glycol, thio-diglycol, hexylene glycol and
diethylene glycol; amides, for example, dimethylformamides; ethers,
for example, tetrahydrofuran; and lower alkylethers of polyhydric
alcohols, for example, glycerol, ethyleneglycolmethyl ether,
diethyleneglycol methyl (or ethyl) ether, triethyleneglycol
monomethylether.
EXAMPLES
[0072] The present invention will be further explained by the
following examples which are merely representative and do not
restrict the scope of the present invention in any way.
[0073] In the examples and comparative examples the term "part" and
"%" are--part by dry solid weight--and--% by dry solid weight,
respectively, unless specifically shown otherwise.
[0074] Note: The primary particle size of the pigment particles
does not change by pulverize-dispersing.
[0075] In Examples I-1 to I-11 and Comparative Examples I-1 to 7,
the following pigment particle sols were prepared and employed.
[0076] (1) Preparation of pigment sols
[0077] Silica sol AI
[0078] Synthetic amorphous silica particles (trademark: NIPSIL
HD-2, made by NIPPON SILICA INDUSTRIAL CO., LTD.) having an average
secondary particle size of 3 .mu.m and an average primary particle
size of 11 nm were pulverize-dispersed by a sand grinder and then
further pulverize-dispersed by a pressure-type homogenizer. The
pulverize-dispersing procedures by the sand grinder and the
pressure-type homogenizer were alternately repeated until the
average secondary particle size of the amorphous silica particles
reached 60 nm, to prepare an amorphous silica sol AI having a dry
solid content of 7%.
[0079] Silica sol BI
[0080] Synthetic amorphous silica particles (trademark: NIPSIL LP,
made by NIPPON SILICA INDUSTRIAL CO., LTD.) having an average
secondary particle size of 3 .mu.m and an average primary particle
size of 16 nm were pulverize-dispersed by a sand grinder and then
further pulverize-dispersed by a pressure-type homogenizer. The
pulverize-dispersing procedures by the sand grinder and the
pressure-type homogenizer were alternately repeated until the
average secondary particle size of the amorphous silica particles
reached 100 nm, to prepare an amorphous silica sol BI having a dry
solid content of 9%.
[0081] Silica sol CI
[0082] Synthetic amorphous silica particles (trademark: NIPSIL
E-1011, made by NIPPON SILICA INDUSTRIAL CO., LTD.) having an
average secondary particle size of 1.5 .mu.m and an average primary
particle size of 24 nm were pulverize-dispersed by a sand grinder
and then further pulverize-dispersed by a pressure-type
homogenizer. The pulverize-dispersing procedures by the sand
grinder and the pressure-type homogenizer were alternately repeated
until the average secondary particle size of the amorphous silica
particles reached 200 nm, to prepare an amorphous silica sol CI
having a dry solid content of 12%.
[0083] Silica sol DI
[0084] Synthetic amorphous silica particles (trademark: NIPSIL
E-1011, made by NIPPON SILICA INDUSTRIAL CO., LTD.) having an
average secondary particle size of 1.5 .mu.m and an average primary
particle size of 24 nm were pulverize-dispersed by a sand grinder
and then further pulverize-dispersed by a pressure-type
homogenizer. The pulverize-dispersing procedures by the sand
grinder and the pressure-type homogenizer were alternately repeated
until the average secondary particle size of the amorphous silica
particles reached 350 nm, to prepare an amorphous silica sol DI
having a dry solid content of 12%.
[0085] Alumina silicate sol I
[0086] Isopropyl alcohol in an amount of 10 g was placed in a glass
reactor having a capacity of 2 liters and equipped with a stirrer,
having a diameter of 3 cm and comprising three stirring rings, and
a thermometer, and heated to a liquid temperature of 60.degree. C.
by using an oil bath heater. While the stirrer was rotated at a
rotation speed of 100 rpm to agitate the liquid in the reactor, 5 g
of aluminum isopropoxide (made by WAKO PURE CHEMICAL INDUSTRIES,
LTD.) were added, and then 1 g of an acid catalyst consisting of
acetic acid (made by WAKO PURE CHEMICAL INDUSTRIES, LTD.) was
further added to the isopropyl alcohol. The reaction mixture was
refluxed, while maintaining the refluxing temperature constant, for
24 hours.
[0087] Separately, in a glass reactor was charged 100 g of
ion-exchanged water and the charge was heated to a temperature
60.degree. C., and 1.8 g ethyl orthosilicate (made by WAKO PURE
CHEMICAL INDUSTRIES, LTD.) was added and then 1 g of an acid
catalyst consisting of nitric acid (made by WAKO PURE CHEMICAL
INDUSTRIES, LTD.) was added to the ion-exchanged water. The mixture
was refluxed for 24 hours while maintaining the refluxing
temperature constant.
[0088] The ethyl orthosilicate-nitric acid-ion-exchanged water
solution was mixed with the aluminum isopropoxide-acetic
acid-ispropyl alcohol solution, and the mixture was stirred and
heated at a temperature of 60.degree. C. for 6 hours to prepare
fine particles of alumina silicate. Then, the reaction mixture was
concentrated by evaporation at a temperature of 60.degree. C., to
provide agglomerated particles of alumina silicate. In the
resultant particles, the composition molar ratio of alumina to
silica was 3:2. The agglomerated particles were mixed with water
and subjected to repeated pulverizing and dispersing procedures
with a sand grinder and then with a pressure-type homogenizer until
the average secondary particles size reached 100 nm, to provide a
10% aqueous alumina silicate sol I.
[0089] In the alumina silicate sol I, the alumina silicate
particles had an average primary particle size of 10 nm.
Example I-1
[0090] A 7% aqueous coating liquid was prepared by mixing 100 parts
of the silica sol AI with 3 parts of an ultraviolet ray absorber
consisting of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole
(trademark: SEESORB 701, made by SHIRAISHI CALCIUM CO.) and 35
parts of polyvinyl alcohol (trademark: PVA-135H, made by KURARAY
CO., LTD.) having a polymerization degree of 3500 and a
saponification degree of 99% or more.
[0091] A surface of a trade coated paper sheet (trademark: OK COAT,
made by OJI PAPER CO., LTD.) having a basis weight of 127.9
g/m.sup.2 was coated with the aqueous coating liquid and dried to
form an ink receiving layer with a dry weight of 20 g/m.sup.2.
[0092] An ink jet recording material of the present invention was
obtained.
Example I-2
[0093] An 8% aqueous coating liquid was prepared by mixing 100
parts of the silica sol AI with 15 parts of a cationic resin
consisting of a copolymer of diallyldimethyl ammonium chloride with
acrylamide (trademark: PAS-J-81, made by NITTO BOSEKI CO., LTD.);
coagulating and thickening the mixture; pulverize-dispersing the
mixture by a pressure-type homogenizer to an extent such that the
average particle size of the mixture reached 100 nm; and then
mixing the resultant cationic resin-containing silica sol with 3
parts of an ultraviolet ray absorber consisting of
2-(2'-hydroxy-5'-methylphenyl)benzotriazole (trademark: SEESORB
701, made by SHIRAISHI CALCIUM CO.) and 20 parts of polyvinyl
alcohol (trademark: PVA-135H, made by KURARAY CO., LTD.) having a
polymerization degree of 3500 and a saponification degree of 99% or
more.
[0094] A surface of a trade coated paper sheet (trademark: OK COAT,
made by OJI PAPER CO., LTD.) having a basis weight of 127.9
g/m.sup.2 was coated with the aqueous coating liquid and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0095] An ink jet recording material of the present invention was
obtained.
Example I-3
[0096] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that as
an ultraviolet ray absorber,
2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)--
5'-methylphenyl]benzotriazole (trademark: SEESORB 706, made by
SHIRAISHI CALCIUM CO.) was employed.
Example I-4
[0097] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that as
an ultraviolet ray absorber, 2-hydroxy-4-octoxybenzophenone
(trademark: SEESORB 102, made by SHIRAISHI CALCIUM CO.) was
employed.
Example I-5
[0098] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that as
an ultraviolet ray absorber, p-octylphenylsalicylate (trademark:
OPS, made by YASHIRO SEIYAKU K. K.) was employed.
Example I-6
[0099] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that the
silica sol AI was replaced by the silica sol BI.
Example I-7
[0100] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that the
silica sol AI was replaced by the silica sol CI.
Example I-8
[0101] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that the
silica sol AI was replaced by the alumina silica sol I.
Example I-9
[0102] An 8% aqueous coating liquid was prepared by mixing 100
parts of the silica sol AI with 15 parts of titanium dioxide
(trademark: ST-440, made by TITAN KOGYO K. K.) having a particle
size of 30 to 50 nm, as an ultraviolet ray absorber, 15 parts of a
cationic resin consisting of a copolymer of diallyldimethyl
ammonium chloride with acrylamide (trademark: PAS-J-81, made by
NITTO BOSEKI CO., LTD.); coagulating and thickening the mixture;
pulverize-dispersing the mixture by a pressure-type homogenizer to
an extent such that the average particle size of the mixture
reached 150 nm; and then mixing the resultant sol 20 parts of the
same polyvinyl alcohol as mentioned in Example I-1.
[0103] A surface of the same trade coated paper sheet as in Example
I-1 was coated with the aqueous coating liquid and dried to form an
ink receiving layer having a dry weight of 20 g/m.sup.2.
[0104] An ink jet recording material of the present invention was
obtained.
Example I-10
[0105] An 8% aqueous coating liquid was prepared by mixing 100
parts of the silica sol AI with 15 parts of a cationic resin
consisting of a copolymer of diallyldimethyl ammonium chloride with
acrylamide (trademark: PAS-J-81, made by NITTO BOSEKI CO., LTD.);
coagulating and thickening the mixture; pulverize-dispersing the
mixture by a pressure-type homogenizer to an extent such that the
average particle size of the mixture reached 100 nm; and then
mixing the resultant cationic resin-containing silica sol with 10
parts of an ultraviolet ray absorber consisting of cerium oxide
having a particle size of 8 nm (trademark: NEEDRAL U-15, made by
TAKI CHEMICAL CO., LTD.) and 20 parts of the same polyvinyl alcohol
as an Example I-1.
[0106] A surface of the same trade coated paper sheet as in Example
I-1 was coated with the aqueous coating liquid and dried to form an
ink receiving layer having a dry weight of 20 g/m.sup.2.
[0107] An ink jet recording material of the present invention was
obtained.
Example I-11
[0108] The same aqueous coating liquid as in Example I-2 was coated
on a surface of a casting film consisting of a PET film having a
thickness of 50 .mu.m (trademark: LUMILER T, made by TORAY
INDUSTRIES INC.) and dried to form a cast-coated layer
corresponding to an outermost ink receiving layer and having a dry
weight of 15 g/m.sup.2.
[0109] A 10% aqueous coating liquid for an additional ink receiving
layer was prepared by mixing 100 parts of the silica sol CI with 25
parts of the same polyvinyl alcohol as in Example I-1. The
resultant coating liquid was coated on a surface of a trade
woodfree paper sheet having a basis weight of 127.9 g/m.sup.2 to
form an additional ink receiving layer having a weight
corresponding to a dry weight of 10 g/m.sup.2.
[0110] The additional ink receiving layer on the support sheet was
superposed on and bonded to the cast-coated layer on the casting
PET film, dried, and then the PET film was removed from the
cast-coated layer.
[0111] An ink jet recording material of the present invention was
obtained.
Comparative Example I-1
[0112] An aqueous coating liquid having a total solid content of 7%
was prepared by mixing 100 parts of the silica sol AI with 35 parts
of polyvinyl alcohol (trademark: PVA-135H, made by KURARAY CO.,
LTD.) having a polymerization degree of 3500 and a saponification
degree of 99% or more.
[0113] The aqueous coating liquid was coated on a surface of a
trade coated paper sheet (trademark: OK COAT, made by OJI PAPER
CO., LTD.) having a basis weight of 127.9 g/m.sup.2 and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0114] A comparative ink jet recording material was obtained.
Comparative Example I-2
[0115] An aqueous coating liquid having a total solid content of
10% was prepared by mixing 100 parts of the silica sol DI with 3
parts of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (ultraviolet
ray absorber, trademark: SEESORB-701, made by SHIRAISHI CALCIUM
CO., LTD.) and 35 parts of polyvinyl alcohol (trademark: PVA-135H,
made by KURARAY CO., LTD.) having a polymerization degree of 3500
and a saponification degree of 99% or more.
[0116] The aqueous coating liquid was coated on a surface of a
trade coated paper sheet (trademark: OK COAT, made by OJI PAPER
CO., LTD.) having a basis weight of 127.9 g/m.sup.2 and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0117] A comparative ink jet recording material was obtained.
Comparative Example I-3
[0118] An aqueous coating liquid having a total solid content of
10% was prepared by mixing 100 parts of amorphous silica
(trademark: FINESIL 45, made by TOKUYAMA CORP.) having an average
particle size of 4.5 .mu.m with 30 parts of polyvinyl alcohol
(trademark: R-1130, made by KURARAY CO., LTD.).
[0119] The aqueous coating liquid was coated on a surface of a
trade coated paper sheet (trademark: OK COAT, made by OJI PAPER
CO., LTD.) having a basis weight of 127.9 g/m.sup.2 and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0120] A comparative ink jet recording material was obtained.
Comparative Example I-4
[0121] An aqueous coating liquid having a total solid content of
10% was prepared by mixing 100 parts of amorphous silica
(trademark: FINESIL 45, made by TOKUYAMA CORP.) having an average
particle size of 4.5 .mu.m with 3 parts of an ultraviolet ray
absorber consisting of 2-[2'-hydroxy-5'-methylphenyl)benzotriazole
(trademark: SEESORB-701, made by SHIRAISHI CALCIUM CO.) and 30
parts of polyvinyl alcohol (trademark: R-1130, made by KURARAY CO.,
LTD.).
[0122] The aqueous coating liquid was coated on a surface of a
trade coated paper sheet (trademark: OK COAT, made by OJI PAPER
CO., LTD.) having a basis weight of 127.9 g/m.sup.2 and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0123] A comparative ink jet recording material was obtained.
Comparative Example I-5
[0124] A trade mat-type ink jet recording paper sheet (trademark:
MJA4SP1, made by EPSON CORP.) was subjected to the tests which will
be illustrated later.
Comparative Example I-6
[0125] A trade gloss paper-type ink jet recording paper sheet
(trademark: GP-101, made by CANON CORP.) was subjected to the tests
which will be illustrated later.
Comparative Example I-7
[0126] A trade ink jet recording paper sheet (trademark: PHOTO JET
PAPER-GLOSS SHEET KJPA4-GH20, made by KONIKA CO.) was subjected to
the tests which will be illustrated later.
Example I-12
[0127] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that 3
parts of the ultraviolet ray-absorber (trademark: SEESORB 701, made
by SHIRAISHI CALCIUM CO.) were replaced by 10 parts of the
ultraviolet ray-absorbing sol prepared by the following
procedures.
[0128] Preparation of ultraviolet ray-absorbing sol
[0129] A cerium oxide sol (trademark: W-10, made by TAKI CHEMICAL
CO., LTD., anion) containing no agglomerated particles and having a
primary particle size of about 5 nm and in an amount of 100 parts
was mixed with 100 parts of a cerium oxide sol (trademark: NEEDRAL
U-15, made by TAKI CHEMICAL CO., LTD., cation) containing no
agglomerated particles and having a primary particle size of about
5 nm, to form a coagulation. The coagulation was
pulverize-dispersed by a sand grinder, and further
pulverize-dispersed with a pressure-type homogenizer. The
pulverize-dispersing operation was repeated by alternately using
the sand grinder and the pressure-type homogenizer until the
average secondary particle size reached 0.4 .mu.m. A 10% cerium
oxide dispersion was obtained. The pulverize-dispersing operations
did not result in change in the primary particle size.
Example I-13
[0130] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that the
cationic resin (trademark: PAS-J-81) used in Example I-2 was
replaced by a diallyl-dimethyl ammonium chloride-sulfur dioxide
copolymer (trademark: PAS-A-5, made by NITTO BOSEKI CO., LTD.).
Example I-14
[0131] An ink jet recording material of the present invention was
produced by the same procedures as in Example I-2, except that the
cationic resin (trademark: PAS-J-81) used in Example I-2 was
replaced by a diallylamine-maleic acid copolymer (trademark:
PAS-410, made by NITTO BOSEKI CO., LTD.) of the following formula:
1
[0132] wherein a molar ratio m:n is 1:1.
[0133] TESTS
[0134] The ink jet recording materials prepared in the
above-mentioned examples and comparative examples were subjected to
testing of water resistance of coated layer, water resistance of
printed ink images, ink-absorbing property and gloss, color density
and light resistance of printed ink images, by the testing methods
shown below.
[0135] Note: (1) The printer used for the testing was a Printer
PM-700C (trademark) made by EPSON CORP.
[0136] (2) In the testings for the gloss, color density and light
resistance of printed ink images, a solid print prepared by the
above-mentioned printer was used.
[0137] (A) Water resistance of coated layer
[0138] A sample of an ink jet recording material was immersed in
water at a temperature of 20.degree. C. for one hour, then the
recording surface of the recording material in wetted condition was
rubbed by finger. The result was evaluated as follows.
1 Class Rubbing result 3 No damage occurs on the coated layer. 2 A
portion of the coated layer is removed. 1 The coated layer was
completely removed.
[0139] (B) Water resistance of printed ink images
[0140] An ink jet recording material was printed and then left to
stand under conditions of a temperature of 23.degree. C., and a
relative humidity of 65% RH, for 24 hours. Then, a water drop was
placed on the printed ink images for one minute, and removed by
wiping. The result of water-dropping was evaluated as follows.
2 Class Water dropping result 3 Substantially no removal of ink
images is found. 2 A portion of ink images is removed. 1 The ink
images are completely removed.
[0141] (C) Ink absorbing property
[0142] An ink jet recording material was printed with yellow,
magenta and cyan-colored ink images superposed on each other to
form black-colored images. Every five seconds after the completion
of the printing operations, a woodfree paper sheet was
press-contacted with the black-colored images to test whether the
ink transfer to the paper sheet. This testing was repeated until no
transfer of ink was confirmed. The time between the completion of
the printing operations and the confirmation of no transfer of the
black-colored ink images, namely an ink image-drying time was
measured. The test result was evaluated as follows.
3 Class Ink image-drying time 3 15 seconds or less 2 More than 15
seconds and less than 60 seconds 1 60 second or more
[0143] (D) Gloss of printed ink images
[0144] Black, yellow, cyan and magenta-colored ink images printed
on an ink jet recording material were observed by the naked eye at
an inclined angle, and the glosses of the images were evaluated as
follows.
4 Class Gloss 4 The ink image gloss is similar to that on a silver
salt type color photograph. 3 The ink image gloss is slightly lower
than that on the silver salt type color photograph and higher than
that on conventional coated or art paper sheet. 2 The ink image
gloss is similar to that on conventional coated or art paper sheet.
1 The ink image gloss is very low.
[0145] (E) Color density of printed ink images
[0146] A ink jet recording sheet was solid printed with a
black-colored ink, and the colored density of the solid printed
images was measured by a Macbeth refraction color density meter
(RD-920). The measurement was repeated five times, and the
measurement results were averaged. The averaged data were shown in
Table 1.
[0147] (F) Light resistance
[0148] The printed sample was subjected to a continuous fading test
using a Xenon lamp type FADE-OMETER (made by ATLAS ELECTRIC DEVICES
CO., Model: CI 35F) at a temperature of 63.degree. C. at a relative
humidity of 50% for 72 hours in accordance with JIS B 7754 (1991).
The color densities of the printed images before and after the
fading test were measured. The light resistance of the printed
images were represented by a fading rate calculated in accordance
with the following equation. 1 Fading rate ( % ) = D 0 - D 1 D 0
.times. 100
[0149] wherein D.sub.0 represents a color density of the unfaded
colored images, D.sub.1 represents a color density of the faded
colored images.
[0150] Note, the higher the fading rate, the lower the light
resistance.
[0151] The test results are shown in Table 1.
5 TABLE 1 Item Water- Water- Color Fading rate (%).sup.(*)
resistance resistance Ink- Gloss density Black Magenta Cyan Yellow
of coated of ink absorbing of of ink colored colored colored
colored Example No. layer images property print images images
images images images Example I-1 3 2 3 3 2.56 3.5 15.5 0 6.5 I-2 3
3 3 3 2.53 5.5 20.4 0.1 7.9 I-3 3 3 3 3 2.52 6.1 21.2 0 8.7 I-4 3 3
3 3 2.50 11.5 27.1 2.7 10.0 I-5 3 3 3 3 2.47 13.1 28.7 4.1 11.1 I-6
3 3 3 3 2.29 5.4 19.6 0 7.7 I-7 3 3 3 3 2.04 5.5 19.7 0.2 7.8 I-8 3
3 3 3 2.42 5.4 18.5 0 7.5 I-9 3 3 3 3 2.41 7.1 21.5 0.3 8.9 I-10 3
3 3 3 2.50 4.5 17.6 0 8.1 I-11 3 3 3 4 2.58 5.4 19.9 0.1 7.8
Comparative I-1 3 2 3 3 2.55 22.5 48.4 11.5 24.6 Example I-2 3 2 3
3 1.68 5.3 19.2 0 8.0 I-3 2 2 3 1 1.65 26.1 50.1 10.9 26.8 I-4 2 2
3 1 1.62 6.7 22.1 1.3 9.1 I-5 2 3 3 1 1.85 25.0 47.8 6.7 23.8 I-6 2
3 3 2 2.05 31.8 51.3 11.5 30.2 I-7 1 1 1 2 2.61 35.7 55.0 12.2 22.5
Example I-12 3 3 3 3 2.50 5.1 16.8 0 8.0 I-13 3 3 3 3 2.49 4.5 15.7
0.2 7.1 I-14 3 3 3 3 2.51 4.5 16.2 0.2 7.0 Note: The higher the
fading rate, the lower the light resistance.
[0152] Table 1 clearly shows that the ink jet recording materials
in accordance with the present invention exhibited excellent water
resistance, ink absorbing property, gloss and color density of the
printed ink images and a superior light resistance.
[0153] In Examples II-1 to II-8 and Comparative Examples II-1 to
II-6, the following pigment particle sols were prepared and
employed.
[0154] (1) Preparation of pigment sols
[0155] Silica sol AII
[0156] Synthetic amorphous silica particles (trademark: NIPSIL
HD-2, made by NIPPON SILICA INDUSTRIAL CO., LTD.) having an average
secondary particle size of 3 .mu.m and an average primary particle
size of 11 nm were pulverize-dispersed by a sand grinder and then
further pulverize-dispersed by a pressure-type homogenizer. The
pulverize-dispersing procedures by the sand grinder and the
pressure-type homogenizer were alternately repeated until the
average secondary particle size of the amorphous silica particles
reached 75 nm, to prepare an amorphous silica sol AII having a dry
solid content of 7%.
[0157] Silica sol BII
[0158] Synthetic amorphous silica particles (trademark: NIPSIL
E-1011, made by NIPPON SILICA INDUSTRIAL CO., LTD.) having an
average secondary particle size of 1.5 .mu.m and an average primary
particle size of 24 nm were pulverize-dispersed by a sand grinder
and then further pulverize-dispersed by a pressure-type
homogenizer. The pulverize-dispersing procedures by the sand
grinder and the pressure-type homogenizer were alternately repeated
until the average secondary particle size of the amorphous silica
particles reached 200 nm, to prepare an amorphous silica sol BII
having a dry solid content of 12%.
[0159] Silica sol CII
[0160] Synthetic amorphous silica particles (trademark: NIPSIL
E-1011, made by NIPPON SILICA INDUSTRIAL CO., LTD.) having an
average secondary particle size of 1.5 .mu.m and an average primary
particle size of 24 nm were pulverize-dispersed by a sand grinder
and then further pulverize-dispersed by a pressure-type
homogenizer. The pulverize-dispersing procedures by the sand
grinder and the pressure-type homogenizer were alternately repeated
until the average secondary particle size of the amorphous silica
particles reached 350 nm, to prepare an amorphous silica sol CII
having a dry solid content of 12%.
[0161] Alumina silicate sol II
[0162] Alumina silicate sol II was prepared by the same procedures
as the alumina silicate sol I.
Example II-1
[0163] An aqueous coating liquid having a total solid content of 7%
was prepared by mixing 100 parts of the silica sol AII with 3 parts
of an ultraviolet ray absorber consisting
2-(2'-hydroxy-5'-methylphenyl)benzotr- iazole (trademark: SEESORB
701, made by SHIRAISHI CALCIUM CO.), 3 parts of an antioxidant
consisting of 2,2'-methylene-bis(4-ethyl-6-tert-butylpheno- l)
(trademark: ANTAGE W-500, made by KAWAGUCHI CHEMICAL CO.) and 35
parts of polyvinyl alcohol (trademark: PVA-135H, made by KURARAY
CO., LTD.) having a polymerization degree of 3500 and a
saponification degree of 99% or more.
[0164] A surface of a trade coated paper sheet (trademark: OK COAT,
made by OJI PAPER CO., LTD.) having a basis weight of 127.9
g/m.sup.2 was coated with the aqueous coating liquid and dried to
form an ink receiving layer with a dry weight of 20 g/m.sup.2.
[0165] An ink jet recording material of the present invention was
obtained.
Example II-2
[0166] An aqueous coating liquid having a total solid content of 8%
was prepared by mixing 100 parts of the silica sol AII with 15
parts of a cationic resin consisting of a copolymer of
diallyldimethyl ammonium chloride with acrylamide (trademark:
PAS-J-81, made by NITTO BOSEKI CO., LTD.); coagulating and
thickening the mixture; pulverize-dispersing the mixture by a
pressure-type homogenizer to an extent such that the average
particle size of the mixture reached 100 nm; and then mixing the
resultant cationic resin-containing silica sol with 3 parts of an
ultraviolet ray absorber consisting of
2-(2'-hydroxy-5'-methylphenyl)benz- otriazole (trademark: SEESORB
701, made by SHIRAISHI CALCIUM CO.), 3 parts of an antioxidant
consisting of 2,2'-methylene-bis(4-ethyl-6-tert-butylph- enol)
(trademark: ANTAGE W-500, made by KAWAGUCHI CHEMICAL CO.) and 20
parts of polyvinyl alcohol (trademark: PVA-135H, made by KURARAY
CO., LTD.) having a polymerization degree of 3500 and a
saponification degree of 99% or more.
[0167] A surface of a trade coated paper sheet (trademark: OK COAT,
made by OJI PAPER CO., LTD.) having a basis weight of 127.9
g/m.sup.2 was coated with the aqueous coating liquid and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0168] An ink jet recording material of the present invention was
obtained.
Example II-3
[0169] An ink jet recording material of the present invention was
produced by the same procedures as in Example II-2, except that as
an antioxidant, 4,4'-thio-bis(3-methyl-6-tert-butylphenol)
(trademark: SUMIRIZER WX, made by SUMITOMO CHEMICAL CO., LTD.) was
employed.
Example II-4
[0170] An ink jet recording material of the present invention was
produced by the same procedures as in Example II-2, except that as
an antioxidant,
1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane (trademark:
ARKLS DH-43, made by ASAHI DENKA KOGYO K. K.) was employed.
Example II-5
[0171] An ink jet recording material of the present invention was
produced by the same procedures as in Example II-2, except that as
an antioxidant, dilauryl 3,3-thio-dipropionate (trademark:
SUMIRIZER-TPL, made by SUMITOMO CHEMICAL CO., LTD.) was
employed.
Example II-6
[0172] An ink jet recording material of the present invention was
produced by the same procedures as in Example II-2, except that the
silica sol AII was replaced by the silica sol BII.
Example II-7
[0173] An ink jet recording material of the present invention was
produced by the same procedures as in Example II-2, except that the
silica sol AII was replaced by the alumina silicate sol II.
Example II-8
[0174] The same aqueous coating liquid as in Example II-2 was
coated on a surface of a casting film consisting of a PET film
(trademark: LUMILAR T, made by TORAY INDUSTRIES INC.) having a
thickness of 50 .mu.m and a surface roughness Ra of 0.02 .mu.m, and
dried to form a cast-coated layer corresponding to an outermost ink
receiving layer and having a dry weight of 15 g/m.sup.2.
[0175] A 10% aqueous coating liquid for an additional ink receiving
layer was prepared by mixing 100 parts of the silica sol BII with
25 parts of polyvinyl alcohol (trademark: PVA-135H, made by KURARAY
CO., LTD.) having a polymerization degree of 3500 and a
saponification degree of 99% or more. The resultant coating liquid
was coated on a surface of a trade woodfree paper sheet having a
basis weight of 127.9 g/m.sup.2 to form an additional ink receiving
layer having a weight corresponding to a dry weight of 10
g/m.sup.2.
[0176] The additional ink receiving layer on the support sheet was
superposed on and bonded to the cast-coated layer on the casting
PET film, dried, and then the PET film was removed from the
cast-coated layer.
[0177] An ink jet recording material of the present invention was
obtained.
Comparative Example II-1
[0178] An aqueous coating liquid having a total solid content of 7%
was prepared by mixing 100 parts of the silica sol AII with 35
parts of polyvinyl alcohol (trademark: PVA-135H, made by KURARAY
CO., LTD.) having a polymerization degree of 3500 and a
saponification degree of 99% or more.
[0179] The aqueous coating liquid was coated on a surface of a
trade coated paper sheet (trademark: OK COAT, made by OJI PAPER
CO., LTD.) having a basis weight of 127.9 g/m.sup.2 and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0180] A comparative ink jet recording material was obtained.
Comparative Example II-2
[0181] An aqueous coating liquid having a total solid content of
10% was prepared by mixing 100 parts of the silica sol CII with 3
parts of an ultraviolet ray absorber consisting of
2-(2'-hydroxy-5'-methylphenyl)benz- otiazole (trademark: SEESORB
701, made by SHIRAISHI CALCIUM CO.), 3 parts of an antioxidant
consisting of 2,2'-methylene-bis(4-ethyl-6-tert-butylph- enol)
(trademark: ANTAGE W-500, made by KAWAGUCHI CHEMICAL CO.) and 35
parts of polyvinyl alcohol (trademark: PVA-135H, made by KURARAY
CO., LTD.) having a polymerization degree of 3500 and a
saponification degree of 99% or more.
[0182] The aqueous coating liquid was coated on a surface of a
trade coated paper sheet (trademark: OK COAT, made by OJI PAPER
CO., LTD.) having a basis weight of 127.9 g/m.sup.2 and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0183] A comparative ink jet recording material was obtained.
Comparative Example II-3
[0184] An aqueous coating liquid having a total solid content of
10% was prepared by mixing 100 parts of amorphous silica
(trademark: FINESIL 45, made by TOKUYAMA CORP.) having an average
particle size of 4.5 .mu.m with 3 parts of an ultraviolet ray
absorber consisting of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole
(trademark: SEESORB 701, made by SHIRAISHI CALCIUM CO.), 3 parts of
an antioxidant consisting of
2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) (trademark: ANTAGE
W-500, made by KAWAGUCHI CHEMICAL CO.) and 30 parts of
silyl-modified polyvinyl alcohol (trademark: R-1130, made by
KURARAY CO., LTD.).
[0185] The aqueous coating liquid was coated on a surface of a
trade coated paper sheet (trademark: OK COAT, made by OJI PAPER
CO., LTD.) having a basis weight of 127.9 g/m.sup.2 and dried to
form an ink receiving layer having a dry weight of 20
g/m.sup.2.
[0186] A comparative ink jet recording material was obtained.
Comparative Example II-4
[0187] A trade non-gloss-type ink jet recording paper sheet, namely
a mat paper sheet (trademark: MJA4SP1, made by EPSON CORP.) was
subjected to the tests which will be described later.
Comparative Example II-5
[0188] A trade gloss ink jet recording paper sheet (trademark:
GP-101, made by CANON CORP.) was subjected to the tests which will
be described later.
Comparative Example II-6
[0189] A trade gloss ink jet recording paper sheet (trademark:
PHOTO JET PAPER-GLOSS SHEET KJPA 4-GH20, made by KONIKA CO.) was
subjected to the tests which will be described below.
[0190] TESTS
[0191] The ink jet recording materials prepared in the
above-mentioned examples and comparative examples were subjected to
testing of water resistance of coated layer, water resistance of
printed ink images, ink-absorbing property and gloss, color density
and light resistance of printed ink images, by the testing methods
shown below.
[0192] Note: (1) The printer used for the testing was a Printer
PM-700C (trademark) made by EPSON CORP.
[0193] (2) In the testings for the gloss, color density and light
resistance of printed ink images, a solid print prepared by the
above-mentioned printer was used.
[0194] (A) Water resistance of coated layer
[0195] A sample of an ink jet recording material was immersed in
water at a temperature of 20.degree. C. for one hour, then the
recording surface of the recording material in wetted condition was
rubbed by finger. The result was evaluated as follows.
6 Class Rubbing result 3 No damage occurs on the coated layer. 2 A
portion of the coated layer is removed. 1 The coated layer was
completely removed.
[0196] (B) Water resistance of printed ink images
[0197] An ink jet recording material was printed and then left to
stand under conditions of a temperature of 23.degree. C., and a
relative humidity of 65% RH, for 24 hours. Then, a water drop was
placed on the printed ink images for one minute, and removed by
wiping. The result of water-dropping was evaluated as follows.
7 Class Water dropping result 3 Substantially no removal of ink
images is found. 2 The ink images are partially removed. 1 The ink
images are completely removed.
[0198] (C) Ink absorbing property
[0199] An ink jet recording material was printed with yellow,
magenta and cyan-colored ink images superposed on each other to
form black-colored images. Every five seconds after the completion
of the printing operations, a woodfree paper sheet was
press-contacted with the black-colored images to test whether the
ink transfer to the paper sheet. This testing was repeated until no
transfer of ink was confirmed. The time between the completion of
the printing operations and the confirmation of no transfer of the
black-colored ink images, namely an ink image-drying time was
measured. The test result was evaluated as follows.
8 Class Ink image-drying time 3 15 seconds or less 2 More than 15
seconds and less than 60 seconds
[0200] 1 60 second or more
[0201] (D) Gloss of printed ink images
[0202] Black, yellow, cyan and magenta-colored ink images printed
on an ink jet recording material were observed by the naked eye at
an inclined angle, and the glosses of the images were evaluated as
follows.
9 Class Gloss 4 The ink image gloss is similar to that on a silver
salt type color photograph. 3 The ink image gloss is slightly lower
than that on the silver salt type color photograph and higher than
that on conventional coated or art paper sheet. 2 The ink image
gloss is similar to that on conventional coated or art paper sheet.
1 The ink image gloss is very low.
[0203] (E) Color density of printed ink images
[0204] An ink jet recording sheet was solid printed with a
black-colored ink, and the colored density of the solid printed
images was measured by a Macbeth refraction color density meter
(RD-920). The measurement was repeated five times, and the
measurement results were averaged. The averaged data were shown in
Table 1.
[0205] (F) Light resistance
[0206] The printed sample was subjected to a continuous fading test
using a Xenon lamp type FADE-OMETER (made by ATLAS ELECTRIC DEVICES
CO., Model: CI 35F) at a temperature of 63.degree. C. at a relative
humidity of 50% for 72 hours in accordance with JIS B 7754 (1991).
The color densities of the printed sample before and after the
fading test were measured. The light resistance of the printed
images were represented by a fading rate calculated in accordance
with the following equation. 2 Fading rate ( % ) = D 0 - D 1 D 0
.times. 100
[0207] wherein D.sub.0 represents a color density of the unfaded
colored images, D.sub.1 represents a color density of the faded
colored images.
[0208] Note, the higher the fading rate, the lower the light
resistance.
[0209] The test results are shown in Table 2.
10 TABLE 2 Item Water- Water- Color Fading rate (%).sup.(*)
resistance resistance Ink- Gloss density Black Magenta Cyan Yellow
of coated of ink absorbing of of ink colored colored colored
colored Example No. layer images property print images images
images images images Example II-1 3 2 3 3 2.49 4.5 12.3 0.1 6.0
II-2 3 3 3 3 2.47 5.2 14.5 0 7.1 II-3 3 3 3 3 2.47 5.4 15.1 0 6.8
II-4 3 3 3 3 2.48 7.2 17.8 0.9 9.9 II-5 3 3 3 3 2.44 13.5 24.5 2.6
13.5 II-6 3 3 3 3 2.28 5.1 15.0 0.1 7.0 II-7 3 3 3 3 2.42 4.9 13.5
0 7.2 II-8 3 3 3 4 2.51 5.1 14.5 0 6.5 Comparative II-1 3 2 3 3
2.47 20.5 45.2 10.1 21.5 Example II-2 3 2 3 3 1.71 5.9 15.5 0.1 9.1
II-3 2 2 3 1 1.62 7.2 18.2 1.2 10.5 II-4 2 3 3 1 1.85 22.5 44.3 5.6
20.8 II-5 2 3 3 2 2.03 30.1 49.2 10.1 29.8 II-6 1 1 1 2 2.59 33.5
52.7 13.1 23.3
[0210] Table 2 clearly shows that the ink jet recording materials
in accordance with the present invention exhibited excellent water
resistance of the coated layer, ink absorbing property, gloss and
color density of the printed ink images and a superior light
resistance.
* * * * *