U.S. patent application number 11/538734 was filed with the patent office on 2007-04-12 for lithographic printing plate precursor and lithographic printing method.
This patent application is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Ryuki KAKINO, Kazuto Kunita, Hidekazu Oohashi, Yasuhito Oshima.
Application Number | 20070082291 11/538734 |
Document ID | / |
Family ID | 34914572 |
Filed Date | 2007-04-12 |
United States Patent
Application |
20070082291 |
Kind Code |
A1 |
KAKINO; Ryuki ; et
al. |
April 12, 2007 |
Lithographic Printing Plate Precursor and Lithographic Printing
Method
Abstract
An image-recording material containing (A) a compound having a
specific partial structure and at least one group selected from an
acid group having a pKa of 11 or less, the derivative of the acid
group and a group capable of generating the acid group, a
lithographic printing plate precursor having an image-recording
layer containing the compound (A), and a lithographic printing
method using the lithographic printing plate precursor, are
provided.
Inventors: |
KAKINO; Ryuki; (Shizuoka,
JP) ; Kunita; Kazuto; (Shizuoka, JP) ;
Oohashi; Hidekazu; (Shizuoka, JP) ; Oshima;
Yasuhito; (Shizuoka, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Assignee: |
Fuji Photo Film Co., Ltd.
Minami-Ashigara-shi
JP
|
Family ID: |
34914572 |
Appl. No.: |
11/538734 |
Filed: |
October 4, 2006 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11101530 |
Apr 8, 2005 |
|
|
|
11538734 |
Oct 4, 2006 |
|
|
|
Current U.S.
Class: |
430/270.1 |
Current CPC
Class: |
B41C 2201/14 20130101;
Y10S 430/146 20130101; B41C 2201/04 20130101; B41C 2210/04
20130101; B41C 2210/24 20130101; B41M 5/368 20130101; B41C 2201/02
20130101; C09B 69/04 20130101; B41C 1/1016 20130101; C09B 57/00
20130101; B41C 1/1008 20130101; B41C 2210/20 20130101; Y10S 430/145
20130101; B41C 2210/22 20130101; B41C 2210/08 20130101 |
Class at
Publication: |
430/270.1 |
International
Class: |
G03C 1/00 20060101
G03C001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 9, 2004 |
JP |
2004-115121 |
Sep 22, 2004 |
JP |
2004-275449 |
Claims
1. A lithographic printing plate precursor comprising a support and
an image-recording layer, wherein the image-recording layer
comprises (1) an infrared absorber and (2) a photochromic
compound.
2. The lithographic printing plate precursor as claimed in claim 1,
wherein the image-recording layer is capable of image recording by
an infrared laser exposure, and the lithographic printing plate
precursor is capable of performing a printing by being loaded on a
printing machine without a development processing after image
recording, or by image recording after, being loaded on a printing
machine.
3. The lithographic printing plate precursor as claimed in claim 1,
wherein the photochromic compound (2) is selected from the group
consisting of a spiropyran compound, a naphthopyran compound, a
spiroxazine compound, a fulgide compound, a chromene compound and a
diarylethene compound.
4. The lithographic printing plate precursor as claimed in claim 1,
wherein the image-recording layer further comprises (3) a radical
polymerizable compound and a radical polymerization initiator.
5. The lithographic printing plate precursor as claimed in claim 17
wherein the image-recording layer contains a microgel.
6. The lithographic printing plate precursor as claimed in claim 5,
wherein the microgel is a microcapsule.
7. A method of plate making a lithographic printing plate
precursor, comprising: loading the lithographic printing plate
precursor as claimed in claim 1 on a printing machine and then
imagewise exposing the lithographic printing plate precursor with
an infrared laser, or imagewise exposing the lithographic printing
plate precursor as claimed in claim 1 with an infrared laser and
then loading the lithographic printing plate precursor on a
printing machine; and feeding a printing ink and a fountain
solution to the lithographic printing plate precursor to remove the
unexposed portion with the infrared laser of the image-recording
layer.
8. A lithographic printing method comprising: loading the
lithographic printing plate precursor as claimed in claim 1 on a
printing machine and then imagewise exposing the lithographic
printing plate precursor with an infrared laser, or imagewise
exposing the lithographic printing plate precursor as claimed in
claim 1 with an infrared laser and then loading the lithographic
printing plate precursor on a printing machine; feeding a printing
ink and a fountain solution to the lithographic printing plate
precursor to remove the unexposed portion with the infrared laser
of the image-recording layer; and performing a printing.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an image-recording material
capable of obtaining a printing out image having good visibility
after image exposure, a lithographic printing plate precursor, and
a lithographic printing method of printing by using the
lithographic printing plate precursor.
[0003] 2. Background Art
[0004] A lithographic printing plate generally comprises a
lipophilic image area that receives ink during printing process and
a hydrophilic non-image area that receives a fountain solution.
Lithographic printing is a printing method of making difference in
ink-adhering property on the surface of a lithographic printing
plate with the lipophilic image area of the lithographic printing
plate as the ink-receptive area and the hydrophilic non-image area
as the fountain solution-receptive area (an ink-repellent area) by
making use of the natures of water and oily ink of repelling to
each other, adhering ink only on the image area, and transferring
the ink to the material to be printed, e.g., paper.
[0005] For manufacturing this lithographic printing plate, a
lithographic printing plate precursor (a PS plate) comprising a
hydrophilic support having provided thereon a lipophilic
photosensitive resin layer (an image-recording layer) has so far
been widely used. A lithographic printing plate is generally
obtained by a plate making method of exposing a lithographic
printing plate precursor through an original image of a lith film
and the like, and then, for leaving the image-recording layer of
the image area, dissolving and removing the image-recording layer
of the non-image area with an alkali developing solution or an
organic solvent, to whereby bare a hydrophilic support surface.
[0006] In a conventional plate making process of a lithographic
printing plate precursor, a process of dissolving and removing a
non-image area with a developing solution and the like
corresponding to the image-recording layer after exposure is
necessary, but the exclusion or simplification of such an
additional wet process is one of the objects in the industry. Since
the discard of waste solutions discharged with wet processes is a
particularly great interest in the industry at large in recent
years from the consideration of the global environmental
protection, the solution of the above problem is increasingly
desired.
[0007] For coping with this problem, as a non-processing
(non-development) type plate making process that does not
necessitate a wet process, a lithographic printing plate precursor
having an image-recording layer whose affinity with a fountain
solution or ink changes on the surface by exposure and capable of
printing without being accompanied by the removal of an
image-recording layer is proposed.
[0008] As a simple plate-making method, a method that is called
on-press development is proposed, which is a method of using an
image-recording layer capable of removal of a non-image area of a
lithographic printing plate precursor in an ordinary printing
process, and removing a non-image area after exposure on a printing
machine to whereby obtain a lithographic printing plate.
[0009] As the specific examples of on-press development, e.g., a
method of using a lithographic printing plate precursor having an
image-recording layer soluble or dispersible in, e.g., a fountain
solution, an ink solvent, or an emulsified product of a fountain
solution and ink, a method of mechanically removing an
image-recording layer by the contact with the rollers and the
blanket of a printing machine, and a method of mechanically
removing an image-recording layer by the contact with the rollers
and the blanket after weakening the cohesive strength of an
image-recording layer or the adhesive strength of an
image-recording layer and a support by the permeation of a fountain
solution, an ink solvent and the like are exemplified.
[0010] In the present invention, unless otherwise indicated,
"development process" means a process of removing an unexposed
portion with an infrared laser of a lithographic printing plate
precursor by being brought into contact with a liquid (generally an
alkali developing solution) to thereby bare the hydrophilic support
surface by using an apparatus other than a printing machine
(generally an automatic processor), and "on-press development"
means a method and a process of removing an unexposed portion with
an infrared laser of a lithographic printing plate precursor by
being brought into contact with a liquid (generally printing ink
and/or a fountain solution) to thereby bare the hydrophilic support
surface by using a printing machine.
[0011] However, when a conventional image-recording layer of an
image-recording system utilizing ultraviolet rays and visible rays
is used, since the image-recording layer is not fixed after
exposure, it is necessary to take a method requiring much labor,
such that the exposed lithographic printing plate precursor must be
stored under a completely light-shielding condition or a constant
temperature condition until it is mounted on a printing
machine.
[0012] On the other hand, in recent years, digitized techniques of
electronically processing, accumulating and outputting image data
by using a computer have prevailed, and various image output
systems corresponding to these digitized techniques have been put
to practical use. Under such circumstances, a computer-to-plate
technique of directly making a printing plate without using a lith
film is attracting public attention, which technique comprises
scanning exposing a lithographic printing plate precursor with high
convergent radiant rays such as laser beams carrying digitized
image data. With such a tendency, it is an important technical
subject to obtain a lithographic printing plate precursor well
adapted to such a technique.
[0013] Accordingly, in recent years, the simplification of
plate-making operation, and the realization of dry system and
non-processing system have been more and more strongly required
from both aspects of the above-described global environmental
protection and the adaptation for digitization.
[0014] Since high output lasers such as semiconductor lasers and
YAG lasers radiating infrared rays of the wavelength of from 760 to
1,200 nm are inexpensively available nowadays, methods of using
these high output lasers as image recording means are now promising
as the manufacturing method of a lithographic printing plate by
scanning exposure that is easy to be included in digitized
techniques.
[0015] In conventional plate-making methods, image recording is
performed by imagewise exposing a photosensitive lithographic
printing plate precursor by low to middle intensity of illumination
to cause imagewise change of physical properties by photochemical
reaction in the image-recording layer. While in the above method of
using high output lasers, an exposure area is irradiated with a
great quantity of light energy in an extremely short period of
time, and the light energy is efficiently converted to heat energy,
the heat energy causes thermal changes such as chemical changes,
phase changes and morphological or structural changes in the
image-recording layer, and these changes are utilized in
image-recording. Accordingly, image data are inputted by light
energy, e.g., laser beams, but image recording is performed in the
state including the reaction by heat energy in addition to light
energy. A recording system making use of heat generation by such
high power density exposure is generally called heat mode
recording, and converting light energy to heat energy is called
light/heat conversion. Such an image-recording layer is also called
a image-recording layer in the invention.
[0016] Great advantages of a plate-making method using heat mode
recording are that image-recording layers are insensitive to the
lights of ordinary levels of illuminance such as room illumination,
and that the fixation of images recorded by high illuminance
exposure is not necessary. That is, lithographic printing plate
precursors for use in heat mode recording are free of sensitization
by room illumination before exposure and fixation of images is not
essential after exposure. Therefore, for example, when a
plate-making process is performed by on-press development with an
image-recording layer that is insolubilized or solubilized by
exposure with high output laser beams, and the exposed
image-recording layer is made an imagewise lithographic printing
plate, a printing system that an image is not influenced even if
exposed to room light after exposure becomes possible. Therefore,
it is expected that a lithographic printing plate precursor
preferably used for on-press development can be obtained if heat
mode recording is used.
[0017] As one example, a lithographic printing plate precursor
comprising a hydrophilic support having provided thereon an
image-forming layer containing hydrophobic thermoplastic polymer
particles dispersed in a hydrophilic binder is disclosed in
Japanese Patent 2938397. Japanese Patent 2938397 discloses that it
is possible to perform on-press development with a fountain
solution and/or ink by subjecting the lithographic printing plate
precursor to exposure with an infrared laser to coalesce the
hydrophobic thermoplastic polymer particles by heat to thereby form
an image, and then mounting the lithographic printing plate
precursor on the cylinder of a printing machine.
[0018] However, it was found that a method of forming an image by
coalescence of fine particles by mere heat fusion as above
certainly shows a good on-press developing property, but image
strength is weak and press life is insufficient.
[0019] Therefore, the improvement of press life by making use of
polymerization reaction is proposed. For example, a lithographic
printing plate precursor comprising a hydrophilic support having
thereon an image-recording layer (a heat-sensitive layer)
containing microcapsules containing a polymerizable compound is
disclosed JP-A-2001-277740 (The term "JP-A" as used herein refers
to an "unexamined published Japanese patent application"). Further,
JP-A-2002-287334 discloses a lithographic printing plate precursor
comprising a support having provided thereon an image-recording
layer (a photosensitive layer) containing an infrared absorber, a
radical polymerization initiator and a polymerizable compound.
[0020] In general, as the preprocess of mounting a printing plate
on a printing machine, the inspection and discrimination of images
on a printing plate, i.e., works for ascertaining whether the
images fitting for the purpose are recorded on the printing plate
or not, and ascertaining for what a color of ink the plate is, are
operated. In ordinary lithographic printing plate precursors
including a development process, an image can be easily ascertained
after plate-making (after development process), or before printing
(before a printing plate is mounted on the printing machine)
generally by coloring an image-recording layer in advance.
[0021] However, in a lithographic printing plate precursor of an
on-press development type or a non-processing (non development)
type not accompanied by development process before printing, the
discrimination of a plate cannot be done, since there is no image
on the printing plate, which sometimes leads to the error in
operation. In particular in multicolor printing, it is important
for printing work to be capable of distinguishing whether register
marks for register are clearly written so as to be distinguished or
not. The invention aims at solving this problem.
SUMMARY OF THE INVENTION
[0022] That is, an object of the invention is to provide an
image-recording material capable of obtaining a printing out image
having good visibility with laser exposure. Another object is to
provide an on-press development type or a non-processing
(non-development) type lithographic printing plate precursor
capable of obtaining a printing out image having great visibility
capable of easily discriminating the plate at the stage of
imagewise heating or light radiation with an infrared laser, and a
further object of the invention is to provide a lithographic
printing method using the lithographic printing plate
precursor.
[0023] As a result of eager investigation for achieving the above
objects, the present inventors have found that a printing out image
having good visibility can be obtained by using a spiro compound or
an indolinooxazine compound having a specific group, thus the
invention was attained.
[0024] That is, the invention is as follows.
[0025] 1. A compound comprising: a partial structure represented by
the following formula (I); and at least one group selected from the
group consisting of an acid group having a pKa of 11 or less, the
derivative of the acid group and a group capable of generating the
acid group: ##STR1## wherein X and Y each independently represents
an atom selected from N, O and S; Q represents an atom selected
from C, N, O and S.
[0026] 2. An image-recording material comprising (A) a compound
comprising: a partial structure represented by the following
formula (I); and at least one group selected from the group
consisting of an acid group having a pKa of 11 or less, the
derivative of the acid group and a group capable of generating the
acid group: ##STR2## wherein X and Y each independently represents
an atom selected from N, O and S. Q represents an atom selected
from C, N, O and S.
[0027] 3. The image-recording material as described in the item 2,
which further comprises an infrared absorber.
[0028] 4. A lithographic printing plate precursor comprising a
support and an image-recording layer, wherein the image-recording
layer comprises (A) a compound comprising: a partial structure
represented by the following formula (I); and at least one group
selected from the group consisting of an acid group having a pKa of
11 or less, the derivative of the acid group and a group capable of
generating the acid group: ##STR3## wherein X and Y each
independently represents an atom selected from N, O and S; Q
represents an atom selected from C, N, O and S.
[0029] 5. The lithographic printing plate precursor as described in
the item 4, wherein the image-recording layer further comprises an
infrared absorber.
[0030] 6 The lithographic printing plate precursor as described in
the item 4 or 5, wherein the image-recording layer is capable of
image recording by an infrared laser exposure, and the lithographic
printing plate precursor is capable of performing a printing by
being loaded on a printing machine without a development processing
after image recording, or by image recording after being loaded on
a printing machine.
[0031] 7. A lithographic printing plate precursor comprising a
support and an image-recording layer, wherein the image-recording
layer comprises (1) an infrared absorber and (2) a photochromic
compound.
[0032] 8. The lithographic printing plate precursor as described in
the item; wherein the image-recording layer is capable of image
recording by an infrared laser exposure, and the lithographic
printing plate precursor is capable of performing a printing by
being loaded on a printing machine without a development processing
after image recording, or by image recording after being loaded on
a printing machine.
[0033] 9. The lithographic printing plate precursor as described in
the item 7 or 8, wherein the photochromic compound (2) is selected
from the group consisting of a spiropyran compound, a naphthopyran
compound, a spiroxazine compound, a fulgide compound, a chromene
compound and a diarylethene compound.
[0034] 10. The lithographic printing plate precursor as described
in any one of the items 4 to 6, wherein the image-recording layer
further comprises (3) a radical polymerizable compound and a
radical polymerization initiator.
[0035] 11. The lithographic printing plate precursor as described
in any one of the items 7 to 9, wherein the image-recording layer
further comprises (3) a radical polymerizable compound and a
radical polymerization initiator.
[0036] 12. The lithographic printing plate precursor as described
in any one of the items 4 to 6 and 10, wherein the image-recording
layer contains a microgel.
[0037] 13. The lithographic printing plate precursor as described
in the item 12, wherein the microgel is a microcapsule.
[0038] 14. The lithographic printing plate precursor as described
in any one of the items 7 to 9 and 11, wherein the image-recording
layer contains a microgel.
[0039] 15. The lithographic printing plate precursor as described
in the item 14, wherein the microgel is a microcapsule.
[0040] 16. A method of plate making a lithographic printing plate
precursor; comprising:
[0041] loading the lithographic printing plate precursor as
described in any one of the items 4 to 6, 10 and 12 on a printing
machine and then imagewise exposing the lithographic printing plate
precursor with an infrared laser, or imagewise exposing the
lithographic printing plate precursor as described in any one of
the items 4 to 6, 10 and 12 with an infrared laser and then loading
the lithographic printing plate precursor on a printing machine;
and
[0042] feeding a printing ink and a fountain solution to the
lithographic printing plate precursor to remove the unexposed
portion with the infrared laser of the image-recording layer.
[0043] 17. A method of plate making a lithographic printing plate
precursor, comprising:
[0044] loading the lithographic printing plate precursor as
described in any one of the items 7 to 9, 11 and 14 on a printing
machine and then imagewise exposing the lithographic printing plate
precursor with an infrared laser, or imagewise exposing the
lithographic printing plate precursor as described in any one of
the items 7 to 9, 11 and 14 with an infrared laser and then loading
the lithographic printing plate precursor on a printing machine;
and
[0045] feeding a printing ink and a fountain solution to the
lithographic printing plate precursor to remove the unexposed
portion with the infrared laser of the image-recording layer.
[0046] 18. A lithographic printing method comprising:
[0047] loading the lithographic printing plate precursor as
described in any one of the items 4 to 6, 10 and 12 on a printing
machine and then imagewise exposing the lithographic printing plate
precursor with an infrared laser, or imagewise exposing the
lithographic printing plate precursor as described in any one of
the items 4 to 6, 10 and 12 with an infrared laser and then loading
the lithographic printing plate precursor on a printing
machine;
[0048] feeding a printing ink and a fountain solution to the
lithographic printing plate precursor to remove the unexposed
portion with the infrared laser of the image-recording layer;
and
[0049] performing a printing.
[0050] 19. A lithographic printing method comprising:
[0051] loading the lithographic printing plate precursor as
described in any one of the items 7 to 9, 11 and 14 on a printing
machine and then imagewise exposing the lithographic printing plate
precursor with an infrared laser; or imagewise exposing the
lithographic printing plate precursor as described in any one of
the items 7 to 9, 11 and 14 with an infrared laser and then loading
the lithographic printing plate precursor on a printing
machine;
[0052] feeding a printing ink and a fountain solution to the
lithographic printing plate precursor to remove the unexposed
portion with the infrared laser of the image-recording layer;
and
[0053] performing a printing.
[0054] In the invention, a printing out image having good
visibility can be obtained by using a spiro compound or an
indolinooxazine compound having an acid group having a pKa of 11 or
less, the derivative of the acid group, or a group capable of
generating the acid group. The mechanism of such a function of the
invention is not clear known, but it is thought that an acid
generated by the function of light or heat and a hetero atom bonded
to a spiro carbon interact, whereby the cleavage of the spiro
carbon occurs and the conjugation expands, as a result the compound
causes absorption in the visible region, as shown in the following
reaction scheme. ##STR4##
[0055] The invention can provide an image-recording material
capable of obtaining a printing out image having good visibility
with infrared laser exposure. Further, the invention can provide an
on-press development type or a non-processing (non-development)
type lithographic printing plate precursor capable of easily
discriminating the plate at the stage of imagewise exposure with an
infrared laser by a printing out image having great visibility, and
can provide a lithographic printing method using an on-press
development type lithographic printing plate precursor.
DETAILED DESCRIPTION OF THE INVENTION
Image-Recording Material:
[0056] The image-recording material according to the invention
contains (A) a compound having a partial structure represented by
the following formula (I) and at least one group selected from an
acid group having a pKa of 11 or less, the derivative of the acid
group and a group capable of generating the acid group (hereinafter
the compound is sometimes referred to as "the compound of the
invention"). ##STR5## wherein X and Y each independently represents
an atom selected from N, O and S, and Q represents an atom selected
from C, N, O and S.
[0057] As the compound having a partial structure represented by
formula (I) of the invention, e.g., spiro compounds such as
spiropyran and spirooxazine, and indolinooxazolidine compounds are
exemplified.
[0058] A spiro compounds, a spiro compound represented by the
following formula (IA) can be exemplified. ##STR6##
[0059] wherein Q, X and Y have the same megs as described in
formula (I), Z represents CH or N, .alpha. represents an atomic
group for constituting a ring formed by bonding to Q and Y, and
.beta. represents an atomic group for constituting a ring formed by
bonding to Y and Z.
[0060] In formula (IA), the specific examples of atomic groups
represented by .alpha. or .beta. include an alkyl group, a
substituted alkyl group, an alkenyl group, a substituted alkenyl
group, an alkynyl group, a substituted alkynyl group, an aryl
group, a substituted aryl group, and a divalent linking group
obtained by eliminating one hydrogen from a heteroaryl group;
linking groups having a partial structure having a hetero atom such
as shown below; and groups obtained by combining two or more of
these linking groups. ##STR7##
[0061] As the specific examples of the above alkyl group,
substituted alkyl group, alkenyl group, substituted alkenyl group,
alkynyl group, substituted alkynyl group, aryl group and
substituted aryl group, the following groups are exemplified
[0062] As the alkyl group, a straight chain, branched or cyclic
alkyl group having from 1 to 20 carbon atoms can be exemplified,
and the specific examples thereof include a methyl group, an ethyl
group, a propyl group, a butyl group, a pentyl group, a hexyl
group, a heptyl group, an octyl group, a nonyl group, a decyl
group, an undecyl group, a dodecyl group, a tridecyl group, a
hexadecyl group, an octadecyl group, an eicosyl group, an isopropyl
group, an isobutyl group, an s-butyl group, a t-butyl group, an
isopentyl group, a neopentyl group, a 1-methylbutyl group, an
isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a
cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Of
these alkyl groups, a straight chain alkyl group having from 1 to
12 carbon atoms, a branched alkyl group having from 3 to 12 carbon
atoms, and a cyclic alkyl group laving from 5 to 10 carbon atoms
are more preferred.
[0063] The substituted alkyl group consists of bonding of a
substituent and an alkylene group, and monovalent non-metallic
atomic groups exclusive of a hydrogen atom are used as the
substituents. The examples of preferred substituents include a
halogen atom (--F, --Br, --Cl, --I), a hydroxyl group, an alkoxyl
group, an aryloxy group, a mercapto group, an alkylthio group, an
arylthio group, an alkyldithio group, an aryldithio group, an amino
group, an N-alkylamino group, an N,N-dialkylamino group, an
N-arylamino group, an N,N-diarylamino group, an N-alkyl-N-arylamino
group, an acyloxy group, a carbamoyloxy group, an
N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an
N,N-dialkylcarbamoyloxy group, an N,N-diaryl-cabamoyloxy group, an
N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an
arylsulfoxy group, an acylthio group, an acylamino group, an
N-alkylacylamino group, an N-aryl-acylamino group, a ureido group,
an N'-alkylureido group, an N',N'-dialkylureido group, an
N'-arylureido group, an N',N'-diarylureido group, an
N'-alkyl-N'-arylureido group, an N-alkylureido group, an
N-arylureido group, an N'-alkyl-N-alkylureido group, an
N'-alkyl-N-arylureido group, an N',N'-dialkyl-N-alkylureido group,
an N',N'-diallyl-N'-arylureido group, an N'-aryl-N-alkylureido
group, an N'-aryl-N-aryl-ureido group, an
N',N'-diaryl-N-alkylureido group, an N',N'-diaryl-N-arylureido
group, an N'-alkyl-N'-aryl-N-alkylureido group, an
N'-alkyl-N'-aryl-N-arylureido group, an alkoxycarbonylamino group,
an aryloxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino
group, an N-alkyl-N-aryloxy-carbonylamino group, an
N-aryl-N-alkoxycarbonylamino group, an
N-aryl-N-aryloxycarbonylamino group, a formyl group, an acyl group,
a carboxyl group, and a conjugate base group thereof (hereinafter
referred to as a carboxylato group), an alkoxy-carbonyl group, an
aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl
group, an N,N-dialkylcarbamoyl group, an N-arylcarbamoyl group, an
N,N-diarylcarbamoyl group, an N-alkyl-N-arylcarbamoyl group, an
alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group,
an arylsulfonyl group, a sulfo group (--SO.sub.3H), and a conjugate
base group thereof (hereinafter referred to as a sulfonato group),
an alkoxy-sulfonyl group, an aryloxysulfonyl group, a sulfinamoyl
group, an N-alkylsulfinamoyl group, an N,N-dialkylsulfinamoyl
group, an N-arylsulfinamoyl group, an N,N-diarylsulfinamoyl group,
an N-alkyl-N-arylsulfinamoyl group, a sulfamoyl group, an
N-alkylsulfamoyl group, an N,N-dialkylsulfamoyl group, an
N-arylsulfamoyl group, an N,N-diarylsulfamoyl group, an
N-alkyl-N-arylsulfamoyl group, an N-acylsulfamoyl group, and a
conjugate base group thereof, an N-alkylsulfonylsulmoyl group
(--SO.sub.2SO.sub.2(alkyl)), and a conjugate base group thereof, an
N-arylsulfonylsulfamoyl group (--SO.sub.2NHSO.sub.2(allyl)), and a
conjugate base group thereof, an N-alklsulfonylcarbamoyl group
(--CONHSO.sub.2(alkyl)), and a conjugate base group thereof, an
N-arylsufonylcarbamoyl group (--CONHSO.sub.2(allyl)), and a
conjugate base group thereof, an alkoxysilyl group
(--Si(Oalkyl).sub.3), an aryloxysilyl group (--Si)Oallyl).sub.3), a
hydroxysilyl group (--Si(OH).sub.3), and a conjugate base group
thereof, a phosphono group (--PO.sub.3H.sub.2), and a conjugate
base group thereof (hereinafter referred to as a phosphonato
group), a dialkylphosphono group (--PO.sub.3(alkyl).sub.2), a
diarylphosphono group (--PO.sub.3(aryl).sub.2), an
alkylarylphosphono group (--PO.sub.3(alkyl)-(aryl)), a
monoalkylphosphono group (--PO.sub.3H(alkyl)), and a conjugate base
group thereof (hereinafter referred to as an alkylphosphonato
group), a monoarylphosphono group (--PO.sub.3H--(aryl)), and a
conjugate base group thereof (hereinafter referred to as an
arylphosphonato group), a phosphonoxy group (--OPO.sub.3H.sub.2),
and a conjugate base group thereof (hereinafter referred to as a
phosphonatoxy group), a dialkylphosphonoxy group
(--OPO.sub.3(alkyl).sub.2), a diarylphosphonoxy group
(--OPO.sub.3-(aryl).sub.2), an alkylarylphosphonoxy group
(--OPO.sub.3(alkyl)(aryl)), a monoalkylphosphonoxy group
(--OPO.sub.3H(alkyl)), and a conjugate base group thereof
(hereinafter referred to as an alkyl-phosphonatoxy group), a
monoarylphosphonoxy group (--OPO.sub.3H--(aryl)), and a conjugate
base group thereof (hereinafter referred to as an arylphosphonatoxy
group), a cyano group, a nitro group, a hydroxyl group, an aryl
group, an alkenyl group, and an alkynyl group.
[0064] As the specific examples of the alkyl groups in these
substituents, the above alkyl groups can be exemplified, and the
specific examples of the aryl groups include a phenyl group, a
biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a
mesityl group, a cumenyl group, a fluorophenyl group, a
chlorophenyl group, a bromophenyl group, a chloromethylphenyl
group, a hydroxyphenyl group, a methoxyphenyl group, an
ethoxyphenyl group, a phenoxyphenyl group, an acetoxyphenyl group,
a benzoyloxyphenyl group, a methylthiophenyl group, a
phenylthiophenyl group, a methylaminophenyl group, a
dimethylaminophenyl group, an acetylaminophenyl group, a
carboxyphenyl group, a methoxycarbonylphenyl group, an
ethoxycarbonylphenyl group, a phenoxycarbonylphenyl group, an
N-phenylcarbamoylphenyl group, a phenyl group, a nitrophenyl group,
a cyanophenyl group, a sulfophenyl group, a sulfonatophenyl group,
a phosphonophenyl group, and a phosphonatophenyl group. As the
examples of the alkenyl groups, a vinyl group, a 1-propenyl group,
a 1-butenyl group, a cinnamyl group, and a 2-chloro-1-ethenyl group
can be exemplified, and as the examples of the alkynyl groups, an
ethynyl group, a 1-propynyl group, a 1-butynyl group, a
trimethylsilylethynyl group, and a phenylethynyl group can be
exemplified.
[0065] The specific examples of preferred substituted alkyl groups
include a chloromethyl group, a bromomethyl group, a 2-chloroethyl
group, a trifluoromethyl group, a methoxymethyl group, a
methoxyethoxyethyl group, an allyloxymethyl group, a phenoxymethyl
group, a methylthiomethyl group, a tolylthio-methyl group, an
ethylaminoethyl group, a diethylaminopropyl group, a
morpholinopropyl group, an acetyloxymethyl group, a
benzoyloxymethyl group, an N-cyclohexylcarbamoyloxyethyl group, an
N-phenylcarbamoyloxyethyl group, an acetylamino-ethyl group, an
N-methylbenzoylaminopropyl group, a 2-oxo-ethyl group, a
2-oxopropyl group, a carboxypropyl group, a methoxycarbonylethyl
group, a methoxycarbonylmethyl group, a methoxycarbonylbutyl group,
an ethoxycarbonylmethyl group, a butoxycarbonylmethyl group, an
allyloxycarbonylmethyl group, a benzyloxycarbonylmethyl group, a
methoxycarbonylphenyl-methyl group, a trichloromethylcarbonylmethyl
group, an allyloxycarbonylbutyl group, a
chlorophenoxycarbonylmethyl group, a cabamoylmethyl group, an
N-methylcarbamoylethyl group, an N,N-dipropylcarbamoylmethyl group,
an N-(methoxy-phenyl)carbamoylethyl group, an
N-methyl-N-(sulfophenyl)-carbamoylmethyl group, a sulfopropyl
group, a sulfobutyl group, a sulfonatobutyl group, a sulfamoylbutyl
group, an N-ethyl-sulfamoylmethyl group, an
N,N-dipropylsulfamoylpropyl group, an N-tolylsulfamoylpropyl group,
an N-methyl-N-(phosphonophenyl)sulfamoyloctyl group, a
phosphonobutyl group, a phosphonatohexyl group, a
diethylphosphonobutyl group, a diphenylphosphonopropyl group, a
methylphosphonobutyl group, a methylphosphonatobutyl group, a
tolylphosphonohexyl group, a tolylphosphonatohexyl group, a
phosphonoxypropyl group, a phosphonatoxybutyl group, a benzyl
group, a phenethyl group, an .alpha.-methylbenzyl group, a
1-methyl-1-phenylethyl group, a p-methylbenzyl group, a cinnamyl
group, an allyl group, a 1-propenylmethyl group, a 2-butenyl group,
a 2-methylallyl group, a 2-methylpropenyl-methyl group, a
2-propynyl group, a 2-butynyl group, a 3-butynyl group, and the
following shown groups. ##STR8##
[0066] As the aryl groups, a condensed ring formed by 1 to 3
benzene rings and a condensed ring formed by a benzene ring and a
5-membered unsaturated flog can be exemplified. The specific
examples include a phenyl group, a naphthyl group, an anthryl
group, a phenanthryl group, an indenyl group, an acenaphthenyl
group, and a fluorenyl group. Of these groups, a phenyl group and a
naphthyl group are more preferred.
[0067] The substituted aryl group is that which is obtained by
bonding a substituent to an aryl group, and those having a
monovalent non-metallic atomic group exclusive of a hydrogen atom
as a substituent on the ring-forming carbon atoms of the above aryl
groups are used as the substituted aryl groups. As the preferred
examples of the substituents, the above alkyl groups, substituted
alkyl groups, and those described above as the examples of the
substituents in the substituted alkyl groups can be
exemplified.
[0068] The preferred specific examples of these substituted aryl
groups include a biphenyl group, a tolyl group, a xylyl group, a
mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl
group, a fluorophenyl group, a chloromethyl-phenyl group, a
trifluoromethylphenyl group, a hydroxyphenyl group, a methoxyphenyl
group, a methoxyethoxyphenyl group, an allyloxyphenyl group, a
phenoxyphenyl group, a methylthio-phenyl group, a tolylthiophenyl
group, a phenylthiophenyl group, an ethylaminophenyl group, a
diethylaminophenyl group, a morpholinophenyl group, an
acetyloxyphenyl group, a benzoyl-oxyphenyl group, an
N-cyclohexylcarbamoyloxyphenyl group, an N-phenylcarbamoyloxyphenyl
group, an acectylaminophenyl group, an N-methylbenzoylaminophenyl
group, a carboxyphenyl group, a methoxycarbonylphenyl group, an
allyloxycarbonylphenyl group, a chlorophenoxycarbonylphenyl group,
a carbamoylphenyl group, an N-methylcarbamoylphenyl group, an
N,N-dipropyl-carbamoylphenyl group, an
N-(methoxyphenyl)carbamoylphenyl group, an
N-methyl-N-(sulfophenyl)carbamoylphenyl group, a sulfophenyl group,
a sulfonatophenyl group, a sulfamoylphenyl group, an
N-ethylsulfamoylphenyl group, an N,N-dipropyl-sulfamoylphenyl
group, an N-tolylsulfoylphenyl group, an
N-methyl-N-(phosphonophenyl)sulfamoylphenyl group, a
phosphonophenyl group, a phosphonatophenyl group, a
diethyl-phosphonophenyl group, a diphenylphosphonophenyl group, a
methylphosphonophenyl group, a methylphosphonatophenyl group, a
tolylphosphonophenyl group, a tolylphosphonatophenyl group, an
allyl group, a 1-propenylmethyl group, a 2-butenyl group, a
2-methylallylphenyl group, a 2-methylpropenylphenyl group, a
2-propynylphenyl group, a 2-butynylphenyl group, and a
3-butynylphenyl group.
[0069] As the preferred examples of the heteroaryl groups, a
pyrrole ring group, a furan ring group, a thiophene ring group, a
benzopyrrole ring group, a benzofuran ring group, a benzothiophene
ring group, a pyrazole ring group, an isoxazole ring group, an
isothiazole ring group, an indazole ring group, a benzisoxazole
ring group, a benzisothiazole ring group, an imidazole ring group,
an oxazole ring group, a thiazole ring group, a benzimidazole ring
group, a benzoxazole ring group, a benzothiazole ring group, a
pyridine ring group, a quinoline ring group, an isoquinoline ring
group, a pyridazine ring group, a pyrimidine ring group, a pyrazine
ring group, a phthalazine ring group, a quinazoline ring group, a
quinoxaline ring group, an aziridine ring group, a phenanthridine
ring group, a carbazole ring group, a purine ring group, a pyran
ring group, a piperidine ring group, a piperazine ring group, a
morpholine ring group, an indole ring group, an indolizine ring
group, a chromene ring group, a cinnoline ring group, an acridine
ring group, a phenothiazine ring group, a tetrazole ring group, and
a triazine ring group are exemplified.
[0070] The heterocyclic ring groups may have a substituent, and
monovalent non-metallic atomic groups exclusive of a hydrogen atom
can be used as the substituents. As the examples of such
substituents, the above-described alkyl groups, substituted alkyl
groups, and the substituents in the substituted alkyl groups
described above are exemplified.
[0071] As the examples of the alkenyl groups, a vinyl group, a
1-propenyl group, a 1-butenyl group, a cinnamyl group, and a
2-chloro-1-ethenyl group are exemplified, and as the examples of
the alkynyl groups, an ethynyl group, a 1-propynyl group, a
1-butynyl group and a trimethylsilylethynyl group are
exemplified.
[0072] The substituted alkenyl group is an alkenyl group having a
substituent bonded to the alkenyl group by replacing with the
hydrogen atom in the alkenyl group, and as the substituents of the
substituted alkenyl group, the above substituents in the
substituted alkyl group can be used. As the alkenyl group, the
above alkenyl groups can be used. As the preferred examples of the
substituted alkenyl groups, the following groups can be
exemplified. ##STR9##
[0073] The substituted alkynyl group is an alkynyl group having a
substituent bonded to the alkynyl group by replacing with the
hydrogen atom in the alkynyl group, and as the substituents of the
substituted alkynyl group, the above substituents in the
substituted alkyl group can be used. As the alkynyl group, the
above alkynyl groups can be used.
[0074] The spiro compound represented by formula (IA) is
particularly preferably represented by the following formula (IB):
##STR10## wherein X' represents NR.sup.1, O or s; R.sup.1
represents an alkyl group having from 1 to 20 carbon atoms which
may be substituted, an alkenyl group having from 2 to 20 carbon
atoms which may be substituted, an alkynyl group having from 2 to
20 carbon atoms which may be substitute an aralkyl group having
from 7 to 20 carbon atoms which may be substituted, or an aryl
group having from 6 to 19 carbon atoms which may be substituted;
.alpha. and .beta. cach represents an atomic group for constituting
a ring formed with the carbon atom to which .alpha. or .beta. is
bonded, and the specific examples of atomic groups represented by
.alpha. or .beta. include the above alkyl group, substituted alkyl
group, alkenyl group, substituted alkenyl group, alkynyl group,
substituted alkynyl group, aryl group, substituted aryl group, and
a divalent linking group obtained by eliminating one hydrogen from
a heteroaryl group; linking groups having a partial structure
having a hetero atom such as shown below; and groups obtained by
combining two or more of these linking groups. ##STR11##
[0075] In formula (IB), Q' represents O, S or CR.sup.2R.sup.3. In
the case where Q' represents CR.sup.2R.sup.3 and and R.sup.3 are
independent each of them represents a substituent selected from an
alkyl group having from 1 to 20 carbon atoms, an alkenyl group
having from 2 to 20 carbon atoms, an alkynyl group having from 2 to
20 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms,
and an aryl group having from 6 to 19 carbon atoms; and when
R.sup.2 and R.sup.3 are not independent, they may have carbon atoms
jointly and form a ring having from 3 to 20 carbon atoms Y'
represents N, O or S, and Z' represents CH or N.
[0076] The specific examples of spiropyran compounds preferably
used in the invention include benzospiropyran compounds, e.g.,
1,3,3-trimethylindolino-8'-methoxybenzopyrylospiran,
1,3,3-trimethylindolino-6'-nitrobenzopyrylospiran,
1,3,3-trimethylindolino-6'-nitro-8'-methoxybenzopyrylospiran,
1,3,3-trimethylindolino-5-methoxy-6'-nitrobenzopyrylospiran,
1,3,3-trimethylindolino-6'-bromo-8'-nitrobenzopyrylospiran, and
1,3,3-trimethylindolinobenzopyrylospiran, naphthospiropyran
compounds, e.g.,
1,3,3-trimethylindolino-7'-nitronaphthopyrylospiran,
1,3,3-trimethylindolino-8'-nitronaphthopyrylospiran, and
1,3,3-trimethylindolino-naphthospiropyran, and
1,3,3-timethylindolinobenzospiro-thiopyran.
[0077] The specific examples of spirooxazine preferably used in the
invention include
1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
4-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]-benzo-
xazine],
5-fluoro-1,3,3-trimthylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4-
]benzoxazine],
6-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]-benzo-
xazine],
5-chloro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,-
4]benzoxazine],
5-bromo-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]-benzox-
azine],
1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyrid-
o[4,3-f][1,4]benzoxazine],
4-fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyr-
ido[4,3-f][1,4]benzoxazine],
5-fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyr-
ido[4,3-f][1,4]benzoxazine],
6-fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2
'(1'H),3''-[3H]-pyrido[4,3-f][1,4]benzoxazine],
5-chloro-1'-methyldispiro-[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]py-
rido[4,3-f]-[1,4]benzoxazine],
5-bromo-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1H),3''-[3H]pyrid-
o[4,3-f][1,4]-benzoxazine], and the compounds exemplified below.
##STR12## ##STR13## ##STR14## ##STR15## ##STR16## ##STR17##
##STR18## ##STR19## ##STR20## ##STR21## ##STR22## ##STR23##
##STR24## ##STR25## ##STR26## ##STR27## ##STR28##
[0078] The specific examples of indolinooxazolidine compounds
preferably used in the invention include
2-{2-[4-(dimethylamino)phenyl]ethenyl}-3,3-dimethylindolino[2,1-b]-oxazol-
idino,
2-{4-[4-(dimethylamino)phenyl]-1,3-butadienyl}-3,3-dimethylindolino-
[2,1-b]oxazolidine, and
3,3-dimethyl-2-{2-[9-ethyl-3-carbazolyl]ethenyl}indolino-[2,1-b]oxazolidi-
ne.
[0079] Of the above compounds, compounds having spiropyran or
spirooxazine as the mother nucleus are most preferred for ensuring
sufficient visibility
[0080] As the above acid groups having a pKa of 11 or less, the
acid groups shown in the following
(1) to (6) are preferred.
(1) A phenolic hydroxyl group (--Ar--OH)
(2) A sulfonamido group (--SO.sub.2NH--R)
(3) A substituted sulfonamido-based acid group (--SO.sub.2NHCOR,
--SO.sub.2NHSO.sub.2R, --CONHSO.sub.2R)
(4) A carboxylic acid group (--CO.sub.2H)
(5) A sulfonic acid group (--SO.sub.3H)
(6) A phosphoric acid group (--OPO.sub.3H.sub.2)
[0081] In the above (1) to (6), Ar represents a divalent aryl
linking group which may have a substituent, and R represents a
hydrocarbon group which may have a substituent. Of the acid groups
selected from (1) to (6), it is preferred to have (3) a substituted
sulfonamido-based acid group, (4) a carboxylic acid group or (5) a
sulfonic acid group, and (5) a sulfonic acid group is most
preferred for ensuring sufficient visibility.
[0082] As the derivatives of the acid group having a pKa of 11 or
less, the esters, amides and acetals of the acid groups having a
pKa of 11 or less are exemplified. Of these compounds, esters and
acetals are preferred for high sensitivity, and esters are
particularly preferred.
[0083] The specific examples of groups capable of generating acid
groups having a pKa of 11 or less include, e.g., onium groups such
as a sulfonium group, an iodonium group and a diazonium group. The
onium groups preferably used in the invention are onium groups
represented by the following formulae (R-I) to (R-III).
##STR29##
[0084] In formula (RI-I), Ar.sub.11 represents an aryl group having
20 or less carbon atoms, which may have from 1 to 6 substituents,
and as the preferred substituents, an alkyl group having from 1 to
12 carbon atoms, an alkenyl group having from 1 to 12 carbon atoms,
an alkynyl group having from 1 to 12 carbon atoms, an aryl group
having from 1 to 12 carbon atoms, an alkoxyl group having from 1 to
12 carbon atoms, an aryloxy group having from 1 to 12 carbon atoms,
a halogen atom, an alkylamino group having from 1 to 12 carbon
atoms, a dialkylamino group having from 1 to 12 carbon atoms, an
alkylamido group or arylamido group having from 1 to 12 carbon
atoms, a carbonyl group, a carboxyl group, a cyano group, a
sulfonyl group, a thioalkyl group having from 1 to 12 carbon atoms,
and a thioaryl group having from 1 to 12 carbon atoms are
exemplified. Z.sub.11.sup.- represents a monovalent anion, and
specifically a halogen ion, a perchlorate ion, a
hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion,
a sulfinate ion, a thiosulfonate ion and a sulfate ion are
exemplified. In particular, in view of stability, a perchlorate
ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a
sulfonate ion and a sulfinate ion are preferred.
[0085] In formula (RI-II), Ar.sub.21 and Ar.sub.22 each represents
an aryl group having 20 or less carbon atoms, which may have from 1
to 6 substituents, and as the preferred substituents, an alkyl
group having from 1 to 12 carbon atoms, an alkenyl group having
from 1 to 12 carbon atoms, an alkynyl group having from 1 to 12
carbon atoms, an aryl group having from 1 to 12 carbon atoms, an
alkoxyl group having from 1 to 12 carbon atoms, an aryloxy group
having from 1 to 12 carbon atoms, a halogen atom, an alkylamino
group having from 1 to 12 carbon atoms, a dialkylamino group having
from 1 to 12 carbon atoms, an alkylamido group or arylamido group
having from 1 to 12 carbon atoms, a carbonyl group, a carboxyl
group, a cyano group, a sulfonyl group, a thioalkyl group having
from 1 to 12 carbon atoms, and a thioaryl group having from 1 to 12
carbon atoms are exemplified, Z.sub.21.sup.- represents a
monovalent anion, and specifically a halogen ion, a perchlorate
ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a
sulfonate ion, a sulfonate ion, a thiosulfonate ion and a sulfate
ion are exemplified. In view of stability and reactivity, a
perchlorate ion, a hexafluorophosphate ion, a tetrafluoro-borate
ion, a sulfonate ion, a sulfonate ion and a carboxylate ion are
preferred.
[0086] In formula (RI-II), R.sub.31, R.sub.32 and R.sub.33 each
represents an aryl, alkyl, alkenyl or alkynyl group having 20 or
less carbon atoms, which may have from 1 to 6 substituents. Above
all, in view of stability and reactivity, an aryl group is
preferred. As the substituents, an alkyl group having from 1 to 12
carbon atoms, an alkenyl group having from 1 to 12 carbon atoms, an
alkynyl group having from 1 to 12 carbon atoms, an aryl group
having from 1 to 12 carbon atoms, an alkoxyl group having from 1 to
12 carbon atoms, an aryloxy group having from 1 to 12 carbon atoms,
a halogen atom, an alkylamino group having from 1 to 12 carbon
atoms, a dialkylamino group having from 1 to 12 carbon atoms, an
alkylamido group or arylamido group having from 1 to 12 carbon
atoms, a carbonyl group, a carboxyl group, a cyano group, a
sulfonyl group, a thioalkyl group having from 1 to 12 carbon atoms,
and a thioaryl group having from 1 to 12 carbon atoms are
exemplified, Z.sub.31.sup.- represents a monovalent anion, and
specifically a halogen ion, a perchlorate ion, a
hexafluoro-phosphate ion, a tetrafluoroborate ion, a sulfonate ion,
a sulfinate ion, a thiosulfonate ion, and a sulfate ion are
exemplified. In particular; in view of stability and reactivity, a
perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate
ion, a sulfonate ion, a sulfinate ion and a carboxylate ion are
preferred. As more preferred carboxylate ions, the carboxylate ions
disclosed in JP-A-2001-343742 are exemplified, and the carboxylate
ions disclosed in JP-A-2002-148790 are particularly preferred.
[0087] Of these onium groups, sulfonium groups and iodonium groups
are preferred, and sulfonium groups are most preferred for high
sensitivity.
[0088] The compound of the invention can be used alone, but two
kinds or more may be used in combination. The addition amount is
preferably from 1 .mu.mol to 10 mmol/m.sup.2, and more preferably
from 10 .mu.mol to 1 mmol/cm.sup.2.
[0089] The specific examples of the compounds of the invention are
exemplified below but the invention is by no means limited thereto.
##STR30## ##STR31## ##STR32## ##STR33## ##STR34## Infrared
Absorber:
[0090] It is preferred for the image-recording material in the
invention to contain infrared absorbers for increasing sensitivity
to infrared lasers. Infrared absorbers have a function to convert
absorbed infrared rays to heat. Infrared absorbers fore use in the
invention are dyes or pigments having an absorption maximum in the
wavelength of from 760 to 1,200 nm.
[0091] As dyes for this purpose, commercially available dyes and
well-known dyes described in literatures, e.g., Senryo Binran (Dye
Handbook), compiled by Yuki Gosei Kagaku Kyolai (1970) can be used.
Specifically, azo dyes, metal complex azo dyes, pyrazolone azo
dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes,
carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes,
squarylium dyes, pyrylium salts and metal thiolate complexes are
exemplified.
[0092] As preferred dyes, cg, the cyanine dyes disclosed in
JP-A-58-125246, JP-A-59-94356 and JP-A-60-78787 the methine dyes
disclosed in JP-A-53-173696, JP-A-58-181690 and JP-A-SS-194595, the
naphthoquinone dyes disclosed in JP-A-58-112793, JP-A-58-224793,
JP-A-59-48187, JP-A-59-73996, JP-A-60-52940 and JP-A-60-63744, the
squarylium dyes disclosed in JP-A-58-112792, and the cyanine dyes
disclosed in British Patent 434,875 are exemplified.
[0093] Further, the near infrared absorbing sensitizers disclosed
in U.S. Pat. No. 5,156,938 are also preferably used, in addition,
the substituted arylbenzo(thio)pyrylium salts disclosed in U.S.
Pat. No. 3,881,924, the trimethine thiapyrylium salts disclosed in
JP-A-57-142645 (corresponding to U.S. Pat. No. 4,327,169), the
pyrylium-based compounds disclosed in JP-A-58-181051,
JP-A-58-220143, JP-A-5941363, JP-A-59-84248, JP-A-59-84249,
JP-A-59-146063 and JP-A-59-146061, the cyanine dyes disclosed in
JP-A-59-216146, the pentamethine thiopyrylium salts disclosed in
U.S. Pat. No. 4,283,475, and the pyrylium compounds disclosed in
JP-B-5-13514 (the term "JP-B" as used herein refers to an "examined
Japanese patent publication") and JP-B-5-19702 are also preferably
used in the invention. As other examples of preferred dyes, the
near infrared absorbing dyes disclosed in U.S. Pat. No. 4,756,993
as the compounds represented by formulae (I) and (II) can be
exemplified.
[0094] As other preferred examples of fared absorbing dyes in the
invention, the specific indolenine cyanine dyes disclosed in
JP-A-2002-278057 as shown below can be exemplified. ##STR35##
[0095] Of these dyes, cyanine dyes, squarylium dyes, pyrylium
salts, nickel thiolate complexes and indolenine canine dyes are
exemplified as particularly preferred dyes. Cyanine dyes and
indolenine cyanine dyes are more preferred, and as one particularly
preferred example, a cyanine dye represented by the following
formula (II) is exemplified. ##STR36## wherein X.sup.1 represents a
hydrogen atom, a halogen atom, --NPh.sub.2, X.sup.2-L.sup.1, or a
group shown below. ##STR37## wherein X.sup.2 represents an oxygen
atom, a nitrogen atom or a sulfur atom; L.sup.1 represents a
hydrocarbon group having from 1 to 12 carbon atoms, an aromatic
ring having a hetero atom, or a hydrocarbon group containing a
hetero atom having from 1 to 12 carbon atoms. The hetero atoms here
mean N, S, O, a halogen atom and Se. X.sub.a.sup.- is defined as
the same with the later-described Z.sub.a.sup.-, and R.sup.a
represents a substituent selected from a hydrogen atom, an alkyl
group, an aryl group, a substituted or unsubstituted amino group
and a halogen atom.
[0096] In formula (II), R.sup.1 and R.sup.2 each represents a
hydrocarbon group having from 1 to 12 carbon atoms. In view of the
storage stability of a recording layer coating solution, R.sup.1
and R.sup.2 each preferably represents a hydrocarbon group having 2
or more carbon atoms, and particularly preferably R.sup.1 and
R.sup.2 are bonded to each other to form a 5- or 6-membered
ring.
[0097] Ar.sup.1 and Ar.sup.2, which may be the same or different
each represents an aromatic hydrocarbon group which may have a
substituent The examples of preferred aromatic hydrocarbon groups
include a benzene ring and a naphthalene ring. The preferred
examples of the substituents include a hydrocarbon group having 12
or less carbon atoms, a halogen atom, and an alkoxyl group having
12 or less carbon atoms. Y.sup.1 and Y.sup.2, which may be the same
or different, each represents a sulfur atom or a dialkylmethylene
group having 12 or less carbon atoms. R.sup.3 and R.sup.4, which
may be the same or different each represents a hydrocarbon group
having 20 or less carbon atoms which my have a substituent. The
preferred examples of the substituents include an alkoxyl group
having 12 or less carbon atoms, a carboxyl group and a sulfo group.
R.sup.5, R.sup.6, R.sup.7 and R.sup.8, which may be the same or
different, each represents a hydrogen atom or a hydrocarbon group
having 12 or less carbon atoms, preferably a hydrogen atom because
of easy availability of the material. Z.sub.a.sup.+ represents a
counter anion, provided that when a cyanine dye represented by
formula (II) has an anionic substituent within the structure and
the neutralization of the electric charge is not necessary
Z.sub.a.sup.+ is not necessary. Z.sub.a.sup.+ preferably represents
a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a
hexafluorophosphate ion or a sulfonate ion for the storage
stability of the recording layer coating solution, and particularly
preferably Z.sub.a.sup.- represents a perchlorate ion, a
hexafluorophosphate ion or an arylsulfonate ion.
[0098] As the specific examples of cyanine dyes represented by
formula (II) that can be preferably used in the invention, those
disclosed in JP-A-2001-133969, paragraphs [0017] to [0019] are
exemplified.
[0099] Further, as particularly preferred other examples of bed
absorbers, the specific indolenine cyanine dyes disclosed in
JP-A-2002-278057 are exemplified.
[0100] As the pigments for use in the present invention,
commercially available pigments and the pigments described in Color
Index (C.I.) Binran (Color Index Bulletin), Shaishin Ganryo Binran
(The Latest Pigment Handbook), compiled by Nippon Ganryo Gijutsu
Kyokai (1977), Shaishin Ganryo Oyo Gijutsu (The Latest Pigment
Applied Techniques), CMC Publishing Co. Ltd. (1986), Insatsu Ink
Gijutsu (Printing Ink Techniques), CMC Publishing Co. Ltd. (1984)
can be used.
[0101] Various kinds of pigments can be used in the invention,
e.g., black pigments, yellow pigments, orange pigments, brown
pigments, red pigments, purple pigments, blue pigments, green
pigments, fluorescent pigments, metallic powder pigments, and
polymer-bond pigments can be exemplified. Specifically, insoluble
azo pigments, azo lake pigments, condensation azo pigments, chelate
azo pigments, phthalocyaninc pigment anthraquinone pigments,
perylene and perinone pigments, thioindigo pigments, quinacridone
pigments, dioxazine pigments, isoindolinone pigments,
quinophthalone pigments, in-mold lake pigments, azine pigments,
nitroso pigments, nitro pigments, natural pigments, fluorescent
pigments, inorganic pigments, and carbon black can be used. Of
these pigments, carbon black is preferably used.
[0102] These pigments can be used without surface treatment or the
surfaces may be treated. As the methods of surface treatments, a
method of coating the surfaces of pigments with resins and waxes, a
method of adhering surfactants, and a method of bonding reactive
substances (e.g., silane coupling agents, epoxy compounds, or
polyisocyanate) on the surfaces of pigments can be exemplified.
These surface treatment methods are described in Kinzoku Sekken no
Seishitsu to Oyo (Natures and Applications of Metal Soaps), Saiwai
Shobo, Insatsu Ink Gijutsu (Printing Ink Techniques), CMC
Publishing Co., Ltd. (1984), and Shaishin Ganryo Oyo Gijutsu (The
Latest Pigment Applied Techniques), CMC Publishing Co., Ltd.
(1986).
[0103] The particle size of pigments is preferably from 0.01 to 10
.mu.m, more preferably from 0.05 to 1 .mu.m, and particularly
preferably from 0.1 to 1 .mu.m. When the particle size of pigments
is in this range, stability of the pigment dispersion in an
image-recording layer coating solution and uniformity of an
image-recording layer can be obtained.
[0104] Well-know dispersing techniques used in the manufacture of
inks and toners can be used as the dispersing method of pigments in
the invention. The examples of dispersing apparatus include an
ultrasonic disperser, a sand mill, an attritor, a pearl mill, a
super-mill, a ball mill, an impeller, a disperser; a KD mill, a
colloid mill, a dynatron, a three-roll mill and a pressure kneader,
and details are described in Shaishin Ganryo Oyo Gijutsu (The
Latest Pigment Application Techniques), CMC Publishing Co., Ltd.
(1986).
[0105] These infrared absorbers may be added to the same layer with
other components, or a separate layer may be provided and added
thereto. Alternatively, infrared absorbers may be added as the form
of being encapsulated in microcapsules.
[0106] When a negative lithographic printing plate precursor is
prepared, it is preferred that infrared absorbers are added so that
the absorbance of an image-recording layer at the maximum
absorption wavelength in the wavelength range of from 760 to 1,200
nm is from 0.3 to 1.2 by reflection measuring method, more
preferably from 0.4 to 1.1. In this range of the addition amount,
the polymerization reaction proceeds uniformly in the depth
direction of the image-recording layer and good layer strength of
the image area and sufficient adhesion to the support can be
obtained.
[0107] The absorbance of an image-recording layer can be adjusted
by the addition amount of an infrared absorber to the
image-recording layer and the thickness of the image-recording
layer, Absorbance can be measured by ordinary methods, e.g., a
method of forming an image recording layer having an arbitrarily
determined thickness in a dry coating weight necessary as the
lithographic printing plate on a reflective support, such as an
aluminum support and measuring the reflection density with an
optical densitometer, and a method of measuring the absorbance by a
reflection method with a spectrophotometer using an integrating
sphere are exemplified.
Lithographic Printing Plate Precursor:
[0108] As a preferred embodiment of the image-recording material in
the invention, a lithographic printing plate precursor is
exemplified.
[0109] As the image-recording layer of the lithographic printing
plate precursor in the invention, (i) an embodiment that contains
(1) an infrared absorber and (2) the compound (A), and (ii) an
embodiment that contains (1) an infrared absorber and (2) a
photochromic compound, are preferably exemplified.
[0110] A photochromic compound is a compound having the properties
that when it absorbs light, a reversible isomerization reaction
occurs in the molecule, and absorption wavelength changes with the
structural change, and is disclosed in JP-B-6-99681 (the term
"JP-B" as used herein refers to an "examined Japanese patent
publication"), and JP-A-7-278444 (the term "JP-A" as used herein
refers to an "unexamined published Japanese patent
application").
[0111] As the photochromic compounds in the invention,
specifically, e.g., spiropyran compounds such as spiropyran,
naphthopyan and spiroxazine, fulgide compounds as disclosed in U.S.
Pat. Nos. 4,882,438, 4,960,678, 5,130,058 and 5,106,998, chromene
compounds and diarylethene compounds are exemplified.
[0112] The specific examples of spiropyran and naphthopyran
compounds preferably used in the invention include benzospiropyran
compounds, e.g.,
1,3,3-trimethylindolino-8'-methoxybenzopyrylospiran,
1,3,3-trimethylindolino-6'-nitrobenzopyrylospiran,
1,3,3-trimethylindolino-6'-nitro-8'-methoxybenzopyrylospiran,
1,3,3-trimethylindolino-5-methoxy-6'-nitrobenzopyrylospiran,
1,3,3-trimethylindolino-6'-bromo-8'-nitrobenzopyrylospiran,
1,3,3-trimethylindolinobenzopyrylospiran
1,3,3-trimethylindolino-8'-hydroxybenzopyrylospiran,
1,3,3-trimethylindolino-7'-hydroxybenzopyrylospiran, 1,3,3
trimethylindolino-6'-hydroxybenzopyrylospiran,
1,3,3-trimethylindolino-8'-carboxybenzopyrylospiran,
1-(4-carboxybenzyl)-3,3-dimethylindolinobenzopyrylospiran, and
1-(2-carboxyethyl)-3,3-dimethylindolinobenzopyrylospiran,
naphthospiropyran compounds, e.g.,
1,3,3-trimethylindolino-7'-nitronaphthopyrylospiran and
1,3,3-trimethylindolino-8'-nitronaphthopyrylospiran, and the
compound having the following structure, ##STR38##
[0113] The specific examples of the spirooxazine compounds
preferably used in the invention include
1,3,3-trimethyl-spiro[2H-indole-2,3'-[3H]pyrido[4,3-f][1,4]benzoxazine],
4-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido-[4,3-f][1,4]benzo-
xazine],
5-fluoro-1,3,3-trimethylspiro-[2H-indole-2,3'-[3H]pyrido[4,3-f][1-
,4]benzoxazine],
6-fluoro-1,3,3-trimethylspiro[2H-indole-2,3'[3H]pyrido-[4,3-f][1,4]benzox-
azine],
5-chloro-1,3,3-trimethylspiro-[2H-indole-2,3'-[3H]pyrido[4,3-f][1,-
4]benzoxazine],
5-bromo-1,3,3-trimethylspiro[2H-indole-2,3'-[3H]pyrido-[4,3-f][1,4]-benzo-
xazine],
1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyri-
do[4,3-f][1,4]benzoxazine],
4-fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyr-
ido[4,3-f][1,4]benzoxazine],
5-fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyr-
ido[4,3-f][1,4]benzoxazine,
6-fluoro-1'-methyldispiro[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]-py-
rido[4,3-f][1,4]benzoxazine],
5-chloro-1'-methyldispiro-[cyolohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]py-
rido[4,3-f]-[1,4]benzoxazine], and
5-bromo-1'-methyldispiro-[cyclohexane-1,3'-[3H]indole-2'(1'H),3''-[3H]pyr-
ido-[4,3-f][1,4]benzoxazine].
[0114] The specific examples of the fulgide compounds preferably
used in the invention include
N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro(5,6-benzo[b]thiophene
dicarboxyimido-7,2-tricyclo[3,3,1,1]decane),
N-cyanomethyl-6,7-dihydro-2-p-methoxyphenyl)-4-methylspiro(5,6-benzo[b]th-
iophenedicarboxyimido-7,2-tricyclo[3,3,1,1)decane),
N-cyanomethyl-6,7-dihydro-4-methylspiro(5,6-benzo[b]thiophenedicarboxyimi-
do-7,2-tricylo[3,3,1,1]decane),
6,7-dihydro-N-methoxycarbonyl-methyl-4-methyl-2-phenylspiro(5,6-benzo[b]t-
hiophene-dicarboxyimido-7,2-tricyclo[3,3,1,1]decane),
6,7-dihydro-4-methyl-2-(p-methylphenyl)-N-nitromethylspiro(5,6-benzo[b]th-
iophenedicarboxyimido-7,2-tricyclo[3,3,1,1]-decane),
N-cyanomethyl-6,7-dihydro-4-cyclopropyl-3-methylspiro(5,6-benzo[b]thiophe-
nedicarboxyimido-7,2-tricyclo-[3,3,1,1]decane) and
N-cyanomethyl-6,7-dihydro-4-cyclopropyl-spiro(5,6-benzo[b]thiophenedicarb-
oxyimido-7,2-tricyclo-[3,3,1,1]decane).
[0115] The specific examples of the chromene compounds preferably
used in the invention include
spiro[norbornane-2,2'-[2H]benzo[h]chromene],
spiro[bicyclo[3,3,1]nonane-9,2'-[2H]benzo[f]chromene],
7'-methoxyspiro[bicyclo-[3,3,1]nonane-9,2'-[2H]benzo[f]chromene],
7'-methoxyspiro-[norbornane-2,2'-[2H]benzo[f]chromene],
2,2-dimethyl-7-octoxy[2H]benzo[h]chromene-6)spiro[2-bicyclo(3,3,1)-nonene-
-9,2'-(2H]benzo(h)chromene], and
spiro[2-bicyclo-(3,3,1)nonene-9,2'-(2H)benzo(f)chromene].
[0116] The specific examples of the diarylethene compounds
preferably used in the invention include the following compounds.
##STR39## ##STR40## ##STR41##
[0117] Of the above compounds, spiropyran, naphthopyran,
spiroxazine compounds, and the compound (A) as above-mentioned are
preferred and spiropyran compounds are particularly preferred
[0118] The photochromic compounds in the invention can be used
alone but two or more compounds may be used in combination.
[0119] The photochromic compounds are preferably used in an amount
of from 1 .mu.mol/m.sup.2 to 10 mmol/m.sup.2, more preferably from
10 .mu.mol/m.sup.2 to 1 mmol/m.sup.2. When the photochromic
compounds are used in this range, good visibility can be
obtained.
[0120] Further, as a preferred embodiment of the lithographic
printing plate precursor of the invention, (1) an on-press
development type lithographic printing plate precursor, and (2) a
non-processing (non-development) type lithographic printing plate
precursor as described below are exemplified.
(1) On-Press Development Type Lithographic Printing Plate
Precursor:
[0121] A lithographic printing plate precursor having an
image-recording layer whose solubility or dispersibility in a
fountain solution and/or ink changes by exposure or an
image-recording layer whose adhering property to the adjoining
layer having different affinity to a fountain solution or ink
changes by exposure, and capable of development on a printing
machine by feeding a fountain solution and/or ink to the plate
after image exposure.
(2) Non-Processing (Non-Development) Type Lithographic Printing
Plate Precursor:
[0122] A lithographic printing plate precursor having an
image-recording layer whose affinity with a fountain solution or
ink changes on the surface by exposure and capable of printing
without being accompanied by the removal of an image-recording
layer after image exposure.
[0123] Specifically, the plate materials as disclosed in Japanese
Patent No, 2938397, JP-A-2001-277740, JP-A-2001-277742,
JP-A-2002-287334, JP-A-2001-969363, JP-A-2001-96938,
JP-A-2001-180141, JP-A-2001-162960, WO 00/16987, WO 01/39985,
EP-A-990517, EP-A-1225041, U.S. Pat. No. 6,465,152, JP-A-6-317899,
WO 96/35143, FP-A-652483, JP-A-10-10737, JP-A-11-309952, U.S. Pat.
Nos. 6,017,677 and 6,413,694 are exemplified.
[0124] The lithographic printing plate precursor in the invention
and a printing method using the lithographic printing plate
precursor are described in detail below.
Image-Recording Layer:
[0125] As an image-forming component in the on-press development
type and non-processing (non-development) type lithographic
printing plate precursors, the image-recording layer in the
invention can further contain either of (A) an image-forming
component using radical polymerization or (B) an image-forming
component utilizing thermal fusion and thermal reaction of a
hydrophobitizing precursor can be used.
(A) Image-Forming Component Using Radical Polymerization:
[0126] An image-forming component making use of radical
polymerization contains a radical polymerizable compound and a
radical generator. Since radical polymerization components are high
in image-forming sensitivity, exposure energy can be effectively
shared for the formation of a printing out image, so that radical
polymerization components are more preferred for obtaining a
printing out image having a great difference in brightness of
colors.
<Radical Polymerizable Compound>
[0127] For efficiently perform a hardening reaction, it is
preferred for the image-recording layer in the invention to contain
radical polymerizable compounds (hereinafter also referred to as
merely polymerizable compounds). The radical polymerizably
compounds usable in the invention are addition polymerizable
compounds having at least one ethylenic unsaturated double bond,
and they are selected from the compounds having at least one,
preferably two or more, ethylenic unsaturated bond. These compounds
are well known in the field of this industry, and they can be used
with no particular restriction in the invention. These
polymerizable compounds have chemical forms of, e.g., a monomer or
a prepolymer, i.e., a dimer, a trimer or an oligomer; and a mixture
and a copolymer of them. As the examples of monomers and copolymers
of them, unsaturated carboxylic acids (e.g., acrylic acid,
methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid,
maleic acid, etc.), and esters and amides of these unsaturated
carboxylic acids are exemplified, and preferably esters of
unsaturated carboxylic acids and aliphatic polyhydric alcohol
compounds, and amides of unsaturated carboxylic acids and aliphatic
polyhydric amine compounds are used. Further, the addition reaction
products of unsaturated carboxylic acid esters and amides having a
nucleophilic substituent such as a hydroxyl group, an amino group
or a mercapto group with monofunctional or polyfunctional
isocyanates or epoxies, and the dehydration condensation reaction
products of unsaturated carboxylic acid esters and amides with
monofunctional or polyfunctional carboxylic acids are also
preferably used. Furthermore, the addition reaction products of
unsaturated carboxylic acid esters or amides having an
electrophilic substituent such as an isocyanate group or an epoxy
group with monofunctional or polyfunctional alcohols, amines or
thiols, and the substitution reaction products of unsaturated
carboxylic acid esters or amides having a separable substituent
such as a halogen group or a tosyloxy group with monofunctional or
polyfunctional alcohols, amines or thiols are also preferably used.
As another example, it is also possible to use compounds obtained
by substituting the unsaturated carboxylic acids with unsaturated
phosphonic acid, styrene, vinyl ether, etc.
[0128] The specific examples of the monomers of esters of aliphatic
polyhydric alcohol compounds and unsaturated carboxylic acids
include, as acrylic esters, ethylene glycol diacrylate, triethylene
glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol
diacrylate, propylene glycol diacrylate, neopentyl glycol
diacrylate, trimethylolpropane triacrylate, trimethylolpropane
tri(acryloyloxypropyl) ether, trimethylolethane triacrylate,
hexanediol diacrylate, 1,4-cyclohexanediol diacrylate,
tetraethylene glycol diacrylate, pentaerythritol diacrylate,
pentaerythrtol triacrylate, pentaerythritol tetraacrylate,
dipentaerythritol diacrylate, dipentaerythritol hexaacrylate,
sorbitol triacrylate, sorbitol tetraacrylate, sorbitol
pentaacrylate, sorbitol hexaacrylate tri(acryloyloxyethyl)
isocyanurate, polyester acrylate oligomer, isocyanuric acid
EO-modified triacrylate etc.
[0129] As methacrylic esters, the examples include tetramethylene
glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl
glycol dimethacrylate, trimethylolpropane trimethacrylate,
trimethylolethane trimethacrylate, ethylene glycol dimethacrylate,
1,3-butanediol dimethacrylate, hexanediol dimethacrylate,
pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,
pentaerythritol tetramethacrylate, dipentaerythritol
dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol
trimethacrylate, sorbitol tetramethacrylate,
bis[p-(3-methacryloxy-2-hydroxypropoxy)-phenyl]dimethylmethane,
bis-[p-(methacryloxyethoxy)phenyl]-dimethylmethane, etc.
[0130] As itaconic esters, the examples include ethylene glycol
diitaconate, propylene glycol diitaconate, 1,3-butanediol
diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol
diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate,
etc. As crotonic esters, the examples include ethylene glycol
dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol
dicrotonate, sorbitol tetradicrotonate, etc. As isocrotonic esters,
the examples include ethylene glycol diisocrotonate,
pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. As
maleic esters, the examples include ethylene glycol dimaleate,
triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol
tetramaleate, etc.
[0131] As the examples of other esters, e.g., the aliphatic alcohol
esters disclosed in JP-B-51-47334 and JP-A-57-196231, the esters
having an aromatic skeleton disclosed in JP-A-59-5240, JP-A-59-5241
and JP-A-2-226149, and the esters containing an amino group
disclosed in JP-A-1-165613 are also preferably used in the
invention. The above ester monomers can also be used as
mixtures.
[0132] Further, the specific examples of the amide monomers of
aliphatic polyhydric amine compounds and unsaturated carboxylic
acids include methylenebis-acrylamide, methylenebis-methacrylamide,
1,6-hexamethylenebis-acrylamide,
1,6-hexamethylenebis-methacrylamide,
diethylenetriaminetris-acrylamide, xylylenebis-acrylamide,
xylylenebis-methacrylamide, etc. As other preferred amide monomers,
the amide monomers having a cyclohexylene structure disclosed in
JP-B-54-21726 can be exemplified.
[0133] Further, urethane based addition polymerizable compounds
manufactured by the addition reaction of isocyanate and hydroxyl
groups are also preferably used. As the specific example of such a
compound, as disclosed in JP-B-48-41708, a vinyl urethane compound
containing two or more polymerizable vinyl groups in one molecule
obtained by adding vinyl monomer having a hydroxyl group
represented by the following formula (a) to a polyisocyanate
compound having two or more isocyanate groups in one molecule is
exemplified. CH.sub.2.dbd.C(R.sub.4)COOCH.sub.2CH(R.sub.5)OH (a)
wherein R.sub.4 and R.sub.5 each represents H or CH.sub.3.
[0134] The urethane acrylates disclosed in JP-A-51-37193,
JP-B-2-32293 and JP-B-2-16765, and the urethane compounds having an
ethylene oxide skeleton disclosed in JP-B-58-49860, JP-B-56-17654,
JP-B-62-39417 and JP-B-62-39418 are also preferably used in the
invention. In addition, extremely high speed photopolymerizable
compositions can be obtained by using addition polymerizable
compounds having an amino structure or a sulfide structure in the
molecule as disclosed in JP-A-63-277653, JP-A-63-260909 and
JP-A-1-105238
[0135] As other examples, polyfunctional acrylates and
methacrylates, such as polyester acrylates, and epoxy acrylates
obtained by reacting epoxy resins with (meth)acrylic acids as
disclosed in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 can be
exemplified. The specific unsaturated compounds disclosed in
JP-B-46-43946, JP-B1-40337 and JP-B1-40336, and the vinyl sulfonic
acid compounds disclosed in JP-A-2-25493 can also be exemplified.
Further, according to cases, the structures containing a
perfluoroalkyl group disclosed in JP-A-61-22048 are preferably
used. In addition, the compounds introduced as the photo-curable
monomers and oligomers into Bulletin of Nippon Setchaku Kyokai,
Vol. 20, No. 7, pp. 300-308 (1984) can also be used.
[0136] The details in usage of these addition polymerizable
compounds, e.g., what structure is to be used, whether the
compounds are to be used alone or in combination, or what an amount
is to be used, can be optionally set up according to the final
design of the performances of the lithographic printing plate
precursor. For example, these conditions are selected on the basis
of the following aspects.
[0137] In the point of sensitivity, the structure containing many
unsaturated groups per a molecule is preferred and bifunctional or
higher functional groups are preferred in many oases. For
increasing the strength of an image area, i.e., a hardened film,
trifunctional or higher functional groups are preferred, and it is
also effective to use different functional numbers and different
polymerizable groups (e.g., acrylic ester, methacrylic ester;
styrene compounds, vinyl ether compounds) in combination to control
both speed and strength.
[0138] Further, the selection and usage of the addition
polymerizable compounds are important factors for the compatibility
with other components in an image-recording layer (e.g., a binder
polymer; a polymerization initiator, a colorant) and
dispersibility, for example, in some cases compatibility can be
improved by using low purity compounds or two or more compounds in
combination. Further, it is also possible to select a compound
having a specific structure for the purpose of improving the
adhesion property to a support and an overcoat layer described
later.
[0139] Polymerizable compounds are used preferably in an amount of
from 5 to 80mass % to the nonvolatile components in an
image-recording layer, and more preferably from 25 to 75 mass %.
Polymerizable compounds may be used alone, or two or more compounds
may be used in combination, In addition, the structure, blending
and addition amount of addition polymerizable compounds can be
properly selected in view of the degree of polymerization hindrance
by oxygen, resolution, a fogging property, refractive index change
and surface stickiness and, further, in some cases, a layer
constitution and a coating method of undercoating and upper coating
may be taken.
<Radical Polymerization Initiator>
[0140] A radical polymerization initiator for use in the invention
is a compound capable of generating a radical by light or heat, or
both energies, and initiating and accelerating polymerization of a
compound having polymerizable unsaturated groups. As the
polymerization initiators that can be used in the invention,
well-known thermal polymerization initiators, compounds having a
bond small in bond-dissociating energy, and photopolymerization
initiators are exemplified. The radical polymerization initiators
that can be preferably used in the invention are compounds capable
of generating radicals by heat energy. The radical polymerization
initiators for use in the invention are specifically described
below. The radical polymerization initiators can be used alone or
in combination of two or more.
[0141] As such radical polymerization initiators, e.g., organic
halogen compounds, carbonyl compounds, organic peroxides, azo-based
compounds, azide compounds, metallocene compounds,
hexaarylbiimidazole compounds, organic boron compounds, disulfone
compounds, oxime ester compounds, and onium salt compounds are
exemplified.
[0142] As the organic halogen compounds, specifically, the
compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan,
42, 2924 (1969), U.S. Pat. No. 3,905,815, JP-B464605,
JP-A-48-36281, JP-A-53-133428, JP-A-55-32070, JP-A-60-239736,
JP-A-1-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401,
JP-A-63-70243, JP-A-63-298339, and M P. Hutt Journal of
Heterocyclic Chemistry, 1 (No 3) (1970) are exemplified. Of these
compounds, oxazole compounds and s-triazine compounds substituted
with a trihalomethyl group are preferably used.
[0143] More preferably, s-triazine derivatives in which at least
one mono-, di- or tri-halogen-substituted methyl group is bonded to
the s-triazine ring, specifically, e.g.,
2,4,6-tris(monochloromethyl)-s-triazine,
2,4,6-tris(dichloro-methyl)-s-triazine,
2,4,6-tris(trichloromethyl)-s-triazine,
2-methyl-4,6-bis(trichloromethyl)-s-triazine,
2-n-propyl-4,6-bis(trichloromethyl)-s-triazine,
2-(.alpha.,.alpha.,.beta.-trichloro-ethyl)-4,6-bis(trichloromethyl)-triaz-
ine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine,
2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-[1-(p-methoxyphenyl)-2,4-butadienyl]4,6-bis(trichloromethyl)-s-triazine-
, 2-styryl-4,6-bis(trichloromethyl)-s-triazine,
2-(p-methoxy-styryl)-4,6-bis(trichloromethyl)-s-triazine,
2-(p-1-propyl-oxystyryl)-4,6-bis(trichloromethyl)-s-triazine,
2-(p-tolyl)-4,6-bis(trichloromethyl)-s-azine,
2-(4-methoxy-naphthyl)-4,6-bis(trichloromethyl)-s-triazine,
2-phenyl-thio-4,6-bis(trichloromethyl)-s-triazine,
2-benzylthio-4,6-bis(trichloromethyl)-s-triazine,
2,4,6-tris(dibromomethyl)-s-triazine,
2,4,6-tris(tribromomethyl)-s-triazine,
2-methyl-4,6-bis(tribromomethyl)-s-triazine, and
2-methoxy-4,6-bis(tribromomethyl)-s-triazine are exemplified.
[0144] As the carbonyl compounds, benzophenone derivatives, e.g.,
benzophenone, Michler's ketone, 2-methylbenzophenone,
3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone,
4-bromobenzophenone, and 2-carboxybenzophenone; acetophenone
derivatives, e.g., 2,2-dimethoxy-2-phenyl-acetophenone,
2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone,
.alpha.-hydroxy 2-methylphenylpropanone,
1-hydroxy-1-methylethyl-(p-isopropylphenyl) ketone,
1-hydroxy-1-p-dodecylphenyl) ketone,
2-methyl-[4'-(methylthio)phenyl]-2-morpholino-1-propanone, and
1,1,1-trichloromethyl-(p-butyl-phenyl) ketone, thioxanthone
derivatives, e.g., thioxanthone, 2-etlylthioxanthone,
2-isopropylthioxanthone, 2-chloro-thioxanthone,
2,4-dimethylthioxanthone, 2,4-diethylthio-xanthone, and
2,4-diisopropylthioxanthone, and benzoic ester derivatives, e.g.,
ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate are
exemplified.
[0145] As the azo-based compounds, the azo compounds disclosed in
JP-A-8-108621 can be used.
[0146] As the organic peroxides, e.g., trimethylcyclohexanone
peroxide, acetylacetone peroxide,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,
1,1-bis(tert-butylperoxy)cyclo-hexane,
2,2-bis(tert-butylperoxy)butane, tert butyl hydro-peroxide, cumene
hydroperoxide, diisopropylbenzene hydro peroxide,
2,5-dimethylhexane-2,5-dihydroperoxide, 1,173,3-tetramethylbutyl
hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)-hexane-2,5-oxanoyl peroxide,
succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl
peroxide, diisopropylperoxy dicarbonate, di-2-ethylhexylperoxy
dicarbonate, di-2-ethoxy-ethylperoxy dicarbonate,
dimethoxyisopropylperoxy carbonate,
di(3-methyl-3-methoxybutyl)peroxy dicarbonate, tert-butyl-peroxy
acetate, tert-butylperoxy pivalate tert-butylperoxy neodecanoate,
tert-butylperoxy octanoate, tert-butylperoxy laurate, tersyl
carbonate, 3,3'4,4'-tetra(t-butylperoxy-carbonyl)benzophenone,
3,3',4,4''-tetra(t-hexylperoxy-carbonyl)benzophenone,
3,3',4,4'-tetra(p-isopropylcumyl-peroxycarbonyl)benzophenone,
carbonyldi(t-butylperoxy-dihydrogendiphthalate), and
carbonyldi(t-hexylperoxy-dihydrogendiphthalate) are
exemplified.
[0147] As the metallocene compounds, various titanocene compounds
disclosed in JP-A-59-152396, JP-A-61-151197, JP-A-63-41484,
JP-A-2-249, JP-A-2-4705 and JP-A-5-83588, e.g.,
dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti
bis-2,6-difluorophen-1-yl,
dicyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl,
dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,
dicyclopentadienyl-T-bis-2,3,5,6-tetrafluorophen-1-yl,
dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl,
dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl,
dimethylcyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl,
dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl
dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, and
the iron-arene complexes disclosed in JP-A1-304453 and
JP-A-1-152109 are exemplified.
[0148] As the hexaarylbiimidazole compounds, various compounds
disclosed in JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783 and
4,622,286, specifically, e.g., 2,2'-bis(o-chlorophenyl)-4,4',5,5
tetraphenylbiimidazole,
2,2'-bis(o-bromophenyl)-4,4',5,5-tetraphenylbiimidazole,
2,2'-bis(o,p-dichloro-phenyl)-4,4',5,5'-tetraphenylbiimidazole,
2,2'-bis-(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole,
2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5-tetraphenyl-biimidazole,
2,2'-bis(o-nitrophenyl)-4,4',5'-tetraphenyl-biimidazole,
2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, and
2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole are
exemplified.
[0149] As the organic boron compounds, e.g., the organic borates
disclosed in JP-A-62-143044, JP-A-62-150242, JP-A-9-188685,
JP-A-9-188686, JP-A-9-188710, JP-A-2000-131837, JP-A-2002-107916,
Japanese Patent No, 2764769, JP-A-2002-116539, and Kunz, Martin,
"Rad Tech '98 Proceeding Apr. 19-22, 1998, Chicago", the organic
boron sulfonium complexes or the organic boron oxosulfonium
complexes disclosed in JP-A6-157623, JP-A-6-175564 and
J-A-6-175561, the organic boron iodonium complexes disclosed in
JP-A-6-175554 and JP-A-6-175553, the organic boron phosphonium
complexes disclosed in JP-A-9-188710, and the organic boron
transition metal coordination complexes disclosed in JP-A-6-343011,
JP-A-7-128785, JP-A-7-140589, JP-A-7-306527 and JP-A-7-292014 are
exemplified.
[0150] As the disulfone compounds, the compounds disclosed in
JP-A-61-166544 and JP-A-2003-328465 are exemplified.
[0151] As the oxime ester compounds, the compounds described in J.
C. S. Perkin II, 1653-1660 (1979), J. C. S. Perkin II, 156-162
(1979), Journal of Photopolymer Science and Technology, 202-232
(1995), JP-A-2000-66385, the compounds disclosed in
JP-A-2000-80068, specifically the compounds represented by the
following formulae are exemplified. ##STR42## ##STR43## ##STR44##
##STR45##
[0152] As the onium salt compounds, onium salts, e.g., the
diazonium salt described in S. I. Schlesinger, Photogr. Sci. Eng.,
18, 387 (1974), and T. S. Bal et al., Polymer 217423 (1980), the
ammonium salts disclosed in U.S. Pat. No. 4,069,055 and
JP-A-4-365049, the phosphonium salts disclosed in U.S. Pat. Nos.
4,069,055 and 4,069,056, the iodonium salts disclosed in EP
104,143, U.S. Pat. No. 339,049, 410,201, JP-A-2-150848 and
JP-A-2-296514, the sulfonium salts disclosed in EP 370,693, EP
390,214, BP 233,567, EP 297,443, EP 297,442, U.S. Pat. Nos.
4,933,377, 161, 811, 410,201, 339,049, 4,760,013, 4,734,444,
2,833,827, German Patent Nos. 2,904,626, 3,604,580 and 3,604,581,
the selenonium salts described in J. V. Crivello et al.,
Macromolecules, 10 (6), 1307 (1977), and J. V Crivello et al, J.
Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), and the arsonium
salts described in C. S. Wen et al., Teh. Proc. Conf. Rad. Curing
ASIA, p. 478, Tokyo, October (1988) are exemplified.
[0153] As preferred compounds particularly from the aspects of
reactivity and stability, the oxime ester compounds and the onium
salts (diazonium salts, iodonium salts and sulfonium salts) are
exemplified.
[0154] The onium salts preferably used in the invention are onium
salts represented by the following formulae (RI-I) to (RI-III).
##STR46##
[0155] In formula (RI-I), Ar.sub.11 represents an aryl group having
20 or less carbon atoms, which may have from 1 to 6 substituents,
and as the preferred substituents, an alkyl group having from 1 to
12 carbon atoms, an alkenyl group having from 1 to 12 carbon atoms,
an alkynyl group having from 1 to 12 carbon atoms, an aryl group
having from 1 to 12 carbon atoms, an alkoxyl group having from 1 to
12 carbon atoms, an aryloxy group having from 1 to 12 carbon atoms,
a halogen atom, an alkylamino group having from 1 to 12 carbon
atoms, a dialkylamino group having from 1 to 12 carbon atoms, an
alkylamido group or arylamido group having from 1 to 12 carbon
atoms, a carbonyl group, a carboxyl group, a cyano group, a
sulfonyl group, a thioalkyl group having from 1 to 12 carbon atoms,
and a thioaryl group having from 1 to 12 carbon atoms are
exemplified. Z.sub.11.sup.- represents a monovalent anion, and
specifically a halogen ion, a perchlorate ion, a
hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion,
a sulfinate ion, a thiosulfonate ion and a sulfate ion are
exemplified. In particular, in view of stability, a perchlorate
ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a
sulfonate ion and a sulfinate ion are preferred.
[0156] In formula (RI-II), Ar.sub.21 and Ar.sub.22 each represents
an aryl group having 20 or less carbon atoms, which may have from 1
to 6 substituents, and as the preferred substituents, an alkyl
group having from 1 to 12 carbon atoms, an alkenyl group having
from 1 to 12 carbon atoms, an alkynyl group having from 1 to 12
carbon atoms, an aryl group having from 1 to 12 carbon atoms, an
alkoxyl group having from 1 to 12 carbon atoms, an aryloxy group
having from 1 to 12 carbon atoms, a halogen atom, an alkylamino
group having from 1 to 12 carbon atoms, a dialkylamino group having
from 1 to 12 carbon atoms, an alkylamido group or arylamido group
having from 1 to 12 carbon atoms, a carbonyl group, a carboxyl
group, a cyano group, a sulfonyl group, a thioalkyl group having
from 1 to 12 carbon atoms, and a thioaryl group having from 1 to 12
carbon atoms are exemplified Z.sub.21 represents a monovalent
anion, and specifically a halogen ion, a perchlorate ion, a
hexafluoro-phosphate ion, a tetrafluoroborate ion, a sulfonate ion,
a sulfinate ion, a thiosulfonate ion and a sulfate ion are
exemplified. In view of stability and reactivity, a perchlorate
ion, a hexafluorophosphate ion, a tetrafluoro-borate ion, a
sulfonate ion, a sulfinate ion and a carboxylate ion are
preferred.
[0157] In formula (RI-III), R.sub.31, R.sub.32 and R.sub.33 each
represents an aryl, alkyl, alkenyl or alkynyl group having 20 or
less carbon atoms, which may have from 1 to 6 substituents. Above
alt in view of stability and reactivity, an aryl group is
preferred. As the substituents, an alkyl group having from 1 to 12
carbon atoms, an alkenyl group having from 1 to 12 carbon atoms, an
alkynyl group having from 1 to 12 carbon atoms, an aryl group
having from 1 to 12 carbon atoms, an alkoxyl group having from 1 to
12 carbon atoms, an aryloxy group having from 1 to 12 carbon atoms,
a halogen atom, an alkylamino group having from 1 to 12 carbon
atoms, a dialkylamino group having from 1 to 12 carbon atoms, an
alkylamido group or arylamido group having from 1 to 12 carbon
atoms, a carbonyl group, a carboxyl group, a cyano group, a
sulfonyl group, a thioalkyl group having from 1 to 12 carbon atoms,
and a thioaryl group having from 1 to 12 carbon atoms are
exemplified, Z.sub.31.sup.31 represents a monovalent anion, and
specifically a halogen ion, a perchlorate ion, a
hexafluoro-phosphate ion, a tetrafluoroborate ion, a sulfonate ion,
a sulfinate ion, a thiosulfonate ion, and a sulfate ion are
exemplified. In particular in view of stability and reactivity a
perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate
ion, a sulfonate ion, a sulfinate ion and a carboxylate ion are
preferred. As more preferred carboxylate ions, the carboxylate ions
disclosed in JP-A-2001-343742 are exemplified, and the carboxylate
ions disclosed in JP-A-2002-148790 are particularly preferred.
[0158] The specific examples of the compounds represented by
formulae (RI-I), (RI-II) and (RI-III) are shown below, but the
invention is not limited to these compounds. ##STR47## ##STR48##
##STR49## ##STR50##
[0159] Radical polymerization initiators can be used preferably in
an amount of from 0.1 to 50 mass % to the total solids content
constituting the image-recording layer, more preferably from 0.5 to
30 mass %, and still more preferably from 1 to 20 mass %. By using
polymerization initiators in this range, good sensitivity and
soiling resistance of a non-image area in printing can be obtained.
Radical polymerization initiators may be used alone or two or more
kinds of initiators may be used in combination. These radical
polymerization initiators may be added with other components to the
same layer, or another layer may be provided for radical
polymerization initiators.
<Other Image-Recording Layer Components>
[0160] If necessary, additives such as binder polymers,
surfactants, polymerization inhibitors, higher fatty acid
derivatives, plasticizers, inorganic fine particles and low
molecular weight hydrophilic compounds may further be added to the
radical polymerization system image-recording layer of the
invention. These additives are described below.
<Binder Polymer>
[0161] Binder polymers can be used in the image-recording layer in
the invention. Well known binder polymers can be used in the
invention with no restriction, and linear organic polymers having a
film-forming property are preferably used. The examples of such
binder polymers include acrylic resins, polyvinyl acetal resins,
polyurethane resins, polyurea resins, polyimide resins, polyamide
resins, epoxy resins, methacrylic resins, polystyrene resins,
novolak type phenolic resins, polyester resin, synthetic rubber and
natural rubber.
[0162] It is preferred that binder polymers have a crosslinking
property for the purpose of improving the layer strength of an
image area. For giving a crosslinkable property to binder polymers,
it is effective to introduce a crosslinkable functional group such
as an ethylenic unsaturated bond into the main chain or side chain
of the binder polymers. The crosslinkable functional group may be
introduced by copolymerization.
[0163] As the examples of the polymers having an ethylenic
unsaturated bond in the main chain of the molecule,
poly-1,4-butadiene and poly-1,4-isoprene are exemplified.
[0164] As the examples of the polymers having an ethylenic
unsaturated bond in the side chain of the molecule, polymers of
esters or amides of acrylic acid or methacrylic acid, wherein the
residue of the ester or amide(R of --COOR or --CONHR) has an
ethylenic unsaturated bond are exemplified.
[0165] The examples of the residues having an ethylenic unsaturated
bond (the above-described R) include,
--(CH.sub.2).sub.n(CR.sup.1.dbd.CR.sup.2R.sup.3,
--(CH.sub.2O).sub.nCH.sub.2CR.sup.1.dbd.CR.sup.2R.sup.3,
--(CH.sub.2CH.sub.2O).sub.nCH.sub.2CR.sup.1.dbd.CR.sup.2R.sup.3,
--(CH.sub.2).sub.nNH--CO--O--CH.sub.2CR.sup.1.dbd.CR.sup.2R.sup.3,
--(CH.sub.2).sub.n--O--CO--CR.sup.1.dbd.CR.sup.2R.sup.3 and
--(CH.sub.2CH.sub.2O).sub.2--X (wherein R.sup.1,R.sup.2 and R.sup.3
each represents a hydrogen atom, a halogen atom, an alkyl group
having from 1 to 20 carbon atoms, an aryl group, an alkoxyl group
or an aryloxy group, and R.sup.1 and R.sup.2 or R.sup.3 may be
bonded to each other to form a ring) n represents an integer of
from 1 to 10, and X represents a dicyclopentadienyl residue).
[0166] The specific examples of the ester residues include
--CH.sub.2CH.dbd.CH.sub.2 (disclosed in JP-B-7-21633),
--CH.sub.2CH.sub.2O--CH.sub.2CH.dbd.CH.sub.2,
--CH.sub.2C(CH.sub.3).dbd.CH.sub.2,
--CH.sub.2CH.dbd.CH--C.sub.6H.sub.5,
--CH.sub.2CH.sub.2OCOCH.dbd.CH--C.sub.6H.sub.5,
--CH.sub.2CH.sub.2--NHCOO--CH.sub.2CH.dbd.CH.sub.z and
--CH.sub.2CH.sub.2O--X (wherein X represents a dicyclopentadienyl
residue).
[0167] The examples of the amido residues include
--CH.sub.2CH.dbd.CH.sub.2, --CH.sub.2CH.sub.2--Y (wherein Y
represents a cyclohexene residue), and
--CH.sub.2CH.sub.2--OCO--CH.dbd.CH.sub.2.
[0168] When free radicals polymerization initiation radicals or the
grown radicals of a polymerizable compound in the polymerization
process) are added to the crosslinkable functional groups of a
binder polymer having a crosslinking property, addition
polymerization occurs directly between the polymers or via the
polymerization chains of the polymerizable compound, as a result,
crosslinking is formed between the molecules of the polymers, and
the binder polymer is hardened. Alternatively, the atoms in the
polymer (e.g., the hydrogen atoms on the carbon atoms contiguous to
crosslinkable functional groups) are extracted by free radicals and
polymer radicals are grown, and the polymer radicals are bonded to
each other, whereby crosslinking is formed between the polymer
molecules, so that the binder polymer is hardened.
[0169] The content of crosslinkable groups in a binder polymer (the
content of radical polymerizable unsaturated double bonds by an
iodometric titration method) is preferably from 0-1 to 10,0 mmol
per gram of the binder polymer, more preferably from 1.0 to 7.0
mmol, and most preferably from 2.0 to 5.5 mmol. Good sensitivity
and good storage stability can be obtained with this range of the
content of crosslinkable groups.
[0170] From the viewpoint of the improvement of an on-press
developing property, it is preferred that binder polymers have high
solubility and dispersibility in ink and/or a fountain
solution.
[0171] For improving the solubility and dispersibility in ink,
binder polymers are preferably lipophilic, and for improving the
solubility and dispersibility in a fountain solution, binder
polymers are preferably hydrophilic. Accordingly, in the invention,
it is also effective to use a lipophilic binder polymer and a
hydrophilic binder polymer in combination.
[0172] As hydrophilic binder polymers, binder polymers having a
hydrophilic group, e.g., a hydroxyl group, a carboxyl group, a
carboxylate group, a hydroxyethyl group, a polyoxyethyl group, a
hydroxypropyl group, a polyoxypropyl group, an amino group, an
aminoethyl group, an aminopropyl group, an ammonium group, an amido
group, a carboxymethyl group, a sulfonic acid group and a
phosphoric acid group are preferably exemplified.
[0173] The specific examples of hydrophilic binder polymers include
gum arabic, casein, gelatin, starch derivative, carboxymethyl
cellulose and the sodium salt thereof cellulose acetate, sodium
alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid
copolymers, polyacrylic acids and the salts thereof,
polymethacrylic acids and the salts thereof homopolymers and
copolymers of hydroxyethyl methacrylate, homopolymers and
copolymers of hydroxyethyl acrylate, homopolymers and copolymers of
hydroxypropyl methacrylate, homopolymers and copolymers of
hydroxypropyl acrylate, homopolymers and copolymers of hydroxybutyl
methacrylate, homopolymers and copolymers of hydroxybutyl acrylate,
polyethylene glycols, hydroxypropylene polymers, polyvinyl
alcohols, hydrolyzed polyvinyl acetate having a hydrolysis degree
of 60 mol % or more, preferably 80 mol % or more, polyvinyl formal,
polyvinyl butyral, polyvinyl pyrrolidone, homopolymers and
copolymers of acylamide, homopolymers and copolymers of
methacrylamide, homopolymers and copolymers of
N-methylolacrylamide, polyvinyl pyrrolidone, alcohol-soluble nylon,
and polyether of 2,2-bis(4-hydroxy-phenyl)propane and
epichlorohydrin.
[0174] The binder polymers preferably have a mass average molecular
weight of preferably 5,000 or higher, more preferably from 10,000
to 300,000, and a number average molecular weight of preferably
1,000 or higher, more preferably from 2,000 to 250,000. The
polydisperse degree (mass average molecular weight/number average
molecular weight is preferably from 1.1 to 10.
[0175] The binder polymers may be any of random polymers, block
polymers and graft polymers, but random polymers are preferred. The
binder polymers may be used alone or as a mixture of two or
more.
[0176] The binder polymers can be synthesized by conventionally
well known methods. As the solvents for use in the synthesis, e.g.,
tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl
ketone, acetone, methanol, ethanol, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether; 2-methoxyethyl acetate,
diethylene glycol dimethyl ether, 1-methoxy-2-propanol,
1-methoxy-2-propyl acetate, N,N-dimethylformamide,
N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate,
ethyl lactate, dimethyl sulfoxide, and water are exemplified. These
solvents may be used alone or two or more solvents may be used as a
mixture.
[0177] As the radical polymerization initiators used in the
synthesis of the binder polymers, well known compounds, e.g., azo
initiators and peroxide initiators can be used.
[0178] The binder polymers are used in an amount of preferably from
10 to 90 mass % to the total solids content of the image-recording
layer, more preferably from 20 to 80 mass %, and still more
preferably from 30 to 70 mass %. When the binder polymers are used
in this range, preferred strength of an image area and good
image-forming property can be obtained.
[0179] It is preferred to use a polymerizable compound and the
binder polymer in mass ratio of from 1/9 to 7/3.
<Surfactant>
[0180] In the invention, it is preferred to use a surfactant in an
image-recording layer to accelerate the on-press development
property at the time of initiating printing and to improve the
conditions of coating surface. As the surfactants for these
purposes, nonionic surfactants, anionic surfactants, cationic
surfactants, ampholytic surfactants and fluorine surfactants are
used. Surfactants may be used alone or two or more surfactants may
be used in combination.
[0181] The nonionic surfactants for use in the invention are not
particularly restricted and conventionally well known surfactants
can be used, e.g., polyoxyethylene alkyl ethers, polyoxyethylene
alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers,
polyoxyethylene polyoxypropylene alkyl ethers, glycerol fatty acid
partial esters, sorbitan fatty acid partial esters, pentaerythritol
fatty acid partial esters, propylene glycol fatty acid mono esters,
sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty
acid partial esters, polyoxyethylene sorbitol fatty acid partial
esters, polyethylene glycol fatty acid esters, polyglycerol fatty
acid partial esters, polyoxyethylenated castor oils,
polyoxyethylene glycerol fatty acid partial esters, fatty acid
diethanolamides, N,N-bis-2-hydroxyalkylamines, polyoxyethylene
alkylamine, triethanolamine fatty acid esters, trialkylamine oxide,
polyethylene glycol, and copolymers of polyethylene glycol and
polypropylene glycol are exemplified.
[0182] The anionic surfactants for use in the invention are not
particularly restricted and conventionally well known surfactants
can be used, e.g., fatty acid salts, abietates,
hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinic
esters, straight chain alkylbenzenesulfonates, branched chain
alkylbenzenesulfonates, alkylnaphthalene-sulfonates, alkylphenoxy
polyoxyethylene propyl sulfonates, polyoxyethylene alkyl
sulfophenyl ethers, sodium N-methyl-N-oleyltaurine, disodium
N-alkylsulfosuccinic acid monoamide, petroleum sulfonates, sulfated
beef tallow, sulfuric esters of fatty acid alkyl ester,
alkylsulfuric esters, polyoxyethylene alkyl ether sulfuric esters,
fatty acid monoglyceride sulfuric esters, polyoxyethylene alkyl
phenyl ether sulfuric esters, polyoxyethylene styryl phenyl ether
sulfuric esters, alkylphosphoric esters, polyoxyethylene alkyl
ether phosphoric esters, polyoxyethylene alkyl phenyl ether
phosphoric esters, partial saponification products of
styrene/maleic anhydride copolymers, partial saponification
products of olefin/maleic anhydride copolymers, and naphthalene
sulfonate formaldehyde condensation products are exemplified.
[0183] The cationic surfactants for use in the invention are not
particularly restricted and conventionally well known surfactants
can be used, e.g., alkylamine salts, quaternary ammonium salts,
polyoxyethyene alkylamine salts, and polyethylene polyamine
derivatives are exemplified.
[0184] The ampholytic surfactants for use in the invention are not
particularly restricted and conventionally well known surfactants
can be used, e.g., carboxybetaines, amino-carboxylic acids,
sulfobetaines, aminosulfuric esters and imidazolines are
exemplified.
[0185] In the above surfactants, "polyoxyethylene" can be taken as
"polyoxyalkylene" such as polyoxymethylene, polyoxy-propylene, and
polyoxybutylene, and these surfactants can also be used in the
invention.
[0186] As more preferred surfactants, fluorine surfactants
containing a perfluoroalkyl group in the molecule are exemplified.
As such surfactants, anionic surfactants, e.g.,
perfluoroalkylcarboxylate, perfluoroalkylsulfonate, and
perfluoroalkylphosphate; ampholytic surfactants, e.g.,
perfluoroalkylbetaine; cationic surfactants, e.g.,
perfluoroalkyltrimethylanimonium salt; and nonionic surfactants,
e.g., perfluoroalkylamine oxide, perfluoroalkyl ethylene oxide
addition products, oligomers containing a perfluoroalkyl group and
a hydrophilic group, oligomers containing a perfluoroalkyl group
and a lipophilic group, oligomers containing a perfluoroalkyl
group, a hydrophilic group, and a lipophilic group, and urethane
containing a perfluoroalkyl group and a lipophilic group are
exemplified. Further, the fluorine surfactants disclosed in
JP-A62-170950, JP-A-62-226143 and JP-A-60-168144 are also
preferably used.
[0187] Surfactants can be used alone, or two or more surfactants
can be used in combination.
[0188] Surfactants are preferably used in an amount of from 0.001
to 10 mass % to the total solids content of the image recording
layer more preferably from 0.01 to 7 mass %.
<Polymerization Inhibitor>
[0189] For preventing unnecessary thermal polymerization of a
radical polymerizable compound during manufacture or preservation
of an image-recording layer, it is preferred that a small amount of
thermal polymerization inhibitor be added to an image-recording
layer in the invention.
[0190] As the thermal polymerization inhibitors, e.g.,
hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol,
t-butylcatechol, benzoquinone,
4,4'-thiobis(3-methyl-6-t-butylphenol),
2,2'-methylenebis(4-methyl-6-t-butylphenol), and
N-nitroso-N-phenylhydroxylamine aluminum salt are exemplified.
[0191] The amount of the thermal polymerization inhibitor to be
added to an image-recording layer is preferably from about 0.01 to
about 5 mass % to all the solids content of the image recording
layer.
<Higher Fatty Acid Derivatives and the Like>
[0192] For preventing the polymerization hindrance due to oxygen
higher fatty acid derivatives, e.g., behenic acid and behenic acid
amide, may be added to an image-recording layer in the invention
and locally exist on the surface of the image-recording layer in
the drying process after coating. The addition amount of the higher
fatty acid derivatives is preferably from about 0.1 to about 10
mass % to the total solids content of the image-recording
layer.
<Plasticizer>
[0193] An image-recording layer in the present invention may
contain a plasticizer to improve an on-press developing
property.
[0194] The examples of the plasticizers include phthalic esters,
e.g., dimethyl phthalate, diethyl phthalate, dibutyl phthalate,
diisobutyl phthalate, dioctyl phthalate, octylcapryl phthalate,
dicyclohexyl phthalate, ditridecyl phthalate, butylbenzyl
phthalate, diisodecyl phthalate, and diallyl phthalate; glycol
esters, e.g., dimethyl glycol phthalate, ethyl phthalyl ethyl
glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl
glycolate, and triethylene glycol dicaprylate; phosphoric esters,
e.g., tricresyl phosphate and triphenyl phosphate; aliphatic
dibasic esters, e.g., diisobutyl adipate, dioctyl adipate, dimethyl
sebacate, dibutyl sebacate, dioctyl azelatc, and dibutyl maleate;
and polyglycidyl methacrylate, triethyl citrate, glycerol triacetyl
ester and butyl laurate.
[0195] The amount of the plasticizers is preferably about 30 mass %
or less to all the solids content of the image recording layer.
<Inorganic Fine Particles>
[0196] For the improvement of the hardened layer strength of an
image area and the on-press developing property of a non-image
area, an image-recording layer may contain inorganic fine
particles.
[0197] As the inorganic fine particles, e.g., silica, alumina,
magnesium oxide, titanium oxide, magnesium carbonate, calcium
alginate and mixtures of these fine particles are preferably used.
Even when inorganic fine particles are not light/heat convertible,
they can be used for layer strengthening and the reinforcement of
interfacial adhesion by surface roughening.
[0198] The average particle size of the inorganic fine particles is
preferably from 5 nm to 10 .mu.m, more preferably from 0.5 to 3
.mu.m. When the average particle size is in this range, the
inorganic fine particles are stably dispersed in an image-recording
layer, and the layer strength of the image-recording layer can be
sufficiently maintained, so that a non-image area difficult to be
soiled and excellent in hydrophilicity can be formed.
[0199] These inorganic fine particles are easily available as
commercial products of colloidal silica dispersion and the
like.
[0200] The addition amount of the inorganic fine particles is
preferably 20 mass % or less to all the solids content of the image
recording layer, more preferably 10 mass % or less.
<Low Molecular Weight Hydrophilic Compound>
[0201] For the improvement of an on-press developing property, an
image-recording layer in the invention may contain hydrophilic low
molecular weight compounds. As the hydrophilic low molecular weight
compounds, water-soluble organic compounds, such as glycols, e.g.,
ethylene glycol, diethylene glycol, triethylene glycol, propylene
glycol, dipropylene glycol, tripropylene glycol, and ether or ester
derivatives of these glycols, polyhydroxies, e.g., glycerol and
pentaerythritol, organic amines, e.g., triethanolamine,
diethanolamine and monoethanolamine, and salts of these organic
amines, organic sulfonic acids, e.g., toluenesulfonic acid and
benzenesulfonic acid, and salts of these organic sulfonic acids,
organic phosphonic acids, e.g., phenyl-phosphonic acid, and salts
of phenylphosphonic acid, and organic carboxylic acids, e.g.,
tartaric acid, oxalic acid, citric acid, malic acid, lactic acid,
gluconic acid and amino acid, and salts of these organic carboxylic
acids are exemplified.
<Formation Radical Polymerization Type Image-Recording
Layer>
[0202] As the method of adding the above constitutional components
of image-recording layer to an image-recording layer, some
embodiments can be used in the invention. One means is to dissolve
the constitutional components in an appropriate solvent and coating
as disclosed in JP-A-2002-287334, and another means is to use a
microgel.
[0203] As the microgel, a microcapsule is exemplified, and the
microcapsule encapsulates the constitutional components and is
added to an image-recording layer (a microcapsule-type
image-recording layer) as disclosed in JP-A-2001-277740 an
JP-A-2001-277742. In addition, in a microcapsule-type
image-recording layer, the constitutional components may also be
contained outside of the microcapsules.
[0204] As described above, it is preferred in the invention that a
compound causing color change by oxidation or reduction and an
infrared absorber (a reaction system for printing out) to be
combined with the compound are contained in the same microcapsule
in the light of obtaining a printing out image having good
visibility. Further, it is more preferred that reaction systems for
forming a print image, such as a radical polymerizable compound and
a radical polymerization initiator, are added to a microcapsule
different from the microcapsule containing the compound for
printing out and the infrared absorber to be combined, or added to
the outside of the microcapsule to be separated from the printing
out system to avoid the hindrance of reactions each other.
[0205] Constitutional components of an image-recording layer can be
microencapsulated by well-known methods. For example, as the
manufacturing method of microcapsules, a method making use of
coacervation as disclosed in U.S. Pat. Nos. 2,800,457 and
2,800,458, an interfacial polymerization method as disclosed in
U.S. Pat. No. 3,287,154, JP-B-38-19574 and JP-B42-446, a method by
the precipitation of a polymer as disclosed in U.S. Pat. Nos.
3,418,250 and 3,660,304, a method of using isocyanate polyol wall
materials as disclosed in U.S. Pat. No. 3,796,669, a method of
using isocyanate wall materials as disclosed in U.S. Pat. No.
3,914,511, a method of using urea-formaldehyde series or
urea-formaldehyde-resorcinol series wall materials as disclosed in
U.S. Pat. Nos. 4,001,140, 4,087,376 and 4,089,802, a method of
using melamine-formaldehyde resins or hydroxy cellulose wall
materials as disclosed in U.S. Pat. No. 4,025,445, a monomer
polymerization in situ method as disclosed in JP-B-36-9163 and
JP-B-51-9079, a spray drying method as disclosed in British Patent
930,422 and U.S. Pat. No. 3,111,407, and an electrolytic dispersion
cooling method as disclosed in British Patents 952,807 and 967,074
can be exemplified, but the invention is not limited to these
methods.
[0206] The microcapsule walls preferably used in the invention have
a three dimensional crosslinking structure and a property of
swelling by a solvent, and the microcapsule having the microcapsule
wall is an embodiment of the microgel. From this point of view,
polyurea, polyurethane, polyester, polycarbonate polyamide, and the
mixtures of these compounds are preferably used as the microcapsule
wall materials, and polyurea and polyurethane are particularly
preferred. Compounds having crosslinkable functional groups such as
ethylenic unsaturated bonds that can be introduced into the above
binder polymers may be introduced into microcapsule walls.
[0207] The average particle size of the microcapsules is preferably
from 0.01 to 3.0 .mu.m, more preferably from 0.05 to 2.0 .mu.m, and
particularly preferably from 0.10 to 1.0 .mu.m. Good resolution and
aging stability can be obtained in this range of the particle
size.
[0208] An image-recording layer in the invention is formed by
coating a coating solution prepared by dispersing or dissolving the
above necessary components in a solvent. As the solvents used here,
ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol,
ethanol, propanol, ethylene glycol monomethyl ether,
1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl
acetate, dimethoxyethane, methyl lactate, ethyl lactate,
N,N-dimethylacetamide, N,N-dimethyl-formamide, tetramethylurea,
N-methylpyrrolidone, dimethyl sulfoxide, sulforan,
.gamma.-butyrolactone, toluenc, and water are exemplified, but the
solvents are not limited thereto. These solvents are used alone or
as mixture. The concentration of the solids content of the coating
solution is preferably from 1 to 50 mass %.
[0209] It is also possible to form an image-recording layer in the
invention by preparing a plurality of coating solutions by
dispersing or dissolving the same or different components in the
same or different solvents, and repeating the coating and drying a
plurality of times.
[0210] The coating amount of an image-recording layer (solids
content) obtained on a support after coating and drying is
generally preferably from 0.3 to 3.0 g/m.sup.2, although the
coating amount differs depending upon the usage of the
image-recording layer; Good sensitivity and good layer properties
of a image-recording layer can be obtained in this range of the
coating amount.
[0211] As the coating method, various coating methods can be used,
e.g., bar coating, rotary coating, spray coating, curtain coating,
dip coating, air knife coating, blade coating, and roll coating can
be used.
(B) Image-Forming Component of Hydrophobitizing Precursor:
<Hydrophobitizing Precursor>
[0212] Hydrophobitizing precursors in the invention are fine
particles capable of converting a hydrophilic image-recording layer
to hydrophobic upon heating. Such fine particles are preferably at
least one kind of fine particles selected from thermoplastic
polymer fine particles and thermo-reactive polymer fine particles.
Further, the fine particles may be microcapsules encapsulating a
compound having a thermo-reactive group.
[0213] As the thermoplastic polymer fine particles used in the
invention, the thermoplastic polymer fine particles described in
Research Disclosure, No. 33303, January (1992), JP-A-9-123387,
JP-A-9-131850, JP-A-9-171249 JP-A-9-171250, and EP 931647 can be
preferably exemplified. The specific examples of the polymers
constituting these polymer fine particles include homopolymers or
copolymers of monomers such as ethylene, styrene, vinyl chloride,
methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl
methacrylate, vinylidene chloride, acrylate, and vinyl carbazole,
and mixtures thereof. Of these polymers, polystyrene and polymethyl
methacrylate are more preferred.
[0214] The average particle size of the thermoplastic polymer fine
particles for use in the invention is preferably from 0.01 to 2.0
.mu.m. As the synthesizing methods of these thermoplastic polymer
fine particles, a method of dissolving the above compounds in a
water-insoluble organic solvent, mixing and emulsifying the
solution with an aqueous solution containing a dispersant and
applying heat to the emulsion to thereby solidify the emulsion to a
fine particle state with volatizing the organic solvent (a
dissolution dispersion method) can be used, in addition to an
emulsion polymerization method and a suspension polymerization
method.
[0215] As the thermo-reactive polymer fine particles used in the
invention, thermosetting polymer fine particles and polymer fine
particles having a thermo-reactive group are exemplified.
[0216] As the thermosetting polymer fine particles, resins having a
phenolic skeleton, urea resins (e.g., resins obtained by the
resinification of urea or urea derivatives, e.g., methoxymethylated
urea, with aldehydes, e.g., formaldehyde), melamine resins (e.g.,
resins obtained by the resinification of melamine or melamine
derivatives with aldehydes, e.g., formaldehyde), alkyd resins,
unsaturated polyester resins, polyurethane resins, and epoxy resins
can be exemplified. Of these resins, resins having a phenolic
skeleton, melamine resins, urea resins and epoxy resins are
particularly preferred.
[0217] As preferred resins having a phenolic skeleton e.g.,
phenolic resins obtained by resinifying phenol or cresol with
aldehydes, e.g., formaldehyde, hydroxystyrene resins, and polymers
and copolymers of methacrylamide or acrylamide or methacrylate or
acrylate having a phenolic skeleton such as
N-(p-hydroxyphenyl)methacrylamide and p-hydroxyphenyl methacrylate
can be exemplified.
[0218] The average particle size of the thermosetting polymer fine
particles for use in the invention is preferably from 0.01 to 2.0
.mu.m. These thermosetting polymer fine particles can be easily
obtained by a dissolution dispersion method, but a thermosetting
polymer may be made fine particles when the thermosetting polymer
is synthesized. The invention is not limited to these methods.
[0219] As the thermo-reactive group of the polymer fine particles
having a thermo-reactive group used in the invention, functional
groups showing any reaction can be used so long as chemical bonds
are formed. Ethylenic unsaturated groups showing a radical
polymerization reaction (e.g., an acryloyl group, a methacryloyl
group, a vinyl group, an allyl group, etc.), cationic polymerizable
groups (e.g., a vinyl group, a vinyloxy group, etc.), isocyanate
groups showing an addition reaction or blocks thereof epoxy groups,
vinyloxy groups and functional groups having active hydrogen atoms
of the other side compounds of the reaction (e.g., an amino group,
a hydroxyl group, a carboxyl group, etc.), carboxyl groups showing
a condensation reaction and hydroxyl groups and amino groups of the
other side compounds of the reaction, and acid anhydrides showing a
ring opening addition reaction and amino groups and hydroxyl groups
of the other side compounds of the reaction can be preferably
exemplified.
[0220] These functional groups may be introduced into polymer fine
particles in the time of polymerization or they may be added after
polymerization by a polymer reaction.
[0221] When functional groups are introduced in the time of
polymerization, it is preferred that the monomers having these
functional groups are emulsion polymerized or suspension
polymerized. The specific examples of the monomers having the
functional groups include allyl methacrylate, allyl acrylate, vinyl
methacrylate, vinyl acrylate, 2-(vinyloxy)ethyl methacrylate,
p-vinyloxystyrene, p-[2-(vinyloxy)ethyl]-styrene, glycidyl
methacrylate, glycidyl acrylate, 2-isocyanate ethyl methacrylate or
block isocyanate thereof by alcohol, 2-isocyanate ethyl acrylate or
block isocyanate thereof by alcohol, 2-aminoethyl methacrylate,
2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl
acrylate, acrylic acid, methacrylic acid, maleic anhydride,
bifunctional acrylate, and bifunctional methacrylate, but the
invention is not limited to these compounds.
[0222] In the invention, copolymers of these monomers and monomers
copolymerizable with these monomers not having thermo-reactive
groups can also be used. As the examples of copolymerizable
monomers not having thermo-reactive groups, styrene, alkyl
acrylate, alkyl methacrylate, acrylonitrile and vinyl acetate can
be exemplified, for instance, but monomers not having
thermo-reactive groups are not limited to these monomers.
[0223] As the polymer reaction used in the case where the
thermo-reactive groups are introduced after polymerization, the
polymer reactions disclosed in WO 96/34316 can be exemplified.
[0224] Of the above polymer fine particles having thermo-reactive
groups, polymers that are coalesced with each other by heat are
preferred, and those having hydrophilic surfaces and dispersible in
water are particularly preferred. It is preferred that the contact
angle of a film (a water droplet in air) prepared by coating only
polymer fine particles and drying by a temperature tower than the
solidification temperature is lower than the contact angle of a
film (a water droplet in air) prepared by drying by a temperature
higher than the solidification temperature. For making the surfaces
of polymer fine particles hydrophilic, it is effective to let a
hydrophilic polymer or oligomer, e.g., polyvinyl alcohol or
polyethylene glycol or a low molecular weight compound be adsorbed
onto the surfaces of the polymer fine particles. However, the
methods of surface hydrophilization treatment are not restricted
thereto.
[0225] The solidification temperature of these polymer fine
particles having thermo-reactive groups is preferably 70.degree. C.
or higher, but considering the aging stability, 100.degree. C. or
higher is more preferred. The average particle size of the polymer
fine particles is preferably from 0.01 to 2.0 .mu.m, more
preferably from 0,05 to 20 .mu.m and particularly preferably from
0.1 to 1.0 .mu.m. Good resolution and aging stability can be
obtained in is range of average particle size
[0226] As the thremo-reactive groups in the microcapsules
encapsulating a compound having a thermo-reactive group for use in
the invention, the same thermo-reactive groups as used in the
polymer fine particles having thermo-reactive groups are preferably
exemplified. Compounds having a thermo-reactive group are described
below.
[0227] As the compound having a radical polymerizable unsaturated
group, the same compounds as shown in the radical polymerizable
microcapsules are preferably used.
[0228] As the compound having a vinyloxy group that can be
preferably used in the invention, the compounds disclosed in
JP-A-2002-29162 are exemplified. As the specific examples,
tetramethylene glycol divinyl ether, trimethylolpropane trivinyl
ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl
ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl
ether, 1,4-bis[2-(vinyloxy)-ethyloxy]benzene,
1,2-bis[2-(vinyloxy)ethyloxy]benzene,
1,3-bis[2-(vinyloxy)ethyloxy]benzene,
1,3,5-tris[2-(vinyloxy)ethyloxy]benzene,
4,4'-bis[2-(vinyloxy)ethyloxy]-biphenyl,
4,4'-bis[2-(vinyloxy)ethyloxy]diphenyl ether,
4,4'-bis[2-(vinyloxy)ethyloxy]diphenylmethane,
1,4-bis[2-(vinyloxy)ethyloxy]naphthalene,
2,5-bis[2-(vinyloxy)-ethyloxy]furan,
2,5-bis[2-(vinyloxy)ethyloxy]thiophene,
2,5-bis[2-(vinyloxy)ethyloxy]imidazole,
2,2-bis{4-[2-(vinyloxy)ethyloxy]phenyly}propane
(bis[vinyloxyethyl]ether of bisphenol
A),2,2-bis[4-(vinyloxymethyloxy)phenyl]propane, and
2,2-bis[4-(vinyloxy)phenyl]propane are exemplified but the
invention is not limited to these compounds.
[0229] As the compound having an epoxy group suitable used in the
invention, compounds having 2 or more epoxy groups are preferred,
and glycidyl ether compounds obtained by the reaction of polyhydric
alcohol or polyhydric phenol with epichlorohydrin and prepolymers
thereof, polymers and copolymers of glycidyl acrylate or glycidyl
methacrylate can be exemplified.
[0230] The specific examples thereof include propylene glycol
diglycidyl ether; tripropylene glycol diglycidyl ether,
polypropylene glycol diglycidyl other, neopentyl glycol diglycidyl
ether, trimethylolpropane triglycidyl ether, diglycidyl ether of
hydrogenated bisphenol A, hydroquinone diglycidyl ether, resorcinol
diglycidyl ether, diglycidyl ether of bisphenol A or
epichlorohydrin polyaddition products, diglycidyl ether of
bisphenol F or epichlorohydrin polyaddition products, diglycidyl
ether of halogenated bisphenol A or epichlorohydrin polyaddition
products, diglycidyl ether of biphenyl-type bisphenol A or
epichlorohydrin polyaddition products, glycidyl etherified product
of novolak resins, copolymers of methyl methacrylate/glycidyl
methacrylate, and copolymers of ethyl methacrylate/glycidyl
methacrylate.
[0231] Commercially available products of these compounds include,
e.g., Epicote 1001 (molecular weight; about 900, epoxy equivalence:
450-500 manufactured by Japan Epoxy Resin Co., Ltd.), Epicote 1002
(molecular weight: about 1,600, epoxy equivalence: 600-700),
Epicote 1004 (molecular weight: about 1,060, epoxy equivalence:
875-975), Epicote 1007 (molecular weight: about 2,900, epoxy
equivalence: 2,000), Epicote 1009 (molecular weight: about 3,750,
epoxy equivalence-3,000), Epicote 1010 (molecular weight: about
5,500, epoxy equivalence: 4,000), Epicote 1100L (epoxy equivalence:
4,000), Epicote YX31575 (epoxy equivalence: 1,200), Sumiepoxy
ESCN-195XHN, ESCN-195XL and ESCN-195XF (manufactured by Sumitomo
Chemical Co., Ltd.), etc.
[0232] As the isocyanate compounds preferably used in the
invention, tolylene diisocyanate, diphenylmethane diisocyanate,
polymethylene polyphenyl polyisocyanate, xylylene diisocynate,
naphthalene diisocyanate, cyclohexane phenylene diisocyanate,
isophorone diisocyanate, hexamethylene diisocyanate, cyclohexyl
diisocyanate, and blocked products of these compounds with alcohol
or amine can be exemplified.
[0233] As preferred amine compounds, ethylenediamine,
diethylenetriamine, triethylenetetramine, hexamethylene-diamine,
propylenediamine and polyethyleneimine are exemplified.
[0234] As the compounds having a hydroxyl group preferably usable
in the invention, compounds having methylol groups at terminals,
polyhydric alcohols such as pentaerythritol, and
bisphenol-polyphenols are exemplified.
[0235] As the compounds having a carboxyl group preferably usable
in the invention, aromatic polycarboxylic acids, e.g., pyromellitic
acid, trimellitic acid, and phthalic acid, and aliphatic
polycarboxylic acids, e.g., adipic acid are exemplified. As the
preferred acid anhydrides preferably used in the invention,
pyromellitic anhydride and benzophenone-tetracarboxylic anhydride
are exemplified.
[0236] The compounds having a thermo-reactive group can be
microencapsulated by the well-known methods described above in the
radical polymerization.
<Other Image Recording Layer Components>
[0237] For the purpose of improving an on-press developing property
and the layer strength of an image-recording layer itself, an
image-recording layer in the invention may contain a hydrophilic
resin. As the hydrophilic resins, resins having a hydrophilic
group, e.g., a hydroxyl group, an amino group, a carboxyl group, a
phosphoric acid group, a sulfonic acid group, and an amido group
are preferred, Further, since hydrophilic resins awe crosslinked by
the reaction with the thermoreactive group of a hydrophobitizing
precursor to thereby increase image strength and resistance to
printing machine, it is preferred that the hydrophilic resins have
a group reactive with thermo-reactive groups. For example, when
hydrophobitizing precursors have a vinyloxy group or an epoxy
group, hydrophilic resins having a hydroxyl group, a carboxyl
group, a phosphoric acid group or a sulfonic acid group are
preferred. Hydrophilic resins having a hydroxyl group or a carboxyl
group are particularly preferred.
[0238] The specific examples of hydrophilic resins include gum
arabic, casein, gelatin, starch derivative, soya gum, hydroxypropyl
cellulose, methyl cellulose, carboxymethyl cellulose and sodium
salts of it, cellulose acetate, sodium alginate, vinyl
acetate-maleic acid copolymers, styrene-maleic acid copolymers,
polyacrylic acids and salts of them, polymethacrylic acids and
salts of them, homopolymers and copolymers of hydroxyethyl
methacrylate, homopolymers and copolymers of hydroxyethyl acrylate,
homopolymers and copolymers of hydroxypropyl methacrylate,
homopolymers and copolymers of hydroxypropyl acrylate, homopolymers
and copolymers of hydroxybutyl methacrylate, homopolymers and
copolymers of hydroxybutyl acrylate, polyethylene glycols,
hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl
acetate having a hydrolysis degree of at least 60 mol %, preferably
at least 80 mol %, polyvinyl formal, polyvinyl pyrrolidone,
homopolymers and copolymers of acrylamide, homopolymers and
copolymers of methacrylamide, homopolymers and copolymers of
N-methylolacrylamide, homopolymers and copolymers of
2-acrylamide-2-methyl-1-propanesulfonic acid, and homopolymers and
copolymers of 2-methacryloyloxyethyl-sulfonic acid.
[0239] The addition amount of the hydrophilic resins to an image
recording layer is preferably 20 mass % or less, more preferably 10
mass % or less.
[0240] The hydrophilic resins may be crosslinked in advance in such
a degree that an unexposed portion can be subjected to on-press
development. The examples of the crosslinking agents include
aldehydes, e.g., glyoxal melamine-formaldehyde resin, and
urea-formaldehyde resin, methylol compounds, e.g., N-methylolurea,
N-methylolmelamine, and methylolated polyamide resin, active vinyl
compounds, e.g., divinylsulfone and bis(.beta.-hydroxyethylsulfonic
acid), epoxy compounds, e.g., epichlorohydrin, polyethylene glycol
diglycidyl ether; polyamide, polyamine, epichlorohydrin addition
product, and polyamide-epichlorohydrin resin, ester compounds,
e.g., monochloroacetic ester and thioglycolic ester, polycarboxylic
acids, e.g., polyacrylic acid and methyl vinyl ether/maleic acid
copolymer, inorganic crosslinking agents, e.g., boric acid, titanyl
sulfate, Cu, A, Sn, V, Cr salts, and modified polyamide-polyimide
resins. In addition, crosslinking catalysts such as ammonium
chloride, silane coupling agents, and titanate coupling agents can
be used in combination.
[0241] An image-recording layer in the invention can contain
reaction accelerators for initiating or accelerating the reaction
of the thermo-reactive groups. As such reaction accelerators,
photo-acid generators or radical generators in the color changing
system and radical polymerization initiators in the polymerization
system can be exemplified as preferred accelerators.
[0242] The reaction accelerators can be used in combination of two
or more. The reaction accelerators may be directly added to an
image-recording layer coating solution or may be added to the
polymer fine particles. The content of the reaction accelerators in
an image-recording layer is preferably from 0.01 to 20 mass % of
the total solids content of the image-recording layer, more
preferably from 0.1 to 10 mass %. In this range of reaction
accelerator content, on-press developing properties are not
impaired and good reaction initiation and accelerating effect can
be ensured.
[0243] In the image-recording layer utilizing hydrophobitizing
precursor series, polyfunctional monomers can be added to the
matrix of the image-recording layer for further increasing the
press life. As the polyfunctional monomers, the polymerizable
compounds exemplified above can be used, Trimethylolpropane
triacrylate and pentaerythritol triacrylate are preferred above
all.
[0244] Further, the hydrophobitizing precursor series
image-recording layer can contain additives such as the
surfactants, polymerization inhibitors, higher fatty acid
derivatives, plasticizers, inorganic fine particles and low
molecular weight hydrophilic compounds described in the item of
<Other image-recording layer components>in the polymerization
series image-recording layer, according to necessity.
<Formation of Hydrophobitizing Precursor Series Image Recording
Layer>
[0245] Similarly to the case of the radical polymerization series
image-recording layer, the hydrophobitizing precursor series
image-recording layer in the invention is formed by preparing a
coating solution by dispersing or dissolving the above necessary
components in a solvent, and coating the coating solution on a
support and drying.
[0246] The coating weight (solids content) of the image recording
layer on a support obtained after coating and drying is generally
preferably from 0.5 to 5.0 g/m.sup.2, although it differs according
to uses.
[0247] A lithographic printing plate precursor capable of on-press
development can be manufactured by using the hydrophobitizing
precursor series image-recording layer.
[0248] On the other hand, by giving sufficient resistance to
printing machine to the hydrophobitizing precursor series image
recording layer (a hydrophilic layer having a crosslinking
structure) even when the image-recording layer is unexposed, the
lithographic printing plate precursor in the invention can be
applied to a non-processing (non-development) type lithographic
printing plate precursor.
[0249] It is preferred for a hydrophilic layer having such a
crosslinking structure to contain at least one kind of a
hydrophilic resin having a crosslinking structure and an inorganic
hydrophilic binder resin formed by sol/gel conversion. Of these
resins, the hydrophilic resin is described first. By the addition
of the hydrophilic resin, the affinity of the hydrophilic
components in emulsion ink is increased and, at the same time, the
film strength of the image-recording layer itself is also improved.
As the hydrophilic resins, those having a hydrophilic group, e.g.,
hydroxyl, carboxyl, hydroxyethyl, hydroxypropyl, amino, aminoethyl,
aminopropyl and carboxymethyl, are preferred.
[0250] The specific examples of the hydrophilic resins include gum
arabic, casein, gelatin, starch derivative, carboxymethyl cellulose
and the sodium salt thereof, cellulose acetate, sodium alginate,
vinyl acetate-maleic acid copolymers, styrene-maleic acid
copolymers, polyacrylic acids and the salts thereof,
polymethacrylic acids and the salts thereof homopolymers and
copolymers of hydroxyethyl methacrylate, homopolymers and
copolymers of hydroxyethyl acrylate, homopolymers and copolymers of
hydroxypropyl methacrylate, homopolymers and copolymers of
hydroxypropyl acrylate, homopolymers and copolymers of hydroxybutyl
methacrylate, homopolymers and copolymers of hydroxybutyl acrylate,
polyethylene glycols, hydroxypropylene polymers, polyvinyl
alcohols, hydrolyzed polyvinyl acetate having a hydrolysis degree
of at least 60 mol %, preferably at least 80 mol %, polyvinyl
formal, polyvinyl butyral, polyvinyl pyrrolidone, homopolymers and
copolymers of acrylamide, homopolymers and copolymers of
methacrylamide, and homopolymers and copolymers of
N-methylolacrylamide.
[0251] When the hydrophilic resin is used in an image-recording
layer in the invention, it is effective to use the hydrophilic
resin by crosslinking. As crosslinking agents for forming a
crosslinking structure, the compounds exemplified above as the
crosslinking agents are used.
[0252] As preferred non-processing (non-development) type
image-recording layer, an imago-recording layer containing an
inorganic hydrophilic binder resin formed by sol/gel conversion can
also be exemplified. Preferred sol/gel convertible binder resins
are polymers wherein the bonding groups of polyvalent elements form
a network structure, i.e., a three-dimensional crosslinking
structure, via oxygen atoms and, at the same time, polyvalent
metals also have hydroxyl groups and alkoxyl groups not bonded and
they are mixed and form resinous structure. The systems are in a
sol state at a stage abundant in alkoxyl groups and hydroxyl
groups, and the network resinous structure comes to heighten with
the advancement of dehydration condensation. The polyvalent bonding
elements of the compounds having sol/gel convertible hydroxyl
groups and alkoxyl groups are aluminum, silicon, titanium and
zirconium, and all of which can be used in the invention. More
preferred sol/gel convertible systems are those using silicon, and
particularly preferred system is a sol/gel convertible system
containing a silane compound having at least one silanol group. A
sol/gel convertible system using silicon is described below.
Sol/gel conversions using aluminum, titanium and zirconium can also
be cared out by the substitution of the silicon in the following
description with respective elements.
[0253] Sol/gel convertible binder resins are preferably resins
having a siloxane bond and a silanol group, and a coating solution
of sol system containing a compound having at least one silanol
group is used in an image-recording layer in the invention.
Condensation and gelation of the silanol group progress during
coating and drying processes, and the structure of a siloxane
skeleton is formed.
[0254] An image-recording layer containing a sol/gel convertible
binder resin and the above hydrophilic resins and crosslinking
agents can be used in combination for the purpose of the
improvement of physical properties, e.g., layer strength and the
flexibility of the layer, and the betterment of coating
property.
[0255] A siloxane resin for forming a gel structure is represented
by the following formula (III), and a silane compound having at
least one silanol group is represented by the following formula
(IV). A material added to an image recording layer need not be a
silane compound represented by formula (IV) alone and, in general,
the material may comprise an oligomer of a silane compound
partially condensed, or may be mixture of a silane compound
represented by formula (XV) and the oligomer. ##STR51##
[0256] A siloxane resin represented by formula (III) is formed by
sol/gel conversion from the dispersion containing at least one
silane compound represented by formula (IV). In formula (III), at
least one of R.sup.01, R.sup.02 and R.sup.03 represents a hydroxyl
group, and the remaining represent an organic residue selected from
R.sup.0 and Y in formula (IV). (R.sup.0).sub.nSi(Y).sub.4+n (IV)
wherein R.sup.0 represents a hydroxyl group, a hydrocarbon group or
a heterocyclic group; Y represents a hydrogen atom, a halogen atom,
--OR.sup.1, --OCOR.sup.2 or --N(R.sup.3)(R.sup.4); R.sup.1 and
R.sup.2 each represents a hydrocarbon group; R.sup.3 and R.sup.4,
which may be the same or different, each represents a hydrocarbon
group or a hydrogen atom; and n represents 0, 1, 2 or 3.
[0257] R.sup.0 represents, as the hydrocarbon group or the
heterocyclic group, e.g., a straight chain or branched allyl group
having from 1 to 12 carbon atoms which may be substituted (e.g., a
methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group, a hexyl group, a heptyl group, an octyl group, a
nonyl group, a decyl group, a dodecyl group, etc.; as the
substituents of these groups, a halogen atom (a chlorine atom, a
fluorine atom, a bromine atom), a hydroxyl group, a thiol group, a
carboxyl group, a sulfo group, a cyano group, an epoxy group, an
--OR' group (R' represents a methyl group, an ethyl group, a propyl
group, a butyl group, a heptyl group, a hexyl group, an octyl
group, a decyl group, a propenyl group, a butenyl group, a hexenyl
group, an octenyl group, a 2-hydroxyethyl group, a 3-chloropropyl
group, a 2-cyanoethyl group, an N,N-dimethylaminoethyl group, a
2-bromoethyl group, a 2-(2-methoxyethyl)oxyethyl group, a
2-methoxycarbonylethyl group, a 3-carboxyethyl group, a
3-carboxypropyl group, a benzyl group), an --OCOR'' group (R''has
the same meaning as R' above), a --COOR'' group, a --COR'' group,
an --N(R''')(R''') group (R''' represents a hydrogen atom or the
same meaning as R' and two R''' may be the same or different), an
--NHCONHR'' group, an NHCOOR'' group, an --Si(R'').sub.3 group, and
a --CONHR'' group can be exemplified, and a plurality of
substituents may be substituted on the alkyl group), a straight
chain or branched alkenyl group having from 2 to 12 carbon atoms
which may be substituted (e.g., a vinyl group, a propenyl group, a
butenyl group, a pentenyl group, a hexenyl group, an octenyl group,
a decenyl group, a dodecenyl group, etc.; as the substituents of
these groups, the same groups described above as the substituents
of the alkyl group can be exemplified), an aralkyl group having
from 7 to 14 carbon atoms which may be substituted (e.g., a benzyl
group, a phenethyl group, a 3-phenylpropyl group, a naphthylmethyl
group, a 2-naphthylethyl group; as the substituents of these
groups, the same groups described above as the substituents of the
alkyl group can be exemplified, and a plurality of substituents may
be substituted on the aralkyl group), an alicyclic group having
from 5 to 10 carbon atoms which may be substituted (e.g., a
cyclopentyl group, a cyclohexyl group, a 2-cyclohexylethyl group, a
norbornyl group, an adamantyl group, etc.; as the substituents of
these groups, the same groups described above as the substituents
of the alkyl group can be exemplified, and a plurality of
substituents may be substituted), an aryl group having from 6 to 12
carbon atoms which may be substituted (e.g., a phenyl group, a
naphthyl group, as the substituents of these groups, the same
groups described above as the substituents of the alkyl group can
be exemplified, and a plurality of substituents may be
substituted), or a heterocyclic group containing at least one atom
selected from a nitrogen atom, an oxygen atom and a sulfur atom
which may be condensed (e, a pyran ring, a furan ring, a thiophene
ring, a morpholine ring, a pyrrole ring, a thiazole ring, an
oxazole ring, a pyridine ring, a piperidine ring, a pyrrolidone
ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, a
tetrahydrofuran ring, etc.; each of which may have a substituent as
the substituents of these groups, the same groups described above
as the substituents of the alkyl group can be exemplified, and a
plurality of substituents may be substituted).
[0258] The substituents of the --OR.sup.1 group, --OCOR.sup.2 group
or --N(R.sup.3)(R.sup.4) group represented by Y in formula (IV) are
as follows. In the --OR.sup.1 group, R.sup.1 represents an
aliphatic group having from 1 to 10 carbon atoms which may be
substituted (e.g., a methyl group, an ethyl group, a propyl group,
a butyl group, a heptyl group, a hexyl group, a pentyl group, an
octyl group, a nonyl group, a decyl group, a propenyl group, a
butenyl group, a heptenyl group, a hexenyl group, an octenyl group,
a decenyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a
2-methoxyethyl group, a 2-(2-methoxyethyl)oxyethyl group, a
2-(N,N-dimethylamino)ethyl group, a 2-methoxypropyl group, a
2-cyanoethyl group, a 3-methyloxypropyl group, a 2-chloroethyl
group, a cyclohexyl group, a cyclopentyl group, a cyclooctyl group,
a chlorocyclohexyl group, a methoxycyclohexyl group, a benzyl
group, a phenethyl group, a dimethoxybenzyl group, a methylbenzyl
group, a bromobenzyl group, etc.).
[0259] In the --OCOR.sup.2 group, R.sup.2 represents an aliphatic
group of the same meaning as R1 has, or an aromatic group having
from 6 to 12 carbon atoms which may be substituted (as the aromatic
group, those described above in the aryl group represented by R can
be exemplified). In the --N(R.sup.3)(R.sup.4) group, R.sup.3 and
R.sup.4, which may be the same or different, each represents a
hydrogen atom or an aliphatic group having from 1 to 10 carbon
atoms which may be substituted (e.g., the same groups described in
R.sup.1 of the --OR.sup.1 group can be exemplified). More
preferably, the total number of the carbon atoms of R.sup.3 and
R.sup.4 is not more than 16. As the specific examples of the silane
compound represented by formula (IV), the following compounds can
be exemplified, but the present invention is not limited to these
compounds.
[0260] Tetrachlorosilane, tetramethoxysilane, tetraethoxysilane,
tetraisopropoxysilane, tetra-n-propylsilane, methyltrichlorosilane,
methyltrimethoxysilane, methyltriethoxysilane,
ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane,
n-propyltrichlorosilane, n-propyltrimethoxysilane,
n-hexyltrimethoxysilane, n-decyltrimethoxysilane
phenyltrichlorosilane, phenyltrimethoxysilane,
dimethoxyditriethoxysilane dimethyldichlorosilane,
dimethyldimethoxysilane, diphenyldimethoxysilane,
phenylmethyldimethoxysilane triethoxyhydrosilane,
trimethoxyhydrosilane, vinyltrichlorosilane, vinyltrimethoxysilane,
trifluoropropyltrimetoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldiethoxysilane,
.gamma.-glycidoxypropyltriethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-aminopropylmethyldimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-mercaptopropylmethyldimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-mercaptopropyltriethoxysilane, and
.beta.-3,4-epoxycyclohexyl)ethyltrimethoxysilane.
[0261] Together with a silane compound represented by formula (IV),
metallic compounds capable of conjoining with resins to form a film
at the time of sol/gel conversion, e.g., Ti, Zr, Sn, Zr, Al, etc.,
can be used in the image-recording layer in combination. The
examples of the metallic compounds for use for this purpose
include, e.g., Ti(OR'').sub.4, TiCl.sub.4, Zn(OR'').sub.2,
Zn(CH.sub.3COCHCOCH.sub.3).sub.2, Sn(OR'').sub.4,
Sn(CH.sub.3COCHCOCH.sub.3).sub.4, Sn(OCOR'').sub.4, SnCl.sub.4,
Zr(OR'').sub.4, Zr(CH.sub.3COCHCOCH.sub.3).sub.4,
(NH.sub.4).sub.2ZrO(CO.sub.3).sub.2, Al(OR'').sub.3,
Al(CH.sub.3COCHCOCH.sub.3), etc, (wherein R.sup.11 represents a
methyl group, an ethyl group, a propyl group, a butyl group, a
pentyl group, a hexyl group).
[0262] For accelerating hydrolysis and polycondensation reaction of
the silane compound represented by formula (IV) and the above
metallic compound to be used in combination, it is preferred to use
an acidic catalyst or a basic catalyst together. As the catalyst an
acidic or basic compound may be used as it is, or may be dissolved
in water or a solvent such as alcohol (hereinafter referred to as
the acidic catalyst or the basic catalyst). The concentration of
the catalyst is not particularly restricted but when the
concentration is high, hydrolysis and polycondensation reaction are
liable to become fast. However, when the basic catalyst in high
concentration is use, a precipitate is formed in some cases, so
that the concentration of the basic catalyst is preferably IN (in
terms of the concentration in an aqueous solution) or less.
[0263] The specific examples of the acidic catalysts include
hydroghalogenic acid such as hydrochloric acid, carboxylic acids
such as nitric acid, sulfuric acid, sulfurous acid, hydrogen
sulfide, perchloric acid, hydrogen peroxide, carbonic acid, formic
acid and acetic acid, and sulfonic acid such as benzenesulfonic
acid. The specific examples of the basic catalysts include
ammoniacal bases such as aqueous ammonia, and amines such as
ethylamine and aniline, but the catalysts are not limited to these
compounds.
[0264] As described above, an image-recording layer produced by the
sol/gel method is particularly preferred as the constitution of the
image-recording layer according to the present invention. The
details of the sol/gel method are described in Sumio Sakuhana,
Sol/Gel Ho no Kagaku (Chemistry of Sol/Gel Method), Agune Shofu-Sha
(1988) and Seki Hirashima, Saishin Sol/Gel Ho ni yoru Kino-Sei
Hakumaku Sakusei Gijutsu (Producing Techniques of Functional Thin
Films by the Latest Sol/Gel Methods), Sogo Gijutsu Center
(1992).
[0265] The addition amount of the hydrophilic resins to an image
recording layer having a crosslinking structure is preferably from
5 to 70 mass % of the solids content of the image-recording layer,
more preferably from 5 to 50 mass %.
Support:
[0266] Supports for use in the image-recording layer in the
invention are not particularly limited and any materials can be
used so long as they are dimensionally stable and plate-like
materials. As the support for an on-press development type
lithographic printing plate precursor, supports having a
hydrophilic surface are preferred. For example, paper, paper
laminated with plastics (e.g., polyethylene, polypropylene,
polystyrene, etc.), metal plates (e.g., aluminum, zinc, copper,
etc.), plastic films (e.g., cellulose diacetate, cellulose
triacetate, cellulose propionate, cellulose butyrate, cellulose
acetate butyrate, cellulose nitrate polyethylene terephthalate,
polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl
acetal, etc.), and paper and plastic films laminated or deposited
with the above metals can be exemplified as the materials of the
support. Preferred supports are a polyester film and an aluminum
plate. Above all, aluminum sheets, which are dimensionally stable
and comparatively inexpensive, are preferred.
[0267] Aluminum plates are a pure aluminum plate, alloy plates
containing aluminum as a main component and a trace amount of
different elements, and aluminum or aluminum alloy thin films
laminated with plastics. The examples of different elements
contained in aluminum alloys include silicon, iron, manganese,
copper, magnesium, chromium zinc, bismuth, nickel, titanic etc. The
different element content in aluminum alloys is preferably 10 mass
% or less. In the invention, a pure aluminum plate is preferred but
100% pure aluminum is difficult to produce from the refining
technique, accordingly, an extremely small amount of different
elements may be contained. Thus, the compositions of aluminum
plates used in the invention are not specified, and aluminum plates
of conventionally well known and commonly used materials can be
optionally used.
[0268] A support for use in the invention has a thickness of
preferably from 0.1 to 0.6 mm more preferably from 0.15 to 0.4 mm,
and still more preferably from 0.2 to 0.3 mm.
[0269] Prior to the use of an aluminum plate, it is preferred for
the aluminum plate to be subjected to surface treatment, e.g.,
surface roughening treatment and hydrophilic film forming
treatment. By surface treatment, the improvement of hydrophilicity
and the security of the adhesion of an image-recording layer and a
support become easy. Prior to the surface roughening treatment of
an aluminum plate, if necessary, degreasing treatment with a
surfactant, an organic solvent or an alkaline aqueous solution is
carried out to remove the rolling oil on the surface of an aluminum
plate.
Surface Roughening Treatment:
[0270] Surface roughening treatment of the surface of an aluminum
plate is performed by various methods, e.g., mechanical surface
roughening treatment, electrochemical surface roughening treatment
(surface roughening treatment of electrochemically dissolving the
surface), and chemical surface roughening treatment (surface
roughening treatment of chemically selectively dissolving the
surface) are exemplified.
[0271] As the method of mechanical surface roughening treatment,
well-known methods, e.g., a ball rubbing method, a brush abrading
method, a blast abrading method, or a buffing method, can be
used.
[0272] As the method of electrochemical surface roughening
treatment, a method of roughening in an electrolyte containing an
acid such as a hydrochloric acid or a nitric acid by alternating
current or direct current can be used. Further, a method of using
mixed acids can be used as disclosed in JP-A-54-63902.
Formation of Hydrophilic Layer:
[0273] The aluminum plate having been subjected to the surface
roughening treatment, and other treatments according to necessity,
undergoes the treatment for forming a hydrophilic layer having low
thermal conductivity. The thermal conductivity of the hydrophilic
layer in the thickness direction is 0.05 W/mK or more, preferably
from 0.08 to 0.5 W/mK more preferably 0.3 W/mK or less, and still
more preferably 0.2 W/mK or less. When the thermal conductivity of
the hydrophilic layer in the layer thickness direction is from 0.05
0.5 W/mK, the diffusion of the heat generated in the
image-recording layer by laser exposure to the support can be
prevented. As a result, when the lithographic printing plate
precursor is used as an on-press development type or non-processing
type lithographic printing plate precursor, the heat generated by
laser exposure can be effectively used, so that high sensitivity,
sufficient print image formation and printing out image formation
become possible.
[0274] The thermal conductivity of a hydrophilic film in the
thickness direction prescribed in the invention is described below.
Various measuring methods of thermal conductivity of a thin film
have so far been reported. Ono et al. have reported the thermal
conductivity of a thin film in the plane direction by using a
thermograph in 1986. Further, a trial to apply an alternating
current heating method to the measurement of thermal physical
properties of a thin film is reported. The origin of the
alternating current heating method can be retroactive to the report
in 1863. Various measuring methods are proposed in recent years by
the development of a heating method by laser and by the combination
with Fourier transform. Apparatus using a laser angstrom method are
really now on the market. All of these methods are to find the
thermal conductivity of a thin film in the plane direction
(in-plane).
[0275] However, thermal diffusion in the depth direction is a
rather important factor in considering the thermal conduction of a
thin film.
[0276] It is said that the thermal conductivity of a thin film is
not isotropic as reported variously In particular, in the case of
the present invention, the direct measurement of the thermal
conductivity of a in film in the thickness direction is very
important. From this point of view, as a trial to measure the
thermal physical properties of a thin film in the thickness
direction, the method using a thermocomparator is reported in
Lambropoulos et al, J. Appl. Phys., 66 (9) (1 Nov., 1989) and
Henager et al, Applied Optics Vol. 32, No. 1 (1 Jan., 1993)
Further, in recent years, a method of measuring thermal diffusivity
of a polymer thin film by the temperature wave thermal analysis
applying Fourier analysis is reported in Hashimoto et al., Netsu
Sokutei (Thermal Measurement), 27 (3) (2000).
[0277] The thermal conductivity of a hydrophilic film in the
thickness direction prescribed in the invention is measured by the
above method of using a thermocomparator. The measuring method of
the above method is specifically described below, but the
fundamental principles of the method are described in detail in the
article of Lambropoulos et al. and the article of Henager et al. In
the invention, measurement was performed with a thermocomparator
shown in FIG. 3 in JP-A-2003-103951 and according to the method
disclosed in the same patent.
[0278] The relationships between each temperature and the heat
conductivities of the film are as the following equation (1).
Equation .times. .times. ( 1 ) .times. .times. ( T r - T b ) ( T r
- T t ) = ( 4 .times. .times. K 1 .times. r .times. .times. 1 K 1
.times. .times. f .times. A 3 ) .times. t + ( 1 + ( 4 .times.
.times. K 1 .times. r .times. .times. 1 K 2 .times. A 2 ) .times. t
2 + ( K 1 .times. r .times. .times. 1 K 2 .times. r .times. .times.
1 ) ) ( 1 ) ##EQU1##
[0279] The signs in the equation are as follows.
T.sub.t: Temperature at the tip of chip
T.sub.b: Temperature of heat sink
T.sub.r: Temperature of reservoir
K.sub.tf: Thermal conductivity of film
K.sub.1: Thermal conductivity of reservoir
K.sub.2: Thermal conductivity of chip (in the case of oxygen free
copper: 400 W/mK)
K.sub.4: Thermal conductivity of metal substrate (in the case of
not having a thin film)
rl: Radius of curvature of the tip of chip
A.sub.2: Contact area of reservoir and chip
A.sub.3: Contact area of chip and film
t: Thickness of film
t.sub.2: Contact thickness (about 0)
[0280] By measuring each temperature (T.sub.t, T.sub.h and T.sub.r)
and plotting with changing the film thickness (t), the gradient of
equation (1) and the thermal conductivity of the film (K.sub.tf)
can be, found. That is, as is apparent from of equation (1), the
gradient is a value determined by the thermal conductivity of the
reservoir (K.sub.1), the radius of curvature of the tip of the chip
(rl). The thermal conductivity of the film (K.sub.tf), and the
contact area of the chip and the film (A.sub.3), and K.sub.1, rl
and A.sub.3 are already known values, so that K.sub.tf can be
obtained from the gradient.
[0281] The inventors searched for the thermal conductivity of the
hydrophilic film (an anodic oxide film Al.sub.2O.sub.3) formed on
the aluminum substrate according to the above measuring method. The
temperature was measured with changing the film thickness, and the
thermal conductivity of Al.sub.2O.sub.3 found from the gradient of
the resulted graph was 0.69 W/mK. This value well coincides with
the results in the article of Lambropoulos et al., and this result
also shows that the thermal physical value of a in film is
different from the thermal physical value of the bulk (the thermal
conductivity of Al.sub.2O.sub.3 of bulk is 28 W/mK).
[0282] When the above measuring method is used in the measurement
of the thermal conductivity in the thickness direction of a
hydrophilic film of a lithographic printing plate precursor in the
invention, a result free of dispersion can be preferably obtained
even with a roughened surface for lithographic printing by making
the tip of a chip minute and maintaining the pressing load
constant. It is preferred to find the value of thermal conductivity
as the average value of measurement at a plurality of points on a
sample, e.g., at fine points.
[0283] From the aspects of scratch resistance and press life, the
thickness of a hydrophilic film is preferably 0.1 .mu.m or more,
more preferably 0.3 .mu.m or more, and particularly preferably 0.6
pin or more, and considering from the manufacturing costs that a
great energy is required for forming a thick film, the thickness is
preferably 5 .mu.m or less, more preferably 3 .mu.m or less, and
particularly preferably 2 .mu.m or less.
[0284] It is preferred that the hydrophilic film in the invention
has a density of from 1,000 to 3,200 kg/m from the thermal
insulating effect, film strength and soiling resistance in
printing.
[0285] The density can be computed according to the following
equation from the mass measured by a Mason method (a weighing
method of anodic oxide film by dissolution with a chromic
acid/phosphoric acid mixed solution) and the film thickness
obtained by observing the cross section of a film with an SEM.
Density (kg/cm.sup.3)=(mass of a hydrophilic film per a unit
area/film thickness)
[0286] The forming methods of a hydrophilic film are not especially
restricted, and an anodizing method, a vacuum evaporation method, a
CVD method, a sol/gel method, a sputtering method, an ion plating
method, and a diffusing method can be arbitrarily used. Further, it
is also possible to use a method of coating a solution obtained by
mixing hollow particles in a hydrophilic resin or a sol/gel
solution.
[0287] A process of producing an oxide by anodization, that is,
using an anodizing process, is most preferred. Anodizing process
can be carried out by the methods conventionally used in the
industry. Specifically, by the application of DC or AC to an
aluminum plate in an aqueous solution or nonaqueous solution
comprising sulfuric acid, phosphoric acid, chromic acid, oxalic
acid, sulfamic acid or benzenesulfonic acid alone or in combination
of two or more, an anodic oxide film that is a hydrophilic film can
be formed on the surface of the aluminum plate. The conditions of
anodizing process change variously by the electrolytes used and
cannot be determined unconditionally, but generally the
concentration of an electrolyte of from 1 to 80 mass %, a liquid
temperature of from 5 to 70.degree. C., electric current density of
from 0.5 to 60 A/dm.sup.2, voltage of from 1 to 200V, and
electrolysis time of from 1 to 1,000 seconds are preferred. Of the
anodizing processes, an anodizing process in a sulfuric acid
electrolyte by high electric current density as disclosed in
British Patent 1,412,768, and an anodizing process with a
phosphoric acid as the electrolytic bath as disclosed in U.S. Pat.
No. 3,511,661 are preferred. It is also possible to perform a
multistage anodizing process comprising anodization in a sulfinic
acid electrolyte and further anodization in a phosphoric acid
[0288] In the points of scratch resistance and press life, the
anodic oxide film in the invention is preferably 0.1 g/m.sup.2 or
more, more preferably 0.3 g/m.sup.2 or more, still more preferably
2 g/m.sup.2 or more, and particularly preferably 3.2 g/m.sup.2 or
more. Considering that a great energy is required for forming a
thick film, the anodic oxide film is preferably 100 g/m.sup.2 or
less, more preferably 40 g/m.sup.2 or less, and particularly
preferably 20 g/m.sup.2 or less.
[0289] Minute concavities called micro pores evenly distributed are
formed on the surface of an anodic oxide film. The density of micro
pores on the surface of an anodic oxide film can be controlled by
arbitrarily selecting the processing conditions. The thermal
conductivity in the thickness direction of an anodic oxide film can
be made from 0.05 to 0.5 W/mK by increasing the density of micro
pores. In addition, the diameter of micro pores can be adjusted by
arbitrarily selecting the processing conditions. The thermal
conductivity in the thickness direction of an anodic oxide film can
be made from 0.05 to 0.5 W/mK by making the diameter of micro pores
larger
[0290] It is preferred in the invention to perform a pore widening
process of enlarging the pore diameter of micro pores after
anodizing process for the purpose of lowering the thermal
conductivity. The pore widening process is a process of dissolving
an anodic oxide film to thereby enlarge the pore diameter of micro
pores by immersing an aluminum substrate on which an anodic oxide
film is formed in an acid aqueous solution or an alkali aqueous
solution. The pore widening process is performed in the range of
the dissolving amount of an anodic oxide film of preferably from
0.01 to 20 g/m.sup.2, more preferably from 0.1 to 5 g/m.sup.2, and
particularly preferably from 0.2 to 4 g/m.sup.2.
[0291] When an acid solution is used in a pore widening process, it
is preferred to use an aqueous solution of inorganic acid such as
sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid,
or an aqueous solution of the mixture of these acids. The
concentration of an acid aqueous solution is preferably from 10 to
1,000 g/liter, more preferably from 20 to 500 g/liter. The
temperature of an acid aqueous solution is preferably from 10 to
90.degree. C., more preferably from 30 to 70.degree. C. The time of
immersion in an acid aqueous solution is preferably from 1 to 300
seconds, more preferably from 2 to 100 seconds. On the other hand,
when an alkali aqueous solution is used in a pore widening process,
it is preferred to use an aqueous solution containing at least one
alkali selected from the group consisting of sodium hydroxide,
potassium hydroxide and lithium hydroxide. The pH of an alkali
aqueous solution is preferably from 10 to 13, more preferably from
1.5 to 130. The temperature of an alkali aqueous solution is
preferably from 10 to 90.degree. C., more preferably from 30 to
50.degree. C. The time of immersion in an alkali aqueous solution
is preferably from 1 to 500 seconds, more preferably from 2 to 100
seconds. However; too large an enlargement of the micro pore
diameter on the outermost surface results in the deterioration of
soiling resistance in printing, so that the micro pore diameter on
the outermost surface is preferably 40 nm or less, more preferably
20 nm or less, and most preferably 10 nm or less. Accordingly, a
more preferred anodic oxide film capable of compatibility of a heat
insulating property and soiling resistance is an anodic oxide film
having a surface micro pore diameter of from 0 to 40 nm and an
inside micro pore diameter of from 20 to 300 nm. For example, it is
known that when the kind of the electrolyte is the same, the pore
diameter of the pore that occurs by the electrolysis is
proportional to the electrolytic voltage at the time of
electrolysis. By making use of the nature, a method of forming
pores having a widened bottom part can be used by gradually
increasing electrolytic voltage. It is also known that a pore
diameter changes by changing the kind of electrolyte, and a pore
diameter becomes larger in the order of a sulfuric acid, an oxalic
acid, and a phosphoric acid. Accordingly, a method of anodization
of using a sulfuric acid in the electrolyte of the first stage and
a phosphoric acid in the second stage can be used. In addition, a
support for a lithographic printing plate obtained by an anodizing
process and a pore widening process may be subjected to a sealing
process described later.
[0292] In addition to the above anodic oxide film a hydrophilic
film may be an inorganic film formed by a sputtering method, a CVD
method, etc. As the compounds constituting an inorganic film, e.g.,
oxide, nitride, silicide, boride and carbide are exemplified. An
inorganic film may be composed of a simple substance of a compound
alone or may be composed of a mixture of compounds. As the
compounds constituting an inorganic film, aluminum oxide, silicon
oxide, titanium oxide, zirconium oxide, hafnium oxide, vanadium
oxide, niobium oxide, tantalum oxide, molybdenum oxide, tungsten
oxide, chromium oxide, aluminum nitride, silicon nitride, titanium
nitride, zirconium nitride, hafnium nitride, vanadium nitride,
niobium nitride, tantalum nitride, molybdenum nitride, tungsten
nitride, chromium nitride, silicon nitride, boron nitride; titanium
silicide, zirconium silicide, hafnium silicide, vanadium silicide,
niobium silicide, tantalum silicide; molybdenum silicide, tungsten
silicide, chromium silicide; titanium boride, zirconium boride,
hafnium boride, vanadium boride, niobium boride, tantalum boride,
molybdenum boride, tungsten boride, chromium boride; aluminum
carbide, silicon carbide, titanium carbide, zirconium carbide,
hafnium carbide, vanadium carbide, niobium carbide, tantalum
carbide, molybdenum carbide, tungsten carbide, chromium carbide are
specifically exemplified.
Sealing Process:
[0293] As described above, in the invention, a support for a
lithographic printing plate provided with a hydrophilic film may be
subjected to a sealing process. As the sealing process used in the
invention, sealing processes of an anodic oxide film by steam
sealing under pressure and boiling water sealing as disclosed in
JP-A4-176690 and JP-A-11-301135 are exemplified. Well-known sealing
processes can also be used in the invention, e.g., a silicate
process, a bichromate aqueous solution process, a nitrite process,
a ammonium acetate process an electrodeposition sealing process, a
triethanolamine process, a barium carbonate process, and a sealing
process by boiling water containing a trace amount of phosphate,
can be used. A forming system of a pore varies according to the
manner of sealing process, for example, a pore is formed from the
bottom when sealing is performed by an electrodeposition sealing
process and a pore is formed from the top when steam sealing is
performed. In addition, an immersing process in a solution, a
spraying process, a coating process, a vacuum evaporation process,
sputtering, ion plating, flame spray coating and metal plating are
exemplified as sealing processes, but the process of sealing is not
particularly limited in the invention. As a particularly preferred
process, a sealing process using particles having an average
particle size of from 8 to 800 nm as disclosed in JP-A-2002-214764
is exemplified.
[0294] The average particle size of the particles used in the
sealing process using particles is from 8 to 800nm, preferably from
10 to 500 nm, and more preferably from 10 to 150 nm. When sealing
is performed with this range of particles, there is no possibility
of the particles entering into the micro pores on a hydrophilic
film and the effect of increasing sensitivity can be sufficiently
obtained. Usher, the adhesion with an image-recording layer becomes
sufficient and excellent press life be ensured, The thickness of a
particle layer is preferably from 8 to 800 nm, more preferably from
10 to 500 nm.
[0295] The thermal conductivity of the particles used in the
invention is preferably 60 W/mK or less, more preferably 40 W/mK or
less, and particularly preferably from 0.3 to 10 W/mK. When the
thermal conductivity is 60 W/mK or less, the diffusion of heat to
an aluminum substrate can be sufficiently controlled and the effect
of increasing sensitivity can be sufficiently obtained.
[0296] As the method of forming a particle layer, e.g., an
immersing process in a solution, a spraying process, a coating
process, an electrolytic process, a vacuum evaporation process,
sputtering, ion plating, flame spray coating and metal plating are
exemplified but the method is not particularly restricted.
[0297] An electrolytic process is performed with DC or AC. As the
waveforms of AC used in the electrolytic process, a sine wave, a
rectangular wave, a triangular wave and a trapezoidal wave are
exemplified. From the viewpoint of the manufacturing costs of an
electric power unit the frequencies of AC are preferably from 30 to
200 Hz, more preferably from 40 to 120 Hz. When a trapezoidal wave
is used as the waveform of AC, the time required for the electric
current to reach the peak from 0 (tp) is preferably from 0.1 to 2
msec, more preferably from 0.3 to 1.5 msec.
[0298] As hydrophilic particles, it is preferred to use
Al.sup.2O.sup.3, TiO.sup.2, SiO.sup.2 and ZrO.sup.2 respectively
alone or in combination of two or more. An electrolyte can be
obtained by suspending the above hydrophilic particles in water and
the like so that the content of the particles becomes from 0.01 to
20 mass % of the total content. The pH of an electrolyte can be
adjusted by adding, e.g., a sulfuric acid, to be charged positively
or negatively. Electrolytic process is performed, e.g., by using DC
with an aluminum plate as the cathode and with the above
electrolyte on the conditions of the voltage of from 10 to 200 V
for 1 to 600 seconds. According to this method, micro pores can be
easily sealed while leaving voids in the micro pores on the anodic
oxide film.
[0299] As sealing processes, the methods of providing any of the
following layers by coating are exemplified, e.g., a layer
comprising a compound having at least one amino group, and at least
one group selected from the group consisting of a carboxyl group
and a group of the salt thereof, a sulfo group and a group of the
salt thereof as disclosed in JP-A-60-149491, a layer comprising a
compound having at least one amino group and at least one hydroxyl
group, and a compound selected from the salts thereof as disclosed
in JP-A-60-232998, a layer containing a phosphate as disclosed in
JP-A-62-19494, and a layer comprising a polymer compound having at
least one monomer unit having a sulfo group as the repeating unit
in the molecule as disclosed in JP-A-59-101651.
[0300] The methods of providing a layer of a compound selected from
the following compounds are also exemplified, e.g., carboxymethyl
cellulose; dextrin; gum arabic; phosphonic acids having an amino
group such as 2-aminoethylphosphonic acid; organic phosphonic acids
such as phenylphosphonic acid, naphthylphosphonic acid,
alkylphosphonic acid, glycero phosphonic acid,
methylenediphosphonic acid, ethylene-diphosphonic acid, each of
which may have a substituent; organic phosphoric esters such as
phenylphosphoric ester, naphthylphosphoric ester, alkylphosphoric
ester; glycero-phosphoric ester, each of which may have a
substituent; organic phosphinic acids such as phenylphosphinic
acid, naphthyl-phosphinic acid, alkylphosphinic acid,
glycerophosphinic acid, cach of which may have a substituent; amino
acids such as glycine, .beta.-alanine, and amine hydrochloride
having a hydroxyl group such as methanolamine hydrochloride.
[0301] Coating of a silane coupling agent having an unsaturated
group can also be used in sealing process. The examples of silane
coupling agents include N-3-(acryloxy-2-hydroxy
propyl)-3-aminopropyltriethoxysilane,
(3-acryloxypropyl)-dimethylmethoxysilane,
(3-acryloxypropyl)methyldimethoxy-silane,
(3-acryloxypropyl)trimethoxysilane,
3-(N-allyl-amino)propyltrimethoxysilane, allyldimethoxysilane,
allyltriethoxysilane, allyltrimethoxysilane,
3-butenyl-triethoxysilane, 2-(chloromethyl)allyltrimethoxysilane,
methacrylamidopropyltriethoxysilane;
N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,
(methacryloxy-methyl)dimethylethoxysilane,
methacryloxymethyltriethoxy-silane,
methacryloxymethyltrimethoxysilane,
methacryloxy-propyldimethylethoxysilane,
methacryloxypropyldimethyl-methoxysilane,
methacryloxypropylmethyldiethoxysilane,
methacryloxypropylmethyldimethoxysilane,
methacryloxy-propylmethyltriethoxysilane,
methacryloxypropylmethyl-trimethoxysilane;
methacryloxypropyltris(methoxyethoxy)-silane,
methoxydimethylvinylsilane, 1-methoxy-3-trimethyl-siloxy)butadiene,
styrylethyltrimethoxysilane,
3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane
hydrochloride, vinyldimethylethoxysilane,
vinyldiphenyl-ethoxysilane, vinylmethyldiethoxysilane,
vinylmethyl-dimethoxysilane,
O-(vinyloxyethyl)-N-(triethoxysilyl-propyl)urethane,
vinyltriethoxysilane, vinyltrimethoxy-silane,
vinyltri-t-butoxysilane, vinyltriisopropoxysilane,
vinyltriphenoxysilane, vinyltris(2-methoxyethoxy)silane,
diallylaminopropylmethoxysilane. Of these silane coupling agents,
silane coupling agents having a methacryloyl group or an acryloyl
group fist in the reactivity of an unsaturated group are
preferred.
[0302] Besides the above, a sol/gel coating process as disclosed in
JP-A-5-50779, a coating process of phosphonic acids as disclosed in
JP-A-5-246171, a process of coating materials for back coating as
disclosed in JP-A-6-234284, JP-A-6-191173 and JP-A-6-230563, a
process of phosphonic acids as disclosed in JP-A-6-262872, a
coating process as disclosed in JP-A-6-297875, an anodizing process
as disclosed in JP-A-10-109480, and an immersion process method as
disclosed in JP-A-2000-81704 and JP-A2000-89466 are exemplified,
and any method can be used.
[0303] After forming a hydrophilic film, if necessary, the surface
of the aluminum plate is subjected to hydrophilizing process. As
the hydrophilizing process, alkali metal silicate methods as
disclosed in U.S. Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and
3,902,734 are known. These methods comprise immersion processing of
a support in an aqueous solution of sodium silicate, or
electrolytic processing. In addition, a method of processing an
aluminum plate with potassium fluorozirconate as disclosed in
JP-B-36-22063, and methods of processing with polyvinylphosphonic
acid as disclosed in U.S. Pat. Nos. 3,276,868, 4,153,461 and
4,689,272 are exemplified.
[0304] When a polyester film insufficient in a hydrophilic property
of surface is used as a support in the invention, it is preferred
to coat a hydrophilic layer to make the surface hydrophilic. As the
hydrophilic layers, a hydrophilic layer provided by coating a
coating solution containing the colloid of oxide or hydroxide of at
least one element selected from beryllium, magnesium, aluminum,
silicon, titanium boron, germanium, tin, zirconium, iron, vanadium,
antimony and transition metals as disclosed in JP-A-2001-199175, a
hydrophilic layer having an organic hydrophilic matrix obtained by
the crosslinking or pseudo-crosslinking of an organic hydrophilic
polymer as disclosed in JP-A-2002-79772, a hydrophilic layer having
an inorganic hydrophilic matrix obtained by sol/gel conversion
comprising hydrolysis and condensation reaction of
polyalkoxysilane, titanate, zirconate or aluminate, and a
hydrophilic layer comprising an inorganic thin film having a
surface containing a metallic oxide are preferred. Of these
hydrophilic layers, a hydrophilic layer provided by coating a
coating solution containing the colloid of oxide or hydroxide of
silicon is preferred.
[0305] When a polyester film is used as a support in the invention,
it is preferred to provide an antistatic layer on the hydrophilic
layer side of the support or on the opposite side to the
hydrophilic layer, or on both sides. When an antistatic layer is
provided between a support and a hydrophilic layer, the antistatic
layer also contributes to the adhesion of the hydrophilic layer and
the support. The polymer layers containing the dispersion of
metallic oxide fine particles and a matting agent as disclosed in
JP-A-2002-79772 can be used as the antistatic layers.
[0306] It is preferred that a support for use in the invention has
a central line average surface roughness of from 0.10 to 1.2 .mu.m.
In this range of average surface roughness, good adhesion of the
support and an image-recording layer, good press life and good
soiling resistance can be obtained.
[0307] The color density of a support is preferably from 0.15 to
0.65 in terms of a reflection density value. A good image forming
property due to antihalation in the time of image exposure and a
good plate-detecting property after development can be obtained
when the color density of a support is in this ranges.
Back Coat Layer:
[0308] After surface treatment of a support or after forming an
undercoat layer, if necessary, a backcoat can be provided an the
back surface of the support.
[0309] As the backcoat, e.g., coating layers comprising organic
polymer compounds as disclosed in JP-A-5-45885, and coating layers
comprising metallic oxides obtained by hydrolysis and
polycondensation of organic or inorganic metallic compounds as
disclosed in JP-A-6-35174 are preferably used. Alkoxy compounds of
silicon, e.g., Si(OCH.sub.3).sub.4, Si(OC.sub.2H.sub.5).sub.4,
Si(OC.sub.3H.sub.5).sub.4, Si(OC.sub.4H.sub.9).sub.4, are
preferably used for the inexpensiveness and easy availability of
the materials.
Undercoat Layer:
[0310] In the lithographic printing plate precursor in the
invention, if necessary, an undercoat layer can be provided between
an image-recording layer and a support. Since the undercoat layer
functions as a heat insulating layer, the heat generated by
infrared laser exposure does not diffuse to the support and is
efficiently utilized, so that the improvement of sensitivity can be
contrived. Further, the image-recording layer comes to be easily
peeled off the support at an unexposed portion, so that on-press
developability is improved.
[0311] As the undercoat layer, specifically the silane coupling
agent having an addition polymerizable ethylenic double bond
reactive group disclosed in JP-A-10-282679, and the phosphorus
compounds having an ethylenic double bond reactive group disclosed
in JP-A-2-304441 are preferred, Further, compounds having both a
polymerizable group such as a methacrylic group or an allyl group
and support-adsorptive group such as a sulfonic acid group, a
phosphoric acid group or a phosphoric ester group are also
preferred Compounds obtained by adding a hydrophilicity-imparting
group, e.g., an ethyleneoxy group, to these compounds can also be
preferably used.
[0312] The coating amount of an undercoat layer (solids content) is
preferably from 0.1 to 100 mg/m.sup.2, more preferably from 1 to 30
mg/m.sup.2.
Protective Layer:
[0313] For preventing the generation of scratches on an image
recording layer, for shielding oxygen, and for preventing ablation
at the time of exposure with high intensity laser, if necessary, a
protective layer may be provided on a image recording layer of the
lithographic printing plate precursor of the invention.
[0314] Exposure is generally performed in the air in the invention,
and the protective layer prevents the mixture into the image
recording layer of low molecular weight compounds such as oxygen
and basic substance in the air that hinder the image forming
reaction occurring in the image-recording layer by exposure, by
which the hindrance of the image forming reaction by exposure in
the air can be prevented. Accordingly, the characteristics required
of the protective layer are to be low in permeability of low
molecular weight compounds such as oxygen, good in transmission of
light used for exposure, excellent in adhesion with an
image-recording layer, and capable of being removed easily by
on-press development after exposure. Protective layers having such
characteristics have so far been variously examined and they are
disclosed in detail: e.g., in U.S. Pat. No. 3,458,311 and
JP-B-55,49729.
[0315] As the materials that are used for the protective layer, for
example, water-soluble polymer compounds relatively excellent in
crystallizability are exemplified. Specifically water-soluble
polymers, e.g., polyvinyl alcohol, polyvinyl pyrrolidone, acid
celluloses, gelatin, gum arabic, and polyacrylic acid are
exemplified.
[0316] Above alt when polyvinyl alcohol (PVA) is used as the main
component, the best results can be given to the fundamental
characteristics such as an oxygen-shielding property and the
removal by development. Polyvinyl alcohols may be partially
substituted with ester, ether or acetal, or may partially contain
other copolymer component so long as they contain an unsubstituted
vinyl alcohol unit for imparting an oxygen-shielding property and
solubility in water that are necessary to the protective layer.
[0317] As the specific examples of polyvinyl alcohols, those having
a hydrolyzed rate of from 71 to 100 mol % and the degree of
polymerization of from 300 to 2,400 are preferably exemplified.
Specifically, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120,
PVA-124, PVA-124H, PVA CS, PVA-CST, PVA-HC, PVA-203, PVA-204,
PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217E, PVA-217F,
PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613, and L-8
(manufactured by Kuraray Co., Ltd.) are exemplified.
[0318] The components of the protective layer (the selection of
PVA, the use of additives, etc.), and the coating amounts are
suitably selected by considering fogging characteristic, adhesion
and scratch resistance besides the oxygen shielding property and
the removal by development. In general, the higher the hydrolyzing
rate of PVA (that is, the higher the unsubstituted vinyl alcohol
unit content in the protective layer), and the higher the layer
thickness, the higher is the oxygen-shielding property, thus
advantageous in the point of sensitivity. For the prevention of the
generation of unnecessary polymerization reaction during
manufacture and storage or the generation of unnecessary fog and
thickening of image lines in image expose, it is preferred that an
oxygen-permeating property is not too high. Therefore, oxygen
permeability A at 25.degree. C. under 1 atm is preferably, 0.2
.quadrature. A .quadrature. 20 (cm.sup.3/m.sup.2day).
[0319] As other components of the protective layer, glycerol
dipropylene glycol and the like can be added in an amount of
several mass % to the water-soluble polymer compounds to provide
flexibility, and further, anionic surfactants, e.g., sodium
alkylsulfate and sodium alkylsulfonate; ampholytic surfactants,
e.g., alkylaminocarboxylate and alkylaminodi-carboxylate; and
nonionic surfactants, edge, polyoxyethylene alkyl phenyl ether, can
be added to the (co)polymers each in an amount of several mass %.
The layer thickness of the protective layer is preferably from 0.1
to 5 .mu.m, and particularly preferably from 0.2 to 2 .mu.m.
[0320] The adhesion of the protective layer with an image part and
scratch resistance are also very important in treating a
lithographic printing plate precursor. That is, when a protective
layer that is hydrophilic by containing a water-soluble polymer
compound is laminated on a lipophilic image-recording layer, layer
peeling of the protective layer due to insufficient adhesion is
liable to occur, and sometimes a defect such as film hardening
failure attributing to polymerization hindrance by oxygen is caused
at the peeled part.
[0321] Various countermeasures have been proposed for improving the
adhesion of an image-recording layer and a protective layer. For
example, it is disclosed in JP-A-49-0702 and British Patent
Application No, 1,303,578 that sufficient adhesion can be obtained
by mixing from 20 to 60 mass % of an acryl-based emulsion or a
water-insoluble vinyl pyrrolidone/vinyl acetate copolymer with a
hydrophilic polymer mainly comprising polyvinyl alcohol and
laminating the resulting product on an image-recording layer. Any
of these well-known techniques can be used in the present
invention. The coating methods of a protective layer are disclosed
in detail e.g., in U.S. Pat. No. 3,458,311 and JP-8-5549729.
[0322] Further, other functions can be imparted to a protective
layer. For example, by the addition of colorants excellent in
transmission of infrared rays that are used in exposure and capable
of efficiently absorbing lights of other wavelengths (e.g.,
water-soluble dyes), safelight aptitude can be improved without
causing sensitivity reduction.
Plate-Making Method and Lithographic Printing Method:
[0323] In the lithographic printing method using the lithographic
printing plate precursor in the invention, the lithographic
printing plate precursor is imagewise exposed with an infrared
laser.
[0324] The infrared lasers for use in the present invention are not
particularly restricted, but solid state lasers and semiconductor
lasers radiating the infrared rays of the wavelength of from 760 to
1,200 nm are preferably used. The output of infrared lasers is
preferably 100 mW or higher. It is preferred to use a multi-beam
laser device for expediting exposure.
[0325] The exposure time per a pixel is preferably not longer than
20 .mu.sec. The quantity of irradiation energy is preferably from
10 to 300 mJ/cm.sup.2.
[0326] In the lithographic printing method in the invention, as
described above, after a lithographic printing plate precursor is
imagewise exposed with infrared laser beams, printing can be cared
out by supplying oily ink and aqueous component without being
subjected to development process.
[0327] Specifically, a method of subjecting a lithographic printing
plate precursor to infrared laser exposure, and then mounting the
exposed printing plate precursor on a printing press without
undergoing development process and performing printing, and a
method of mounting a lithographic printing plate precursor on a
printing press, and then exposing the printing plate precursor with
laser beams on the printing press, and performing printing without
subjecting to development process are exemplified.
[0328] For example, in one embodiment of a negative on-press type
lithographic printing plate precursor, when a lithographic printing
plate precursor is imagewise exposed with laser beams and printing
is performed by supplying oily ink and aqueous component without
being subjected to development process such as wet development
process, the image-recording layer hardened by exposure forms an
oily ink-accepting area having a lipophilic surface at the exposed
portion of the image-recording layer. On the other hand, at the
unexposed portion, unhardened image-recording layer is dissolved or
dispersed with the supplied aqueous component and/or oily ink and
removed, whereby a hydrophilic surface is bared at that area.
[0329] As a result, the aqueous component adheres to the bared
hydrophilic surface, the oily ink adheres to the image recording
layer in the exposed portion, and printing is initiated. Here, the
one that is supplied first to the printing plate may be an aqueous
component or may be oily ink, but for preventing the aqueous
component from becoming din by the image recording layer at the
unexposed portion, it is preferred to supply oily ink in the first
place. As the aqueous component and the oily ink fountain solutions
and oily inks used in ordinary lithographic printing are used.
[0330] Thus, the lithographic printing plate precursor is subjected
to on-press development on an offset printing press and used in
printing of a plenty of sheets.
EXAMPLE
[0331] The invention will be described more specifically with
referring to examples but the invention is not limited thereto.
Synthesis Example 1
Synthesis of Compound 13 of the Invention
[0332] 2,3,3-Trimethylindolenine (159.2 g) (1.0 mol) was dissolved
by the addition of 300 ml of toluene. To the solution was added
136.2 g (1.0 mol) of 1,4-butanesultone, and the reaction system was
allowed to react for 2 hours at inner temperature of 120.degree. C.
The precipitated solids were filtered out and washed with toluene,
whereby the Precursor 13-A of Compound 13 of the invention was
obtained as a white solid (244 g, yield: 830%).
[0333] The physical properties of the obtained white solid are as
follows.
[0334] .sup.1H-NMR (DMSO-d.sub.6): .delta.8.06-8.02 (m, 1H),
7.87-7.82 (m, 1H), 7.63-7.60 (m, 2H), 4.48 (t, 2H), 2.86 (s, 3H),
2.54-2.50 (m, 2H), 2.02-1.92 (m, 2H), 1.80-1.70 (m, 2H), 1.53 (s,
6H)
[0335] The chemical reaction scheme in the synthesis example is
shown below. ##STR52##
[0336] In the next place, 25.0 g (0.085 mol) of Precursor 13-A,
salicylaldehyde (0.085 mol), and triethylamine (0.085 mol) were
dissolved in 100 mo of ethanol, and the reaction system was allowed
to react for 2 hours at inner temperature of 110.degree. C. Ethanol
was removed from the reaction mixture with a vacuum pump under
reduced pressure, and the obtained solid was washed with 40 ml of
ethyl acetate three times, whereby Compound 13 was obtained.
[0337] The physical properties of the obtained compound are as
follows.
[0338] .sup.1H-NMR(Acetone-d.sub.6): .delta.7.18-7.08 (m, 4), 6.99
(d, 1H), 6.84-7.74 (m, 2H), 6.65-6.61 (m, 2H), 5.87 (d, 1H),
3.22-3.13 (m, 8H), 2.66-2.54 (m, 2H), 1.84-1.68 (m, 4H), 1.34-1.27
(m, 12H), 1.17 (s, 3H)
[0339] The chemical reaction scheme in the synthesis example is
shown below. ##STR53##
Synthesis Example 2
Synthesis of Compound 42 of the Invention
[0340] Triphenylsulfonyl bromide (0.4 g) (1.16 mmol) was dissolved
by the addition of 28 ml of acetonitrile and 9 ml of water.
Immediately after the addition of 0.208 g (1.25 mmol) of silver
acetate dissolved in 28 ml of acetonitrile and 9 ml of water
thereto, white powder was precipitated. Thereafter the reaction
system was stirred at room temperature for 15 minutes, the
precipitated solids were filtered out, 0.6 g (1.13 mmol) of SP-150
(manufactured by Hayashibara Biochemical Laboratories, Inc.)
dissolved in 28 ml of acetonitrile and 9 ml of water was added to
the filtrate, and the system was stirred at room temperature for 30
minutes. Subsequently, the mixture was concentrated under reduced
pressure, and 20 ml of chloroform was added to the obtained
mixture. The chloroform solution was washed with 30 ml of water
three times and then concentrated, whereby objective Compound 42
was obtained.
[0341] The physical properties of the obtained Compound 42 are as
follows
[0342] .sup.1H-NMR (CDCl.sub.3): .delta.8.00-7.93 (m, 2H),
7.82-7.63 (m, 15H), 7.17-7.03 (m, 2H), 6.88-6.80 (m, 2H),
.delta.6.71-6.64 (m, 2H), .delta.5.92-5.87 (d, 1H),
.delta.3.38-3.21 (m, 2H), .delta.2.97-2.80 (m, 2H),
.delta.2.28-2.17 (m, 2H), 1.25 (s, 3H), 1.17 (s, 3H)
[0343] The chemical reaction scheme in the synthesis example is
shown below. ##STR54##
Synthesis Example 3
Synthesis of Compound 43 of the Invention
[0344] Precursor 13-A (5.9 g) (0.02 mmol) obtained in Synthesis
Example 1, 3.47 g (0.02 mmol) of 1-nitroso-2-naphthol, and 1.64 g
(0.02 mmol) of sodium acetate were dissolved in 300 ml of ethanol.
After that, the solution was allowed to react for 2.5 hours at
inner temperature of 100.degree. C., and then concentrated under
reduced pressure) whereby a mixture containing 43-A was
obtained.
[0345] Subsequently, 1.2 g (2.12 mmol) of iodonium salt A shown
below and 0.491 g (0.12 mmol) of Ag.sub.2O were dissolved in
methanol, and the solution was allowed to react at room temperature
for 2 hours. The precipitated solids were filtered, and 0.3 ml of
acetic acid and 1.0 g (2.12 mmol) of the above obtained 43-A were
and allowed to react for 1 hour. After that, the reaction mixture
as filtered and the obtained filtrate was concentrated, whereby
objective Compound 43 was obtained.
[0346] The physical properties of the obtained Compound 43 are as
follows:
[0347] .sup.1H-NMR (DMSO-6): .delta.8.49-8.47 (d, 1H), 8.07 (m,
4H), 7.90-7.75 (m, 3H) 7.66-7.56 (m, 2H9, 7.43 (m, 5H), 7.16-7.09
(m, 4H), 6.80 (t, 1H9, 6.65 (d, 1H), 3.14 (bs, 2H), 2.33 (m, 2H)
1.60 (m, 4), 1.21 (s, 18H), 0.85 (m, 2H9, 0.57 (t, 6H)
[0348] The chemical reaction scheme in the synthesis example is
shown below. ##STR55##
Example 1
Manufacture of Aluminum Support:
[0349] For removing the rolling oil of the surface, an aluminum
plate having a thickness of 0.3 mm (material 1050) was subjected to
decreasing treatment with a 10 mass % sodium alminate aqueous
solution at 50.degree. C. for 30 seconds, and after decreasing the
aluminum surface was subjected to brush-graining with three nylon
brushes planted with hairs having a hair diameter of 0.3 mm and a
suspension of pumice stone and water of a median diameter of 25
.mu.m (the specific gravity: 1.1 g/cm.sup.3), and the surface of
the plate was thoroughly washed with water. The plate was immersed
in a 25% sodium hydroxide aqueous solution at 45.degree. C. for 9
seconds for etching, and then washed with water. After water
washing, the plate was further immersed in a 20% nitric acid
aqueous solution for 20 seconds, followed by washing with water.
The etched amount of the surface by graining was about 3
g/m.sup.2.
[0350] Electrochemical surface roughening treatment was performed
continuously by alternating voltage of 60 Hz. The electrolyte at
this time was an aqueous solution containing 1 mass % of a nitric
acid (containing a 0.5 mass % of an aluminum ion) and the liquid
temperature was 50.degree. C. As the alternating current electric
source waveform, trapezoidal rectangular waveform alternating
current was used, the time TP required for the electric current
value to reach the peak from 0 was 0.8 msec, the duty ratio was
1/1, and electrochemical surface roughening treatment was performed
with a carbon electrode as the counter electrode. Ferrite was used
as the auxiliary anode. The electric current density was 30
A/dm.sup.2 at a peak value of electric current, and 5% of the
electric current from the electric source was diverted to the
auxiliary anode. The quantity of electricity was 175 C/dm.sup.2 in
the quantity of electricity in the case where the aluminum plate
was the anode. The aluminum plate was then washed with water.
[0351] Subsequently, electrochemical surface roughening treatment
of the aluminum plate was performed in the same manner as in the
above nitric acid electrolysis with an electrolyte containing a 0.5
mass % hydrochloric acid aqueous solution (containing 0.5 mass % of
an aluminum ion) at a liquid temperature of 50.degree. C. on the
condition of 50 C/dm.sup.2 of the quantity of electricity in the
case where the aluminum plate was the anode and the plate was then
subjected to spray washing. The plate was provided with 2.5
g/m.sup.2 of a direct current anodic oxide film with a 15% sulfuric
acid aqueous solution (containing 0.5 mass % of an aluminum ion) as
the electrolyte and the electric current density of 15 A/dm.sup.2,
washed with water, dried, and further subjected to treatment with a
2.5 mass % sodium silicate aqueous solution at 30.degree. C. for 10
seconds. The central line average surface roughness (Ra) of the
plate measured with a needle having a diameter of 2 .mu.u was 0.51
.mu.nm.
Formation of Undercoat Layer:
[0352] The undercoat layer coating solution (1) having the
composition shown below was coated on the above support with bar
coating, dried at 80.degree. C. for 20 seconds in an oven, whereby
an undercoat layer having a dry coating weight of 0.005 g/m.sup.2
was formed
[0353] Undercoat Layer Coating Solution (1): TABLE-US-00001 Water
10 g Methanol 90 g Polymer (1) shown below 0.09 g Polymer (1)
##STR56## ##STR57##
Formation of Image-Recording Layer:
[0354] The image-recording layer coating solution (1) having the
composition shown below was coated on the above undercoat layer
with bar coating, dried at 70.degree. C. for 60 seconds in an oven,
whereby a image-recording layer having a dry coating weight of 1.0
g/m.sup.2 was formed, whereby a lithographic priming plate
precursor 1 was obtained.
[0355] Image-Recording Layer Coating Solution (1): TABLE-US-00002
Water 50 g Propylene glycol monomethyl ether 50 g Microcapsule (1)
(in terms of solids content) 6 g Microcapsule (2) (in terms of
solids content) 2.5 g Polymerization initiator (1) shown below 1 g
Isocyanuric acid EO-modified triacrylate 0.5 g (ARONIX M-315,
manufactured by TOAGOSEI CO., LTD.) Fluorine surfactant (1) shown
below 0.1 g Polymerization initiator (1) ##STR58## ##STR59##
Fluorine surfactant (1) ##STR60## ##STR61##
Synthesis of Microcapsule (1):
[0356] As the oil phase component 8.7 g of the addition product of
trimethylolpropane and xylene diisocyanate (Takenate D-110N,
manufactured by Mitsui Takeda Chemicals Inc.), 1 g of
2-methacryloyloxyethyl isocyanate (Currens MOI, manufactured by
Showa Denko K. K.), 5.5 g of isocyanuric acid EO-modified
triacrylate (ARONIX M-315, manufactured by TOAGOSEI CO., LTD.), 0.5
g of infrared absorber (1) shown below, and 0.1 g of sodium
dodecylbenzenesulfonate (Pionin A-41C, manufactured by Takemoto Oil
& Fat) were dissolved in 17 g of ethyl acetate. As the aqueous
phase component 40 g of a 4 mass % aqueous solution of PVA-205 was
prepared. The oil phase component and the aqueous phase component
were mixed, and emulsified with a homogenizer at 12,000 rpm for 10
minutes. Distilled water (25 g) was added to the obtained
emulsified product, and the mixture was stirred at room temperature
for 30 minutes, and then stirred at 40.degree. C. for 3 hours. The
concentration of the solids content of the obtained microcapsule
solution (1) was diluted to reach 20 mass % with distilled water.
The average particle size was 0.3 .mu.m. ##STR62## Synthesis of
Microcapsule (2):
[0357] As the oil phase component, 10 g of the addition product of
trimethylolpropane and xylene diisocyanate (Takenate D-110N,
manufactured by Mitsui Takeda Chemicals Inc.), 5 g of
1,3,3-trimethylindolino-8'-carboxybenzopyrylospiran (manufactured
by Tokyo Kasei Co., Ltd.), 5 g of infrared absorber (1) shown
above, and 0.1 g of sodium dodecylbenzenesulfonate (Pionin A-41C,
manufactured by Takemoto Oil & Fat) were dissolved in 17 g of
ethyl acetate. As the aqueous phase component, 40 g of a 4 mass %
aqueous solution of PVA-205 was prepared. The oil phase component
and the aqueous phase component were mixed, and emulsified with a
homogenizer at 12,000 rpm for 10 minutes. Tetraethylene-pentamine
(038 g) and 25 g of distilled water were added to the obtained
emulsified product, and the mixture was stirred at room temperature
for 30 minutes, and then stirred at 65.degree. C. for 3 hours. The
concentration of the solids content of the obtained microcapsule
solution (2) was diluted to reach 20 mass % with distilled water.
The average particle size was 0.3 .mu.m.
Example 2
[0358] A lithographic printing plate precursor 2 was manufactured
by the same manner as in Example 1 except that the image-recording
layer coating solution (2) having the composition shown below was
coated on a support with bar coating, and dried at 100.degree. C.
for 60 seconds in an oven to form a image-recording layer having a
dry coating weight of 1,0 g/m.sup.2.
[0359] Image-Recording Layer Coating Solution (2): TABLE-US-00003
Infrared absorber (1) shown above 0.3 g Polymerization initiator
(1) shown above 0.9 g Binder polymer (1) shown below 2.5 g
Polymerizable compound 5.4 g Isocyanuric acid EO-modified
triacrylate (ARONIX M-315, manufactured by TOAGOSEI CO, LTD.)
1,3,3-Trimethylindolino-8'-carboxybenzo- 0.8 g pyrylospiran
(manufactured by Tokyo Kasei Co., Ltd.) Fluorine surfactant (1)
shown above 0.1 g Methanol 4 g Methyl ethyl ketone 96 g Binder
Polymer (1) ##STR63## ##STR64##
Example 3
[0360] A lithographic printing plate precursor 3 was manufactured
by the same manner as in Example 1 except that the image-recording
layer coating solution (3) having the composition shown below was
coated on a support with bar coating, and dried at 80.degree. C.
for 60 seconds in an oven to form a image-recording layer having a
dry coating weight of 110 g/m.sup.2.
[0361] Image-Recording Layer Coating Solution (3): TABLE-US-00004
Infrared absorber (2) shown below 0.3 g Polymerization initiator
(1) shown above 0.9 g Binder polymer (1) shown above 2.5 g
Polymerizable compound 5.4 g Pentaerythritol triacrylate (SR444,
manufactured by Nippon Kayaku Co., Ltd.) Microcapsule (2) (in terms
of solids content) 2.5 g Fluorine surfactant (1) shown above 0.1 g
Methanol 10 g Water 35 g Propylene glycol monomethyl ether 50 g
Infrared Absorber (2) ##STR65##
Example 4
[0362] A lithographic printing plate precursor 4 was manufactured
by the same manner as in Example 1 except that the image-recording
layer coating solution (4) having the composition shown below was
coated on a support with bar coating, and dried at 100.degree. C.
for 60 seconds in an oven to from a image-recording layer having a
dry coating weight of 1.0 g/m.sup.2.
[0363] Image-Recording Layer Coating Solution (4): TABLE-US-00005
Infrared absorber (2) shown above 0.3 g Polymerization initiator
(1) shown above 0.9 g Binder polymer (1) shown above 1.8 g
Polymerizable compound 2.0 g Pentaerythritol triacrylate (SR444,
manufactured by Nippon Kayaku Co., Ltd) Microcapsule (2) (in terms
of solids content) 2.5 g Microcapsule (3) (in terms of solids
content) 2.5 g Fluorine surfactant (1) shown above 0.1 g Methanol
10 g Water 35 g Propylene glycol monomethyl ether 50 g
Synthesis of Microcapsule (3):
[0364] As the oil phase component, 8.7 g of the addition product of
trimethylolpropane and xylene diisocyanate (Takenate D-110N,
manufactured by Mitsui Takeda Chemicals Inc.), 1 g of
2-methacryloyloxyethyl isocyanate (Currens MOI, manufactured by
Showa Denko K.K.), 6 g of pentaerythritol triacrylate (SR444,
manufactured by Nippon Kayatu Co., Ltd.), and 0.1 g of sodium
dodecylbenzenesulfonate (Pionin A41C, manufactured by Takemoto Oil
& Fat) were dissolved in 17 g of ethyl acetate. As the aqueous
phase component, 40 g of a 4 mass % aqueous solution of PVA-205 was
prepared. The oil phase component and the aqueous phase component
were mixed, and emulsified with a homogenizer at 12,000 rpm for 10
minutes. Distilled water (25 g) was added to the obtained
emulsified product and the mixture was stirred at room temperature
for 30 minutes, and then stirred at 40.degree. C. for 3 hours. The
concentration of the solids content of the obtained microcapsule
solution (3) was diluted to reach 20 mass % with distilled water.
The average particle size was 0.3 .mu.m.
Example 5
[0365] A lithographic printing plate precursor 5 was manufactured
by the same manner as in Example 4 except that the protective layer
coating solution (1) having the composition shown below was further
coated on the image-recording layer in Example 4 with bar coating,
and dried at 100.degree. C. for 60 seconds in an oven to form a
protective layer having a dry coating weight of 0.5 g/m.sup.2.
[0366] Protective Layer Coating Solution (1): TABLE-US-00006
Polyvinyl alcohol 10 g (PVA-105, manufactured by Kuraray Co., Ltd.,
degree of saponification: 98.5%) Polyoxyethylene lauryl ether 0.01
g (EMALEX 710, manufactured by Nihon Emulsion Co.) Water 19.0 g
Comparative Example 1
[0367] A lithographic printing plate precursor C1 was manufactured
by the same manner as in Example 1 except that microcapsule (2)
used in image-recording layer coating solution (1) was completely
replaced with microcapsule (4).
Synthesis of Microcapsule (4):
[0368] As the oil phase component, 10 g of the addition product of
trimethylolpropane and xylene diisocyanate (Takenate D-110N,
manufactured by Mitsui Takeda Chemicals Inc.), 0.5 g of infrared
absorber (1), and 0.1 g of sodium dodecylbenzene-sulfonate (Pionin
A-41C, manufactured by Takemoto Oil & Fat) were dissolved in 17
g of ethyl acetate. As the aqueous phase component, 40 g of a 4
mass % aqueous solution of PVA-205 was prepared. The oil phase
component and the aqueous phase component were mixed, and
emulsified with a homogenizer at 12,000 rpm for 10 minutes.
Tetraethylenepentamine (0.38 g) and 25 g of distilled water were
added to the obtained emulsified product, and the mixture was
stirred at room temperature for 30 minutes, and then stirred at
65.degree. C. for 3 hours. The concentration of the solids content
of the obtained microcapsule solution (4) was diluted to reach 20
mass % with distilled water. The average particle size was 03
.mu.m.
Comparative Example 2
[0369] A lithographic printing plate precursor C2 was manufactured
by the same manner as in Example 2 except that image-recording
layer coating solution (2) was replaced with image-recording layer
coating solution (5) shown below.
[0370] Image-Recording Layer Coating Solution (5): TABLE-US-00007
Infrared absorber (1) shown above 0.3 g Polymerization initiator
(1) shown above 0.9 g Binder polymer (1) shown above 2.5 g
Polymerizable compound 5.4 g Isocyanuric acid EO-modified
triacrylate (ARONIX M-315, manufactured by TOAGOSEI CO., LTD.)
Fluorine surfactant (1) shown above 0.1 g Methanol 4 g Methyl ethyl
ketone 96 g
Comparative Example 3
[0371] A lithographic printing plate precursor C3 was manufactured
by the same manner as in Example 3 except that microcapsule (2)
used in image-recording layer coating solution (3) was completely
replaced with microcapsule (4).
Comparative Example 4
[0372] A lithographic printing plate precursor C4 was manufactured
by the same manner as in Example 4 except that microcapsule (2)
used in image-recording layer coating solution (4) was completely
replaced with microcapsule (4).
Comparative Example 5
[0373] A lithographic printing plate precursor C5 was manufactured
by the same manner as in Comparative Example 4 except that the
protective layer coating solution (1) having the composition shown
below was further coated on the image-recording layer in
Comparative Example 4 with bar coating and dried at 100.degree. C.
for 60 seconds in an oven to form a protective layer having a dry
coating weight of 0.5 g/m.sup.2.
Evaluation of Lithographic Printing Plate Precursor;
1. Measurement of the Difference in Brightness of Colors .DELTA.L
in the Exposed Area and the Unexposed Area (Evaluation of Printing
Out Image)
[0374] Each of the lithographic printing plate precursors obtained
was subjected to exposure with Trendsetter 3244VX (manufactured by
Creo Products Incorporated) loading a water-cooling type 40 W
infrared semiconductor laser on the conditions of the quantity of
exposure energy shown in Table 1 below and resolution of 2,400 dpi.
For the evaluation of printing out images, L*values in the exposed
area and the unexposed area were measured with a color difference
meter (Color difference meter CR-221, manufactured by Minorta), and
the difference in the brightness of colors: .DELTA.L was obtained
from the absolute value of color difference.
[0375] The results obtained are shown in Table 1. The result was
shown as index with the .DELTA.L value of Example 1 as standard
(100), as well as the .DELTA.L value. The greater the value in the
index of .DELTA.L, the higher is the visibility and preferred.
[0376] As is apparent from Table 1 that the lithographic printing
plate precursors of the invention were good in the contrast of the
exposed area and the unexposed area, and fine lines and letters
could be confirmed.
2. Evaluation of on-Press Developability and Printing
[0377] The exposed printing precursor was mounted on SOR-M cylinder
(manufactured by Heidelberg Japan K.K.) without performing
development. A fountain solution (EU-3 (an etching solution
manufactured by Fuji Photo Film Co., Ltd.)water/isopropyl
alcohol=1/89/10 (by volume)) and TRANS-G (N) Sumi ink (manufactured
by Dainippon Ink and Chemicals Inc.) were supplied as the fountain
solution and ink, and 100 sheets of paper were printed at a
printing speed of 6,000 sheets per hour.
[0378] The number of the sheets of printing paper required up to
the time when the on-press development of the unexposed area of the
image-recording layer finished and the ink did not transfer to
printing paper was counted, and the number of sheets was taken as
the on-press developability. Printed substance free from staining
could be obtained within 100 sheets when the lithographic printing
plate precursors of the invention were used.
[0379] Subsequently, 5,000 sheets of paper were printed. Good
printed substances free from the reduction of ink density in the
image area and soiling in the non-image area could be obtained
TABLE-US-00008 TABLE 1 Result of Measurement of Difference in
Brightness of Colors .DELTA.L Lithographic Exposure Example
Printing Plate Energy No. Precursor Used (mJ/cm.sup.2) Index of
.DELTA.L .DELTA.L value Example 1 1 100 100 5 Example 2 2 100 110
5.5 Example 3 3 100 115 5.75 Example 4 4 100 105 5.25 Example 5 5
100 125 6.25 Comparative C1 100 5 0.25 Example 1 Comparative C2 100
10 0.5 Example 2 Comparative C3 100 10 0.5 Example 3 Comparative C4
100 10 0.5 Example 4 Comparative C5 100 10 0.5 Example 5
Example 6
[0380] Lithographic printing plate precursor 6 was prepared by the
same manner as in Example 1 except that microcapsule (2) in
photosensitive/light-sensitive layer coating solution (1) was
replaced with microcapsule (5) shown below.
Synthesis of Microcapsule (5):
[0381] As the oil phase component 10 g of the addition product of
trimethylolpropane and xylene diisocyanate (Takenate D-110N,
manufactured by Mitsui Takeda Chemicals Inc), 5 g of spirooxazine
(1) shown below (manufactured by Tokyo Kasei Co., Ltd.), 0.5 g of
infrared absorber (1), and 0.1 g of sodium dodecylbenzenesulfonate
(Pionin A-41C, manufactured by Takemoto Oil & Fat) were
dissolved in 17 g of ethyl acetate. As the aqueous phase component,
40 g of a 4 mass % aqueous solution of PVA-205 was prepared The oil
phase component and the aqueous phase component were mixed, and
emulsified with a homogenizer at 12,000 rpm for 10 minutes.
Tetraethylene-pentamine (0.38 g) and 25 g of distilled water were
added to the obtained emulsified product, and the mixture was
stirred at room temperature for 30 minutes, and then stirred at
65.degree. C. for 3 hours. The concentration of the solids content
of the obtained microcapsule solution (5) was diluted to reach 20
mass % with distilled water. The average particle size was 0.3
.mu.m. ##STR66##
Example 7
[0382] A lithographic printing plate precursor 7 was manufactured
by the same manner as in Example 2 except that
1,3,3-trimethylindolino-8'-carboxybenzospiran used in
photosensitive/light-sensitive layer coating solution (2) was
replaced with the above spirooxazine (1).
Example 8
[0383] A lithographic printing plate precursor 8 was manufactured
by the same manner as in Example 3 except that microcapsule (2)
used in photosensitive/light-sensitive layer coating solution (3)
was replaced with microcapsule (5),
Example 9
[0384] A lithographic printing plate precursor 9 was manufactured
by the same manner as in Example 4 except that microcapsule (2)
used in photosensitive/light-sensitive layer coating solution (4)
was replaced with microcapsule (5).
Example 10
[0385] A lithographic printing plate precursor 10 was manufactured
by the same manner as in Example 9 except that the protective layer
coating solution (1) having the composition shown above was further
coated on the photosensitive/light-sensitive layer in Example 9
with bar coating, and dried at 100.degree. C. for 60 seconds in an
oven to form a protective layer having a dry coating weight of 0.5
g/m.sup.2.
[0386] With every lithographic printing plate precursor in Examples
6 to 10, the difference in brightness of colors .DELTA.L was
measured in the same manner as in Example 1. The results obtained
are shown in Table 2 below. TABLE-US-00009 TABLE 2 Example No.
Index of .DELTA.L .DELTA.L value Example 6 120 6 Example 7 130 6.5
Example 8 135 6.75 Example 9 115 5.75 Example 10 150 7.5
Example 11
[0387] The image-recording layer coating solution (6) having the
composition shown below was coated on the above undercoat layer
with bar coating, dried at 70.degree. C. for 60 seconds in an oven,
whereby an image-recording layer having a dry coating weight of 1.0
g/m.sup.2 was formed, whereby a lithographic printing plate
precursor 11 was obtained.
[0388] Image-Recording Layer Coating Solution (6): TABLE-US-00010
Water 50 g Propylene glycol monomethyl ether 50 g Microcapsule (6)
(in terms of solids content) 6 g Microcapsule (7) (in terms of
solids content) 2.5 g Polymerization initiator (1) shown above 1 g
Isocyanuric acid EO-modified triacrylate 0.5 g (M-315, manufactured
by TOAGOSEI CO., LTD.) Fluorine surfactant (1) shown above 0.1
g
Synthesis of Microcapsule (6):
[0389] As the oil phase component 8.7 g of the addition product of
trimethylolpropane and xylene diisocyanate (Takenate D-110 N,
manufactured by Mitsui Takeda Chemicals Inc.), 1 g of
2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by
Showa Denko K.K.), 5,5 g of isocyanuric acid EO-modified
triacrylate (M-315, manufactured by TOAGOSEI CO., LTD.), and 0.1 g
of sodium dodecylbenzenesulfonate (Pionin A-41C, manufactured by
Takemoto Oil & Fat) were dissolved in 17 g of ethyl acetate. As
the aqueous phase component, 40 g of a 4 mass % aqueous solution of
PVA 205 was prepared. The oil phase component and the aqueous phase
component were mixed, and emulsified with a homogeizer at 12,000
rpm for 10 minutes. Distilled water (25 g) was added to the
obtained emulsified product, and the mixture was stirred at room
temperature for 30 minutes, and then stirred at 40.degree. C. for 3
hours. The concentration of the solids content of the obtained
microcapsule solution (6) was diluted to reach 20 mass % with
distilled water. The average particle size was 0.3 .mu.n.
Synthesis of Microcapsule (7):
[0390] As the oil phase component, 10 g of the addition product of
trimethylolpropane and xylene diisocyanate (Takenate D-110N,
manufactured by Mitsui Takeda Chemicals Inc.), 5 g of Compound 13
(exemplified compound in the specification), 0.5 g of infrared
absorber (1) shown above, and 0.1 g of sodium
dodecylbenzenesulfonate (Pionin A-41C, manufactured by Takemoto Oil
& Fat) were dissolved in 17 g of ethyl acetate. As the aqueous
phase component, 40 g of a 4 mass % aqueous solution of PVA-205 was
prepared. The oil phase component and the aqueous phase component
were mixed, and emulsified with a homogenizer at 12,000 rpm for 10
minutes. Tetraethylene-pentamine (0.38 g) and 25 g of distilled
water were added to the obtained emulsified product, and the
mixture was stirred at room temperature for 30 minutes, and then
stirred at 65.degree. C. for 3 hours. The concentration of the
solids content of the obtained microcapsule solution (7) was
diluted to reach 20 mass % with distilled water. The average
particle size was 0.3 .mu.m.
Example 12
[0391] A lithographic printing plate precursor 12 was manufactured
by the same manner as in Example 1 except that the image recording
layer coating solution (7) having the composition shown below was
coated on a support with bar coating, and dried at 100.degree. C.
for 60 seconds in an oven to from an image-recording layer having a
dry coating weight of 1.0 g/m.sup.2.
[0392] Image-Recording Layer Coating Solution (7): TABLE-US-00011
Infrared absorber (1) shown above 0.3 g Polymerization initiator
(1) shown above 0.9 g Binder polymer (1) shown above 2.5 g
Polymerizable compound 5.4 g Isocyanuric acid EO-modified
triacrylate (ARONIX M-315, manufactured by TOAGOSEI CO., LTD.)
Compound 13 (compound of the invention) 0.8 g Fluorine surfactant
(1) shown above 0.1 g Methanol 4 g Methyl ethyl ketone 96 g
Example 13
[0393] A lithographic printing plate precursor 13 was manufactured
by the same manner as in Example 1 except that the image recording
layer coating solution (8) having the composition shown below was
coated on a support with bar coating, and dried at 80.degree. C.
for 60 seconds in an oven to form an image-recording layer having a
dry coating weight of 1.0 g/m.sup.2.
[0394] Image-Recording Coating Solution: TABLE-US-00012 Infrared
absorber (2) shown above 0.3 g Polymerization initiator (1) shown
above 0.9 g Binder polymer (1) shown above 2.5 g Polymerizable
compound 5.4 g Pentaerythritol triacrylate (SR444, manufactured by
Nippon Kayaku Co., Ltd.) Microcapsule (7) (in terms of solids
content) 2.5 g Fluorine surfactant (1) shown above 0.1 g Methanol
10 g Water 35 g Propylene glycol monomethyl ether 50 g
Example 14
[0395] A lithographic printing plate precursor 14 was manufactured
by the same manner as in Example 1 except that the image recording
layer coating solution (9) having the composition shown below was
coated on a support with bar coating, and dried at 100.degree. C.
for 60 seconds in an oven to form an image-recording layer having a
dry coating weight of 10 g/m.sup.2.
[0396] Image-Recording Layer Coating Solution: TABLE-US-00013
Infrared absorber (2) shown above 0.3 g Polymerization initiator
(1) shown above 0.9 g Binder polymer (1) shown above 1.8 g
Polymerizable compound 2.0 g Pentaerythritol triacrylate (SR444,
manufactured by Nippon Kayaku Co., Ltd.) Microcapsule (7) (in terms
of solids content) 2.5 g Microcapsule (3) shown above (in terms of
solids content) 2.5 g Fluorine surfactant (1) shown above 0.1 g
Methanol 10 g Water 35 g Propylene glycol monomethyl ether 50 g
Example 15
[0397] A lithographic printing plate precursor 15 was manufactured
by the same manner as in Example 14 except that the protective
layer coating solution (1) shown above was flirt coated on the
image-recording layer in Example 14 with bar coating, and dried at
100.degree. C. for 60 seconds in an oven to form a protective layer
having a dry coating weight of 0.5 g/m.sup.2.
Examples 16 to 20
[0398] Lithographic printing plate precursors 16 to 20 were
prepared by the same manner as in Examples 11 to 15 respectively
except that Compound 13 of the invention used in Examples 11 to 15
was replaced with Compound 42 of the invention.
Examples 21 to 25
[0399] Lithographic printing plate precursors 21 to 25 were
prepared by the same manner as in Examples 11 to 15 respectively
except that Compound 13 of the invention used in Examples 11 to 15
was replaced with Compound 43 of the invention.
Comparative Example 6
[0400] A lithographic printing plate precursor C6 was manufactured
by the same manner as in Example 11 except that microcapsule (7)
used in image-recording layer coating solution (6) was completely
replaced with microcapsule (4).
Evaluation of Lithographic Printing Plate Precursors 11 to 25 and
C6
[0401] The evaluation was performed in the same manner as in
Examples 1 to 10, and the result is shown in Table 3. The quantity
of exposure energy was 100 mJ/m.sup.2. TABLE-US-00014 TABLE 3
Result of Measurement of Difference in Brightness of Colors
.DELTA.L Lithographic Printing Plate Precursor Used Index of
.DELTA.L .DELTA.L value Example 11 11 152 7.6 Example 12 12 136 6.8
Example 13 13 118 5.9 Example 14 14 142 7.1 Example 15 15 144 7.2
Example 16 16 172 8.6 Example 17 17 182 9.1 Example 18 18 150 7.5
Example 19 19 164 8.2 Example 20 20 166 8.3 Example 21 21 130 6.5
Example 22 22 132 6.6 Example 23 23 112 5.6 Example 24 24 138 6.9
Example 25 25 138 6.9 Comparative C6 6 0.3 Example 6
[0402] It is apparent from the above results that the lithographic
printing plate precursors according to the invention show great
difference in brightness of colors by exposure, and produce
printing out images having excellent visibility.
[0403] This application is based on Japanese patent applications JP
2004-115121, filed on Apr. 9, 2004 and JP 2004-275449, filed on
Sep. 22, 2004, the entire content of which is hereby incorporated
by reference, the same as if set forth at length.
* * * * *